CN113178587A - Solid oxide fuel cell anode material and preparation method and application thereof - Google Patents

Solid oxide fuel cell anode material and preparation method and application thereof Download PDF

Info

Publication number
CN113178587A
CN113178587A CN202110480312.7A CN202110480312A CN113178587A CN 113178587 A CN113178587 A CN 113178587A CN 202110480312 A CN202110480312 A CN 202110480312A CN 113178587 A CN113178587 A CN 113178587A
Authority
CN
China
Prior art keywords
anode material
fuel cell
solid oxide
oxide fuel
lscm
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.)
Pending
Application number
CN202110480312.7A
Other languages
Chinese (zh)
Inventor
马文会
于洁
王彬
乔翠
吕国强
万小涵
李绍元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN202110480312.7A priority Critical patent/CN113178587A/en
Publication of CN113178587A publication Critical patent/CN113178587A/en
Pending legal-status Critical Current

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
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a solid oxide fuel cell anode material and a preparation method and application thereof, belonging to the technical field of energy materials, wherein the preparation method of the solid oxide fuel cell anode material comprises the following steps: uniformly dispersing copper source, nickel source and LSCM powder in a water solvent, adding alkali until no blue flocculent precipitate is generated in the reaction, obtaining an intermediate product, and sintering the intermediate product at 600-700 ℃ for 0.5-3 h to obtain a precursor; in a hydrogen atmosphere, preserving the heat of the precursor at 600-700 ℃ for 0.5-3 h to obtain the solid oxide fuel cell anode material;the general formula of the LSCM is LaxSr1‑xCryMn1‑yO3‑δWherein x is 0.2 to 0.5, and y is 0.4 to 0.6. The preparation method has the advantages of simple preparation process, short preparation period, low price of raw materials, safety, simple required equipment and suitability for large-scale production.

Description

Solid oxide fuel cell anode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of energy, in particular to a solid oxide fuel cell anode material and a preparation method and application thereof.
Background
Solid Oxide Fuel Cells (SOFCs) are energy conversion devices that have high power generation efficiency and are environmentally friendly, and thus are applied to various mobile and stationary development devices. The SOFC is a device that can convert chemical energy stored inside fuel into electrical energy, does not need to go through a combustion process, is not limited by carnot cycle, and has the advantages of high energy conversion rate, low pollution, low noise and the like. The supply gas to the anode side of the solid oxide fuel cell is generally a reducing gas such as hydrogen or carbon monoxide. The hydrogen production by reforming the anode end methane and the carbon dioxide is a relatively economic and convenient hydrogen production technology. However, the biggest problem of hydrogen production by reforming methane and carbon dioxide is that severe carbon deposition and coarsening of Ni particles occur on the conventional anode material (such as Ni-YSZ), which causes the reduction of anode porosity and catalytic efficiency, resulting in the drastic reduction of battery performance, and is therefore important for improving the surface material of the catalyst.
The above-mentioned carbon deposition phenomenon of the cell anode and the coarsening phenomenon of Ni particles are two main problems which plague the development of the existing SOFC, and at this stage, the research of the solid oxide fuel cell is mainly focused on the anode material. During the research of the anode, Ni-YSZ anode is the very classic and most commonly used solid oxide fuel cell anode material in SOFC, but the cell with Ni-YSZ as the anode is operated at 1000 ℃, and the high-temperature environment operation can cause CH4Cracking occurs on the surface of the anode, and carbon deposition easily occurs to cause anode materialsLose its activity and suffer structural destruction problems, resulting in degradation of the battery performance.
LSCM(LaxSr1-xCryMn1-yO3-δ) The composite perovskite material is a novel composite perovskite material with ionic conduction and electronic conduction, and is mainly used for an anode end of a solid oxide fuel cell. In the prior art, the preparation scheme for synthesizing the LSCM by the solid phase method is complex in flow and difficult to operate; and the powder is severely expanded during the preparation of LSCM by the glycine-nitrate method, resulting in difficulty in collection and waste of raw materials.
Disclosure of Invention
In order to solve the defects of the conventional anode material, the invention provides the solid oxide fuel cell anode material and the preparation method and application thereof.
