CN102683721B - A kind of Solid Oxide Fuel Cell, functional gradient composite cathode and preparation method - Google Patents
A kind of Solid Oxide Fuel Cell, functional gradient composite cathode and preparation method Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 71
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 110
- 239000011651 chromium Substances 0.000 claims abstract description 84
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
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- 239000003792 electrolyte Substances 0.000 abstract description 12
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- 230000003197 catalytic effect Effects 0.000 description 11
- 239000002346 layers by function Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910017060 Fe Cr Inorganic materials 0.000 description 9
- 229910002544 Fe-Cr Inorganic materials 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
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- 229910000480 nickel oxide Inorganic materials 0.000 description 6
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- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 241000968352 Scandia <hydrozoan> Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- -1 oxonium ion Chemical class 0.000 description 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
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- 229910002074 (La0.8Sr0.2)0.95MnO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to a kind of Solid Oxide Fuel Cell, functional gradient composite cathode and preparation method.A kind of Solid Oxide Fuel Cell functional gradient composite cathode, comprising: material is LNF-doped Ce O
2anti-chromium poison layer; Be positioned at that anti-chromium poisons on layer, material is LSM-doped Ce O
2active layer; Be positioned on active layer, material is the current collection layer of LSM.Prepare a method for above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode, comprise the following steps: slurry a) anti-chromium being poisoned layer to be attached on dielectric substrate and after drying, namely to make anti-chromium and poison layer; B) slurry of active layer is attached to anti-chromium to poison on layer and after drying, namely to make active layer; C) slurry of current collection layer to be attached on active layer and after drying, namely to make current collection layer, obtain base substrate; D) by blank sintering.Present invention reduces high-volatile CrO
3and CrO
2(OH)
2chromium deposition in cathode/electrolyte interface.
Description
Technical field
The present invention relates to a kind of Solid Oxide Fuel Cell, particularly relate to a kind of Solid Oxide Fuel Cell functional gradient composite cathode; The invention still further relates to the preparation method of this Solid Oxide Fuel Cell functional gradient composite cathode.
Background technology
At present, in the evolution of Solid Oxide Fuel Cell (SolidOxideFuelCell, SOFC), people more and more recognize the importance reducing battery operating temperature.If battery operating temperature can be reduced to middle temperature (700 ~ 800 DEG C), then can improve the stability of electrode, reduce thermal stress, extending battery life, cheap metal alloy also can be used as the bipolar plate material of battery.
In various metal alloy, containing Cr metal alloy because there is low, the easy processing of cost, electronic conductivity and thermal conductivity is high, mechanical stability is high, the advantage such as high temperature resistant and anti-oxidant and become the most promising bipolar plate material.Under cathode oxidation atmosphere, because Cr is preferentially oxidized to chrome green Cr
2o
3(solid-state) and at the very thin fine and close diaphragm of Surface Creation one deck of alloy.But, when by containing Cr metal alloy be used for the bipolar plates of SOFC time, the volatilization of high-valence state Cr compound is one of problem needing emphasis to consider.As under the oxidizing atmosphere of cathode side, particularly deposit in case at steam, Cr base alloy easily generates high-volatile chromium trioxide CrO
3(gaseous state) and chromic acid CrO
2(OH)
2(gaseous state) etc.The volatilization of Cr not only can accelerate Cr
2o
3the growth of oxide-film, and Cr can be caused to the diffusion of porous cathode.Find by literature search, the people such as TeruhisaHorita deliver " ChromiumPoisoningandDegradationat (La, Sr) MnO
3and (La, Sr) FeO
3cathodesforSolidOxideFuelCells " (Solid Oxide Fuel Cell (La, Sr) MnO
3(La, Sr) FeO
3the chromium poisoning of cathode material and hydraulic performance decline) literary composition, see " JournalofTheElectrochemicalSociety " (electrochemistry meeting will) 157 (5) (2010) B614-B620.This article introduce: when have electric current by time, at (La
0.8sr
0.2)
0.95mnO
3negative electrode/Ce
0.8gd
0.2o
2the Cr compound of electrolyte interface place high-valence state is reduced to Cr
2o
3, the Cr of low electric conductivity on the one hand
2o
3generation and gathering can reduce the electric output performance of SOFC, CrO on the other hand
3(gaseous state), chromic acid CrO
2(OH)
2(gaseous state) and Cr
2o
3with cathode material (La, Sr) MnO
3there is the Spinel (Cr, Mn) that chemical reaction generates insulation
3o
4s (), can make the performance of battery sharply decline equally, " Cr is poisoning " phenomenon of Here it is negative electrode.
Therefore, classical sofc cathode material (La, Sr) MnO
3anti-Cr to poison performance be problem demanding prompt solution.The people such as S.P.Jiang deliver " La (Ni, Fe) O
3asacathodematerialwithhightolerancetochromiumpoisoningfo rsolidoxidefuelcells " (cathode material for solid-oxide fuel cell La (Ni, the Fe) O that anti-chromium poisons
3) literary composition, see " JournalofPowerSources " (power technology) 170 (2007) 61-66.This article describes and adopts synthesis by solid state reaction to prepare LaNi
0.6fe
0.4o
3(La
0.8sr
0.2)
0.9mnO
3two kinds of cathode materials, and have studied its performance when directly contacting with Fe-Cr alloy connector.Research shows LaNi
0.6fe
0.4o
3have than (La
0.8sr
0.2)
0.9mnO
3more stable chemical property, at LaNi
0.6fe
0.4o
3surface and LaNi
0.6fe
0.4o
3/ YSZ interface (YSZ: the zirconia of stabilized with yttrium oxide) there is the Cr of minute quantity to deposit, and at (La
0.8sr
0.2)
0.9mnO
3there is a large amount of Cr depositions and Spinel (Cr, Mn) in/YSZ interface
3o
4(s), therefore LaNi
0.6fe
0.4o
3that very potential anti-chromium poisons sofc cathode material.However, La (Ni, Fe) O
3under identical sintering temperature, than (La, Sr) MnO of classics
3more easily and ZrO
2base electrolyte react, as in temperature higher than LaNi during 1000 ° of C
0.6fe
0.4o
3and ZrO namely
2base electrolyte reacts and generates the La of insulation
2zr
2o
7, significantly reduce battery performance.On the other hand, due to the characteristic of LNF material itself, as LNF cathode material reoxidizing and the decline of oxygen vacancy concentration subsequently at the working temperature, the initial performance of LNF negative electrode is caused to be not very well (see S.I.Hashimoto, K.Kammer, P.H.Larsen, F.W.Poulsen, M.Mogensen, SolidStateIonics176 (2005) 1013).Author is application of cold temperature combustion synthesis LaNi once
0.6fe
0.4o
3cathode material, with ScSZ (Sc
0.1zr
0.9o
1.95) electrolyte makes the symmetrical system of bipolar electrode, test cathode material is under the condition directly contacted with Fe-Cr alloy, and under 750 ° of C open-circuit condition during long-play, Fe-Cr alloy is to LaNi
0.6fe
0.4o
3the impact of cathode material chemical property.Found that, when 750 DEG C cathodic polarization resistance by 0.70 Ω cm
2be increased to the 42.86 Ω cm of 370h
2.SEM finds, LaNi
0.6fe
0.4o
3/ ScSZ interface deposits the Cr of low electric conductivity
2o
3, slow down the diffusion of active particle at three phase boundary, add cathodic polarization resistance.
