CN107946618A - Based on Ag SrTiO3The symmetrical SOFC and preparation method of electrode - Google Patents
Based on Ag SrTiO3The symmetrical SOFC and preparation method of electrode Download PDFInfo
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- CN107946618A CN107946618A CN201711200381.8A CN201711200381A CN107946618A CN 107946618 A CN107946618 A CN 107946618A CN 201711200381 A CN201711200381 A CN 201711200381A CN 107946618 A CN107946618 A CN 107946618A
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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
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- 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
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- 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
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- 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 present invention provides one kind to be based on Ag SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, cathode and anode are respectively coated in electrolyte both sides, electrolyte Ce0.8Gd0.2O1.9(GDC), cathode and anode are Ag SrTiO3Electrode, Ag SrTiO3Electrode is with powder Ag SrTiO3For raw material, powder Ag SrTiO3It is that to account for the mass ratio of metallic element according to silver be 5 20wt% by Ag+It is reduced to what Ag nano particles modification STO was obtained.It is of the present invention to be based on Ag SrTiO3The symmetrical SOFC of electrode, electrode is loose porous, is contacted between electrode and electrolyte good.Ag SrTiO are based on present invention also offers described3The preparation method of the symmetrical SOFC of electrode, comprises the following steps：(1) preparation of powder；(2) preparation of symmetry electrode；(3) assembling of monocell.
Description
Technical field
The invention belongs to solid oxide fuel cell technical field, and Ag-SrTiO is based on more particularly to one kind3Electrode
Symmetrical SOFC and preparation method.
Background technology
Solid oxide fuel cell (SOFC) be it is a kind of can in fuel and oxidant chemical energy directly and continuously
The total solids component energy conversion device of electric energy is converted into, in each types of fuel cells, solid oxide fuel cell, which has, is
Unite simple in structure, photoelectric transformation efficiency is high, it is environmentally friendly, be applicable in that fuel range is wide and the advantages of long lifespan etc. is unique.It is big,
Medium and small power station, portable, portable power, and the field such as military affairs, aerospace have a wide range of applications, quilt
It is known as the new-generation technology with good development prospect.It is real although SOFC technologies have achieved major progress at present
Existing commercial applications, much remains to be done.The device operating temperature that this is primarily due to develop is excessive, causes composition material
Thermal coefficient of expansion between material is difficult to match, and the stability of battery pile longtime running is poor.Therefore, the operation temperature of SOFC is reduced into
Temperature, is the current research focus of this technology.
Since SOFC anodes are different with the working environment of cathode, thus its performance requirement is also differed, such as anode material
Material requires to stablize in reducing atmosphere, and cathode material requirement is stablized in oxidizing atmosphere, while also requires anode and cathode
There are certain electrical conductivity, intensity etc., at present for the SOFC of unsymmetric structure, its main problem is to work as to use carbon containing combustion
During material, the carbon distribution at anode position can cause the rapid decay of battery performance, while the increase of battery composition material also brings processing
Complexity.If using the SOFC of symmetrical structure, there was only two kinds of material systems of electrolyte and electrode on composition, manufacturing process can be reduced
Technology difficulty, can also exchange electrode function after carbon distribution is produced, can easily decarbonizing, ensure that battery performance is steady
It is fixed.And the Major Difficulties of symmetrical SOFC are to select suitable electrode material to allow it in the oxidizing atmosphere of cathode and anode
Reducing atmosphere in keep stablize, to oxygen reduction and oxidation of hydrogen reaction at the same time there is good catalytic activity.
The content of the invention
It is an object of the invention to provide one kind to be based on Ag-SrTiO3The symmetrical SOFC of electrode, contemplates stable perovskite
The thinking of supported nano-gold metal catalyst in material, prepares combination electrode, assembles Symmetrical cells, and study its performance.The present invention
With SrTiO3(STO) load nanometer Ag composite material makees the electrode symmetrical SOFC of structure, since STO is in very wide partial pressure of oxygen and temperature
The stabilization of scope interior energy holding structure and property, becomes the candidate of SOFC anode materials.STO electrical conductivity is very low, it is impossible to directly
For anode material；But omission STO or Mg, La etc. doping STO can effectively improve the electrical conductivity of its material, and STO is
Full ceramic component, has higher chemical stability and structural stability, also possesses higher electrical conductivity at high temperature.The present invention is also
Ag-SrTiO is based on described in providing3The preparation method of the symmetrical SOFC of electrode.
