CN108288724A - A kind of solid oxide fuel cell and preparation method of low-temperature stabilization - Google Patents
A kind of solid oxide fuel cell and preparation method of low-temperature stabilization Download PDFInfo
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- CN108288724A CN108288724A CN201810092997.6A CN201810092997A CN108288724A CN 108288724 A CN108288724 A CN 108288724A CN 201810092997 A CN201810092997 A CN 201810092997A CN 108288724 A CN108288724 A CN 108288724A
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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
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
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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 proposes that a kind of solid fuel cell and preparation method of low-temperature stabilization, battery structure include five layers from bottom to top：Magnetostrictive layer is arranged on the anode support in anode support, and cerium base electrolyte layer is arranged on magnetostrictive layer, magnetostrictive layer is arranged on the cerium base electrolyte layer, cathode active layers are arranged on magnetostrictive layer.The present invention passes through in CeO2Base electrolyte layer applies magnetostrictive layer, and micro- magnetic that battery generates at work makes magnetostrictive layer that miniature deformation occur, and to which buffering is due to the change in size of electrolyte layer, overcomes CeO in existing solid oxide fuel cell2There is Ce in electrolyte4+/Ce3+Mixed state leads to the defect of electrolyte layer change in size caused by oxygen vacancy, effectively prevent deflection deformation and cracking during solid oxide fuel cell use, extends solid oxide fuel cell service life.
Description
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of solid oxide fuel cell of low-temperature stabilization and
Preparation method.
Background technology
Fuel cell is a kind of energy conversion device based on redox reaction.It can be direct by the chemical energy of fuel
It is converted to electric energy, carnot's cycle process is not undergone in conversion process, effect more higher than conventional heat engines electricity generation system can be obtained
Rate, have many advantages, such as efficiently, it is low noise, environmental-friendly and safe and reliable.
Fuel cell can be divided into alkaline fuel cell, phosphate fuel electricity by the property of fuel cell electrolyte
Pond, molten carbonate fuel cell, Proton Exchange Membrane Fuel Cells and solid oxide fuel cell.With other four kinds of fuel electricity
Pond is compared, and solid oxide fuel cell has its unique advantage.First, higher operating temperature has widened the choosing of fuel gas
Range is selected, the alkane class A fuel A of relative low price can be reformed in inside battery, oxidation produces electricl energy.Second, solid oxidation
A large amount of waste heat is generated when object operation of fuel cells, Co-generation may be implemented, and improves the efficiency of electricity generation system.Third, solid
Oxide fuel cell is structure of whole solid state, can mutually be corroded to avoid between battery component existing for other kind of types of fuel cells
The problem of.
Main three big component of solid oxide fuel cell is anode, electrolyte and cathode respectively.Wherein, electrolyte is
The most crucial component of solid oxide fuel cell, solid-oxide fuel battery electrolyte material, which should meet the following, to be wanted
It asks：Good ionic conductivity and simple ionic conductivity（Close to 1 transference number of ions）；In high temperature and redox condition
Physics and chemical stability；Air-tightness；Chemical compatibility between electrode；High temperature thermal matching between electrode；Heat
The coefficient of expansion matches；Superior performance is cheap.Existing solid oxide fuel cell still uses traditional yttrium oxide mostly
Stabilizing zirconia（YSZ）For electrolyte, operating temperature is at 750 DEG C -1000 DEG C.Working long hours at such high temperatures can lead
Cause cell components material between side reaction, electrode microstructure due to sintering and by destroy the problems such as.In addition to this, higher
Operating temperature make the optional material of each component of solid oxide fuel cell very limited, relative inexpensiveness cannot be used
Sealing and electrode material.
Ceria-based electrolyte is face-centered cubic fluorite structure, and cerium ion is located in the simple cubic lattice of oxonium ion composition
Heart position, ligancy 8, and oxonium ion then occupies the tetrahedron center of cerium ion formation, ligancy 4.Pure zirconia cerium
Conductivity is very low, and oxygen ionic conductivity at 600 DEG C is about 1 × 10-5S/cm, but when golden with aliovalent ion such as divalent alkaline earth
Belong to ion or rare earth cation part replaces CeO2In Ce4+When, in order to keep charge balance, will be produced in lattice
Raw certain Lacking oxygen, the oxygen ionic conductivity that doped cerium oxide can greatly improve.In CeO2The member adulterated in base is known as
Gd, Y, Sm, Sr, La, Pr, Ba etc., as Chinese invention patent application number 200910062001.8 discloses a kind of oxidation Gd2 O3
The preparation method of the composite oxide solid solution gel of cerium oxide, using with the active acetylacetone,2,4-pentanedione cerium hydrate of low in hydrolysis,
Precursor of the acetylacetone,2,4-pentanedione gadolinium hydrate as colloidal sol-gel, can be made the gadolinia-doped ceria with high density sum
Composite oxide solid solution gel, aoxidize the CeO of Gd2 O32The high and oxygen of the oxygen ionic conductivity ratio YSZ of electrolyte from
Electron conductivity is excellent in 500~600 DEG C of performances.However, in CeO2Base electrolyte is under reducing atmosphere, it may occur that Ce4+'s
Partial reduction and there is Ce4+/Ce3+Mixed state generates useless electronic conductance, reduces battery open circuit voltage, reduces the defeated of battery
Go out power density.In addition, oxygen vacancy will make film generate violent change in size, so as to cause deflection deformation, dielectric film is influenced
Service life.
It is therefore proposed that a kind of process program is simply controllable, effectively overcome existing solid oxide fuel cell due to CeO2
Change in size is generated when dielectric film use, so as to cause deflection deformation, the defect of fuel cell service life is influenced, prepares work
The update of skill scheme has high practical value to the raising of fuel cell service life.
Invention content
For CeO in existing solid oxide body fuel cell2There is Ce in electrolyte4+/Ce3+Mixed state, oxygen vacancy cause
The defect of change in size, the present invention propose a kind of solid fuel cell and preparation method of low-temperature stabilization, to which buffering is due to electricity
The change in size for solving matter layer effectively prevent battery deflection deformation and cracking, improves battery.
To solve the above problems, the present invention uses following technical scheme：A kind of solid oxide fuel electricity of low-temperature stabilization
Pond includes five layers from bottom to top：
Anode-supported material；
Magnetostrictive layer on the anode support layer is set：The magnetostrictive layer is Conjugate ferrite magnetostriction material
Material；
Cerium base electrolyte layer；
Conjugate ferrite magnetostrictive layer on the cerium base electrolyte layer is set；
Cathode active layers on the Conjugate ferrite magnetostrictive layer are set.
Preferably, the thickness of the anode support is 500-1800 microns, and the anode-supported material conducts for electronics
Mutually with the combination of ionic conduction phase composite materials and porous carbon materials, the electronics conduction is mutually one kind in NiO, CuO, ZnO
Or two or more combinations, the ionic conduction are mutually the titanium of the lanthanum manganate of strontium and chromium codope, La doped calcium titanate, La doped
The combination of one or more of sour strontium and layered perovskites.
Preferably, the thickness of the Conjugate ferrite magnetostriction materials is 5-120 microns, and consistency is more than 99%.
Preferably, the cerium base electrolyte layer is in gadolinium doped-ceria, yttria-doped ceria, samarium neodymium codope cerium oxide
One or more and the combinations of zirconium oxide, the wherein volumetric concentration of zirconium oxide is 30%-65%.
Preferably, the thickness of the cathode active layers is 5-80 μm, and the cathode active layers are Er ions bismuth oxide and yttrium
Adulterate one kind in bismuth oxide.
A kind of preparation method of the solid oxide fuel cell of low-temperature stabilization is provided, specific preparation method is as follows：
（1）Anode-supported material is mixed with porous carbon materials, compression moulding obtains anode support presoma；
（2）The Conjugate ferrite magnetostriction materials are prepared on the anode support presoma, are set after high temperature sintering
It is equipped with the anode support of magnetostriction materials；
（3）By cathode activity layer material compression moulding, cathode active layers are obtained, then the Conjugate ferrite magnetostriction materials are starched
Material is coated on cathode active layers, by high temperature sintering, obtains magnetostriction materials/cathode active layers composite layer；
（4）The cerium base electrolyte slurry is provided with coated in described on the anode support layer of magnetostriction materials, then will
On magnetostriction materials/cathode activity lamination cerium base electrolyte, after low temperature co-fired, solid oxide fuel cell is obtained.
Preferably, the porous carbon materials be selected from porous T carbon materials, carbon foam, one or both of carbon aerogels with
On combination, aperture be 30-80 microns.
Preferably, the mass ratio of the porous carbon materials and the anode-supported material is 1：6-9.
Preferably, step（2）With（3）Described in the temperature of high temperature sintering be 1200-1400 DEG C, the time of high temperature sintering is
5-20h, step（4）Described in low temperature co-fired temperature be 700-900 DEG C, time 5-30h.
CeO in existing solid oxide body fuel cell2There is Ce in electrolyte4+/Ce3+Mixed state, oxygen vacancy lead to size
The defect of variation, the present invention propose a kind of solid fuel cell and preparation method of low-temperature stabilization.Technology point is that a kind of low temperature is steady
Magnetostrictive layer is arranged on the anode support in fixed solid oxide fuel cell, including anode support, is stretched in mangneto
Cerium base electrolyte layer is set on contracting layer；Magnetostrictive layer is set on the cerium base electrolyte layer；It is arranged on magnetostrictive layer
Cathode active layers.The magnetostrictive layer is the complex of rare earth metal and transition metal.Significant advantage is, by CeO2
Base electrolyte layer applies magnetostrictive layer, and micro- magnetic that battery generates at work makes magnetostrictive layer that miniature deformation occur, to
The change in size due to electrolyte layer is buffered, battery deflection deformation and cracking are effectively prevent.
The solid fuel cell of low-temperature stabilization prepared by the present invention is obtained with the cerium oxide electrolyte that buffer layer is not arranged
Battery material test temperature be 400-550 DEG C under the conditions of test performance, as shown in table 1.
Table 1：
| Project | Battery operating temperature（℃） | Continue working duration | Fire matter efficiency（%） |
| The present invention | 600-720 | 3000 hours | 90 |
| Common cerium oxide electrolyte battery | 750-1000 | 2000 hours | 84 |
The present invention provides a kind of solid oxide fuel cell and preparation method of low-temperature stabilization, compared with prior art, dashes forward
The characteristics of going out and excellent effect are：
1, the present invention provides a kind of solid oxide fuel cell and preparation method of low-temperature stabilization, by CeO2Base electrolyte
Layer coating magnetostrictive layer, at work battery generate micro- magnetic make magnetostrictive layer occur miniature deformation, to buffering due to
CeO2Base electrolyte oxygen vacancy causes electrolyte layer to generate change in size, effectively prevent electrode microstructure due to sintering and by broken
Bad battery deflection deformation and cracking.
2, a kind of solid oxide fuel cell preparation process scheme of low-temperature stabilization provided by the invention is simple, at low cost
It is honest and clean, prepare it is pollution-free, be suitable for promote production.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually NiO, and the ionic conduction is mutually the lanthanum manganate of strontium and chromium codope, is 65 micro- by anode-supported material and aperture
The mass ratio of the porous T carbon materials mixing of rice, porous carbon materials and the anode-supported material is 1：7, compression moulding obtains thickness
Degree is 1200 microns Anode supporter presomas；
（2）It is 56 microns that thickness is prepared on the anode support presoma, and Conjugate ferrite mangneto of the consistency more than 99% is stretched
Compression material, high temperature sintering temperature are 1230 DEG C, sintering time 12h, obtain being provided with Conjugate ferrite magnetostriction material after sintering
The anode support of material；
（3）It is 12 μm of cathode activity layer material Er ions bismuth oxide compression mouldings by thickness, obtains cathode active layers, then will be described
Conjugate ferrite magnetostriction materials slurry is coated on cathode active layers, is 1200 DEG C through excess temperature, the time of high temperature sintering is
5-20h high temperature sinterings obtain magnetostriction materials/cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the gadolinium doped-ceria that the volumetric concentration containing zirconium oxide is 35%, wherein the cerium base electricity
Solution chylema material is provided with described in being coated on the anode support layer of magnetostriction materials, then magnetostriction materials/cathode is lived
Property lamination cerium base electrolyte on, through excess temperature be 780 DEG C, after time 10h is low temperature co-fired, obtain solid oxide fuel cell,
Its structure is followed successively by anode-supported material from top to bottom；Magnetostrictive layer on the anode support layer is set；Cerium base electricity
Solve matter layer；Conjugate ferrite magnetostrictive layer on the cerium base electrolyte layer is set；Setting is stretched in the Conjugate ferrite mangneto
Cathode active layers on contracting layer.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C, continue working 5 hours measure maximum output current density and reach 3.5A/cm2, voltage is
0.5V, peak power output reach 1.7W.
Embodiment 2
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually the combination of two kinds of CuO, ZnO, and the ionic conduction is mutually two kinds of the strontium titanates of La doped calcium titanate, La doped
Combination；Anode-supported material is mixed with the carbon aerogels that aperture is 80 microns, porous carbon materials and the anode-supported material
Mass ratio be 1：6, compression moulding, it is 500 microns Anode supporter presomas to obtain thickness；
（2）It is 5 microns that thickness is prepared on the anode support presoma, and Conjugate ferrite mangneto of the consistency more than 99% is stretched
Compression material, high temperature sintering temperature are 1400 DEG C, sintering time 5h, and the anode branch for being provided with magnetostriction materials is obtained after sintering
Support body；
（3）It is 50 μm of cathode activity layer material doped yttrium bismuth oxide compression mouldings by thickness, obtains cathode active layers, then will be described
Conjugate ferrite magnetostriction materials slurry is coated on cathode active layers, is 1350 DEG C through excess temperature, the time of high temperature sintering is
10h high temperature sinterings obtain magnetostriction materials/cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the yttria-doped ceria that the volumetric concentration containing zirconium oxide is 45%, wherein the cerium base electricity
Solution chylema material is provided with described in being coated on the anode support layer of magnetostriction materials, then magnetostriction materials/cathode is lived
Property lamination cerium base electrolyte on, through excess temperature be 760 DEG C, after time 12h is low temperature co-fired, obtains structure and be followed successively by sun from top to bottom
Pole backing material；Magnetostrictive layer on the anode support layer is set；Cerium base electrolyte layer；Setting is in cerium base electricity
Solve the Conjugate ferrite magnetostrictive layer on matter layer；The solid of cathode active layers on the Conjugate ferrite magnetostrictive layer is set
Oxide fuel cell.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C, continue working 5 hours measure maximum output current density and reach 5 A/cm2, voltage is
0.6V, peak power output reach 3W.
Embodiment 3
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually two kinds in NiO, ZnO of combination, and the ionic conduction is mutually the strontium titanates of La doped；By anode-supported material with
The porous carbon materials carbon foam that aperture is 36 microns mixes, and the mass ratio of porous carbon materials and the anode-supported material is 1：6,
Compression moulding, it is 500-1800 microns Anode supporter presomas to obtain thickness；
（2）It is 5 meters that thickness is prepared on the anode support presoma, and consistency is more than 99% Conjugate ferrite magnetostriction
Material, high temperature sintering temperature are 1400 DEG C, sintering time 20h, and the anode branch for being provided with magnetostriction materials is obtained after sintering
Support body；
（3）It is 80 μm of cathode activity layer material Er ions bismuth oxide compression mouldings by thickness, obtains cathode active layers, then will be described
Conjugate ferrite magnetostriction materials slurry is coated on cathode active layers, is 1340 DEG C through excess temperature, the time of high temperature sintering is
5-20h high temperature sinterings obtain magnetostriction materials/cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the yttria-doped ceria that the volumetric concentration containing zirconium oxide is 65%, wherein the cerium base electricity
Solution chylema material is provided with described in being coated on the anode support layer of magnetostriction materials, then magnetostriction materials/cathode is lived
Property lamination cerium base electrolyte on, through excess temperature be 700 DEG C, after time 20h is low temperature co-fired, obtains structure and be followed successively by sun from top to bottom
Pole backing material；Magnetostrictive layer on the anode support layer is set；Cerium base electrolyte layer；Setting is in cerium base electricity
Solve the Conjugate ferrite magnetostrictive layer on matter layer；The solid of cathode active layers on the Conjugate ferrite magnetostrictive layer is set
Oxide fuel cell.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C, continue working 5 hours measure maximum output current density and reach 4.5A/cm2, voltage is
0.8V, peak power output reach 3.6W.
Embodiment 4
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually the combination of one or more of ZnO, and the ionic conduction is mutually layered perovskites；By anode branch
Timbering material is mixed with the carbon aerogels that aperture is 36 microns, and the mass ratio of porous carbon materials and the anode-supported material is 1：7,
Compression moulding, it is 1100 microns Anode supporter presomas to obtain thickness；
（2）It is 78 microns that thickness is prepared on the anode support presoma, and Conjugate ferrite mangneto of the consistency more than 99% is stretched
Compression material, high temperature sintering temperature are 1400 DEG C, sintering time 6h, obtain being provided with Conjugate ferrite magnetostriction materials after sintering
Anode support；
（3）It is 35 μm of cathode activity layer material Er ions bismuth oxide compression mouldings by thickness, obtains cathode active layers, then will be described
Conjugate ferrite magnetostriction materials slurry is coated on cathode active layers, is 1250 DEG C through excess temperature, the time of high temperature sintering is
15h high temperature sinterings obtain magnetostriction materials/cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the yttria-doped ceria that the volumetric concentration containing zirconium oxide is 55%, wherein the cerium base electricity
Solution chylema material is provided with described in being coated on the anode support layer of magnetostriction materials, then magnetostriction materials/cathode is lived
Property lamination cerium base electrolyte on, through excess temperature be 800 DEG C, after time 20h is low temperature co-fired, obtains structure and be followed successively by sun from top to bottom
Pole backing material；Magnetostrictive layer on the anode support layer is set；Cerium base electrolyte layer；Setting is in cerium base electricity
Solve the Conjugate ferrite magnetostrictive layer on matter layer；The solid of cathode active layers on the Conjugate ferrite magnetostrictive layer is set
Oxide fuel cell.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C, continue working 5 hours measure maximum output current density and reach 4.4A/cm2, voltage is
0.6V, peak power output reach 2.64W.
Embodiment 5
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually CuO, the ionic conduction be mutually the lanthanum manganate of strontium and chromium codope, La doped strontium titanates combination；It will be positive
Pole backing material is mixed with the porous T carbon materials that aperture is 65 microns, the quality of porous carbon materials and the anode-supported material
Than being 1：7, compression moulding, it is 1200 microns Anode supporter presomas to obtain thickness；
（2）It is 25 microns that thickness is prepared on the anode support presoma, and Conjugate ferrite mangneto of the consistency more than 99% is stretched
Compression material, high temperature sintering temperature are 1300 DEG C, and sintering time 18h obtains the anode for being provided with magnetostriction materials after sintering
Supporter；
（3）It is 72 μm of cathode activity layer material Er ions bismuth oxides and doped yttrium bismuth oxide compression moulding by thickness, obtains cathode
Active layer, then the Conjugate ferrite magnetostriction materials slurry is coated on cathode active layers, it is 1200 DEG C through excess temperature, it is high
The time of temperature sintering is 5-20h high temperature sinterings, obtains magnetostriction materials/cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the samarium neodymium codope cerium oxide that the volumetric concentration containing zirconium oxide is 55%, wherein the cerium
Base electrolyte slurry be coated in it is described be provided on the anode support layer of magnetostriction materials, then by magnetostriction materials/the moon
Extremely on activity lamination cerium base electrolyte, it is 790 DEG C through excess temperature, after the time is low temperature co-fired for 24 hours, obtains structure from top to bottom successively
For anode-supported material；Magnetostrictive layer on the anode support layer is set；Cerium base electrolyte layer；It is arranged in the cerium
Conjugate ferrite magnetostrictive layer on base electrolyte layer；Cathode active layers on the Conjugate ferrite magnetostrictive layer are set
Solid oxide fuel cell.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C, continue working 5 hours measure maximum output current density and reach 5.1 A/cm2, voltage
For 0.65V, peak power output reaches 3.32 W.
Comparative example 1
（1）It is molten according to doping concentration 15mol% and cerous nitrate preparation mixing with nitric acid dissolving with 10mol% gadolinium doped-cerias
Liquid；
（2）2-4 times to mixed solution ion total mole number is added citric acid, heats and is stirred until liquid changes at 200 DEG C
For sticky gel, continue to stir, heat, it is dry, until rapid burning obtains fine powder, by the fine powder of gained 850
DEG C sintering 10 hours, that is, obtain oxide fuel battery electrolyte material.
Conductivity is tested using DDSJ-308F type electric conductivity instrument, is sintered together with membrane electrode after test, is assembled
Fuel cell is obtained, hydrogen is fuel, and air is oxidant, under the conditions of test temperature is 600-720 DEG C, maximum output current
Density reaches 2.1 A/cm2, voltage 0.5V, peak power output reaches 1.05W.
Comparative example 2
（1）Anode-supported material is the electronics conduction mutually combination with ionic conduction phase composite materials and porous carbon materials, the electricity
Son conduction is mutually the combination of two kinds of CuO, ZnO, and the ionic conduction is mutually two kinds of the strontium titanates of La doped calcium titanate, La doped
Combination；Anode-supported material is mixed with the carbon aerogels that aperture is 80 microns, porous carbon materials and the anode-supported material
Mass ratio be 1：6, compression moulding, it is 500 microns Anode supporter presomas to obtain thickness；
（2）By the anode support presoma by high temperature sintering temperature be 1400 DEG C, sintering time 5h is obtained after sintering
It is provided with the anode support of magnetostriction materials；
（3）It is 50 μm of cathode activity layer material doped yttrium bismuth oxide compression mouldings by thickness, cathode active layers is obtained, through excess temperature
It it is 1350 DEG C, the time of high temperature sintering is 10h high temperature sinterings, obtains cathode active layers composite layer；
（4）By the cerium base electrolyte layer for the yttria-doped ceria that the volumetric concentration containing zirconium oxide is 45%, wherein the cerium base electricity
It solves chylema material to be coated on the anode support layer, then cathode activity is laminated on cerium base electrolyte, be 760 through excess temperature
DEG C, after time 12h is low temperature co-fired, obtain solid oxide fuel cell.
By single fuel cell manufactured in the present embodiment, using hydrogen as fuel, air is oxidant, is in test temperature
Test performance under the conditions of 600-720 DEG C measures maximum output current density and reaches 5 A/cm2, voltage 0.6V, maximum work output
Rate reaches 3W, and output current density is reduced to 2A/cm after 2 hours2, voltage is reduced to 0.3, and output power is reduced to 0.6W.
Claims (9)
1. a kind of solid oxide fuel cell of low-temperature stabilization, which is characterized in that include five layers from bottom to top：
Anode-supported material；
Magnetostrictive layer on the anode support layer is set：The magnetostrictive layer is Conjugate ferrite magnetostriction material
Material；
Cerium base electrolyte layer；
Conjugate ferrite magnetostrictive layer on the cerium base electrolyte layer is set；
Cathode active layers on the Conjugate ferrite magnetostrictive layer are set.
2. a kind of solid oxide fuel cell of low-temperature stabilization according to claim 1, which is characterized in that the anode
The thickness of supporting layer be 500-1800 micron, the anode-supported material be electronics conduction phase with ionic conduction phase composite materials and
The combination of porous carbon materials, the electronics conduction are mutually the combination of one or more of NiO, CuO, ZnO, the ion
Conduction is mutually the lanthanum manganate of strontium and chromium codope, in the strontium titanates and layered perovskites of La doped calcium titanate, La doped
A combination of one or more.
3. a kind of solid oxide fuel cell of low-temperature stabilization according to claim 1, which is characterized in that the ferro-cobalt
The thickness of oxysome magnetostriction materials is 5-120 microns, and consistency is more than 99%.
4. a kind of solid oxide fuel cell of low-temperature stabilization according to claim 1, which is characterized in that the cerium base
Electrolyte layer is one or more of gadolinium doped-ceria, yttria-doped ceria, samarium neodymium codope cerium oxide and oxidation
The combination of zirconium, the wherein volumetric concentration of zirconium oxide are 30%-65%.
5. a kind of solid oxide fuel cell of low-temperature stabilization according to claim 1, which is characterized in that the cathode
The thickness of active layer is 5-80 μm, and the cathode active layers are one kind in Er ions bismuth oxide and doped yttrium bismuth oxide.
6. a kind of preparation method of the solid oxide fuel cell of low-temperature stabilization, which is characterized in that specific preparation method is as follows：
（1）Anode-supported material is mixed with porous carbon materials, compression moulding obtains anode support presoma；
（2）The Conjugate ferrite magnetostriction materials are prepared on the anode support presoma, are set after high temperature sintering
It is equipped with the anode support of magnetostriction materials；
（3）By cathode activity layer material compression moulding, cathode active layers are obtained, then the Conjugate ferrite magnetostriction materials are starched
Material is coated on cathode active layers, by high temperature sintering, obtains magnetostriction materials/cathode active layers composite layer；
（4）The cerium base electrolyte slurry is provided with coated in described on the anode support layer of magnetostriction materials, then will
On magnetostriction materials/cathode activity lamination cerium base electrolyte, after low temperature co-fired, solid oxide fuel cell is obtained.
7. a kind of preparation method of the solid oxide fuel cell of low-temperature stabilization according to claim 6, feature exist
In the porous carbon materials are selected from the combination of one or more of porous T carbon materials, carbon foam, carbon aerogels, aperture
It is 30-80 microns.
8. a kind of preparation method of the solid oxide fuel cell of low-temperature stabilization according to claim 6, feature exist
In the mass ratio of the porous carbon materials and the anode-supported material is 1：6-9.
9. a kind of preparation method of the solid oxide fuel cell of low-temperature stabilization according to claim 6, feature exist
In step（2）With（3）Described in the temperature of high temperature sintering be 1200-1400 DEG C, time of high temperature sintering is 5-20h, step
（4）Described in low temperature co-fired temperature be 700-900 DEG C, time 5-30h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686986A (en) * | 2018-11-02 | 2019-04-26 | 全球能源互联网研究院有限公司 | A kind of unidirectional electron conducting solid oxide fuel cell and preparation method thereof |
| CN109768286A (en) * | 2018-12-21 | 2019-05-17 | 西安交通大学 | A kind of Direct Carbon Fuel Cells anode and its cell apparatus being made of no nickel composite material |
-
2018
- 2018-01-31 CN CN201810092997.6A patent/CN108288724A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686986A (en) * | 2018-11-02 | 2019-04-26 | 全球能源互联网研究院有限公司 | A kind of unidirectional electron conducting solid oxide fuel cell and preparation method thereof |
| CN109768286A (en) * | 2018-12-21 | 2019-05-17 | 西安交通大学 | A kind of Direct Carbon Fuel Cells anode and its cell apparatus being made of no nickel composite material |
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