The invention is realized by the following technical scheme:
the first object of the invention is to provide a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
uniformly dispersing copper source, nickel source and LSCM powder in a water solvent, adding alkali until no blue flocculent precipitate is generated in the reaction, ensuring that copper ions in the copper source are completely precipitated to obtain an intermediate product, and sintering the intermediate product at 600-700 ℃ for 0.5-3 h to obtain a precursor, namely CuO-NiO-LSCM;
under the atmosphere of hydrogen, preserving the heat of the precursor at 600-700 ℃ for 0.5-3 h to obtain the anode material of the solid oxide fuel cell, namely Cu-Ni-LSCM;
the general formula of the LSCM is LaxSr1-xCryMn1-yO3-δWherein x is 0.2 to 0.8, and y is 0.4 to 0.6.
Further, the mass ratio of the total mass of the copper source and the nickel source to the LSCM powder is 1: 1-2.
Further, the copper source is copper nitrate; the nickel source is nickel nitrate; the alkali is sodium hydroxide or potassium hydroxide.
Further, the mass ratio of the total amount of the copper nitrate and the nickel nitrate to the LSCM powder was 1: 1.5.
Further, the flow rate of the hydrogen is 45-55 mL/min.
Further, the copper source, the nickel source and the LSCM powder are stirred and uniformly dispersed in a water solvent at the temperature of 70-90 ℃.
Further, the LSCM powder is prepared according to the following steps:
according to the ratio of strontium: lanthanum: chromium: manganese is in an element molar ratio of 1: 1-4: 1-3, strontium nitrate, lanthanum nitrate, chromium nitrate and manganese nitrate are weighed, water is added, and the mixture is stirred and dissolved until the solution is homogeneous; adding citric acid, stirring uniformly, and heating and boiling until spontaneous combustion occurs to obtain a combustion product;
the combustion products are collected and calcined to obtain LSCM powder.
Further, the molar ratio of the total element molar amount of lanthanum, strontium, chromium and manganese to the citric acid is: 1: 1-3.
Further, the calcination treatment is carried out at the temperature of 1000-1500 ℃ for 2-6 h.
A second object of the present invention is to provide a solid oxide fuel cell anode material prepared according to the above preparation method.
Further, the anode material has high specific surface area, high-temperature sintering resistance and carbon deposition resistance.
The third purpose of the invention is to provide an application of the solid oxide fuel cell anode material LSCM in catalyzing dry reforming of methane and carbon dioxide to prepare hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
the invention enhances the catalytic performance of the anode material by alloying Cu and Ni, wherein Ni can enhance the conductivity and has catalytic capability, and Cu has better affinity to the graphite layer and can inhibit the enrichment of the graphite layer on the surface of Cu particles, and the anode material Cu-Ni-LSCM is developed by considering the superiority of a catalyst to chemical reaction (compared with Ni), resistance to carbon deposition (Cu, LSCM) and enhanced conductivity.
The preparation method has the advantages of simple preparation process, short preparation period, low price of raw materials, safety, simple required equipment and suitability for large-scale production.
Compared with the LSCM synthesized by the solid phase method, the preparation process is simpler and easier to operate, and the specific surface area of the prepared LSCM is larger than that of the LSCM prepared by the solid phase method.
According to the invention, the LSCM is prepared by a citric acid-nitrate method, a low-temperature combustion synthesis technology is adopted, the preparation method is stable, raw materials are saved, and the problems of difficult precursor collection, raw material waste and the like caused by severe expansion of powder in the process of preparing the LSCM by a glycine-nitrate method are avoided.
Drawings
FIG. 1 is a schematic diagram of the precursor reduction of examples 1-3 to obtain an anode material;
FIG. 2 is a bar graph of the conversion rates of methane and carbon dioxide in the catalytic methane hydrogen production reaction of the anode material of the present invention; wherein, Case1 is a bar chart of the conversion rate of methane and carbon dioxide in the hydrogen production reaction of methane by using the anode material catalyst of comparative example 1; case2 is a bar graph of methane and carbon dioxide conversion in a methane hydrogen production reaction using the anode material catalyst of example 1; case3 is a bar graph of methane and carbon dioxide conversion in a methane hydrogen production reaction using the anode material catalyst of example 2; case4 is a bar graph of methane and carbon dioxide conversion in a methane hydrogen production reaction using the anode material catalyst of example 3; case2 is a bar graph of methane and carbon dioxide conversion in a methane hydrogen production reaction using the anode material catalyst of example 4.
