CN112779555A - High-performance solid oxide electrolytic cell and preparation method thereof - Google Patents
High-performance solid oxide electrolytic cell and preparation method thereof Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003792 electrolyte Substances 0.000 claims abstract description 91
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 56
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002001 electrolyte material Substances 0.000 claims abstract description 47
- 239000011229 interlayer Substances 0.000 claims abstract description 44
- 239000000446 fuel Substances 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000007650 screen-printing Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000007888 film coating Substances 0.000 claims abstract description 4
- 238000009501 film coating Methods 0.000 claims abstract description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- -1 salt compound Chemical class 0.000 claims description 8
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 7
- 229910016285 MxNy Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009766 low-temperature sintering Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 14
- 239000010408 film Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 7
- 238000010345 tape casting Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910002127 La0.6Sr0.4Co0.2Fe0.8O3 Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 3
- 229910002138 La0.6Sr0.4CoO3 Inorganic materials 0.000 description 2
- 229910002805 Sm0.2Ce0.8O2 Inorganic materials 0.000 description 2
- 229910002810 Sm0.5Sr0.5CoO3−δ Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910021320 cobalt-lanthanum-strontium oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a high-performance solid oxide electrolytic cell and a preparation method thereof, wherein the solid oxide electrolytic cell adopts a fuel electrode as a support body, adopts a doped zirconia-based material to prepare an electrolyte film, adopts a nano-scale doped cerium oxide-based electrolyte material and/or adopts a salt solution corresponding to the cerium oxide-based electrolyte material to prepare a cerium oxide-based electrolyte interlayer on the electrolyte film after sintering and compacting, and sinters and compacts the cerium oxide-based electrolyte interlayer between 900-1250 ℃; and preparing the high-activity cobalt-containing composite oxygen electrode by adopting a screen printing or film coating method. The cerium oxide-based electrolyte interlayer is prepared by low-temperature sintering in the solid oxide electrolytic cell prepared by the invention, so that the contact performance of an oxygen electrode and an electrolyte interface is effectively improved, the contact resistance of the oxygen electrode and the electrolyte interface is reduced, and the performance of the electrolytic cell is improved.
Description
Technical Field
The invention relates to the field of solid oxide electrolytic cells, in particular to a high-performance solid oxide electrolytic cell and a preparation method thereof.
Background
A Solid Oxide Electrolysis Cell (SOEC) is an electrochemical device that converts electrical and thermal energy to chemical energy in fuels in an efficient and environmentally friendly manner at medium and high temperatures. It can be considered as a reverse reaction device of a Solid Oxide Fuel Cell (SOFC). The solid oxide electrolytic cell is of an all-solid structure, gas products are easy to separate, the problems of evaporation, corrosion, electrolyte loss and the like caused by using liquid electrolyte are avoided, the electrode reaction rate is high, noble metal electrodes such as Pt and the like are not needed, the cost is greatly reduced, and the method is considered to be one of the most feasible and most promising technical paths for converting water vapor and/or carbon dioxide into fuel at present.
In order to reduce the manufacturing cost and meet the application requirements of commercialization, the improvement of the performance and stability of the solid oxide electrolytic cell becomes the key point of research and development at home and abroad. An effective way to improve the performance and stability of the electrolytic cell is to use highly active electrode materials and to improve the compatibility between the electrolytic cell materials, for example, to use highly active cobalt-containing oxygen electrode materials to reduce the polarization resistance of the electrode. However, the most mature zirconia-based electrolytes (e.g., Y) are currently available2O3Stabilized ZrO2、Sc2O3Stabilized ZrO2) Compared with the currently used middle-low temperature high-performance cobalt-containing oxygen electrode material, such as BaxSr1-xCoyFe1-yO3(BSCF)(0＜x＜1，0＜y＜1)、LnxSr1-xCoyFe1-yO3(LSCF) (Ln ═ La, Sm, Nd, Gd, or Dy, 0 < x < 1, 0 < y < 1), LaxSr1- xCoO3(LSC)(0＜x＜1)、SmxSr1-xCoO3(SSC) (0 < x < 1), etc., which are poor in chemical compatibility, are liable to undergo harmful chemical reactions during sintering and operation of the oxygen electrode, and are liable to occur at the interface between the oxygen electrode and the electrolyteHigh-impedance phase impurities are generated, so that the performance of the electrolytic cell is sharply attenuated.
