CN104201409B - A kind of preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane - Google Patents
A kind of preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane Download PDFInfo
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- CN104201409B CN104201409B CN201410508136.3A CN201410508136A CN104201409B CN 104201409 B CN104201409 B CN 104201409B CN 201410508136 A CN201410508136 A CN 201410508136A CN 104201409 B CN104201409 B CN 104201409B
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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
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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
- H01M8/126—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
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
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- 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
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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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The preparation method who the invention discloses a kind of SOFC 1Ce10ScSZ electrolytic thin-membrane, its step is as follows: ethyl cellulose is dissolved in to terpinol, and adds 1Ce10ScSZ powder, obtain the monodispersed slurry of 1Ce10ScSZ after ball milling; Then drip appropriate 1Ce10ScSZ slurry to anode substrate center, form the uniform 1Ce10ScSZ dielectric film of one deck embryo at NiO-ScSZ anode surface, after heat treatment, multiple rotary applies, finally by 1Ce10ScSZ dielectric film embryo high temperature sintering. The SOFC 1Ce10ScSZ electrolytic thin-membrane that the method obtains is even, fine and close, smooth, and battery open circuit voltage is close to theoretical value, and output performance is high. Preparation does not need expensive equipment to carry out, and with low cost, technique is simple, easy to operate, and the thickness of 1Ce10ScSZ film can be readily controlled by rotary coating number of times, is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of solid-oxide fuel battery electrolyte film, be specifically related to a kind of employingSpin coating method is prepared the method for SOFC 1Ce10ScSZ electrolytic thin-membrane.
Background technology
Fuel cell is a kind of hair Denso that by electrochemical reaction, the chemical energy of fuel is converted into electric energyPut, there is the advantages such as efficient, environmentally friendly, be after waterpower, firepower, nuclear energy power generation technology the 4th generation generation technology, quiltU.S.'s Time is called first of the ten large science and technology that change future world. Wherein SOFC ((So1idOxideFuelCell, SOFC) can utilize cogeneration that the comprehensive utilization ratio of energy is brought up to more than 80%, and haveThe outstanding advantages such as structure of whole solid state, suitability of fuel are strong, have been subject to generally paying attention in the world, and various countries drop into one after another huge fund and carry outThe technical research of SOFC and commercialization.
Zirconia (the yttria-that traditional high temperature modification SOFC is stabilized with yttrium oxide due to its electrolyte usedStabilizedzirconia, YSZ), oxygen ionic conductivity is lower, must under the high temperature more than 1000 DEG C, operate, not only closeEnvelope is difficult, and has aggravated the generation of side reaction between battery component, very harsh to other assembly requirement of battery, thereby increasesBattery material select and preparation on difficulty, make the cost of SOFC high, slowly fail to realize industrialization. So,Reduce the operating temperature of SOFC, in exploitation, warm type SOFC becomes the only way of SOFC development.
The most effective approach of operating temperature that reduces SOFC is to adopt the novel electrolytes material with high oxygen ionic conductivityMaterial. 1mol%CeO2-10mol%Sc2O3-89mol%ZrO2(1Ce10ScSZ) be the ZrO that electrical conductivity is the highest2Base electrolyte, 1000 DEG CTime electrical conductivity be about 2.5 times of YSZ, 800 DEG C time, electrical conductivity is about 3 times of YSZ, phase structure is stable, and mechanical strength and heatThe coefficient of expansion and YSZ are suitable, become the very potential Novel middle-temperature SOFC of one electrolyte.
Through prior art is retrieved and found, the current domestic relevant SOFC 1Ce10ScSZ that there is not yetThe report of method for manufacturing thin film or technology. Use in the world at present the system of 1Ce10ScSZ film for SOFCStandby, be mainly employing electron beam-physical vapour deposition (PVD) (ElectronBeam-Physical such as AndrzejczukMVapourDeposition, EB-PVD) technology and ZhangX etc. adopt electron beam evaporation plating condensation (electronbeamEvaporationandcondensation, EBEC) technology successfully prepared 1Ce10ScSZ film. But electronic beam method is establishedStandby expensive, preparation cost is high, is difficult for promoting, and is difficult to meet the commercialization of SOFC.
