CN100359739C - Method for manufacturing solid oxide fuel cell electrolyte - Google Patents
Method for manufacturing solid oxide fuel cell electrolyte Download PDFInfo
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- CN100359739C CN100359739C CNB2005100431037A CN200510043103A CN100359739C CN 100359739 C CN100359739 C CN 100359739C CN B2005100431037 A CNB2005100431037 A CN B2005100431037A CN 200510043103 A CN200510043103 A CN 200510043103A CN 100359739 C CN100359739 C CN 100359739C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
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- Fuel Cell (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The present invention discloses a method for making an electrolyte layer of a solid-oxide fuel cell (SOFC). The electrolyte layer is formed by that molten or semi-molten state particle beams impact the surface of a base at high speed, the particles are flattened, and the flattened particles are accumulated. A part of the overlap region of the flattened particles and other one or more flattened particles are chemically combined, the combination rate exceeds more than 50% of the surface area of the flattened particles, and the conductivity of the electrolyte layer which is made by the method and is perpendicular to the surface direction of the electrolyte layer is more than half of the conductivity of an electrolyte block. When the electrolyte layer made by the method is treated in an after-densification mode, not only is the air tightness of the electrolyte layer further improved, but also the conductivity of the electrolyte layer and the combination rate of the flattened particles are further improved. The electrolyte layer of the solid-oxide fuel cell is made by the method of the present invention, the manufacture process of the solid-oxide fuel cell is simplified, and the manufacturing cost of the solid-oxide fuel cell is reduced.
Description
Technical field
The invention belongs to the energy, materials processing and power domain, relate to a kind of manufacture method of solid oxide fuel cell electrolyte.
Background technology
High temperature solid oxide fuel cell (Solid Oxide Fuel Cell:SOFC) can be converted into electric energy with the chemical energy of fuel, has the high and eco-friendly characteristics of generating efficiency.Utilize gas turbine to carry out cogeneration, its generating efficiency is a kind of desirable generation mode up to more than 60%, again by rationally, effectively utilize waste heat, the heat of its fuel can reach 90% in efficient.While SOFC has can use H
2, numerous hydrocarbon fuel gas such as natural gas, oil liquefied gas, coal gas gasification advantage.For this reason, the exploitation of SOFC is for effective utilization of limited resources, and the discharge capacity that reduces environmental contaminants is significant.At present, the subject matter of SOFC existence is how to reduce the manufacturing cost of SOFC.In case the manufacturing cost problem is resolved, have generating efficiency based on it and can reach nearly 2 times and of conventional thermal power generation near the characteristics of zero disposal of pollutants, might substitute the many Blast Furnace Top Gas Recovery Turbine Unit (TRT) and the system of present use, produce the revolution of energy industry.
Solid electrolyte layer is one of key stratum structure of SOFC, and SOFC to the requirement of solid electrolyte layer is: the oxygen ionic conductivity that (1) is high and low electron transfer number; (2) phase stability and the certain mechanical strength during high temperature; (3) air-tightness; (4) good thermal shock resistance; (5) for the chemical stability of reacting gas; (6) solid electrolyte film and electrode and be connected thermal expansion matching between the material.Consider combination property requirements such as cost, calorifics and mechanics, the zirconium dioxide of stabilisation (hereinafter to be referred as YSZ) is the electrolyte that current SOFC system mainly uses.In order to prepare fine and close dielectric substrate, the preparation technology that can be applied to SOFC at present mainly comprises methods such as high temperature sintering, vapour deposition, vacuum plasma spray coating, The tape casting, silk screen printing, sol-gal process and sputter.
SOFC generally comprises supporting layer, anode, electrolyte, negative electrode and extremely a plurality of structure sheafs that conflux, and being chosen in of each structure sheaf preparation method satisfied outside the requirement of SOFC to this structure sheaf, also must consider the influence of this preparation method to other structure sheaf.Because SOFC is to the harsh requirement of dielectric substrate, often the complicated process of preparation of dielectric substrate, manufacturing cost is higher is the main cause that causes SOFC manufacturing cost height, commercial applications difficulty.The cathode support type SOFC that the Siemens Westinghouse Electric that always is in a leading position as the research field at SOFC develops has adopted expensive electrochemical vapour deposition (EVD) technology to prepare dielectric substrate.With the Mitsubishi heavy industry serves as that the SOFC dielectric substrate of tens multikilowatts of main exploitation has adopted technology than complexity and the method preparation of expensive vacuum plasma spray coating (VPS) of cost.
