CN102683721A - Solid oxide fuel cell and functional gradient composite cathode and preparation method thereof - Google Patents
Solid oxide fuel cell and functional gradient composite cathode and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000446 fuel Substances 0.000 title abstract description 14
- 239000007787 solid Substances 0.000 title abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 88
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 70
- 238000001035 drying Methods 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims description 107
- 238000000034 method Methods 0.000 claims description 64
- 239000002574 poison Substances 0.000 claims description 50
- 231100000614 poison Toxicity 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 36
- 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 28
- 238000012545 processing Methods 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 230000000607 poisoning effect Effects 0.000 abstract description 11
- 231100000572 poisoning Toxicity 0.000 abstract description 10
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 88
- 239000000843 powder Substances 0.000 description 56
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 39
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
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- 238000000498 ball milling Methods 0.000 description 28
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- 229910052760 oxygen Inorganic materials 0.000 description 15
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 15
- 229920001223 polyethylene glycol Polymers 0.000 description 15
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- 230000010287 polarization Effects 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 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
- 239000002346 layers by function Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001301 oxygen Substances 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
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012467 final product 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
- 230000009467 reduction Effects 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
- 239000012298 atmosphere Substances 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
- 238000009413 insulation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 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
- 238000003860 storage Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
Abstract
The invention relates to a solid oxide fuel cell and a functional gradient composite cathode and a preparation method thereof. The functional gradient composite cathode for the solid oxide fuel cell comprises a chromium poisoning resistant layer, an activation layer and a current collection layer, wherein the chromium poisoning resistant layer is made of LNF (LaNi0.6Fe0.4O3) and doped CeO2, the activation layer is positioned above the chromium poisoning resistant layer and made of LSM (La0.8Sr0.2MnO3) and doped CeO2, and the current collection layer is positioned above the activation layer and made of LSM. The preparation method of the functional gradient composite cathode for the solid oxide fuel cell includes the steps: a, attaching paste of the chromium poisoning resistant layer onto an electrolyte layer and drying to obtain the chromium poisoning resistant layer; b, attaching paste of the activation layer onto the chromium poisoning resistant layer and drying to obtain the activation layer; c, attaching paste of the current collection layer to the activation layer and drying to obtain the current collection layer, so that a blank is obtained; and d, sintering the blank to obtain the functional gradient composite cathode. Chromium deposition of high-volatility CrO3 and CrO2 (OH)2 on cathode/electrolyte interfaces is reduced.
Description
Technical field
The present invention relates to a kind of SOFC, relate in particular to a kind of SOFC functionally gradient composite cathode; The invention still further relates to the preparation method of this SOFC functionally gradient composite cathode.
Background technology
At present, (Solid Oxide Fuel Cell, in evolution SOFC), People more and more is recognized the importance that reduces battery operated temperature at SOFC.If can battery operated temperature be reduced to middle temperature (700～800 ℃), then can improve the stability of electrode, reduce thermal stress, extending battery life also can use the bipolar plate material of cheap metal alloy as battery.
In various metal alloys, contain the Cr metal alloy because of have cost low, be prone to that processing, electronic conductivity and thermal conductivity are high, mechanical stability is high, high temperature resistant and advantage such as anti-oxidant becomes the most promising bipolar plate material.Under cathode oxidation atmosphere, because Cr preferentially is oxidized to chrome green Cr
2O
3(solid-state) and generate the very thin fine and close diaphragm of one deck on the surface of alloy.But in the time will containing the Cr metal alloy and be used for the bipolar plates of SOFC, the volatilization of high valence state Cr compound is to need one of problem that emphasis considers.As under the oxidizing atmosphere of cathode side, particularly under the situation that steam exists, Cr base alloy generates high-volatile chromium trioxide CrO easily
3(gaseous state) and chromic acid CrO
2(OH)
2(gaseous state) etc.The volatilization of Cr not only can be quickened Cr
2O
3The growth of oxide-film, and can cause the diffusion of Cr to porous cathode.Find that through the document retrieval people such as Teruhisa Horita deliver " Chromium Poisoning and Degradation at (La, Sr) MnO
3And (La, Sr) FeO
3Cathodes for Solid Oxide Fuel Cells " (SOFC (La, Sr) MnO
3(La, Sr) FeO
3The chromium poisoning of cathode material and decreased performance) literary composition, see " Journal of The Electrochemical Society " (electrochemistry meeting will) 157 (5) (2010) B614-B620.This article is introduced: when electric current passes through, at (La
0.8Sr
0.2)
0.95MnO
3Negative electrode/Ce
0.8Gd
0.2O
2The Cr compound of the high valence state in electrolyte interface place is reduced to Cr
2O
3, the Cr of one side low electric conductivity
2O
3Generation with assemble the electric output performance that can reduce 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
3The spinelle phase of generation chemical reaction generation insulation (Cr, Mn)
3O
4(s), the performance of battery is sharply descended, " Cr poisoning " phenomenon of Here it is negative electrode.
Therefore, SOFC cathode material (La, Sr) MnO of classics
3Anti-Cr to poison performance be problem demanding prompt solution.People such as S.P.Jiang deliver " La (Ni, Fe) O
3As a cathode material with high tolerance to chromium poisoning for solid oxide fuel cells " (cathode material for solid-oxide fuel cell La (Ni, Fe) O that anti-chromium poisons
3) literary composition, see " Journal of Power Sources " (power technology) 170 (2007) 61-66.This article has been introduced the employing synthesis by solid state reaction and has been prepared LaNi
0.6Fe
0.4O
3(La
0.8Sr
0.2)
0.9MnO
3Two kinds of cathode materials, and 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 is at LaNi
0.6Fe
0.4O
3Surface and LaNi
0.6Fe
0.4O
3/ YSZ interface (YSZ: the Cr deposition of minute quantity is arranged the zirconia of stabilized with yttrium oxide), and at (La
0.8Sr
0.2)
0.9MnO
3Cr deposition that the appearance of/YSZ interface is a large amount of and spinelle phase (Cr, Mn)
3O
4So LaNi (s),
0.6Fe
0.4O
3Be that very potential anti-chromium poisons the SOFC cathode material.However, La (Ni, Fe) O
3Under identical sintering temperature, than (La, Sr) MnO of classics
3More be prone to and ZrO
2Base electrolyte reaction, LaNi when being higher than 1000 ° of C in temperature
0.6Fe
0.4O
3Promptly and ZrO
2Base electrolyte reacts and generates the La of insulation
2Zr
2O
7, significantly reduce battery performance.On the other hand, because the characteristic of LNF material itself, like LNF cathode material reoxidizing and the decline of subsequently oxygen vacancy concentration under working temperature; The initial performance that causes the LNF negative electrode is not finely (to see S.I.Hashimoto; K.Kammer, P.H.Larsen, F.W.Poulsen; M.Mogensen, Solid State Ionics 176 (2005) 1013).The author is the synthetic LaNi of application of cold temperature firing method once
0.6Fe
0.4O
3Cathode material is with ScSZ (Sc
0.1Zr
0.9O
1.95) electrolyte makes bipolar electrode symmetry system, the test cathode material with condition that the Fe-Cr alloy directly contacts under, during long-play, the Fe-Cr alloy is to LaNi under 750 ° of C open-circuit condition
0.6Fe
0.4O
3The influence of cathode material chemical property.The result finds that cathodic polarization resistance is by 0.70 Ω cm of beginning in the time of 750 ℃
2Be increased to the 42.86 Ω cm of 370h
2SEM finds, LaNi
0.6Fe
0.4O
3Deposit the Cr of low electric conductivity on the/ScSZ interface
2O
3, slow down the diffusion of active particle at three phase boundary, increased cathodic polarization resistance.
Therefore, as the cathode material that anti-chromium poisons, La (Ni, Fe) O
3Performance also needs further to improve; As the classical cathode material of high-performance, (La, Sr) MnO
3Performance also needs further to improve.
Summary of the invention
First aspect purpose of the present invention is the deficiency to above prior art, adopts the method for function gradient structure design, with at present known catalytic activity is high, 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 good, electronic conductivity is high, anti-chromium poisons excellent performance
0.6Fe
0.4O
3(LNF), and catalytic performance is good, has the doped Ce O of outstanding oxonium ion storage, release and transmittability
2Three kinds of candidate materials combine; Anticathode multiple requirement is born by the different functions layer, and each functional layer is cooperatively interacted, utilize synergy to reach the effect of mutual supplement with each other's advantages; Thereby neither can influence the catalytic performance and the electric conductivity of negative electrode, can significantly reduce high-volatile CrO again
3And CrO
2(OH)
2Chromium deposition on cathode/electrolyte interface improves the oxygen reduction kinetics performance of functionally gradient negative electrode, thereby improves the performance of SOFC.
The present invention adopts following technical scheme to solve the problems of the technologies described above, and reaches the object of the invention:
A kind of SOFC functionally gradient composite cathode comprises:
Anti-chromium poisons layer, and the material that said 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), said anti-chromium poisons layer and is positioned on the dielectric substrate.
Active layer, the material of said active layer are LSM-doped Ce O
2(this active layer also can be described as LSM-doped Ce O
2), said active layer is positioned at said anti-chromium to be poisoned on the layer;
Current collection layer, the material of said current collection layer are LSM (this current collection layer also can be described as the LSM layer), and said current collection layer is positioned on the said active layer.
When practical implementation of the present invention, preferably, said LNF-doped Ce O
2In, LNF and doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2.
When practical implementation of the present invention, preferably, said LSM-doped Ce O
2In, LSM and doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2.
When practical implementation of the present invention, preferably, said LNF-doped Ce O
2In doped Ce O
2, and said LSM-doped Ce O
2In doped Ce O
2, dopant ion is Gd
3+Or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9.
When practical implementation of the present invention, preferably, the thickness that said anti-chromium poisons layer is 8 ~ 10 microns, and the thickness of said active layer is 8 ~ 10 microns, and the thickness of said current collection layer is 8 ~ 10 microns.
When practical implementation of the present invention, preferably, said doped Ce O
2Be doped Ce O
2Nano particle.
Second aspect purpose of the present invention is to propose a kind of SOFC.
A kind of SOFC; Comprise dielectric substrate and negative electrode; Said negative electrode is positioned on the said dielectric substrate, it is characterized in that, the material of said dielectric substrate is ScSZ; Said negative electrode is aforesaid SOFC functionally gradient composite cathode, and said anti-chromium poisons layer and is positioned on the said dielectric substrate.
When practical implementation of the present invention, the material of dielectric substrate described in the present invention is any electrolyte that is applicable to SOFC, is preferably ScSZ (zirconia of scandia stabilized).
SOFC functionally gradient composite cathode of the present invention can with the use of arranging in pairs or groups jointly of any anode of solid oxide fuel cell.
Third aspect of the invention purpose is to propose to prepare the method for above-mentioned SOFC functionally gradient composite cathode.Especially, this method prepares applicable to suitability for industrialized production that the anti-chromium of large scale poisons, high performance SOFC functionally gradient composite cathode; This method technology is simple, manufacturing cycle weak point, with low cost, is suitable for commercial application.