Cerium oxide based electrolyte thin films (e.g. Gd)2O3Doped CeO2、Sm2O3Doped CeO2) The electrolyte has higher ionic conductance, but is easy to reduce with fuel in the operation process of the solid oxide electrolytic cell to generate electronic conductance, so that the performance of the electrolytic cell is reduced, and the reduction of cerium oxide can cause the rupture of an electrolyte film, so that the electrolytic cell is completely scrapped.
Disclosure of Invention
Based on the technical problems, the invention provides a high-performance solid oxide electrolytic cell and a preparation method thereof. The invention prepares the cerium oxide-based electrolyte interlayer by low-temperature sintering on the zirconium oxide-based electrolyte film, combines the high-performance cobalt-containing oxygen electrode material with the zirconium oxide-based electrolyte to prepare the high-performance solid oxide electrolytic cell, and improves the long-term stability and reliability of the electrolytic cell.
The technical solution adopted by the invention is as follows:
a high-performance solid oxide electrolytic cell comprises a fuel electrode support body, a zirconia-based electrolyte film and a cobalt-containing composite oxygen electrode, wherein a ceria-based electrolyte interlayer is arranged on the zirconia-based electrolyte film;
the cerium oxide-based electrolyte interlayer is prepared by adopting a nano-grade doped cerium oxide-based electrolyte material and/or adopting a salt solution corresponding to the cerium oxide-based electrolyte material.
Preferably, the fuel electrode support body is a composite electrode made of nickel oxide and zirconia-based electrolyte material, wherein the nickel oxide accounts for 30-70%, and the zirconia-based electrolyte material accounts for 30-70%, by mass percent;
the zirconia-based electrolyte material is MxNyZr1-x-yO2M, N is one of Y, Sc and Ce, x is more than or equal to 0.02 and less than or equal to 0.2, and Y is more than or equal to 0 and less than or equal to 0.2.
Preferably, the zirconia-based electrolyte thin film is made of a zirconia-based electrolyte material, and the zirconia-based electrolyte materialThe material is MxNyZr1-x-yO2M, N is one of Y, Sc and Ce, x is more than or equal to 0.02 and less than or equal to 0.2, and Y is more than or equal to 0 and less than or equal to 0.2.
Preferably, the cerium oxide-based electrolyte material is LnxCe1-xO3Ln is one or more of Gd, Sm, Y and La, and x is more than or equal to 0.05 and less than or equal to 0.5.
Preferably, the zirconia-based electrolyte thin film has a thickness of 1 micron to 100 microns, more preferably 5 microns to 40 microns; the thickness of the cerium oxide-based electrolyte barrier layer is 50 nm to 10 micrometers, more preferably 100 nm to 5 micrometers.
The preparation method of the high-performance solid oxide electrolytic cell comprises the following steps:
(1) preparing a fuel electrode support body by adopting nickel oxide and zirconia-based electrolyte materials;
(2) preparing a zirconia-based electrolyte film on one side of a fuel electrode support;
(3) preparing a cerium oxide-based electrolyte interlayer on the zirconium oxide-based electrolyte film by adopting nano-scale doped cerium oxide-based electrolyte material and/or adopting a salt solution corresponding to the cerium oxide-based electrolyte material, and sintering and compacting the cerium oxide-based electrolyte interlayer at the temperature of 900-1250 ℃;
(4) and preparing the high-performance cobalt-containing composite oxygen electrode by adopting a screen printing or film coating method, thereby obtaining the high-performance solid oxide electrolytic cell.
In the step (1): 30-70% of nickel oxide and 30-70% of zirconia-based electrolyte material by mass percentage; specifically, a tape casting method or the like may be employed for preparing the fuel electrode support.
In the step (2): the zirconia-based electrolyte film is made of a zirconia-based electrolyte material, wherein the zirconia-based electrolyte material is MxNyZr1-x-yO2M, N is one of Y, Sc and Ce, x is more than or equal to 0.02 and less than or equal to 0.2, and Y is more than or equal to 0 and less than or equal to 0.2. For example, the zirconia-based electrolyte material can be yttria-doped zirconia (YSZ), scandia-doped zirconia (ScSZ), ceria and scandia-doped zirconia (CeScSZ), and the like.