Summary of the invention
The object of the invention is to overcome the defect that above-mentioned prior art exists, provide a kind of with low cost and simple to operationThe preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for SOFC 1Ce10ScSZ electrolytic thin-membrane, adopts rotary coating legal systemStandby SOFC 1Ce10ScSZ electrolytic thin-membrane, concrete steps are as follows:
(1) join in terpinol ethyl cellulose as binding agent, stir 30 ~ 60 minutes, obtain ethyl celluloseTerpineol solution;
(2) 1Ce10ScSZ powder is joined in above-mentioned terpineol solution of ethyl cellulose, with planetary ball mill withThe rotating speed ball milling of 200 ~ 400 revs/min 10 ~ 12 hours, preparation 1Ce10ScSZ slurry;
(3) NiO-ScSZ anode support is fixed on desk-top sol evenning machine as matrix, drips in anodes centre positionAdd appropriate 1Ce10ScSZ slurry, open sol evenning machine, make it under certain rotating speed, move 30 ~ 120 seconds, at NiO-ScSZ anode tableFace forms the uniform 1Ce10ScSZ dielectric film of one deck embryo;
(4) then above-mentioned 1Ce10ScSZ dielectric film embryo being put into Muffle furnace heat-treats;
(5) repeating step (3) and (4) 0 ~ 5 times, obtain the 1Ce10ScSZ dielectric film embryo of different-thickness;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace and carry out sintering, obtaining thickness is 2.5 ~ 15 μ m's1Ce10ScSZ electrolytic thin-membrane.
In step (1), described terpineol solution of ethyl cellulose refers to that the mass fraction of ethyl cellulose accounts for 3 ~ 4% pineOleyl alcohol solution.
In step (2), the particle size of described 1Ce10ScSZ powder, at 30 ~ 60nm, is single dispersed in terpinolState.
In step (2), described 1Ce10ScSZ powder can be synthetic according to sol-gal process, and its preparation process is as follows:
(a) take respectively the Ce (NO of respective quality according to stoichiometric proportion Ce:Sc:Zr=1:20:893)4·6H2O、Sc(NO3)3·6H2O and ZrN2O7, join in deionized water and stirring and dissolving, volumetric concentration be metal cation: water=1:20 ~40；
(b) citric acid (CA) that takes certain mass is dissolved in deionized water, and volumetric concentration is CA: water=1:2 ~ 5;
(c) according to mol ratio citric acid (CA): the ratio of metal cation=2 ~ 3:1, is dropwise added drop-wise to citric acid solutionIn nitrate solution, stir 15 ~ 30 minutes;
(d) in solution, add ethylene glycol according to the ratio of mol ratio ethylene glycol: citric acid=60:40, stir 40 ~ 60 pointsClock, obtains colourless transparent solution;
(e) above-mentioned solution is placed in to 80 DEG C of oil baths and heats, and continue to be stirred to formation gel;
(f) above-mentioned gel is put into 120 DEG C of baking ovens dry 4 ~ 12 hours, obtained the foaming shape xerogel that volume increases;
(g) above-mentioned xerogel is transferred in agate mortar, grinds 0.5 ~ 1 hour, obtain powdery presoma;
(h) above-mentioned powdery presoma is put into Muffle furnace, 600 ~ 850 DEG C of temperature lower calcinations 1 ~ 3 hour, obtain lightYellow pure phase 1Ce10ScSZ powder.
