CN104934614B - It is a kind of with the doped cerium oxide catalytic film of preferred orientation and its preparation and application - Google Patents
It is a kind of with the doped cerium oxide catalytic film of preferred orientation and its preparation and application Download PDFInfo
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- CN104934614B CN104934614B CN201410105729.5A CN201410105729A CN104934614B CN 104934614 B CN104934614 B CN 104934614B CN 201410105729 A CN201410105729 A CN 201410105729A CN 104934614 B CN104934614 B CN 104934614B
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- cerium oxide
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 38
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 46
- 238000004544 sputter deposition Methods 0.000 claims description 34
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000012528 membrane Substances 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 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 9
- 229910052771 Terbium Inorganic materials 0.000 claims description 9
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002737 fuel gas Substances 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 229910002607 Gd0.1Ce0.9O1.95 Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910008253 Zr2O3 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses it is a kind of have preferentially expose crystal face doped cerium oxide film, can as SOFC electrode, can also as catalyst be used for catalytic reaction；The film is prepared using the method for reactive magnetron sputtering.Use with the doped cerium oxide film for preferentially exposing crystal face, effectively increases cathode of solid oxide fuel cell to oxygen, anode to the electro catalytic activity of fuel gas, reduces electrode polarization resistance, effectively raise in battery, cryogenic property.
Description
Technical field
It is specifically a kind of that there is the doping oxygen for preferentially exposing crystal face the present invention relates to field of solid oxide fuel
Change the preparation and its application of cerium thin-film electrode material.
Background technology
SOFC is a kind of energy conversion device, can be efficiently by fuel gas（Such as hydrogen, naturally
Gas, coal gas etc.）In chemical energy be converted into electric energy and heat energy, and do not need noble metal catalyst, using structure of whole solid state, low row
Noise is lowerd, is preferably to disperse power station and concentrate power station technology, vehicle accessory power supply, compact power can also be applied to
Deng.
In order to reduce manufacturing cost, battery long-time stability and reliability are improved, shortens the startup time, running temperature exists
400-700 DEG C of intermediate temperature solid oxide fuel cell turns into the emphasis researched and developed both at home and abroad.Cerium oxide base film can conduct
Negative electrode or anode, for SOFC of the running temperature within the scope of 400-800 DEG C.
Doped cerium oxide material has to oxygen, to H2Or CH4Deng the electrocatalysis of fuel gas, using preferred orientation
Doped cerium oxide material film can be to the oxygen reduction process of cell cathode, to H2、CH4Oxidizing process Deng fuel gas rises
To catalytic action, accelerate electro-reduction process of the negative electrode to oxygen, or anode reduces battery to the electro-oxidation process of fuel gas
Negative electrode or anode polarization resistance, so as to improve the performance of battery.
Because traditional ceramic post sintering method can not prepare the doped cerium oxide film with preferred orientation, therefore, have
Necessity prepares doped cerium oxide film using physical gas phase deposition technology.The magnetron sputtering technique energy in physical gas phase deposition technology
Enough ceria films that even compact is prepared in large-area substrates, and process repeatability is good, it is adaptable to prepare with scale,
Therefore, the technology of magnetron sputtering is suitable for preparing the doped cerium oxide film with preferred orientation.
The content of the invention
In order to improve the performance of battery, improve the electrocatalysis characteristic of SOFC, the purpose of the present invention exists
In providing a kind of doped cerium oxide catalytic film with preferred orientation, the electro-catalysis of negative electrode or anode can be effectively improved
Performance, reduces the polarization resistance of battery, improves battery performance.
When the electrolytic thin-membrane is used in SOFC, with oxidation zirconium base or ceria-based electrolyte substrate
It is well combined, even compact, and film crystal is preferentially to expose（111）（110）Or（100）Crystal face.
To reach above-mentioned purpose, the technical scheme is that：
In the anode/zirconium oxide base electrolyte or anode/ceria-based electrolyte membrane electrode substrate, Huo Zhe of anode-supported
Magnetron sputtering deposition has and selected on the negative electrode of cathode support/zirconium oxide base electrolyte film, negative electrode/ceria-based electrolyte film
The doped cerium oxide catalytic film of excellent orientation.