Air plasma spraying (APS) is with the difference of VPS: APS prepares coating under air atmosphere, and VPS prepares coating under low pressure atmosphere.In order to guarantee the low pressure atmosphere of VPS, plasma gun must be positioned in the closed container that can adjust atmosphere pressures with the object for the treatment of deposited coatings and spray, this has limited the size of preparation sample with regard to the size owing to closed container, and increased operation easier, compare with APS, also improved preparation cost.
Plasma spraying ceramic coat be typical layer structure (C.-J Li, et al., Journal ThermalSpry Technology, Volume 11,2002, p365), the porosity in the general coating is from a few percent to percent tens.Pore in the coating generally is made of size number micron to tens of microns the gross blow hole and the spilehole of submicron order.Different with the subglobose pore in the material of common process such as powder metallurgy preparation, the pore in the coating is lenticular more.Hole in the coating is divided three classes according to the difference of shape:
(a) gross blow hole
This type of pore comprise the gross blow hole that forms in the incomplete filling and the infiltration of matrix or established coating surface owing to molten melt drop and with do not melt the boundary hole that the insufficient flattening of particle forms fully.Gross blow hole is a distributed in three dimensions in the space, the pore in the porous material of the similar melting sintering of shape.Size generally from sub-micron to greater than ten microns.
(b) calmodulin binding domain CaM not between particle layer in the coating
In the coating between particle layer not calmodulin binding domain CaM be because gas is involved in, between the low-temperature condition of deposition surface and molten drop and the deposition surface time of contact short due to.The spatial distribution of this type of pore is two-dimentional, have only sub-micron in vertical coating direction, and the size of two other direction is suitable with flat particle.
(c) crackle of flat particle internal vertical coating direction
This crackle runs through flat particle with particle plane vertical distribution and major part, and this type of crackle is because in the particle cooling procedure due to the chilling.Because the deposition of each molten drop is separate basically in the deposition, after last molten drop had solidified cooling, follow-up molten drop just arrived.Therefore can think that every molten drop is to finish flat and solidify under the interference that does not have other molten drop.The molten drop of high temperature impinges upon on the cold surface, and quick cooled and solidified will take place, and the quick cooling procedure after solidifying will produce contraction, but with following layer of surface combine and limit its contraction, thereby thermal stress appears in flat particle inside.In the coating of fragile material, particularly in the ceramic coating, thermal stress can not discharge by the flow or the creep of material, has only by cracking to discharge, so vertical crack will occur in the coating.The spatial distribution of vertical crack is two-dimentional, but with in the coating between particle layer not calmodulin binding domain CaM different be that this crackle has only the submicron order yardstick in parallel coating direction, one in two other direction is suitable with flat particle thickness, another is generally about ten microns to tens microns by the inner complicated crackle network decision of particle.