A kind of method for preparing above-mentioned SOFC functionally gradient composite cathode may further comprise the steps:
A), with LNF and doped Ce O
2Mixture and terpinol be mixed into slurry, with this slurry be attached on the said dielectric substrate and drying after, promptly processing material is LNF-doped Ce O
2Said anti-chromium poison layer;
B), with LSM and doped Ce O
2Mixture and terpinol be mixed into slurry, with this slurry be attached to that said anti-chromium poisons that layer is gone up and drying after, promptly processing material is LSM-doped Ce O
2Said active layer;
C), LSM and terpinol are mixed into slurry, with this slurry be attached on the said active layer and drying after, promptly processing material is the said current collection layer of LSM, obtains the base substrate of said SOFC functionally gradient composite cathode;
D), with the blank sintering of said SOFC functionally gradient composite cathode, promptly obtain said SOFC functionally gradient composite cathode.
When practical implementation of the present invention, preferably, in the said step a), said LNF and said doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2, said LNF and doped Ce O
2Mixture and the mass ratio of said terpinol be 1:0.7 ~ 1; Said this slurry is attached on the said dielectric substrate, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
When practical implementation of the present invention, preferably, in the said step b), said LSM and said doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2, said LSM and doped Ce O
2Mixture and the mass ratio of said terpinol be 1:0.7 ~ 1; Saidly this slurry is attached to said anti-chromium poisons on the layer, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
When practical implementation of the present invention, preferably, in the said step c), the mass ratio of said LSM and said terpinol is 1:0.7 ~ 1; Said this slurry is attached on the said active layer, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
When practical implementation of the present invention, preferably, in the said step d), the temperature of said sintering is 1050 ℃ ~ 1100 ℃, and the time of said sintering is 2 h ~ 3 hours.
Preferred implementation of preparation method of the present invention is: be the LNF-doped Ce O of 1:1 with mass ratio
2Mixture (LNF: doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2) be mixed into slurry, be deposited on the dielectric substrate that material is ScSZ and after 0.5 hour, promptly process anti-chromium and poison layer in 110 ℃ of dryings through the silk screen printing method with terpinol; Be the LSM-doped Ce O of 1:1 then with mass ratio
2Mixture (LSM and doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2) be mixed into slurry, be deposited on said anti-chromium through the silk screen printing method and poison layer and go up and after 0.5 hour, promptly process active layer in 110 ℃ of dryings with terpinol; Be that LSM and the terpinol of 1:1 is mixed into slurry with mass ratio at last, be deposited on the said active layer and through the silk screen printing method and after 0.5 hour, promptly process the LSM current collection layer, obtain the base substrate of SOFC functionally gradient composite cathode in 110 ℃ of dryings; The base substrate of said SOFC functionally gradient composite cathode was promptly obtained said SOFC functionally gradient composite cathode in 2 hours at 1100 ℃ of sintering.
Silk screen print method of the present invention is a silk screen print method general in the prior art.
The sintering that the present invention mentioned is a sintering in air.
Advantage of the present invention is:
Adopt the method for functionally gradient composite cathode structural design, with at present known catalytic activity is high, 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 good, electronic conductivity is high, anti-chromium poisons excellent performance
0.6Fe
0.4O
3(LNF) and catalytic performance is good, doped Ce O with outstanding oxonium ion storage, release and transmittability
2Three kinds of candidate materials combine; Anticathode multiple requirement is born by the different functions layer, and each functional layer is cooperatively interacted, utilize synergy to reach the effect of mutual supplement with each other's advantages; Thereby neither can influence the catalytic performance and the electric conductivity of negative electrode, can significantly reduce high-volatile CrO again
3And CrO
2(OH)
2Chromium deposition on cathode/electrolyte interface improves the oxygen reduction kinetics performance of composite cathode, thereby improves the performance of SOFC.
Main raw material(s) NiO of the present invention (nickel oxide), YSZ (zirconia of stabilized with yttrium oxide), ScSZ (zirconia of scandia stabilized), its average grain diameter is the 0.5-10 micron.Constitute each functional layer material La of functionally gradient composite cathode
0.8Sr
0.2MnO
3, LaNi
0.6Fe
0.4O
3And doped Ce O
2All be to adopt low-temperature combustion method synthetic, the success of this method be applied to many simple or complicated compound systems, can be easy under lower temperature and prepare the oxide superfine powder efficiently, be that a kind of advanced ceramics of novelty prepares approach.The present invention adopts the synthetic oxide La of low-temperature combustion method
0.8Sr
0.2MnO
3Powder, LaNi
0.6Fe
0.4O
3Powder and doped Ce O
2Powder, its particle size be nanoscale (＜100nm), the specific area of powder is big.Like this, each functional layer of functionally gradient composite cathode can keep loose structure and preferable oxygen reduction kinetics performance preferably like 1000～1100 ℃ of sintering at a lower temperature, and anti-chromium poisons a layer LNF-doped Ce O
2Can also keep excellent contact and chemical reaction does not take place with electrolyte ScSZ;
SOFC functionally gradient composite cathode of the present invention is analyzed from function, and LNF has higher conductivity and to the catalytic activity of oxygen electrochemical reducting reaction, splendid anti-poisoning property of chromium; Doped Ce O
2Mix, increased the ionic conductivity of cathode material, especially the less doped Ce O of particle diameter
2Powder is wrapped in and carries out on the bigger LNF powder granule of particle diameter (1100 ℃ of following sintering) forming the ion-electron conductive path in negative electrode inside behind the sintering, has suppressed LNF and electrolyte ScSZ on the one hand the La that the chemical reaction generation is insulated takes place
2Zr
2O
7Prevented that the negative electrode Ohmic resistance from increasing, also increased the three-phase reaction interface of LNF and electrolyte ScSZ on the other hand, made cathodic polarization resistance significantly reduce; Thereby improved the electrochemical catalysis performance of LNF, and the effect that can effectively prevent the Fe-Cr alloy that the LNF negative electrode is poisoned.So doped Ce O
2Relative amount, LNF and doped Ce O
2Sintering temperature (LNF and doped Ce O in other words
2Crystallite dimension) etc. determined the catalytic activity and anti-the poisoning property of chromium of this functional layer, this just requires LNF and doped Ce O
2Mass ratio, LNF and doped Ce O
2Technological parameters such as sintering temperature be optimized.Change CeO
2In dopant ion, thereby adjust its oxygen ionic conductivity etc., also be one of catalytic activity optimization approaches.Poison a layer LNF-doped Ce O for improving anti-chromium
2The electrochemical catalysis performance and the anti-chromium of Fe-Cr alloy poisoned performance, in this functional layer, doped Ce O
2Be preferably 0.2～0.3 with the mass ratio of LNF: 0.8 ~ 0.7, CeO
2In dopant ion be preferably Gd
3+Or Sm
3+, the sintering temperature of LNF powder is preferably 1100 ℃, doped Ce O
2The sintering temperature of powder is preferably 600 ℃, the average grain particle diameter of preferred LNF powder: doped Ce O
2A layer LNF-doped Ce O poisoned in average grain particle diameter=9 ~ 16 of powder, anti-chromium
2Sintering temperature be preferably 1100 ℃.
