CN113299934A - Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell - Google Patents
Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell Download PDFInfo
- Publication number
- CN113299934A CN113299934A CN202110523451.3A CN202110523451A CN113299934A CN 113299934 A CN113299934 A CN 113299934A CN 202110523451 A CN202110523451 A CN 202110523451A CN 113299934 A CN113299934 A CN 113299934A
- Authority
- CN
- China
- Prior art keywords
- fuel electrode
- electrode material
- carbon dioxide
- solution
- carbon
- 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
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
- H01M4/90—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- 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
-
- 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
Abstract
The invention provides an anti-carbon deposition and carbon dioxide resistant fuel electrode material, which has a chemical formula shown in a formula I: sr2Fe1.5Mo0.5‑ xSbxO6‑δFormula I; wherein x is the doping amount of Sb, x is more than 0 and less than 0.2, and delta is the non-stoichiometry of oxygen. The invention is perovskite type structure ABO3Sr of2Fe1.5Mo0.5O6‑δ(SFM) is used for doping Sb at the B position and partially replacing Mo element, and experimental results show that the Sb-doped fuel electrode material has better stability in humid hydrogen and carbon dioxide atmosphere, and in addition, the Sb-doped fuel electrode material has excellent carbon deposition resistanceEven if the synthesis gas or the ethanol is used as fuel, no carbon deposition is generated after long-time operation. The Sb-doped SFM has excellent performance and good stability. The invention also provides a preparation method of the anti-carbon deposition and carbon dioxide resistant fuel electrode material and a solid oxide battery.
Description
Technical Field
The invention belongs to the technical field of solid oxide batteries, and particularly relates to an anti-carbon deposition and carbon dioxide resistant fuel electrode material, a preparation method thereof and a solid oxide battery.
Background
A solid oxide battery (SOC) is an all-solid-state energy conversion device, and has the advantages of high energy conversion efficiency, low pollution, low noise, and the like, and thus has been widely studied. There are two modes of operation of the SOC, Solid Oxide Fuel Cell (SOFC) and Solid Oxide Electrolysis Cell (SOEC), which are reversible operations of each other. The SOFC can directly convert chemical energy in fuels such as hydrogen, carbon monoxide and synthesis gas into electric energy; conversely, SOEC can perform electrolysis of water, carbon dioxide, and co-electrolysis to convert electrical energy into fuels such as hydrogen, carbon monoxide, and syngas. The key components of the SOC are mainly composed of a fuel electrode, an air electrode, an electrolyte and a current collector, wherein the fuel electrode mainly undergoes electrochemical oxidation and reduction reactions and needs to operate in various atmospheres, such as hydrogen, hydrocarbon fuel gas, carbon dioxide and the like, and therefore, the selection of the fuel electrode material is highly required. The fuel electrode material needs to have higher catalytic activity and better oxidation-reduction cycle performance, and has the capabilities of carbon deposition resistance and carbon dioxide poisoning resistance, and the performance and the stability of the fuel electrode material directly determine the running condition of the whole SOC.
Among SOC fuel electrode materials, a cermet composite electrode (Ni-YSZ) composed of metallic nickel (Ni) and yttria-stabilized zirconia (YSZ) is the most widely used fuel electrode material, in which metallic Ni has excellent electron conductivity and catalytic activity, and YSZ has higher oxygen ion conductivity, and thus, the Ni-YSZ cermet composite fuel electrode has excellent electrochemical properties. However, according to the reports of the documents Properties and maintenance of Ni-YSZ as an inorganic material in solid oxide fuel cell A review (B.Shri Prakash, S.Senthil Kumar, S.T.Arena.Renewable and Sustainable Energy Reviews 36(2014) 149) in SOC actual operation, when the battery is operated for a long time, the metal Ni is easy to migrate and agglomerate; when using hydrocarbon fuels, metallic Ni is prone to carbon deposition; this will cause degradation in SOC battery performance. In addition, Ni-YSZ composite fuel has no redox cycling capability. The above disadvantages limit the commercial application of Ni-YSZ.
