CN112290034B - Anode material of solid oxide fuel cell and preparation method thereof - Google Patents

Anode material of solid oxide fuel cell and preparation method thereof Download PDF

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CN112290034B
CN112290034B CN201910679940.0A CN201910679940A CN112290034B CN 112290034 B CN112290034 B CN 112290034B CN 201910679940 A CN201910679940 A CN 201910679940A CN 112290034 B CN112290034 B CN 112290034B
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powder
fuel cell
anode material
perovskite
oxide
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CN112290034A (en
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钟秦
陈华林
朱腾龙
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • 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
    • H01M2004/8689—Positive electrodes
    • 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 discloses a solid oxide fuel cell anode material and a preparation method thereof. The anode material of the solid oxide fuel cell is perovskite strontium titanate oxide powder coated by gadolinium oxide doped cerium oxide, and 30-50 wt% of GDC is coated on the perovskite anode precursor powder by a sol-gel method. The anode material of the fuel cell improves the oxygen ion conduction capability of the anode material by mixing GDC, so that the three-phase interface area of the anode material is improved, and the anode material has stable structure and high conductivity and carbon deposition resistance under a reducing atmosphere.

Description

Anode material of solid oxide fuel cell and preparation method thereof
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and relates to a solid oxide fuel cell anode material and a preparation method thereof.
Background
A Solid Oxide Fuel Cell (SOFC) is a novel clean and environment-friendly power generation device, and is an effective way for solving the energy problem of the traditional fossil Fuel. Oxides containing 2 or more different cations are called composite oxides. It has different properties compared to simple oxides and is structurally diverse. The perovskite type oxide structure can be ABO 3 Wherein a and B represent two different cations. Due to the diversity of structure and chemical composition, perovskite-type oxides exhibit diverse properties, such as good catalytic properties, good mixed ion electron conductivity, and the like, in reactions. At present, the perovskite oxide is mainly prepared by a solid-phase synthesis method. However, Ni-based anodes, based on Ni-YSZ, tend to carbon deposits over long periods of operation when using hydrocarbon fuels. Using doped (La, Sr) CrO 3 The stability of the operation of SOFC anodes can be improved to a certain extent by replacing Ni with perovskite oxide materials, but the catalytic activity of the materials on fuel is low, so that the performance of the cell is poor. Therefore, a perovskite oxide anode having excellent electrochemical properties was developedThe material is an effective method for solving the problem of high efficiency and stability of SOFC operation.
The solution dipping method is a means for effectively improving the electrochemical performance of the anode, and the principle is that a high-activity catalyst is dissolved by a solution, then the solution is dripped on an anode support body and is further loaded on a support framework of the anode, so that the performance is improved. However, the process is complex and long in time, uniform dispersion and loading on the anode framework are difficult to guarantee, and the nano-particle catalyst can be agglomerated and the reaction performance is reduced when the catalyst is operated in a reducing atmosphere for a long time. The precipitation of the metal particles with oxidation catalysis from the perovskite skeleton can be carried out very simply by the desolvation method. But it is necessary to ensure the stability of the material under hydrogen.
For solid oxide fuel cell anode materials, the porous anode consists of ionic and electronic conductors. The ionic and electronic conductivity may be from a single phase or a composite of an ionically conductive phase and an electronically conductive phase. The intersection of these three phases is called the three-phase boundary (TPB). The anode is a key part of an anode and an electrochemical reaction site of the anode, and needs a fine microstructure to provide good performance, and the larger the three-phase interface of the reaction is, the better the electrochemical performance is.
Disclosure of Invention
The invention aims to provide a solid oxide fuel cell anode material which is simple and easy to obtain and is tightly combined with an electrolyte and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the anode material of the solid oxide fuel cell is perovskite strontium titanate oxide powder coated by gadolinium oxide doped cerium oxide (GDC), and the general formula of the perovskite strontium titanate oxide is A 1-x B 1-y-z B’ y B” z O 3 Wherein, A site defect, B site doping, A is selected from strontium, calcium or barium, B is titanium or chromium, B 'and B' are two of manganese, iron, cobalt, nickel, scandium, niobium and molybdenum respectively, x is more than 0 and less than or equal to 0.04, y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.1, the general formula of the gadolinium oxide doped cerium oxide is Ce 0.9 Gd 0.1 O 2-m ，0＜m≤0.05。
The invention also provides a preparation method of the solid oxide battery anode material, which comprises the following steps:
step 1, according to the number of metal ions: ethylene glycol: citric acid 1: 1.2: 1.5, molar ratio of Ce (NO) 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 Mixing O, glycol and citric acid, and dissolving in water to obtain a mixed solution;
step 2, by a sol-gel method, according to the content of the GDC in the GDC-coated perovskite strontium titanate oxide powder of 30-50 wt%, SrTiO is added 3 Adding the perovskite precursor powder into the mixed solution, heating and stirring, evaporating to dryness until combustion, calcining the combusted powder for 6 +/-0.5 hours at 400-600 ℃ in an air atmosphere, and carrying out ball milling after calcining;
