CN114400332A - Electrode material of reversible solid oxide battery, composite material thereof, preparation method and application - Google Patents
Electrode material of reversible solid oxide battery, composite material thereof, preparation method and application Download PDFInfo
- Publication number
- CN114400332A CN114400332A CN202210025477.XA CN202210025477A CN114400332A CN 114400332 A CN114400332 A CN 114400332A CN 202210025477 A CN202210025477 A CN 202210025477A CN 114400332 A CN114400332 A CN 114400332A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- less
- solid oxide
- powder
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 48
- 239000007787 solid Substances 0.000 title claims abstract description 31
- 230000002441 reversible effect Effects 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 239000006256 anode slurry Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000006257 cathode slurry Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 229910003199 NdBaCo2O5+δ Inorganic materials 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910002214 La0.9Sr0.1Ga0.8Mg0.2O3−δ Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
Images
Classifications
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- 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
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
An electrode material of a reversible solid oxide battery, a composite material, a preparation method and application thereof relate to the field of electrode materials, and solve the problems of high cost and short service life of the conventional battery. The electrode material is perovskite structure oxide, and the structural formula is Sr2‑ xBixFe1.5Mo0.5O6‑δWherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1. The SBFM material with the perovskite structure prepared by the invention has the characteristics of simpler and more uniform components, simpler synthesis process and the like. Reducing at high temperature in hydrogen atmosphere to separate out a great amount of uniformly distributed nano particles and generate more oxygen vacancies at the same time. The nano particles can obviously improve the conductivity of the SBFM electrode material, provide a large number of active sites, take the SBFM as an anode and react with reaction gasHas the function of quick catalysis. In the hydrocarbon fuel atmosphere, the nano-particles precipitated from the perovskite anode have good catalytic activity and show good electrochemical performance. Meanwhile, when the SBFM material is used for preparing a porous anode, the porous anode can stably work in hydrocarbon fuel atmosphere.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to an electrode material of a reversible solid oxide battery, a composite material of the electrode material, a preparation method and application of the electrode material.
Background
The overuse of fossil fuels, such as petroleum and coal, has caused many problems, such as air pollution, greenhouse effect and animal extinction. The reversible symmetrical solid oxide cell (RSOC) is used as an energy conversion device and can realize the reversible conversion of chemical energy and electric energy with high efficiency, cleanness and no pollution. The fuel cell can be operated in a Solid Oxide Fuel Cells (SOFCs) mode, chemical energy in fuel is converted into electric energy in an electrochemical reaction mode, compared with the traditional power generation technology limited by Carnot cycle, the fuel cell reduces energy loss in the middle process, and meanwhile has the advantages of high conversion efficiency, low pollution, no noise and the like. And can also efficiently convert surplus electric energy into chemical energy for storage under a Solid Oxide Electrolysis Cell (SOECs) mode. However, commercialization of SOCs technology is hampered by a series of problems (high cost and short lifetime, etc.) arising from high operating temperatures (>850 ℃). Therefore, the operation temperature of the SOCs is required to be reduced to a middle temperature range (600-800 ℃). However, the decrease in temperature sharply increases the polarization resistance of the electrode, resulting in the degradation of the performance of the entire battery. Therefore, the development of efficient, stable and low-cost electrode materials in the intermediate temperature zone is of great significance for realizing the commercialization of SOCs.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an electrode material of a reversible solid oxide battery, a composite material of the electrode material, a preparation method and application of the electrode material, and solves the problems of high cost and short service life of the conventional battery.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the electrode material of the reversible solid oxide battery is perovskite structure oxide, and the structural formula is Sr2-xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
A method of preparing an electrode material for a reversible solid oxide cell, the method comprising the steps of:
the method comprises the following steps: weighing powder containing Sr, Bi, Fe and Mo elements according to a stoichiometric ratio, adding absolute ethyl alcohol, and stirring to obtain a solid-liquid mixture;
step two: ball-milling the solid-liquid mixture obtained in the step one until the mixture is fully and uniformly mixed;
step three: drying the substance obtained in the step two, sintering the obtained powder at 1100-1200 ℃ for 10-15 h to obtain Sr with a perovskite structure2-xBixFe1.5Mo0.5O6-δPowder, wherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
Preferably, the powder in the first step is: the Sr element-containing powder is carbonate, and Bi, Fe and Mo element powder is oxide.