Disclosure of Invention
The invention aims to provide an anti-carbon deposition and carbon dioxide resistant fuel electrode material, a preparation method thereof and a solid oxide cell.
The invention provides an anti-carbon deposition and carbon dioxide resistant fuel electrode material, which has a chemical formula shown in a formula I:
Sr2Fe1.5Mo0.5-xSbxO6-δformula I;
wherein x is the doping amount of Sb, and x is more than 0 and less than 0.2.
Preferably, x is 0.05, 0.10 or 0.15.
Preferably, the particle size of the fuel electrode material is 100-500 nm.
The invention provides a preparation method of the anti-carbon deposition and carbon dioxide resistant fuel pole material, which comprises the following steps:
A) dissolving citric acid and glycine in secondary distilled water to obtain a solution A;
B) adding antimony oxide into the solution A, and dropwise adding dilute acid until the antimony oxide is completely dissolved to obtain a solution B;
C) adding strontium salt, ferric salt and molybdenum salt into the solution B, adjusting the pH value to 6-7, and stirring to obtain a solution C;
D) heating the solution C until spontaneous combustion reaction occurs to obtain powder A;
E) and calcining the powder A at a high temperature to obtain the anti-carbon deposition and carbon dioxide resistant fuel electrode material.
Preferably, in the solution C, the total amount of metal ions, the molar ratio of glycine to citric acid is 1: (2-4): (0.1-0.5).
Preferably, the strontium salt is strontium nitrate; the ferric salt is ferric nitrate and/or ferric acetate; the molybdenum salt is (NH)4)6Mo7O24·4H2O。
Preferably, the heating temperature in the step D) is 200-400 ℃.
Preferably, the temperature of the high-temperature calcination in the step E) is 500-1200 ℃; the high-temperature calcination time is 1-10 hours.
Preferably, the high-temperature calcination in step E) is performed in an air atmosphere.
The present invention provides a solid oxide cell characterised by comprising an anti-carbon and carbon dioxide resistant fuel electrode material as hereinbefore described.
The invention provides an anti-carbon deposition and carbon dioxide resistant fuel electrode material, which has a chemical formula shown in a formula I: sr2Fe1.5Mo0.5-xSbxO6-δFormula I; wherein x is the doping amount of Sb, x is more than 0 and less than 0.2, and delta is the non-stoichiometry of oxygen. The invention is perovskite type structure ABO3Sr of2Fe1.5Mo0.5O6-δ(SFM) is doped with Sb at the B position, Mo is partially replaced, and experimental results show that the Sb-doped fuel electrode material has better stability in humid hydrogen and carbon dioxide atmospheres, and the Sb doping promotes the reduction process of the material, so that the Sb-doped fuel electrode material has more oxygen vacancies and higher catalytic activity, and in addition, the Sb-doped fuel electrode material has better carbon deposition resistance, and no carbon deposition is generated even if the fuel electrode material is operated for more than 70 hours for a long time by taking synthesis gas or ethanol as fuel. The Sb-doped SFM has excellent performance and good stability, and is a solid oxidation battery fuel electrode material with carbon deposition resistance and carbon dioxide resistance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Sr in example 2 of the present invention2Fe1.5Mo0.4Sb0.1O6-δAnd Sr2Fe1.5Mo0.5O6-δRespectively reducing the oxide powder in a humid hydrogen atmosphere at 800 ℃ for 5 hours to obtain X-ray diffraction patterns;
FIG. 2 shows Sr in example 2 of the present invention2Fe1.5Mo0.4Sb0.1O6-δA transmission electron micrograph of the oxide powder, wherein (a) is a topographic map and (b) is a high resolution map;
FIG. 3 shows Sr in example 2 of the present invention2Fe1.5Mo0.4Sb0.1O6-δAnd Sr2Fe1.5Mo0.5O6-δTemperature programmed reduction curve of oxide powder in 5% hydrogen/95% nitrogen;
FIG. 4 shows Sr in example 2 of the present invention2Fe1.5Mo0.4Sb0.1O6-δProcessing the powder in a pure carbon dioxide atmosphere for 5 hours to obtain an X-ray diffraction pattern;
FIG. 5 shows Sr in example 2 of the present invention2Fe1.5Mo0.4Sb0.1O6-δRaman spectra of fuel electrode materials after running for over 70 hours in (a) syngas and (b) ethanol, respectively.
