CN115528259A - Bismuth ion modified praseodymium ferrite-based solid oxide fuel cell anode material and preparation method thereof - Google Patents

Bismuth ion modified praseodymium ferrite-based solid oxide fuel cell anode material and preparation method thereof Download PDF

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CN115528259A
CN115528259A CN202110702586.6A CN202110702586A CN115528259A CN 115528259 A CN115528259 A CN 115528259A CN 202110702586 A CN202110702586 A CN 202110702586A CN 115528259 A CN115528259 A CN 115528259A
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anode material
solid oxide
oxide fuel
fuel cell
feo
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CN115528259B (en
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金芳军
孙宁
刘小伟
***
沈羽
王芳
徐铭泽
楚学影
翟英娇
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Changchun University of Science and Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/0018Mixed oxides or hydroxides
    • C01G49/0054Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/009Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/12Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1231Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/12Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293Fuel cells with solid oxide electrolytes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention relates to an anode material of a solid oxide fuel cell and a preparation method and application thereof, belonging to the technical field of anode materials of solid oxide fuel cells. The invention aims to solve the problem that the anode material of a solid oxide fuel cell is easy to decompose in a reducing atmosphere, thereby affecting the performance of the cell. The anode material is perovskite structure oxide with a chemical formula of Pr 2 O 3 ‑BiFe@Pr x1‑ Bi x FeO 3 Wherein 0 is<x<1. The anode material can improve the stability in reducing atmosphere by doping bismuth ions, and uniformly distributed nano particles are separated out, and the anode material has the advantages ofHas good conductivity, lower polarization resistance, good catalytic activity and the like. SOFCs prepared by the anode material of the invention have better stability and higher power output density under the hydrocarbon fuel atmosphere, and can be used as a novel SOFCs anode material.