FIG. 3 is an XRD spectrum of the materials obtained after the anode materials of comparative example 1 and example 2 are subjected to a catalytic methane hydrogen production reaction;
FIG. 4 is a plot of the size of the nickel (111) crystal face calculated by the Debye-Scherrer formula of the materials obtained by the hydrogen production reaction of the anode materials of comparative example 1 and example 2 by catalyzing methane;
FIG. 5 is an FE-SEM image of active particles in the material obtained after the anode material of the present invention is subjected to a catalytic methane hydrogen production reaction; wherein FIG. 5a is an FE-SEM image of active particles in the material obtained after the anode material of comparative example 1 is subjected to a catalytic methane hydrogen production reaction; wherein FIG. 5b is an FE-SEM image of active particles in the material obtained after the anode material of example 1 is subjected to a catalytic methane hydrogen production reaction; wherein FIG. 5c is an FE-SEM image of active particles in the material obtained after the anode material of example 2 is subjected to a catalytic methane hydrogen production reaction; wherein FIG. 5d is an FE-SEM image of active particles in the material obtained after the anode material of example 3 is subjected to a catalytic methane hydrogen production reaction;
FIG. 6 is a transmission electron micrograph (200nm size) of the material obtained after the anode material of the present invention undergoes a catalytic methane hydrogen production reaction; wherein, FIG. 6a is a transmission electron microscope image of the material obtained after the anode material of comparative example 1 is subjected to a catalytic methane hydrogen production reaction; FIG. 6b is a transmission electron microscope image of the material obtained by catalyzing the hydrogen production reaction of methane with the anode material of example 2 of the present invention;
FIG. 7 is a transmission electron micrograph (3 μm size) of the material obtained after the anode material of the present invention undergoes a catalytic methane hydrogen production reaction; wherein, FIG. 7a is a transmission electron microscope image of the material obtained after the anode material of comparative example 1 is subjected to a catalytic methane hydrogen production reaction; FIG. 7b is a transmission electron microscope image of the material obtained by catalyzing the hydrogen production reaction of methane with the anode material of example 2 of the present invention; FIG. 7c is an enlarged view of a portion of FIG. 7b at box;
fig. 8 is a thermogram of the anode materials of comparative example 1 and example 2 of the present invention after catalytic methane hydrogen production reaction.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to manganese of 3:7:5:53)2·6H2O、La(NO3)3·6H2O、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to 1.5 times of the molar weight of the total elements of lanthanum, strontium, chromium and manganese, stirring uniformly in a magnetic stirrer for 2 hours, placing a beaker on an electric furnace to be heated and boiled until spontaneous combustion occurs, collecting a product after reaction, placing the product in a tubular furnace, and calcining for 4 hours in air atmosphere at 1350 ℃ to obtain LSCM powder LaxSr1-xCryMn1-yO3-δWhere x is 0.7 and y is 0.5, i.e., the LSCM powder of this example has the formula La0.7Sr0.3Cr0.5Mn0.5O3-δ。
Weighing 6g of calcined LSCM powder in a beaker, adding 3.43g of nickel nitrate and 0.57g of copper nitrate, adding deionized water to uniformly disperse the nickel nitrate and the copper nitrate, placing the beaker containing the mixed solution in a high-power magnetic stirrer, and stirring for 2 hours at 80 ℃; and then adding excessive 0.1g/mL sodium hydroxide solution into the solution until no blue flocculent precipitate is generated, completely precipitating, then putting the solution accompanied with the precipitate into an ultrasonic cleaner for ultrasonic treatment for 30min, then performing suction filtration, washing filter residues for 5 times by using deionized water, completely removing nitrate in the sample, performing suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace for sintering for 30min at 650 ℃ in the air atmosphere to obtain a precursor.
The precursor obtained in this example was subjected to high purity nitrogen gas (f)>99.9%) at room temperature to 650 deg.C, then introducing hydrogen gas under the condition of argon gas as shielding gas, i.e. introducing 10% H at the flow rate of 50mL/min2+ 10% of Ar, and keeping for 1 hour for reduction to obtain a final product.
Example 2
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to manganese of 3:7:5:53)2·6H2O、La(NO3)3·6H2O、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to the amount which is 1.5 times of the total molar weight of the elements of lanthanum, strontium, chromium and manganese, stirring uniformly in a magnetic stirrer for 2 hours, placing a beaker on an electric furnace to heat and boil until spontaneous combustion occurs, collecting a product after reaction, placing the product in a tubular furnace, calcining for 4 hours in air atmosphere at 1350 ℃ to obtain the product with the structural formula of La0.7Sr0.3Cr0.5Mn0.5O3-δThe LSCM powder of (a).
