CN107946618B - Based on Ag-SrTiO3Symmetrical SOFC (solid oxide Fuel cell) of electrode and preparation method - Google Patents

Based on Ag-SrTiO3Symmetrical SOFC (solid oxide Fuel cell) of electrode and preparation method Download PDF

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CN107946618B
CN107946618B CN201711200381.8A CN201711200381A CN107946618B CN 107946618 B CN107946618 B CN 107946618B CN 201711200381 A CN201711200381 A CN 201711200381A CN 107946618 B CN107946618 B CN 107946618B
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powder
electrode
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CN107946618A (en
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全桂英
陈钉
宋雨蔷
张晶晶
田冬
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HUAINAN TONGBA STORAGE BATTERY Co.,Ltd.
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Huainan Normal University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a silver-strontium titanate (Ag-SrTiO) -based material3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole coat in electrolyte both sides respectively, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), both cathode and anode were Ag-SrTiO3Electrode, Ag-SrTiO3The electrode is made of Ag-SrTiO powder3Is prepared from Ag-SrTiO powder3Ag is added according to the mass ratio of 5-20 wt% of silver in metal elements+Reducing the Ag nanoparticles to obtain the product by modifying STO. The invention is based on Ag-SrTiO3The symmetrical SOFC of the electrode has loose and porous electrodes and good contact between the electrodes and electrolyte. The invention also provides the Ag-SrTiO-based material3A method for the preparation of a symmetrical SOFC of electrodes, comprising the steps of: preparing powder; (II) preparing a symmetrical electrode; and (III) assembling the single cells.

Description

Based on Ag-SrTiO3Symmetrical SOFC (solid oxide Fuel cell) of electrode and preparation method
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a fuel cell based on Ag-SrTiO3Symmetrical SOFC of the electrode and a preparation method.
Background
Among various fuel cells, a Solid Oxide Fuel Cell (SOFC) is an all-solid-component energy conversion device that can directly and continuously convert chemical energy in fuel and oxidant into electrical energy, and has the unique advantages of simple system structure, high electrical conversion efficiency, environmental friendliness, wide applicable fuel range, long service life, and the like. The power generation device has wide application prospect in the fields of large, medium and small power stations, mobile and portable power supplies, military, aerospace and the like, and is known as a novel power generation technology with good development prospect. Despite significant advances in SOFC technology, there is much work to do to achieve commercial applications. This is mainly because the developed devices operate at too high a temperature, which makes it difficult to match the thermal expansion coefficients of the constituent materials, and the stability of the stack during long-term operation is poor. Therefore, lowering the SOFC operation temperature to an intermediate temperature is the current research focus of this technology.
The performance requirements of the SOFC anode and cathode are different due to different working environments, for example, the anode material is required to be stable in a reducing atmosphere, the cathode material is required to be stable in an oxidizing atmosphere, and the anode and cathode are also required to have certain electrical conductivity, strength and the like. If the SOFC with the symmetrical structure is used, only two material systems of the electrolyte and the electrode are formed, the process difficulty in the manufacturing process can be reduced, the function of the electrode can be changed after carbon deposition is generated, the carbon deposition can be easily removed, and the stability of the performance of the battery is guaranteed. The main difficulty of the symmetrical SOFC is that a proper electrode material is selected to be stable in the oxidizing atmosphere of a cathode and the reducing atmosphere of an anode, and the symmetrical SOFC has good catalytic activity on oxygen reduction and hydrogen oxidation reactions.
Disclosure of Invention
The invention aims to provide a material based on Ag-SrTiO3The symmetrical SOFC of the electrode, has conceived the thinking of loading the nanometer metal catalyst in the stable perovskite material, prepare the composite electrode, assemble the symmetrical battery, and study its performance. The invention uses SrTiO3(STO) load nano Ag composite material is used as an electrode to construct a symmetrical SOFC, and the STO can keep the stability of structure and properties in a wide oxygen partial pressure and temperature range, so that the (STO) load nano Ag composite material becomes a candidate of SOFC anode material. The STO conductivity is very low and cannot be directly used for anode materials; but the electrical conductivity of the material can be effectively improved by the missing STO or the doped STO such as Mg, La and the like, and the STO is an all-ceramic component and has higher chemical stability at high temperatureQualitative and structural stability, and high conductivity. The invention also provides the Ag-SrTiO-based material3A method for preparing symmetrical SOFC of electrode.
The technical scheme adopted by the invention is as follows:
based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole, negative pole with the positive pole coats respectively in the electrolyte both sides, the electrolyte is Ce0.8Gd0.2O1.9(GDC), said cathode and said anode being both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of 5-20 wt% of silver in metal elements+Reducing the Ag nanoparticles to obtain the product by modifying STO.