and 3, drying the powder subjected to ball milling, calcining for 6 +/-0.5 hours at 800 +/-50 ℃ in an air atmosphere, and finally sieving by a 200-mesh sieve to obtain the GDC-coated perovskite strontium titanate oxide powder, namely the solid oxide battery anode material.
Preferably, in the step 2, the ball milling medium is zirconia balls and absolute ethyl alcohol, and the ball milling time is 1-2 days.
Further, the invention provides a fuel cell based on the solid oxide cell anode material, and the preparation method comprises the following steps:
according to the mass ratio of 1: 1.5 mixing GDC-coated perovskite strontium titanate oxide powder with a binder, and screen-printing the resulting electrode paste on LSGM (La) 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3 ) On the electrolyte sheet, with LSCF (La) 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 ) The cathode material is prepared by mixing LSCF powder and an adhesive according to the mass ratio of 1: 1.5, mixing, screen-printing on the other side of the electrolyte sheet, and calcining for 4 +/-0.5 hours at 1050-1150 ℃ in an air atmosphere to obtain the fuel cell.
Compared with the prior art, the invention has the following advantages:
the invention adopts a sol-gel method to realize the coating of GDC, GDC grows in the electrode material, the dispersion is uniform, the synthesized powder particles are small, the specific surface area is large, and the ionic conductivity of the powder is improved, thereby increasing the area of a three-phase interface and reducing the impedance. In application, as the fuel cell anode works in a reducing atmosphere, the B site element of the perovskite precipitates a nano-grade transition metal alloy on the anode material framework, and the nano-grade transition metal alloy is uniformly dispersed and has good capability of catalyzing and oxidizing hydrogen.
Drawings
FIG. 1 is SrTiO prepared in example 1 3 X-ray diffraction patterns of perovskite-based precursor powder (STFN) and GDC-coated perovskite strontium titanate oxide powder (STFN-GDC).
Fig. 2 is a sectional scanning electron micrograph of the full Cell1 prepared in example 1 on the anode side.
Fig. 3 is a graph of electrochemical ac impedance of each fuel cell.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
(1)SrTiO 3 Preparing perovskite precursor powder:
the perovskite anode precursor powder is SrTiO 3 Based on perovskite having as the main component Sr 1-x Ti 1-y-z Fe y Ni z O 3 The preparation method is characterized by comprising the following steps:
the first step is as follows: according to Sr: ti: fe: ni ═ 0.95: 0.35: 0.6: 0.05 mol ratio, weighing SrCO 3 、TiO 2 、Fe 2 O 3 、Ni(NO 3 ) 2 ·6H 2 Putting the mixture into a ball milling tank, and ball milling for 4 days in a roller ball mill by taking zirconia balls and absolute ethyl alcohol as ball milling media;
the second step is that: drying the uniformly mixed precursor, and calcining for 10 hours at 1200 ℃ in an air atmosphere to obtain STFNi powder with a perovskite structure;
the third step: ball-milling the calcined powder for 4 days to obtain fine electrode powder, and sieving with 200 mesh sieve to obtain target precursor powder, namely SrTiO 3 Perovskite-based precursorsPowder flooding (STFN).
(2) Preparation of solid oxide cell anode material:
the first step is as follows: by the sol-gel method, in terms of the number of metal ions: ethylene glycol: citric acid 1: 1.2: 1.5, molar ratio of Ce (NO) 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 Mixing 6H2O, ethylene glycol and citric acid, and dissolving in water to obtain a mixed solution;
the second step is that: according to the GDC content of 50 wt% in GDC coated perovskite type strontium titanate oxide powder, SrTiO is added 3 Adding the perovskite-based precursor powder into the mixed solution, heating and stirring, evaporating to dryness until combustion, calcining the combusted powder for 6 hours at 600 ℃ in air atmosphere, and ball-milling the obtained powder for 2 days in a roller ball mill by using zirconia balls and absolute ethyl alcohol as ball-milling media;
the third step: and drying the powder subjected to ball milling, calcining the powder at 800 ℃ for 10 hours in an air atmosphere, and finally sieving the powder by a 200-mesh sieve to obtain the GDC-coated perovskite strontium titanate oxide powder (STFN-GDC).
(3) Preparation of fuel cell:
according to the mass ratio of 1: 1.5 mixing GDC-coated perovskite strontium titanate oxide powder with a binder, and screen-printing the resulting electrode paste on LSGM (La) 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3 ) On the electrolyte sheet, LSCF (La) is used as the cathode material 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 ) And mixing LSCF powder and a binder in a mass ratio of 1: 1.5, screen printing the other side of the electrolyte sheet, and calcining at 1100 ℃ for 4 hours in an air atmosphere to obtain the full Cell 1.
Correspondingly, the content of GDC in the perovskite strontium titanate oxide powder is 50wt percent and the GDC is formed by SrTiO 3 Preparing full Cell2 from anode material prepared by mechanically mixing perovskite precursor powder with GDC, and only SrTiO 3 The Cell prepared by taking the perovskite precursor powder as an anode material is Cell 3. The cell was heated to 750 ℃ and room temperature humidified hydrogen (3% H) was fed to the anode side 2 O-97％H 2 ) And starts after 3 hours of stabilizationAnd testing the electrochemical alternating-current impedance diagram.
FIG. 1 is SrTiO prepared in example 1 3 The X-ray diffraction patterns of the perovskite-based precursor powder (STFN), the GDC-coated perovskite strontium titanate oxide powder (STFN-GDC) and the PDF card of JADE of the GDC show that the GDC is successfully coated on the STFN.
Fig. 2 is a sectional scanning electron microscope image of the full Cell1 prepared in example on the anode side. It can be seen from the figure that after operation under hydrogen, metal alloy particles are precipitated on the skeleton.
Fig. 3 is a graph of electrochemical ac impedance of each fuel cell. It can be seen from the figure that the anode impedance of the Cell is Cell1 < Cell2 < Cell3, indicating that the GDC-coated perovskite strontium titanate oxide powder of the present invention promotes the catalytic hydrogen reaction.

