CN107645000B - A kind of solid oxide fuel cell dual-phase composite cathode material and preparation method thereof - Google Patents

A kind of solid oxide fuel cell dual-phase composite cathode material and preparation method thereof Download PDF

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CN107645000B
CN107645000B CN201710737400.4A CN201710737400A CN107645000B CN 107645000 B CN107645000 B CN 107645000B CN 201710737400 A CN201710737400 A CN 201710737400A CN 107645000 B CN107645000 B CN 107645000B
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李付绍
夏书标
闫宇星
成飞翔
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Qujing Normal University
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Abstract

本发明属于中温固体氧化物燃料电池(SOFC)技术领域,具体涉及一种SOFC双相复合阴极新材料及其制备方法。设定复合材料的两相比例构成(1‑x)Ca3Co2O6/xCe1.8Sm0.2O1.9(0≤x<1),采用溶胶‑凝胶法“一锅”同步制备复相阴极材料。先按复合组成的化学计量比配制金属盐(硝酸盐或醋酸盐)溶液;再按总金属离子:乙二胺四乙酸:柠檬酸=1:1:1的比例加入两种络合剂,用氨水调节pH至8‑9;最后再将络合溶液烘干、煅烧、退火即可得目标产物。其中,Ca3Co2O6为六方结构,空间群为R‑3C,Ce1.8Sm0.2O1.9为立方结构,空间群为FM3‑M

Figure 201710737400

The invention belongs to the technical field of medium-temperature solid oxide fuel cells (SOFC), and in particular relates to a new SOFC dual-phase composite cathode material and a preparation method thereof. The two-phase ratio composition of the composite material was set to (1‑ x )Ca 3 Co 2 O 6 / x Ce 1.8 Sm 0.2 O 1.9 (0≤ x <1), and the sol-gel method was used to prepare the composite phase simultaneously in one pot cathode material. First prepare the metal salt (nitrate or acetate) solution according to the stoichiometric ratio of the composite composition; then add two complexing agents according to the ratio of total metal ions: EDTA: citric acid = 1:1:1, The pH is adjusted to 8-9 with ammonia water; finally, the complex solution is dried, calcined and annealed to obtain the target product. Among them, Ca 3 Co 2 O 6 is a hexagonal structure, the space group is R‑3C , and Ce 1.8 Sm 0.2 O 1.9 is a cubic structure, and the space group is FM3‑M .

Figure 201710737400

Description

Solid oxide fuel cell two-phase composite cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of intermediate-temperature Solid Oxide Fuel Cells (SOFC), and particularly relates to a novel dual-phase composite cathode material (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9(0 ≤x< 1) and a process for producing the same.
Technical Field
A Solid Oxide Fuel Cell (SOFC) is a power generation device that directly converts hydrocarbon fuel into electric energy, and has the advantages of high efficiency, low pollution, flexible fuel and the like. The traditional SOFC has the operation temperature as high as about 1000 ℃, which puts high requirements on electrode materials, battery components and accessory equipment, and the construction, operation and maintenance costs of the battery are high. Reducing the operating temperature will help improve the matching between the various components of the cell, reducing operating costs. However, once the operating temperature is lowered, the ohmic resistance of the electrolyte and the interfacial resistance of the electrodes are increased. With the application of the anode-supported cell structure and the perfection of the electrolyte membrane preparation process, the polarization resistance in the oxygen reduction process on the SOFC cathode becomes the most important impedance source of the cell, and the polarization resistance plays a decisive role in the output characteristics of the cell. Therefore, the selection of a suitable catalytic component is one of the fundamental measures to improve the electrochemical performance of the cathode.
In medium and low temperature SOFCs, ABO3Perovskite structureHave been studied in large numbers. The oxide has good catalytic activity of oxygen reduction reaction and higher 'ion-electron' mixed conductivity, is one of the current medium-low temperature SOFC cathode materials which are widely concerned, and mainly comprises La x1-Sr x CoO δ3-δOxygen vacancy, the same shall apply hereinafter), Ba x1-Sr x Co y1-Fe y O δ3-、Sr x1-RE x CoO δ3-(RE is rare earth element), REBaCo2O δ5+And derivatives thereof, and the like. However, the Thermal Expansion Coefficient (TEC) of such materials is mostly very high and is much different from the TEC of the mainstream SOFC electrolyte material, such as Y x2Zr x1-2O x2-(YSZ)、Ce x1-Sm x O δ2-(SDC) and La x1-Sr x Ga y1-Mg y O δ3-(LSGM), etc., thereby increasing the sintering difficulty of the battery components and also being not beneficial to the stable operation of the battery. In addition, many of the cathode materials have problems of low conductivity, poor thermal stability of crystal lattice, and the like.