The doped cerium oxide electrode material is LnxCe1-xO2-d, Ln be Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn,
One kind in Cu, Zn, Co, Nb, 0≤x≤0.5；0≤d≤0.2；Or be LnxByCe1-x-yO2-d, wherein Ln be Pr, Nd, Eu,
One kind in Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu, Zn, Co, Nb, B be Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu,
One kind in Zn, Co, Nb, La, Sm, Gd, Y, Mn, 0≤x≤0.3；0≤y≤0.2；0≤d≤0.2.The doped cerium oxide electricity
Pole gross thickness is between 1 nanometer -8 microns, between preferably 6 nanometers -5 microns；Cerium oxide base electrode catalyst film uses magnetic
It is prepared by the method for controlling reactive sputtering；Target used in magnetron sputtering is the cerium-base alloy target of corresponding proportion component.
Gases used is oxygen and argon gas, and purity is all on 99.99%.
First in anode/zirconium oxide base electrolyte of anode-supported, in anode/ceria-based electrolyte membrane electrode substrate,
Or magnetic control reacts in the negative electrode of cathode support/zirconium oxide base electrolyte film, negative electrode/ceria-based electrolyte membrane electrode substrate
Sputtering has the doped cerium oxide catalytic film of preferred orientation, and its sputtering parameter is：Target-substrate distance is 5-9cm, the rotating speed of chip bench
In 1-20 circles/minute, sputtering pressure is 0.1Pa-1.5Pa, Sputtering power density P=3-12W/cm2, oxygen flow and argon gas stream
The ratio between amount is 1/2-1/20, and sputtering base reservoir temperature is at 30-800 DEG C, by controlling the change of sputtering parameter to realize doping oxygen
Change cerium film preferentially to expose（111）、（110）Or（100）Crystal face.
The excellent results of the present invention are：
By on anode/zirconium oxide base electrolyte of anode-supported or anode/ceria-based electrolyte membrane electrode substrate,
Magnetic control reacts in the negative electrode of cathode support/zirconium oxide base electrolyte film, negative electrode/ceria-based electrolyte film electrode basement
Doped cerium oxide catalytic film of the sputtering with preferred orientation, improves electro-catalysis reducing property of the cell cathode to oxygen, or
Person's anode is to H2、CH4Deng the electrocatalytic oxidation ability of fuel gas, the polarization resistance of battery is reduced, battery performance is improved.
1. the SOFC prepared using the present invention, the cerium oxide of doping is effectively changed as cathode material
It has been apt to electrocatalysis characteristic of the negative electrode to oxygen, has reduced the cathodic polarization resistance of battery.
2. the SOFC prepared using the present invention, the cerium oxide of doping is effectively changed as anode material
It has been apt to electrocatalytic oxidation property of the anode to fuel gas, has reduced the anode polarization resistance of battery.
3. SOFC of the present invention available for a variety of configurations such as plate, casts.
4. the present invention be applied to it is a variety of temperature, low-temperature solid oxide fuel cell application field, such as disperse power station, portable
Formula power supply, vehicle-mounted accessory power supply.
Embodiment
Embodiment 1
In nickel oxide and Y2O3Stable ZrO2Composite anode/Y2O3Stable ZrO2Membrane electrode（NiO-YSZ/YSZ）On splash
Penetrating Solute Content in Grain is（100）Fine and close Zr2O3The CeO of doping2（Zr0.2Ce0.8O1.9）Film, successively with acetone, ethanol, steaming
After distilled water is cleaned by ultrasonic the membrane electrode of anode-supported and dried, put within the vacuum chamber of magnetic control sputtering device, adjust
Target-substrate distance is about 6cm, using cerium/gadpolinium alloy material as target, and target purity is on 99.99%, and cerium/zirconium mol ratio is 8/2, is taken out
Vacuum is to 8*10-4Pa, then carries out chip bench heating, and heating is stable to 300 DEG C, is passed through argon flow amount for 10.0sccm, oxygen
Flow is 1.2sccm, and sputtering power is 9W/cm2, sputtering pressure is 0.5Pa, and the speed setting of chip bench is 5 circles/minute, thick
Degree is about 500nm, completes Zr0.2Ce0.8O1.9After the sputtering of film, silver paste is coated thereon, in four-terminal method battery testing
Battery performance test is carried out on device, using air as negative electrode gas, wet hydrogen be anode gas, battery under 700 DEG C of running temperature,
Battery maximum power density can reach 1.6W/cm2, determining battery performance under voltage and can reach 1.41mW/cm in 0.8V2；
Under 550 DEG C of running temperature, battery maximum power density can reach 830mW/cm2, battery under voltage is determined in 0.8V
Performance can reach 690mW/cm2；Effectively increase in battery, cryogenic property, and the power after battery operation 200 hours
Substantially do not decay.