Preferably, the ball milling speed in the second step is 350-500 r/min, and the ball milling time is 12-24 h.
Preferably, the electrode material is used as an anode layer in the preparation of a solid oxide fuel cell.
Use of an electrode material for a reversible solid oxide cell, the use comprising the steps of:
the method comprises the following steps: electrode powder Sr2-xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, x is more than 0 and less than or equal to 0.1, terpineol-ethyl cellulose are added for mixing and grinding, and evenly mixed slurry is prepared to be used as anode slurry; mixing cathode powder NdBaCo2O5+δAdding terpineol-ethyl cellulose, mixing and grinding to prepare uniformly mixed cathode slurry;
step two: coating the anode slurry obtained in the step one on two sides of an electrolyte layer, and sintering in an air atmosphere to obtain perovskite Sr2-xBixFe1.5Mo0.5O6-δA solid oxide fuel cell half cell of the porous electrode layer of (a);
step three: coating the anode slurry obtained in the step one 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 perovskite Sr2-xBixFe1.5Mo0.5O6-δThe porous electrode layer of (3) in the solid oxide fuel cell.
The composite electrode material is Sr3FeMoO6.5-BiFe@ Sr2-xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
A method for preparing a composite material by reacting an electrode material Sr2-xBixFe1.5Mo0.5O6-δDelta is more than 0 and less than 0.2, x is more than 0 and less than or equal to 0.1, and the catalyst is obtained by calcining in a reducing atmosphere.
The preparation method of the composite material comprises the steps of reducing hydrogen in a reducing atmosphere for 4-6 h, and calcining at 800-900 ℃.
The invention has the beneficial effects that: the SBFM material with the perovskite structure prepared by the invention belongs to a novel electrode material and has the characteristics of simpler and more uniform components, simpler synthesis process and the like. The high-temperature reduction can be carried out in a hydrogen atmosphere, so that a large amount of uniformly distributed nano particles are separated out, and more oxygen vacancies are generated. The nano particles can obviously improve the conductivity of the SBFM electrode material, provide a large number of active sites, and have a quick catalytic effect on reaction gas by taking the SBFM as an anode. In the hydrocarbon fuel atmosphere, the nano-particles precipitated from the perovskite anode have good catalytic activity and show good electrochemical performance. Meanwhile, when the SBFM material is used for preparing a porous anode, the porous anode can stably work in hydrocarbon fuel atmosphere.
Drawings
FIG. 1 shows Sr of the present invention2Fe1.5Mo0.5O6-δ(SFM) and Sr1.9Bi0.1Fe1.5Mo0.5O6-δ(SBFM0.1) XRD pattern of electrode material.
FIG. 2 is an XRD pattern of the SBFM0.1 electrode material of the present invention after reduction.
FIG. 3 is a transmission electron microscope image of the SBFM0.1 electrode material of the present invention after reduction.
FIG. 4 is a graph of power density measured at different temperatures for a solid oxide fuel cell of the invention SBFM0.1 LSGM NBC using hydrogen as fuel.
FIG. 5 is a graph of power density measured at different temperatures for a solid oxide fuel cell of the invention SBFM0.1 LSGM NBC using ethanol as fuel.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples, but the scope of the present invention is not limited to the following examples.
