CN103887549B - A kind of Solid Oxide Fuel Cell composite electrolyte film and preparation thereof - Google Patents
A kind of Solid Oxide Fuel Cell composite electrolyte film and preparation thereof Download PDFInfo
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- CN103887549B CN103887549B CN201210562619.2A CN201210562619A CN103887549B CN 103887549 B CN103887549 B CN 103887549B CN 201210562619 A CN201210562619 A CN 201210562619A CN 103887549 B CN103887549 B CN 103887549B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—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 zirconium oxide
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- 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 discloses a kind of Solid Oxide Fuel Cell composite electrolyte film, include zirconium oxide base electrolyte film and ceria-based electrolyte film, wherein zirconium oxide base electrolyte thin film deposition is in anode substrate, effectively can completely cut off electronic conductance, ceria-based electrolyte thin film deposition is on zirconium oxide base electrolyte film, effectively can completely cut off chemical reaction and the Elements Diffusion of negative electrode and zirconium oxide base electrolyte film, and the contact performance of cathode/electrolyte interface can be improved; This composite electrolyte film all adopts the method for magnetron sputtering to prepare, and avoids the reaction of zirconia base and ceria-based electrolyte; The use of this composite electrolyte film, has effectively completely cut off the diffusion of electrolyte both sides gas, has reduced Ohmic resistance, improve battery performance.
Description
Technical field
The present invention relates to field of solid oxide fuel, is a kind of composite electrolyte film in electrode basement and preparation method thereof specifically.
Background technology
Solid Oxide Fuel Cell is a kind of energy conversion device, the chemical energy in fuel gas (as hydrogen, natural gas, coal gas etc.) can be converted to electric energy and heat energy efficiently, and without noble metal catalyst, adopt structure of whole solid state, low emission low noise, be desirable dispersion power station and concentrated power station technology, also can be applied to vehicle accessory power supply, compact power etc.
In order to reduce manufacturing cost, improving battery long-time stability and reliability, shortening start-up time, meeting business-like application requirement, the operating temperature reducing Solid Oxide Fuel Cell becomes the emphasis of research and development both at home and abroad.Reduce cell operating temperature and have two kinds of main paties, one adopts highly active electrode material, as highly active containing the cathode material of cobalt class, reduces polarization of electrode resistance; Be the thickness reducing dielectric film, and improve electrode and electrolytical contact performance, or adopt the electrolyte with high oxygen-ion conduction, reduce the Ohmic resistance of battery on the whole.
But zirconium oxide base electrolyte film the most ripe is at present (as Y
2o
3stable ZrO
2, Sc
2o
3stable ZrO
2) oxygen ionic conductivity lower, the Ohmic resistance causing battery is comparatively large, and with current used in low temperature high-performance containing cobalt class cathode material, as Ba
xsr
1-xco
yfe
1-yo
3(BSCF) (0 < x < 1,0 < y < 1), La
xsr
1-xco
yfe
1-yo
3(LSCF) (Ln=La, Sm, Nd, Gd or Dy, 0 < x < 1,0 < y < 1), La
xsr
1-xcoO
3(LSC) (0 < x < 1), Sm
xsr
1-xcoO
3(SSC) (0 < x < 1) etc., chemical compatibility is poor, in the sintering and running of negative electrode, easily there is harmful chemicals react, negative electrode with electrolyte interface generate high resistant phase impurity, makes battery performance sharp-decay.
Ceria-based electrolyte film is (as Gd
2o
3the CeO of doping
2, Sm
2o
3the CeO of doping
2) there is higher ionic conductance, but in the running of battery easily and anode side fuel occur reduce and produce electronic conductance, reduce the performance of battery, and more fatal be breaking of the reduction of the cerium oxide electrolytic thin-membrane that can cause, can thoroughly make battery scrap.
Therefore, adopt the laminated film of zirconia base and ceria-based electrolyte, ceria-based electrolyte can either be prevented to be reduced, zirconium oxide base electrolyte can be prevented again and highly actively contain the cathode reaction of cobalt class, improve battery performance.