Therefore, as the cathode material that anti-chromium poisons, La (Ni, Fe) O
3performance also needs further improvement; As the cathode material of high-performance classics, (La, Sr) MnO
3performance also needs further improvement.
Summary of the invention
A first aspect of the present invention object is for above the deficiencies in the prior art, adopt function gradient structure design method, by high for catalytic activity known at present, electronic conductivity is high, the cathode material La of good stability
0.8sr
0.2mnO
3(LSM) the cathode material LaNi that, catalytic performance is excellent, electronic conductivity is high, anti-chromium poisons excellent performance
0.6fe
0.4o
3(LNF), and catalytic performance is excellent, has that outstanding oxonium ion stores, a doped Ce O of release and transmittability
2three kinds of candidate materials combine, anticathode multiple requirement is born by different functional layers, and each functional layer is cooperatively interacted, utilize synergy to reach the effect of mutual supplement with each other's advantages, thus both can not affect catalytic performance and the electric conductivity of negative electrode, can significantly reduce high-volatile CrO again
3and CrO
2(OH)
2chromium deposition in cathode/electrolyte interface, improves the redox reactions dynamic performance of functionally gradient negative electrode, thus improves the performance of SOFC.
The present invention solves the problems of the technologies described above by the following technical solutions, reaches object of the present invention:
A kind of Solid Oxide Fuel Cell functional gradient composite cathode, comprising:
Anti-chromium poisons layer, and the material that described anti-chromium poisons layer is LNF-doped Ce O
2(this anti-chromium poisons layer and also can be described as LNF-doped Ce O
2layer), described anti-chromium poisons layer and is positioned on dielectric substrate.
Active layer, the material of described active layer is LSM-doped Ce O
2(this active layer also can be described as LSM-doped Ce O
2), described active layer is positioned at described anti-chromium and poisons on layer;
Current collection layer, the material of described current collection layer is LSM (this current collection layer also can be described as LSM layer), and described current collection layer is positioned on described active layer.
When the present invention specifically implements, preferably, described LNF-doped Ce O
2in, LNF and doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2.
When the present invention specifically implements, preferably, described LSM-doped Ce O
2in, LSM and doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2.
When the present invention specifically implements, preferably, described LNF-doped Ce O
2in doped Ce O
2, and described LSM-doped Ce O
2in doped Ce O
2, Doped ions is Gd
3+or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9.
When the present invention specifically implements, preferably, the thickness that described anti-chromium poisons layer is 8 ~ 10 microns, and the thickness of described active layer is 8 ~ 10 microns, and the thickness of described current collection layer is 8 ~ 10 microns.
When the present invention specifically implements, preferably, described doped Ce O
2for doped Ce O
2nano particle.
A second aspect of the present invention object is to propose a kind of Solid Oxide Fuel Cell.
A kind of Solid Oxide Fuel Cell, comprise dielectric substrate and negative electrode, described negative electrode is positioned on described dielectric substrate, it is characterized in that, the material of described dielectric substrate is ScSZ, described negative electrode is Solid Oxide Fuel Cell functional gradient composite cathode as above, and described anti-chromium poisons layer and is positioned on described dielectric substrate.
When the present invention specifically implements, the material of dielectric substrate described in the present invention is any electrolyte being applicable to Solid Oxide Fuel Cell, is preferably ScSZ (zirconia of scandia stabilized).
Solid Oxide Fuel Cell functional gradient composite cathode of the present invention jointly can be arranged in pairs or groups with any anode of solid oxide fuel cell and be used.
A third aspect of the present invention object is the method proposing the above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode of preparation.Especially, the method is applicable to suitability for industrialized production and prepares that the anti-chromium of large scale poisons, high performance Solid Oxide Fuel Cell functional gradient composite cathode; The method technique is simple, manufacturing cycle is short, with low cost, be suitable for commercial application.
Prepare a method for above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode, comprise the following steps:
A), by LNF and doped Ce O
2mixture and terpinol be mixed into slurry, this slurry to be attached on described dielectric substrate and after drying, namely making material is LNF-doped Ce O
2described anti-chromium poison layer;
B), by LSM and doped Ce O
2mixture and terpinol be mixed into slurry, this slurry is attached to described anti-chromium and poisons on layer and after drying, namely making material is LSM-doped Ce O
2described active layer;
C), by LSM and terpinol be mixed into slurry, this slurry be attached on described active layer and after drying, namely make the described current collection layer that material is LSM, obtain the base substrate of described Solid Oxide Fuel Cell functional gradient composite cathode;
D), by the blank sintering of described Solid Oxide Fuel Cell functional gradient composite cathode, described Solid Oxide Fuel Cell functional gradient composite cathode is namely obtained.