Weighing 6g of calcined LSCM powder in a beaker, adding 3g of nickel nitrate, 1g of copper nitrate and deionized water, placing the beaker filled with the mixed solution in a high-power magnetic stirrer, and stirring for 2 hours at 80 ℃; and then adding excessive 0.1g/mL sodium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residues with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace for sintering for 30min at 650 ℃ in the air atmosphere to obtain a precursor.
The precursor obtained in this example was subjected to high purity nitrogen gas (f)>99.9%) at room temperature to 650 deg.C, then introducing hydrogen gas under the condition of argon gas as shielding gas, i.e. introducing 10% H at the flow rate of 50mL/min2+ 10% of Ar, and keeping for 1 hour for reduction to obtain a final product.
Example 3
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to manganese of 3:7:5:53)2·6H2O、La(NO3)3·6H2O、Cr(NO3)2·6H2O and Mn(NO3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; and weighing citric acid with corresponding mass according to the amount which is 1.5 times of the total molar weight of the elements of lanthanum, strontium, chromium and manganese, stirring uniformly in a magnetic stirrer for 2 hours, placing a beaker on an electric furnace to be heated and boiled until spontaneous combustion occurs, collecting a product after reaction, placing the product in a tubular furnace, and calcining for 4 hours at 1350 ℃ in the air atmosphere to obtain LSCM powder.
Weighing 6g of calcined LSCM powder in a beaker, adding 2g of nickel nitrate, 2g of copper nitrate and deionized water, placing the beaker filled with the mixed solution in a high-power magnetic stirrer, and stirring for 2 hours at 80 ℃; and then adding excessive 0.1g/mL sodium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residues with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace for sintering for 30min at 650 ℃ in the air atmosphere to obtain a precursor.
The precursor obtained in this example was subjected to high purity nitrogen gas (f)>99.9%) at room temperature to 650 deg.C, then introducing hydrogen gas under the condition of argon gas as shielding gas, i.e. introducing 10% H at the flow rate of 50mL/min2+ 10% of Ar, and keeping for 1 hour for reduction to obtain a final product.
Example 4
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps: according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to manganese of 3:7:5:53)2·6H2O、La(NO3)3·6H2O 、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to the amount which is 1.5 times of the total molar weight of the lanthanum, strontium, chromium and manganese, and then putting the citric acid into a magnetic stirrerStirring for 2 hours, uniformly stirring, then placing the beaker on an electric furnace to be heated and boiled until spontaneous combustion occurs, collecting the reacted product, placing the reacted product in a tubular furnace, and calcining for 4 hours in air atmosphere at 1350 ℃ to obtain the product with the structural formula of La0.7Sr0.3Cr0.5Mn0.5O3-δThe LSCM powder of (a).
Weighing 6g of calcined LSCM powder in a beaker, adding 4g of copper nitrate and deionized water, placing the beaker containing the mixed solution in a high-power magnetic stirrer, and stirring for 2 hours at 80 ℃; and then adding excessive 0.1g/mL sodium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residues with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace for sintering for 30min at 650 ℃ in the air atmosphere to obtain a precursor.
The precursor obtained in this example was subjected to high purity nitrogen gas (f)>99.9%) at room temperature to 650 deg.C, then introducing hydrogen gas under the condition of argon gas as shielding gas, i.e. introducing 10% H at the flow rate of 50mL/min2+ 10% of Ar, and keeping for 1 hour for reduction to obtain a final product.
Example 5
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to 1:1:1:13)2·6H2O and corresponding mass of La (NO)3)3·6H2O、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to the amount which is 1 time of the total molar weight of the elements of lanthanum, strontium, chromium and manganese, stirring the citric acid in a magnetic stirrer for 2 hours, uniformly stirring the citric acid, and then placing a beaker on an electric furnace to be heated and boiled until spontaneous combustion occursCollecting the reacted product, calcining in a tubular furnace at 1250 deg.c in air atmosphere for 5 hr to obtain La0.5Sr0.5Cr0.5Mn0.5O3-δThe LSCM powder of (a).
Weighing 6g of calcined LSCM powder in a beaker, adding 3g of nickel nitrate, 1g of copper nitrate and deionized water, placing the beaker containing the mixed solution in a high-power magnetic stirrer, and stirring for 1 hour at 90 ℃; adding excessive 0.1g/mL sodium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residue with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace for sintering for 2 hours at 650 ℃ in the air atmosphere to obtain a precursor;
subjecting the precursor to high-purity nitrogen gas (>99.9%) at room temperature to 650 deg.C, then introducing hydrogen gas under the condition of argon gas as shielding gas, i.e. introducing 10% H at the flow rate of 50mL/min2+ 10% of Ar, and keeping for 2 hours for reduction to obtain a final product.
Example 6
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of 1:1.5:1:1.5 of manganese3)2·6H2O and corresponding mass of La (NO)3)3·6H2O、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to 2 times of the molar weight of the total elements of lanthanum, strontium, chromium and manganese, stirring uniformly in a magnetic stirrer for 2 hours, placing a beaker on an electric furnace to heat and boil until spontaneous combustion occurs, collecting the reacted product, placing the reacted product in a tubular furnace, calcining for 6 hours in an air atmosphere at 1000 DEG CTo obtain a compound of formula La0.6Sr0.4Cr0.4Mn0.6O3-δThe LSCM powder of (a).
Weighing 6g of calcined LSCM powder in a beaker, adding 2.5g of nickel nitrate, 0.5g of copper nitrate and deionized water, placing the beaker with the mixed solution in a high-power magnetic stirrer, and stirring for 3 hours at 70 ℃; adding excessive 0.1g/mL sodium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residue with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, placing the product in a forced air drying oven for drying for 12 hours, and then placing the dried product in a tubular resistance heating furnace to sinter for 3 hours at 600 ℃ in the air atmosphere to obtain a precursor;
subjecting the precursor to high-purity nitrogen gas (>99.9%) at room temperature to 600 deg.C, introducing hydrogen gas at 45mL/min flow rate, i.e., 10% H, under the protection of argon gas as shielding gas2+ 10% of Ar, and keeping for 1 hour for reduction to obtain a final product.
Example 7
The embodiment provides a preparation method of an anode material of a solid oxide fuel cell, which comprises the following steps:
according to the ratio of strontium: lanthanum: chromium: weighing Sr (NO) according to the molar ratio of manganese to 1:3:3:23)2·6H2O and corresponding mass of La (NO)3)3·6H2O、Cr(NO3)2·6H2O and Mn (NO)3)2Placing the mixture into a beaker, adding deionized water, stirring and dissolving until the solution is mixed and homogeneous; weighing citric acid with corresponding mass according to the amount which is 3 times of the total molar weight of the elements of lanthanum, strontium, chromium and manganese, stirring uniformly in a magnetic stirrer for 2 hours, placing a beaker on an electric furnace to be heated and boiled until spontaneous combustion occurs, collecting a product after reaction, placing the product in a tubular furnace, calcining for 2 hours in 1500 ℃ air atmosphere to obtain the product with the structural formula of La0.75Sr0.25Cr0.6Mn0.4O3-δThe LSCM powder of (a).
Weighing 6g of calcined LSCM powder in a beaker, adding 4g of nickel nitrate, 2g of copper nitrate and deionized water, placing the beaker containing the mixed solution in a high-power magnetic stirrer, and stirring for 1 hour at 90 ℃; adding excessive 0.1g/mL potassium hydroxide solution into the solution until the precipitation is complete, then putting the solution accompanied with the precipitation into an ultrasonic cleaner for ultrasonic treatment for 30min, then carrying out suction filtration, washing filter residue with deionized water for 5 times, completely removing nitrate in the sample, carrying out suction filtration again to obtain a product after water washing, putting the product into a forced air drying oven for drying for 12 hours, and then putting the dried product into a tubular resistance heating furnace to sinter for 1 hour in the air atmosphere at 700 ℃ to obtain a precursor;
subjecting the precursor to high-purity nitrogen gas (>99.9%) at room temperature to 700 deg.C, introducing hydrogen gas at 55mL/min under the protection of argon gas, i.e. introducing 10% H2+ 10% of Ar, and keeping for 0.5 hour for reduction to obtain the final product.
Example 8
The embodiment provides an application of the solid oxide fuel cell anode material in catalyzing dry reforming of methane and carbon dioxide to produce hydrogen.
Comparative example 1
Same as in example 1, except that no copper source was added to the raw material, an anode material (Ni-LSCM) was obtained.
In order to illustrate the catalytic performance of the anode material prepared by the preparation method, the invention carries out a catalytic test and tests the material obtained after catalytic reaction, wherein the specific test conditions are as follows:
test section
(one) catalytic test:
600mg of the precursor powders of comparative example 1 and examples 1 to 4 were weighed into a catalytic reaction tube having an inner diameter of 11mm, respectively, under a high-purity nitrogen gas (f)>99.9%) at room temperature to 650 deg.C, and introducing hydrogen gas at 50mL/min flow rate of 10% H under the protection of argon gas2+ 10% Ar, for 1 hour, to obtain the corresponding final products of comparative example 1 and examples 1-4, respectively.
After the reduction, the residual hydrogen in the tube was purged with high-purity nitrogen again, and a mixed gas of methane and carbon dioxide (10% CH) was introduced at a flow rate of 50mL/min using the final products of comparative example 1 and examples 1 to 4 obtained in the above-mentioned steps as catalysts, respectively4+10％CO2+ 80% Ar) completed the catalytic reaction process, wherein the catalytic reaction lasted 13 hours.
(II) fuel conversion in catalytic test:
and collecting and detecting the gas at the outlet through a flue gas analyzer. The relevant reaction equation is as follows:
Figure RE-GDA0003093939600000131
Figure RE-GDA0003093939600000132
CH4→C+2H2
fig. 2 is a bar graph of methane and carbon dioxide conversion in the above catalytic test, and it can be seen from fig. 2 that the maximum conversion of methane catalyzed by the anode materials of comparative example 1 and examples 1-4 was 37.5%, 45.8%, 44.62%, 34.01% and 1.85%, respectively, at 650 ℃. And the maximum fuel conversion occurs in example 1, while the fuel conversion is the lowest in example 4.
(III) carbon deposition amount of the catalyzed material:
table 1 shows the mass of the carbon deposited on the catalyzed materials obtained in comparative example 1 and examples 1 to 4 after the above-mentioned reaction in the catalytic test, and the mass of the carbon deposited on the catalyzed materials obtained in the above-mentioned comparative example 1 and examples 1 to 4 after the reaction in the above-mentioned catalytic test with H2The quality of the catalyzed material after removal of the carbon deposit can be seen to be that the carbon deposit amount after methane dry reforming is obviously reduced along with the introduction of Cu.
TABLE 1650 carbon deposition after methane Dry reforming
Figure RE-GDA0003093939600000141
Wherein, a1Represents the mass of the catalyzed material (after carbon deposition) after the catalytic reaction; is represented by H2And removing the carbon deposit, and then obtaining the material after catalysis.
(IV) XRD testing of the catalyzed material:
in order to investigate the effect of Cu addition on the catalytic performance of the product, XRD tests were performed on the catalyzed materials obtained in comparative example 1 (Ni-LSCM) and example 2(Cu-Ni-LSCM), and the results are shown in FIG. 3. As can be seen from FIG. 4, the Ni (111) plane grain sizes of Ni-LSCM and Cu-Ni-LSCM were 36.95nm and 31.10nm, respectively, i.e., Cu-Ni-LSCM showed better sintering resistance than Ni-LSCM. Furthermore, the specific surface areas of Cu-Ni-LSCM and Ni-LSCM after reduction at 650 ℃ were 14.60m, respectively2G and 3.56m2/g。
(V) FE-SEM test of the catalyzed material:
in order to study the effect of Cu introduction on the morphology and size of Cu-Ni-LSCM active particles, the morphology of the anode materials of comparative example 1 and examples 1-4 was examined by using FE-SEM. As shown in fig. 5, FE-SEM images of active particles in the materials obtained after catalytic methane hydrogen production reaction of the anode materials of comparative example 1 and examples 1 to 4. As can be seen from fig. 5: with the introduction of Cu, the particle size of the active particles was significantly reduced and the dispersibility could be improved, especially in examples 1 and 2.
(VI) transmission electron microscope test of the catalyzed material:
fig. 6 is a transmission electron microscope image of the materials obtained after the anode materials of comparative example 1 and example 2 are subjected to the catalytic methane hydrogen production reaction at the size of 200nm, and comparing the two images, both images show filamentous carbon (carbon nano tube). And comparative example 1 has both the active particle size and the diameter of the carbon nanotubes larger than example 2. In addition, a more intense agglomeration phenomenon occurred in comparative example 1. Comparing the two figures, it can be seen that there is more platelet-shaped catalyst and soot formation as Cu is introduced (as shown in fig. 5 b). The introduction of a certain amount of copper increases the fuel conversion rate to some extent, because with the introduction of Cu, small fragments are generated more so as to improve the dispersibility, which greatly increases the probability of contact of gas molecules with the active particles Ni. However, the introduction of excessive Cu reduces the probability of contact of gas molecules with active particle Ni, although small fragments are increased, and finally the conversion rate is reduced.
