CN113299934B - 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 PDF

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CN113299934B
CN113299934B CN202110523451.3A CN202110523451A CN113299934B CN 113299934 B CN113299934 B CN 113299934B CN 202110523451 A CN202110523451 A CN 202110523451A CN 113299934 B CN113299934 B CN 113299934B
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fuel electrode
electrode material
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carbon dioxide
carbon deposition
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CN113299934A (en
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夏长荣
张少威
胡学禹
夏玉玲
张璐
宦道明
衡泽凤
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University of Science and Technology of China USTC
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
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    • H01M4/9025Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/12Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/12Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293Fuel cells with solid oxide electrolytes
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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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: sr 2 Fe 1.5 Mo 0.5‑ x Sb x O 6‑δ Formula 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 ABO 3 Sr of 2 Fe 1.5 Mo 0.5 O 6‑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 good stability in humid hydrogen and carbon dioxide atmospheres, and in addition, the Sb-doped fuel electrode material has excellent anti-carbon deposition capability, and no carbon deposition is generated after long-time operation even if synthesis gas or ethanol is used as fuel. 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

Anti-carbon deposition and carbon dioxide resistant fuel electrode material, preparation method thereof and solid oxide cell
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 mainly include 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 electronic 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 definition of Ni-YSZ as an inorganic material in solid oxide fuel cell A review (B.Shri Prakash, S.Senthil Kumar, S.T.Arena.Recewable and Sustainable Energy Reviews 36 (2014) 149-179), in actual operation of SOC, metal Ni is easily migrated and agglomerated when the battery is operated for a long time; 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:
Sr 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ formula 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 to 500nm.
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 ) 6 Mo 7 O 24 ·4H 2 O。
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,has the chemical formula shown in formula I: sr (strontium) 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ Formula 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 ABO 3 Sr of 2 Fe 1.5 Mo 0.5 O 6-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 invention 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ And Sr 2 Fe 1.5 Mo 0.5 O 6-δ Respectively 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 invention 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ A 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 invention 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ And Sr 2 Fe 1.5 Mo 0.5 O 6-δ Temperature programmed reduction curve of oxide powder in 5% hydrogen/95% nitrogen;
FIG. 4 shows Sr in example 2 of the present invention 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ Processing 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 invention 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ Raman 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:
Sr 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ formula 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 be 0.05, 0.10 or 0.15. In addition, the delta is the non-stoichiometry of oxygen, the specific numerical value is uncertain, the delta value is related to the properties, the temperature, the atmosphere and the like of the material, the delta value is not limited generally, and the content of oxygen in the chemical formula can be directly expressed as O 6-δ . In the present invention, the preferred chemical formula is Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ (Sb-SFM)。
In the present invention, the particle size of the anti-carbon deposition and carbon dioxide resistant fuel electrode material is preferably 100 to 500nm, and more preferably 200 to 400nm.
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 Sr 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ In stoichiometric ratio, antimony oxides, e.g. Sb, are weighed 2 O 3 Adding 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 Sr 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ Weighing strontium salt, ferric salt and molybdenum salt according to the stoichiometric ratio, and adding the strontium salt, the ferric salt and the molybdenum salt into the solution.
In the present invention, the strontium salt is strontium nitrate; the iron salt is preferably ferric nitrate and/or ferric acetate; the molybdenum salt is (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
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 the antimony oxide can be dissolved.
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 present invention, the heating temperature is preferably 200 to 400 ℃, more preferably 300 ℃.
Collecting the brown black powder, grinding, and calcining at high temperature in air atmosphere to obtain Sr 2 Fe 1.5 Mo 0.5- x Sb x O 6-δ Solid oxide cell fuel electrode materials.
In the present invention, the temperature of the high-temperature calcination phase is preferably 500 to 1200 ℃, more preferably 800 to 1100 ℃, such as 500 ℃,600 ℃,700 ℃,800 ℃,900 ℃,1000 ℃,1100 ℃,1200 ℃, and preferably any of the above values is used as an upper limit or a lower limit. The high-temperature calcination is preferably carried out for 1 to 10 hours, more preferably for 3 to 8 hours, most preferably for 5 to 6 hours,
the invention also provides a solid oxide cell, which comprises 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 commonly used in the field of air electrodes, electrolytes and current collectors.