Therefore, a novel cobalt-based oxide Ca having a relatively small thermal expansion coefficient is used3Co2O6The material has obvious advantages as the SOFC cathode material. However, the thermoelectric cathode material also has a great challenge, and is limited by the hexagonal lattice structure and the oxygen ion transport property of the cathode material and the cubic or quasi-cubic ABO structure when being used as a cathode only3Cobalt-based perovskite is relatively poor, resulting in poor catalytic performance. Ca can be improved to a certain extent by means of doping, compounding other cobalt-based perovskite compounds and the like3Co2O6The electrochemical performance of the cathode material is simple, but the conventional methods have the limitations. For example, doping has limited improvement on the intrinsic properties of the material, and other cobalt-based perovskites are compounded to introduce more cobalt element, so that the cathode thermal expansion coefficient is improvedThe number will increase.
Disclosure of Invention
Oxide Ca for further developing hexagonal lattice structure3Co2O6Cathode catalytic potential of (2), increasing Ca3Co2O6The invention adopts the introduction of a fast ion conductor Ce0.8Sm0.2O1.9(SDC) method for overcoming the shortage of oxygen ion transport property of the material to expand Ca3Co2O6The three-phase interface during working designs a SOFC two-phase composite cathode material with novel structure and composition.
The solid oxide fuel cell two-phase composite cathode material prepared by the invention comprises the following chemical components: (1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9xNominal mole fraction of SDC in the complex phase composition), wherein Ca3Co2O6Is of hexagonal structure and space groupR-3C;Ce1.8Sm0.2O1.9Is of cubic structure, space groupFM3-M
Two-phase composite cathode material (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9The preparation method comprises the following steps.
A cerium nitrate and calcium nitrate are used as a two-phase composite cathode material of a solid oxide fuel cell (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9The respective molar ratio of the medium calcium to the cerium is prepared into a mixed solution of calcium nitrate and cerium nitrate, and the concentration of the cerium nitrate and the calcium nitrate solution is 2-3 mol/L.
B preparing cobalt acetate or cobalt nitrate as a two-phase composite cathode material (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9Adding the molar ratio of the medium cobalt element into the calcium cerium nitrate mixed solution prepared in the step A, and stirring to obtain a metal cation mixed solutionWherein the concentration of the cobalt acetate or cobalt nitrate solution is 2-3 mol/L.
Sm is a compound of general formula (I)2O3Two-phase composite cathode material (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9Adding the samarium element into the concentrated nitric acid solution according to the molar ratio of the samarium element, and slightly heating, stirring and dissolving to obtain a samarium nitrate solution, wherein the concentration of the samarium nitrate solution is 2-3 mol/L.
D, mixing the samarium nitrate solution obtained in the step C with the metal cation mixed solution obtained in the step B to obtain the composite cathode material (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9All metal ion sources in the desired molar ratio.
E, adding Ethylene Diamine Tetraacetic Acid (EDTA) and citric acid into the solution obtained in the step D as complexing agents, and adding the following metal ions in mass ratio: ethylene diamine tetraacetic acid: citric acid = 1: 1: 1 (molar ratio) with constant stirring.
F, adding concentrated ammonia water into the mixture obtained in the step E until the ethylenediamine tetraacetic acid is completely dissolved and the solution is clear, and adjusting the pH value of the solution to 8-9 by using the concentrated ammonia water and dilute nitric acid to finally obtain a tan solution.
And G, putting the brown solution obtained in the step F into an oven at 100 ℃ for evaporation to obtain viscous gel, and putting the viscous gel into an oven at 150 ℃ for completely drying the water to obtain dry gel.
