CN112408490A - Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material - Google Patents

Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Method for preparing double perovskite nano material Download PDF

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CN112408490A
CN112408490A CN201910767494.9A CN201910767494A CN112408490A CN 112408490 A CN112408490 A CN 112408490A CN 201910767494 A CN201910767494 A CN 201910767494A CN 112408490 A CN112408490 A CN 112408490A
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周娟
蒲江戈
刘超
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Nanjing University of Science and Technology
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Abstract

本发明公开了一种水热合成Ba掺杂Sr2Fe1.5Mo0.5O6双钙钛矿纳米材料的方法。按照双钙钛矿阳极材料Sr2‑x Ba x Fe1.5Mo0.5O6中Sr、Ba、Fe和Mo的化学计量数，将Sr(NO3)2、Ba(NO3)2、Fe(NO3)3·9H2O和(NH4)6Mo7O24·4H2O依次加入水中，其中，0＜x≤1；随后加入络合剂柠檬酸与分散剂聚乙二醇；调节pH值至3~5之间，获得前驱体溶液；将前驱体溶液于220 oC~260 oC下水热反应，离心、清洗、干燥；所得干燥产物于950 oC～1150℃下煅烧，煅烧气氛为5~10%H2/N2，即得所述纳米材料。本发明制备得到的双钙钛矿阳极材料的相结构较好，作为固体氧化物燃料电池的阳极材料，在还原性气氛中较为稳定，与电解质GDC热匹配性质较好，可以提高固体氧化物燃料电池的阳极材料的性能。

Figure 201910767494

The invention discloses a method for hydrothermally synthesizing Ba-doped Sr 2 Fe 1.5 Mo 0.5 O 6 double perovskite nanomaterials. According to the stoichiometric numbers of Sr, Ba, Fe and Mo in the double perovskite anode material Sr 2- x Ba x Fe 1.5 Mo 0.5 O 6 , Sr(NO 3 ) 2 , Ba(NO 3 ) 2 , Fe(NO 3 3 ) 3 ·9H 2 O and (NH 4 ) 6 Mo 7 O 24 ·4H 2 O were added to water in turn, wherein, 0<x≤1; then add complexing agent citric acid and dispersing agent polyethylene glycol; adjust pH The value of the precursor solution is between 3 and 5, and the precursor solution is obtained; the precursor solution is hydrothermally reacted at 220 o C ~ 260 o C, centrifuged, washed, and dried; the obtained dried product is calcined at 950 o C ~ 1150 ℃, and the calcination atmosphere is 5~10%H 2 /N 2 , the nanomaterial is obtained. The double perovskite anode material prepared by the invention has good phase structure, is used as the anode material of the solid oxide fuel cell, is relatively stable in a reducing atmosphere, has good thermal matching properties with the electrolyte GDC, and can improve the solid oxide fuel. The properties of the anode material of the battery.

Figure 201910767494

Description

Hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6Double calciumMethod for preparing titanium ore nano material
Technical Field
The invention belongs to the technical field of preparation of anode materials of solid oxide fuel cells, and particularly relates to Ba-doped Sr2Fe1.5Mo0.5O6A preparation method of a double perovskite nano material.
Background
Solid Oxide Fuel Cells (SOFC) have low sensitivity to impurities in fuel, have higher energy conversion efficiency and all-solid-state mechanical structure, do not need noble metal catalysts and the like, and become the focus of current scientific research and industrial attention. The selection of anode materials can have important influence on the performance and long-term stability of the anode materials, so that the continuous improvement of material performance and cell preparation process is the key point of the development of high-performance SOFCs. Conventional SOFC fuels are typically H2However, because of the problems of high hydrogen production cost, difficult transportation and the like, the current most suitable SOFC fuel gas is still hydrocarbon fuel gas, and the performance of the traditional SOFC anode Ni/YSZ in hydrocarbon fuel is poor, so that the problems of carbon deposition, sulfur poisoning and the like exist, and the circulation of fuel is influenced. In order to improve the long-term stability of SOFC in hydrocarbon fuels, one approach is to use a mixed-valence perovskite or double-perovskite type material having oxygen vacancies as the anode, the perovskite type material having stability and good catalytic activity in hydrocarbon fuels.
The existing main methods for preparing the double-perovskite type electrode material are a traditional solid phase method, a coprecipitation method, a sol-gel method and the like, and the methods have the problems of poor crystal form, high sintering temperature, long heat treatment time and the like, so that the performance of the anode material used as a solid oxide fuel cell is reduced.
Disclosure of Invention
The invention aims to provide Ba-doped Sr2Fe1.5Mo0.5O6The preparation method of (1).
The technical solution for realizing the purpose of the invention is as follows: hydrothermal synthesis of Ba doped Sr2Fe1.5Mo0.5O6A method of making a double perovskite nanomaterial comprisingThe method comprises the following steps:
(1) according to the double perovskite anode material Sr x2-Ba x Fe1.5Mo0.5O6The stoichiometry of Sr, Ba, Fe and Mo in the molar ratio of 2-x: x1.5: 0.5 Sr (NO)3)2、Ba(NO3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2Adding O into water in sequence according to the proportion, wherein the ratio of O to O is more than 0x≤1；
(2) Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions (Sr, Ba, Fe and Mo) is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions (Sr, Ba, Fe and Mo) is 1: 1;
(3) adding ammonia water to adjust the pH value of the solution to 3-5 to obtain a precursor solution;
(4) the precursor solution is put at 220oC~260 oC, carrying out hydrothermal reaction for 18-24 h, centrifuging, cleaning and drying;
(5) the resulting dried product is at 950oCalcining for 10 hours at the temperature of C-1150 ℃, wherein the calcining atmosphere is 5-10% of H2/N2To obtain Ba-doped Sr2Fe1.5Mo0.5O6A double perovskite nanomaterial.
Compared with the prior art, the material prepared by the invention has better performance, can be used for power generation of a solid oxide fuel cell, has higher value, can provide heat required by natural gas reforming, can be utilized in the aspects of steam production and combined cycle with a gas turbine, and is very practical for distributed power generation.
Drawings
FIG. 1 shows preparation of Sr in examples 1 to 5 of the present invention2Fe1.5Mo0.5O6、Sr1.75Ba0.25Fe1.5Mo0.5O6、Sr1.5Ba0.5Fe1.5Mo0.5O6、Sr1.25Ba0.75Fe1.5Mo0.5O6And SrBaFe1.5Mo0.5O6Material X-ray diffraction (XRD) pattern.
FIG. 2 shows Sr prepared in examples 1-5 of the present invention2Fe1.5Mo0.5O6、Sr1.75Ba0.25Fe1.5Mo0.5O6、Sr1.5Ba0.5Fe1.5Mo0.5O6、Sr1.25Ba0.75Fe1.5Mo0.5O6And SrBaFe1.5Mo0.5O6Materials anode materials in H2Conductivity curve under atmosphere.
FIG. 3 shows Sr prepared in example 2 of the present invention1.75Ba0.25Fe1.5Mo0.5O6SEM images of different multiples of anode material.
FIG. 4 shows Sr prepared in example 2 of the present invention1.75Ba0.25Fe1.5Mo0.5O6X-ray diffraction (XRD) pattern of chemical compatibility of the anode material with the GDC electrolyte material.
FIG. 5 shows Sr in example 2 of the present invention1.75Ba0.25Fe1.5Mo0.5O6Anode material in H2X-ray diffraction (XRD) pattern of stability under atmosphere.
Detailed Description
Therefore, the invention provides a hydrothermal synthesis method for preparing Ba-doped Sr2Fe1.5Mo0.5O6The preparation method of the double perovskite nano material can obtain particles which are simple in preparation method, complete in crystal grain development, small in particle size, large in specific surface area, uniform in distribution and light in particle agglomeration.
For further understanding of the present invention, the present invention will now be described with reference to the following examples2Fe1.5Mo0.5O6、Sr1.75Ba0.25Fe1.5Mo0.5O6、Sr1.5Ba0.5Fe1.5Mo0.5O6、Sr1.25Ba0.75Fe1.5Mo0.5O6And SrBaFe1.5Mo0.5O6The preparation method of the electrode material is illustrated, and the protection scope of the present invention is not limited by the following examples.
Example 1
According to the double perovskite anode material Sr2Fe1.5Mo0.5O6The stoichiometric ratio of Sr, Fe and Mo is that Sr (NO) is added according to the molar ratio of 2: 1.5: 0.53)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2O are added to water in sequence.
Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions is 1: 1.
And adding ammonia water to adjust the pH value of the solution to about 4 to obtain a precursor solution prepared by a hydrothermal method.
Pouring the precursor solution into a hydrothermal reaction kettle, wherein the volume ratio of the solution is about 60-70%, sealing the reaction kettle, and then putting the reaction kettle into an oven. Oven temperature of 220 deg.CoC~260 oAnd C, reacting for 18-24 h.
And after taking out the reactant, centrifuging the product for 5 min at the rotating speed of 8000 r/min by using absolute ethyl alcohol as a solvent, repeating the operation for 5 times, and drying to obtain sample powder.
Next, the sample powder was calcined. The temperature of calcination was 950 deg.CoC-1150 ℃, and the calcining atmosphere is 5-10% of H2/N2The calcination time is 10h, namely Sr is obtained2Fe1.5Mo0.5O6。
Its X-ray diffraction (XRD) pattern is shown in figure 1.
The double perovskite anode material prepared in example 1 was pressed to a length of 15mm and a cross-sectional area of 25 mm2The two ends of the prepared sample strip are connected with four silver wires with the diameter of 0.3mm, then the silver wires at the two ends of the sample are connected into a conductivity tester, and conductive silver paste is coated on the contact position of the double perovskite anode material and the silver wires. At 700oH of C2The test was carried out under an atmosphere and the results are shown in FIG. 2.
Sr synthesized in example 12Fe1.5Mo0.5O6The sample material was examined by Hitachi S-4800 field emission electron microscopy for the microstructure of the prepared powder, and the results are shown in FIGS. 3(A) and (B), where the particle size of the prepared sample was in the nanometer level.
Example 2
According to the double perovskite anode material Sr1.75Ba0.25Fe1.5Mo0.5O6The stoichiometric ratio of Sr, Ba, Fe and Mo is 1.75: 0.25: 1.5: 0.5 mol ratio of Sr (NO)3)2、Ba(NO3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2O are added to water in sequence.
Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions is 1: 1.
And adding ammonia water to adjust the pH value of the solution to about 4 to obtain a precursor solution prepared by a hydrothermal method.
Pouring the precursor solution into a hydrothermal reaction kettle, wherein the volume ratio of the solution is about 60-70%, sealing the reaction kettle, and then putting the reaction kettle into an oven. Oven temperature of 220 deg.CoC~260 oAnd C, reacting for 18-24 h.
And after taking out the reactant, centrifuging the product for 5 min at the rotating speed of 8000 r/min by using absolute ethyl alcohol as a solvent, repeating the operation for 5 times, and drying to obtain sample powder.
Next, the sample powder was calcined. The temperature of calcination was 950 deg.CoC-1150 ℃, and the calcining atmosphere is 5-10% of H2/N2The calcination time is 10h, namely Sr is obtained1.75Ba0.25Fe1.5Mo0.5O6。
Its X-ray diffraction (XRD) pattern is shown in figure 1.
The double perovskite anode material prepared in example 2 was pressed to a length of 15mm and a cross-sectional area of 25 mm2A rectangular parallelepiped sample strip of (2), a sample to be preparedThe two ends of the strip are connected with four silver wires with the diameter of 0.3mm, then the silver wires at the two ends of the sample are connected into a conductivity tester, and conductive silver paste is coated on the contact position of the double perovskite anode material and the silver wires. At 700oH of C2The test was carried out under an atmosphere and the results are shown in FIG. 2.
The powder synthesized in example 2 was placed in a high temperature furnace at 800 deg.CoH of C2Calcining for 10h in the atmosphere, cooling to room temperature, and measuring XRD. The results are shown in FIG. 3, and FIG. 3 shows Sr1.75Ba0.25Fe1.5Mo0.5O6And is stable under a reducing atmosphere.
Sr prepared in example 21.75Ba0.25Fe1.5Mo0.5O6Performing compatibility analysis of the powder with GDC, mixing the synthesized electrode material with electrolyte, grinding in a mortar for 40 min-1 h, and placing the ground sample into a high-temperature furnace 800oCalcining for 24h, cooling to room temperature, and measuring XRD. The results are shown in FIG. 4, where Sr is shown in FIG. 42Fe1.5Mo0.5O6Compatibility data with GDC.
The XRD pattern of the single-phase GDC powder is given in fig. 5. For Sr2Fe1.5Mo0.5O6In the sample, it can be seen that the diffraction peaks of the spectra do not change obviously after mixing, and each of them maintains the original diffraction peak, indicating that no reaction occurs. The peak position is not shifted and cleaved. Therefore, we consider Sr under high temperature conditions2Fe1.5Mo0.5O6The electrode material and the GDC electrolyte do not react chemically, and the electrode material and the GDC electrolyte have good high-temperature chemical compatibility.
Example 3