Example 1
A novel reversible solid oxide cell electrode material with a specific molecular formula of Sr1.9Bi0.1Fe1.5Mo0.5O6-δ。
The preparation method of the reversible solid oxide battery electrode material comprises the following steps: 5.6098g of strontium carbonate, 0.4659g of bismuth trioxide, 2.3953g of ferric oxide and 1.4396g of molybdenum trioxide are taken, and proper amount of ethanol is added for stirring treatment to obtain a solid-liquid mixture; and (3) placing the solid-liquid mixture into a ball mill, carrying out ball milling for 24h at the speed of 350 r/min, and drying the ball-milled powder in a drying oven at the temperature of 80 ℃. Finally, the obtained product is roasted for 12 hours at 1200 ℃ in the air atmosphere to obtain Sr with a perovskite phase structure1.9Bi0.1Fe1.5Mo0.5O6-δAn electrode material. The prepared electrode material is in 5% H2After being reduced for 5 hours at 850 ℃ in the/Ar atmosphere, Sr with a perovskite support structure is obtained3FeMoO6.5-BiFe@Sr1.9Bi0.1Fe1.5Mo0.5O6-δThe composite material of (1).
Example 2
A novel reversible solid oxide cell electrode material with a specific molecular formula of Sr1.92Bi0.08Fe1.5Mo0.5O6-δ。
The preparation method of the reversible solid oxide battery electrode material comprises the following steps: 5.6689g of strontium carbonate, 0.3728g of bismuth trioxide, 2.3953g of ferric oxide and 1.4396g of molybdenum trioxide are taken, and proper amount of ethanol is added for stirring treatment to obtain a solid-liquid mixture; and (3) placing the solid-liquid mixture into a ball mill, carrying out ball milling for 20h at the speed of 450 revolutions per minute, and drying the ball-milled powder in a drying oven at the temperature of 80 ℃. Finally, roasting the mixture for 14 hours at 1150 ℃ in the air atmosphere to obtain Sr with a perovskite phase structure1.92Bi0.08Fe1.5Mo0.5O6-δAn electrode material. The prepared electrode material is in 5% H2After reducing for 4 hours at 900 ℃ in a/Ar atmosphere, Sr with a perovskite support structure is obtained3FeMoO6.5-BiFe@Sr1.92Bi0.08Fe1.5Mo0.5O6-δThe composite material of (1).
Example 3
A novel reversible solid oxide cell electrode material with a specific molecular formula of Sr1.95Bi0.05Fe1.5Mo0.5O6-δ。
The preparation method of the reversible solid oxide battery electrode material comprises the following steps: 5.7575g of strontium carbonate, 0.2329g of bismuth trioxide, 2.3953g of ferric oxide and 1.4396g of molybdenum trioxide are taken, and proper amount of ethanol is added for stirring treatment to obtain a solid-liquid mixture; and (3) placing the solid-liquid mixture into a ball mill, carrying out ball milling for 12h at the speed of 500 r/min, and drying the ball-milled powder in a drying oven at the temperature of 80 ℃. Finally, roasting for 15h at 1100 ℃ in air atmosphere to obtain Sr with perovskite phase structure1.95Bi0.05Fe1.5Mo0.5O6-δAn electrode material. The prepared electrode material is in 5% H2After reducing for 6h at 800 ℃ in the Ar atmosphere, Sr with a perovskite support structure is obtained3FeMoO6.5-BiFe@Sr1.95Bi0.05Fe1.5Mo0.5O6-δThe composite material of (1).
XRD analysis of the electrode material obtained in example 1 shows that the prepared oxide corresponds to the standard peak of perovskite, as shown in figure 1, no impurity peak appears, which indicates that the sample is successfully synthesized; the electrode material prepared in example 1 was at 5% H2XRD analysis is carried out after reduction for 5h at 850 ℃ in the/Ar atmosphere, and as shown in figure 2, the dissolution of metal nano particles is shown; the surface morphology of the reduced material was observed by a transmission electron microscope, as shown in fig. 3, which also indicates the dissolution of the metal nanoparticles.