The technical solution adopted by the present invention is：
One kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, the cathode and described
Anode is respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), the cathode and the anode
It is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3Be by
It is 5-20wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to what Ag nano particles modification STO was obtained.
It is of the present invention to be based on Ag-SrTiO3The symmetrical SOFC of electrode, wherein, the powder Ag-SrTiO3It is according to silver
It is 15wt% by Ag to account for the mass ratio of metallic element+It is reduced to what Ag nano particles modification STO was obtained.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, comprises the following steps：
(1) preparation of powder
(1) citric acid self-propagating combustion prepares STO powders：Weigh Sr (NO3)3In beaker, after deionized water dissolving
The butyl titanate of respective volume is added, adds citric acid, then adds 15-20ml oxidants HNO3, with glass bar stir to
Grain dissolution, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution clarifying；Solution is shifted to evaporating dish, evaporating dish is placed in electric furnace
Upper heating concentrate solution, until self-propagating combustion reaction occurs, initial powder is made by 1000-1100 DEG C of insulation 3-4h of powder calcination
Body STO；
(2) hydro-thermal method prepares Ag-SrTiO3Powder：Using hydro-thermal method by Ag+Ag nano particles modification STO is reduced to, is made
Powder Ag-SrTiO3；
(3) citric acid self-propagating combustion prepares electrolyte GDC powders：Gd (NO are weighed respectively3)3With Ce (NO3)3Add
Deionized water dissolving, adds citric acid, then adds 15-20ml oxidants HNO3, stir to grain dissolution, adjusted with ammonium hydroxide
PH is 7-9, is stirred for solution clarifying, and transfer solution to evaporating dish, evaporating dish is placed on electric furnace and heats concentrate solution, until
Generation self-propagating combustion reacts, and 700-800 DEG C of insulation 3-4h of powder calcination is made initial powder GDC；
(2) preparation of symmetry electrode
(a)Ag-SrTiO3The preparation of electrode slurry：The powder Ag-SrTiO prepared in step (2) is weighed respectively3With
The GDC powders in mass ratio 1 prepared in step (3)：1 ratio is added in agate mortar, then it is above-mentioned powder to weigh quality
2 times of binding agent of body, adds in agate mortar and grinds 2-3h, it is spare to obtain electrode slurry；
(b) preparation of electrolyte GDC pieces：Weigh and grind the disks of powder GDC extrusion described in uniform step (3), finally
1400-1500 DEG C of sintering 5-6h obtains GDC electrolyte sheets in muffle furnace；
(c) preparation of monocell：The electrode slurry prepared in step (a) is uniformly coated in step (b) respectively
Symmetrical cells are made on the two sides of the GDC electrolyte sheets of middle sintering, and cathode and anode are repeated to brush 4 times respectively, be placed in baking oven
Dry, finally the 800-900 DEG C of calcining 3-4h in muffle furnace；Conductive silver paste is uniformly coated in the anode and cathode of Symmetrical cells again
On, it is placed in baking oven and dries, obtains monocell；
(3) assembling of monocell
Conducting resinl is used as sealing-in agent, the monocell prepared in step (c) is encapsulated in the suitable bamboo trunk one end of a size,
By the use of silver wire as cathode and anode current lead, obtain being based on Ag-SrTiO3The symmetrical SOFC of electrode.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, wherein, comprise the following steps：
(1) preparation of powder
(1) citric acid self-propagating combustion prepares STO powders：Weigh Sr (NO3)3In beaker, after deionized water dissolving
The butyl titanate of respective volume is added, adds citric acid, then adds 15ml oxidants HNO3, stirred with glass bar to particle
Dissolving, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution clarifying；Solution is shifted to evaporating dish, evaporating dish is placed on electric furnace and is added
Until self-propagating combustion reaction occurs, initial powder STO is made in 1000 DEG C of insulation 3h of powder calcination by thermal concentration solution；