When the present invention specifically implements, preferably, described step a) in, described LNF and described doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2, described LNF and doped Ce O
2mixture and the mass ratio of described terpinol be 1:0.7 ~ 1; Describedly be attached on described dielectric substrate by this slurry, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
When the present invention specifically implements, preferably, described step b) in, described LSM and described doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2, described LSM and doped Ce O
2mixture and the mass ratio of described terpinol be 1:0.7 ~ 1; Describedly this slurry is attached to described anti-chromium and poisons on layer, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
When the present invention specifically implements, preferably, described step c) in, the mass ratio of described LSM and described terpinol is 1:0.7 ~ 1; Describedly be attached on described active layer by this slurry, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
When the present invention specifically implements, preferably, described steps d) in, the temperature of described sintering is 1050 DEG C ~ 1100 DEG C, and the time of described sintering is 2 hours ~ 3 hours.
Preparation method of the present invention preferred implementation is: the LNF-doped Ce O by mass ratio being 1:1
2mixture (LNF: doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2) be mixed into slurry with terpinol, to be deposited on dielectric substrate that material is ScSZ through silk screen print method and in 110 DEG C of dryings after 0.5 hour, namely to make anti-chromium and poison layer; Then be the LSM-doped Ce O of 1:1 by mass ratio
2mixture (LSM and doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2) be mixed into slurry with terpinol, be deposited on described anti-chromium through silk screen print method and poison on layer and after 0.5 hour, namely to make active layer in 110 DEG C of dryings; Be finally that LSM and the terpinol of 1:1 is mixed into slurry by mass ratio, be deposited on described active layer through silk screen print method and after 0.5 hour, namely make LSM current collection layer in 110 DEG C of dryings, obtaining the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode; Namely the base substrate of described Solid Oxide Fuel Cell functional gradient composite cathode is obtained described Solid Oxide Fuel Cell functional gradient composite cathode for 2 hours at 1100 DEG C of sintering.
Silk screen print method of the present invention is silk screen print method general in prior art.
The sintering that the present invention mentions sinters in atmosphere.
Advantage of the present invention is:
Adopt the method for functional gradient composite cathode structural design, by high for catalytic activity known at present, electronic conductivity is high, the cathode material La of good stability
0.8sr
0.2mnO
3(LSM) the cathode material LaNi that, catalytic performance is excellent, electronic conductivity is high, anti-chromium poisons excellent performance
0.6fe
0.4o
3(LNF) and catalytic performance good, have that outstanding oxonium ion stores, the doped Ce O of release and transmittability
2three kinds of candidate materials combine, anticathode multiple requirement is born by different functional layers, and each functional layer is cooperatively interacted, utilize synergy to reach the effect of mutual supplement with each other's advantages, thus both can not affect catalytic performance and the electric conductivity of negative electrode, can significantly reduce high-volatile CrO again
3and CrO
2(OH)
2chromium deposition in cathode/electrolyte interface, improves the redox reactions dynamic performance of composite cathode, thus improves the performance of SOFC.
Main raw material(s) NiO (nickel oxide) of the present invention, YSZ (zirconia of stabilized with yttrium oxide), ScSZ (zirconia of scandia stabilized), its average grain diameter is 0.5-10 micron.Form each functional layer material La of functional gradient composite cathode
0.8sr
0.2mnO
3, LaNi
0.6fe
0.4o
3and doped Ce O
2be all adopt low-temperature combustion method synthesis, this method has successfully been applied to many simple or complicated compound systems, and getting final product easy at a lower temperature and prepare oxide ultra fine powder efficiently, is that a kind of advanced ceramics of novelty prepares approach.The oxide La that the present invention adopts low-temperature combustion method to synthesize
0.8sr
0.2mnO
3powder, LaNi
0.6fe
0.4o
3powder and doped Ce O
2powder, its particle size is nanoscale (< 100nm), and the specific area of powder is large.Like this, each functional layer of functional gradient composite cathode can keep good loose structure and preferably redox reactions dynamic performance as 1000 ~ 1100 DEG C of sintering at a lower temperature, and anti-chromium poisons a layer LNF-doped Ce O
2can also good contact be kept with electrolyte ScSZ and chemical reaction not occur;
Solid Oxide Fuel Cell functional gradient composite cathode of the present invention, functionally analyzes, and LNF has higher conductivity and the catalytic activity to Electrochemical reduction of oxygen reaction, and splendid anti-chromium is poisoning; Doped Ce O
2mix, add the ionic conductivity of cathode material, the doped Ce O that especially particle diameter is less
2powder forms ionic-electronic conductive path at cathode internal after being wrapped in and the larger LNF powder granule of particle diameter (sintering at 1100 DEG C) sintering, and inhibits LNF and electrolyte ScSZ that chemical reaction occurs on the one hand and generates the La insulated
2zr
2o
7prevent cathode ohmic resistance to increase, too increase the three-phase reaction interface of LNF and electrolyte ScSZ on the other hand, cathodic polarization resistance is significantly reduced, thus improve the electrochemical catalysis performance of LNF, and effectively can prevent the effect that Fe-Cr alloy poisons LNF negative electrode.Therefore doped Ce O
2relative amount, LNF and doped Ce O
2sintering temperature (LNF and doped Ce O in other words
2crystallite dimension) etc. determine the catalytic activity of this functional layer and anti-chromium poisoning, this just requires LNF and doped Ce O
2mass ratio, LNF and doped Ce O
2the technological parameter such as sintering temperature be optimized.Change CeO
2in Doped ions, thus adjusting its oxygen ionic conductivity etc., is also one of approach of optimizing of catalytic activity.A layer LNF-doped Ce O is poisoned for improving anti-chromium
2electrochemical catalysis performance and performance is poisoned to the anti-chromium of Fe-Cr alloy, in this functional layer, doped Ce O
20.2 ~ 0.3: 0.8 ~ 0.7, CeO is preferably with the mass ratio of LNF
2in Doped ions be preferably Gd
3+or Sm
3+, the sintering temperature of LNF powder is preferably 1100 DEG C, doped Ce O
2the sintering temperature of powder is preferably 600 DEG C, the average particle size of preferred LNF powder: doped Ce O
2average particle size=9 ~ 16 of powder, anti-chromium poisons a layer LNF-doped Ce O
2sintering temperature be preferably 1100 DEG C.
LSM had both had very high ionic conductivity, there is again sufficiently high electron conduction, and there is very high activity, but because it at high temperature can react with electrolyte ScSZ, and do not possess the performance that anti-chromium poisons, the present invention it can be used as the functional layer at top, the main effect playing its high conductivity.For improving the performance of current collection layer LSM, in this functional layer, the sintering temperature of LSM powder is 1200 DEG C.Be LSM-doped Ce O for material
2active layer, its polarization overpotential is little, and reactivity is strong, but does not possess the performance that anti-chromium poisons, and it is LNF-doped Ce O that the present invention is placed on material
2anti-chromium poison under the protection of layer, hope give full play to LSM-doped Ce O
2to the electrochemical catalysis performance of redox reactions.For improving the electrochemical catalysis performance of active layer, in this functional layer, doped Ce O
20.2 ~ 0.3: 0.8 ~ 0.7, CeO is preferably with the mass ratio of LSM
2in Doped ions be preferably Gd
3+or Sm
3+, the sintering temperature of LSM powder is preferably 700 DEG C, doped Ce O
2the sintering temperature of powder is preferably 600 DEG C, and the sintering temperature of active layer is preferably 1100 DEG C.Solid Oxide Fuel Cell functional gradient composite cathode prepared by the present invention has excellent anti-chromium and poisons performance and electrochemical catalysis performance, is convenient to the power density improving fuel cell, ensures the stable operation of fuel cell.The uniform large area LNF-doped Ce O of preparation method's energy Forming Quality adopted
2/ LSM-doped Ce O
2/ LSM Solid Oxide Fuel Cell functional gradient composite cathode, technique is simple, possesses low-cost advantage, easily realizes industrialization.
Be described further to the technique effect of design of the present invention, concrete structure and generation below, understand object of the present invention, characteristic sum effect fully to make those skilled in the art.
Embodiment
A kind of Solid Oxide Fuel Cell, comprise dielectric substrate and negative electrode, negative electrode is positioned on dielectric substrate, and the material of dielectric substrate is ScSZ, and negative electrode is a kind of Solid Oxide Fuel Cell functional gradient composite cathode as described in this embodiment.
A kind of Solid Oxide Fuel Cell functional gradient composite cathode, comprising:
Anti-chromium poisons layer, and the material that anti-chromium poisons layer is LNF-doped Ce O
2, in Solid Oxide Fuel Cell, anti-chromium poisons layer and is positioned on dielectric substrate, and dielectric substrate is positioned on anode layer; Preferably, LNF-doped Ce O
2in, LNF and doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2; LNF-doped Ce O
2in doped Ce O
2, preferably, Doped ions is Gd
3+or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9; The thickness that anti-chromium poisons layer is preferably 8 ~ 10 microns;
Active layer, the material of active layer is LSM-doped Ce O
2, active layer is positioned at anti-chromium and poisons on layer; Preferably, LSM-doped Ce O
2in, LSM and doped Ce O
2mass ratio be 7 ~ 8: 3 ~ 2; LSM-doped Ce O
2in doped Ce O
2, preferably, Doped ions is Gd
3+or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9; The thickness of active layer is preferably 8 ~ 10 microns;
Current collection layer, the material of current collection layer is LSM, and current collection layer is positioned on active layer; The thickness of current collection layer is preferably 8 ~ 10 microns.
The preparation method of above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode, comprises the following steps:
A), by LNF and doped Ce O
2mixture (by LNF and doped Ce O
2directly to mix) be mixed into slurry with terpinol, this slurry to be attached on dielectric substrate and after drying, namely making material is LNF-doped Ce O
2anti-chromium poison layer; LNF and doped Ce O
2mass ratio be preferably 7 ~ 8: 3 ~ 2; LNF and doped Ce O
2mixture and the mass ratio of terpinol be preferably 1:0.7 ~ 1; Be attached on dielectric substrate by this slurry, the method used is silk screen print method; Dry temperature is preferably 100 DEG C ~ 120 DEG C, and the dry time is preferably 0.5 hour ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as be evaporated by moisture);
B), by LSM and doped Ce O
2mixture (by LSM and doped Ce O
2directly to mix) be mixed into slurry with terpinol, this slurry is attached to anti-chromium and poisons on layer and after drying, namely making material is LSM-doped Ce O
2active layer; LSM and doped Ce O
2mass ratio be preferably 7 ~ 8: 3 ~ 2, LSM and doped Ce O
2mixture and the mass ratio of terpinol be preferably 1: 0.7 ~ 1; This slurry is attached to anti-chromium to be poisoned on layer, and the method used is silk screen print method; Dry temperature is preferably 100 DEG C ~ 120 DEG C, and the dry time is preferably 0.5 hour ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as by moisture drying);
C), by LSM and terpinol be mixed into slurry, this slurry be attached on active layer and after drying, namely make the current collection layer that material is LSM, obtain the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode; The mass ratio of LSM and terpinol is preferably 1: 0.7 ~ 1; Be attached on active layer by this slurry, the method used is silk screen print method; Dry temperature is preferably 100 DEG C ~ 120 DEG C, and the dry time is preferably 0.5 hour ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as by moisture drying);
D), by the blank sintering of Solid Oxide Fuel Cell functional gradient composite cathode, Solid Oxide Fuel Cell functional gradient composite cathode is namely obtained; The temperature of sintering is preferably 1050 DEG C ~ 1100 DEG C, and the time of sintering is preferably 2 hours ~ 3 hours.
The sintering mentioned in this embodiment, is and sinters in atmosphere.
Raw material used in the following examples is described below (specifically do not indicate the chemical reagent of purity in following raw material, be analysis pure):
ScSZ powder used is Zr
0.89sc
0.1ce
0.01o
2(ScSZ, manufacturer is DaiichiKigensoKagakuKogyo, Japan);
Butanone: analyze pure, purity >=99%;
Ethanol: analyze pure, purity >=99.7%;
Triethanolamine: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Polyvinyl butyral resin: aviation-grade, butyraldehyde base 45% ~ 49%, manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Polyethylene glycol: chemical pure, mean molecule quantity 190 ~ 210, manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
NiO: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
YSZ:Zr
0.92y
0.08o
2(YSZ, manufacturer is DaiichiKigensoKagakuKogyo, Japan);
Terpinol: analyze pure, purity >=99%, manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
La (NO
3)
36H
2o: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Ni (NO
3)
2: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Fe (NO
3)
39H
2o: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Sr (NO
3)
2: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Mn (NO
3)
2: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Gd (NO
3)
36H
2o: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Sm (NO
3)
3: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Ce (NO
3)
36H
2o: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Citric acid C
6h
8o
7h
2o: manufacturer is Chemical Reagent Co., Ltd., Sinopharm Group;
Silk screen print method is: slurry powder and terpinol are mixed into is printed on dielectric substrate respectively by 80 object screen clothes, anti-chromium poisons on layer and active layer.
LaNi described in following examples
0.6fe
0.4o
3preparation method be: by the La (NO of mol ratio La: Ni: Fe=1: 0.6: 0.4
3)
36H
2o, Ni (NO
3)
2with Fe (NO
3)
39H
2o is dissolved in distilled water (to the consumption of distilled water without specific requirement, usual employing can make the lucky consoluet amount of solute) in, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor (to the mass percent of ammoniacal liquor without specific requirement, usual employing is containing the aqueous solution of ammonia 25% ~ 28%) solution is adjusted to neutrality, at 120 DEG C of transpiring moistures, directly obtain the xerogel of brown, xerogel is put in crucible furnace and (is preheating to 300 DEG C), xerogel is smoldered rapidly burning, black powder is obtained after Thorough combustion, again products therefrom is sintered 2 hours at 1100 DEG C, obtain described LaNi
0.6fe
0.4o
3, particle diameter is 0.5 ~ 0.8 μm.
La described in following examples
0.8sr
0.2mnO
3preparation method be: by the La (NO of mol ratio La: Sr: Mn=0.8: 0.2: 1
3)
36H
2o, Sr (NO
3)
2with Mn (NO
3)
2be dissolved in distilled water (to the consumption of distilled water without specific requirement, usual employing can make the lucky consoluet amount of solute) in, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor (to the mass percent of ammoniacal liquor without specific requirement, usual employing is containing the aqueous solution of ammonia 25% ~ 28%) solution is adjusted to neutrality, at 135 DEG C of transpiring moistures, directly obtain the xerogel of brown, xerogel is put in crucible furnace and (is preheating to 450 DEG C), xerogel is smoldered rapidly burning, black powder is obtained after Thorough combustion, again products therefrom is sintered 2 hours respectively at 700 DEG C and 1200 DEG C, obtain described La
0.8sr
0.2mnO
3, particle diameter is respectively 0.05 ~ 0.08 μm and 0.5 ~ 1.0 μm., particle diameter is that the LSM of 0.05 ~ 0.08 μm is used for the preparation of active layer, and particle diameter is the preparation that the LSM of 0.5 ~ 1.0 μm is used for current collection layer.
Gd described in following examples
0.2ce
0.8o
2preparation method be: by the Gd (NO of mol ratio Gd: Ce=0.2: 0.8
3)
36H
2o and Ce (NO
3)
36H
2o is dissolved in distilled water (to the consumption of distilled water without specific requirement, usual employing can make the lucky consoluet amount of solute) in, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor (to the mass percent of ammoniacal liquor without specific requirement, usual employing is containing the aqueous solution of ammonia 25% ~ 28%) solution is adjusted to neutrality, at 110 DEG C of transpiring moistures, directly obtain flaxen xerogel, xerogel is put in crucible furnace and (is preheating to 450 DEG C), xerogel is smoldered rapidly burning, faint yellow powder is obtained after Thorough combustion, again products therefrom is sintered 2 hours at 600 DEG C, obtain described Gd
0.2ce
0.8o
2, particle diameter 0.05 ~ 0.06 μm.
Sm described in following examples
0.2ce
0.8o
2preparation method be: be the Sm (NO of Sm: Ce=0.2: 0.8 by mol ratio
3)
36H
2o and Ce (NO
3)
36H
2o is dissolved in distilled water, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor solution is adjusted to neutrality, at 110 DEG C of transpiring moistures, directly obtain flaxen xerogel, xerogel is put in crucible furnace and (is preheating to 450 DEG C), xerogel is smoldered rapidly burning, obtain faint yellow powder after Thorough combustion, then products therefrom is sintered 2 hours at 600 DEG C, obtain described Sm
0.2ce
0.8o
2, particle diameter 0.05 ~ 0.06 μm.
The stoichiometric proportion of citric acid recited above is calculated by following principle: La
0.8sr
0.2mnO
3, LaNi
0.6fe
0.4o
3, doped Ce O
2(Gd
0.2ce
0.8o
2or Sm
0.2ce
0.8o
2) needed raw material stoichiometry have employed advance chemistry thermochemical theory: (the S.R.Jain such as Jain, K.C.Adiga, V.R.P.Vemeker, Anewapproachtothermochemicalcalculationofcondensedfuel-o xidizermixtures, CombustionandFlame, 1981,40 (1): 71-76.) define a kind of straightforward procedure calculating redox reaction characteristic, assuming that all elements all with it at product (as CO
2, H
2o and N
2deng) in exist valence state calculate, so the valence state of reproducibility Elements C and H is respectively+4 and+1, and the valence state of oxidizing elements O is-2, and the valence state of element N is considered to 0.This concept extrapolated, product ceramic oxide is (as ZnO, Bi
2o
3and ZrO
2deng) in metallic element Zn, Bi and Zr, can be used as reproducibility element, and valence state is respectively+2 ,+3 and+4, citric acid C
6h
8o
7h
2the valence state of O is+18.Total chemical valence of divalent metal nitrate is-10; Total chemical valence of the metal nitrate of trivalent is-15; Whether the existence of the crystallization water does not affect the calculating of total chemical valence of nitrate.To synthesize La
0.8sr
0.2mnO
3for example, need La (NO
3)
36H
2o, Sr (NO
3)
2with Mn (NO
3)
2mol ratio be 0.8: 0.2: 1, their total oxidation valency is-15 × 0.8+ (-10 × 0.2)+(-10 × 1)=-24; As taken citric acid as fuel, then in raw material, total also original cost is+18 valencys, so oxidant: the mol ratio of citric acid is 18: 24=3: 4, n (La (NO
3)
36H
2o): n (Sr (NO
3)
2): n (Mn (NO
3)
2): n (C
6h
8o
7h
2o)=0.8: 0.2: 1: 4/3.To synthesize LaNi
0.6fe
0.4o
3for example, need La (NO
3)
36H
2o, Ni (NO
3)
2with Fe (NO
3)
39H
2the mol ratio of O is 1: 0.6: 0.4, and their total oxidation valency is-15 × 1+ (-10 × 0.6)+(-15 × 0.4)=-27; As taken citric acid as fuel, then in raw material, total also original cost is+18 valencys, so oxidant: the mol ratio of citric acid is 18: 27=2: 3, n (La (NO
3)
36H
2o): n (Ni (NO
3)
2): n (Fe (NO
3)
39H
2o): n (C
6h
8o
7h
2o)=1: 0.6: 0.4: 1.5 (n: amount of substance).To synthesize Gd
0.2ce
0.8o
2for example, need Gd (NO
3)
36H
2o and Ce (NO
3)
36H
2the mol ratio of O is 0.2: 0.8, and their total oxidation valency is-15 × 0.2+ (-15 × 0.8)=-15; As taken citric acid as fuel, then in raw material, total also original cost is+18 valencys, so oxidant: the mol ratio of citric acid is 18: 15=6: 5, i.e. n (Gd (NO
3)
36H
2o): n (Ce (NO
3)
36H
2o): n (C
6h
8o
7h
2o)=0.2: 0.8: (5/6).
