CN112952171A - Barium cerate substrate sub-conductor-based integrated fully-symmetrical solid oxide fuel cell electrode material and preparation and application thereof - Google Patents
Barium cerate substrate sub-conductor-based integrated fully-symmetrical solid oxide fuel cell electrode material and preparation and application thereof Download PDFInfo
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- CN112952171A CN112952171A CN202110124392.2A CN202110124392A CN112952171A CN 112952171 A CN112952171 A CN 112952171A CN 202110124392 A CN202110124392 A CN 202110124392A CN 112952171 A CN112952171 A CN 112952171A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—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
- H01M8/126—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 the electrolyte containing cerium oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an electrode material based on a barium cerate substrate and a conductor integrated fully-symmetrical solid oxide fuel cell, and preparation and application thereof0.5Fe0.4Ni0.1O3‑δTo contain Ba2+Compound of (2) and containing Ce3+Compound of (1), containing Fe3+Compound of (2) containing Ni2+The compound of (1) is used as a raw material and is prepared by a solution combustion method. Mixing BaCe0.5Fe0.4Ni0.1O3‑δAnd mixing the electrode powder material with a binder to prepare electrode slurry, respectively coating the electrode slurry on two sides of the BZCY electrolyte sheet, drying and sintering once to obtain the single cell. The barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell has excellent electrochemical performance, good chemical compatibility among the components and simple preparation process.
Description
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, relates to a proton conductor-based solid oxide fuel cell, and particularly relates to an integrated full-symmetrical solid oxide fuel cell electrode material based on a barium cerate matrix and a proton conductor, and preparation and application thereof.
Background
Solid Oxide Fuel Cells (SOFCs) have attracted worldwide attention due to their potential to be the cleanest, most efficient chemical-to-electrical energy conversion systems. While small SOFC systems are ready for commercialization in distributed power generation applications, extensive market penetration will require constant innovation in materials and manufacturing processes to extend system life and reduce costs. Current relatively mature SOFCs typically use high temperature oxygen ion conductors YSZ or LSGM as the electrolyte material due to their good stability and mechanical properties. However, their ionic conductivity is greatly limited at low temperatures. For example, SSOFC with YSZ electrolyte is typically operated at temperatures in excess of 800 ℃ to reduce ohmic resistance. Therefore, a cell material with high conductivity and high electrochemical catalytic activity at medium and low temperature is searched, the running temperature of the SOFC is reduced, and the method has important practical significance and application prospect for the development of the SOFC.
Proton conductor-based solid oxide fuel cells (PCFCs) are an important class of medium-low temperature solid oxide fuel cells due to the relatively mild operating temperature, low cost and considerable application prospect. During the operation of the PCFC, water is generated at the cathode, so that the improvement of the mechanical property of the battery is facilitated; the proton is conducted between the adjacent 2 oxygen atoms, has relatively low activation energy, can complete the generation and oxidation reaction of the proton at relatively low temperature, greatly reduces the reaction temperature, widens the selection range of sealing connection materials, and reduces the cost of the battery. Symmetric Solid Oxide Fuel Cells (SSOFC) have a unique configuration of identical anode and cathode materials that greatly simplifies their processing techniques and improves the thermo-mechanical compatibility between the electrodes and the electrolyte. More importantly, it can eliminate carbon deposition and sulfur poisoning to some extent by reversing air and fuel gas. Doped BaCeO3 perovskite materials with high proton conductivity and appropriate Thermal Expansion Coefficients (TEC) are considered to be an ideal cathode choice.
Disclosure of Invention
One of the purposes of the invention is to provide an integrated fully-symmetrical solid oxide fuel cell electrode material based on a barium cerate substrate sub-conductor.
The invention aims to provide a preparation method of the electrode material of the integrated fully-symmetrical solid oxide fuel cell based on the barium cerate substrate sub-conductor.
The invention also aims to provide application of the electrode material based on the barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an integrated full-symmetrical solid oxide fuel cell electrode material based on a barium cerate substrate sub-conductor has a chemical formula of BaCe0.5Fe0.4Ni0.1O3-δWhere δ is a number that ensures the electroneutrality of the material.