(2) hydro-thermal method prepares Ag-SrTiO3Powder：Using hydro-thermal method by Ag+Ag nano particles modification STO is reduced to, is made
Powder Ag-SrTiO3；
(3) citric acid self-propagating combustion prepares electrolyte GDC powders：Gd (NO are weighed respectively3)3With Ce (NO3)3Add
Deionized water dissolving, adds citric acid, then adds 15ml oxidants HNO3, stir to grain dissolution, pH adjusted with ammonium hydroxide
For 7-9, it is stirred for solution clarifying, transfer solution to evaporating dish, evaporating dish is placed on electric furnace and heats concentrate solution, until hair
Propagating combustion reaction is born from, initial powder GDC is made in 700 DEG C of insulation 3h of powder calcination；
(2) preparation of symmetry electrode
(a)Ag-SrTiO3The preparation of electrode slurry：Mass ratio is weighed respectively as 9：1 terpinol and ethyl cellulose, puts
It is stand-by as binding agent that 24h is dissolved in beaker, in 60 DEG C of water-bath；The powder prepared in step (2) is weighed respectively
Ag-SrTiO3With the GDC powders in mass ratio 1 prepared in step (3)：1 ratio is added in agate mortar, then weighs matter
2 times of the binding agent for above-mentioned powder is measured, adds in agate mortar and grinds 2h, it is spare to obtain electrode slurry；
(b) preparation of electrolyte GDC pieces：Weigh and grind the disks of powder GDC extrusion described in uniform step (3), finally
1400 DEG C of sintering 5h obtain GDC electrolyte sheets in muffle furnace；
(c) preparation of monocell：The electrode slurry prepared in step (a) is uniformly coated in step (b) respectively
Symmetrical cells are made on the two sides of the GDC electrolyte sheets of middle sintering, and cathode and anode are repeated to brush 4 times respectively, be placed in baking oven
Dry, finally 800 DEG C of calcining 3h in muffle furnace；Conductive silver paste is uniformly coated in the anode and cathode of Symmetrical cells again, is put
Dried in baking oven, obtain monocell；
(3) assembling of monocell
Conducting resinl is used as sealing-in agent, the monocell prepared in step (c) is encapsulated in the suitable bamboo trunk one end of a size,
By the use of silver wire as cathode and anode current lead, obtain being based on Ag-SrTiO3The symmetrical SOFC of electrode.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, wherein, hydro-thermal in step (2)
Method prepares Ag-SrTiO3Powder is specifically, weigh 1-2g block copolymers polyvinyl alcohol-POLYPROPYLENE GLYCOL-polyvinyl alcohol (P123),
Stirring, after clarifying, adds AgNO3After stirring 30min, the stirring of six methines, four ammonia 1h, AgNO are then added3With six methines
Four ammonia molar ratios 1:3, powder STO described in step (1) is added, continues to stir 2h, using hydrothermal synthesis method at 100-110 DEG C
Reduction reaction 4-6h is carried out, is dried after suction filtration, 550 DEG C of calcining 6h in high temperature furnace is placed on, powder Ag-SrTiO is made3。
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, wherein, lemon in step (1)
The amount of acid and metal ion species is than 1.8:1.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, wherein, metal in step (3)
Ion is 1 with citric acid molar ratio:1.5, Gd (NO3)3With Ce (NO3)3Molar ratio is 1:9.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, wherein, it will claim in step (b)
Take the uniform powder GDC of grinding to be placed in the mould of a diameter of 12cm, extrude circle on tablet press machine under the pressure of 3MPa
Piece.
Beneficial effect of the present invention：
It is of the present invention to be based on Ag-SrTiO3The symmetrical SOFC of electrode, electrode is loose porous, between electrode and electrolyte
Contact is good, and the ratio of catalyst can be adjusted, the vacant STO of argentiferous mass ratio 5wt%, 10wt%, 15wt% and 20wt%
Maximum open circuit voltage at 550-700 DEG C is respectively 0.78V, 0.72V, 0.80V and 0.82V, and maximum power density is distinguished
For 7mW, 7.2mW, 75mW and 18mW, above open-circuit voltage is close to theoretical value；The output work of the symmetrical SOFC of argentiferous 15wt%
Output power of the rate substantially than other symmetrical SOFC is much higher.