Fig. 7a and 7b are transmission electron micrographs of the materials obtained after the hydrogen production reaction by catalyzing methane of the anode materials of comparative example 1 and example 2, respectively, at a size of 3 microns, and it can be seen that: the carbon nanotubes are present in both comparative example 1 and example 2, and comparative example 1 is higher than example 2 in both active particle size and carbon nanotube diameter. In comparative example 1, the diameter of the carbon nanotubes produced by the methane dry reforming process was between 104.6nm and 196 nm. And most active particles are larger than 168nm in diameter. However, in example 2, the diameter of the carbon nanotubes was between 27.21nm and 38.29 nm. And most of the active particles in example 2 have a diameter of less than 121nm, between 40nm and 70 nm. While the interaction between the large diameter particles in comparative example 1 reduces the chance of contact between the gas molecules and the particles and thus the catalytic performance of the catalyst. Example 2 has very good catalytic properties after the introduction of copper. And the diameter size change in example 2 was not strong for fresh catalyst (FE-SEM). This shows the better resistance to carbon deposition, metal sintering and better catalytic performance of example 2.
(seventh) thermogravimetric testing of the catalyzed material:
fig. 8 is a thermogravimetric plot of the anode materials of comparative example 1 and example 2 at 3 micron size after catalytic methane hydrogen production reaction, and it can be seen that: the mass loss amount/(deposited carbon amount) of Ni-LSCM and Cu-Ni-LSCM was 36.76% and 28.94%, respectively. I.e. the introduction of copper reduces the amount of deposited carbon.
In summary, the present invention enhances the catalytic performance of the anode material of the present invention by alloying Cu and Ni, Ni can enhance the conductivity and has the catalytic ability, and Cu has a better affinity for the graphite layer and can inhibit the graphite layer from enriching on the surface of Cu particles, and the anode material Cu-Ni-LSCM of the present invention is developed by considering the superiority of the catalyst to the chemical reaction (compared to Ni), the resistance to carbon deposition (Cu, LSCM) and the enhanced conductivity. The preparation method has the advantages of simple preparation process, short preparation period, low price of raw materials, safety, simple required equipment and suitability for large-scale production.
Compared with the LSCM synthesized by the solid phase method, the preparation process is simpler and easier to operate, and the specific surface area of the prepared LSCM is larger than that of the LSCM prepared by the solid phase method.
According to the invention, the LSCM is prepared by a citric acid-nitrate method, a low-temperature combustion synthesis technology is adopted, the preparation method is stable, raw materials are saved, and the problems of difficult precursor collection, raw material waste and the like caused by severe expansion of powder in the process of preparing the LSCM by a glycine-nitrate method are avoided.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. A preparation method of an anode material of a solid oxide fuel cell is characterized by comprising the following steps:
uniformly dispersing copper source, nickel source and LSCM powder in a water solvent, adding alkali until no blue flocculent precipitate is generated in the reaction, obtaining an intermediate product, and sintering the intermediate product at 600-700 ℃ for 0.5-3 h to obtain a precursor;
in a hydrogen atmosphere, preserving the heat of the precursor at 600-700 ℃ for 0.5-3 h to obtain the solid oxide fuel cell anode material;
the general formula of the LSCM is LaxSr1-xCryMn1-yO3-δWherein x is 0.2 to 0.8, and y is 0.4 to 0.6.
2. The method of preparing the solid oxide fuel cell anode material of claim 1, wherein the mass ratio of the total mass of the copper source and the nickel source to the LSCM powder is 1: 1-2.
3. The method of making a solid oxide fuel cell anode material of claim 2, wherein the copper source is copper nitrate; the nickel source is nickel nitrate; the alkali is sodium hydroxide or potassium hydroxide.
4. The method for preparing the anode material of the solid oxide fuel cell according to claim 1, wherein the flow rate of the hydrogen gas is 45 to 55 mL/min.
5. The method of claim 1, wherein the copper source, the nickel source and the LSCM powder are uniformly dispersed in the aqueous solvent at a temperature of 70-90 ℃.
6. The method of making a solid oxide fuel cell anode material of any of claims 1-5, wherein the LSCM powder is made by the steps of:
according to the ratio of strontium: lanthanum: chromium: manganese is in an element molar ratio of 1: 1-4: 1-3, strontium nitrate, lanthanum nitrate, chromium nitrate and manganese nitrate are weighed, water is added, and the mixture is stirred and dissolved until the solution is homogeneous; adding citric acid, stirring uniformly, and heating and boiling until spontaneous combustion occurs to obtain a combustion product;
the combustion products are collected and calcined to obtain LSCM powder.