The preparation method that Anodic of the present invention supports composite membrane is: ScSZ powder joins in the mixed solvent of butanone and ethanol by (1), then add dispersant triethanolamine and ball milling 2 hours to control the degree of powder reuniting, obtain high-quality stable suspension, make powder in the slurry dispersed, binding agent polyvinyl butyral resin is added in the mixed slurry after ball milling, plasticizer polyethylene glycol and again ball milling 2 hours there is best rheological behavior to make powdery pulp when flow casting molding, by slurry good for ball milling being kept in a vacuum within 10 minutes, eliminate the bubble in slurry, this is casting slurry one,
(2) zirconia (YSZ) mixed powder of nickel oxide (NiO) and stabilized with yttrium oxide is joined in the mixed solvent of butanone and ethanol, then add dispersant triethanolamine and ball milling 2 hours to control the degree of powder reuniting, obtain high-quality stable suspension, make powder in the slurry dispersed, add in the mixed slurry after ball milling binding agent polyvinyl butyral resin, plasticizer polyethylene glycol and again ball milling 2 hours there is best rheological behavior to make powdery pulp when flow casting molding.By being kept in a vacuum by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry, this is casting slurry two;
In described casting slurry preparation, constituent mass number used is: slurry one: ScSZ powder 10 parts, binding agent polyvinyl butyral resin 0.4 part, plasticizer polyethylene glycol 1.5 parts, dispersant triethanolamine 0.5 part, butanone 8 parts, ethanol 4 parts; Slurry two: NiO powder 50 parts, YSZ powder 50 parts, binding agent polyvinyl butyral resin 10 parts, plasticizer polyethylene glycol 13.5 parts, dispersant triethanolamine 3 parts, butanone 48 parts, ethanol 24 parts;
(3) homogeneous, stable casting slurry one is poured in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping, by dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 ~ 1450 DEG C of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film.
Embodiment 1:
It is the ScSZ powder of 10 grams by weight, add in the mixed solvent of the butanone of 8 grams and 4 grams of ethanol, then add triethanolamine 0.5 gram of ball milling and mix 2 hours, add 0.4 gram of polyvinyl butyral resin again, 1.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry one; 50gNiO and 50gYSZ mixed powder is joined in the mixed solvent of the butanone of 48 grams and 24 grams of ethanol, then add triethanolamine 3 grams of ball millings and mix 2 hours, add 10 grams of polyvinyl butyral resins again, 13.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry two.Pour homogeneous, stable slurry one in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping.By dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 DEG C of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz forms dielectric substrate).
By 0.7gLNF powder and 0.3gGd doped Ce O
2(Gd
0.2ce
0.8o
2, GDC) and the mixture of powder and 1g terpinol be mixed into slurry, and to be deposited on dielectric substrate that material is ScSZ through silk screen print method and in 110 DEG C of dryings after 0.5 hour, namely to make anti-chromium and poison layer; Then the mixture of 0.7gLSM powder and 0.3gGDC powder and 1g terpinol are mixed into slurry, are deposited on anti-chromium through silk screen print method and poison on layer and after 0.5 hour, namely to make active layer in 110 DEG C of dryings; Finally 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on active layer through silk screen print method and after 0.5 hour, namely make current collection layer in 110 DEG C of dryings, obtaining the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode.Namely the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode is obtained Solid Oxide Fuel Cell functional gradient composite cathode in 2 hours at 1100 DEG C of sintering.The Solid Oxide Fuel Cell functional gradient composite cathode of the present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, 750 DEG C, under Fe-Cr alloy connector existence condition in 50mAcm
-2current density under run 1000h after, cathodic polarization resistance is only 12.1 Ω cm
2, and for pure LSM negative electrode, at 750 DEG C in 50mAcm
-2current density under run 433h after, its polarization resistance reaches 32.2 Ω cm
2.
Embodiment 2:
Be the ScSZ powder of 10 grams by weight, add in the mixed solvent of the butanone of 8 grams and 4 grams of ethanol, then add triethanolamine 0.5 gram of ball milling and mix 2 hours, add 0.4 gram of polyvinyl butyral resin again, 1.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry one; 50gNiO and 50gYSZ mixed powder is joined in the mixed solvent of the butanone of 48 grams and 24 grams of ethanol, then add triethanolamine 3 grams of ball millings and mix 2 hours, add 10 grams of polyvinyl butyral resins again, 13.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry two.Pour homogeneous, stable slurry one in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping.By dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 DEG C of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz forms dielectric substrate).