According to the double perovskite anode material Sr1.5Ba0.5Fe1.5Mo0.5O6The stoichiometric ratio of Sr, Ba, Fe and Mo is 1.5: 0.5: 1.5: 0.5 mol ratio of Sr (NO)3)2、Ba(NO3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2O are added to water in sequence.
Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions is 1: 1.
And adding ammonia water to adjust the pH value of the solution to about 4 to obtain a precursor solution prepared by a hydrothermal method.
Pouring the precursor solution into a hydrothermal reaction kettle, wherein the volume ratio of the solution is about 60-70%, sealing the reaction kettle, and then putting the reaction kettle into an oven. Oven temperature of 220 deg.CoC~260 oAnd C, reacting for 18-24 h.
And after taking out the reactant, centrifuging the product for 5 min at the rotating speed of 8000 r/min by using absolute ethyl alcohol as a solvent, repeating the operation for 5 times, and drying to obtain sample powder.
Next, the sample powder was calcined. The temperature of calcination was 950 deg.CoC-1150 ℃, and the calcining atmosphere is 5-10% of H2/N2The calcination time is 10h, namely Sr is obtained1.5Ba0.5Fe1.5Mo0.5O6。
Its X-ray diffraction (XRD) pattern is shown in figure 1.
The double perovskite anode material prepared in example 3 was pressed to a length of 15mm and a cross-sectional area of 25 mm2The two ends of the prepared sample strip are connected with four silver wires with the diameter of 0.3mm, then the silver wires at the two ends of the sample are connected into a conductivity tester, and conductive silver paste is coated on the contact position of the double perovskite anode material and the silver wires. At 700oH of C2The test was carried out under an atmosphere and the results are shown in FIG. 2.
Example 4
According to the double perovskite anode material Sr1.25Ba0.75Fe1.5Mo0.5O6The stoichiometric ratio of Sr, Ba, Fe and Mo is 1.25: 0.75: 1.5: 0.5 mol ratio of Sr (NO)3)2、Ba(NO3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2O are added to water in sequence.
Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions is 1: 1.
And adding ammonia water to adjust the pH value of the solution to about 4 to obtain a precursor solution prepared by a hydrothermal method.
Pouring the precursor solution into a hydrothermal reaction kettle, wherein the volume ratio of the solution is about 60-70%, sealing the reaction kettle, and then putting the reaction kettle into an oven. Oven temperature of 220 deg.CoC~260 oAnd C, reacting for 18-24 h.
And after taking out the reactant, centrifuging the product for 5 min at the rotating speed of 8000 r/min by using absolute ethyl alcohol as a solvent, repeating the operation for 5 times, and drying to obtain sample powder.
Next, the sample powder was calcined. The temperature of calcination was 950 deg.CoC-1150 ℃, and the calcining atmosphere is 5-10% of H2/N2The calcination time is 10h, namely Sr is obtained1.25Ba0.75Fe1.5Mo0.5O6。
Its X-ray diffraction (XRD) pattern is shown in figure 1.
The double perovskite anode material prepared in example 4 was pressed to a length of 15mm and a cross-sectional area of 25 mm2The two ends of the prepared sample strip are connected with four silver wires with the diameter of 0.3mm, then the silver wires at the two ends of the sample are connected into a conductivity tester, and conductive silver paste is coated on the contact position of the double perovskite anode material and the silver wires. At 700oH of C2The test was carried out under an atmosphere and the results are shown in FIG. 2.
Example 5
According to double perovskite anode material SrBaFe1.5Mo0.5O6The stoichiometric ratio of Sr, Ba, Fe and Mo is that Sr (NO) is added according to the molar ratio of 1: 1: 1.5: 0.53)2、Ba(NO3)2、Fe(NO3)3·9H2O and (NH)4)6Mo7O24·4H2O are added to water in sequence.
Then adding complexing agent citric acid and dispersant polyethylene glycol, wherein the molar ratio of the citric acid to all metal ions is 1.5: 1, and the molar ratio of the polyethylene glycol to all metal ions is 1: 1.
And adding ammonia water to adjust the pH value of the solution to about 4 to obtain a precursor solution prepared by a hydrothermal method.
Pouring the precursor solution into a hydrothermal reaction kettle, wherein the volume ratio of the solution is about 60-70%, sealing the reaction kettle, and then putting the reaction kettle into an oven. Oven temperature of 220 deg.CoC~260 oAnd C, reacting for 18-24 h.
And after taking out the reactant, centrifuging the product for 5 min at the rotating speed of 8000 r/min by using absolute ethyl alcohol as a solvent, repeating the operation for 5 times, and drying to obtain sample powder.
Next, the sample powder was calcined. The temperature of calcination was 950 deg.CoC-1150 ℃, and the calcining atmosphere is 5-10% of H2/N2Calcining for 10h to obtain SrBaFe1.5Mo0.5O6。
Its X-ray diffraction (XRD) pattern is shown in figure 1.
The double perovskite anode material prepared in example 5 was pressed to a length of 15mm and a cross-sectional area of 25 mm2The two ends of the prepared sample strip are connected with four silver wires with the diameter of 0.3mm, then the silver wires at the two ends of the sample are connected into a conductivity tester, and conductive silver paste is coated on the contact position of the double perovskite anode material and the silver wires. At 700oH of C2The test was carried out under an atmosphere and the results are shown in FIG. 2.
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 (7)