The invention also provides a preparation method of the integrated full-symmetrical solid oxide fuel cell electrode material based on the barium cerate substrate sub-conductor, which comprises the following steps:
(1) to contain barium ion Ba2+Compound of (5) and cerium ion Ce3+Compound of (1), containing iron ion Fe3+Compound of (2), Ni containing nickel ion2+Is taken as a raw material and is prepared according to the chemical formula BaCe0.5Fe0.4Ni0.1O3-δWeighing each raw material according to the stoichiometric ratio of the corresponding metal elements; weighing Ba ions2+Compound of (5) and cerium ion Ce3+Compound of (1), containing iron ion Fe3+Compound of (2), Ni containing nickel ion2+The compounds of (a) are sequentially added into water to obtain a mixed solution;
(2) adding a complexing agent into the mixed solution obtained in the step (1), wherein the complexing agent is one or two of ethylenediamine tetraacetic acid and citric acid, the addition amount of the complexing agent is 1-2 times of the mole number of metal ions in the solution, stirring until the complexing agent is dissolved, and adding ammonia water to adjust the pH value of the solution to 7-8 to obtain a clear solution;
(3) heating and concentrating the solution, then carrying out self-sustaining combustion, and calcining the powder obtained after combustion at 900-1000 ℃ in air atmosphere to obtain BaCe0.5Fe0.4Ni0.1O3-δAnd (3) electrode powder material.
Preferably, the barium ion Ba is contained in the step (1)2+The compound of (1) is one of barium nitrate, barium acetate and barium carbonate; the nickel ion containing Ni2+The compound of (2) is one of nickel nitrate and nickel acetate.
More preferably, the barium ion Ba is contained in the step (1)2+The compound of (A) is barium acetate, and the cerium ion Ce is contained3+The compound of (A) is cerium nitrate, and the iron ion Fe3+The compound of (A) is ferric nitrate, and the nickel ion Ni is contained2+The compound of (a) is nickel nitrate.
Preferably, in the step (2), the complexing agent is citric acid and ethylenediamine tetraacetic acid, and the molar ratio of the citric acid to the ethylenediamine tetraacetic acid is 1: 0.8.
preferably, the calcination temperature in the step (3) is 1000 ℃ and the calcination time is 3 hours.
The invention also provides application of the barium cerate-based substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell electrode material in preparation of a solid oxide fuel cell.
(1) In BaCe0.5Fe0.4Ni0.1O3-δAdding a certain amount of binder into the electrode powder material and grinding to prepare electrode slurry;
(2) the BaCe prepared in the step (1) is added0.5Fe0.4Ni0.1O3-δUniformly coating the electrode slurry on two sides of a BZCY electrolyte sheet and drying to obtain a battery sheet;
(3) placing the dried battery piece into a muffle furnace to be sintered in air atmosphere to obtain the battery piece containing BaCe0.5Fe0.4Ni0.1O3-δSolid oxide fuel cells for electrodes.
Preferably, BaCe in the step (1)0.5Fe0.4Ni0.1O3-δElectrode powder material and binderThe mass ratio of (1): 1.5; the binder is prepared from terpineol and ethyl cellulose in a mass ratio of 9: 1, mixing the components.
Preferably, in the step (3), the sintering temperature is 900-1000 ℃, and the sintering time is 2-3 hours.
Preferably, BaCe of the solid oxide fuel cell0.5Fe0.4Ni0.1O3-δThe thickness of the electrode layer is 20-40 μm.
The invention provides an integrated full-symmetrical solid oxide fuel cell electrode material based on a barium cerate substrate sub-conductor, and the chemical formula of the electrode material is BaCe0.5Fe0.4Ni0.1O3-δAnd has good chemical compatibility with the proton conductor BZCY. It decomposes at high temperature into two uniformly dispersed and stable perovskite oxides: a main proton conductor phase and a main electron conductor phase, the transport of protons and electrons in the two phases greatly increases the conductivity and enlarges the three-phase boundaries. The transition metal Fe has variable oxidation and spin states, which have high catalytic activity for the cathode. BaFeO3-δPerovskite-based materials are considered promising cathodes for intermediate temperature SOFCs. Research has shown that cubic BaFeO is due to the presence of disordered oxygen vacancies and three-dimensional oxygen transport channels3-δHas excellent oxygen ion conduction and electrocatalytic activity. However, BaFeO3-δThe cubic lattice structure of (a) is unstable, and B-site doping is an effective method for stabilizing an oxygen vacancy disordered cubic lattice. BaCe provided by the invention0.5Fe0.4Ni0.1O3-δThe electrode material has Ni substituted partial Fe in the perovskite B site and thus raised catalytic activity and electrochemical performance of the cell.