When the zirconia-based electrolyte film is prepared, zirconia-based electrolyte material can be prepared into slurry, then the slurry is coated on one side of a fuel electrode support body, and the slurry is sintered and compacted at about 1400 ℃.
In the step (3), the nano-doped cerium oxide-based electrolyte material can be prepared into slurry or salt solution, then coated on the zirconium oxide-based electrolyte film by adopting a coating or dipping method, and then sintered and compacted under a low-temperature condition to form the cerium oxide-based electrolyte interlayer. Wherein, the salt solution can be prepared by nano-grade doped cerium oxide-based electrolyte material and salt compound aqueous solution which can be dissolved in water.
Preferably, step (3) further comprises the following steps: the sintered cerium oxide-based electrolyte barrier layer is impregnated with an aqueous solution of a salt compound and then calcined. The salt compound aqueous solution is an aqueous solution of gadolinium nitrate and cerium nitrate, or an aqueous solution of samarium nitrate and cerium nitrate. The calcination temperature after impregnation is preferably 1100-.
Preferably, the molar ratio of the gadolinium nitrate to the cerium nitrate in the aqueous solution of the gadolinium nitrate and the cerium nitrate or the aqueous solution of the samarium nitrate and the cerium nitrate is 2: 8, and the molar ratio of the samarium nitrate to the cerium nitrate is 2: 8.
The concentration of the aqueous solution of the salt compound is 0.1 to 45% by mass, more preferably 0.5 to 30% by mass.
The compactness of the cerium oxide-based electrolyte interlayer can be further improved by continuously impregnating the salt compound aqueous solution and sintering.
Preferably, the cerium oxide-based electrolyte material is LnxCe1-xO3Ln is one or more of Gd, Sm, Y and La, and x is more than or equal to 0.05 and less than or equal to 0.5.
Preferably, the zirconia-based electrolyte thin film has a thickness of 1 micron to 100 microns, more preferably 5 microns to 40 microns; the thickness of the cerium oxide-based electrolyte interlayer is 50 nanometers to 10 micrometers, and more preferably 100 nanometers to 5 micrometers; the particle size of the nano-scale doped cerium oxide-based electrolyte material is 0.1-100 nanometers, and more preferably 1-40 nanometers.
The beneficial technical effects of the invention are as follows:
the invention adopts the nano-grade doped cerium oxide-based electrolyte material and/or the salt solution corresponding to the cerium oxide-based electrolyte material to prepare the cerium oxide-based electrolyte interlayer through low-temperature sintering, effectively prevents chemical reaction and element diffusion between the high-activity cobalt-containing oxygen electrode and the zirconium oxide-based electrolyte, relieves the difference of thermal expansion properties between the high-activity cobalt-containing oxygen electrode and the zirconium oxide-based electrolyte, improves the contact performance between the oxygen electrode and an electrolyte interface, simultaneously avoids the high-temperature reaction with the zirconium oxide-based electrolyte to generate a high-impedance phase cerium-zirconium oxide solid solution in the preparation process of the cerium oxide-based electrolyte interlayer, and greatly improves the performance of an electrolytic cell.
The high-performance solid oxide electrolytic cell can prevent the reduction of the cerium oxide-based electrolyte and the chemical reaction and element diffusion between the zirconium oxide-based electrolyte and the high-activity cobalt-containing oxygen electrode by preparing the cerium oxide-based electrolyte interlayer on the zirconium oxide-based electrolyte film, and can greatly improve the performance of the solid oxide electrolytic cell.
The effects of the present invention will be described more specifically below:
1. the cerium oxide-based electrolyte interlayer is prepared by low-temperature sintering in the solid oxide electrolytic cell prepared by the invention, so that the contact performance of an oxygen electrode and an electrolyte interface is effectively improved, the contact resistance of the oxygen electrode and the electrolyte interface is reduced, and the performance of the electrolytic cell is improved.
2. The solid oxide electrolytic cell prepared by the invention adopts low-temperature sintering to prepare the cerium oxide-based electrolyte interlayer, effectively improves the matching property of the chemical compatibility and the thermal expansion property of the cobalt-containing oxygen electrode and the zirconium oxide-based electrolyte, and improves the long-term stability and the reliability of the electrolytic cell.
3. The cerium oxide-based electrolyte interlayer prepared by the method can be sintered and compacted at the temperature of 900-.