Detailed Description
The invention provides an anti-carbon deposition and carbon dioxide resistant fuel electrode material, which has a chemical formula shown in a formula I:
Sr2Fe1.5Mo0.5-xSbxO6-δformula I;
wherein x is the doping amount of Sb, x is more than 0 and less than 0.2, and delta is the non-stoichiometry of oxygen.
In the present invention, x may be0.05, 0.10 or 0.15. In addition, delta is the non-stoichiometry of oxygen, and the specific numerical value is uncertain, the delta value is related to the properties of the material, temperature, atmosphere and the like, the delta value is not limited in general, and the oxygen content in the chemical formula can be directly expressed as O6-δ. In the present invention, the preferred chemical formula is Sr2Fe1.5Mo0.4Sb0.1O6-δ(Sb-SFM)。
In the invention, the particle size of the anti-carbon deposition and carbon dioxide resistant fuel electrode material is preferably 100-500nm, and more preferably 200-400 nm.
The invention also provides a preparation method of the anti-carbon deposition and carbon dioxide resistant fuel electrode material, which comprises the following steps:
A) dissolving citric acid and glycine in secondary distilled water to obtain a solution A;
B) adding antimony oxide into the solution A, and dropwise adding dilute nitric acid until the antimony oxide is completely dissolved to obtain a solution B;
C) adding strontium salt, ferric salt and molybdenum salt into the solution B, adjusting the pH value to 6-7, and stirring to obtain a solution C;
D) heating the solution C until spontaneous combustion reaction occurs to obtain powder A;
E) and calcining the powder A at a high temperature to obtain the solid oxide cell fuel electrode material.
According to the invention, citric acid and glycine are used as chelating agents and combustion agents, and a citric acid-glycine salt combustion method is used for preparing the anti-carbon and carbon dioxide resistant fuel electrode material.
Firstly, dissolving glycine and citric acid in water according to a certain molar ratio to obtain a clear solution.
Then according to Sr2Fe1.5Mo0.5-xSbxO6-δIn stoichiometric ratio, antimony oxide such as Sb is weighed2O3Adding into the above clarified solution, and adding diluted acid such as dilute nitric acid dropwise into the solution until antimony oxide is completely dissolved.
Then according to Sr2Fe1.5Mo0.5-xSbxO6-δIn (2) stoichiometryWeighing strontium salt, iron salt and molybdenum salt, and adding into the solution.
In the present invention, the strontium salt is strontium nitrate; the ferric salt is preferably ferric nitrate and/or ferric acetate; the molybdenum salt is (NH)4)6Mo7O24·4H2O。
The strontium salt, the iron salt, the molybdenum salt and the antimony oxide are weighed according to the stoichiometric ratio in the formula I, and the invention is not described in detail herein.
In the present invention, the solution contains all the metal ions required in formula I, and the total amount of metal ions, glycine and citric acid are preferably in a molar ratio of 1: (2-4): (0.1 to 0.5), more preferably 1: (2.5-3): (0.2 to 0.4), most preferably 1: 2.5: 0.3.
the concentration of the dilute nitric acid is not particularly limited, and antimony oxide can be dissolved.
And then slowly dropwise adding ammonia water into the solution to adjust the pH value of the solution to about 6.5, stirring for 10-12 hours, heating the solution, and gradually volatilizing the solvent until spontaneous combustion reaction occurs to obtain fluffy brown black powder.
In the invention, the heating temperature is preferably 200-400 ℃, and more preferably 300 ℃.
Collecting the brown black powder, grinding, and calcining at high temperature in air atmosphere to obtain Sr2Fe1.5Mo0.5- xSbxO6-δSolid oxide cell fuel electrode materials.