LSM had both had very high ionic conductivity; Has sufficiently high electron conduction again; And have very high activity, but owing to it at high temperature can react with electrolyte ScSZ, and do not possess the performance that anti-chromium poisons; The present invention mainly brings into play the effect of its high conductivity with its functional layer as the top.For improving the performance of current collection layer LSM, in this functional layer, the sintering temperature of LSM powder is 1200 ℃.For material is LSM-doped Ce O
2Active layer, its polarization overpotential is little, reactivity is strong, but do not possess the performance that anti-chromium poisons, it is LNF-doped Ce O that the present invention is placed on material
2Anti-chromium poison under the protection of layer, hope and to give full play to LSM-doped Ce O
2Electrochemical catalysis performance to the oxygen reduction reaction.For improving the electrochemical catalysis performance of active layer, in this functional layer, doped Ce O
2Be preferably 0.2～0.3 with the mass ratio of LSM: 0.8 ~ 0.7, CeO
2In dopant ion be preferably Gd
3+Or Sm
3+, the sintering temperature of LSM powder is preferably 700 ℃, doped Ce O
2The sintering temperature of powder is preferably 600 ℃, and the sintering temperature of active layer is preferably 1100 ℃.The SOFC functionally gradient composite cathode of the present invention's preparation has excellent anti-chromium and poisons performance and electrochemical catalysis performance, is convenient to improve the power density of fuel cell, guarantees the stable operation of fuel cell.The preparation method who is adopted can the uniform large tracts of land LNF-doped Ce of Forming Quality O
2/ LSM-doped Ce O
2/ LSM SOFC functionally gradient composite cathode, technology is simple, possesses low-cost advantage, easy realization of industrialization.
Below will the technique effect of design of the present invention, concrete structure and generation be described further, so that those skilled in the art understands the object of the invention, characteristic and effect fully.
Embodiment
A kind of SOFC comprises dielectric substrate and negative electrode, and negative electrode is positioned on the dielectric substrate, and the material of dielectric substrate is ScSZ, and negative electrode is like the described a kind of SOFC functionally gradient composite cathode of this embodiment.
A kind of SOFC functionally gradient composite cathode comprises:
Anti-chromium poisons layer, and the material that anti-chromium poisons layer is LNF-doped Ce O
2, in SOFC, anti-chromium poisons layer and is positioned on the dielectric substrate, and dielectric substrate is positioned on the 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, dopant ion 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 are LSM-doped Ce O
2, active layer is positioned at anti-chromium to be poisoned on the 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, dopant ion 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 are LSM, and current collection layer is positioned on the active layer; The thickness of current collection layer is preferably 8 ~ 10 microns.
The preparation method of above-mentioned SOFC functionally gradient composite cathode may further comprise the steps:
A), with LNF and doped Ce O
2Mixture (with LNF and doped Ce O
2Directly mix and get final product) be mixed into slurry with terpinol, this slurry is attached on the dielectric substrate also drying after, promptly processing 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; This slurry is attached on the dielectric substrate, and employed method is a silk screen print method; Dry temperature is preferably 100 ℃ ~ 120 ℃, and the dry time is preferably 0.5 h ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as water evaporates is intact);
B), with LSM and doped Ce O
2Mixture (with LSM and doped Ce O
2Directly mix and get final product) be mixed into slurry with terpinol, this slurry is attached to after anti-chromium poisons layer and go up also drying, promptly processing 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
2The mass ratio of mixture and terpinol be preferably 1: 0.7 ~ 1; This slurry is attached to anti-chromium poisons on the layer, employed method is a silk screen print method; Dry temperature is preferably 100 ℃ ~ 120 ℃, and the dry time is preferably 0.5 h ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as with moisture drying);
C), LSM and terpinol are mixed into slurry, with this slurry be attached on the active layer and drying after, promptly process the current collection layer that material is LSM, obtain the base substrate of SOFC functionally gradient composite cathode; The mass ratio of LSM and terpinol is preferably 1: 0.7 ~ and 1; This slurry is attached on the active layer, and employed method is a silk screen print method; Dry temperature is preferably 100 ℃ ~ 120 ℃, and the dry time is preferably 0.5 h ~ 2 hours (drying time and temperature, those skilled in the art can adjust according to actual conditions, as long as with moisture drying);
D), with the blank sintering of SOFC functionally gradient composite cathode, promptly obtain SOFC functionally gradient composite cathode; The temperature of sintering is preferably 1050 ℃ ~ 1100 ℃, and the time of sintering is preferably 2 h ~ 3 hours.