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 examples are provided to describe the fuel electrode material of a solid oxide cell, the preparation method thereof and the solid oxide cell in detail, but they should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of Sr by citric acid-glycinate combustion method 2 Fe 1.5 Mo 0.45 Sb 0.05 O 6-δ Fuel electrode material
Sr 2 Fe 1.5 Mo 0.45 Sb 0.05 O 6-δ The fuel electrode material adoptsThe citric acid-glycinate is prepared by combustion method, wherein citric acid and glycine are used as chelating agent and combustion agent, and the metal ion source is Sr (NO) respectively 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Sb 2 O 3 (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.
And 2, step: weighing Sb according to the stoichiometric ratio 2 O 3 Placing 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 Sb 2 O 3 And completely dissolving.
And 3, step 3: respectively weighing Sr (NO) according to the stoichiometric ratio 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 And 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 brownish black powder obtained in the step 5, finally transferring the powder into a muffle furnace, and calcining the powder for 5 hours in an air atmosphere at 1100 ℃ to obtain Sr 2 Fe 1.5 Mo 0.45 Sb 0.05 O 6-δ A fuel electrode material.
EXAMPLE 2 preparation of Sr by citric acid-glycinate combustion method 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ Fuel electrode material
Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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) respectively 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Sb 2 O 3 (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.
And 2, step: weighing Sb according to the stoichiometric ratio 2 O 3 Placing 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 Sb 2 O 3 And completely dissolving.
And step 3: respectively weighing Sr (NO) according to the stoichiometric ratio 3 ) 2 、Fe(NO 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 And O, and then dissolving in the solution obtained in the step 2 in turn.
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 brownish black powder obtained in the step 5, finally transferring the powder into a muffle furnace, and calcining the powder for 5 hours in an air atmosphere at 1100 ℃ to obtain the expected Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ A fuel electrode material.
2 1.5 0.4 0.1 6-δ Phase structure and morphology analysis of SrFeMoSbO fuel electrode material
The compound obtained in example 2Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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 is 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ And Sr 2 Fe 1.5 Mo 0.5 O 6-δ A 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. Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The transmission electron micrographs of (A) and (B) are shown in FIG. 2, 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 pattern.
2 1.5 0.4 0.1 6-δ Stability of SrFeMoSbO fuel electrode material in reducing atmosphere
To verify Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ Stability of Fuel electrode Material in reducing atmosphere, sr, which had been in phase in example 2 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ And (3) placing the powder in a tube furnace, reducing the powder for 5 hours at 800 ℃ in a humid 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), sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The diffraction pattern after reduction is consistent with that before reduction, indicating that Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The product has good stability in reducing atmosphere; the (110) diffraction peak was further enlarged 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. Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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 Sr 2 Fe 1.5 Mo 0.5 O 6-δ Compared 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 a solid oxide cell fuel electrode.
2 1.5 0.4 0.1 6-δ Carbon dioxide resistance of SrFeMoSbO fuel electrode material
To verify Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The fuel electrode material has resistance to carbon dioxide, and Sr, which has been formed in phase in example 2, is used 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The powder is processed for 5 hours at 800 ℃ in pure carbon dioxide atmosphere, and then the processed powder is subjected to X-ray diffraction characterization to identify the phase structure. The experimental result is shown in FIG. 4, sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The X-ray diffraction pattern after treatment is consistent with that before treatment, which shows that Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The phase structure in the carbon dioxide atmosphere is very stable, and therefore, sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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-δ Carbon deposition resistance of SrFeMoSbO fuel electrode material
To verify Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The anti-carbon deposition capability of the fuel electrode material is to add Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ Fuel electrode on hydrocarbon fuel gasAfter the operation for a medium and long time, whether carbon deposition is generated is detected, and the selected hydrocarbon fuels are 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 added 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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 -1 And 1580cm -1 No Raman signal peak of carbon was observed, indicating Sr 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ No carbon deposition and Sr generation in the process of long-term operation in synthesis gas and ethanol 2 Fe 1.5 Mo 0.4 Sb 0.1 O 6-δ The 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered 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:
Sr 2 Fe 1.5 Mo 0.5-x Sb x O 6-δ formula I;
wherein x is the doping amount of Sb, and x is more than 0 and less than 0.2;
the preparation method of the anti-carbon deposition and carbon dioxide resistant fuel electrode material 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.
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 for preparing carbon deposition resistant 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 ) 6 Mo 7 O 24 ·4H 2 O。
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, characterized in that 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.
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