The invention is based on Ag-SrTiO3Symmetrical SOFC of the electrode, wherein the Ag-SrTiO powder3Ag is added according to the mass ratio of silver to metal elements of 15wt percent+Reducing the Ag nanoparticles to obtain the product by modifying STO.
The invention is based on Ag-SrTiO3A method for the preparation of a symmetrical SOFC of electrodes, comprising the steps of:
preparation of powder
(1) Preparing STO powder by a citric acid self-propagating combustion method: weighing Sr (NO)3)3Dissolving in deionized water, adding butyl titanate with corresponding volume, adding citric acid, and adding 15-20ml of HNO as oxidant3Stirring with a glass rod until the particles are dissolved, adjusting the pH value to 7-9 with ammonia water, and stirring until the solution is clear; transferring the solution to an evaporation vessel, placing the evaporation vessel on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 1000 ℃ and 1100 ℃ and preserving the temperature for 3-4h to prepare initial powder STO;
(2) preparation of Ag-SrTiO by hydrothermal method3Powder: hydrothermal method is adopted to make Ag+Reducing the Ag into nanometer Ag particles to modify STO to prepare Ag-SrTiO powder3；
(3) Preparing electrolyte GDC powder by a citric acid self-propagating combustion method: respectively weighing Gd (NO)3)3And Ce (NO)3)3Adding deionized water for dissolving, adding citric acid, and adding 15-20ml of HNO as oxidant3Stirring until the particles are dissolved, adjusting the pH value to 7-9 by ammonia water, stirring until the solution is clear, transferring the solution to an evaporation dish, placing the evaporation dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 700-;
preparation of (II) symmetrical electrode
(a)Ag-SrTiO3Preparing electrode slurry: respectively weighing the Ag-SrTiO powder prepared in the step (2)3And the GDC powder prepared in the step (3) is prepared according to the mass ratio of 1: adding the powder into an agate mortar according to the proportion of 1, weighing a binder which is 2 times of the powder in mass, adding the binder into the agate mortar, and grinding for 2-3h to obtain electrode slurry for later use;
(b) preparation of electrolyte GDC sheet: weighing the powder GDC extruded wafer in the step (3) which is uniformly ground, and finally sintering the powder GDC extruded wafer in a muffle furnace at the temperature of 1400 ℃ and 1500 ℃ for 5-6h to obtain a GDC electrolyte sheet;
(c) preparation of single cells: respectively and uniformly coating the electrode slurry prepared in the step (a) on two sides of the GDC electrolyte sheet sintered in the step (b) to form a symmetrical battery, respectively and repeatedly coating a cathode and an anode for 4 times, placing the battery in an oven for drying, and finally calcining the battery in a muffle furnace at 800-900 ℃ for 3-4 h; uniformly coating conductive silver paste on the cathode and the anode of the symmetrical battery, and placing the battery in a drying oven for drying to obtain a single battery;
(III) Assembly of Single cells
Adopting conductive adhesive as a sealing agent, packaging the single cell prepared in the step (c) at one end of a bamboo tube with the same size, and using silver wires as current leads of a cathode and an anode to obtain the Ag-SrTiO-based single cell3Symmetrical SOFC of the electrode.