In order to reduce the Ohmic resistance of battery further, needing the thickness reducing electrolytic thin-membrane, improving negative electrode/electrolytical contact interface.Wherein the preparation of electrolytic thin-membrane has multiple method, there are the tape casting, slurry cladding process, spraying process, silk screen print method, electrochemical vapor deposition, chemical vapour deposition technique, sol-gal process (needing to consult pertinent literature) etc., wherein belong to physical vapour deposition (PVD) magnetron sputtering method has deposit film densification, thickness is even, composition is controlled, with the feature such as substrate excellent bonding performance, can be applied to and prepare electrolytic thin-membrane.
Summary of the invention
In order to reduce Ohmic resistance and the polarization resistance of battery, reduce the operating temperature of battery, the object of the present invention is to provide composite electrolyte film that a kind of thickness is even, compactness is good and preparation method thereof, when this composite electrolyte film is used in Solid Oxide Fuel Cell, can effectively stop electrolytical electronic conductance, improve the compatibility with high-activity cathode material, reduce Ohmic resistance and the polarization resistance of battery, thus effectively improve the power output of battery under middle cryogenic conditions, improve long-time stability and the reliability of battery.
For achieving the above object, technical scheme of the present invention is:
First reactive magnetron sputtering zirconium oxide base electrolyte compacted zone on NiO and the substrate of doped zirconia composite anode, then magnetron sputtering ceria-based electrolyte layer on zirconia base compacted zone, ceria-based electrolyte layer has compacted zone and weaker zone two parts, first at zirconium oxide base electrolyte surface magnetic control sputtering ceria-based electrolyte compacted zone, after completing, change sputtering parameter, then sputter the weaker zone of ceria-based electrolyte.Wherein zirconium oxide base electrolyte compacted zone is used for isolated electronic conductance, ceria-based electrolyte compacted zone is for stoping Elements Diffusion and the chemical reaction of high-activity cathode and zirconium oxide base electrolyte, and ceria-based electrolyte weaker zone is for improving the contact performance of cathode/electrolyte interface.
Described zirconium oxide base electrolyte material is M
xn
yzr
1-x-yo
2(M, N are the one in Y, Sc, Ce, Yb, La, 0.02≤x≤0.2,0.02≤y≤0.2).Described electrolytical gross thickness between 30 nanometer-10 microns, preferably between 60 nanometer-8 microns.
Described ceria-based electrolyte interlayer material is Ln
xce
1-xo
2-δ(Ln is Gd, Sm, Y, La, 0.05≤x≤0.5), the gross thickness of described interlayer, 32 nanometer-5 microns, is preferably 30 nanometer-3 microns.Wherein the thickness of compacted zone is 30 nanometer-3 microns, preferably 50 nanometer-1 micron; The thickness of weaker zone 2 nanometer-1 micron, preferably in 10 nanometer-600 nanometers.
Reactive magnetron sputtering target used is the alloy target material of respective components metal.
Gases used is oxygen and argon gas, and purity is all on 99.99%.
First reactive magnetron sputtering zirconium oxide base electrolyte compacted zone on nickel oxide and the substrate of zirconia base composite anode, its sputtering parameter is: target-substrate distance is 5-9cm, the rotating speed of chip bench 1-20 circle/minute, sputtering pressure is 0.1Pa-3.0Pa, Sputtering power density P=3-15W/cm
2, oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and sputtering base reservoir temperature is at 30-800 DEG C.
The membrane electrode that sputtering has a zirconium oxide base electrolyte film is preferably in air atmosphere, 800-1600 DEG C of annealing in process, annealing time was at 5 minutes-6 hours.