Description

Bismuth ion modified praseodymium ferrite-based solid oxide fuel cell anode material and preparation method thereof
Technical Field
The invention relates to the field of anode materials, in particular to an anode material of novel Solid Oxide Fuel Cells (SOFCs) and a preparation method and application thereof.
Background
Fossil fuels provide power for various technologies, and greatly promote the development of human beings. However, the overuse of fossil fuels, such as petroleum and coal, has caused many problems, such as air pollution, greenhouse effect and animal extinction. Furthermore, the efficiency of direct use of fossil fuels by combustion has yet to be improved, since the efficiency of burning fuels is limited by the temperature difference between the two media, which is known as the carnot cycle. Solid Oxide Fuel Cells (SOFCs), also known as ceramic fuel cells, are an attractive high-temperature electrochemical energy conversion device that converts chemical energy in fuel into electrical energy in an electrochemical reaction, surpasses the carnot cycle limit, and have the advantages of high conversion efficiency, low pollution, no noise, and the like. The traditional anode material of the current solid oxide fuel cell is a Ni-based metal ceramic composite anode which has very high stability under high temperature and reducing atmosphere, has good thermal expansion matching property with electrolytes such as YSZ and the like, and ensures the stability of the anode in the high-temperature and long-term operation process. In addition, during SOFCs operation, the anode may come into contact with oxygen in the air due to occasional fuel leakage or the like, but the Ni-based cermet anode is easily broken due to large volume change of Ni/NiO during oxidation/reduction. Therefore, the development of new anode materials has become one of the hot spots of research on SOFCs.
Disclosure of Invention
The invention provides an anode material of a solid oxide fuel cell and a preparation method thereof, aiming at solving the problem that the conventional SOFCs anode material is unstable in a reducing atmosphere. The composite anode material with the perovskite support body structure prepared by the method has the advantages of relatively simple process, low cost and easy industrialization, and simultaneously has higher power output density in hydrocarbon fuel atmosphere.
The purpose of the invention is realized by the following technical scheme.
An anode material of a solid oxide fuel cell is an oxide with a single perovskite structure and has a chemical formula of Pr 2 O 3 -BiFe@Pr 1-x Bi x FeO 3 Wherein 0 is< x < 1。
The preparation method of the anode material of the solid oxide fuel cell comprises the following steps:
1) Weighing powder containing Pr, bi and Fe according to a specific stoichiometric ratio, adding a proper amount of absolute ethyl alcohol, and stirring to obtain a solid-liquid mixture;
2) Ball-milling the solid-liquid mixture obtained in the step 1) in a ball mill until the solid-liquid mixture is fully and uniformly mixed;
3) Drying the substance obtained in the step 2) in a drying box, and sintering the obtained powder at 800-1000 ℃ to obtain Pr of a single perovskite structure 1-x Bi x FeO 3 A powder;
4) Calcining the substance obtained in the step 3) in a reducing atmosphere to obtain Pr with a perovskite support structure 2 O 3 -BiFe@Pr 1-x Bi x FeO 3 The composite anode material of (1).
In a preferred embodiment of the present invention, in step 1), the powders containing Pr, bi, and Fe are all oxides.
In a preferred embodiment of the present invention, in step 2), the ball milling speed is 350 revolutions per second, and the ball milling time is 24 hours.
In a preferred embodiment of the present invention, in step 3), the sintering time is 10 hours.
As a preferred embodiment of the present invention, in step 4), the reduction time is 5h.
Use of the anode material as described above as an anode layer of an SOFC in the manufacture of a solid oxide fuel cell.
As a preferred embodiment of the present invention, the application comprises the steps of:
1) Mixing anode powder Pr 1-x Bi x FeO 3 (PBF) adding terpineol-ethyl cellulose, mixing and grinding to prepare uniformly mixed anode slurry, and mixing cathode powder NdBaCo 2 O 5+δ (NBC) adding terpineol-ethyl cellulose, mixing and grinding to prepare uniformly mixed cathode slurry;
2) Coating the anode slurry obtained in the step 1) on two sides of an electrolyte layer, and sintering in an air atmosphere to obtain single perovskite Pr 1-x Bi x FeO 3 SOFC half-cells of the porous electrode layer of (a);
3) Coating the anode slurry obtained in the step 1) on one side of an electrolyte layer, coating the cathode slurry on the other side of the electrolyte, and sintering in an air atmosphere to obtain single perovskite Pr 1-x Bi x FeO 3 The porous electrode layer of (3).
The PBF material with a single perovskite structure prepared by the invention belongs to a new anode material and has the characteristics of simpler and more uniform components, simpler synthesis process and the like. The method can perform high-temperature reduction in a hydrogen atmosphere, so that a large number of uniformly distributed nano particles are separated out, and more oxygen vacancies are generated at the same time. The nano particles can remarkably improve the conductivity of the PBF anode material, provide a large number of active sites and play a role in quickly catalyzing reaction gas at the PBF anode. Meanwhile, the stability of the material in the reducing atmosphere can be greatly improved by doping bismuth ions. In the hydrocarbon fuel atmosphere, the nano particles precipitated from the single perovskite anode have good catalytic activity and show good electrochemical performance. Meanwhile, the porous anode prepared from the PBF material can stably work in hydrocarbon fuel atmosphere.
Drawings
Figure 1 is an XRD pattern of PBF0.1 and PBF0.2 anode materials.
Figure 2 is an XRD pattern of PBF0.2 anode material after reduction.
FIG. 3 is a TEM image of PBF0.2 anode material after reduction.
FIG. 4 is a graph of power density measured at various temperatures for a PBF0.2| LSGM | NBC solid oxide fuel cell fueled with hydrogen.
FIG. 5 is a graph of power density of a PBF0.2| LSGM | NBC solid oxide fuel cell fueled with ethanol measured at different temperatures.
Detailed Description
The invention is described in detail below with reference to the drawings and examples, but the scope of the invention is not limited to the following embodiments.
Example 1
A novel solid oxide fuel cell anode material with a specific molecular formula of Pr 2 O 3 -BiFe@Pr 0.9 Bi 0.1 FeO 3 (PBF0.1)。