The invention is based on Ag-SrTiO3Method for the preparation of a symmetrical SOFC of electrodes, comprising the steps of:
preparation of powder
(1) Preparing STO powder by a citric acid self-propagating combustion method: weighing Sr (NO)3)3In a beaker, useDissolving in ionic water, adding butyl titanate with corresponding volume, adding citric acid, and adding 15ml of oxidizing agent HNO3Stirring with a glass rod until the particles are dissolved, adjusting the pH value to 7-9 with ammonia water, and stirring until the solution is clear; transferring the solution to an evaporating dish, placing the evaporating dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 1000 ℃ and preserving the heat for 3 hours to obtain initial powder STO;
(2) preparation of Ag-SrTiO by hydrothermal method3Powder: hydrothermal method is adopted to make Ag+Reducing the Ag into nanometer Ag particles to modify STO to prepare Ag-SrTiO powder3；
(3) Preparing electrolyte GDC powder by a citric acid self-propagating combustion method: respectively weighing Gd (NO)3)3And Ce (NO)3)3Adding deionized water for dissolving, adding citric acid, and adding 15ml of HNO as oxidant3Stirring until the particles are dissolved, adjusting the pH value to 7-9 by using ammonia water, stirring until the solution is clear, transferring the solution to an evaporation dish, placing the evaporation dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 700 ℃, and preserving the temperature for 3 hours to obtain initial powder GDC;
preparation of (II) symmetrical electrode
(a)Ag-SrTiO3Preparing electrode slurry: respectively weighing the components in a mass ratio of 9: 1, placing terpineol and ethyl cellulose in a beaker, and dissolving the terpineol and the ethyl cellulose in a water bath kettle at the temperature of 60 ℃ for 24 hours to serve as a binder for standby application; respectively weighing the Ag-SrTiO powder prepared in the step (2)3And the GDC powder prepared in the step (3) is prepared according to the mass ratio of 1: adding the powder into an agate mortar according to the proportion of 1, weighing a binder which is 2 times of the powder in mass, adding the binder into the agate mortar, and grinding for 2 hours to obtain electrode slurry for later use;
(b) preparation of electrolyte GDC sheet: weighing the powder GDC in the step (3) which is uniformly ground to be extruded into a wafer, and finally sintering the wafer in a muffle furnace at 1400 ℃ for 5 hours to obtain a GDC electrolyte sheet;
(c) preparation of single cells: respectively and uniformly coating the electrode slurry prepared in the step (a) on two sides of the GDC electrolyte sheet sintered in the step (b) to form a symmetrical battery, respectively and repeatedly coating a cathode and an anode for 4 times, placing the battery in an oven for drying, and finally calcining the battery in a muffle furnace at 800 ℃ for 3 hours; uniformly coating conductive silver paste on the cathode and the anode of the symmetrical battery, and placing the battery in a drying oven for drying to obtain a single battery;
(III) Assembly of Single cells
Adopting conductive adhesive as a sealing agent, packaging the single cell prepared in the step (c) at one end of a bamboo tube with the same size, and using silver wires as current leads of a cathode and an anode to obtain the Ag-SrTiO-based single cell3Symmetrical SOFC of the electrode.
The invention is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of the electrode comprises the step (2) of preparing Ag-SrTiO by a hydrothermal method3The powder is prepared by weighing 1-2g block copolymer polyvinyl alcohol-polypropylene alcohol-polyvinyl alcohol (P)123) Stirring, clarifying, adding AgNO3Stirring for 30min, adding hexamethylene tetramine, and stirring for 1 hr, AgNO3Adding the powder STO obtained in the step (1) into a hexamethylenetetramine with a molar ratio of 1:3, continuously stirring for 2h, performing a reduction reaction at 110 ℃ of 100 ℃ by adopting a hydrothermal synthesis method for 4-6h, performing suction filtration, drying, calcining for 6h at 550 ℃ in a high-temperature furnace to obtain the powder Ag-SrTiO3。
The invention is based on Ag-SrTiO3Method for the preparation of a symmetrical SOFC of electrodes, wherein the amount ratio of citric acid to metal ion species in step (1) is 1.8: 1.
The invention is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of the electrode comprises the steps that in the step (3), the molar ratio of metal ions to citric acid is 1:1.5, and Gd (NO) is added3)3And Ce (NO)3)3The molar ratio is 1: 9.
The invention is based on Ag-SrTiO3And (b) placing the powder GDC which is weighed and uniformly ground in a die with the diameter of 12cm in the step (b), and pressing out a wafer on a tablet press under the pressure of 3 MPa.
The invention has the beneficial effects that:
the invention is based on Ag-SrTiO3The symmetrical SOFC of the electrode has loose and porous electrodes, good contact between the electrodes and electrolyte, adjustable catalyst proportion,maximum open circuit voltages of the vacancy STO with the silver content of 5 wt%, 10 wt%, 15 wt% and 20 wt% at the temperature of 550-700 ℃ are respectively 0.78V, 0.72V, 0.80V and 0.82V, maximum power densities are respectively 7mW, 7.2mW, 75mW and 18mW, and the open circuit voltages are close to theoretical values; the output of a symmetric SOFC containing 15 wt% silver is significantly higher than that of other symmetric SOFCs.
The invention is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of the electrode has simple equipment requirement, clear technical route and credible and feasible method, because the nano Ag particles are generated in situ in the liquid phase, the nano Ag particles can be loaded in the carrier more uniformly, the uniform stability after the electrode is constructed is ensured, the whole monocell has simple structure and strong adaptability to fuel, and has certain practical value.
Drawings
FIG. 1 shows Ag-SrTiO powders as described in examples 1 to 43A powder X-ray diffraction (XRD) pattern of the sample;
FIG. 2 is a Scanning Electron Microscope (SEM) view of a cross section of the single cell described in example 1;
fig. 3 is an SEM image of a cross section of the single cell described in example 2;
fig. 4a is a graph of the electrochemical output performance of the SOFC single cell in example 1 with humidified hydrogen as fuel at different temperatures and impedance at open circuit;
fig. 4b is a graph of the electrochemical output performance of the SOFC single cell in example 2 fueled with humidified hydrogen at different temperatures and impedance at open circuit;
fig. 4c is a graph of the electrochemical output performance of the SOFC single cell in example 3 fuelled with humidified hydrogen at different temperatures and impedance at open circuit;
fig. 4d is a graph of the electrochemical output performance of the SOFC cell described in example 4, using humidified hydrogen as fuel at different temperatures and impedance at open circuit.
The invention will be further described with reference to specific embodiments and drawings.
Detailed Description
In the following examples, the phase and chemical compatibility of the powder were analyzed by X-ray diffractometry, CuK α radiation, λ 0.15418nm, voltage 40.0kV, current 30mA, step size 0.03, and scanning range 2 θ 20 to 80 °. The polarization behavior of the cell was tested using a ZahnerIM 6-type electrochemical workstation with a sweep frequency range of 1MHz to 10mHz and a voltage perturbation of 5 mV. The output performance of the battery was tested using a laboratory-built evaluation device. The section microstructure of the battery sample is observed by a KYKY EM-3200 type scanning electron microscope.
Example 1
Based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole, negative pole with the positive pole coats respectively in the electrolyte both sides, the electrolyte is Ce0.8Gd0.2O1.9(GDC), said cathode and said anode being both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of 5wt percent of silver to metal elements+Reducing the Ag nanoparticles to obtain the product by modifying STO.
Ag-SrTiO-based materials as described in this example3A method for the preparation of a symmetrical SOFC of electrodes, comprising the steps of:
preparation of powder
(1) Preparing STO powder by a citric acid self-propagating combustion method: weighing a certain amount of Sr (NO)3)3Dissolving in deionized water, adding butyl titanate with corresponding volume, adding citric acid with the amount ratio of citric acid to metal ion substances of 1.8:1, and adding 15ml of HNO as oxidant3Stirring with a glass rod until the particles are dissolved, adjusting the pH value to 7-9 with ammonia water, and stirring until the solution is clear; transferring the solution to an evaporating dish, placing the evaporating dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 1000 ℃ and preserving the heat for 3 hours to obtain initial powder STO;
(2) preparation of Ag-SrTiO by hydrothermal method3Powder: ag is added into the silver alloy according to the mass ratio of 5 wt% of silver in metal elements by adopting a hydrothermal method+Reducing the modified STO into nano Ag particles, and the preparation method comprises the following steps: 1.5g of block copolymer polyvinyl alcohol-polypropylene alcohol-polyethylene is weighedEnol (P)123) Stirring with a magnetic stirrer, clarifying, and adding AgNO3Stirring for 30min, adding hexamethylene tetramine, and stirring for 1 hr, AgNO3Adding the powder STO obtained in the step (1) into hexamethylene tetramine according to the molar ratio of 1:3, continuously stirring for 2 hours, carrying out reduction reaction for 5 hours at 100 ℃ by adopting a hydrothermal synthesis method, carrying out suction filtration, drying, and calcining for 6 hours at 550 ℃ in a high-temperature furnace to obtain the powder Ag-SrTiO3；
(3) Preparing electrolyte GDC powder by a citric acid self-propagating combustion method: gd (NO) was weighed in a molar ratio of 1:9, respectively3)3And Ce (NO)3)3Adding deionized water to dissolve in a beaker, adding citric acid with the molar ratio of metal ions to citric acid being 1:1.5, and adding 15ml of an oxidant HNO3Stirring until the particles are dissolved, adjusting the pH value to 7-9 by using ammonia water, stirring until the solution is clear, transferring the solution to an evaporation dish, placing the evaporation dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 700 ℃, and preserving the temperature for 3 hours to obtain initial powder GDC;
preparation of (II) symmetrical electrode
(a)Ag-SrTiO3Preparing electrode slurry: respectively weighing the components in a mass ratio of 9: 1, placing terpineol and ethyl cellulose in a beaker, and dissolving the terpineol and the ethyl cellulose in a water bath kettle at the temperature of 60 ℃ for 24 hours to serve as a binder for standby application; respectively weighing the Ag-SrTiO powder prepared in the step (2)3And the GDC powder prepared in the step (3) is prepared according to the mass ratio of 1: adding the powder into an agate mortar according to the proportion of 1, weighing a binder which is 2 times of the powder in mass, adding the binder into the agate mortar, and grinding for 2 hours to obtain uniform electrode slurry with good fluidity for later use;
(b) preparation of electrolyte GDC sheet: weighing the powder GDC uniformly ground in the step (3), placing the powder GDC in a die with the diameter of 12cm, pressing out a wafer on a tablet press under the pressure of about 3MPa, and finally sintering the wafer in a muffle furnace at 1400 ℃ for 5 hours to obtain a GDC electrolyte sheet;
(c) preparation of single cells: respectively and uniformly coating the electrode slurry prepared in the step (a) on two side surfaces of the GDC electrolyte sheet sintered in the step (b) by using a small brush to form a symmetrical battery, respectively and repeatedly coating a cathode and an anode for 4 times, placing the battery in an oven for drying, and finally calcining the battery in a muffle furnace at 800 ℃ for 3 hours; uniformly coating conductive silver paste on the cathode and the anode of the symmetrical battery by using a small brush, and placing the battery in an oven for drying to obtain a single battery;
(III) Assembly of Single cells
Adopting conductive adhesive as a sealing agent, packaging the single cell prepared in the step (c) at one end of a bamboo tube with the same size, and using silver wires as current leads of a cathode and an anode to obtain the Ag-SrTiO-based single cell3Symmetrical SOFC of the electrode.
Example 2
Based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole, negative pole with the positive pole coats respectively in the electrolyte both sides, the electrolyte is Ce0.8Gd0.2O1.9(GDC), said cathode and said anode being both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of silver to metal element of 10wt percent+Reducing the Ag nanoparticles to obtain the product by modifying STO.
Ag-SrTiO-based materials as described in this example3The preparation method of the symmetrical SOFC of the electrode comprises the steps of modifying STO according to the mass ratio of silver to metal elements of 10 wt% in the step (2), and sintering to obtain powder Ag-SrTiO3Otherwise, the same procedure as in example 1 was repeated.
Example 3
Based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole, negative pole with the positive pole coats respectively in the electrolyte both sides, the electrolyte is Ce0.8Gd0.2O1.9(GDC), said cathode and said anode being both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of silver to metal elements of 15wt percent+Reducing the Ag nanoparticles to obtain the product by modifying STO.
This example is based on Ag-SrTiO3Preparation method of symmetrical SOFC (solid oxide Fuel cell) of electrodeModifying STO according to the mass ratio of silver to metal elements of 15 wt% in the step (2), and sintering to obtain powder Ag-SrTiO3Otherwise, the same procedure as in example 1 was repeated.
Example 4
Based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, negative pole and positive pole, negative pole with the positive pole coats respectively in the electrolyte both sides, the electrolyte is Ce0.8Gd0.2O1.9(GDC), said cathode and said anode being both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of silver to metal elements of 20wt percent+Reducing the Ag nanoparticles to obtain the product by modifying STO.
This example is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of the electrode comprises the steps of modifying STO according to the mass ratio of silver to metal elements of 20 wt% in the step (2), and sintering to obtain powder Ag-SrTiO3Otherwise, the same procedure as in example 1 was repeated.
FIG. 1 shows Ag-SrTiO powders prepared in examples 1 to 43An XRD pattern of the sample, in which diffraction peaks at 2 theta angles of 22.9 °, 32.8 °, 40.1 °, 46.0 °, 52.7 °, 57.6 °, 67.7 °, 72.4 ° and 77.1 ° correspond to structures of (100), (110), (111), (200), (210), (211), (220), (221) and (310) crystal planes of the STO perovskite type, respectively, and 4 sharp diffraction peaks at around 38.1 °, 44.4 °, 64.55 ° and 77.5 ° correspond to characteristic diffraction peaks of face-centered cubic metallic silver, which are attributed to diffraction of the (111), (200), (220) and (311) planes. Diffraction peaks were evident for all samples with no miscellaneous peaks. With the change of the silver content, the position of the diffraction peak on the XRD spectrum is hardly changed, which shows that the change of the silver content does not influence the phase of the STO powder, the compatibility of the two is good, no chemical reaction occurs, and the intensity of the diffraction peak of the silver is increased. Compared with PDF cards 00-040-1500(STO) and 00-001-1164(Ag), the positions of the diffraction peaks of the silver and STO powder are hardly shifted.
FIG. 2 and FIG. 3 are Ag-SrTiO, respectively3(5 wt%) and Ag-SrTiO3(10 wt%) of a single cell as an electrodeThe SEM of the cross section is a SEM of the cross section of a representative single cell, and as can be seen from fig. 2 and 3, the electrolyte is dense with only a small distribution of closed pores that do not cause gas molecules to pass directly through the electrolyte, thus ensuring the gas tightness of the battery and providing the battery with a good open circuit voltage. It can also be seen from fig. 2 that the prepared electrode is porous and has good contact between the electrode and the electrolyte, and these conditions can provide a battery with a normal output.
Ag-SrTiO-based compositions of examples 1-4, respectively3The electrodes were tested for output performance of a symmetric SOFC and for impedance at open circuit. FIGS. 4a,4b,4c and 4d are the electrochemical output performance of SOFC single cells of examples 1-4, respectively, based on Ag-SrTiO with humidified hydrogen as fuel at different temperatures3The effective part of the symmetrical SOFC of the electrode is arranged in a constant temperature area of a high temperature tubular resistance furnace, humidified hydrogen with the flow rate of 20mL/min is introduced to the anode side to be used as fuel gas, the cathode is arranged in air, the electrochemical performance of the battery is tested, the test temperature range is 550-700 ℃, the current-voltage curve of the battery is tested by a linear sweep voltammetry, and the sweep rate is 5 mv/s. As can be seen from FIGS. 4a,4b,4c and 4d, the maximum open circuit voltages at 550-700 ℃ of the vacancy STO containing 5 wt%, 10 wt%, 15 wt% and 20 wt% of silver were 0.78V, 0.72V, 0.80V and 0.82V, respectively, and the maximum power densities were 7mW, 7.2mW, 75mW and 18mW, respectively, which are close to the theoretical values. From the maximum power density of the symmetrical batteries with different silver contents, the catalytic activity of the electrode is changed along with the change of the content of the silver in the electrode material, which shows that the doping of the nano silver in the cathode or the anode has the effect of improving the performance of the electrode. It can therefore be guessed that: there is an optimum amount of silver incorporated to maximize the electrochemical output performance of the cell. As can be seen from fig. 4a,4b,4c and 4d, the power output of the symmetrical SOFC containing 15 wt% silver of example 3 is significantly higher than that of other symmetrical SOFCs.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (7)

1. Based on Ag-SrTiO3The preparation method of the symmetrical SOFC of the electrode is characterized in that: the electrolyte comprises an electrolyte, a cathode and an anode, wherein the cathode and the anode are respectively coated on two sides of the electrolyte, and the electrolyte is Ce0.8Gd0.2O1.9The cathode and the anode are both Ag-SrTiO3An electrode of Ag-SrTiO3The electrode is made of Ag-SrTiO powder3The raw material is Ag-SrTiO powder3Ag is added according to the mass ratio of 5-20 wt% of silver in metal elements+Reduced into nano Ag particles to modify SrTiO3The preparation method comprises the following steps:
preparation of powder
(1) Method for preparing SrTiO by citric acid self-propagating combustion method3Powder: weighing Sr (NO)3)3Dissolving in deionized water, adding butyl titanate with corresponding volume, adding citric acid, and adding 15-20ml of HNO as oxidant3Stirring with a glass rod until the particles are dissolved, adjusting the pH value to 7-9 with ammonia water, and stirring until the solution is clear; transferring the solution to an evaporation pan, placing the evaporation pan on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 1000 ℃ and 1100 ℃ for 3-4h to obtain initial powder SrTiO3；
(2) Preparation of Ag-SrTiO by hydrothermal method3Powder: hydrothermal method is adopted to make Ag+Reduced into nano Ag particles to modify SrTiO3To prepare Ag-SrTiO powder3；
(3) Electrolyte Ce prepared by citric acid self-propagating combustion method0.8Gd0.2O1.9Powder: respectively weighing Gd (NO)3)3And Ce (NO)3)3Adding deionized water for dissolving, adding citric acid, and adding 15-20ml of HNO as oxidant3Stirring until the particles are dissolved, adjusting pH to 7-9 with ammonia water, stirring until the solution is clear, transferring the solution to an evaporation dish, evaporatingPlacing the vessel on an electric furnace to heat the concentrated solution until a self-propagating combustion reaction occurs, calcining the powder at 700-0.8Gd0.2O1.9；
Preparation of (II) symmetrical electrode
(a)Ag-SrTiO3Preparing electrode slurry: respectively weighing the Ag-SrTiO powder prepared in the step (2)3And the Ce prepared in step (3)0.8Gd0.2O1.9The powder comprises the following components in percentage by mass 1: adding the powder into an agate mortar according to the proportion of 1, weighing a binder which is 2 times of the powder in mass, adding the binder into the agate mortar, and grinding for 2-3h to obtain electrode slurry for later use;
(b) electrolyte Ce0.8Gd0.2O1.9Preparation of tablets: weighing the powder Ce uniformly ground in the step (3)0.8Gd0.2O1.9Pressing out a wafer, and finally sintering the wafer in a muffle furnace at 1400 ℃ and 1500 ℃ for 5 to 6 hours to obtain Ce0.8Gd0.2O1.9An electrolyte sheet;
(c) preparation of single cells: respectively uniformly coating the electrode slurry prepared in step (a) on the Ce sintered in step (b)0.8Gd0.2O1.9The two sides of the electrolyte sheet are used as a symmetrical battery, the cathode and the anode are respectively coated for 4 times repeatedly, the electrolyte sheet is placed in a drying oven for drying, and finally the electrolyte sheet is calcined in a muffle furnace at 800-900 ℃ for 3-4 h; uniformly coating conductive silver paste on the cathode and the anode of the symmetrical battery, and placing the battery in a drying oven for drying to obtain a single battery;
(III) Assembly of Single cells
Adopting conductive adhesive as a sealing agent, packaging the single cell prepared in the step (c) at one end of a main tube with the same size, and using silver wires as current leads of a cathode and an anode to obtain the Ag-SrTiO-based single cell3Symmetrical SOFC of the electrode.
2. Ag-SrTiO-based according to claim 13The preparation method of the symmetrical SOFC of the electrode is characterized in that: the powder Ag-SrTiO3Ag is added according to the mass ratio of silver to metal elements of 15wt percent+Reduced into nano Ag particles to modify SrTiO3And (4) obtaining the product.
3. Ag-SrTiO-based according to claim 13The preparation method of the symmetrical SOFC of the electrode is characterized in that: the method comprises the following steps:
preparation of powder
(1) Method for preparing SrTiO by citric acid self-propagating combustion method3Powder: weighing Sr (NO)3)3Dissolving in deionized water, adding butyl titanate with corresponding volume, adding citric acid, and adding 15ml of HNO as oxidant3Stirring with a glass rod until the particles are dissolved, adjusting the pH value to 7-9 with ammonia water, and stirring until the solution is clear; transferring the solution to an evaporating dish, placing the evaporating dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 1000 ℃ and preserving the temperature for 3 hours to prepare initial powder SrTiO3；
(2) Preparation of Ag-SrTiO by hydrothermal method3Powder: hydrothermal method is adopted to make Ag+Reduced into nano Ag particles to modify SrTiO3To prepare Ag-SrTiO powder3；
(3) Electrolyte Ce prepared by citric acid self-propagating combustion method0.8Gd0.2O1.9Powder: respectively weighing Gd (NO)3)3And Ce (NO)3)3Adding deionized water for dissolving, adding citric acid, and adding 15ml of HNO as oxidant3Stirring until the particles are dissolved, adjusting the pH value to 7-9 by ammonia water, stirring until the solution is clear, transferring the solution to an evaporation dish, placing the evaporation dish on an electric furnace to heat and concentrate the solution until a self-propagating combustion reaction occurs, calcining the powder at 700 ℃ and keeping the temperature for 3 hours to prepare initial powder Ce0.8Gd0.2O1.9；
Preparation of (II) symmetrical electrode
(a)Ag-SrTiO3Preparing electrode slurry: respectively weighing the components in a mass ratio of 9: 1, placing terpineol and ethyl cellulose in a beaker, and dissolving the terpineol and the ethyl cellulose in a water bath kettle at the temperature of 60 ℃ for 24 hours to serve as a binder for standby application; respectively weighing the Ag-SrTiO powder prepared in the step (2)3And the Ce prepared in step (3)0.8Gd0.2O1.9The powder comprises the following components in percentage by mass 1: ratio of 1Adding the powder into an agate mortar, weighing a binder with the mass 2 times that of the powder, adding the powder into the agate mortar, and grinding for 2 hours to obtain electrode slurry for later use;
(b) electrolyte Ce0.8Gd0.2O1.9Preparation of tablets: weighing the powder Ce uniformly ground in the step (3)0.8Gd0.2O1.9Pressing out a wafer, and finally sintering for 5 hours in a muffle furnace at 1400 ℃ to obtain Ce0.8Gd0.2O1.9An electrolyte sheet;
(c) preparation of single cells: respectively uniformly coating the electrode slurry prepared in step (a) on the Ce sintered in step (b)0.8Gd0.2O1.9The two sides of the electrolyte sheet are used as a symmetrical battery, the cathode and the anode are respectively coated and brushed repeatedly for 4 times, the battery is placed in a drying oven for drying, and finally the battery is calcined in a muffle furnace for 3 hours at 800 ℃; uniformly coating conductive silver paste on the cathode and the anode of the symmetrical battery, and placing the battery in a drying oven for drying to obtain a single battery;
(III) Assembly of Single cells
Adopting conductive adhesive as a sealing agent, packaging the single cell prepared in the step (c) at one end of a main tube with the same size, and using silver wires as current leads of a cathode and an anode to obtain the Ag-SrTiO-based single cell3Symmetrical SOFC of the electrode.