By 0.7gLNF powder and 0.3gSm doped Ce O
2(Sm
0.2ce
0.8o
2, SDC) and the mixture of powder and 1g terpinol be mixed into slurry, and to be deposited on dielectric substrate that material is ScSZ through silk screen print method and in 110 DEG C of dryings after 0.5 hour, namely to make anti-chromium and poison layer; Then the mixture of 0.7gLSM powder and 0.3gSDC powder and 1g terpinol are mixed into slurry, are deposited on anti-chromium through silk screen print method and poison on layer and after 0.5 hour, namely to make active layer in 110 DEG C of dryings; Finally 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on active layer through silk screen print method and after 0.5 hour, namely make LSM current collection layer in 110 DEG C of dryings, obtaining the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode.The base substrate of above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode is sintered 2 hours at 1100 DEG C, namely obtains Solid Oxide Fuel Cell functional gradient composite cathode.The Solid Oxide Fuel Cell functional gradient composite cathode of the present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, 750 DEG C, under Fe-Cr alloy connector existence condition in 50mAcm
-2current density under run 1000h after, cathodic polarization resistance is only 13.0 Ω cm
2, and for pure LSM negative electrode, at 750 DEG C in 50mAcm
-2current density under run 433h after, its polarization resistance reaches 32.2 Ω cm
2.
Embodiment 3:
Be the ScSZ powder of 10 grams by weight, add in the mixed solvent of the butanone of 8 grams and 4 grams of ethanol, then add triethanolamine 0.5 gram of ball milling and mix 2 hours, add 0.4 gram of polyvinyl butyral resin again, 1.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry one; 50gNiO and 50gYSZ mixed powder is joined in the mixed solvent of the butanone of 48 grams and 24 grams of ethanol, then add triethanolamine 3 grams of ball millings and mix 2 hours, add 10 grams of polyvinyl butyral resins again, 13.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry two.Pour homogeneous, stable slurry one in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping.By dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 DEG C of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz forms dielectric substrate).
The mixture of 0.7gLNF powder, 0.15gGDC powder and 0.15gSDC powder and 1g terpinol are mixed into slurry, are deposited on dielectric substrate that material is ScSZ through silk screen print method and in 110 DEG C of dryings after 0.5 hour, namely make anti-chromium and poison layer; Then the mixture of 0.7gLSM powder, 0.15gGDC powder and 0.15gSDC powder and 1g terpinol are mixed into slurry, are deposited on anti-chromium through silk screen print method and poison on layer and after 0.5 hour, namely to make active layer in 110 DEG C of dryings; Finally 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on active layer through silk screen print method and after 0.5 hour, namely make LSM current collection layer in 110 DEG C of dryings, obtaining the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode.The base substrate of above-mentioned Solid Oxide Fuel Cell functional gradient composite cathode is sintered 2 hours at 1100 DEG C, namely obtains Solid Oxide Fuel Cell functional gradient composite cathode.Solid Oxide Fuel Cell functional gradient composite cathode prepared by the present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, 750 DEG C, under Fe-Cr alloy connector existence condition in 50mAcm
-2current density under run 1000h after, cathodic polarization resistance is only 12.5 Ω cm
2, and for pure LSM negative electrode, at 750 DEG C in 50mAcm
-2current density under run 433h after, its polarization resistance reaches 32.2 Ω cm
2.
Embodiment 4:
It is the ScSZ powder of 10 grams by weight, add in the mixed solvent of the butanone of 8 grams and 4 grams of ethanol, then add triethanolamine 0.5 gram of ball milling and mix 2 hours, add 0.4 gram of polyvinyl butyral resin again, 1.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry one; 50gNiO and 50gYSZ mixed powder is joined in the mixed solvent of the butanone of 48 grams and 24 grams of ethanol, then add triethanolamine 3 grams of ball millings and mix 2 hours, add 10 grams of polyvinyl butyral resins again, 13.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry two.Pour homogeneous, stable slurry one in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping.By dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 DEG C of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz forms dielectric substrate).
By 0.8gLNF powder and 0.2gGd doped Ce O
2(Gd
0.2ce
0.8o
2, GDC) and the mixture of powder and 1g terpinol be mixed into slurry, and to be deposited on dielectric substrate that material is ScSZ through silk screen print method and in 110 DEG C of dryings after 0.5 hour, namely to make anti-chromium and poison layer; Then the mixture of 0.7gLSM powder and 0.3gGDC powder and 1g terpinol are mixed into slurry, are deposited on anti-chromium through silk screen print method and poison on layer and after 0.5 hour, namely to make active layer in 110 DEG C of dryings; Finally 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on active layer through silk screen print method and after 0.5 hour, namely make current collection layer in 110 DEG C of dryings, obtaining the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode.Namely the base substrate of Solid Oxide Fuel Cell functional gradient composite cathode is obtained Solid Oxide Fuel Cell functional gradient composite cathode in 2 hours at 1100 DEG C of sintering.The Solid Oxide Fuel Cell functional gradient composite cathode of the present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, 750 DEG C, under Fe-Cr alloy connector existence condition in 50mAcm
-2current density under run 800h after, cathodic polarization resistance is only 19.5 Ω cm
2, and for pure LSM negative electrode, at 750 DEG C in 50mAcm
-2current density under run 433h after, its polarization resistance reaches 32.2 Ω cm
2.
The preparation method of the pure LSM negative electrode mentioned in each embodiment of this embodiment is as follows:
Be the ScSZ powder of 10 grams by weight, add in the mixed solvent of the butanone of 8 grams and 4 grams of ethanol, then add triethanolamine 0.5 gram of ball milling and mix 2 hours, add 0.4 gram of polyvinyl butyral resin again, 1.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry one; 50gNiO and 50gYSZ mixed powder is joined in the mixed solvent of the butanone of 48 grams and 24 grams of ethanol, then add triethanolamine 3 grams of ball millings and mix 2 hours, add 10 grams of polyvinyl butyral resins again, 13.5 grams of polyethylene glycol also continue that ball milling is stablized for 2 hours, homogeneous slurry, kept by slurry good for ball milling within 10 minutes, eliminating the bubble in slurry under vacuum degree 100 millibars of conditions, this is slurry two.Pour homogeneous, stable slurry one in the feed bin of casting machine flow casting molding, after its drying, slurry two is poured into and it carries out Secondary Flow prolongs shaping.By dry, the obtained NiO-YSZ/ScSZ anodic composite film biscuit of section, biscuit is organic substance in 600 DEG C of heat treatment 3h are with burn off biscuit, finally in 1350 DEG C of sintering 3h, obtains NiO-YSZ/ScSZ anodic composite film.