The material synthesized in example 1 was used as an anode material, and NdBaCo was used as a cathode material2O5+δAs a cathode material, La0.9Sr0.1Ga0.8Mg0.2O3-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 4h at 950 ℃ in an air atmosphere to finally finish the preparation of the SBFM | LSGM | NBC solid oxide fuel single cell. For the anode layer of the single cell (SBFM0.1 is taken as an example), H2The 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 and 5. With hydrogen or ethanol as the fuel, the power density of the cell increases with increasing temperature. The open circuit voltage is slightly lower when ethanol is used as a fuel, and the power density is also slightly lower at the same temperature, compared to hydrogen.
Claims (9)
1. The electrode material of the reversible solid oxide battery is characterized in that the electrode material is an oxide with a perovskite structure, and the structural formula is Sr2-xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
2. A method for preparing an electrode material for a reversible solid oxide cell according to claim 1, comprising the steps of:
the method comprises the following steps: weighing powder containing Sr, Bi, Fe and Mo elements according to a stoichiometric ratio, adding absolute ethyl alcohol, and stirring to obtain a solid-liquid mixture;
step two: ball-milling the solid-liquid mixture obtained in the step one until the mixture is fully and uniformly mixed;
step three: drying the substance obtained in the step two, sintering the obtained powder at 800-1200 ℃ for 10-15 h to obtain Sr with a perovskite structure2-xBixFe1.5Mo0.5O6-δPowder, wherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
3. The method for preparing an electrode material of a reversible solid oxide battery according to claim 2, wherein the powder of the first step is: the Sr element-containing powder is carbonate, and Bi, Fe and Mo element powder is oxide.
4. The method as claimed in claim 2, wherein the ball milling speed in step two is 350-500 rpm, and the ball milling time is 12-24 h.
5. The use of the electrode material for a reversible solid oxide cell according to claim 1, wherein the electrode material is used as an anode layer in the preparation of a solid oxide fuel cell.
6. Use of an electrode material for a reversible solid oxide cell according to claim 5, characterized in that it comprises the following steps:
the method comprises the following steps: electrode powder Sr2-xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, x is more than 0 and less than or equal to 0.1, terpineol-ethyl cellulose are added for mixing and grinding, and evenly mixed slurry is prepared to be used as anode slurry; mixing cathode powder NdBaCo2O5+δAdding terpineol-ethyl cellulose, and mixingMixing and grinding to prepare uniformly mixed cathode slurry;
step two: coating the anode slurry obtained in the step one on two sides of an electrolyte layer, and sintering in an air atmosphere to obtain perovskite Sr2-xBixFe1.5Mo0.5O6-δA solid oxide fuel cell half cell of the porous electrode layer of (a);
step three: coating the anode slurry obtained in the step one 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 perovskite Sr2-xBixFe1.5Mo0.5O6-δThe porous electrode layer of (3) in the solid oxide fuel cell.
7. The composite material is characterized in that the composite electrode material is Sr3FeMoO6.5-BiFe@Sr2- xBixFe1.5Mo0.5O6-δWherein delta is more than 0 and less than 0.2, and x is more than 0 and less than or equal to 0.1.
8. A method of producing a composite material as claimed in claim 7, characterized in that the electrode material Sr is used2- xBixFe1.5Mo0.5O6-δDelta is more than 0 and less than 0.2, x is more than 0 and less than or equal to 0.1, and the catalyst is obtained by calcining in a reducing atmosphere.