The sintering of being mentioned in this embodiment is sintering in air.
Below embodiment in used raw material introduction (specifically indicate the chemical reagent of purity in the following raw material, it is pure to be analysis) as follows:
Used ScSZ powder is Zr
0.89Sc
0.1Ce
0.01O
2(ScSZ, manufacturer are Daiichi Kigenso Kagaku Kogyo, Japan);
Butanone: analyze pure, purity >=99%;
Ethanol: analyze pure, purity >=99.7%;
Triethanolamine: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Polyvinyl butyral resin: aviation-grade, butyraldehyde base 45% ~ 49%, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Polyethylene glycol: chemical pure, mean molecule quantity 190 ~ 210, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
NiO: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
YSZ:Zr
0.92Y
0.08O
2(YSZ, manufacturer are Daiichi Kigenso Kagaku Kogyo, Japan);
Terpinol: analyze pure, purity >=99%, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
La (NO
3)
36H
2O: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Ni (NO
3)
2: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Fe (NO
3)
39H
2O: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Sr (NO
3)
2: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Mn (NO
3)
2: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Gd (NO
3)
36H
2O: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Sm (NO
3)
3: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Ce (NO
3)
36H
2O: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Citric acid C
6H
8O
7H
2O: manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Silk screen print method is: powder and the composite slurry of terpinol are printed on dielectric substrate, anti-chromium respectively through 80 purpose screen clothes poison on layer and the active layer and get final product.
LaNi described in following examples
0.6Fe
0.4O
3The preparation method be: with mol ratio La: Ni: Fe=1: 0.6: 0.4 La (NO
3)
36H
2O, Ni (NO
3)
2And Fe (NO
3)
39H
2O is dissolved in the distilled water (consumption to distilled water does not have specific requirement, and employing can make the lucky consoluet amount of solute usually), in solution, dissolves in the citric acid of stoichiometric proportion then; And add ammoniacal liquor (mass percent to ammoniacal liquor does not have specific requirement, adopts the aqueous solution that contains ammonia 25%～28% usually) solution is transferred to neutrality, at 120 ℃ of transpiring moistures; Directly obtain the xerogel of brown; Xerogel is put in the crucible furnace (is preheating to 300 ℃), the xerogel burning of smoldering rapidly fully obtains the black powder after the burning; Again with products therefrom 1100 ℃ of following sintering 2 hours, promptly get said LaNi
0.6Fe
0.4O
3, particle diameter is 0.5 ~ 0.8 μ m.
La described in following examples
0.8Sr
0.2MnO
3The preparation method be: with mol ratio La: Sr: Mn=0.8: 0.2: 1 La (NO
3)
36H
2O, Sr (NO
3)
2And Mn (NO
3)
2Be dissolved in the distilled water (consumption to distilled water does not have specific requirement, and employing can make the lucky consoluet amount of solute usually), in solution, dissolve in the citric acid of stoichiometric proportion then; And add ammoniacal liquor (mass percent to ammoniacal liquor does not have specific requirement, adopts the aqueous solution that contains ammonia 25%～28% usually) solution is transferred to neutrality, at 135 ℃ of transpiring moistures; Directly obtain the xerogel of brown; Xerogel is put in the crucible furnace (is preheating to 450 ℃), the xerogel burning of smoldering rapidly fully obtains the black powder after the burning; Again with products therefrom respectively 700 ℃ and 1200 ℃ of following sintering 2 hours, promptly get said La
0.8Sr
0.2MnO
3, particle diameter is respectively 0.05 ~ 0.08 μ m and 0.5 ~ 1.0 μ m., particle diameter is the preparation that the LSM of 0.05 ~ 0.08 μ m is used for active layer, particle diameter is the preparation that the LSM of 0.5 ~ 1.0 μ m is used for current collection layer.
Gd described in following examples
0.2Ce
0.8O
2The preparation method be: with mol ratio Gd: Ce=0.2: 0.8 Gd (NO
3)
36H
2O and Ce (NO
3)
36H
2O is dissolved in the distilled water (consumption to distilled water does not have specific requirement, and employing can make the lucky consoluet amount of solute usually), in solution, dissolves in the citric acid of stoichiometric proportion then; And add ammoniacal liquor (mass percent to ammoniacal liquor does not have specific requirement, adopts the aqueous solution that contains ammonia 25%～28% usually) solution is transferred to neutrality, at 110 ℃ of transpiring moistures; Directly obtain flaxen xerogel; Xerogel is put in the crucible furnace (is preheating to 450 ℃), the xerogel burning of smoldering rapidly fully obtains faint yellow powder after the burning; Again with products therefrom 600 ℃ of following sintering 2 hours, promptly get said Gd
0.2Ce
0.8O
2, particle diameter 0.05 ~ 0.06 μ m.
Sm described in following examples
0.2Ce
0.8O
2The preparation method be: with mol ratio is Sm: Ce=0.2: 0.8 Sm (NO
3)
36H
2O and Ce (NO
3)
36H
2O is dissolved in the distilled water, in solution, dissolves in the citric acid of stoichiometric proportion then, and adding ammoniacal liquor transfers to neutrality with solution; At 110 ℃ of transpiring moistures, directly obtain flaxen xerogel, xerogel is put in the crucible furnace (is preheating to 450 ℃); The xerogel burning of smoldering rapidly; Fully obtain faint yellow powder after the burning, again with products therefrom 600 ℃ of following sintering 2 hours, promptly get said Sm
0.2Ce
0.8O
2, particle diameter 0.05 ~ 0.06 μ m.