The basis of sputtering zirconium oxide base electrolyte compacted zone sputters ceria-based electrolyte layer, first sputters ceria-based electrolyte compacted zone, then sputter ceria-based electrolyte weaker zone.Ceria-based electrolyte compacted zone sputtering parameter be: target-substrate distance is 5-9cm, the rotating speed of chip bench 1-20 circle/minute, sputtering pressure is 0.1Pa-1.5Pa, Sputtering power density P=3-15W/cm
2, oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and sputtering base reservoir temperature is at 150-800 DEG C; The sputtering parameter of ceria-based electrolyte weaker zone is: target-substrate distance is 5-9cm, the rotating speed of chip bench 1-20 circle/minute, sputtering pressure is 0.5Pa-5Pa, Sputtering power density P=0.5-10W/cm
2, oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and sputtering base reservoir temperature is at 0-300 DEG C.
Ceria-based electrolyte interlayer preferably carries out annealing in process, annealing can after compacted zone has sputtered, weaker zone sputtered before or compacted zone and weaker zone sputter all complete after carry out, sputtering has the membrane electrode of ceria-based electrolyte interlayer in air atmosphere, 400-1000 DEG C of annealing in process, annealing time was at 5 minutes-6 hours.
Excellent results of the present invention is:
By sputtering the composite electrolyte layer of zirconium oxide base electrolyte and ceria-based electrolyte on nickel oxide and the substrate of zirconium oxide base electrolyte composite anode, effectively reducing electrolytical thickness, reducing electrolytical Ohmic resistance; Effectively prevent containing the chemical reaction between cobalt class negative electrode and zirconium oxide base electrolyte and Elements Diffusion, alleviate hot expansion property difference between the two, improve the contact performance between negative electrode and electrolyte interface, it also avoid simultaneously and generate high resistant phase cerium-Zirconium oxide solid solution with zirconium oxide base electrolyte pyroreaction in ceria-based electrolyte interlayer preparation process, effectively improve the output performance of battery.
1. the Solid Oxide Fuel Cell adopting the present invention to prepare, effectively reduces the thickness of dielectric substrate, reduces the Ohmic resistance of battery, improve the performance of battery.
2. the Solid Oxide Fuel Cell adopting the present invention to prepare, effectively improves the contact performance of negative electrode and electrolyte interface, reduces negative electrode and electrolyte interface contact resistance, improve the performance of battery.
3. adopt Solid Oxide Fuel Cell prepared by the present invention, composite electrolyte film compactness is good, and can effectively completely cut off negative electrode gas and anode gas, open circuit voltage is higher.
4. adopt the Solid Oxide Fuel Cell prepared of the present invention, effectively improve containing cobalt class negative electrode and the chemical compatibility of zirconium oxide base electrolyte and the matching of hot expansion property, improve long-time stability and the reliability of battery.
5. the composite electrolyte film prepared of the present invention, thickness can accurately control to 10 nanometer scale, and it is controlled that thickness is adjustable.
6. the composite electrolyte film that prepared by the present invention contacts with anode substrate well, and the interracial contact of zirconium oxide base electrolyte and ceria-based electrolyte is good, and in preparation process, interface generates mutually without high resistant.
7. the present invention can be used for the Solid Oxide Fuel Cell of the multiple configurations such as plate, cast.
8. the present invention is applicable to multiple middle temperature, low-temperature solid oxide fuel cell application, as dispersion power station, compact power, vehicle-mounted accessory power supply.
Accompanying drawing explanation
Fig. 1 is the structural representation of Solid Oxide Fuel Cell composite electrolyte film.1 is anode substrate, and 2 is zirconium oxide base electrolyte compacted zone, and 3 is ceria-based electrolyte compacted zone, and 4 is ceria-based electrolyte weaker zone.
Fig. 2 is that sputtering sedimentation is at Y
2o
3the ZrO of doping
2(YSZ) the fine and close Gd on electrode surface
2o
3the CeO of doping
2(GDC) microcosmic surface.
Fig. 3 is that sputtering sedimentation is at Y
2o
3the ZrO of doping
2(YSZ) the loose Gd on electrode surface
2o
3the CeO of doping
2(GDC) microcosmic surface.