9. The method for preparing the composite material according to claim 8, wherein the reducing atmosphere is hydrogen, the reducing time is 4-6 h, and the calcining temperature is 800-900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210025477.XA CN114400332B (en) | 2022-01-11 | 2022-01-11 | Composite material of electrode material of reversible solid oxide battery and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210025477.XA CN114400332B (en) | 2022-01-11 | 2022-01-11 | Composite material of electrode material of reversible solid oxide battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114400332A true CN114400332A (en) | 2022-04-26 |
| CN114400332B CN114400332B (en) | 2024-01-23 |
Family
ID=81231929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210025477.XA Active CN114400332B (en) | 2022-01-11 | 2022-01-11 | Composite material of electrode material of reversible solid oxide battery and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114400332B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005191153A (en) * | 2003-12-25 | 2005-07-14 | Seiko Epson Corp | Capacitor and its production process, and semiconductor device |
| JP2009152014A (en) * | 2007-12-19 | 2009-07-09 | Tokyo Institute Of Technology | Solid oxide cell |
| US20110189582A1 (en) * | 2010-02-03 | 2011-08-04 | University Of South Carolina | Mixed Ionic and Electronic Conductor Based on Sr2Fe2-x MoXO6 Perovskite |
| CN102290583A (en) * | 2011-07-15 | 2011-12-21 | 天津大学 | Anode material and solid oxide fuel cell utilizing methanol as fuel |
| KR20130040311A (en) * | 2011-10-14 | 2013-04-24 | 한국에너지기술연구원 | Dual layer interconnect for solid oxide fuel cell, solid oxide fuel cell therewith and preparation method thereof |
| JP2013143187A (en) * | 2012-01-06 | 2013-07-22 | Noritake Co Ltd | Solid oxide fuel battery, and material for forming cathode of solid oxide fuel battery |
| WO2016032100A1 (en) * | 2014-08-28 | 2016-03-03 | 한국생산기술연구원 | Single-phase perovskite-based solid electrolyte, solid oxide fuel cell comprising same, and method for manufacturing same |
| 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 |
| 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 |
| US20210091370A1 (en) * | 2019-09-19 | 2021-03-25 | Kabushiki Kaisha Toshiba | Electrode group, nonaqueous electrolyte secondary battery, battery pack, and vehicle |
-
2022
- 2022-01-11 CN CN202210025477.XA patent/CN114400332B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005191153A (en) * | 2003-12-25 | 2005-07-14 | Seiko Epson Corp | Capacitor and its production process, and semiconductor device |
| JP2009152014A (en) * | 2007-12-19 | 2009-07-09 | Tokyo Institute Of Technology | Solid oxide cell |
| US20110189582A1 (en) * | 2010-02-03 | 2011-08-04 | University Of South Carolina | Mixed Ionic and Electronic Conductor Based on Sr2Fe2-x MoXO6 Perovskite |
| CN102290583A (en) * | 2011-07-15 | 2011-12-21 | 天津大学 | Anode material and solid oxide fuel cell utilizing methanol as fuel |
| KR20130040311A (en) * | 2011-10-14 | 2013-04-24 | 한국에너지기술연구원 | Dual layer interconnect for solid oxide fuel cell, solid oxide fuel cell therewith and preparation method thereof |
| JP2013143187A (en) * | 2012-01-06 | 2013-07-22 | Noritake Co Ltd | Solid oxide fuel battery, and material for forming cathode of solid oxide fuel battery |
| WO2016032100A1 (en) * | 2014-08-28 | 2016-03-03 | 한국생산기술연구원 | Single-phase perovskite-based solid electrolyte, solid oxide fuel cell comprising same, and method for manufacturing same |
| 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 |
| US20210091370A1 (en) * | 2019-09-19 | 2021-03-25 | Kabushiki Kaisha Toshiba | Electrode group, nonaqueous electrolyte secondary battery, battery pack, and vehicle |