The stoichiometric proportion of citric acid recited above is calculated through 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 proportioning metering adopted the thermochemical theory that advances chemistry: (S.R.Jain such as Jain; K.C.Adiga, V.R.P.Vemeker, A new approach to thermochemical calculation of condensed fuel-oxidizer mixtures; Combustion and Flame; 1981,40 (1): 71-76.) defined a kind of straightforward procedure of calculating the redox reaction characteristic, suppose all elements all with it at product (like CO
2, H
2O and N
2Deng) in the valence state that exists calculate, so the valence state of reproducibility Elements C and H be respectively+4 and+1, the valence state of oxidizability element O is-2, the valence state of element N is considered to 0.This notion is extrapolated, and the product ceramic oxide (like ZnO, Bi
2O
3And ZrO
2Deng) in metallic element Zn, Bi and Zr can be used as the reproducibility element, 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 influence the calculating of total chemical valence of nitrate.With synthetic La
0.8Sr
0.2MnO
3Be example, need La (NO
3)
36H
2O, Sr (NO
3)
2And 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 being fuel with the citric acid, then total also original cost is+18 valencys in the raw material, so oxidant: the mol ratio of citric acid is 18: 24=3: 4, and n (La (NO
3)
36H
2O): n (Sr (NO
3)
2): n (Mn (NO
3)
2): n (C
6H
8O
7H
2O)=and 0.8: 0.2: 1: 4/3.With synthetic LaNi
0.6Fe
0.4O
3Be example, need La (NO
3)
36H
2O, Ni (NO
3)
2And 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 being fuel with the citric acid, then total also original cost is+18 valencys in the raw material, so oxidant: the mol ratio of citric acid is 18: 27=2: 3, and n (La (NO
3)
36H
2O): n (Ni (NO
3)
2): n (Fe (NO
3)
39H
2O): n (C
6H
8O
7H
2O)=and 1: 0.6: 0.4: 1.5 (n: amount of substance).With synthetic Gd
0.2Ce
0.8O
2Be 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 being fuel with the citric acid, then total also original cost is+18 valencys in the raw material, so oxidant: the mol ratio of citric acid is 18: 15=6: 5, i.e. and 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 of anode-supported composite membrane is among the present invention: (1) joins the ScSZ powder in butanone and the ethanol mixed solvent; Add 2 hours degree of dispersant triethanolamine and ball milling then with the control powder reuniting; Obtain high-quality stable suspension; Powder is dispersed in the slurry; Add in the mixed slurry behind ball milling binding agent polyvinyl butyral resin, plasticizer polyethylene glycol and once more ball milling 2 hours keep the bubble eliminated in the slurry in 10 minutes so that powdery pulp has best rheological behavior when flow casting molding in a vacuum through the slurry that ball milling is good, this is a casting slurry one;
(2) zirconia (YSZ) mixed powder with nickel oxide (NiO) and stabilized with yttrium oxide joins in butanone and the ethanol mixed solvent; Add 2 hours degree of dispersant triethanolamine and ball milling then with the control powder reuniting; Obtain high-quality stable suspension; Powder is dispersed in the slurry, add in the mixed slurry behind ball milling binding agent polyvinyl butyral resin, plasticizer polyethylene glycol and once more ball milling 2 hours so that powdery pulp has best rheological behavior when flow casting molding.Keep 10 minutes bubbles in the elimination slurry in a vacuum through the slurry that ball milling is good, this is a casting slurry two;
Used constituent mass umber is in the said casting slurry preparation: slurry one: 10 parts of ScSZ powders, 0.4 part of binding agent polyvinyl butyral resin, 1.5 parts of plasticizer polyethylene glycol, 0.5 part of dispersant triethanolamine, 8 parts of butanone, 4 parts of ethanol; Slurry two: 50 parts of NiO powders, 50 parts of YSZ powders, 10 parts of binding agent polyvinyl butyral resins, 13.5 parts of plasticizer polyethylene glycol, 3 parts of dispersant triethanolamines, 48 parts of butanone, 24 parts of ethanol;
(3) pour homogeneous, stable casting slurry one in the feed bin of casting machine flow casting molding; After treating its drying; Slurry two poured into carries out Secondary Flow on it and prolong moulding, make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance; In 1350～1450 ℃ of sintering 3h, obtain the NiO-YSZ/ScSZ anodic composite film at last.
Embodiment 1:
With weight is the ScSZ powder of 10 grams; Add in the butanone and 4 gram ethanol mixed solvent of 8 grams; Added triethanolamine 0.5 gram ball mill mixing then 2 hours; Add 0.4 gram polyvinyl butyral resin again; 1.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum, this is a slurry one; 50gNiO and 50gYSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added triethanolamine 3 gram ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum, this is a slurry two.Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding.Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, at last in 1350 ℃ of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz constitutes dielectric substrate).
With 0.7gLNF powder and 0.3gGd doped Ce O
2(Gd
0.2Ce
0.8O
2, GDC) mixture of powder and 1g terpinol are mixed into slurry, are deposited on the dielectric substrate that material is ScSZ and, promptly process anti-chromium and poison layer after 0.5 hour in 110 ℃ of dryings through the silk screen printing method; Mixture and 1g terpinol with 0.7gLSM powder and 0.3gGDC powder is mixed into slurry then, is deposited on anti-chromium through the silk screen printing method and poisons layer and go up and after 0.5 hour, promptly process active layer in 110 ℃ of dryings; At last 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on the active layer and through the silk screen printing method and after 0.5 hour, promptly process current collection layer, obtain the base substrate of SOFC functionally gradient composite cathode in 110 ℃ of dryings.The base substrate of SOFC functionally gradient composite cathode was promptly obtained SOFC functionally gradient composite cathode in 2 hours at 1100 ℃ of sintering.The SOFC functionally gradient composite cathode of present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, under 750 ℃, Fe-Cr alloy connector existence condition in 50mA cm
-2Current density under the operation 1000h after, cathodic polarization resistance is merely 12.1 Ω cm
2, and for pure LSM negative electrode, at 750 ℃ in 50mA cm
-2Current density under the operation 433h after, its polarization resistance reaches 32.2 Ω cm
2
Embodiment 2:
With weight is that the ScSZ powder of 10 grams, the butanone and 4 of adding 8 grams restrain in the ethanol mixed solvent; Added triethanolamine 0.5 gram ball mill mixing then 2 hours; Add 0.4 gram polyvinyl butyral resin again; 1.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry one; 50gNiO and 50gYSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added triethanolamine 3 gram ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry two.Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding.Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, at last in 1350 ℃ of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz constitutes dielectric substrate).