In the invention, the temperature of the high-temperature calcination phase is preferably 500-1200 ℃, more preferably 800-1100 ℃, such as 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, and preferably any value thereof is used as an upper limit or a lower limit. The high-temperature calcination time is preferably 1 to 10 hours, more preferably 3 to 8 hours, most preferably 5 to 6 hours,
the invention also provides a solid oxide cell comprising a fuel electrode, an air electrode, an electrolyte and a current collector, wherein the fuel electrode comprises the solid oxide cell fuel electrode material, and the air electrode, the electrolyte and the current collector are all the air electrode, the electrolyte and the current collector commonly used in the field.
In the present invention, when the solid oxide cell is operated as a solid oxide fuel cell, the fuel electrode is used as an anode, and when the solid oxide cell is operated as a solid oxide electrolysis cell, the fuel electrode is used as a cathode.
In order to further illustrate the present invention, the following will describe a solid oxide cell fuel electrode material, a method for preparing the same, and a solid oxide cell in detail with reference to the examples, but the scope of the invention should not be construed as being limited thereto.
EXAMPLE 1 preparation of Sr by citric acid-glycinate combustion method2Fe1.5Mo0.45Sb0.05O6-δFuel electrode material
Sr2Fe1.5Mo0.45Sb0.05O6-δThe fuel electrode material is prepared by a citric acid-glycinate combustion method, wherein citric acid and glycine are used as a chelating agent and a combustion agent, and the metal ion sources are Sr (NO) respectively3)2、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O and Sb2O3(ii) a In this example, the total amount of metal ions: glycine: the molar ratio of citric acid was set to 1: 2.5: 0.3. the preparation method comprises the following specific steps:
step 1: and respectively weighing citric acid and glycine according to the set molar ratio, and sequentially dissolving the citric acid and the glycine in the secondary distilled water to obtain a clear solution.
Step 2: weighing Sb according to the stoichiometric ratio2O3Placing the solution in the clear solution obtained in the step 1, and then slowly dropwise adding dilute nitric acid into the solution until the solution is Sb2O3And completely dissolving.
And step 3: respectively weighing Sr (NO) according to the stoichiometric ratio3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2And O, and then dissolving in the solution obtained in the step 2 in sequence.
And 4, step 4: and (3) slowly dropwise adding ammonia water into the solution obtained in the step (3) to adjust the pH of the solution to be about 6.5, and then stirring the obtained solution on a magnetic stirrer for 12 hours.
And 5: and (4) transferring the solution obtained in the step (4) to a heating electric furnace, and gradually volatilizing the solvent until spontaneous combustion reaction occurs to obtain fluffy brownish black powder.
Step 6: collecting and grinding the brown black powder obtained in the step 5, finally transferring the brown black powder into a muffle furnace, and calcining the brown black powder for 5 hours in an air atmosphere at 1100 ℃ to obtain Sr2Fe1.5Mo0.45Sb0.05O6-δA fuel electrode material.
EXAMPLE 2 preparation of Sr by citric acid-glycinate combustion method2Fe1.5Mo0.4Sb0.1O6-δFuel electrode material
Sr2Fe1.5Mo0.4Sb0.1O6-δThe fuel electrode material is prepared by a citric acid-glycinate combustion method, wherein citric acid and glycine are used as a chelating agent and a combustion agent, and the metal ion sources are Sr (NO) respectively3)2、Fe(NO3)3·9H2O、(NH4)6Mo7O24·4H2O and Sb2O3(ii) a In this example, the total amount of metal ions: glycine: the molar ratio of citric acid was set to 1: 2.5: 0.3. the preparation method comprises the following specific steps:
step 1: and respectively weighing citric acid and glycine according to the set molar ratio, and sequentially dissolving the citric acid and the glycine in the secondary distilled water to obtain a clear solution.
Step 2: weighing Sb according to the stoichiometric ratio2O3Placing the solution in the clear solution obtained in the step 1, and then slowly dropwise adding dilute nitric acid into the solution until the solution is Sb2O3And completely dissolving.
And step 3: respectively weighing Sr (NO) according to the stoichiometric ratio3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2And O, and then dissolving in the solution obtained in the step 2 in sequence.