And H, putting the dried gel obtained in the step G into a muffle furnace with the temperature of 450 ℃ for combustion and decomposition for 5H to obtain a black ash-burning-shaped product.
I, grinding the black ash-burning products in the step H, and putting the ground black ash-burning products into a high-temperature air furnace at the temperature of 960-x)Ca3Co2O6/xCe1.8Sm0.2O1.9. The temperature control process of the high-temperature air furnace comprises the following steps: heating the mixture from room temperature to 960 ℃ and 1020 ℃ at the heating speed of 2 ℃/min, then preserving the heat for 10h, and then cooling the mixture at the cooling speed of 3 ℃/minAnd cooling to room temperature.
The invention has the beneficial effects that: the invention discloses a novel solid oxide fuel cell cathode catalytic component (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9Wherein 0 is less than or equal toxThe two-phase composite material prepared synchronously by one pot by the sol-gel method has uniform particle size distribution and no generation of any other impurity phase, and simultaneously, compared with the preparation process of the conventional composite component, the preparation process of the material can be greatly simplified by synchronously preparing the one pot. Compared with single-phase cathode material Ca3Co2O6The two-phase composite cathode material has less thermal expansion, interface resistance (area specific resistance,ASR) Lower; at 800 ℃, taking hydrogen as fuel and composition asxWhen the composite material of = 0.5 is used as a cathode, the peak value of the output power of the electrolyte-supported single cell is 620 mW · cm-2Left and right. The invention has low requirements on synthesis equipment, simple operation and no special requirements on a battery sintering process. The synthesized material has stable structure and better comprehensive performance of the electrode.
Drawings
FIG. 1 is an SEM image of the product of example 1 of the present invention.
FIG. 2 shows the product (1-x)Ca3Co2O6/xCe1.8Sm0.2O1.9XRD spectrum of (1).
FIG. 3 is an electrochemical impedance spectrum of the product of example 1 of the present invention.
Fig. 4 is a graph showing the variation trend of the operating voltage and the power density of a single cell of the product of example 1 of the invention with the current density at different temperatures.
FIG. 5 is an SEM image of the product of example 2 of the present invention.
FIG. 6 is an electrochemical impedance spectrum of the product of example 2 of the present invention.
Fig. 7 is a graph showing the variation trend of the operating voltage and the power density with the current density of a single cell of the product of example 2 of the invention at different temperatures.
FIG. 8 is an SEM image of the product of example 3 of the present invention.
FIG. 9 is an electrochemical impedance spectrum of the product of example 3 of the present invention.
Fig. 10 is a graph showing the variation of the operating voltage and the power density with the current density of a single cell of the product of example 3 of the present invention at different temperatures.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Single-phase cathode material Ca for solid oxide fuel cell3Co2O6(i.e. thex= 0) and weighing calcium nitrate and cobalt acetate to prepare a mixed solution; adding Ethylene Diamine Tetraacetic Acid (EDTA) and citric acid into the calcium-cobalt mixed ion solution as complexing agents, wherein the mass ratio of the EDTA to the citric acid is as follows: ethylene diamine tetraacetic acid: citric acid = 1: 1: 1 (molar ratio), continuously stirring, simultaneously adding concentrated ammonia water until the ethylenediamine tetraacetic acid is completely dissolved and the solution is clear, and adjusting the pH value of the solution to 8-9 to obtain a brownish red solution; putting the brownish red solution into an oven, baking at 100 ℃, evaporating most of water to obtain viscous gel, baking at 150 ℃, and completely drying the water in the viscous gel to obtain dry gel; putting the dried gel into a muffle furnace with the temperature of 450 ℃ for combustion and decomposition for 5 hours to obtain a black ash-burning-shaped product; taking out black ash-burning products, grinding, and then putting the products into an air furnace with the temperature of 960 ℃ for annealing for 10 hours to obtain the single-phase cathode material Ca of the solid oxide fuel cell3Co2O6
SEM appearance analysis was performed on the synthesized positive electrode material, and Ca shown in FIG. 13Co2O6Is similar to a fruit commonly called Hovenia dulcis, and has relatively large particles. XRD diffraction is carried out on the prepared anode material, and the test result is shown in figure 2x= 0, and comparison of standard spectral lines in the figure shows that the synthesized sample is pure, has no impurity peak and Ca3Co2O6Has a hexagonal structure and space groups ofR-3C. Electrochemical impedance spectroscopy is carried out on the interface of the sample cathode material and the electrolyteThe results are shown in FIG. 3, and it can be seen that the interface impedance is about 0.28. omega. cm2. The results of the tests performed on the single cell using the sample material as the cathode are shown in fig. 4, and the peak value of the output power of the single cell at 800 ℃ is 410 mw.cm-2Left and right.