It is of the present invention to be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, equipment requirement is simple, technology road
Line is clear and definite, and method is firmly believed feasible, due to in-situ preparation nano Ag particles in the liquid phase, can relatively evenly be loaded in carrier, be protected
The stable homogeneous after structure electrode is hindered, whole single-cell structure is simple, to the adaptable of fuel, has certain practicality
Value.
Brief description of the drawings
Fig. 1 is powder Ag-SrTiO described in embodiment 1-43Powder x-ray diffraction (XRD) figure of sample；
Fig. 2 is scanning electron microscope (SEM) figure of the cross section of monocell described in embodiment 1；
Fig. 3 is the SEM figures of the cross section of monocell described in embodiment 2；
Fig. 4 a are that SOFC monocells described in embodiment 1 are exported using humidifying electrochemistry of the hydrogen as fuel at different temperatures
Performance and the impedance diagram in open circuit；
Fig. 4 b are that SOFC monocells described in embodiment 2 are exported using humidifying electrochemistry of the hydrogen as fuel at different temperatures
Performance and the impedance diagram in open circuit；
Fig. 4 c are that SOFC monocells described in embodiment 3 are exported using humidifying electrochemistry of the hydrogen as fuel at different temperatures
Performance and the impedance diagram in open circuit；
Fig. 4 d are that SOFC monocells described in embodiment 4 are exported using humidifying electrochemistry of the hydrogen as fuel at different temperatures
Performance and the impedance diagram in open circuit.
Below in conjunction with specific embodiment and attached drawing, the invention will be further described.
Embodiment
Thing phase using X-ray diffractometer analysis powder and mutual chemical compatibility, CuK α in following embodiments
Radiation, λ=0.15418nm, voltage 40.0kV, electric current 30mA, step-length 0.03,2 θ of scanning range:20~80 °.Using Zahner
IM6 types electrochemical workstation tests the polarization behavior of battery, and range of scanned frequencies is 1MHz~10mHz, voltage disturbance 5mV.
The evaluating apparatus that cell output is built with laboratory is tested.The section micro-structure of battery sample uses KYKY EM-
3200 type scanning electron microscope are observed.
Embodiment 1
One kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, the cathode and described
Anode is respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), the cathode and the anode
It is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3Be by
It is 5wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to what Ag nano particles modification STO was obtained.
Described in the present embodiment based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, comprises the following steps：
(1) preparation of powder
(1) citric acid self-propagating combustion prepares STO powders：Weigh a certain amount of Sr (NO3)3In beaker, deionization is used
The butyl titanate of respective volume is added after water dissolving, adds citric acid, the amount of citric acid and metal ion species is than 1.8:1,
Then 15ml oxidants HNO is added3, stirred with glass bar to grain dissolution, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution
Clarification；Solution is shifted to evaporating dish, evaporating dish is placed on electric furnace and heats concentrate solution, until self-propagating combustion reaction occurs,
Initial powder STO is made in 1000 DEG C of insulation 3h of powder calcination；
(2) hydro-thermal method prepares Ag-SrTiO3Powder：Hydro-thermal method is used to account for the mass ratio of metallic element according to silver as 5wt%
By Ag+Ag nano particles modification STO is reduced to, preparation method is：Weigh 1.5g block copolymers polyvinyl alcohol-POLYPROPYLENE GLYCOL-
Polyvinyl alcohol (P123), it is stirred using magnetic stirring apparatus, after clarifying, adds AgNO3After stirring 30min, six are then added
Four ammonia of methine stirs 1h, AgNO3With six methines, four ammonia molar ratio 1:3, powder STO described in step (1) is added, is continued
2h is stirred, reduction reaction 5h is carried out at 100 DEG C using hydrothermal synthesis method, is dried after suction filtration, is placed on 550 DEG C of calcinings in high temperature furnace
6h, is made powder Ag-SrTiO3；
(3) citric acid self-propagating combustion prepares electrolyte GDC powders：Molar ratio is weighed respectively as 1:9 Gd (NO3)3With
Ce(NO3)3, add deionized water and dissolved in beaker, add citric acid, metal ion is 1 with citric acid molar ratio:1.5
Then 15ml oxidants HNO is added3, stir to grain dissolution, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution clarifying, transfer
Evaporating dish is placed on electric furnace to evaporating dish and heats concentrate solution, until self-propagating combustion reaction occurs, by powder calcination by solution
Initial powder GDC is made in 700 DEG C of insulation 3h；
(2) preparation of symmetry electrode
(a)Ag-SrTiO3The preparation of electrode slurry：Mass ratio is weighed respectively as 9：1 terpinol and ethyl cellulose, puts
It is stand-by as binding agent that 24h is dissolved in beaker, in 60 DEG C of water-bath；The powder prepared in step (2) is weighed respectively
Ag-SrTiO3With the GDC powders in mass ratio 1 prepared in step (3)：1 ratio is added in agate mortar, then weighs matter
2 times of the binding agent for above-mentioned powder is measured, adds in agate mortar and grinds 2h, obtains the uniform, electrode slurry of good fluidity
It is spare；
(b) preparation of electrolyte GDC pieces：Weigh and grind powder GDC described in uniform step (3), be placed in a diameter of
In the mould of 12cm, disk is extruded on tablet press machine under the pressure of about 3MPa, finally 1400 DEG C of sintering 5h are obtained in muffle furnace
To GDC electrolyte sheets；
(c) preparation of monocell：The electrode slurry prepared in step (a) is uniformly coated in small brushes respectively
Symmetrical cells are made in the two sides of the GDC electrolyte sheets of sintering in step (b), and cathode and anode are repeated to brush 4 times respectively, put
Dried in baking oven, finally 800 DEG C of calcining 3h in muffle furnace；Conductive silver paste is uniformly coated in symmetrical electricity with small brushes again
In the anode and cathode in pond, it is placed in baking oven and dries, obtains monocell；
(3) assembling of monocell
Conducting resinl is used as sealing-in agent, the monocell prepared in step (c) is encapsulated in the suitable bamboo trunk one end of a size,
By the use of silver wire as cathode and anode current lead, obtain being based on Ag-SrTiO3The symmetrical SOFC of electrode.
Embodiment 2
One kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, the cathode and described
Anode is respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), the cathode and the anode
It is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3Be by
It is 10wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to what Ag nano particles modification STO was obtained.
Described in the present embodiment based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, except in step (2) according to silver
Account for the mass ratio of metallic element and modify STO for 10wt%, sintering obtains powder Ag-SrTiO3Outside, the other the same as in Example 1.
Embodiment 3
One kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, the cathode and described
Anode is respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), the cathode and the anode
It is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3Be by
It is 15wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to what Ag nano particles modification STO was obtained.
The present embodiment is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, except accounting for metal according to silver in step (2)
The mass ratio of element modifies STO for 15wt%, and sintering obtains powder Ag-SrTiO3Outside, the other the same as in Example 1.
Embodiment 4
One kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, including electrolyte, cathode and anode, the cathode and described
Anode is respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9(GDC), the cathode and the anode
It is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3Be by
It is 20wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to what Ag nano particles modification STO was obtained.
The present embodiment is based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, except accounting for metal according to silver in step (2)
The mass ratio of element modifies STO for 20wt%, and sintering obtains powder Ag-SrTiO3Outside, the other the same as in Example 1.
Fig. 1 is the powder Ag-SrTiO prepared by embodiment 1-43The XRD diagram of sample, wherein be 22.9 ° at 2 θ angles,
32.8 °, 40.1 °, 46.0 °, 52.7 °, 57.6 °, 67.7 °, 72.4 ° and 77.1 ° of diffraction maximum has corresponded to STO Ca-Ti ore types respectively
(100), (110), (111), (200), (210), (211), (220), (221) and (310) crystal face structure, and 38.1 °,
44.4 °, 64.55 ° and 77.5 ° or so have 4 sharp diffraction maximums, have corresponded to the characteristic diffraction peak of Face-centred Cubic Metals silver, have returned
Belong to the diffraction in (111), (200), (220) and (311) face.The diffraction maximum of all samples is obvious, without miscellaneous peak.With silver content
Change, the position of diffraction maximum illustrates that the change of silver content does not interfere with STO powders almost without changing in XRD spectrum
Thing phase, both compatibilities are good, do not chemically react, and the intensity of diffraction maximum of silver increases therewith.Compare PDF cards
The position of the diffraction maximum of 00-040-1500 (STO) and 00-001-1164 (Ag), silver and STO powders is all inclined almost without occurring
Move.
Fig. 2 and Fig. 3 is Ag-SrTiO respectively3(5wt%) and Ag-SrTiO3(10wt%) is the transversal of the monocell of electrode
The SEM figures in face, are the SEM figures of the cross section of representative monocell, by Fig. 2 and Fig. 3 as it can be seen that electrolyte is fine and close,
The closed pore being only distributed on a small quantity, these closed pores will not cause gas molecule directly through electrolyte, therefore can ensure battery
Air-tightness, makes battery have good open-circuit voltage.Also known by Fig. 2, prepared electrode is loose porous, electrode and electrolyte
Between contact good, these conditions can make battery have normal output.
Embodiment 1-4 is assembled into respectively based on Ag-SrTiO3The output performance of the symmetrical SOFC of electrode and opening a way
When impedance tested.Fig. 4 a, 4b, 4c and 4d be respectively in embodiment 1-4 SOFC monocells at different temperatures with humidification
Hydrogen is the electrochemistry output performance of fuel, and Ag-SrTiO is based on by described in3The live part of the symmetrical SOFC of electrode is placed in height
The flat-temperature zone of warm tube type resistance furnace, is passed through the humidification hydrogen that flow velocity is 20mL/min to anode-side and is placed in as fuel gas, cathode
In atmosphere, it is 550-700 DEG C to the electrochemical property test of battery, Range of measuring temp, the current -voltage curve of battery leads to
Cross linear sweep voltammetry to be tested, sweep speed 5mv/s.Understood by Fig. 4 a, 4b, 4c and 4d, argentiferous mass ratio
Maximum open circuit voltages of the vacant STO of 5wt%, 10wt%, 15wt% and 20wt% at 550-700 DEG C is respectively 0.78V,
0.72V, 0.80V and 0.82V, and maximum power density is respectively 7mW, 7.2mW, 75mW and 18mW, above open-circuit voltage approaches
In theoretical value.The maximum power density of the Symmetrical cells different from argentiferous can be seen that changing with silver-colored content in electrode material
Become, the catalytic activity of electrode also changes correspondingly, and illustrates to play in cathode or anode incorporation nano silver and change electrode performance
Kind effect.Therefore can guess：The silver-colored content of incorporation makes the electrochemistry output performance of battery reach most there are an optimum value
Greatly.The output power of the symmetrical SOFC of 3 argentiferous 15wt% of embodiment be can be seen that by Fig. 4 a, 4b, 4c and 4d substantially than other
The output power of symmetrical SOFC is much higher.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made, should all fall into the protection domain that claims of the present invention determines.
Claims (8)
1. one kind is based on Ag-SrTiO3The symmetrical SOFC of electrode, it is characterised in that：Including electrolyte, cathode and anode, described the moon
Pole and the anode are respectively coated in the electrolyte both sides, and the electrolyte is Ce0.8Gd0.2O1.9, the cathode and the sun
Pole is Ag-SrTiO3Electrode, the Ag-SrTiO3Electrode is with powder Ag-SrTiO3For raw material, the powder Ag-SrTiO3It is
It is 5-20wt% by Ag to account for the mass ratio of metallic element according to silver+It is reduced to Ag nano particles modification SrTiO3Obtain.