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| NING SUN等: "In Situ Coexsolution of Metal Nanoparticle-Decorated Double Perovskites As Anode Materials for Solid Oxide Fuel Cells", 《ACS APPLIED ENERGY MATERIALS》, vol. 4, no. 8, pages 7992 - 8002 * |
| SHAOWEI ZHANG等: "Bismuth doped La0.75Sr0.25Cr0.5Mn0.5O3-δperovskite as a novel redox-stable efficient anode for solid oxide fuel cells", 《JOURNAL OF MATERIALS CHEMISTRY A》, no. 8, pages 11553 - 11563 * |
| 夏天;孟燮;骆婷;占忠亮;: "固体氧化物燃料电池La_xSr_(2-3x/2)Fe_(1.5)Ni_(0.1)Mo_(0.4)O_(6-δ)阳极性能研究（英文）", 无机材料学报, no. 5, pages 617 - 622 * |
| 姚桂彬等: "A位缺位双钙钛矿Sr1.85MgMoO6-δ阳极的电化学性能", 《辽宁石油化工大学学报》, vol. 39, no. 4, pages 28 - 33 * |
| 赵晓虹;王勇;刘立敏;李斌;: "固体氧化物燃料电池新型钙钛矿La_(0.9)Ca_(0.1)Fe_(0.9)Nb_(0.1)O_(3-δ)阳极的制备及其性能研究", 无机材料学报, no. 11, pages 1188 - 1194 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114400332B (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104078687B (en) | Anode material of SOFC containing alkali metal or alkali earth metal and its production and use | |
| CN111477881B (en) | NiFe alloy nanoparticle coated Pr0.8Sr1.2(FeNi)O4-δMaterial and method for producing the same | |
| CN110581283B (en) | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof | |
| WO2004013925A1 (en) | Perovskite-based fuel cell electrode and membrane | |
| CN111430734B (en) | (Pr0.5Sr0.5)xFe1-yRuyO3-δPerovskite material and preparation method and application thereof | |
| Tongyun et al. | NdFeO3 as anode material for S/O2 solid oxide fuel cells | |
| CN113839054B (en) | Reversible proton ceramic battery electrode material and preparation method and application thereof | |
| CN100583516C (en) | A cathode material for A and B adulterated SrTiO3 solid oxide fuel battery | |
| CN112290034B (en) | Anode material of solid oxide fuel cell and preparation method thereof | |
| CN111224140A (en) | Oxide material with iron-based double perovskite structure and preparation method thereof | |
| CN100459250C (en) | A lack phase adulated anode material for solid oxide fuel battery | |
| CN100502117C (en) | B-position omission perovskite anode material used for solid-oxide fuel battery | |
| CN111883789A (en) | Electrode material of solid oxide fuel cell and preparation method and application thereof | |
| CN116014159A (en) | Oxygen electrode material of solid oxide battery, preparation method and application | |
| CN115650312B (en) | Proton conductor reversible battery air electrode, preparation method and application | |
| CN115528259B (en) | Bismuth ion modified praseodymium ferrite base solid oxide fuel cell anode material and preparation method thereof | |
| CN115692806A (en) | High-entropy perovskite electrolyte, preparation method and application thereof, and battery | |
| CN113968596A (en) | Iron-based double perovskite type electrode powder material and preparation method thereof, and fuel cell electrode material based on iron-based double perovskite type electrode powder material and preparation method thereof | |
| CN114400332B (en) | Composite material of electrode material of reversible solid oxide battery and preparation method | |
| Larralde et al. | Defective Sr 0.9 Mo 0.9 O 3− δ perovskites with exsolved Ni nanoparticles as high-performance composite anodes for solid-oxide fuel cells | |
| CN113430548A (en) | Carbon dioxide conversion electrolytic cell and preparation method and application thereof | |
| Jasinski et al. | Single Chamber Solid Oxide Fuel Cell—Investigation of Cathodes | |
| Qin | Study on Preparation and Properties of La0. 6Sr0. 4Co0. 2Fe0. 8O3-Δ-mGd0. 2Ce0. 8O2 (M= 0, 30, 40 and 50) Composite Cathode | |
| CN112952171B (en) | Barium cerate substrate sub-conductor-based integrated fully-symmetrical solid oxide fuel cell electrode material and preparation and application thereof | |
| Yang et al. | Core-Shell Structured Sr0. 88Y0. 08TiO3-Ce0. 8Sm0. 2O1. 9 Composite as an Anode for Solid Oxide Fuel Cells Operating with CH4 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |