CN108123158A - A kind of solid oxide fuel cell low-temp ceramics dielectric film and preparation method - Google Patents
A kind of solid oxide fuel cell low-temp ceramics dielectric film and preparation method Download PDFInfo
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- CN108123158A CN108123158A CN201711470715.3A CN201711470715A CN108123158A CN 108123158 A CN108123158 A CN 108123158A CN 201711470715 A CN201711470715 A CN 201711470715A CN 108123158 A CN108123158 A CN 108123158A
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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 a kind of solid oxide fuel cell low-temp ceramics dielectric film and preparation method, using Ce (NO3)3·6H2O is primary raw material, BaCO3And TiO2For doped raw material, by pulping, ball milling, α MnO are then added in2, aluminum phosphate wire mark film forming, be placed in batch-type furnace in 1,130 1170 DEG C of heat preservation sinterings, form α MnO2、BaTiO3Adulterate CeO2Dielectric film.The dielectric film is due to α MnO2Trigger BaTiO in 200 DEG C of phase transformations3Generate polarization so that electrolyte has significant electrical conductivity at 450 500 DEG C, reduces battery operating temperature, and BaTiO3Be introduced as oxonium ion provide conduction pathway, the present invention can overcome the defects of existing solid oxide fuel cell operating temperature is high, the startup time is long, the problem of ionic conductance is remarkably decreased caused by dielectric film can effectively be alleviated being reduced due to battery operating temperature is advantageously implemented the middle low temperature of solid oxide fuel cell and practical.
Description
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of solid oxide fuel cell low-temp ceramics electricity
Solve plasma membrane and preparation method.
Background technology
Due to non-renewable for traditional fossil fuel, and environmental pollution caused by during use is serious, seeks ring
The renewable sources of energy of guarantor's type are the severe tasks of 21 century facing mankind.Fuel cell (Fuel cell) is a kind of new energy
The chemical energy of fuel is directly converted into electric energy by source technology by electrochemical reaction, and fuel used is hydrogen, methanol and hydrocarbon
The hydrogen-rich materials such as class, there are no pollution to the environment and with high energy efficiency and high power density, therefore, fuel cell has
Have broad application prospects.
Solid oxide fuel cell (Solid Oxide Fuel Cell, SOFC) belongs to third generation fuel cell, is one
The chemical energy being stored in fuel and oxidant directly efficiently, is environmentally friendly changed into the complete solid of electric energy by kind under high temperature
State chemical generated device has high efficiency and fabulous long-term behaviour stability, without catalyst, also can significantly cut down system
Expense.Due to using soild oxide as electrolyte, the problems such as its electroless corrosion；Fuel tolerance is wide, edible
Hydrogen, CO, natural gas (methane), coal boil-off gas, hydrocarbon etc. make fuel.Traditional SOFC operating temperatures more than 750 DEG C,
Control is difficult, starts time length etc., and higher operation temperature can cause the range of choice of battery material narrow, electrode and electrolyte it
Between interfacial reaction occurs, the problems such as cell sealing is difficult, the cost of battery remains high, so as to limit the development in its market,
Therefore the reduction of the operating temperature, particularly electrolyte operating temperature of solid fuel cell is reduced, for promoting solid fuel electricity
Pond has and high practical value in the application of new-energy automobile.
Electrolyte is the most crucial components of SOFC, and charged transport property and hot expansion property not only directly affect battery
Operating temperature and energy conversion efficiency also determine the choosing of matched cathode and anode material and corresponding technology of preparing
It selects.In general, SOFC electrolytes need to have the following conditions：1）Ionic conductivity is high：Electrolyte membrance can be reduced
Ohmic resistance；2）Negligible electronic conductivity：Battery internal short-circuit electric current can be reduced； 3）Under oxidation and reducing atmosphere all
With preferable stability；4）High mechanical strength：Phenomena such as electrolyte cracking is not susceptible under fuel cell operating condition.
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
Electrical 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 substitution 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.
Chinese invention patent application number 200510011957.7 discloses a kind of for low-temperature solid oxide fuel cell
Zinc doping cerium oxide-inorganic salts composite electrolyte, mixed using the cerium oxide of zinc doping of direct low temperature synthesis with inorganic salts,
Two-phase or multiphase composite material after heat treatment formed reaches 1.02V in the open-circuit voltage of 600 DEG C of batteries, and output power reaches
To 600mWcm-2More than.But there is superior performance in 600 DEG C of batteries, when operating temperature continues to be reduced to 450-500 DEG C of temperature
Section, battery performance can not but ensure.
Chinese invention patent application number 200980131358.5 discloses one kind and is used on ceramics or metal surface deposit
The method of ceramic membrane, the method for especially depositing the ceramic membrane of submicron thickness, such as stable zirconium oxide of ceramic membrane and such as
The film of the ceria of the doping of CGO (cerium gadolinium oxide).The invention deposits at least double layer of metal oxide on the surface of a substrate
Crystalline ceramics are used to manufacture the fuel cell of high temperature and medium temperature operation, and also have the metal run in the range of 450 DEG C -650 DEG C
The intermediate temperature SOFC of support.But deposition at least double layer of metal oxide crystallization ceramics are needed in the program, the interface between film layer is not
It is transmitted beneficial to ion, and preparation process is complicated, is unfavorable for large-scale production application.
It is therefore proposed that a kind of process program is simply controllable, existing solid oxide fuel cell operating temperature is effectively overcome
The dielectric film and preparation process scheme of the defects of height, long startup time has pole to the reduction for promoting electrolyte operating temperature
High practical value.
The content of the invention
For the defects of existing solid oxide fuel cell operating temperature is high, the startup time is long, the present invention proposes a kind of
Solid oxide fuel cell low-temp ceramics dielectric film and preparation method can effectively alleviate dielectric film since battery works
The problem of ionic conductance is remarkably decreased caused by temperature reduces is advantageously implemented the middle low temperature of solid oxide fuel cell
With it is practical.
To solve the above problems, the present invention uses following technical scheme：
（1）Weigh 10-50 mass parts Ce (NO3)3·6H2O powders, 8-15 mass parts BaCO3Powder and 10-12 mass parts TiO2
Powder uniformly mixes, and is adding in the crosslinking agent of 1-3 mass parts and enough organic solvents by high energy ball mill ball milling, is obtaining
Precursor pulp；
（2）10-14 mass parts α-MnO are added in into precursor pulp2It is uniform by stirring to obtain with 2-5 mass parts aluminum phosphates
Slurry, then using be screen printed onto electrode both side surface film forming, at least print three times；
（3）The electrode printed is placed in high temperature box furnace, is heated up with 2-5 DEG C/min rates, respectively in 1130-1170
After when DEG C heat preservation sintering heat preservation 8-20 is small, room temperature is then down to 5 DEG C/min rates, obtains α-MnO2、BaTiO3Adulterate CeO2's
Dielectric film.
Preferably, the organic solvent be N, N- dimethyl acetamides, N, N- dimethylformamides, dimethyl sulfoxide (DMSO)
Or the mixed solution of the one or more kinds of compositions of tetrahydrofuran.
Preferably, the crosslinking agent for acrylic acid, acrylamide, dimethacrylate ethanedioic acid esters, acrylic acid second two
One kind in alkoxide.
Preferably, the rotating speed of the high energy ball mill is controlled in 800-1200rpm, and the time control of ball milling is when 2-5 is small.
Preferably, the viscosity of the precursor pulp is 5000-20000mPas, cerium oxide crystal grain grain in the slurry
Footpath is 20-500nm.
Preferably, the silk screen is made of metal silk screen, and screen diameter is 40-300 μm, and the silk-screen printing middle scraper is scraped
Speed control is moved in 1-2mm./s.
Preferably, silk-screen printing film forming thickness is 50-300 μm.
Preferably, step（3）Described in dielectric film inert gas shielding condition is passed through in high-temperature sintering process, it is described
Inert gas is argon gas, one kind in nitrogen, carbon dioxide, and acid-base neutralization is carried out to tail gas in the high-temperature sintering process
Processing, avoids Ce (NO3)3Decompose the sour gas pollution air generated.
On the other hand a kind of solid oxide fuel cell low-temp ceramics dielectric film is provided, by preceding claim side
Method is prepared.
For the defects of existing solid oxide fuel cell operating temperature is high, the startup time is long, doped cerium oxide can
The oxygen ionic conductivity greatly improved, and existing doping process scheme preparation condition is harsh, and running temperature section compared with
Height, in consideration of it, the present invention proposes a kind of solid oxide fuel cell low-temp ceramics dielectric film and preparation method, using Ce
(NO3)3·6H2O is primary raw material, BaCO3And TiO2For doped raw material, by pulping, ball milling, α-MnO are then added in2, phosphoric acid
Aluminium net is printed as film, is placed in batch-type furnace in 1130-1170 DEG C of heat preservation sintering, forms α-MnO2、BaTiO3Adulterate CeO2Electrolyte
Film.Barium titanate is a kind of typical ferroelectric, at room temperature with tetragonal, shows the stronger iron along c-axis spontaneous polarization
Electrically.Significant advantage of the present invention is to utilize α-MnO2Trigger BaTiO in 200 DEG C of phase transformations3Generate polarization so that electrolyte exists
About 450-500 DEG C has significant electrical conductivity, reduces battery operating temperature.And BaTiO3Be introduced as oxonium ion offer
Conduction pathway can effectively alleviate asking of being remarkably decreased of ionic conductance caused by dielectric film is reduced due to battery operating temperature
Topic is advantageously implemented the middle low temperature of solid oxide fuel cell and practical.
The battery material that the compound film electrode of fuel cell prepared by the present invention is obtained with gadolinium doped-ceria electrolyte
The test performance under the conditions of test temperature is 400-550 DEG C, as shown in table 1.
Table 1：
| Project | Electrical conductivity/Scm-1（450℃） | Peak power output/W |
| Electrolyte of the present invention | 0.95 | 18.4-28.5 |
| Gadolinium doped-ceria electrolyte | 0.08 | 6.55-10.35 |
The present invention provides a kind of preparation method of the compound film electrode of fuel cell, compared with prior art, the characteristics of protrusion
It is with excellent effect：
1st, dielectric film of the present invention is due to α-MnO2Trigger BaTiO in 200 DEG C of phase transformations3Generate polarization so that electrolyte exists
450-500 DEG C has significant electrical conductivity, and battery work is reduced for all solid state Oxide electrolyte materials of fuel cell
Temperature.
2、BaTiO3Be introduced as oxonium ion provide conduction pathway, can effectively alleviate dielectric film due to battery operating temperature
The problem of ionic conductance is remarkably decreased caused by reduction is advantageously implemented the middle low temperature and reality of solid oxide fuel cell
With change.
3rd, present invention process method is simple, reduces manufacture cost, promotes solid oxide fuel cell to low temperature, business
Industryization develops.
Specific embodiment
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
Scope be only limitted to following example.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）Weigh 10 mass parts Ce (NO3)3·6H2O powders, 15 mass parts BaCO3Powder and 12 mass parts TiO2Powder, uniformly
Mixing is N adding in 1 mass parts acrylic acid and 30 mass parts organic solvents, and N- dimethyl acetamides adjust high energy ball mill
Rotating speed control in 1200rpm, when 2 is small, by high energy ball mill ball milling, obtain viscosity is the time control of ball milling
5000mPas precursor pulps, cerium oxide size of microcrystal is 350nm in slurry；
（2）10 mass parts α-MnO are added in into precursor pulp2With 2 mass parts aluminum phosphates, uniformly starched by stirring to obtain
Material, then using electrode both side surface film forming is screen printed onto, silk screen is made of metal silk screen, and screen diameter is 300 μm, the silk screen
Scraping for printing middle scraper moves speed control in 1mm./s, at least prints three times, and silk-screen printing film forming thickness is 50 μm；
（3）The electrode printed is placed in high temperature box furnace, argon gas is passed through in high-temperature sintering process, with 2 DEG C/min
Rate heats up, respectively when 1130 DEG C of heat preservation sinterings heat preservation 20 is small after, room temperature is then down to 5 DEG C/min rates, obtain α-
MnO2、BaTiO3Adulterate CeO2Dielectric film, acid-base neutralization processing is carried out to tail gas in high-temperature sintering process, avoids Ce (NO3)3
Decompose the sour gas pollution air generated.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, the dielectric film in embodiment is assembled into flat
Board-like 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, are tested under the conditions of test temperature is 400-550 DEG C
Performance measures maximum output current and reaches 21 amperes, and peak power output reaches 26.3 watts, is 450-500 DEG C of tool in temperature
There is significant electrical conductivity.
Embodiment 2
（1）Weigh 50 mass parts Ce (NO3)3·6H2O powders, 8 mass parts BaCO3Powder and 12 mass parts TiO2Powder, uniformly
Mixing is adding in the acrylamide of 3 mass parts and 35 mass parts N, N- dimethylformamides by high energy ball mill ball milling, high
The rotating speed of energy ball mill is controlled in 800rpm, and the time control of ball milling obtains viscosity as 15000mPas presomas when 5 is small
Slurry, cerium oxide size of microcrystal is 500nm in slurry；
（2）4 mass parts α-MnO are added in into precursor pulp2With 5 mass parts aluminum phosphates, by the uniform slurry of stirring to obtain,
Again using electrode both side surface film forming is screen printed onto, silk screen is made of metal silk screen, and screen diameter is 40 μm, the silk-screen printing
Scraping for middle scraper moves speed control in 2mm./s, at least prints three times, and silk-screen printing film forming thickness is 100 μm；
（3）The electrode printed is placed in high temperature box furnace, inert gas shielding item is passed through in high-temperature sintering process
Part, the inert gas is argon gas, one kind in nitrogen, carbon dioxide, and tail gas is carried out in the high-temperature sintering process
Acid-base neutralization processing, avoids Ce (NO3)3The sour gas pollution air generated is decomposed, is heated up with 2 DEG C/min rates, existed respectively
After when 1150 DEG C of heat preservation sintering heat preservations 12 are small, room temperature is then down to 5 DEG C/min rates, obtains α-MnO2、BaTiO3Adulterate CeO2
Dielectric film.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, the dielectric film in embodiment is assembled into flat
Board-like 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, are tested under the conditions of test temperature is 400-550 DEG C
Performance measures maximum output current and reaches 18 amperes, and peak power output reaches 20.7 watts.
Embodiment 3
（1）Weigh 18 mass parts Ce (NO3)3·6H2O powders, 12 mass parts BaCO3Powder and 11 mass parts TiO2Powder, uniformly
Mixing, it is molten in the mixing for adding in the dimethacrylate ethanedioic acid ester of 1.5 mass parts and dimethyl sulfoxide (DMSO) and tetrahydrofuran composition
Liquid, by high energy ball mill ball milling, the rotating speed of high energy ball mill is controlled in 1000rpm, and the time control of ball milling is obtained when 3 is small
It is 10000mPas precursor pulps to viscosity, cerium oxide size of microcrystal is 80nm in slurry；
（2）12 mass parts α-MnO are added in into precursor pulp2With 4 mass parts aluminum phosphates, uniformly starched by stirring to obtain
Material, then using electrode both side surface film forming is screen printed onto, silk screen is made of metal silk screen, and screen diameter is 120 μm, the silk screen
Scraping for printing middle scraper moves speed control in 1.2mm./s, at least prints three times, and silk-screen printing film forming thickness is 150 μm；
（3）The electrode printed is placed in high temperature box furnace, nitrogen is passed through in high-temperature sintering process, with 4 DEG C/min
Rate heats up, respectively when 1140 DEG C of heat preservation sinterings heat preservation 16 is small after, room temperature is then down to 5 DEG C/min rates, obtain α-
MnO2、BaTiO3Adulterate CeO2Dielectric film, acid-base neutralization processing is carried out to tail gas in the high-temperature sintering process, avoids Ce
(NO3)3Decompose the sour gas pollution air generated.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, the dielectric film in embodiment is assembled into flat
Board-like 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, are tested under the conditions of test temperature is 400-550 DEG C
Performance measures maximum output current and reaches 22 amperes, and peak power output reaches 28.5 watts, and Current Voltage is surveyed in embodiment
Test result is as shown in table 2.
Embodiment 4
（1）Weigh 23 mass parts Ce (NO3)3·6H2O powders, 10 mass parts BaCO3Powder and 11 mass parts TiO2Powder, uniformly
Mixing is adding in the acrylic acid ethylene glycol esters and 42 mass parts N, N- dimethylformamides of 1-3 mass parts, by high-energy ball milling
The rotating speed of machine is controlled in 900rpm, and when 3.5 is small, by high energy ball mill ball milling, obtain viscosity is the time control of ball milling
12000mPas precursor pulps, cerium oxide size of microcrystal is 420nm in slurry；
（2）11 mass parts α-MnO are added in into precursor pulp2With 4 mass parts aluminum phosphates, uniformly starched by stirring to obtain
Material, then using electrode both side surface film forming is screen printed onto, silk screen is made of metal silk screen, and screen diameter is 240 μm, the silk screen
Scraping for printing middle scraper moves speed control in 1mm./s, at least prints three times, and silk-screen printing film forming thickness is 120 μm；
（3）The electrode printed is placed in high temperature box furnace, inert gas shielding item is passed through in high-temperature sintering process
Part, the inert gas is argon gas, one kind in nitrogen, carbon dioxide, and tail gas is carried out in the high-temperature sintering process
Acid-base neutralization processing, avoids Ce (NO3)3The sour gas pollution air generated is decomposed, is heated up with 2 DEG C/min rates, existed respectively
After when 1160 DEG C of heat preservation sintering heat preservations 16 are small, room temperature is then down to 5 DEG C/min rates, obtains α-MnO2、BaTiO3Adulterate CeO2
Dielectric film.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, the dielectric film in embodiment is assembled into flat
Board-like 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, are tested under the conditions of test temperature is 400-550 DEG C
Performance measures maximum output current and reaches 19 amperes, and peak power output reaches 22.8 watts.
Embodiment 5
（1）Weigh 24 mass parts Ce (NO3)3·6H2O powders, 14.5 mass parts BaCO3Powder and 10 mass parts TiO2Powder,
Even mixing passes through high energy ball mill ball milling, high-energy ball milling in the acrylic acid of 3 mass parts of addition and the dimethyl sulfoxide (DMSO) of 30 mass parts
The rotating speed of machine is controlled in 1050rpm, and the time control of ball milling obtains viscosity as 12000mPas forerunner's somaplasm when 3.5 is small
Expect, cerium oxide size of microcrystal is 120nm in slurry；
（2）10-14 mass parts α-MnO are added in into precursor pulp2It is uniform by stirring to obtain with 2-5 mass parts aluminum phosphates
Slurry, then using be screen printed onto electrode both side surface film forming, silk screen be made of metal silk screen, screen diameter be 230 μm, it is described
Scraping for silk-screen printing middle scraper moves speed control in 1.6mm./s, at least prints three times, and silk-screen printing film forming thickness is 270 μm；
（3）The electrode printed is placed in high temperature box furnace, inert gas shielding item is passed through in high-temperature sintering process
Part, the inert gas is argon gas, one kind in nitrogen, carbon dioxide, and tail gas is carried out in the high-temperature sintering process
Acid-base neutralization processing, avoids Ce (NO3)3The sour gas pollution air generated is decomposed, is heated up with 3 DEG C/min rates, existed respectively
After when 1160 DEG C of heat preservation sintering heat preservations 16 are small, room temperature is then down to 5 DEG C/min rates, obtains α-MnO2、BaTiO3Adulterate CeO2
Dielectric film.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, the dielectric film in embodiment is assembled into flat
Board-like 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, are tested under the conditions of test temperature is 400-550 DEG C
Performance measures maximum output current and reaches 20 amperes, and peak power output reaches 18.4 watts.