The results of the examples show that the polarization impedance of the symmetric half cell prepared by the electrode material of the barium cerate substrate and the conductor integrated fully-symmetric solid oxide fuel cell provided by the invention at 700 ℃ is only 0.067 omega cm2(ii) a The maximum output power of an electrolyte-supported single cell prepared by the electrode material of the barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell provided by the invention at 700 ℃ is 140mW cm2And excellent electrochemical performance is shown.
Drawings
FIG. 1 is BaCe0.5Fe0.4Ni0.1O3-δX-ray diffraction patterns of the material after pretreatment and after reduction at 700 ℃.
FIG. 2 is BaCe0.5Fe0.4Ni0.1O3-δHigh resolution transmission electron microscopy images of the material.
FIG. 3 is BaCe0.5Fe0.4Ni0.1O3-δSchematic diagram of a symmetrical half cell with material as electrode.
FIG. 4 is BaCe0.5Fe0.4Ni0.1O3-δThe polarization impedance spectrum of a symmetrical half cell with the material as an electrode comprises (a) air atmosphere and (b) hydrogen atmosphere.
FIG. 5 is BaCe0.5Fe0.4Ni0.1O3-δSingle cell I-V and I-P curves of the material as an electrode.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The invention provides an integrated full-symmetrical solid oxide fuel cell electrode material based on a barium cerate substrate sub-conductor, and the chemical formula is BaCe0.5Fe0.4Ni0.1O3-δIn the formula, the lower subscript delta is a value for ensuring the electroneutrality of the substance. The preparation method of the barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell electrode material comprises the following steps:
(1) mixing barium acetate, cerium nitrate, ferric nitrate and nickel nitrate according to a molar ratio of 1: 0.5: 0.4: 0.1, sequentially adding the mixture into deionized water to form a mixed solution;
(2) adding complexing agent ethylenediamine tetraacetic acid and citric acid, wherein the molar ratio of metal ions, citric acid and ethylenediamine tetraacetic acid in the solution is 1: 1: 0.8, stirring until the complexing agent is dissolved, and then adding ammonia water to adjust the pH value of the solution to 7-8 to form a clear solution;
(3) pouring the solution into an evaporating dish for heating, concentrating and evaporating the solution to dryness, and then performing self-sustaining combustion to generate black powder;
(4) collecting the powder obtained after combustion by using a crucible, placing the crucible in a muffle furnace, and calcining the powder for 3 hours at the temperature of 1000 ℃ in the air atmosphere to obtain BaCe0.5Fe0.4Ni0.1O3-δAnd (3) electrode powder material.
Mixing the BaCe0.5Fe0.4Ni0.1O3-δThe electrode material is used for preparing a solid oxide fuel cell and generating electricity, and comprises the following steps:
(1) in BaCe0.5Fe0.4Ni0.1O3-δAdding a certain amount of binder into the electrode powder material to prepare electrode slurry; the BaCe0.5Fe0.4Ni0.1O3-δThe mass ratio of the electrode powder material to the binder is 1: 1.5; the binder is prepared from terpineol and ethyl cellulose in a mass ratio of 9: 1, mixing the components.
(2) Pressing BaZr by adopting a dry pressing method0.1Ce0.7Y0.2O3-δ(BZCY) electrolyte support wafers, which were placed in a high temperature furnace and sintered at 1400 ℃ for 5 hours to form dense BZCY electrolyte sheets.
(3) And (2) coating the electrode slurry prepared in the step (1) on the surfaces of an anode and a cathode of the electrolyte-supported solid oxide fuel cell for 4 times respectively, and coating different areas of the cathode to obtain a symmetrical half cell and a single cell respectively. Then placing the mixture into a muffle furnace, sintering the mixture for 3 hours in the air at the temperature of 1000 ℃ to prepare the BaCe-carrying ceramic material0.5Fe0.4Ni0.1O3-δA solid oxide fuel cell of the electrode; BaCe after sintering0.5Fe0.4Ni0.1O3-δThe thickness of the electrode is 20 to 40 μm.