Example 2
Two-phase composite cathode material 0.75Ca according to solid oxide fuel cell3Co2O6/0.25Ce1.8Sm0.2O1.9(i.e. thex= 0.25), weighing calcium nitrate, cerium nitrate and cobalt acetate to prepare a mixed solution; then according to the composite cathode material 0.75Ca of the solid oxide fuel cell3Co2O6/0.25Ce1.8Sm0.2O1.9The molar ratio of the medium samarium element is measured2O3Adding into concentrated nitric acid solution for dissolving, and mixing with solution containing calcium, cerium and cobalt ions after the solution is clarified; adding Ethylene Diamine Tetraacetic Acid (EDTA) and citric acid into the calcium cerium cobalt samarium ion solution as complexing agents, wherein the mass ratio of the EDTA to the citric acid is as follows: ethylene diamine tetraacetic acid: citric acid = 1: 1: 1 (molar ratio), continuously stirring, simultaneously adding concentrated ammonia water until the ethylenediamine tetraacetic acid is completely dissolved and the solution is clear, and adjusting the pH value of the solution to 8-9 to obtain a brownish red solution; putting the brownish red solution into an oven, baking at 100 ℃, evaporating most of water to obtain viscous gel, baking at 150 ℃, and completely drying the water in the viscous gel to obtain dry gel; putting the dried gel into a muffle furnace with the temperature of 450 ℃ for combustion and decomposition for 5 hours to obtain a black ash-burning-shaped product; taking out the black ash-burning products, grinding, and then putting into an air furnace at 990 ℃ for annealing for 10h to obtain the composite cathode material 0.75Ca of the solid oxide fuel cell3Co2O6/0.25Ce1.8Sm0.2O1.9
SEM morphology analysis of the synthesized anode material shows that the characteristics of the two-phase components are obvious, and one phase is uniformly attached to the other phase, as shown in FIG. 5. XRD diffraction is carried out on the prepared anode material, and the test result is shown in figure 2x= 0.25,As can be seen by comparing the standard spectral lines in the figure, the synthesized sample is pure and has no impurity peak, Ce, of any third party except the target composition phase1.8Sm0.2O1.9Is of cubic structure and space group isFM3-M. Electrochemical impedance spectroscopy measurement was performed on the interface between the cathode material and the electrolyte of the sample, and the result is shown in fig. 6, where it can be seen that the interface impedance was about 0.25 Ω · cm2. The test of the single cell using the sample material as the cathode was carried out, and the result is shown in fig. 7, where the peak value of the output power of the single cell at 800 ℃ was 420 mw-2Left and right.
Example 3
Two-phase composite cathode material 0.5Ca according to solid oxide fuel cell3Co2O6/0.5Ce1.8Sm0.2O1.9(i.e. thex= 0.5), weighing calcium nitrate, cerium nitrate and cobalt acetate to prepare a mixed solution; further according to the composite cathode material 0.5Ca of the solid oxide fuel cell3Co2O6/0.5Ce1.8Sm0.2O1.9The molar ratio of the medium samarium element is measured2O3Adding into concentrated nitric acid solution for dissolving, and mixing with solution containing calcium, cerium and cobalt ions after the solution is clarified; adding Ethylene Diamine Tetraacetic Acid (EDTA) and citric acid into the calcium cerium cobalt samarium ion solution as complexing agents, wherein the mass ratio of the EDTA to the citric acid is as follows: ethylene diamine tetraacetic acid: citric acid = 1: 1: 1 (molar ratio), continuously stirring, simultaneously adding concentrated ammonia water until the ethylenediamine tetraacetic acid is completely dissolved and the solution is clear, and adjusting the pH value of the solution to 8-9 to obtain a brownish red solution; putting the brownish red solution into an oven, baking at 100 ℃, evaporating most of water to obtain viscous gel, baking at 150 ℃, and completely drying the water in the viscous gel to obtain dry gel; putting the dried gel into a muffle furnace with the temperature of 450 ℃ for combustion and decomposition for 5 hours to obtain a black ash-burning-shaped product; taking out the black ash-burning products, grinding, and then putting the black ash-burning products into an air furnace at the temperature of 1020 ℃ for annealing for 10 hours to obtain the composite cathode material 0.5Ca of the solid oxide fuel cell3Co2O6/0.5Ce1.8Sm0.2O1.9
SEM morphology analysis of the synthesized positive electrode material, as shown in fig. 8, the two-phase composition is characterized in that one phase is uniformly attached to the other phase. XRD diffraction is carried out on the prepared anode material, and the test result is shown in figure 2xAnd = 0.5, and as can be seen by comparing the standard spectral lines in the figure, the synthesized sample is pure, and no impurity peak of a third party is present except the target composition phase. Electrochemical impedance spectroscopy measurement was performed on the interface between the cathode material and the electrolyte of the sample, and the result is shown in fig. 9, where it can be seen that the interface impedance was about 0.12 Ω · cm2. The results of the tests performed on the single cell using the sample material as the cathode are shown in fig. 10, and the peak value of the output power of the single cell at 800 ℃ is 620 mw-2And the electrochemical performance of the cathode is greatly higher than that of a single-phase cathode.

Claims (5)

1.一种固体氧化物燃料电池双相复合阴极材料的制备方法,该复合材料的化学成分组成为:(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9;复合材料中相组成可根据两相的摩尔比例x进行灵活调配,其中0<x<1;Ca3Co2O6为六方结构、空间群为R-3C;Ce0.8Sm0.2O1.9为立方结构、空间群为FM3-M,其特征在于包括以下步骤:1. A preparation method of a solid oxide fuel cell dual-phase composite cathode material, the chemical composition of the composite material is composed of: (1-x) Ca 3 Co 2 O 6 /xCe 0.8 Sm 0.2 O 1.9 ; The composition can be flexibly adjusted according to the molar ratio x of the two phases, where 0<x<1; Ca 3 Co 2 O 6 is a hexagonal structure, and the space group is R-3C; Ce 0.8 Sm 0.2 O 1.9 is a cubic structure, and the space group is FM3-M is characterized in that comprising the following steps: A将硝酸铈和硝酸钙按照固体氧化物燃料电池的双相复合阴极材料(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9中钙与铈元素各自的摩尔占比配制成硝酸盐混合溶液;A The cerium nitrate and calcium nitrate are formulated into nitric acid according to the respective molar ratios of calcium and cerium elements in the dual-phase composite cathode material (1-x) Ca 3 Co 2 O 6 /xCe 0.8 Sm 0.2 O 1.9 of solid oxide fuel cells salt mixed