Claims (5)

1. The anode material of the solid oxide fuel cell is characterized by being perovskite strontium titanate oxide powder coated by gadolinium oxide doped cerium oxide, and the general formula of the perovskite strontium titanate oxide is A 1-x B 1-y-z B’ y B” z O 3 Wherein, A site defect, B site doping, A is selected from strontium, calcium or barium, B is titanium or chromium, B 'and B' are two of manganese, iron, cobalt, nickel, scandium, niobium and molybdenum respectively, x is more than 0 and less than or equal to 0.04, y is more than 0 and less than or equal to 0.7, z is more than 0 and less than or equal to 0.1, the general formula of the gadolinium oxide doped cerium oxide is Ce 0.9 Gd 0.1 O 2-m ，0＜m≤0.05。
2. The method for preparing the anode material of the solid oxide fuel cell according to claim 1, comprising the following steps:
step 1, according to the number of metal ions: ethylene glycol: citric acid 1: 1.2: 1.5, molar ratio of Ce (NO) 3 ) 3 ·6H 2 O、Gd(NO 3 ) 3 ·6H 2 Mixing O, glycol and citric acid, and dissolving in water to obtain a mixed solution;
step 2, through a sol-gel method, coating perovskite type strontium titanate on GDC according to GDCThe content of the oxide powder is 30-50 wt%, and SrTiO is added 3 Adding perovskite precursor powder into the mixed solution, heating and stirring, evaporating to dryness until combustion, calcining the combusted powder at 400-600 ℃ in air atmosphere for 6 +/-0.5 hours, and performing ball milling after calcining;
and 3, drying the powder subjected to ball milling, calcining the powder at 800 +/-50 ℃ for 6 +/-0.5 hours in an air atmosphere, and finally sieving the powder by a 200-mesh sieve to obtain the GDC-coated perovskite strontium titanate oxide powder, namely the anode material of the solid oxide battery.
3. The preparation method according to claim 2, wherein in the step 2, the ball milling media are zirconia balls and absolute ethyl alcohol, and the ball milling time is 1-2 days.
4. A fuel cell made from the solid oxide fuel cell anode material of claim 1.
5. The method for manufacturing a fuel cell according to claim 4, characterized by comprising the following steps:
according to the mass ratio of 1: 1.5, mixing the GDC-coated perovskite strontium titanate oxide powder with an adhesive, screen-printing the obtained electrode slurry on an LSGM electrolyte sheet, taking LSCF as a cathode material, and mixing the LSCF powder with the adhesive according to a mass ratio of 1: 1.5, screen printing the mixture on the other side of the electrolyte sheet, and calcining the mixture for 4 +/-0.5 hours at 1050-1150 ℃ in an air atmosphere to obtain the fuel cell.
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CN114855203A (en) * 2022-05-20 2022-08-05 南京理工大学 Application of perovskite LSCM material in solid oxide electrolytic cell
CN114914506B (en) * 2022-06-17 2024-01-26 福州大学 Method for improving operation stability of unfired metal ceramic anode
CN114976068A (en) * 2022-06-22 2022-08-30 深圳大学 Solid oxide fuel cell and preparation method thereof

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