4. In the process of preparing the cerium oxide-based electrolyte interlayer, the compactness of the cerium oxide-based electrolyte interlayer can be further improved by impregnating the cerium oxide-based electrolyte interlayer with a salt compound aqueous solution and sintering at a certain temperature.
5. The method has the characteristics of low cost, easy amplification, high electrolytic performance of the prepared solid oxide electrolytic cell, good stability and the like.
6. The invention can be used for solid oxide electrolytic cells with various configurations such as flat plates, tubes and the like.
Detailed Description
The invention discloses a high-performance solid oxide electrolytic cell and a preparation method thereof, wherein the solid oxide electrolytic cell adopts a fuel electrode as a support body, adopts a doped zirconia-based material to prepare an electrolyte film, adopts a nano-scale doped cerium oxide-based electrolyte material and/or adopts a salt solution corresponding to the cerium oxide-based electrolyte material to prepare a cerium oxide-based electrolyte interlayer after being sintered and compacted on the electrolyte film, and sinters and compacts the cerium oxide-based electrolyte interlayer between 900-1250 ℃; and preparing the high-activity cobalt-containing composite oxygen electrode by adopting a screen printing or film coating method to finally obtain the solid oxide electrolytic cell. Compared with the electrolytic cell without the cerium oxide-based electrolyte interlayer, the electrolytic performance of the solid oxide electrolytic cell prepared by the invention is obviously improved.
The invention is further illustrated by the following specific examples:
example 1
Nickel oxide and Y2O3Stabilized ZrO2(Y0.08Zr0.92O28YSZ) electrolyte material mix (50: 50) the fuel electrode support was prepared by tape casting, and had a thickness of about 600 μm. Coating a layer of YSZ slurry with thickness of about 15 μm, sintering at 1400 deg.C to compact, and applying Gd with particle size of about 4 nm on the YSZ electrolyte2O3Doped CeO2(Gd0.2Ce0.8O2GDC) was sintered at 1200 c to produce a GDC electrolyte separator layer with a thickness of about 2 microns. La0.6Sr0.4Co0.2Fe0.8O3(LSCF) and GDCAfter mixing (according to the weight ratio of 60: 40), preparing a composite oxygen electrode by adopting a screen printing method, and roasting for 2h at 900 ℃ to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas with volume fraction of 90% of water vapor and 10% of hydrogen into the fuel electrode, and applying voltage of more than 1V to the electrolytic cell to decompose the water vapor into H at the fuel electrode2Forming O at the oxygen electrode2. The performance of the electrolytic cell is tested at 800 ℃, and the electrolytic current can reach 600mA/cm when the electrolytic voltage is 1.1V2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1200mA/cm2. The electrolytic cell is tested at 700 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 300mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 600mA/cm2. The electrolytic cell has better stability, and the electrolytic performance attenuation rate of 800 ℃ per thousand hours is less than 2 percent. Compared with a battery without an interlayer, the performance of the 800 ℃ electrolytic cell is improved by 120 percent, and the performance of the 700 ℃ electrolytic cell is improved by 180 percent.
Example 2
Nickel oxide and Sc2O3Stabilized ZrO2(Sc0.1Zr0.9O210ScSZ) electrolyte material (65: 35) the fuel electrode support was prepared by tape casting, and had a thickness of about 400 microns. Coating a layer of 10ScSZ slurry with the thickness of about 10 μm on the surface, sintering at 1450 ℃ to compact, and then adopting Sm with the particle size of about 2 nanometers on the 10ScSZ electrolyte2O3Doped CeO2(Sm0.2Ce0.8O2SDC) was sintered at 1200 c to produce SDC electrolyte separator layers having a thickness of about 5 microns. La0.6Sr0.4Co0.2Fe0.8O3Mixing with SDC (in a weight ratio of 60: 40), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 1000 ℃ for 2h to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas of 80% water vapor and 20% hydrogen in volume fraction to the fuel electrode, and applying voltage of 1V or more to the electrolytic cell to decompose water vapor into H at the fuel electrode2Forming O at the oxygen electrode2. Testing the cell at 800 deg.C, electrolyzingWhen the voltage is 1.1V, the electrolytic current can reach 800mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1400mA/cm2. When the electrolytic cell is tested at 700 ℃, the electrolytic current can reach 400mA/cm when the electrolytic voltage is 1.1V2When the electrolytic voltage is 1.3V, the electrolytic current can reach 700mA/cm2. The electrolytic cell has better stability, and the electrolytic performance attenuation rate of 800 ℃ per thousand hours is less than 2 percent. Compared with an electrolytic cell without an interlayer, the performance of the electrolytic cell at 800 ℃ is improved by 150%, and the performance of the electrolytic cell at 700 ℃ is improved by 200%.