To single flat particle deposition behavior in the spraying ceramic coat studies show that there is network-like vertical crack in the particle inside of flattening, the equivalent redius in flawless zone is all less than 10 microns [L.Bianchi et al., Thin Solid Films, Volume 305,1997, p35.; A.Ohmori, et al., ThinSolid Films, Volume 201,1991, p241].And plasma spraying ceramic coat presents layer structure, and the inner flat particle be combined into limited combination.Plasma sprayed aluminum ceramic coating microstructure characteristic clear shows by adopting electrocoppering, the interlayer Bmax be about 32% (C.-J Li, et al., Journal ThermalSpray Technology, Volume 11,2002, p365; A.Ohmori, et al., Thin Solid Films, Volume 201,1991, p241; C.-J Li, et al., Material Science Engineering A, VolumeA386,2004, p10), the zirconia coating Bmax of plasma spraying preparation also is lower than 1/3rd (ITSC ' 2005 for C.-J Li, et al.).The limited combination of the layer structure of plasma spraying coating and flat particle thereof makes the thermal conductivity of coating and 1/3rd to 1/5th (R.McPherson Thin Solid Films, Volume, 112,1984, the p89 that conductivity is about corresponding bulk; C.-J Li, et al., Surface andCoating Technology, Volume 198,2005).The released gas rate of the zirconia coating of APS spraying preparation is than 1-2 order of magnitude of zirconia floor height (C.-J.Li, et al., Surfaceand Coatings Technology, Volume, 190,2004, the p60 of VPS and sintering process preparation; H.Tsukuda, et al., Journal ofThermal Spray Technology, Volume9,2000, p364; K Okumura, et al., Journal ofThermal Spray Technology, Volume9,2000, p354).
Because anode, negative electrode and the supporting layer of fuel cell must have certain porosity to guarantee gaseous diffusion, therefore, APS has obtained application at anode, supporting layer and the negative electrode of SOFC with in confluxing extremely as low-cost technology of preparing.But owing to the compactness requirement of SOFC to dielectric substrate, the dielectric substrate of APS preparation generally can not directly use as dielectric substrate.In order to use the dielectric substrate of APS preparation, must carry out densification to coating.As adopt 1500 ℃ high temperature sintering or adopt technology such as discharge plasma sintering to dielectric substrate densification reprocessing, still, the complicated manufacturing cost that can increase dielectric substrate equally of aftertreatment technology.Simultaneously, the low conductivity of dielectric substrate of APS preparation also will limit the output characteristic of SOFC.Therefore, how to utilize the low-cost characteristics that APS can simple, fast preparation dielectric substrate, simplify simultaneously treatment process with the air-tightness that improves the dielectric substrate of preparation thus and conductivity to satisfy the SOFC service requirement, thereby reduce the manufacturing cost of SOFC, this will provide effective method because of the high not commercial applications of manufacturing cost for solving SOFC.
Summary of the invention
The objective of the invention is to, a kind of manufacture method of solid oxide fuel cell electrolyte is provided, this method can be simplified the manufacturing process of Solid Oxide Fuel Cell, reduce the manufacturing cost of Solid Oxide Fuel Cell, and the dielectric substrate that makes this method prepare can satisfy the requirement as the SOFC dielectric substrate on air-tightness and electric conductivity.
To achieve these goals, the technical scheme taked of the present invention is as follows:
A kind of manufacture method of solid oxide fuel cell electrolyte, it is characterized in that, the particle beam high-speed impact of this method by fusion or fritting state is to matrix surface, formation flattening particle is piled up successively and is formed after flattening, the particle of flattening and other one or more flattening particles overlapping region reach the part chemical bond, and its combination rate surpasses 50% microstructure electrolyte coating; Specifically may further comprise the steps:
At first, the different designs of fuel cell structure, select suitable spraying matrix, this matrix can be anode layer or cathode layer or the dielectric substrate that is used for this fuel cell, also can be the anode of this fuel cell and the transition zone between the transition zone between dielectric substrate or negative electrode and dielectric substrate; Secondly, with substrate preheating to the 700 ℃ fusing point a certain temperature below the fusing point of high material in the matrix component; Then, in atmospheric atmosphere, adopt the plasma spraying method preparation to have certain thickness dielectric substrate, in order to improve the coating interlayer temperature, can adjust the translational speed of spray gun and moving range to adjust electric arc in time of staying on sprayed coating surface, make full use of high-temperature electric arc and heat spray-on coating surface once more, with the fine and close more dielectric substrate of preparation.
Some other characteristics of the present invention are:
The plasma spraying method that adopts in the preparation of this dielectric substrate comprises and usedly is adapted at working in the air atmosphere and is the plasma spray technology of thermal source with the plasma-arc.Such as, air plasma spraying, plasma spraying methods such as reaction and plasma spraying, supersonic speed plasma spraying.