solution; B将醋酸钴或硝酸钴按照固体氧化物燃料电池的双相复合阴极材料(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9中钴元素的摩尔占比,加入到步骤A配制成的钙铈硝酸盐混合溶液中,并进行搅拌,得到金属阳离子混合溶液;B Add cobalt acetate or cobalt nitrate to step A to prepare into the mixed solution of calcium cerium nitrate, and stirred to obtain a mixed solution of metal cations; C将Sm2O3按照固体氧化物燃料电池的双相复合阴极材料(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9中钐元素的摩尔占比,加入浓硝酸溶液中微加热搅拌溶解得到硝酸钐溶液;C. Sm 2 O 3 is added to the concentrated nitric acid solution according to the molar ratio of samarium element in the dual-phase composite cathode material (1-x)Ca 3 Co 2 O 6 /xCe 0.8 Sm 0.2 O 1.9 of the solid oxide fuel cell. Heating and stirring to dissolve to obtain samarium nitrate solution; D将步骤C得到的硝酸钐溶液与步骤B中的金属阳离子混合溶液混合得到固体氧化物燃料电池的复合阴极材料(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9所需摩尔占比的全部金属离子源;D Mix the samarium nitrate solution obtained in step C with the metal cation mixed solution in step B to obtain a composite cathode material for solid oxide fuel cells (1-x) Ca 3 Co 2 O 6 /xCe 0.8 Sm 0.2 O 1.9 required moles proportion of all metal ion sources; E向步骤D得到的混合溶液中加入乙二胺四乙酸和柠檬酸两种络合剂,加入质量比例为总金属离子:乙二胺四乙酸:柠檬酸=1:1:1,并不断搅拌;E Add two complexing agents, ethylenediaminetetraacetic acid and citric acid, to the mixed solution obtained in step D, in a mass ratio of total metal ions: ethylenediaminetetraacetic acid: citric acid = 1:1:1, and keep stirring ; F向步骤E中的混合物加入浓氨水,直至乙二胺四乙酸全部溶解和溶液澄清,并用浓氨水和稀硝酸调节溶液pH值至8-9,并最终得到棕褐色溶液;F adds concentrated ammonia water to the mixture in step E, until the EDTA is completely dissolved and the solution is clarified, and the pH value of the solution is adjusted to 8-9 with concentrated ammonia water and dilute nitric acid, and finally a tan solution is obtained; G将步骤F中得到的棕褐色溶液放入100℃的烘箱中蒸发得到粘稠的凝胶,再将粘稠的凝胶放入150℃的烘箱中将其水分彻底烘干,得到干凝胶;G Put the tan solution obtained in step F into an oven at 100°C to evaporate to obtain a viscous gel, and then put the viscous gel into an oven at 150°C to dry the water thoroughly to obtain a dry gel ; H将步骤G中的干凝胶放入450℃的马弗炉中燃烧分解5h,得到黑色燃灰状产物;H Put the dry gel in step G into a muffle furnace at 450°C for combustion and decomposition for 5h to obtain a black ash-like product; I将步骤H中的黑色燃灰状产物磨细,放入960-1020℃的高温空气炉中退火10h,即可得到固体氧化物燃料电池的双相复合阴极材料(1-x)Ca3Co2O6/xCe0.8Sm0.2O1.9I grind the black ash-like product in step H, put it into a high-temperature air furnace at 960-1020° C. for annealing for 10h, and then obtain the dual-phase composite cathode material (1-x) Ca 3 Co of the solid oxide fuel cell. 2 O 6 /xCe 0.8 Sm 0.2 O 1.9 ; 上述步骤中0<x<1。In the above steps, 0<x<1. 2.根据权利要求1所述的固体氧化物燃料电池双相复合阴极材料的制备方法,其特征在于:所述步骤A中铈、钙硝酸盐溶液的浓度为2-3mol/L。2 . The method for preparing a dual-phase composite cathode material for a solid oxide fuel cell according to claim 1 , wherein the concentration of the cerium and calcium nitrate solution in the step A is 2-3 mol/L. 3 . 3.根据权利要求1所述的固体氧化物燃料电池双相复合阴极材料的制备方法,其特征在于:所述步骤B中添加的醋酸钴或硝酸钴溶液的浓度为2-3mol/L。3. The method for preparing a solid oxide fuel cell dual-phase composite cathode material according to claim 1, wherein the concentration of the cobalt acetate or cobalt nitrate solution added in the step B is 2-3 mol/L. 4.根据权利要求1所述的固体氧化物燃料电池双相复合阴极材料的制备方法,其特征在于:所述步骤C中的硝酸钐溶液的浓度为2-3mol/L。4 . The method for preparing a dual-phase composite cathode material for a solid oxide fuel cell according to claim 1 , wherein the concentration of the samarium nitrate solution in the step C is 2-3 mol/L. 5 . 5.根据权利要求1所述的固体氧化物燃料电池双相复合阴极材料的制备方法,其特征在于:所述步骤I中高温炉的控温过程为:从室温用2℃/min的升温速度加热至960-1020℃温度,再保温10h,随后以3℃/min的降温速度冷却至室温。5. the preparation method of solid oxide fuel cell dual-phase composite cathode material according to claim 1, is characterized in that: in described step 1, the temperature control process of high temperature furnace is: from room temperature with the heating rate of 2 ℃/min Heated to a temperature of 960-1020 °C, maintained for another 10 h, and then cooled to room temperature at a cooling rate of 3 °C/min.
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