In step (2), described 1Ce10ScSZ slurry refer to 1Ce10ScSZ powder and terpineol solution of ethyl cellulose byMass ratio 4:6 or 3:7 mix, its addition be make the concentration of 1Ce10ScSZ in described mixture be 40wt% or30wt%。
In step (3), described NiO-ScSZ anode support is to adopt casting technique preparation, and thickness is 0.5 ~ 1mm, diameterBe 1 ~ 17cm; Described appropriate 1Ce10ScSZ slurry refer to the slurry volume of dropping and the area ratio of matrix 0.02 ~0.15ml/cm2In scope; Described rotating speed is recommended as 5000 ~ 10000 revs/min.
In step (4), described heat treatment is at 450 DEG C, to place 1 ~ 2 hour.
In step (6), described sintering is to be warmed up to 1450 ~ 1550 DEG C with the heating rate of 3 ~ 6 DEG C/min, is then incubated 2~ 12 hours.
The present invention has the following advantages with respect to prior art tool:
（) the SOFC 1Ce10ScSZ electrolytic thin-membrane prepared of spin coating method, have evenly, causeClose and smooth pattern, its open-circuit voltage reaches 1.1V, approaches theoretical value, and output performance is high;
（) spin coating method is prepared SOFC 1Ce10ScSZ electrolytic thin-membrane does not need expensive establishingStandby can carrying out, with low cost;
（) to prepare SOFC 1Ce10ScSZ electrolyte thin membrane process simple for spin coating method, operationConvenient, the thickness of 1Ce10ScSZ film can be readily controlled by rotary coating number of times, is suitable for heavy industrialization rawProduce.
Brief description of the drawings
Fig. 1 is that the X-ray diffractogram that utilizes sol-gal process synthetic 1Ce10ScSZ powder under different temperatures (is implementedExample 1);
Fig. 2 be the scanning electron microscope (SEM) photograph that utilizes sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C (embodiment 2,3、4、5）；
Fig. 3 is the scanning electron microscope (SEM) photograph (embodiment 3) of the 1Ce10ScSZ dielectric film embryo surface prepared of 5000rpm;
Fig. 4 is the scanning electron microscope (SEM) photograph (embodiment 3) in the 5000rpm 1Ce10ScSZ dielectric film embryo cross section of preparing;
Fig. 5 is the scanning electron microscope (SEM) photograph (embodiment 2) of the 1Ce10ScSZ dielectric film embryo surface prepared of 6000rpm;
Fig. 6 is the scanning electron microscope (SEM) photograph (embodiment 2) in the 6000rpm 1Ce10ScSZ dielectric film embryo cross section of preparing;
Fig. 7 is the scanning electron microscope (SEM) photograph (embodiment 1) of the 1Ce10ScSZ dielectric film embryo surface prepared of 7000rpm;
Fig. 8 is the scanning electron microscope (SEM) photograph (embodiment 1) in the 7000rpm 1Ce10ScSZ dielectric film embryo cross section of preparing;
Fig. 9 is the scanning electron microscope (SEM) photograph (embodiment 4) of the 1Ce10ScSZ dielectric film embryo surface prepared of 8000rpm;
Figure 10 is the scanning electron microscope (SEM) photograph (embodiment 4) in the 8000rpm 1Ce10ScSZ dielectric film embryo cross section of preparing;
Figure 11 is the scanning electron microscope (SEM) photograph (embodiment 7) in the 1Ce10ScSZ electrolytic thin-membrane cross section of 2 layers of spin coatings;
Figure 12 is the scanning electron microscope (SEM) photograph (embodiment 5) in the 1Ce10ScSZ electrolytic thin-membrane cross section of 4 layers of spin coatings;
Figure 13 is the scanning electron microscope (SEM) photograph (embodiment 6) in the 1Ce10ScSZ electrolytic thin-membrane cross section of 5 layers of spin coatings;
Figure 14 is the scanning electron microscope (SEM) photograph (embodiment 5) of 1Ce10ScSZ electrolyte membrane surface;
Figure 15 is the discharge curve (embodiment 5) taking 1Ce10ScSZ film as electrolytical monocell.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described, but is not limited to this, every to thisInvention technical scheme is modified or is equal to replacement, and does not depart from the spirit and scope of technical solution of the present invention, all should containIn protection scope of the present invention.