Comparative example
（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）Citric acid is added in 2-4 times of mixed solution ion total mole number, heated at 200 DEG C and is stirred until liquid changes
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 it is small when, that is, obtain oxide fuel battery electrolyte material.
Electrical conductivity is tested using DDSJ-308F type electric conductivity instrument, is sintered after test together with membrane electrode, is assembled
Into flat 5 × 5cm2Fuel cell, hydrogen are fuel, and air is oxidant, under the conditions of test temperature is 400-550 DEG C,
Peak power output is 6.55-10.35W, and record parameter is as shown in table 3.
2 embodiment of table, 1 test performance parameter
| Temperature DEG C | Open-circuit voltage（V） | Electric current（A） | Electrical conductivity（S/cm） |
| 550 | 1.60 | 17 | 0.74 |
| 500 | 1.62 | 21 | 0.91 |
| 450 | 1.64 | 22 | 0.95 |
| 400 | 1.61 | 15 | 0.60 |
3 comparative example test performance parameter of table
| Temperature DEG C | Open-circuit voltage（V） | Electric current（A） | Electrical conductivity（S/cm） |
| 550 | 1.25 | 15 | 0.48 |
| 500 | 1.01 | 10 | 0.31 |
| 450 | 0.84 | 9 | 0.08 |
| 400 | 0.85 | 6 | 0.002 |
Claims (9)
1. a kind of solid oxide fuel cell preparation method of low-temp ceramics dielectric film, which is characterized in that specific to prepare
Method is as follows：
（1）Weigh 10-50 mass parts Ce (NO3)3·6H2O powders, 8-15 mass parts BaCO3Powder and 10-12 mass parts TiO2Powder
Body uniformly mixes, and is adding in the crosslinking agent of 1-3 mass parts and the organic solvent of 30-45 mass parts by high energy ball mill ball milling,
Obtain precursor pulp；
（2）10-14 mass parts α-MnO are added in into precursor pulp2It is uniform by stirring to obtain with 2-5 mass parts aluminum phosphates
Slurry, then using electrode both side surface film forming is screen printed onto, at least print three times；
（3）The electrode printed is placed in high temperature box furnace, is heated up with 2-5 DEG C/min rates, respectively in 1130-1170
After when DEG C heat preservation sintering heat preservation 8-20 is small, room temperature is then down to 5 DEG C/min rates, obtains α-MnO2、BaTiO3Adulterate CeO2's
Dielectric film.
2. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
Be characterized in that, the organic solvent be N, N- dimethyl acetamides, N, N- dimethylformamides, dimethyl sulfoxide (DMSO) or tetrahydrochysene
The mixed solution of the one or more kinds of compositions of furans.
3. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, the crosslinking agent is acrylic acid, acrylamide, dimethacrylate ethanedioic acid esters, acrylic acid ethylene glycol esters
In one kind.
4. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, the rotating speed of the high energy ball mill is controlled in 800-1200rpm, and the time control of ball milling is when 2-5 is small.
5. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, the viscosity of the precursor pulp is 5000-20000mPas, and cerium oxide size of microcrystal is 20- in the slurry
500nm。
6. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, the silk screen is made of metal silk screen, and screen diameter is 40-300 μm, and the silk-screen printing middle scraper scrapes shifting speed
Control is in 1-2mm./s.
7. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, silk-screen printing film forming thickness is 50-300 μm.
8. a kind of preparation method of solid oxide fuel cell low-temp ceramics dielectric film as described in claim 1,
It is characterized in that, step（3）Described in dielectric film inert gas shielding condition, the indifferent gas are passed through in high-temperature sintering process
Body is argon gas, one kind in nitrogen, carbon dioxide, and acid-base neutralization processing is carried out to tail gas in the high-temperature sintering process,
Avoid Ce (NO3)3Decompose the sour gas pollution air generated.
9. a kind of solid oxide fuel cell low-temp ceramics dielectric film, which is characterized in that by any power of claim 1-8
Method described in is prepared.
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