With 0.7gLNF powder and 0.3gSm doped Ce O
2(Sm
0.2Ce
0.8O
2, SDC) mixture of powder and 1g terpinol are mixed into slurry, are deposited on the dielectric substrate that material is ScSZ and, promptly process anti-chromium and poison layer after 0.5 hour in 110 ℃ of dryings through the silk screen printing method; Mixture and 1g terpinol with 0.7gLSM powder and 0.3gSDC powder is mixed into slurry then, is deposited on anti-chromium through the silk screen printing method and poisons layer and go up and after 0.5 hour, promptly process active layer in 110 ℃ of dryings; At last 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on the active layer and through the silk screen printing method and after 0.5 hour, promptly process the LSM current collection layer, obtain the base substrate of SOFC functionally gradient composite cathode in 110 ℃ of dryings.The base substrate of above-mentioned SOFC functionally gradient composite cathode 1100 ℃ of sintering 2 hours, is promptly obtained SOFC functionally gradient composite cathode.The SOFC functionally gradient composite cathode of present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, under 750 ℃, Fe-Cr alloy connector existence condition in 50mA cm
-2Current density under the operation 1000h after, cathodic polarization resistance is merely 13.0 Ω cm
2, and for pure LSM negative electrode, at 750 ℃ in 50mA cm
-2Current density under the operation 433h after, its polarization resistance reaches 32.2 Ω cm
2
Embodiment 3:
With weight is that the ScSZ powder of 10 grams, the butanone and 4 of adding 8 grams restrain in the ethanol mixed solvent; Added triethanolamine 0.5 gram ball mill mixing then 2 hours; Add 0.4 gram polyvinyl butyral resin again; 1.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry one; 50gNiO and 50gYSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added triethanolamine 3 gram ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry two.Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding.Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, at last in 1350 ℃ of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz constitutes dielectric substrate).
The mixture and the 1g terpinol of 0.7g LNF powder, 0.15gGDC powder and 0.15gSDC powder are mixed into slurry, are deposited on the dielectric substrate that material is ScSZ and after 0.5 hour, promptly process anti-chromium and poison layer in 110 ℃ of dryings through the silk screen printing method; Mixture and 1g terpinol with 0.7gLSM powder, 0.15gGDC powder and 0.15gSDC powder is mixed into slurry then, is deposited on anti-chromium through the silk screen printing method and poisons layer and go up and after 0.5 hour, promptly process active layer in 110 ℃ of dryings; At last 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on the active layer and through the silk screen printing method and after 0.5 hour, promptly process the LSM current collection layer, obtain the base substrate of SOFC functionally gradient composite cathode in 110 ℃ of dryings.The base substrate of above-mentioned SOFC functionally gradient composite cathode 1100 ℃ of sintering 2 hours, is promptly obtained SOFC functionally gradient composite cathode.The SOFC functionally gradient composite cathode of present embodiment preparation has excellent anti-chromium and poisons performance and electrochemical catalysis performance, under 750 ℃, Fe-Cr alloy connector existence condition in 50mA cm
-2Current density under the operation 1000h after, cathodic polarization resistance is merely 12.5 Ω cm
2, and for pure LSM negative electrode, at 750 ℃ in 50mA cm
-2Current density under the operation 433h after, its polarization resistance reaches 32.2 Ω cm
2
Embodiment 4:
With weight is the ScSZ powder of 10 grams; Add in the butanone and 4 gram ethanol mixed solvent of 8 grams; Added triethanolamine 0.5 gram ball mill mixing then 2 hours; Add 0.4 gram polyvinyl butyral resin again; 1.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum, this is a slurry one; 50gNiO and 50gYSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added triethanolamine 3 gram ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous; The slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum, this is a slurry two.Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding.Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, at last in 1350 ℃ of sintering 3h, obtain NiO-YSZ/ScSZ anodic composite film (wherein ScSz constitutes dielectric substrate).