And 4, step 4: and (3) slowly dropwise adding ammonia water into the solution obtained in the step (3) to adjust the pH of the solution to be about 6.5, and then stirring the obtained solution on a magnetic stirrer for 12 hours.
And 5: and (4) transferring the solution obtained in the step (4) to a heating electric furnace, and gradually volatilizing the solvent until spontaneous combustion reaction occurs to obtain fluffy brownish black powder.
Step 6: collecting and grinding the brown black powder obtained in the step 5, finally transferring the brown black powder into a muffle furnace, and calcining the brown black powder for 5 hours in the air atmosphere at 1100 ℃ to obtain the expected Sr2Fe1.5Mo0.4Sb0.1O6-δA fuel electrode material.
2 1.5 0.4 0.1 6-δPhase structure and morphology analysis of SrFeMoSbO fuel electrode material
Sr obtained in example 22Fe1.5Mo0.4Sb0.1O6-δThe fuel electrode material is subjected to phase structure and morphology analysis, the experimental result is shown in figure 1(a), an X-ray diffraction spectrum shows that Sb doping does not change the phase structure, and Sr is2Fe1.5Mo0.4Sb0.1O6-δAnd Sr2Fe1.5Mo0.5O6-δA cubic perovskite structure; as shown in fig. 1(b), Sb doping shifts the (110) diffraction peak slightly to high angles, indicating that doping causes a slight reduction in the unit cell volume. Sr2Fe1.5Mo0.4Sb0.1O6-δThe transmission electron micrographs are shown in fig. 2(a) and (b), the grain size is 100-500nm, the particle size of the powder is uniform, the powder is favorable for being used as a fuel electrode material, and the high resolution picture further proves that the interplanar spacing of the (110) plane is 0.276nm, which is consistent with the result of an X-ray diffraction picture.
2 1.5 0.4 0.1 6-δStability of SrFeMoSbO fuel electrode material in reducing atmosphere
To verify Sr2Fe1.5Mo0.4Sb0.1O6-δStability of Fuel electrode Material in reducing atmosphere Sr, which had been in phase in example 22Fe1.5Mo0.4Sb0.1O6-δAnd placing the powder in a tube furnace, reducing for 5 hours at 800 ℃ in a wet hydrogen atmosphere, and then carrying out X-ray diffraction characterization on the reduced powder to identify the phase structure of the powder. The experimental result is shown in FIG. 1(a), Sr2Fe1.5Mo0.4Sb0.1O6-δThe diffraction pattern after reduction is consistent with that before reduction, indicating that Sr2Fe1.5Mo0.4Sb0.1O6-δThe product has good stability in reducing atmosphere; the (110) diffraction peak was further amplified for analysis, and as shown in fig. 1(b), the diffraction peak after reduction was shifted to a lower angle than that before reduction, indicating that the reduction process resulted in an increase in unit cell volume due to the reduction process lowering the valence states of Fe and Mo while generating oxygen vacancies. Sr2Fe1.5Mo0.4Sb0.1O6-δThe temperature programmed reduction curve of the fuel electrode powder in 5% hydrogen/95% nitrogen is shown in FIG. 3, and the temperature programmed reduction curve is compared with undoped Sr2Fe1.5Mo0.5O6-δCompared with the prior art, the Sb doping enables the reduction peaks of Fe and Mo to move to low temperature, and the peak area is increased, which shows that the Sb doping promotes the reduction process of the material and generates more oxygen vacancies. The generation of oxygen vacancy is beneficial to the conduction of oxygen ions, so that the Sb doping also improves the catalytic activity of the fuel electrode material, and is beneficial to the application in the fuel electrode of the solid oxide cell.