6.1286g of praseodymium oxide, 0.9319g of bismuth trioxide and 3.1937g of ferric oxide are taken, put into a ball mill, added with a proper amount of ethanol, ball-milled for 24 hours at the speed of 350 revolutions per second, and the ball-milled powder is put into a drying oven at the temperature of 80 ℃ for drying. Finally, roasting the mixture for 10 hours at 1000 ℃ in the air atmosphere to obtain Pr with a perovskite phase structure 0.9 Bi 0.1 FeO 3 An anode material. The prepared anode material was calculated at 10% H 2 Reducing at 900 ℃ for 5 hours in a/Ar atmosphere to obtain Pr with a perovskite support structure 2 O 3 -BiFe@Pr 0.9 Bi 0.1 FeO 3 The composite anode material of (1).
Example 2
A novel solid oxide fuel cell anode material with a specific molecular formula of Pr 2 O 3 -BiFe@Pr 0.8 Bi 0.2 FeO 3 (PBF0.2)。
5.4476g of praseodymium oxide and 1.8638g of praseodymium oxide are takenBismuth trioxide and 3.1937g of ferric oxide are placed in a ball mill, an appropriate amount of ethanol is added, ball milling is carried out for 24 hours at the speed of 350 revolutions per second, and the powder after ball milling is placed in a drying oven at the temperature of 80 ℃ for drying. Finally, roasting the mixture for 10 hours at 1000 ℃ in the air atmosphere to obtain Pr with a perovskite phase structure 0.8 Bi 0.2 FeO 3 An anode material. Mixing the prepared anode material at 10% 2 After reducing at 900 ℃ for 5h in a/Ar atmosphere, obtaining Pr with a perovskite support structure 2 O 3 -BiFe@Pr 0.8 Bi 0.2 FeO 3 The composite anode material of (1).
XRD analysis showed that the prepared oxide corresponded to the standard peak of the perovskite (as shown in fig. 1). XRD analysis was performed on the anode material obtained in example 2 (as shown in fig. 2). The prepared anode material was calculated at 10% H 2 After reduction at 900 ℃ for 5h in the Ar atmosphere, the Bi ion-doped anode material can still maintain the original phase structure. The surface morphology of the reduced material was observed by transmission electron microscopy (as shown in FIG. 3).
Using the synthesized material as anode material, and NdBaCo 2 O 5+δ As a cathode material, la 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ (LSGM) as an electrolyte, mixing the anode powder and the cathode powder with terpineol ethyl cellulose, respectively, grinding in a mortar for 2 hours, and making into uniformly mixed slurry; and respectively brushing the slurry on two sides of the electrolyte by a screen printing mode to assemble single cells, and then sintering for 5h at 950 ℃ in an air atmosphere to finally complete the preparation of the PBF | LSGM | NBC solid oxide fuel single cell. For the anode layer of the single cell (PBF 0.2 as an example), H is first added 2 The reduction treatment was carried out at 850 ℃ for 2h in an atmosphere, followed by electrochemical performance testing in different atmospheres (as shown in fig. 4, 5).
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The anode material of the novel solid oxide fuel cell is characterized in that the anode material is an oxide with a perovskite structure and has a chemical formula of Pr 2 O 3 -BiFe@Pr 1-x Bi x FeO 3 Wherein 0 is< x < 1。
2. The anode material for a solid oxide fuel cell according to claim 1, wherein x =0 to 1.
3. A method for preparing an electrode material for a solid oxide fuel cell according to any one of claims 1 to 2, comprising the steps of:
1) Weighing powder containing Pr, bi and Fe according to a specific stoichiometric ratio, adding a proper amount of absolute ethyl alcohol, and stirring to obtain a solid-liquid mixture;
2) Ball-milling the solid-liquid mixture obtained in the step 1) in a ball mill until the mixture is fully and uniformly mixed;
3) Drying the substance obtained in the step 2) in a drying oven, and sintering the obtained powder at 800-1000 ℃ to obtain Pr of a single perovskite structure 1-x Bi x FeO 3 Powder;
4) Calcining the substance obtained in the step 3) in a reducing atmosphere to obtain Pr with a perovskite support structure 2 O 3 -BiFe@Pr 1-x Bi x FeO 3 The composite anode material of (1).
4. The method according to claim 3, wherein in step 1), the powders containing Pr, bi, and Fe are all oxides.
5. The preparation method according to claim 3, wherein in the step 2), the ball milling speed is 350 revolutions per second, and the ball milling time is 24 hours.
6. The method according to claim 3, wherein the sintering time in step 3) is 10 hours.
7. The production method according to claim 3, wherein in the step 4), the reducing atmosphere is an argon-hydrogen mixture gas or a hydrogen gas atmosphere.
8.Pr 2 O 3 -BiFe@Pr 1-x Bi x FeO 3 The composite anode material with the structure can be suitable for the catalysis of the following hydrocarbon fuels: h 2 、CO、CH 4 、C 3 H 8 Ethanol (C) 2 H 6 O), methanol (CH) 3 OH), syngas, natural gas, etc.
9. A method of making a solid oxide fuel cell using the anode material of claim 1, wherein: the anode material is coated on the La by a screen printing method 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3-δ On the electrolyte with NdBaCo 2 O 5+δ (NBC) as a cathode material, a single cell was prepared, and 50 to 100ml/min of fuel gas was introduced to the anode side while the cathode was in an air atmosphere.
CN202110702586.6A 2021-06-24 Bismuth ion modified praseodymium ferrite base solid oxide fuel cell anode material and preparation method thereof Active CN115528259B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110581283A (en) * 2019-09-19 2019-12-17 中国科学技术大学 Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof
US20200075979A1 (en) * 2016-12-08 2020-03-05 Ceres Intellectual Property Company Limited An anode for a solid oxide fuel cell
CN111477881A (en) * 2020-03-19 2020-07-31 华南理工大学 NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-Material and method for producing the same
CN111883789A (en) * 2020-06-28 2020-11-03 华南理工大学 Electrode material of solid oxide fuel cell and preparation method and application thereof
CN112186201A (en) * 2020-10-22 2021-01-05 浙江氢邦科技有限公司 Metal oxide cathode material, composite cathode material and battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200075979A1 (en) * 2016-12-08 2020-03-05 Ceres Intellectual Property Company Limited An anode for a solid oxide fuel cell
CN110581283A (en) * 2019-09-19 2019-12-17 中国科学技术大学 Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof
CN111477881A (en) * 2020-03-19 2020-07-31 华南理工大学 NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-Material and method for producing the same
CN111883789A (en) * 2020-06-28 2020-11-03 华南理工大学 Electrode material of solid oxide fuel cell and preparation method and application thereof
CN112186201A (en) * 2020-10-22 2021-01-05 浙江氢邦科技有限公司 Metal oxide cathode material, composite cathode material and battery

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Title
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