With 0.8gLNF powder and 0.2gGd doped Ce O
2(Gd
0.2Ce
0.8O
2, GDC) mixture of powder and 1g terpinol are mixed into slurry, are deposited on the dielectric substrate that material is ScSZ and, promptly process anti-chromium and poison layer after 0.5 hour in 110 ℃ of dryings through the silk screen printing method; Mixture and 1g terpinol with 0.7gLSM powder and 0.3gGDC powder is mixed into slurry then, is deposited on anti-chromium through the silk screen printing method and poisons layer and go up and after 0.5 hour, promptly process active layer in 110 ℃ of dryings; At last 1gLSM powder and 1g terpinol are mixed into slurry, are deposited on the active layer and through the silk screen printing method and after 0.5 hour, promptly process current collection layer, obtain the base substrate of SOFC functionally gradient composite cathode in 110 ℃ of dryings.The base substrate of SOFC functionally gradient composite cathode was promptly obtained SOFC functionally gradient composite cathode in 2 hours at 1100 ℃ of sintering.The SOFC functionally gradient composite cathode of present embodiment has excellent anti-chromium and poisons performance and electrochemical catalysis performance, under 750 ℃, Fe-Cr alloy connector existence condition in 50mA cm
-2Current density under the operation 800h after, cathodic polarization resistance is merely 19.5 Ω cm
2, and for pure LSM negative electrode, at 750 ℃ in 50mA cm
-2Current density under the operation 433h after, its polarization resistance reaches 32.2 Ω cm
2
The preparation method of the pure LSM negative electrode of mentioning among each embodiment of this embodiment is following:
With weight is that the ScSZ powder of 10 grams, the butanone and 4 of adding 8 grams restrain in the ethanol mixed solvent; Added triethanolamine 0.5 gram ball mill mixing then 2 hours; Add 0.4 gram polyvinyl butyral resin again; 1.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry one; 50gNiO and 50gYSZ mixed powder are joined in the butanone and 24 gram ethanol mixed solvent of 48 grams; Added triethanolamine 3 gram ball mill mixing then 2 hours; Add 10 gram polyvinyl butyral resins again; 13.5 restrain polyethylene glycol and continue that ball milling was stablized in 2 hours, the slurry of homogeneous, the slurry that ball milling is good keeps 10 minutes bubbles of eliminating in the slurry under 100 millibars of conditions of vacuum degree, this is a slurry two.Homogeneous, stable slurry one are poured into flow casting molding in the feed bin of casting machine, treat its drying after, slurry two poured into carries out Secondary Flow on it and prolong moulding.Make NiO-YSZ/ScSZ anodic composite film biscuit through dry, section, biscuit in 600 ℃ of heat treatment 3h with the burn off biscuit in organic substance, in 1350 ℃ of sintering 3h, obtain the NiO-YSZ/ScSZ anodic composite film at last.
1gLSM powder and 1g terpinol are mixed into slurry; Be deposited on the dielectric substrate that material is ScSZ and in 110 ℃ of dryings after 0.5 hour through the silk screen printing method; Obtain the base substrate of pure LSM negative electrode, the base substrate of pure LSM negative electrode was promptly obtained pure LSM negative electrode in 2 hours at 1100 ℃ of sintering.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variation.Therefore, all technical staff in the art all should be in the determined protection range by claims under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a SOFC functionally gradient composite cathode is characterized in that, comprising:
Anti-chromium poisons layer, and the material that said anti-chromium poisons layer is LNF-doped Ce O
2
Active layer, the material of said active layer are LSM-doped Ce O
2, said active layer is positioned at said anti-chromium to be poisoned on the layer;
Current collection layer, the material of said current collection layer are LSM, and said current collection layer is positioned on the said active layer.
2. SOFC functionally 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. SOFC functionally 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. SOFC functionally gradient composite cathode as claimed in claim 1, wherein said LNF-doped Ce O
2In doped Ce O
2, and said LSM-doped Ce O
2In doped Ce O
2, dopant ion is Gd
3+Or/and Sm
3+, mol ratio is (Gd+Sm): Ce=1 ~ 2:8 ~ 9.
5. SOFC; Comprise dielectric substrate and negative electrode; Said negative electrode is positioned on the said dielectric substrate, it is characterized in that, the material of said dielectric substrate is ScSZ; Said negative electrode is like any described SOFC functionally gradient composite cathode of claim 1 ~ 4, and said anti-chromium poisons layer and is positioned on the said dielectric substrate.
6. a method for preparing SOFC functionally gradient composite cathode as claimed in claim 1 is characterized in that, may further comprise the steps:
A), with LNF and doped Ce O
2Mixture and terpinol be mixed into slurry, with this slurry be attached on the said dielectric substrate and drying after, promptly processing material is LNF-doped Ce O
2Said anti-chromium poison layer;
B), with LSM and doped Ce O
2Mixture and terpinol be mixed into slurry, with this slurry be attached to that said anti-chromium poisons that layer is gone up and drying after, promptly processing material is LSM-doped Ce O
2Said active layer;
C), LSM and terpinol are mixed into slurry, with this slurry be attached on the said active layer and drying after, promptly processing material is the said current collection layer of LSM, obtains the base substrate of said SOFC functionally gradient composite cathode;
D), with the blank sintering of said SOFC functionally gradient composite cathode, promptly obtain said SOFC functionally gradient composite cathode.
7. the preparation method of SOFC functionally gradient composite cathode as claimed in claim 6, in the wherein said step a), said LNF and said doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2, said LNF and doped Ce O
2Mixture and the mass ratio of said terpinol be 1:0.7 ~ 1; Said this slurry is attached on the said dielectric substrate, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
8. the preparation method of SOFC functionally gradient composite cathode as claimed in claim 6, in the wherein said step b), said LSM and said doped Ce O
2Mass ratio be 7 ~ 8: 3 ~ 2, said LSM and doped Ce O
2Mixture and the mass ratio of said terpinol be 1:0.7 ~ 1; Saidly this slurry is attached to said anti-chromium poisons on the layer, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
9. the preparation method of SOFC functionally gradient composite cathode as claimed in claim 6, in the wherein said step c), the mass ratio of said LSM and said terpinol is 1:0.7 ~ 1; Said this slurry is attached on the said active layer, employed method is a silk screen print method; The temperature of said drying is 100 ℃ ~ 120 ℃, and the time of said drying is 0.5 h ~ 2 hours.
10. the preparation method of SOFC functionally gradient composite cathode as claimed in claim 6, in the wherein said step d), the temperature of said sintering is 1050 ℃ ~ 1100 ℃, the time of said sintering is 2 h ~ 3 hours.
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