Embodiment
Embodiment 1
At nickel oxide and Y
2o
3stable ZrO
2composite anode substrate sputters fine and close Y
2o
3the ZrO of doping
2(Y
0.08zr
0.92o
2) electrolytic thin-membrane, use acetone, ethanol, distilled water ultrasonic cleaning anode substrate and after drying successively, it is put within the vacuum chamber of magnetic control sputtering device, target-substrate distance is regulated to be about 6cm, with yttrium/Zirconium alloy material for target, target purity is on 99.99%, and yttrium/zirconium mol ratio is 8/92, is evacuated to 8*10
-4pa, then open chip bench heating, heat up and stablize to 400 DEG C, passing into argon flow amount is 10.0sccm, and oxygen flow is 1.0sccm, and sputtering power is 10W/cm
2, sputtering pressure is 0.5Pa, the speed setting of chip bench be 5 circles/minute, thickness is about 1 μm, completes fine and close Y
0.08zr
0.92o
2sputtering after, under air atmosphere, 1200 DEG C annealing 2 hours, then again membrane electrode is put into vacuum chamber, prepares fine and close Gd
2o
3the CeO of doping
2(Gd
0.1ce
0.9o
1.95) dielectric substrate, with cerium/gadpolinium alloy material for target, target purity is on 99.99%, and cerium/gadolinium mol ratio is 9/1, is evacuated to 8*10
-4pa, then carries out chip bench heating, and heat up and stablize to 400 DEG C, passing into argon flow amount is 30.0sccm, and oxygen flow is 3.0sccm, and sputtering power is 10W/cm
2, sputtering pressure is 0.5Pa, the speed setting of chip bench be 5 circles/minute, thickness is about 350nm, completes fine and close zero defect Gd
0.1ce
0.9o
1.95after the sputtering of interlayer, carry out loose porous Gd
0.1ce
0.9o
1.95the sputtering of interlayer, regulate chip bench temperature to be 30 DEG C, passing into argon flow amount is 30.0sccm, and oxygen flow is 3.0sccm, and sputtering power is 5W/cm
2, sputtering pressure is 4.0Pa, the speed setting of chip bench be 10 circles/minute, thickness is about 25nm, then with Ba
0.5sr
0.5co
0.8fe
0.2o
3and Gd (BSCF)
0.1ce
0.9o
1.95composite material (wherein Gd
0.1ce
0.9o
1.95mass fraction be 30wt.%) be negative electrode, silk screen printing is to sputtering Gd
0.1ce
0.9o
1.95on the membrane electrode of interlayer compacted zone and porous layer, 2 hours are sintered at 950 DEG C, then coating silver is starched thereon, four-terminal method battery tester carries out battery performance test, take air as negative electrode gas, wet hydrogen is anode gas, and battery is under the operating temperature of 700 DEG C, and battery maximum power density can reach 2.1W/cm
2, determining battery performance under voltage and can reach 1.57mW/cm at 0.8V
2; Under the operating temperature of 550 DEG C, battery maximum power density can reach 1.1W/cm
2, determining battery performance under voltage and can reach 760mW/cm at 0.8V
2; Effectively improve in battery, cryogenic property, and power is not obviously decayed after battery operation 200 hours.