2. according to claim 1 be based on Ag-SrTiO3The symmetrical SOFC of electrode, it is characterised in that：The powder Ag-
SrTiO3It is that to account for the mass ratio of metallic element according to silver be 15wt% by Ag+It is reduced to Ag nano particles modification SrTiO3Obtain.
3. described in claim 1 or 2 based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is characterised in that：Including
Following steps：
(1) preparation of powder
(1) citric acid self-propagating combustion prepares SrTiO3Powder：Weigh Sr (NO3)3In beaker, after deionized water dissolving
The butyl titanate of respective volume is added, adds citric acid, then adds 15-20ml oxidants HNO3, with glass bar stir to
Grain dissolution, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution clarifying；Solution is shifted to evaporating dish, evaporating dish is placed in electric furnace
Upper heating concentrate solution, until self-propagating combustion reaction occurs, initial powder is made by 1000-1100 DEG C of insulation 3-4h of powder calcination
Body SrTiO3；
(2) hydro-thermal method prepares Ag-SrTiO3Powder：Using hydro-thermal method by Ag+It is reduced to Ag nano particles modification SrTiO3, it is made
Powder Ag-SrTiO3；
(3) citric acid self-propagating combustion prepares electrolyte Ce0.8Gd0.2O1.9Powder：Gd (NO are weighed respectively3)3With Ce (NO3)3Add
Enter deionized water dissolving, add citric acid, then add 15-20ml oxidants HNO3, stir to grain dissolution, with ammonium hydroxide tune
Section pH is 7-9, is stirred for solution clarifying, and evaporating dish is placed on electric furnace to evaporating dish and heats concentrate solution, directly by transfer solution
To self-propagating combustion reaction occurs, initial powder Ce is made in 700-800 DEG C of insulation 3-4h of powder calcination0.8Gd0.2O1.9；
(2) preparation of symmetry electrode
(a)Ag-SrTiO3The preparation of electrode slurry：The powder Ag-SrTiO prepared in step (2) is weighed respectively3And step
(3) Ce prepared in0.8Gd0.2O1.9Powder in mass ratio 1：1 ratio is added in agate mortar, then it is upper to weigh quality
2 times of binding agent of powder is stated, adds in agate mortar and grinds 2-3h, it is spare to obtain electrode slurry；
(b) electrolyte Ce0.8Gd0.2O1.9The preparation of piece：Weigh and grind powder Ce described in uniform step (3)0.8Gd0.2O1.9Pressure
Go out disk, finally 1400-1500 DEG C of sintering 5-6h obtains Ce in muffle furnace0.8Gd0.2O1.9Electrolyte sheet；
(c) preparation of monocell：The electrode slurry prepared in step (a) is uniformly coated into middle burning in step (b) respectively
The Ce of knot0.8Gd0.2O1.9Symmetrical cells are made on the two sides of electrolyte sheet, and cathode and anode repeat to brush 4 times respectively, are placed in baking
Dried in case, finally the 800-900 DEG C of calcining 3-4h in muffle furnace；Conductive silver paste is uniformly coated in the moon of Symmetrical cells again
On anode, it is placed in baking oven and dries, obtains monocell；
(3) assembling of monocell
Conducting resinl is used as sealing-in agent, the monocell prepared in step (c) is encapsulated in the suitable bamboo trunk one end of a size, with silver
Line obtains being based on Ag-SrTiO as cathode and anode current lead3The symmetrical SOFC of electrode.