Embodiment 1
(1) 1.8g ethyl cellulose is joined in 58.2g terpinol, stir 60 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt the synthetic 1Ce10ScSZ powder of sol-gal process, and 40g1Ce10ScSZ powder is joined above-mentioned moltenIn liquid, with planetary ball mill with the rotating speed ball milling of 200 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.05 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 7000 revs/min, move 40 seconds,Form the uniform 1Ce10ScSZ dielectric film of one deck embryo on NiO-ScSZ anode substrate surface;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 3 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1500 DEG C, be then incubated 6 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 2
(1) 1.8g ethyl cellulose is joined in 58.2g terpinol, stir 60 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C, and 40g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 200 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.05 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 6000 revs/min, move 50 seconds,Form the uniform 1Ce10ScSZ dielectric film of one deck embryo on NiO-ScSZ anode substrate surface;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 2 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1500 DEG C, be then incubated 10 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 3
(1) 1.8g ethyl cellulose is joined in 58.2g terpinol, stir 60 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C, and 40g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 200 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.05 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 5000 revs/min, move 60 seconds,Form the uniform 1Ce10ScSZ dielectric film of one deck embryo on NiO-ScSZ anode substrate surface;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 3 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1550 DEG C, be then incubated 2 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 4
(1) 1.8g ethyl cellulose is joined in 58.2g terpinol, stir 60 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C, and 40g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 200 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.05 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 8000 revs/min, move 30 seconds,Form the uniform 1Ce10ScSZ dielectric film of one deck embryo on NiO-ScSZ anode substrate surface;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 4 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1550 DEG C, be then incubated 2 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 5
(1) 2.1g ethyl cellulose is joined in 67.9g terpinol, stir 50 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C, and 30g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 300 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.05 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 7000 revs/min, move 40 seconds,Form the uniform 1Ce10ScSZ dielectric film of one deck embryo on NiO-ScSZ anode substrate surface;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 3 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1500 DEG C, be then incubated 4 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 6
(1) 2.1g ethyl cellulose is joined in 67.9g terpinol, stir 50 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 850 DEG C, and 30g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 300 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 8cm using diameter is fixed on desk-top sol evenning machine as matrix, in anodeHeart position drips 5 milliliters of 1Ce10ScSZ slurries, and open sol evenning machine and under the rotating speed of 7000 revs/min, move 120 seconds,NiO-ScSZ anode substrate surface forms the uniform 1Ce10ScSZ dielectric film of one deck embryo;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 4 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 3 DEG C/min1500 DEG C, be then incubated 4 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Embodiment 7
(1) 2.1g ethyl cellulose is joined in 67.9g terpinol, stir 50 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) adopt sol-gal process synthetic 1Ce10ScSZ powder at 800 DEG C, and 30g1Ce10ScSZ powder is addedIn above-mentioned solution, with planetary ball mill with the rotating speed ball milling of 300 revs/min 12 hours, preparation 1Ce10ScSZ slurry;
(3) the NiO-ScSZ anode support that is 1.5cm using diameter is fixed on desk-top sol evenning machine as matrix, at anodeCenter position drips 0.1 milliliter of 1Ce10ScSZ slurry, and open sol evenning machine and under the rotating speed of 7000 revs/min, move 60 seconds,NiO-ScSZ anode substrate surface forms the uniform 1Ce10ScSZ dielectric film of one deck embryo;
(4) then film embryo is put into Muffle furnace heat treatment 1 hour at 450 DEG C;
(5) repeating step (3) and (4) 1 times, obtain 1Ce10ScSZ dielectric film embryo;
(6) above-mentioned 1Ce10ScSZ dielectric film embryo is put into Muffle furnace, be warmed up to the heating rate of 5 DEG C/min1500 DEG C, be then incubated 4 hours, obtain SOFC 1Ce10ScSZ electrolytic thin-membrane.