If before the spraying matrix is taked preheating, its preheating method can adopt flame, plasma jet, high-frequency heating, electric heating etc., and all can improve the mode of heating of substrate temperature.The preheat temperature scope of matrix can be from 700 ℃ of fusing points below the fusing point of high material to the matrix component.The state of matrix can be that the condition of high temperature also can be the state that a certain component is in fusion or semi-molten in matrix top layer or matrix part or the matrix before the spraying.
The planform of matrix can be the plane before the spraying, or the face of cylinder, or taper seat, or all of other curved surface of variable curvature start from the surface of plasma spraying.
The dielectric substrate that dielectric substrate by method for preparing can be used as fuel cell directly uses, also can to the flat particle part in part not engaging zones use by the dielectric substrate that filler comes to be re-used as fuel cell after the further densification.The method that densifying method can adopt metal inorganic salting liquid, nanometer electrolyte granular suspension or metal inorganic salting liquid and nanometer electrolyte granular suspension to combine is filled the not engaging zones in the electrolyte layers; by after-baking technology moisture or inorganic salts are decomposed then; oxide particle after nanometer electrolyte granular wherein or inorganic salts decompose is trapped in not in the engaging zones, through repeatedly handling the back with the fine and close more dielectric substrate of preparation.
By adopting this method to prepare solid oxide fuel cell electrolyte, can simplify the manufacturing process of Solid Oxide Fuel Cell, reduce the manufacturing cost of Solid Oxide Fuel Cell, and the dielectric substrate that makes this method prepare can satisfy the requirement as the SOFC dielectric substrate on air-tightness and electric conductivity.
Description of drawings
Fig. 1 sprays the typical flat particle morphology of YSZ in back for adopting the spraying condition shown in the table 1 under to the situation of not preheating of matrix.
Fig. 2, Fig. 3 and Fig. 4 adopt the spraying condition shown in the table 1, after to 700 ℃ of substrate preheatings, and four kinds of flat particle morphologies of typical single YSZ.
Fig. 5 not to substrate preheating, sprays the YSZ coating cross-section morphology of preparation for adopting the spraying condition shown in the table 1.
Fig. 6 after to 1000 ℃ of substrate preheatings, sprays the YSZ coating cross-section morphology of preparation for adopting the spraying condition shown in the table 1.
For a more clear understanding of the present invention, below be the embodiment that the inventor provides, but the invention is not restricted to these embodiment.
Embodiment
The manufacture method of to the effect that a kind of SOFC dielectric substrate of the present invention, this dielectric substrate be particle beam high-speed impact by fusion or fritting state to matrix surface, after flattening, form the flattening particle and pile up successively and form.The particle of flattening and other one or more flattening particles overlapping region reach the part chemical bond, combination rate surpass the flattening particle surface long-pending more than 50%, Zhi Bei dielectric substrate is the over half of corresponding bulk conductivity perpendicular to the conductivity on the dielectric substrate direction thus.This manufacture method is on the high temperature matrix surface, in atmospheric atmosphere, adopts plasma spraying method to make, and its critical process is to spray the dielectric substrate that preparation can be satisfied the SOFC service conditions under to the condition of matrix high temperature preheating.
Table 1 is the APS condition of preparation flat particle of YSZ and YSZ coating.
The APS spraying parameter of table flat particle of 1YSZ and YSZ coating
| Arc current voltage arc power master gas (Ar) pressure and flow are assisted gas (H 2) the air spraying distance | 700A 55V 38.5kW 0.7MPa/47.1?Lmin -1 0.4MPa 60mm |
Accompanying drawing 1 sprays the flat particle morphology of the typical single YSZ in back for adopting the spraying condition shown in the subordinate list 1 under to the situation of not preheating of matrix.Because fusion YSZ particle is in deposition process, cause flat particle cracking with the excessive temperature differentials of matrix, there are a large amount of pattern crackings in flat particle inside, and splash phenomena is more serious, and the size range of cracking back small-particle is about 3～5 μ m.Fig. 2, Fig. 3 and Fig. 4 adopt the spraying condition shown in the table 1, after to 700 ℃ of substrate preheatings, and four kinds of flat particle morphologies of typical YSZ.By finding with accompanying drawing 1 contrast, matrix is through after the preheating, because the temperature difference of particle reduces before matrix and the collision, as Fig. 2, particle hits is behind matrix, the crack number of flat particle inside significantly reduces, and the particle size in flawless zone enlarges markedly, and the flat particle that does not have crackle as shown in Figure 3 and Figure 4 occurred.Matrix is about 10～50 μ m through the small particle size scope that obtains behind the high temperature preheating, and splash phenomena is not remarkable in the particle flattening process.