4. according to claim 3 be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is characterised in that：Including
Following steps：
(1) preparation of powder
(1) citric acid self-propagating combustion prepares SrTiO3Powder：Weigh Sr (NO3)3In beaker, after deionized water dissolving
The butyl titanate of respective volume is added, adds citric acid, then adds 15ml oxidants HNO3, stirred with glass bar to particle
Dissolving, it is 7-9 to adjust pH with ammonium hydroxide, is stirred for solution clarifying；Solution is shifted to evaporating dish, evaporating dish is placed on electric furnace and is added
Until self-propagating combustion reaction occurs, initial powder SrTiO is made in 1000 DEG C of insulation 3h of powder calcination by thermal concentration solution3；
(2) hydro-thermal method prepares Ag-SrTiO3Powder：Using hydro-thermal method by Ag+It is reduced to Ag nano particles modification SrTiO3, it is made
Powder Ag-SrTiO3；
(3) citric acid self-propagating combustion prepares electrolyte Ce0.8Gd0.2O1.9Powder：Gd (NO are weighed respectively3)3With Ce (NO3)3Add
Enter deionized water dissolving, add citric acid, then add 15ml oxidants HNO3, stir to grain dissolution, adjusted with ammonium hydroxide
PH is 7-9, is stirred for solution clarifying, and transfer solution to evaporating dish, evaporating dish is placed on electric furnace and heats concentrate solution, until
Generation self-propagating combustion reacts, and 700 DEG C of insulation 3h of powder calcination are made initial powder Ce0.8Gd0.2O1.9；
(2) preparation of symmetry electrode
(a)Ag-SrTiO3The preparation of electrode slurry：Mass ratio is weighed respectively as 9：1 terpinol and ethyl cellulose, is placed in burning
It is stand-by as binding agent that 24h is dissolved in cup, in 60 DEG C of water-bath；The powder Ag- prepared in step (2) is weighed respectively
SrTiO3With the Ce prepared in step (3)0.8Gd0.2O1.9Powder in mass ratio 1：1 ratio is added in agate mortar, then
2 times of the binding agent that quality is above-mentioned powder is weighed, adds in agate mortar and grinds 2h, it is spare to obtain electrode slurry；
(b) electrolyte Ce0.8Gd0.2O1.9The preparation of piece：Weigh and grind powder Ce described in uniform step (3)0.8Gd0.2O1.9Pressure
Go out disk, finally 1400 DEG C of sintering 5h obtain Ce in muffle furnace0.8Gd0.2O1.9Electrolyte sheet；
(c) preparation of monocell：The electrode slurry prepared in step (a) is uniformly coated into middle burning in step (b) respectively
The Ce of knot0.8Gd0.2O1.9Symmetrical cells are made on the two sides of electrolyte sheet, and cathode and anode repeat to brush 4 times respectively, are placed in baking
Dried in case, finally 800 DEG C of calcining 3h in muffle furnace；Conductive silver paste is uniformly coated in the anode and cathode of Symmetrical cells again
On, it is placed in baking oven and dries, obtains monocell；
(3) assembling of monocell
Conducting resinl is used as sealing-in agent, the monocell prepared in step (c) is encapsulated in the suitable bamboo trunk one end of a size, with silver
Line obtains being based on Ag-SrTiO as cathode and anode current lead3The symmetrical SOFC of electrode.
5. according to claim 3 be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is characterised in that：Step
(1) hydro-thermal method prepares Ag-SrTiO in3Powder is specifically, weigh 1-2g block copolymers polyvinyl alcohol-POLYPROPYLENE GLYCOL-polyethylene
Alcohol, stirring, after clarifying, adds AgNO3After stirring 30min, the stirring of six methines, four ammonia 1h, AgNO are then added3With six first
Four ammonia molar ratio 1 of base:3, add powder SrTiO described in step (1)3, continue to stir 2h, using hydrothermal synthesis method in 100-
110 DEG C carry out reduction reaction 4-6h, are dried after suction filtration, are placed on 550 DEG C of calcining 6h in high temperature furnace, powder Ag-SrTiO is made3。
6. according to claim 3 be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is characterised in that：Step
(1) amount of citric acid and metal ion species is than 1.8 in:1.
7. according to claim 3 be based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is characterised in that：Step
(3) metal ion and citric acid molar ratio are 1 in:1.5, Gd (NO3)3With Ce (NO3)3Molar ratio is 1:9.
8. according to claim 3-7 any one based on Ag-SrTiO3The preparation method of the symmetrical SOFC of electrode, it is special
Sign is：The uniform powder Ce of grinding will be weighed in step (b)0.8Gd0.2O1.9It is placed in the mould of a diameter of 12cm,
Disk is extruded on tablet press machine under the pressure of 3MPa.
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