Compound the moon of two-layer LSM-ScSZ in the 1Ce10ScSZ electrolyte membrane surface spin coating of gained in the above-described embodimentsThe utmost point, the quality of this composite cathode is LSM:ScSZ=1:1, and at 1150 DEG C sintering 2 hours, prepare Ni-ScSZ/1Ce10ScSZ/LSM-ScSZ monocell.
The I-V curve of fuel cell obtains with ArBin fuel battery test system. When test taking hydrogen as fuel gas, weekThe air enclosing is oxic gas, and silver conductive adhesive is current collector, with devitrified glass seal isolation air and oxygen, probe temperature 750 ~850 DEG C, every 50 DEG C of tests once. Test result is shown in Figure 15.
Fig. 1 is the X-ray diffractogram that utilizes sol-gal process synthetic 1Ce10ScSZ powder under different temperatures, canFind out the 1Ce10ScSZ powder that can synthesize pure phase in 600 ~ 850 DEG C.
The scanning electron microscope (SEM) photograph of synthetic 1Ce10ScSZ powder when Fig. 2 is 850 DEG C, can find out that powder granularity is evenly distributed,Average grain diameter is in 50nm left and right.
The 1Ce10ScSZ dielectric film embryo surface that prepare for different rotating speeds Fig. 3-10 and the scanning electron microscope (SEM) photograph in cross section, canFind out the increase along with rotating speed, the thickness of film embryo declines thereupon.
Figure 11-13 are the scanning electron microscope (SEM) photograph of the 1Ce10ScSZ electrolytic thin-membrane section of the different spin coating numbers of plies, can find out electricitySeparate matter compact structure, exist without through hole, and the thickness of film increases along with the increase of the spin coating number of plies.
Figure 14 is the scanning electron microscope (SEM) photograph of 1Ce10ScSZ electrolyte membrane surface, can find out that 1Ce10ScSZ electrolyte hasEvenly, fine and close and smooth pattern.
Figure 15 is the discharge curve taking 1Ce10ScSZ film as electrolytical SOFC monocell, and 850 DEG C time, open-circuit voltage is1.1V, approaches theoretical value, and maximum power density reaches 1.2W/cm2。
Claims (10)
1. a preparation method for SOFC 1Ce10ScSZ electrolytic thin-membrane, is characterized in that described preparationMethod step is as follows:
(1) join in terpinol ethyl cellulose as binding agent, stir 30 ~ 60 minutes, obtain ethyl cellulose pine tarAlcoholic solution;
(2) 1Ce10ScSZ powder is joined in the terpineol solution of ethyl cellulose that step (1) obtains, 200 ~ 400 turning/Minute rotating speed ball milling 10 ~ 12 hours, preparation 1Ce10ScSZ slurry;
(3) NiO-ScSZ anode support is fixed on desk-top sol evenning machine as matrix, drips suitable in anodes centre positionThe 1Ce10ScSZ slurry that amount step (2) obtains, opens sol evenning machine, makes it under certain rotating speed, move 30 ~ 120 seconds, at NiO-ScSZ anode surface forms the uniform 1Ce10ScSZ dielectric film of one deck embryo;
(4) the 1Ce10ScSZ dielectric film embryo then step (3) being obtained is put into Muffle furnace and is heat-treated;
(5) repeating step (3) and (4) 0 ~ 5 times, obtain the 1Ce10ScSZ dielectric film embryo of different-thickness;
(6) 1Ce10ScSZ dielectric film embryo step (5) being obtained is put into Muffle furnace and is carried out sintering, obtain thickness and be 2.5 ~The 1Ce10ScSZ electrolytic thin-membrane of 15 μ m.
2. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be that, in step (1), described terpineol solution of ethyl cellulose refers to that the mass fraction of ethyl cellulose accounts for 3 ~ 4% pine tarAlcoholic solution.
3. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be that in step (2), the particle size of described 1Ce10ScSZ powder is at 30 ~ 60nm.
4. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be in step (2), described 1Ce10ScSZ powder can be synthetic according to sol-gal process, and its preparation process is as follows:
(a) take respectively the Ce (NO of respective quality according to stoichiometric proportion Ce:Sc:Zr=1:20:893)4·6H2O、Sc(NO3)3·6H2O and ZrN2O7, join in deionized water and stirring and dissolving, volumetric concentration be metal cation: water=1:20 ~40；
(b) citric acid that takes certain mass is dissolved in deionized water, and volumetric concentration is CA: water=1:2 ~ 5;
(c), according to the ratio of mol ratio citric acid: metal cation=2 ~ 3:1, the citric acid solution that step b is obtained dropwise dripsBe added in the nitrate solution that step a obtains, stir 15 ~ 30 minutes;
(d) in the solution obtaining to step c according to the ratio of mol ratio ethylene glycol: citric acid=60:40, add ethylene glycol, stir40 ~ 60 minutes, obtain colourless transparent solution;
(e) colourless transparent solution steps d being obtained is placed in 80 DEG C of oil baths and heats, and continues to be stirred to formation gel;
(f) gel step e being formed is put into 120 DEG C of baking ovens dry 4 ~ 12 hours, obtains dry the coagulating of foaming shape that volume increasesGlue;
(g) xerogel step f being obtained is transferred in agate mortar, grinds 0.5 ~ 1 hour, obtains powdery presoma;
(h) powdery presoma step g being obtained is put into Muffle furnace, 600 ~ 850 DEG C of temperature lower calcinations 1 ~ 3 hour, to obtain final productTo faint yellow pure phase 1Ce10ScSZ powder.
5. according to the preparation side of the SOFC 1Ce10ScSZ electrolytic thin-membrane described in claim 1,3 or 4Method, is characterized in that in step (2), described 1Ce10ScSZ slurry refer to 1Ce10ScSZ powder and ethyl cellulose terpinol moltenLiquid in mass ratio 4:6 or 3:7 mixes.
6. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be that, in step (3), the thickness of described NiO-ScSZ anode support is 0.5 ~ 1mm, diameter is 1 ~ 17cm.
7. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be in step (3), described appropriate 1Ce10ScSZ slurry refers to that the slurry volume of dropping and the area ratio of matrix are 0.02~0.15ml/cm2In scope.
8. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be that, in step (3), described rotating speed is 5000 ~ 10000 revs/min.
9. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, its spyLevy and be in step (4), described heat treatment is at 450 DEG C, to place 1 ~ 2 hour.
10. the preparation method of SOFC 1Ce10ScSZ electrolytic thin-membrane according to claim 1, itsBe characterised in that in step (6), described sintering is to be warmed up to 1450 ~ 1550 DEG C with the heating rate of 3 ~ 6 DEG C/min, is then incubated 2~ 12 hours.
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| KR101274809B1 (en) * | 2012-02-27 | 2013-06-13 | 한국생산기술연구원 | Design of improved output in intermediate temperature of solid oxide fuel cell and manufacturing method of the solid oxide fuel cell |
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| KR101274809B1 (en) * | 2012-02-27 | 2013-06-13 | 한국생산기술연구원 | Design of improved output in intermediate temperature of solid oxide fuel cell and manufacturing method of the solid oxide fuel cell |
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| Fabrication characteristics of SOFC single cell using nanocrystalline 1Ce10ScSZ electrolyte powder prepared by co-precipitation process;Ju Hee Kang et al.;《J. fuel cell sci.techno.》;20111227;第9卷(第1期) * |
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