Example 3
Nickel oxide and Sc2O3Stabilized ZrO2(Sc0.1Zr0.9O210ScSZ) electrolyte material (60: 40) the fuel electrode support was prepared by tape casting, and had a thickness of about 400 microns. Coating a layer of 10ScSZ slurry with the thickness of about 10 μm on the surface, sintering at 1450 ℃ to compact, and then adopting Sm with the particle size of about 10 nanometers on the 10ScSZ electrolyte2O3Doped CeO2(Sm0.2Ce0.8O2SDC), a SDC electrolyte separator layer sintered at 1100 c, the separator layer having a thickness of about 3 microns. Then dipping the interlayer with the dipping molar ratio of 2: 8, roasting the aqueous solution of samarium nitrate and cerium nitrate at 1000 ℃ to obtain the compact SDC electrolyte interlayer. Sm0.5Sr0.5CoO3-δMixing with SDC (in a weight ratio of 60: 40), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 1100 ℃ for 2h to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas of 80% water vapor and 20% hydrogen in volume fraction to the fuel electrode, and applying voltage of 1V or more to the electrolytic cell to decompose water vapor into H at the fuel electrode2Forming O at the oxygen electrode2. The electrolytic cell is tested at 800 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 800mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1400mA/cm2. When the electrolytic cell is tested at 700 ℃, the electrolytic current can reach 400mA/cm when the electrolytic voltage is 1.1V2When the electrolytic voltage is 1.3V, the electrolytic current can reach 700mA/cm2. ElectrolysisThe cell has better stability, and the electrolytic performance attenuation rate of 800 ℃ per thousand hours is less than 3 percent. Compared with an electrolytic cell without an interlayer, the performance of the electrolytic cell at 800 ℃ is improved by 150%, and the performance of the electrolytic cell at 700 ℃ is improved by 200%.
Example 4
Nickel oxide and CeO2And Sc2O3Doped ZrO2(Ce0.01Sc0.1Zr0.89O21Ce10ScSZ) electrolyte material (60: 40) the fuel electrode support was prepared by tape casting, and had a thickness of about 300 microns. Coating a layer of slurry with the thickness of about 30 mu m 1Ce10ScSZ thereon, sintering and compacting at 1350 ℃, and then adopting Gd with the grain diameter of about 40 nanometers on the 1Ce10ScSZ electrolyte2O3Doped CeO2(Gd0.2Ce0.8O2GDC) was calcined at 1200 c to produce a GDC electrolyte separator layer with a thickness of about 10 microns. Then dipping the interlayer with the dipping molar ratio of 2: 8, roasting the aqueous solution of gadolinium nitrate and cerium nitrate at 1200 ℃ to obtain the compact GDC electrolyte interlayer. La0.6Sr0.4CoO3Mixing with GDC (at a weight ratio of 50: 50), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 1000 ℃ for 2h to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas of 70% water vapor and 30% hydrogen in volume fraction to the fuel electrode, and applying voltage of 1V or more to the electrolytic cell to decompose water vapor into H at the fuel electrode2Forming O at the oxygen electrode2. The electrolytic cell is tested at 800 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach the performance of 600mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach the performance of 1100mA/cm2. The electrolytic cell is tested at 700 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach the performance of 300mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 550mA/cm2. The electrolytic cell has better stability, and the electrolytic performance attenuation rate of 800 ℃ per thousand hours is less than 3 percent. Compared with an electrolytic cell without an interlayer, the performance of the electrolytic cell at 800 ℃ is improved by 100 percent, and the performance of the electrolytic cell at 700 ℃ is improved by 150 percent.