1gLSM powder and 1g terpinol are mixed into slurry, to be deposited on dielectric substrate that material is ScSZ and in 110 DEG C of dryings after 0.5 hour through silk screen print method, obtain the base substrate of pure LSM negative electrode, namely the base substrate of pure LSM negative electrode is obtained pure LSM negative electrode for 2 hours at 1100 DEG C of sintering.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technical staff in the art, all should by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. a Solid Oxide Fuel Cell functional gradient composite cathode, is characterized in that, comprising:
Anti-chromium poisons layer, and the material that described anti-chromium poisons layer is LNF-doped Ce O
2;
Active layer, the material of described active layer is LSM-doped Ce O
2, described active layer is positioned at described anti-chromium and poisons on layer;
Current collection layer, the material of described current collection layer is LSM, and described current collection layer is positioned on described active layer;
Described LNF refers to LaNi
0.6fe
0.4o
3, described LSM refers to La
0.8sr
0.2mnO
3;
Described LaNi
0.6fe
0.4o
3preparation method be: by the La (NO of mol ratio La:Ni:Fe=1:0.6:0.4
3)
36H
2o, Ni (NO
3)
2with Fe (NO
3)
39H
2o is dissolved in distilled water, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor solution is adjusted to neutrality, at 120 DEG C of transpiring moistures, directly obtain the xerogel of brown, xerogel is preheating to 300 DEG C and obtains black powder after Thorough combustion, then products therefrom is sintered 2 hours at 1100 DEG C, obtains described LaNi
0.6fe
0.4o
3, particle diameter is 0.5 ~ 0.8 μm;
Described La
0.8sr
0.2mnO
3preparation method be: by the La (NO of mol ratio La:Sr:Mn=0.8:0.2:1
3)
36H
2o, Sr (NO
3)
2with Mn (NO
3)
2be dissolved in distilled water, then the citric acid of stoichiometric proportion is dissolved in the solution, and add ammoniacal liquor solution is adjusted to neutrality, at 135 DEG C of transpiring moistures, directly obtain the xerogel of brown, xerogel is preheating to 450 DEG C and obtains black powder after Thorough combustion, then products therefrom is sintered 2 hours respectively at 700 DEG C and 1200 DEG C, obtains the La that particle diameter is 0.05 ~ 0.08 μm and 0.5 ~ 1.0 μm respectively
0.8sr
0.2mnO
3; Particle diameter is the La of 0.05 ~ 0.08 μm
0.8sr
0.2mnO
3for active layer; Particle diameter is the La of 0.5 ~ 1.0 μm
0.8sr
0.2mnO
3for current collection layer.
2. Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 1, wherein said LNF-doped Ce O
2in, LNF and doped Ce O
2mass ratio be 7 ~ 8:3 ~ 2.
3. Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 1, wherein said LSM-doped Ce O
2in, LSM and doped Ce O
2mass ratio be 7 ~ 8:3 ~ 2.
4. Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 1, wherein said LNF-doped Ce O
2in doped Ce O
2, and described LSM-doped Ce O
2in doped Ce O
2, Doped ions is Gd
3+or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9.
5. prepare a method for Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 1, it is characterized in that, comprise the following steps:
A), by LNF and doped Ce O
2mixture and terpinol be mixed into slurry, this slurry to be attached on dielectric substrate and after drying, namely making material is LNF-doped Ce O
2described anti-chromium poison layer;
B), by LSM and doped Ce O
2mixture and terpinol be mixed into slurry, this slurry is attached to described anti-chromium and poisons on layer and after drying, namely making material is LSM-doped Ce O
2described active layer;
C), by LSM and terpinol be mixed into slurry, this slurry be attached on described active layer and after drying, namely make the described current collection layer that material is LSM, obtain the base substrate of described Solid Oxide Fuel Cell functional gradient composite cathode;
D), by the blank sintering of described Solid Oxide Fuel Cell functional gradient composite cathode, described Solid Oxide Fuel Cell functional gradient composite cathode is namely obtained.
6. the preparation method of Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 5, wherein said step a) in, described LNF and described doped Ce O
2mass ratio be 7 ~ 8:3 ~ 2, described LNF and doped Ce O
2mixture and the mass ratio of described terpinol be 1:0.7 ~ 1; Describedly be attached on described dielectric substrate by this slurry, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
7. the preparation method of Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 5, wherein said step b) in, described LSM and described doped Ce O
2mass ratio be 7 ~ 8:3 ~ 2, described LSM and doped Ce O
2mixture and the mass ratio of described terpinol be 1:0.7 ~ 1; Describedly this slurry is attached to described anti-chromium and poisons on layer, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
8. the preparation method of Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 5, wherein said step c) in, the mass ratio of described LSM and described terpinol is 1:0.7 ~ 1; Describedly be attached on described active layer by this slurry, the method used is silk screen print method; The temperature of described drying is 100 DEG C ~ 120 DEG C, and the time of described drying is 0.5 hour ~ 2 hours.
9. the preparation method of Solid Oxide Fuel Cell functional gradient composite cathode as claimed in claim 5, wherein said steps d) in, the temperature of described sintering is 1050 DEG C ~ 1100 DEG C, and the time of described sintering is 2 hours ~ 3 hours.
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| CN105428677B (en) * | 2015-12-02 | 2018-06-19 | 中北大学 | A kind of barium stannate base complex phase electrolyte and preparation method thereof |
| CN109841841B (en) * | 2017-11-29 | 2021-08-31 | 中国科学院大连化学物理研究所 | High-temperature fuel cell cathode material and preparation and application thereof |
| EP3719171A1 (en) * | 2019-04-05 | 2020-10-07 | DynElectro ApS | Electrolysis system with controlled thermal profile |
| CN112310419A (en) * | 2020-11-03 | 2021-02-02 | 湖北大学 | Strontium-free and cobalt-free perovskite type composite oxide, preparation method thereof and battery |
| CN113871636B (en) * | 2021-09-30 | 2023-09-29 | 福州大学 | Chromium poisoning-resistant solid oxide fuel cell nanostructure composite cathode |
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