As shown in Figure 2,3, conclusion:
Embodiment 2
At nickel oxide and Y
2o
3stable ZrO
2composite anode substrate sputters fine and close Y
2o
3the ZrO of doping
2(Y
0.08zr
0.92o
2) electrolytic thin-membrane, use acetone, ethanol, distilled water ultrasonic cleaning anode substrate and after drying successively, it is put within the vacuum chamber of magnetic control sputtering device, target-substrate distance is regulated to be about 7cm, with yttrium/Zirconium alloy material for target, target purity is on 99.99%, and yttrium/zirconium mol ratio is 8/92, is evacuated to 8*10
-4pa, then open chip bench heating, heat up and stablize to 800 DEG C, passing into oxygen with argon flow amount ratio is 1/5, and sputtering power is 12W/cm
2, sputtering pressure is 0.3Pa, the speed setting of chip bench be 8 circles/minute, thickness is about 0.8 μm, completes fine and close Y
0.08zr
0.92o
2sputtering after, change yttrium/zircaloy target be cerium/samarium alloy target (on 99.9%, cerium/samarium mol ratio is 8/2 to purity), carry out Sm
2o
3the CeO of doping
2(Sm
0.2ce
0.8o
1.9) sputtering of compacted zone, heat up and stablize to 300 DEG C, passing into argon flow amount is 40.0sccm, and oxygen flow is 3.0sccm, and sputtering power is 8W/cm
2, sputtering pressure is 1.0Pa, and thickness is about 600nm, the speed setting of chip bench be 10 circles/minute, thickness is 200 nanometers, completes fine and close Sm
0.2ce
0.8o
1.9after the sputtering of interlayer, reducing chip bench temperature is 30 DEG C, and adjustment argon flow amount is 20.0sccm, and oxygen flow is 2.0sccm, and sputtering power is 3W/cm
2, sputtering pressure is 4.0Pa, and thickness is about 15nm, the speed setting of chip bench be 10 circles/minute, the film preparation of combination electrode matter completes.
With Ba
0.5sr
0.5co
0.8fe
0.2o
3(BSCF) material is negative electrode, is sintered at 950 DEG C the preparation completing battery on composite electrolyte.Carrying out battery performance test with four-terminal method, take air as negative electrode gas, and wet hydrogen is anode gas, and battery is under the operating temperature of 700 DEG C, and battery maximum power density can reach 2.2W/cm
2, determining battery performance under voltage and can reach 1.61mW/cm at 0.8V
2; Under the operating temperature of 550 DEG C, battery maximum power density can reach 980mW/cm
2, determining battery performance under voltage and can reach 850mW/cm at 0.8V
2; Effectively raise in battery, cryogenic property, and power is not obviously decayed after battery operation 300 hours.
Embodiment 3
At nickel oxide and Y
2o
3stable ZrO
2composite anode substrate sputters fine and close 10mol%Sc
2o
3with 1mol%CeO
2the ZrO of codope
2(Ce
0.01sc
0.1zr
0.89o
2) electrolytic thin-membrane, use acetone, ethanol, distilled water ultrasonic cleaning anode substrate and after drying successively, it is put within the vacuum chamber of magnetic control sputtering device, target-substrate distance is regulated to be about 7cm, with scandium/cerium/Zirconium alloy material for target, target purity is on 99.99%, and scandium/cerium/zirconium mol ratio is 10/1/89, is evacuated to 8*10
-4pa, then open chip bench heating, heat up and stablize to 600 DEG C, passing into oxygen with argon flow amount ratio is 1/8, and sputtering power is 9W/cm
2, sputtering pressure is 0.5Pa, the speed setting of chip bench be 6 circles/minute, thickness is about 0.8 μm, completes fine and close Ce
0.01sc
0.1zr
0.89o
2sputtering after, change Ce/Gd (mol ratio is 9/1) alloy target material, the fine and close Gd of magnetron sputtering under the base reservoir temperature of 500 ° of C
0.1ce
0.9o
1.95dielectric substrate, sputtering pressure is 0.5Pa, and Sputtering power density is 9W/cm
2, thickness is 300 nanometers, and then regulate base reservoir temperature to be 50 ° of C, sputtering pressure is 3.0Pa, and sputtering power is 5W/cm
2, sputtering sedimentation thickness is the bulk ceria base electrolyte layer of about 30 nanometers, applies La thereon
0.6sr
0.4co
0.2fe
0.8o
3-δ (lSCF6428) cathode material, has sintered battery preparation at the temperature of 1050 ° of C.Take air as negative electrode gas, wet hydrogen is anode gas, and battery is under the operating temperature of 700 DEG C, and battery maximum power density can reach 1.8W/cm
2, determining battery performance under voltage and can reach 1.47mW/cm at 0.8V
2; Under the operating temperature of 550 DEG C, battery maximum power density can reach 810mW/cm
2, determining battery performance under voltage and can reach 730mW/cm at 0.8V
2; Effectively raise in battery, cryogenic property, and power is not obviously decayed after battery operation 100 hours.