Embodiment 2
In nickel oxide and Gd2O3The CeO of doping2Composite anode/Gd2O3The CeO of doping2Membrane electrode（NiO-GDC/GDC）On
Sputtering Solute Content in Grain is（100）Fine and close SnO2The CeO of doping2（Sn0.1Ce0.9O2）Film, regulation target-substrate distance is about 6cm,
Using cerium/gadpolinium alloy material as target, target purity is on 99.99%, and cerium/tin mol ratio is 9/1, is evacuated to 8*10-4Pa,
Then chip bench heating is carried out, heating is stable to 400 DEG C, is passed through argon flow amount for 10.0sccm, oxygen flow is 1.2sccm,
Sputtering power is 9W/cm2, sputtering pressure is 0.5Pa, and the speed setting of chip bench is 5 circles/minute, and thickness is about 200nm,
Complete Sn0.1Ce0.9O2After the sputtering of film, silver paste is coated thereon, battery is carried out on four-terminal method battery tester
Performance test, using air as negative electrode gas, wet hydrogen is anode gas, and battery is under 600 DEG C of running temperature, and battery peak power is close
Degree can reach 0.6W/cm2, determining battery performance under voltage and can reach 0.52mW/cm in 0.8V2；In 550 DEG C of operation
At a temperature of, battery maximum power density can reach 430mW/cm2, determining battery performance under voltage and can reach in 0.8V
380mW/cm2；Effectively increase in battery, cryogenic property, and power does not substantially decline after battery operation 200 hours
Subtract.
Embodiment 3
In La0.6Sr0.4Co0.2Fe0.8O2-x(0≤x≤0.3)/Gd0.1Ce0.9O1.95The membrane electrode of cathode support
Gd0.1Ce0.9O1.95Bath surface sputters Solute Content in Grain（111）Pr0.1Ce0.9O1.95Anode film, wherein
Pr0.1Ce0.9O1.95Film sputter at 200oC at a temperature of carry out, Ar flows be 20.0ml min-1,O2Flow is 2.0ml
min-1, target-substrate distance is about 6cm, with cerium/praseodymium（Mol ratio is 9/1）Alloy material is target, and target purity is taken out on 99.99%
Vacuum is to 8*10-4Pa, sputtering power is 12W/cm2, sputtering pressure is 0.5Pa, and the speed setting of chip bench is 5 circles/minute, thick
Degree is about 200nm, completes Pr0.1Ce0.9O1.95After the sputtering of film, silver paste is coated thereon, is surveyed in four-terminal method battery
Carry out battery performance test is put in trial assembly, using air as negative electrode gas, methane be anode gas, battery under 600 DEG C of running temperature,
Battery maximum power density can reach 0.8W/cm2, determining battery performance under voltage and can reach 0.64W/cm in 0.8V2；
Under 550 DEG C of running temperature, battery maximum power density can reach 480mW/cm2, battery under voltage is determined in 0.8V
Performance can reach 420mW/cm2；And anode surface does not produce carbon distribution after battery operation 200 hours, power is not bright
Aobvious decay, is effectively increased in battery, cryogenic property.
Embodiment 4
In La0.6Sr0.4Co0.2Fe0.8O2-x(0≤x≤0.3)/Gd0.1Ce0.9O1.95The membrane electrode of cathode support
Gd0.1Ce0.9O1.95Bath surface sputters Solute Content in Grain（110）Co0.05Ce0.95O2-y（0≤y≤0.05）Anode is thin
Film, wherein Co0.05Ce0.95O2-yFilm sputter at 100 DEG C at a temperature of carry out, Ar flows be 10.0ml min-1,O2Flow is
2.4ml min-1, target-substrate distance is about 6cm, with cerium/cobalt（Mol ratio is 95/5）Alloy material is target, and target purity is 99.99%
On, it is evacuated to 8*10-4Pa, sputtering power is 6W/cm2, sputtering pressure is 1.0Pa, the speed setting of chip bench for 5 circles/
Minute, thickness is about 100nm, completes Co0.05Ce0.95O2-yAfter the sputtering of film, silver paste is coated thereon, in four terminals
Battery performance test is carried out on method battery tester, using air as negative electrode gas, methane is anode gas, fortune of the battery at 600 DEG C
Under trip temperature, battery maximum power density can reach 0.6W/cm2, determining battery performance under voltage and can reach in 0.8V
0.46W/cm2；Under 550 DEG C of running temperature, battery maximum power density can reach 480mW/cm2, voltage is determined in 0.8V
Under battery performance can reach 360mW/cm2；And anode surface does not produce carbon distribution, work(after battery operation 200 hours
Rate does not substantially decay, and effectively increases in battery, cryogenic property.