Fig. 5 is not under the condition to substrate preheating, the typical YSZ coating fractography of plasma spraying preparation under air atmosphere, A represents the thickness of single flat particle among the figure, two flat particles that B and C represent adjacent contact are calmodulin binding domain CaM not, D represents that adjacent two flat particles become the one zone because of chemical bond, and E and F represent the vertical crack of particle inside.This shows that plasma spraying YSZ coating is layer structure, the interlayer calmodulin binding domain CaM is limited, and there is vertical crack in flat particle inside.
Fig. 6 is that A, B and C represent the thickness of single flat particle respectively among the figure to the YSZ coating fractography behind 1000 ℃ of the substrate preheatings, and D and E represent between flat particle layer not calmodulin binding domain CaM, and F represents to grow into a body region because of chemical bond between the adjacent flat particle.Contrast discovery with Fig. 5, plasma spraying YSZ coating is after to the matrix high temperature preheating, and layer structure as shown in Figure 5 is no longer obvious, and the not engaging zones of adjacent flat particle significantly reduces, and the chemical bond zone significantly improves, and does not find tangible vertical crack.All exist good chemical bond zone significantly to increase between the flat particle of multilayer shown in F.Through being an integral body substantially, show same substantially with the end face structure of fine and close bulk to fractography behind the substrate preheating.
Presentation of results by Fig. 1-shown in Figure 6 through APS behind the matrix high temperature preheating is prepared YSZ, not only can obtain the less flat particle of vertical crack, and the coating of preparation thus, interlayer particle bonding state is good.By the YSZ coating of pre-hot preparation, significantly improved the bonding state of particle in the coating, and can significantly improve the bonding state of coating inner flat particle.Therefore, can prepare the coating that coating texture obviously is different from the conventional method preparation by after matrix is carried out high temperature preheating, Zhi Bei YSZ coating has good density and electric conductivity thus.
Prepare ceramic coating for traditional APS method, open report [the T.Chraska of pair substrate preheating below 450 ℃ also arranged, et al., Surface and coatings technology, Volume 157,2002, p238], but the purpose of its preheating is to remove the adsorbate of basic surface with the relative good coating with matrix bond of preparation coating.Exist a large amount of vertical cracks equally in the flat particle of the coating for preparing under this preheat temperature, the inner flawless particle size range of the flat particle behind the cracking is all less than 10 μ m.The present invention adopts the method for high temperature preheating, purpose is by to matrix high temperature preheating and the electric arc heat effect to coating, change the bonding state of adjacent flat particle, make the combination rate of flat particle be higher than 50%, and flat particle internal vertical crackle is compared remarkable reduction or is prepared the flat particle that does not have vertical crack by adjusting preheat temperature and spraying coating process condition with conventional method, flawless small particle size is prepared the ceramic coating of the similar bulk of institutional framework all greater than 10 microns.Employing is applicable to that the material of SOFC dielectric substrate makes dusty spray, uses the technology of the present invention and can prepare and satisfy the electrolyte coating that SOFC air-tightness and conductivity require.
Embodiment 1:
Adopt oxyacetylene torch that anode (as NiO/YSZ) is preheating to about 700 ℃, the planform of anode substrate is the plane, or the face of cylinder, or taper seat, or other curved surface of variable curvature.To be suitable for spraying the 8YSZ (8mol%Y of usefulness less than 30 μ m
2O
3) powder makes sprayed on material, adopts air plasma spraying to prepare 8YSZ electrolyte coating on the preheating anode.When spraying preparation dielectric substrate, before need guaranteeing that spraying particle deposits to matrix, matrix reaches preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the 8YSZ coating layer thickness of spraying preparation is 30-50 μ m, then, slowly adjust the heating distance of oxyacetylene torch, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate apart from coating.