Example 5
Nickel oxide and CeO2And Sc2O3Doped ZrO2(Ce0.01Sc0.1Zr0.89O21Ce10ScSZ) electrolyte material (60: 40) the fuel electrode support was prepared by tape casting, and had a thickness of about 300 microns. Coating a layer of slurry with the thickness of about 30 mu m 1Ce10ScSZ on the surface, sintering the slurry at 1400 ℃ to be compact, and then adopting Gd with the grain diameter of about 20 nanometers on the 1Ce10ScSZ electrolyte2O3Doped CeO2(Gd0.2Ce0.8O2GDC) was calcined at 1200 c to produce a GDC electrolyte separator layer with a thickness of about 10 microns. Then dipping the interlayer with the dipping molar ratio of 2: 8, roasting at 1100 ℃ to obtain a compact GDC electrolyte interlayer, namely La0.6Sr0.4CoO3Mixing with GDC (at a weight ratio of 50: 50), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 900 ℃ for 2h to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas of 70% water vapor and 30% hydrogen in volume fraction to the fuel electrode, and applying voltage of 1V or more to the electrolytic cell to decompose water vapor into H at the fuel electrode2Forming O at the oxygen electrode2. When the electrolytic cell is tested at 800 ℃, the electrolytic current can reach 600mA/cm when the electrolytic voltage is 1.1V2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1100mA/cm2. The electrolytic cell is tested at 700 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 300mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 550mA/cm2. The electrolytic cell has better stability, and the electrolytic performance attenuation rate of 800 ℃ per thousand hours is less than 3 percent.
Example 6
Nickel oxide and CeO2And Sc2O3Doped ZrO2(Ce0.01Sc0.1Zr0.89O21Ce10ScSZ) electrolyte material (60: 40) the fuel electrode support was prepared by tape casting, and had a thickness of about 200 μm. Coating a layer of 20 μm 1Ce10ScSAnd (3) after sintering and compacting the slurry of Z at 1450 ℃, dip-coating the slurry on a 1Ce10ScSZ electrolyte in a molar ratio of 2: 8, roasting the aqueous solution of gadolinium nitrate and cerium nitrate at 1150 ℃ to obtain a compact GDC electrolyte interlayer, wherein the thickness of the interlayer is about 100 nanometers. Sm0.5Sr0.5CoO3-δMixing with GDC (at a weight ratio of 60: 40), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 950 ℃ for 4h to obtain the high-performance solid oxide electrolytic cell.
Introducing mixed gas with volume fraction of 50% of water vapor, 25% of carbon dioxide and 25% of hydrogen into the fuel electrode, and applying voltage of more than 1V to the electrolytic cell to decompose the water vapor and the carbon dioxide into H at the fuel electrode2And CO, forming O at the oxygen electrode2. The electrolytic cell is tested at 800 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 500mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1000mA/cm2. The electrolytic cell is tested at 700 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 200mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 500mA/cm2。
Example 7
Nickel oxide and CeO2And Sc2O3Doped ZrO2(Ce0.01Sc0.1Zr0.89O21Ce10ScSZ) electrolyte material (60: 40) the fuel electrode support was prepared by extrusion molding, and had a thickness of about 300 μm. Gd having a particle size of about 5 nm is applied thereto2O3Doped CeO2(Gd0.2Ce0.8O2GDC) was calcined at 1200 c to produce a GDC electrolyte separator with a thickness of about 3 microns. Then dipping the interlayer with the dipping molar ratio of 2: 8, roasting the aqueous solution of gadolinium nitrate and cerium nitrate at 1100 ℃ to obtain the compact GDC electrolyte interlayer. La0.6Sr0.4Co0.2Fe0.8O3Mixing with GDC (at a weight ratio of 60: 40), preparing a composite oxygen electrode by adopting a screen printing method, and roasting at 950 ℃ for 4h to obtain the high-performance solid oxide electrolytic cell.
Introducing volume fraction to fuel electrodeIs a mixed gas of 50% of water vapor, 25% of carbon dioxide and 25% of hydrogen, and applies a voltage of 1V or more to the electrolytic cell, so that the water vapor and the carbon dioxide are decomposed into H at the fuel electrode2And CO, forming O at the oxygen electrode2. The electrolytic cell is tested at 800 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 500mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 1000mA/cm2. The electrolytic cell is tested at 700 ℃, when the electrolytic voltage is 1.1V, the electrolytic current can reach 200mA/cm2When the electrolytic voltage is 1.3V, the electrolytic current can reach 500mA/cm2. Compared with an electrolytic cell without an interlayer, the performance of the electrolytic cell at 800 ℃ is improved by 80 percent, and the performance of the electrolytic cell at 700 ℃ is improved by 120 percent.