Embodiment 4
At nickel oxide and Y
2o
3stable ZrO
2composite anode substrate sputters fine and close Y
2o
3the ZrO of doping
2(Y
0.08zr
0.92o
2) electrolytic thin-membrane, base reservoir temperature is 300 ° of C, and sputtering pressure is 0.5Pa, and sputtering power is 8W/cm
2, target-substrate distance is 7cm, and thickness is about 3 microns, then sputters Sm thereon
2o
3the CeO of doping
2(Sm
0.2ce
0.8o
1.95) dielectric substrate, first sputter compacted zone, substrate degree of being is 400 ° of C, and sputtering pressure is 0.7Pa, and sputtering power is 6W/cm
2, target-substrate distance is 7cm, and thickness is about 1 micron, then sputters weaker zone again, and base reservoir temperature is 50 ° of C, and sputtering pressure is 5.0Pa, and sputtering power is 3W/cm
2, target-substrate distance is 7cm, after completing the preparation of composite electrolyte film, with La
0.6sr
0.4co
0.2fe
0.8o
3-δand 30Wt.%Sm (LSCF6428)
0.2ce
0.8o
1.95composite material is negative electrode, sinters 2h, complete the preparation of battery at 1100 ° of C.Take air as negative electrode gas, at room temperature the hydrogen of humidification is fuel gas, and battery is under the operating temperature of 700 DEG C, and battery maximum power density can reach 1.75W/cm
2, determining battery performance under voltage and can reach 1.43mW/cm at 0.8V
2; Under the operating temperature of 550 DEG C, battery maximum power density can reach 790mW/cm
2, determining battery performance under voltage and can reach 670mW/cm at 0.8V
2; Effectively raise in battery, cryogenic property, and power is not obviously decayed after battery operation 100 hours.
Embodiment 5
At nickel oxide and Y
2o
3stable ZrO
2composite anode substrate sputters fine and close Y
2o
3the ZrO of doping
2(Y
0.08zr
0.92o
2) electrolytic thin-membrane, base reservoir temperature is 800 ° of C, and sputtering pressure is 0.5Pa, and sputtering power is 8W/cm
2, target-substrate distance is 6cm, and thickness is about 1 micron, then sputters Sm thereon
2o
3the CeO of doping
2(Sm
0.2ce
0.8o
1.95) dielectric substrate, first sputter compacted zone, substrate degree of being is 400 ° of C, and sputtering pressure is 0.5Pa, and sputtering power is 9W/cm
2, target-substrate distance is 7cm, and thickness is about 200 nanometers, then sputters weaker zone again, and base reservoir temperature is 30 ° of C, and sputtering pressure is 3.0Pa, and sputtering power is 5W/cm
2, target-substrate distance is 6cm, after completing the preparation of composite electrolyte film, with La
0.6sr
0.4co
0.2fe
0.8o
3-δ(LSCF6428) material is negative electrode, sinters 2h, complete the preparation of battery at 1050 ° of C.Take air as negative electrode gas, at room temperature the hydrogen of humidification is fuel gas, and battery is under the operating temperature of 700 DEG C, and battery maximum power density can reach 2.3W/cm
2, determining battery performance under voltage and can reach 1.82mW/cm at 0.8V
2; Under the operating temperature of 550 DEG C, battery maximum power density can reach 1.3W/cm
2, determining battery performance under voltage and can reach 1.0W/cm at 0.8V
2; Effectively raise in battery, cryogenic property, and power is not obviously decayed after battery operation 300 hours.