Embodiment 2:
Adopt oxyacetylene torch that NiO/ScSZ (zirconia of scandia stabilized) surface is heated to about 1000 ℃, make sprayed on material, adopt air plasma spraying preparation ScSZ electrolyte coating on pre-hot basal body with the ScSZ powder that is suitable for spraying usefulness less than 30 μ m.When spraying preparation dielectric substrate, before needing to guarantee that the plasma spraying particle deposits to matrix, matrix surpasses preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the ScSZ coating layer thickness of spraying preparation is 30-50 μ m, then, it is 1000 ℃ holding furnace that the coating of spraying preparation is put into temperature immediately, and the rate of temperature fall of adjusting holding furnace is 3 ℃/min, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 3:
Adopt Electric heating, the Ni/YSZ anode preheating is arrived about 800 ℃, to be suitable for spraying the YSZ (4.5mol%Y of usefulness less than 30 μ m
2O
3) powder makes sprayed on material, adopts air plasma spraying to prepare YSZ electrolyte coating on the preheating anode.When spraying preparation dielectric substrate, before need guaranteeing that spraying particle deposits to matrix, matrix reaches preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the YSZ coating layer thickness of spraying preparation is 30-50 μ m, then, by slowly reducing electric current, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 4:
Adopt oxyacetylene torch that negative electrode (as strontium lanthanum manganese oxide, cobalt strontium lanthanum oxide, lanthanum strontium chromate, strontium ferrite lanthanum or cobalt ferrite strontium lanthanum) surface is heated to about 1000 ℃, with the 8mol%Y of 5-25 μ m
2O
3Stable ZrO
2(8YSZ) make sprayed on material, adopt air plasma spraying on the preheating cathode matrix, to prepare YSZ electrolyte coating.When spraying preparation dielectric substrate, before needing to guarantee that the plasma spraying particle deposits to matrix, matrix surpasses preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the YSZ coating layer thickness of spraying preparation is 10-40 μ m, then, it is 1000 ℃ holding furnace that the coating of spraying preparation is put into temperature immediately, and the rate of temperature fall of adjusting holding furnace is 3 ℃/min, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 5:
Adopt oxyacetylene torch that negative electrode (as strontium lanthanum manganese oxide, cobalt strontium lanthanum oxide, lanthanum strontium chromate, strontium ferrite lanthanum or cobalt ferrite strontium lanthanum) surface is heated to about 1000 ℃, with the strontium magnesium doped lanthanum gallate of 5-30 μ m (as La
0.9Sr
0.1Ga
0.8Mg
0.2O
3, LSGM) make sprayed on material, adopt air plasma spraying on the preheating cathode matrix, to prepare LSGM electrolyte coating.When spraying preparation dielectric substrate, before needing to guarantee that the plasma spraying particle deposits to matrix, matrix surpasses preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the YSZ coating layer thickness of spraying preparation is 10-40 μ m, if the spraying once LSGM size of preparation can not reach design size, when spraying once more, also need guarantee to reach preheat temperature in the temperature that is about to the deposited coatings place, until through repeatedly reaching the dielectric substrate thickness of design after the spraying, then, it is 1000 ℃ holding furnace that the coating of spraying preparation is put into temperature immediately, the rate of temperature fall of adjusting holding furnace is 3 ℃/min, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 6:
Adopt oxyacetylene torch that negative electrode (as strontium lanthanum manganese oxide, cobalt strontium lanthanum oxide, lanthanum strontium chromate, strontium ferrite lanthanum or cobalt ferrite strontium lanthanum) surface is heated to about 900 ℃, with the samarium oxide doping of cerium oxide of 5-30 μ m (as (CeO
2)
0.8(SmO
1.5)