Claims (10)
1. A high-performance solid oxide electrolytic cell comprises a fuel electrode support body, a zirconia-based electrolyte film and a cobalt-containing composite oxygen electrode, and is characterized in that: a cerium oxide-based electrolyte interlayer is arranged on the zirconium oxide-based electrolyte film;
the cerium oxide-based electrolyte interlayer is prepared by adopting a nano-grade doped cerium oxide-based electrolyte material and/or adopting a salt solution corresponding to the cerium oxide-based electrolyte material.
2. A high performance solid oxide electrolytic cell in accordance with claim 1, wherein: the fuel electrode support body is a composite electrode made of nickel oxide and zirconia-based electrolyte material, wherein the nickel oxide accounts for 30-70%, and the zirconia-based electrolyte material accounts for 30-70%;
the zirconia-based electrolyte material is MxNyZr1-x-yO2M, N is one of Y, Sc and Ce, x is more than or equal to 0.02 and less than or equal to 0.2, and Y is more than or equal to 0 and less than or equal to 0.2.
3. A high performance solid oxide electrolytic cell in accordance with claim 1, wherein: the zirconia-based electrolyte film is made of a zirconia-based electrolyte material, wherein the zirconia-based electrolyte material is MxNyZr1-x-yO2And M, N is Y, ScX is more than or equal to 0.02 and less than or equal to 0.2, and y is more than or equal to 0 and less than or equal to 0.2 in one of Ce.
4. A high performance solid oxide electrolytic cell in accordance with claim 1, wherein: the cerium oxide-based electrolyte material is LnxCe1-xO3Ln is one or more of Gd, Sm, Y and La, and x is more than or equal to 0.05 and less than or equal to 0.5.
5. A high performance solid oxide electrolytic cell in accordance with claim 1, wherein: the thickness of the zirconia-based electrolyte film is 5-40 microns; the thickness of the cerium oxide-based electrolyte interlayer is 100 nanometers to 5 micrometers.
6. The method of making a high performance solid oxide electrolytic cell as defined in any one of claims 1 to 5, comprising the steps of:
(1) preparing a fuel electrode support body by adopting nickel oxide and zirconia-based electrolyte materials;
(2) preparing a zirconia-based electrolyte film on one side of a fuel electrode support;
(3) preparing a cerium oxide-based electrolyte interlayer on the zirconium oxide-based electrolyte film by adopting nano-scale doped cerium oxide-based electrolyte material and/or adopting a salt solution corresponding to the cerium oxide-based electrolyte material, and sintering and compacting the cerium oxide-based electrolyte interlayer at the temperature of 900-1250 ℃;
(4) and preparing the high-performance cobalt-containing composite oxygen electrode by adopting a screen printing or film coating method, thereby obtaining the high-performance solid oxide electrolytic cell.
7. The method for preparing a high performance solid oxide electrolytic cell according to claim 6, wherein the step (3) further comprises the steps of: the sintered cerium oxide-based electrolyte barrier layer is impregnated with an aqueous solution of a salt compound and then calcined.
8. The method of claim 7 for making a high performance solid oxide electrolytic cell, wherein: the salt compound aqueous solution is an aqueous solution of gadolinium nitrate and cerium nitrate, or an aqueous solution of samarium nitrate and cerium nitrate.
9. The method of claim 6 for making a high performance solid oxide electrolytic cell, wherein: the zirconia-based electrolyte film is made of a zirconia-based electrolyte material, wherein the zirconia-based electrolyte material is MxNyZr1-x-yO2M, N is one of Y, Sc and Ce, x is more than or equal to 0.02 and less than or equal to 0.2, and Y is more than or equal to 0 and less than or equal to 0.2;
the cerium oxide-based electrolyte material is LnxCe1-xO3Ln is one or more of Gd, Sm, Y and La, and x is more than or equal to 0.05 and less than or equal to 0.5.
10. The method of claim 6 for making a high performance solid oxide electrolytic cell, wherein: the thickness of the zirconia-based electrolyte film is 5-40 microns; the thickness of the cerium oxide-based electrolyte interlayer is 100 nanometers to 5 micrometers; the particle size of the nano-scale doped cerium oxide-based electrolyte material is between 1 nanometer and 40 nanometers.
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