7. The method of claim 6, wherein the molar ratio of the total elemental molar amount of lanthanum, strontium, chromium and manganese to the citric acid is: 1: 1-3.
8. The method for preparing the anode material of the solid oxide fuel cell according to claim 6, wherein the calcination treatment is performed at a temperature of 1000 to 1500 ℃ for 2 to 6 hours.
9. A solid oxide fuel cell anode material produced by the production method according to any one of claims 1 to 5.
10. Use of the solid oxide fuel cell anode material of claim 9 in catalyzing the dry reforming of methane with carbon dioxide to produce hydrogen.
CN202110480312.7A 2021-04-30 2021-04-30 Solid oxide fuel cell anode material and preparation method and application thereof Pending CN113178587A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110480312.7A CN113178587A (en) 2021-04-30 2021-04-30 Solid oxide fuel cell anode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110480312.7A CN113178587A (en) 2021-04-30 2021-04-30 Solid oxide fuel cell anode material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113178587A true CN113178587A (en) 2021-07-27

Family

ID=76925813

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110480312.7A Pending CN113178587A (en) 2021-04-30 2021-04-30 Solid oxide fuel cell anode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113178587A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114855203A (en) * 2022-05-20 2022-08-05 南京理工大学 Application of perovskite LSCM material in solid oxide electrolytic cell

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103165903A (en) * 2011-12-15 2013-06-19 江苏超洁绿色能源科技有限公司 Anti-carbon-deposition, high-performance and functionally-graded anode composite film of solid oxide fuel cells and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103165903A (en) * 2011-12-15 2013-06-19 江苏超洁绿色能源科技有限公司 Anti-carbon-deposition, high-performance and functionally-graded anode composite film of solid oxide fuel cells and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
康丁文: "Cu/Ni-LSCM复合阳极多孔结构抗积碳性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114855203A (en) * 2022-05-20 2022-08-05 南京理工大学 Application of perovskite LSCM material in solid oxide electrolytic cell

Similar Documents

Publication Publication Date Title
CN111659401B (en) Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof
Shi et al. Micro-nanostructural designs of bifunctional electrocatalysts for metal-air batteries
CN109103462B (en) Cobalt-nitrogen co-doped carbon aerogel catalyst for fuel cell and preparation method thereof
CN107282079B (en) Preparation method of strip vanadium carbide electrocatalyst and product
CN103111302A (en) Preparation and application of shell-core-type perovskite-wrapping hydrotalcite-like-based oxide reforming hydrogen production catalyst
CN112221530A (en) Preparation method and application of non-noble metal single-atom dual-function electrocatalyst
CN111952610A (en) FeCo-doped ZIF8 self-derived cnts @ FeCo-NC bifunctional catalyst
CN109395735B (en) Methanation catalyst, preparation method thereof and method for preparing methane by using methanation catalyst
WO2021104087A1 (en) Metal oxide nanoparticles, and preparation method therefor and application thereof
CN110854392A (en) Metal organic framework-based cereal-grain-shaped carbon material and preparation and application thereof
CN112725819A (en) Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof
CN112421062A (en) Preparation method of monoatomic iron dispersion/silver nanoparticle composite structure catalyst
CN112142037A (en) Cobalt and nitrogen doped carbon nano tube and preparation method and application thereof
CN109888314B (en) Preparation method of boron-cobalt-nitrogen doped carbon nanomaterial for zinc-air battery
CN115261921A (en) FeCoNiMnCr high-entropy alloy/high-entropy oxide heterogeneous phase catalyst and preparation method and application thereof
CN113178587A (en) Solid oxide fuel cell anode material and preparation method and application thereof
CN114620772A (en) Doped transition metal oxide and preparation method and application thereof
CN112408320A (en) Load type double-active metal composite oxygen carrier and preparation method and application thereof
CN108306023B (en) BN/CuAg/CNT composite material and preparation method and application thereof
CN109482200B (en) Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof
CN116200773A (en) Transition metal electrocatalyst rich in twin crystal structure, and preparation method and application thereof
CN115058733A (en) Perovskite oxide-transition metal phosphide heterostructure composite electrode material and preparation method and application thereof
CN112779550B (en) Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof
CN111394748B (en) For CO2Electrolytic iron-nickel alloy in-situ desolventizing layered perovskite cathode material
CN111244481B (en) Preparation method of fulvic acid lamella-based MOFs-derived electrocatalyst material

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210727