(4) And (4) sealing the single cell prepared in the step (3) at one end of the ceramic tube by using conductive adhesive, and fixing the single cell in the vertical furnace.
(5) And introducing the fuel into an anode air passage of the solid oxide fuel cell, introducing outside air into a cathode air passage of the solid oxide fuel cell, and outputting direct current to the outside through electrons obtained by the cathode and the anode to convert chemical energy into electric energy so as to test the electrochemical performance.
BaCe prepared according to the invention was subjected to X-ray diffractometry (Bruker model D8)0.5Fe0.4Ni0.1O3-δPhase analysis is carried out on the electrode powder material, and as shown in figure 1, the result shows that the material BCFNi is decomposed into two perovskite phases after high-temperature presintering in air, wherein one perovskite phase is a cubic perovskite phase, and the other perovskite phase is an orthogonal perovskite phase. The orthogonal phase is a main proton conductor, the cubic phase is a main electron conductor, and the transmission of protons and electrons in the two phases greatly improves the conductivity and enlarges the three-phase boundary; mixing BaCe0.5Fe0.4Ni0.1O3-δReducing the electrode powder in hydrogen at 700 ℃ for 3h, and reducing the reduced BaCe0.5Fe0.4Ni0.1O3-δThe powder material is subjected to X-ray diffraction analysis, and the atlas shows that the Ni-Fe alloy is precipitated, so that the powder material has the advantages of catalysis effect on electrochemical oxidation and catalytic reforming on hydrocarbon fuel.
Observation of BaCe with a high-resolution Transmission Electron microscope (Tecnai G2F 20, USA)0.5Fe0.4Ni0.1O3-δThe electrode powder material is shown in fig. 2. As can be seen from fig. 2, the TEM image also confirmed the phase structure of BCFNi. The characteristic lattice fringe spacing of the BCFNi (110) crystal face is
Corresponding to a cubic perovskite structure. (211) Lattice stripe spacing of crystal face
Corresponding to an orthorhombic perovskite structure.
BaCe-containing products of the invention were treated with an electrochemical workstation (Zennium, Zahner, Germany)0.5Fe0.4Ni0.1O3-δAnd carrying out polarization impedance analysis on the symmetrical half cell of the electrode at 600-700 ℃. The polarization impedance of the symmetric half-cell electrode in an air atmosphere is shown in FIG. 4(a), and is 0.07, 0.18, 0.48. omega. cm at 700, 650, 600 deg.C2(ii) a In a hydrogen atmosphere, the polarization impedances of the symmetric half-cell electrodes are 0.50, 1.09, and 2 at 700, 650, and 600 ℃ respectively, as shown in FIG. 4(b).69Ω·cm2。
BaCe-containing products of the invention were treated with an electrochemical workstation (Zennium, Zahner, Germany)0.5Fe0.4Ni0.1O3-δAnd carrying out electrochemical performance test on a single cell of the electrode at 600-700 ℃. The current-voltage-output power curve of the single cell is shown in fig. 5. As can be seen from fig. 5(a), the open circuit voltage increases as the temperature decreases; as can be seen from FIG. 5(b), the maximum output of the unit cell using hydrogen as the fuel gas was 141, 82, and 42 mW/cm at 700, 650, and 600 ℃ respectively2。
Claims (10)
1. An integrated full-symmetrical solid oxide fuel cell electrode material based on a barium cerate substrate sub-conductor is characterized in that the chemical formula of the electrode material is BaCe0.5Fe0.4Ni0.1O3-δWhere δ is a number that ensures the electroneutrality of the material.
2. The preparation method of the barium cerate-based substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell electrode material of claim 1, which is characterized by comprising the following steps:
(1) to contain barium ion Ba2+Compound of (5) and cerium ion Ce3+Compound of (1), containing iron ion Fe3+Compound of (2), Ni containing nickel ion2+Is taken as a raw material and is prepared according to the chemical formula BaCe0.5Fe0.4Ni0.1O3-δWeighing each raw material according to the stoichiometric ratio of the corresponding metal elements; weighing Ba ions2+Compound of (5) and cerium ion Ce3+Compound of (1), containing iron ion Fe3+Compound of (2), Ni containing nickel ion2+The compounds of (a) are sequentially added into water to obtain a mixed solution;
(2) adding a complexing agent into the mixed solution obtained in the step (1), wherein the complexing agent is one or two of ethylenediamine tetraacetic acid and citric acid, the addition amount of the complexing agent is 1-2 times of the mole number of metal ions in the solution, stirring until the complexing agent is dissolved, and adding ammonia water to adjust the pH value of the solution to 7-8 to obtain a clear solution;
(3) heating and concentrating the solution, then carrying out self-sustaining combustion, and calcining the powder obtained after combustion at 900-1000 ℃ in air atmosphere to obtain BaCe0.5Fe0.4Ni0.1O3-δAnd (3) electrode powder material.