Claims (8)
1. the preparation method of a composite electrolyte film, it is characterized in that: composite electrolyte film comprises zirconium oxide base electrolyte compacted zone (1) and one side surface compact ceria-based electrolyte layer (2) with it, and zirconium oxide base electrolyte compacted zone (1) and ceria-based electrolyte layer (2) all adopt the method for reactive magnetron sputtering to prepare; Target used is the alloy target material of respective components;
The power supply of reactive magnetron sputtering is DC power supply, intermediate frequency power supply or radio-frequency power supply;
Described ceria-based electrolyte layer (2) is made up of two parts, comprise the flawless ceria-based electrolyte layer of the compact densification with zirconium oxide base electrolyte, for ceria-based electrolyte compacted zone (3), and the loose porous ceria-based electrolyte layer prepared on its basis, be ceria-based electrolyte weaker zone (4); Wherein first prepare ceria-based electrolyte compacted zone (3) on zirconium oxide base electrolyte compacted zone surface, then prepare ceria-based electrolyte weaker zone (4) on ceria-based electrolyte compacted zone (3) surface.
2. according to preparation method according to claim 1, it is characterized in that: the preparation process of zirconium oxide base electrolyte compacted zone (1) is:
On nickel oxide and the substrate of zirconia base composite anode, reactive magnetron sputtering deposits, its sputtering parameter is: base reservoir temperature is at 200-800 DEG C, and oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and target-substrate distance is 5-9cm, sputtering pressure is 0.1Pa-1.5Pa, Sputtering power density P=3-15W/cm
2.
3. according to preparation method according to claim 2, it is characterized in that: zirconium oxide base electrolyte compacted zone (1) carries out annealing in process between 400-1600 DEG C of temperature.
4. according to preparation method according to claim 1, it is characterized in that: the material of zirconium oxide base electrolyte compacted zone (1) is M
xn
yzr
1-x-yo
2-d, M, N are respectively the one in Y, Sc, Ce, Yb, La, 0.02≤x≤0.2,0≤y≤0.2,0≤d≤0.2;
The material of ceria-based electrolyte layer (2) is Ln
xce
1-xo
2-d, Ln is one or two or more kinds in Gd, Sm, Y or La, 0.05≤x≤0.5,0≤d≤0.2.
5., according to preparation method according to claim 1, it is characterized in that:
The gross thickness of described composite electrolyte film is between 62 nanometer-20 microns;
The thickness of described zirconium oxide base electrolyte compacted zone (1) is between 30 nanometer-15 microns;
The thickness of described ceria-based electrolyte layer (2) is between 32 nanometer-5 microns.
6. according to preparation method according to claim 1, it is characterized in that: the thickness of described ceria-based electrolyte layer (2) is between 32 nanometer-5 microns;
The THICKNESS CONTROL of described ceria-based electrolyte compacted zone (3) is between 30 nanometer-3 microns;
The THICKNESS CONTROL of described ceria-based electrolyte weaker zone (4) is between 2 nanometer-1 micron.
7. according to preparation method according to claim 1, it is characterized in that: the preparation process of ceria-based electrolyte compacted zone (3) is: sputtering the membrane electrode surface sputtering deposited oxide cerium base electrolyte layer of YSZ electrolytic thin-membrane, its sputtering parameter is: target-substrate distance is 5-9cm, sputtering pressure is 0.1Pa-1.5Pa, Sputtering power density P=3-15W/cm
2, oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and sputtering base reservoir temperature is at 250-800 DEG C;
The preparation process of ceria-based electrolyte weaker zone (4) is: on the surface of sputtering ceria-based electrolyte compacted zone (3), sputter ceria-based electrolyte weaker zone (4), sputtering parameter is: target-substrate distance is 5-9cm, sputtering pressure is 0.5Pa-5Pa, Sputtering power density P=0.5-10W/cm
2, oxygen flow is 1/2-1/20 with the ratio of argon flow amount, and sputtering base reservoir temperature is at 0-200 DEG C.
8. according to preparation method according to claim 7, it is characterized in that: ceria-based electrolyte compacted zone (3) carries out annealing in process at the temperature of 400-1200 DEG C.
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| KR102109231B1 (en) * | 2016-09-30 | 2020-05-11 | 주식회사 엘지화학 | Method for operating solid oxide fuel cell |
| CN112599826B (en) * | 2020-12-03 | 2022-02-01 | 山东科技大学 | High-performance solid oxide fuel cell and preparation method thereof |
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