4. Ag-SrTiO-based according to claim 13The preparation method of the symmetrical SOFC of the electrode is characterized in that: step (2) hydrothermal method for preparing Ag-SrTiO3The powder is prepared by weighing 1-2g block copolymer polyvinyl alcohol-polypropylene alcohol-polyvinyl alcohol, stirring, clarifying, and adding AgNO3Stirring for 30min, adding hexamethylene tetramine, and stirring for 1 hr, AgNO3Adding the powder SrTiO in the step (1) into the solution with the molar ratio of hexamethylene tetramine of 1:33Stirring for 2h, carrying out reduction reaction at 110 ℃ of 100-3。
5. Ag-SrTiO-based according to claim 13Electrode for electrochemical cellThe preparation method of the symmetrical SOFC is characterized by comprising the following steps: the amount ratio of the citric acid to the metal ion substances in the step (1) is 1.8: 1.
6. Ag-SrTiO-based according to claim 13The preparation method of the symmetrical SOFC of the electrode is characterized in that: in the step (3), the molar ratio of the metal ions to the citric acid is 1:1.5, and Gd (NO)3)3And Ce (NO)3)3The molar ratio is 1: 9.
7. Ag-SrTiO based composition according to any one of claims 1 to 63The preparation method of the symmetrical SOFC of the electrode is characterized in that: in the step (b), the powder Ce which is weighed and uniformly ground is used0.8Gd0.2O1.9The discs were pressed out on a tablet press under a pressure of 3MPa in a die with a diameter of 12 cm.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101420044A (en) * 2008-12-05 2009-04-29 北京航空航天大学 Method for preparing proton conductive film fuel cell by coating process
CN101475377A (en) * 2009-01-20 2009-07-08 清华大学 Preparation of solid oxide electrolytic cell anode barrier layer nano powder and barrier layer
US7604892B2 (en) * 2003-06-27 2009-10-20 National Research Council Of Canada Y and Nb-doped SrTiO3 as a mixed conducting anode for solid oxide fuel cells
CN101662033A (en) * 2008-08-25 2010-03-03 中国科学院物理研究所 Solid oxide fuel cell and preparation method thereof
CN101820072A (en) * 2010-05-14 2010-09-01 哈尔滨工业大学 Preparation method of solid oxide fuel cell with symmetrical electrodes
CN101978537A (en) * 2008-03-18 2011-02-16 丹麦科技大学 An all ceramics solid oxide fuel cell
CN102617139A (en) * 2012-03-06 2012-08-01 北京科技大学 Preparation method for strontium titanate lanthanum based powder material
CN105655618A (en) * 2016-01-08 2016-06-08 福州大学 Solid-melt hybrid medium-temperature solid oxide fuel cell electrolyte

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7604892B2 (en) * 2003-06-27 2009-10-20 National Research Council Of Canada Y and Nb-doped SrTiO3 as a mixed conducting anode for solid oxide fuel cells
CN101978537A (en) * 2008-03-18 2011-02-16 丹麦科技大学 An all ceramics solid oxide fuel cell
CN101662033A (en) * 2008-08-25 2010-03-03 中国科学院物理研究所 Solid oxide fuel cell and preparation method thereof
CN101420044A (en) * 2008-12-05 2009-04-29 北京航空航天大学 Method for preparing proton conductive film fuel cell by coating process
CN101475377A (en) * 2009-01-20 2009-07-08 清华大学 Preparation of solid oxide electrolytic cell anode barrier layer nano powder and barrier layer
CN101820072A (en) * 2010-05-14 2010-09-01 哈尔滨工业大学 Preparation method of solid oxide fuel cell with symmetrical electrodes
CN102617139A (en) * 2012-03-06 2012-08-01 北京科技大学 Preparation method for strontium titanate lanthanum based powder material
CN105655618A (en) * 2016-01-08 2016-06-08 福州大学 Solid-melt hybrid medium-temperature solid oxide fuel cell electrolyte

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