3. The method for preparing the electrode material of the fuel cell based on the barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide, according to claim 2, wherein the barium ion Ba is contained in the step (1)2+The compound of (1) is one of barium nitrate, barium acetate and barium carbonate; the nickel ion containing Ni2+The compound of (2) is one of nickel nitrate and nickel acetate.
4. The method for preparing the electrode material of the fuel cell based on the barium cerate substrate sub-conductor integrated fully-symmetrical solid oxide, according to claim 3, wherein the barium ion Ba is contained in the step (1)2+The compound of (A) is barium acetate, and the cerium ion Ce is contained3+The compound of (A) is cerium nitrate, and the iron ion Fe3+The compound of (A) is ferric nitrate, and the nickel ion Ni is contained2+The compound of (a) is nickel nitrate.
5. The method for preparing the barium cerate-based substrate sub-conductor integrated fully-symmetric solid oxide fuel cell electrode material as claimed in claim 2, wherein the complexing agent in the step (2) is citric acid and ethylenediaminetetraacetic acid, and the molar ratio of the citric acid to the ethylenediaminetetraacetic acid is 1: 0.8.
6. the method for preparing the barium cerate-based substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell electrode material as claimed in claim 2, wherein the calcination temperature in the step (3) is 1000 ℃ and the calcination time is 3 hours.
7. The application of the barium cerate-based substrate sub-conductor integrated fully-symmetrical solid oxide fuel cell electrode material in the preparation of a solid oxide fuel cell, which is characterized by comprising the following steps:
(1) in BaCe0.5Fe0.4Ni0.1O3-δAdding a certain amount of binder into the electrode powder material and grinding to prepare electrode slurry;
(2) the BaCe prepared in the step (1) is added0.5Fe0.4Ni0.1O3-δUniformly coating the electrode slurry on two sides of a BZCY electrolyte sheet and drying to obtain a battery sheet;
(3) placing the dried battery piece into a muffle furnace to be sintered in air atmosphere to obtain the battery piece containing BaCe0.5Fe0.4Ni0.1O3-δSolid oxide fuel cells for electrodes.
8. Use according to claim 7, wherein the BaCe of step (1) is BaCe0.5Fe0.4Ni0.1O3-δThe mass ratio of the electrode powder material to the binder is 1: 1.5; the binder is prepared from terpineol and ethyl cellulose in a mass ratio of 9: 1, mixing the components.
9. The use according to claim 7, wherein the sintering temperature in step (3) is 900-1000 ℃ and the sintering time is 2-3 hours.
10. Use according to claim 7, wherein the BaCe of the solid oxide fuel cell is0.5Fe0.4Ni0.1O3-δThe thickness of the electrode layer is 20-40 μm.
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| CN114944498A (en) * | 2022-05-26 | 2022-08-26 | 西安交通大学 | Integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor |
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| US20110195342A1 (en) * | 2010-02-09 | 2011-08-11 | The Governors Of The University Of Alberta | Solid oxide fuel cell reactor |
| CN108649236A (en) * | 2018-04-12 | 2018-10-12 | 中国矿业大学 | A kind of the air pole material and preparation method of intermediate temperature solid oxide fuel cell |
| 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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| US20110195342A1 (en) * | 2010-02-09 | 2011-08-11 | The Governors Of The University Of Alberta | Solid oxide fuel cell reactor |
| CN108649236A (en) * | 2018-04-12 | 2018-10-12 | 中国矿业大学 | A kind of the air pole material and preparation method of intermediate temperature solid oxide fuel cell |
| 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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| CN114944498A (en) * | 2022-05-26 | 2022-08-26 | 西安交通大学 | Integrated connector supported electric symbiotic solid oxide fuel cell/cell stack reactor |
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