Claims (6)
1. a kind of doped cerium oxide catalytic film with preferred orientation, it is characterised in that：In anode/zirconium oxide of anode-supported
In base electrolyte, anode/ceria-based electrolyte membrane electrode substrate, or negative electrode/zirconium oxide base electrolyte of cathode support is thin
There is reactive magnetron sputtering the doped cerium oxide for preferentially exposing crystal face to urge in film, negative electrode/ceria-based electrolyte membrane electrode substrate
Change film, its sputtering parameter is：Target-substrate distance is 5-9cm, and the rotating speed of chip bench is in 1-20 circles/minute, and sputtering pressure is 0.1Pa-
1.5Pa, Sputtering power density P=3-12W/cm2, the ratio between oxygen flow and argon flow amount are 1/2-1/20, sputter base reservoir temperature
At 30-800 DEG C, by changing target-substrate distance, the rotating speed of chip bench, sputtering pressure, Sputtering power density, oxygen flow and argon gas stream
The ratio between amount, sputtering base reservoir temperature can realize that the doped cerium oxide for depositing preferentially exposure (111), (110) or (100) crystal face is thin
Film；
Cerium oxide base catalytic film, which has, preferentially exposes crystal face；Cerium oxide base catalytic film material is LnxCe1-xO2- d, Ln be Pr,
One kind in Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu, Zn, Co, Nb, 0≤x≤0.5；0≤d≤0.2；Or be
LnxByCe1-x-yO2-d, wherein Ln is one kind in Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu, Zn, Co, Nb, and B is
One kind in Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu, Zn, Co, Nb, La, Sm, Gd, Y, Mn, 0≤x≤0.3；0≤
y≤0.2；0≤d≤0.2.
2. according to the doped cerium oxide catalytic film described in claim 1, it is characterised in that：The doped cerium oxide catalytic film
Gross thickness is between 1 nanometer -8 microns.
3. according to the doped cerium oxide catalytic film described in claim 1, it is characterised in that：The doped cerium oxide catalytic film
Gross thickness is between 6 nanometers -5 micron.
4. a kind of doped cerium oxide catalytic film according to described in claim 1, it is characterised in that：Doped cerium oxide film is used
It is prepared by the method for reactive magnetron sputtering.
5. according to the preparation method of the doped cerium oxide catalytic film described in claim 4, it is characterised in that：Used in magnetron sputtering
Target is the cerium-base alloy target of corresponding proportion component；The corresponding proportion component refers to and metallic element in cerium oxide base film
Ratio component, specific composition is as follows：LnxCe1-x, wherein Ln be Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu,
One kind in Zn, Co, Nb, 0≤x≤0.5；Or LnxByCe1-x-y, wherein Ln be Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr,
One kind in Sn, Cu, Zn, Co, Nb, B be Pr, Nd, Eu, Tb, Dy, Er, Yb, Ti, Zr, Sn, Cu, Zn, Co, Nb, La, Sm, Gd,
One kind in Y, Mn, 0≤x≤0.3；0≤y≤0.2；In anode/zirconium oxide base electrolyte of anode-supported, anode/cerium oxide
In base electrolyte membrane electrode substrate, or negative electrode/zirconium oxide base electrolyte film, the negative electrode/cerium oxide base of cathode support are electrolysed
Reactive magnetron sputtering has the doped cerium oxide catalytic film for preferentially exposing crystal face in membrane electrode substrate, and its sputtering parameter is：
Target-substrate distance is 5-9cm, and the rotating speed of chip bench is in 1-20 circles/minute, and sputtering pressure is 0.1Pa-1.5Pa, Sputtering power density P=
3-12W/cm2, the ratio between oxygen flow and argon flow amount are 1/2-1/20, and sputtering base reservoir temperature is at 30-800 DEG C, by changing target
The ratio between cardinal distance, the rotating speed of chip bench, sputtering pressure, Sputtering power density, oxygen flow and argon flow amount, sputtering base reservoir temperature can
To realize that deposition preferentially exposes the doped cerium oxide film of (111), (110) or (100) crystal face.
6. a kind of application of the doped cerium oxide catalytic film described in claim 1, it is characterised in that：Described doped cerium oxide
Catalytic film is used on zirconium oxide base electrolyte as electrode, or is used as Catalytic Layer.
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| 氧气在CeO2（111）/Cu（111）模型表面上的吸附与反应;陈博昊 等;《第十四届全国青年催化学术会议会议论文集》;20130728;摘要 * |
| 铈铁复合氧化物的结构特征及其催化应用;李孔斋 等;《化学进展》;20131031;第25卷(第10期);第1692页 * |
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