2 1.5 0.4 0.1 6-δCarbon dioxide resistance of SrFeMoSbO fuel electrode material
To verify Sr2Fe1.5Mo0.4Sb0.1O6-δThe fuel electrode material has resistance to carbon dioxide, and Sr, which has been formed in phase in example 2, is used2Fe1.5Mo0.4Sb0.1O6-δTreating the powder at 800 ℃ in pure carbon dioxide atmosphereAnd 5 hours, then carrying out X-ray diffraction characterization on the treated powder, and identifying the phase structure of the powder. The experimental result is shown in FIG. 4, Sr2Fe1.5Mo0.4Sb0.1O6-δThe X-ray diffraction pattern after treatment is consistent with that before treatment, which shows that Sr2Fe1.5Mo0.4Sb0.1O6-δThe phase structure in the carbon dioxide atmosphere is very stable, and therefore, Sr2Fe1.5Mo0.4Sb0.1O6-δThe fuel electrode material has excellent carbon dioxide resistance and is beneficial to application in a solid oxide cell fuel electrode.
2 1.5 0.4 0.1 6-δCarbon deposition resistance of SrFeMoSbO fuel electrode material
To verify Sr2Fe1.5Mo0.4Sb0.1O6-δThe anti-carbon deposition capability of the fuel electrode material is to add Sr2Fe1.5Mo0.4Sb0.1O6-δAfter the fuel electrode runs in the hydrocarbon fuel gas for a long time, whether carbon deposition is generated or not is detected, and the hydrocarbon fuel selected in the embodiment is synthesis gas and liquid ethanol respectively. When the battery runs for more than 70 hours in the synthesis gas and the ethanol for a long time, Sr of the battery is added2Fe1.5Mo0.4Sb0.1O6-δThe fuel electrode is taken down, Raman spectrum characterization is carried out, and the experimental result is shown in figures 5(a) and (b), and is at 1340cm-1And 1580cm-1No Raman signal peak of carbon was observed, indicating Sr2Fe1.5Mo0.4Sb0.1O6-δNo carbon deposition and Sr generation in the process of long-term operation in synthesis gas and ethanol2Fe1.5Mo0.4Sb0.1O6-δThe fuel pole material has excellent anti-carbon deposition capability and is beneficial to application in the solid oxide cell fuel pole.
The above embodiments show that the Sb-doped perovskite fuel electrode material in the embodiments of the present invention has good chemical and structural stability in oxidizing and reducing atmospheres, and more importantly, the Sb-doped fuel electrode material has excellent carbon deposition resistance and carbon dioxide resistance, and the preparation method of the fuel electrode material of the present invention is simple and easy to operate, has uniform powder particle size and high catalytic activity, and is favorable for application in solid oxide batteries.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An anti-carbon deposition and carbon dioxide resistant fuel electrode material having a chemical formula shown in formula I:
Sr2Fe1.5Mo0.5-xSbxO6-δformula I;
wherein x is the doping amount of Sb, and x is more than 0 and less than 0.2.
2. The carbon deposition resistant and carbon dioxide resistant fuel electrode material as recited in claim 1, wherein x is 0.05, 0.10, or 0.15.
3. The carbon deposition resistant and carbon dioxide resistant fuel electrode material as claimed in claim 1, wherein the particle size of the fuel electrode material is 100-500 nm.
4. The method of preparing an anti-carbon and carbon dioxide resistant fuel electrode material as claimed in claim 1, comprising the steps of:
A) dissolving citric acid and glycine in secondary distilled water to obtain a solution A;
B) adding antimony oxide into the solution A, and dropwise adding dilute acid until the antimony oxide is completely dissolved to obtain a solution B;
C) adding strontium salt, ferric salt and molybdenum salt into the solution B, adjusting the pH value to 6-7, and stirring to obtain a solution C;
D) heating the solution C until spontaneous combustion reaction occurs to obtain powder A;
E) and calcining the powder A at a high temperature to obtain the anti-carbon deposition and carbon dioxide resistant fuel electrode material.
5. The method according to claim 4, wherein the total amount of metal ions, glycine and citric acid in the solution C are in a molar ratio of 1: (2-4): (0.1-0.5).
6. The method according to claim 4, wherein said strontium salt is strontium nitrate;
the ferric salt is ferric nitrate and/or ferric acetate;
the molybdenum salt is (NH)4)6Mo7O24·4H2O。
7. The method according to claim 4, wherein the heating temperature in the step D) is 200 to 400 ℃.
8. The preparation method according to claim 4, wherein the temperature of the high-temperature calcination in the step E) is 500-1200 ℃; the high-temperature calcination time is 1-10 hours.