1.水热合成Ba掺杂Sr2Fe1.5Mo0.5O6双钙钛矿纳米材料的方法，其特征在于，包括以下步骤：1. A method for hydrothermally synthesizing Ba-doped Sr 2 Fe 1.5 Mo 0.5 O 6 double perovskite nanomaterials, comprising the following steps: （1）按照双钙钛矿阳极材料Sr2-x Ba x Fe1.5Mo0.5O6中Sr、Ba、Fe和Mo的化学计量数，将Sr(NO3)2、Ba(NO3)2、Fe(NO3)3·9H2O和(NH4)6Mo7O24·4H2O依次加入水中，其中，0＜x≤1；(1) According to the stoichiometric number of Sr, Ba, Fe and Mo in the double perovskite anode material Sr 2- x Ba x Fe 1.5 Mo 0.5 O 6 , Sr(NO 3 ) 2 , Ba(NO 3 ) 2 , Fe(NO 3 ) 3 ·9H 2 O and (NH 4 ) 6 Mo 7 O 24 ·4H 2 O were added to water in sequence, wherein 0<x≤1; （2）随后加入络合剂柠檬酸与分散剂聚乙二醇；(2) Then add complexing agent citric acid and dispersing agent polyethylene glycol; （3）调节pH值至3~5之间，获得前驱体溶液；(3) Adjust the pH value to between 3 and 5 to obtain the precursor solution; （4）将前驱体溶液于220 oC~260 oC下水热反应，离心、清洗、干燥；(4) hydrothermally react the precursor solution at 220 o C ~ 260 o C, centrifuge, wash and dry; （5）所得干燥产物于950 oC～1150℃下煅烧一段时间，煅烧气氛为5~10%H2/N2，即得所述纳米材料。(5) The obtained dried product is calcined at 950 ° C～1150°C for a period of time, and the calcination atmosphere is 5～10% H 2 /N 2 , to obtain the nanomaterial. 2.如权利要求1所述的方法，其特征在于，柠檬酸与总金属离子的摩尔比为1.5: 1，聚乙二醇与总金属离子的摩尔比为1:1。2. method as claimed in claim 1 is characterized in that, the mol ratio of citric acid and total metal ion is 1.5: 1, and the mol ratio of polyethylene glycol and total metal ion is 1: 1. 3.如权利要求1所述的方法，其特征在于，加入氨水将溶液pH值调至3~5之间。3. method as claimed in claim 1 is characterized in that, adding ammoniacal liquor and adjusting solution pH value to between 3～5. 4. 如权利要求1所述的方法，其特征在于，将前驱体溶液于 220 oC~260 oC下水热反应18~24 h。4. The method of claim 1, wherein the precursor solution is hydrothermally reacted at 220 o C to 260 o C for 18 to 24 h. 5. 如权利要求1所述的方法，其特征在于，所得干燥产物于950 oC～1150℃下煅烧10h。5. The method according to claim 1, wherein the obtained dried product is calcined at 950 ℃ ～1150 ℃ for 10h. 6.如权利要求1-5任一所述的方法制备的Ba掺杂Sr2Fe1.5Mo0.5O6双钙钛矿纳米材料。6. The Ba-doped Sr 2 Fe 1.5 Mo 0.5 O 6 double perovskite nanomaterial prepared by the method according to any one of claims 1-5. 7.如权利要求1-5任一所述的方法制备的Ba掺杂Sr2Fe1.5Mo0.5O6双钙钛矿纳米材料作为固体氧化物燃料电池电极材料的应用。7. Application of the Ba-doped Sr 2 Fe 1.5 Mo 0.5 O 6 double perovskite nanomaterial prepared by the method according to any one of claims 1 to 5 as an electrode material for solid oxide fuel cells.
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