0.2, SDC) make sprayed on material, adopt air plasma spraying on the preheating cathode matrix, to prepare SDC electrolyte coating.When spraying preparation dielectric substrate, before needing to guarantee that the plasma spraying particle deposits to matrix, matrix surpasses preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the SDC coating layer thickness of spraying preparation is 10-40 μ m, if the spraying once SDC size of preparation can not reach design size, when spraying once more, also need guarantee to reach preheat temperature in the temperature that is about to the deposited coatings place, until through repeatedly reaching the dielectric substrate thickness of design after the spraying, then, it is 1000 ℃ holding furnace that the coating of spraying preparation is put into temperature immediately, the rate of temperature fall of adjusting holding furnace is 3 ℃/min, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 7:
Adopt oxyacetylene torch that Ni/GDC (gadolinium oxide doping of cerium oxide) surface is heated to about 900 ℃, with the GDC of 5-30 μ m (as Ce
0.8Gd
0.2O
1.9) make sprayed on material, adopt air plasma spraying on the preheating cathode matrix, to prepare GDC electrolyte coating.When spraying preparation dielectric substrate, before needing to guarantee that the plasma spraying particle deposits to matrix, matrix surpasses preheat temperature in the temperature that is about to the deposited coatings place, make the GDC coating layer thickness of once spraying preparation reach the dielectric substrate thickness of design by adjusting plasma gun translational speed and powder sending quantity, then, it is 1000 ℃ holding furnace that the coating of spraying preparation is put into temperature immediately, the rate of temperature fall of adjusting holding furnace is 3 ℃/min, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 8:
Adopt plasma flame flow that anode (as NiO/YSZ) is preheating to about 1200 ℃, to be suitable for spraying the 8YSZ (8mol%Y of usefulness less than 30 μ m
2O
3) powder makes sprayed on material, adopts air plasma spraying preparation 8YSZ electrolyte coating on the anode of preheating or local anode surface.When spraying preparation dielectric substrate, before need guaranteeing that spraying particle deposits to matrix, matrix reaches preheat temperature in the temperature that is about to the deposited coatings place, make that by adjusting plasma gun translational speed and powder sending quantity once the 8YSZ coating layer thickness of spraying preparation is 30-50 μ m, in the spraying process, also need adopt oxyacetylene torch evenly to heat sprayed coating zone, make dielectric substrate slowly be cooled to room temperature, thereby finish the preparation of dielectric substrate.
Embodiment 9:
Only do not exist together with embodiment 1 to embodiment 8 and to be selection preheat temperature, can be for the preheat temperature scope of matrix from 500 ℃ of fusing points below the fusing point of high material to the matrix component, as select preheat temperatures such as 800 ℃, 1000 ℃, all the other same respective embodiments for use.
Embodiment 10:
Not existing together with embodiment 1 to embodiment 8 only is to preparing the selection of dielectric substrate spraying method, dielectric substrate is in air atmosphere, adopt plasma spraying method to prepare, wherein plasma spraying method comprises that used being adapted at work in the air atmosphere, and is the spraying technology of thermal source with the plasma-arc.Such as, air plasma spraying, methods such as reaction and plasma spraying, high-frequency induction plasma spraying, supersonic speed plasma spraying.All the other are with corresponding embodiment.
Claims (11)
1. the manufacture method of a solid oxide fuel cell electrolyte, it is characterized in that, the particle beam high-speed impact of this method by fusion or fritting state is to matrix surface, formation flattening particle is piled up successively and is formed after flattening, the particle of flattening and other one or more flattening particles overlapping region reach the part chemical bond, combination rate surpass the flattening particle surface long-pending more than 50%; Specifically may further comprise the steps:
At first the different designs of fuel cell structure is selected suitable spraying matrix, and this matrix is anode layer or cathode layer or the dielectric substrate that is used for this fuel cell, or the transition zone between the anode of this fuel cell and dielectric substrate; Or the transition zone between negative electrode and dielectric substrate;
Secondly, with substrate preheating to the 700 ℃ fusing point a certain temperature below the fusing point of high material in the matrix component;
Then, in atmospheric atmosphere, adopt the sprayed on material of plasma spraying method and suitable dielectric substrate on matrix, to spray dielectric substrate.