9. The method according to claim 4, wherein the high-temperature calcination in step E) is performed in an air atmosphere.
10. A solid oxide cell comprising the carbon deposition resistant and carbon dioxide resistant fuel electrode material of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110523451.3A CN113299934B (en) | 2021-05-13 | 2021-05-13 | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110523451.3A CN113299934B (en) | 2021-05-13 | 2021-05-13 | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113299934A true CN113299934A (en) | 2021-08-24 |
| CN113299934B CN113299934B (en) | 2022-12-30 |
Family
ID=77321966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110523451.3A Active CN113299934B (en) | 2021-05-13 | 2021-05-13 | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113299934B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114242996A (en) * | 2021-11-24 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Monoatomic doped MoO3-xPreparation method of lithium battery negative electrode material |
| CN115911421A (en) * | 2022-10-24 | 2023-04-04 | 合肥学院 | SFM-based electrode material of hydrogen energy fuel cell and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007335171A (en) * | 2006-06-13 | 2007-12-27 | Toyota Motor Corp | Particulate carrying carbon particle, its manufacturing method, and electrode for fuel cell |
| CN101359739A (en) * | 2008-09-28 | 2009-02-04 | 南京工业大学 | Cathode material for solid-oxide fuel cell and method for preparing the same |
| CN102074713A (en) * | 2010-12-17 | 2011-05-25 | 天津大学 | Anode material for solid oxide fuel cell, preparation method thereof and fuel cell |
| CN102290583A (en) * | 2011-07-15 | 2011-12-21 | 天津大学 | Anode material and solid oxide fuel cell utilizing methanol as fuel |
| CN102842723A (en) * | 2012-09-18 | 2012-12-26 | 黑龙江大学 | Intermediate temperature solid oxide fuel cell cathode material with perovskite structure and preparation method thereof |
| CN104037429A (en) * | 2014-06-14 | 2014-09-10 | 中国科学技术大学 | High-catalytic-activity anti-carbon-deposition anode material and preparation method thereof |
| CN109473679A (en) * | 2018-10-24 | 2019-03-15 | 武汉大学 | A kind of New Hydrogen air exhaustion material and its application |
-
2021
- 2021-05-13 CN CN202110523451.3A patent/CN113299934B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007335171A (en) * | 2006-06-13 | 2007-12-27 | Toyota Motor Corp | Particulate carrying carbon particle, its manufacturing method, and electrode for fuel cell |
| CN101359739A (en) * | 2008-09-28 | 2009-02-04 | 南京工业大学 | Cathode material for solid-oxide fuel cell and method for preparing the same |
| CN102074713A (en) * | 2010-12-17 | 2011-05-25 | 天津大学 | Anode material for solid oxide fuel cell, preparation method thereof and fuel cell |
| CN102290583A (en) * | 2011-07-15 | 2011-12-21 | 天津大学 | Anode material and solid oxide fuel cell utilizing methanol as fuel |
| CN102842723A (en) * | 2012-09-18 | 2012-12-26 | 黑龙江大学 | Intermediate temperature solid oxide fuel cell cathode material with perovskite structure and preparation method thereof |
| CN104037429A (en) * | 2014-06-14 | 2014-09-10 | 中国科学技术大学 | High-catalytic-activity anti-carbon-deposition anode material and preparation method thereof |
| CN109473679A (en) * | 2018-10-24 | 2019-03-15 | 武汉大学 | A kind of New Hydrogen air exhaustion material and its application |
Non-Patent Citations (3)
| Title |
|---|
| MINGYUE HOU等: ""Investigation into the effect of molybdenum-site substitution on the performance of Sr2Fe1.5Mo0.5O6 dfor intermediate temperature solid oxide fuel cells"", 《JOURNAL OF POWER SOURCES》 * |
| YUQING MENG等: ""Insights into the CO2 Stability-Performance Trade-Off of Antimony Doped SrFeO3-δ Perovskite Cathode for Solid Oxide Fuel Cells"", 《ACS APPL. MATER. INTERFACES》 * |
| 吴其胜主编: "《新能源材料(第二版)》", 30 June 2017, 上海：华东理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114242996A (en) * | 2021-11-24 | 2022-03-25 | 惠州锂威新能源科技有限公司 | Monoatomic doped MoO3-xPreparation method of lithium battery negative electrode material |
| CN115911421A (en) * | 2022-10-24 | 2023-04-04 | 合肥学院 | SFM-based electrode material of hydrogen energy fuel cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113299934B (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hanif et al. | Recent advancements, doping strategies and the future perspective of perovskite-based solid oxide fuel cells for energy conversion | |
| Gou et al. | Nb-doped Sr2Fe1. 5Mo0. 5O6-δ electrode with enhanced stability and electrochemical performance for symmetrical solid oxide fuel cells | |
| Niu et al. | Performance of double perovskite symmetrical electrode materials Sr2TiFe1–xMoxO6–δ (x= 0.1, 0.2) for solid oxide fuel cells | |
| Ji et al. | Electrochemical performance of La-doped Sr2MgMoO6− δ in natural gas | |
| CN110581283B (en) | Bismuth-doped solid oxide cell fuel electrode material and preparation method and application thereof | |
| US11298691B2 (en) | Prussian blue derived catalysts | |
| Yu et al. | BaZr0. 1Co0. 4Fe0. 4Y0. 1O3-SDC composite as quasi-symmetrical electrode for proton conducting solid oxide fuel cells | |
| CN113299934B (en) | Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell | |
| Yang et al. | An efficient and prospective self-assembled hybrid electrocatalyst for symmetrical and reversible solid oxide cells | |
| CN112687900B (en) | Electric energy-value-added chemical symbiotic fuel cell and preparation method thereof | |
| Duranti et al. | Electrochemical performance and stability of LSFMn+ NiSDC anode in dry methane | |
| Zhong et al. | Defect-induced pyrochlore Pr2Zr2O7 cathode rich in oxygen vacancies for direct ammonia solid oxide fuel cells | |
| CN112408490B (en) | Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material | |
| Wang et al. | Structure-dependent electrocatalytic activity of La 1-x Sr x MnO 3 for oxygen reduction reaction | |
| Wang et al. | A highly stable of tungsten doped Pr0. 6Sr0. 4Fe0. 9W0. 1O3-δ electrode for symmetric solid oxide fuel cells | |
| CN111224140B (en) | Oxide material with iron-based double perovskite structure and preparation method thereof | |
| Yang et al. | Promoting effective electrochemical oxidation of CO by Cu-doping for highly active hybrid direct carbon fuel cell anode | |
| Hou et al. | Enhanced electrochemical activity and durability of a direct ammonia protonic ceramic fuel cell enabled by an internal catalyst layer | |
| Gao et al. | Voltage-driven reduction method to optimize in-situ exsolution of Fe nanoparticles at Sr2Fe1. 5+ xMo0. 5O6-δ interface | |
| Chen et al. | Layered perovskites with exsolved Co-Fe nanoalloy as highly active and stable anodes for direct carbon solid oxide fuel cells | |
| Wang et al. | Rational design of favourite lithium-ion cathode materials as electrodes for symmetrical solid oxide fuel cells | |
| CN111394748B (en) | For CO2Electrolytic iron-nickel alloy in-situ desolventizing layered perovskite cathode material | |
| Wang et al. | Characterization of Pr 0.5 A 0.5 Fe 0.9 W 0.1 O 3− δ (A= Ca, Sr and Ba) as symmetric electrodes for solid oxide fuel cells | |
| Huang et al. | UIO-66-NH2-Derived Porous Carbon Doping with Nitrogen-Supported Pt as an Electrocatalyst for Hydrogen Evolution Reaction | |
| CN113363543B (en) | Solid oxide cell fuel electrode material, preparation method thereof and solid oxide cell |
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 |