2. the method for claim 1 is characterized in that, described plasma spraying method is to be adapted at working in the air atmosphere and is the heat spraying method of thermal source with the plasma-arc.
3. method as claimed in claim 2 is characterized in that, described heat spraying method is air plasma spraying or reaction and plasma spraying or supersonic speed plasma spraying or induction plasma spraying.
4. the method for claim 1, it is characterized in that, described is one of the mode of flame preheating, plasma arc preheating, high-frequency heating, electric heating, illumination heating to the substrate preheating mode, and the state of matrix is the state that a certain component is in fusion or semi-molten in the condition of high temperature or matrix top layer or matrix part or the matrix before the spraying.
5. the method for claim 1 is characterized in that, the planform of described matrix is the plane, or the face of cylinder, or taper seat, or other curved surface of variable curvature.
6. the method for claim 1 is characterized in that, described matrix is the zone that is used to carry the single flattening particle of deposition, and this zone is the regional area that male or female layer and the flattening particle that is about to deposition are in contact with one another.
7. the method for claim 1 is characterized in that, described dielectric substrate combination rate is: the long-pending sum of the particle surface of flattening in the surface area sum/coating of calmodulin binding domain CaM not in combination rate=1-coating.
8. as claim 1 or 4 described methods, it is characterized in that, described substrate preheating is selected from the mode of auxiliary outer preheating, promptly adopts the thermal source that adds that matrix is heated, and matrix heated guarantees that substrate temperature reaches the setting preheat temperature before spraying with in the spraying process.
9. the method for claim 1, it is characterized in that, described dielectric substrate is being the over half of electrolyte bulk conductivity perpendicular to the conductivity on the dielectric substrate surface direction, the act as a fuel dielectric substrate of battery of this dielectric substrate directly uses, or to local flat particle part wherein not engaging zones use by the dielectric substrate that filler comes to be re-used as fuel cell after the further densification.
10. method as claimed in claim 9, it is characterized in that, described densification employing metal inorganic salting liquid is filled the not engaging zones in the dielectric substrate, the oxide particle that inorganic salt solution is resolved into by after-baking technology is trapped in not in the engaging zones then, through repeatedly densification and after-baking with the fine and close more dielectric substrate of preparation; Or
The method that adopts nanometer electrolyte granular suspension or metal inorganic salting liquid and nanometer electrolyte granular suspension to combine is filled the not engaging zones in the dielectric substrate, by after-baking technology water evaporates or inorganic salts are decomposed then, oxide particle after nanometer electrolyte granular wherein and inorganic salts decompose is trapped in not in the engaging zones, through repeatedly densification and after-baking with the fine and close more dielectric substrate of preparation; Or
Adopt the method that finally can be decomposed into the collosol and gel that is used for solid-oxide fuel battery electrolyte material to be coated to the surface of the dielectric substrate that has prepared, by after-baking technology collosol and gel is decomposed then, oxide particle after the decomposition is trapped in not in the engaging zones and the dielectric substrate surface, through repeatedly densification and after-baking with the fine and close more dielectric substrate of preparation.
11. method as claimed in claim 10 is characterized in that, describedly carries out further densification through sintering processes technology again through the coating after repeatedly densification and the after-baking.
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| CN102412408B (en) * | 2011-09-16 | 2014-01-29 | 西安交通大学 | Preparation method of SOFC electrolyte surface micro-convex structure and product thereof |
| CN106065457A (en) * | 2016-07-29 | 2016-11-02 | 西安交通大学 | Deposited particles combines sufficient plasma spraying ceramic of compact coating and preparation method thereof |
| CN107858628A (en) * | 2017-11-27 | 2018-03-30 | 东北大学 | The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker |
| CN111029596B (en) * | 2019-12-25 | 2021-09-21 | 清华大学 | Solid oxide fuel cell cathode and method for producing the same, solid oxide fuel cell and method for producing the same, and electric device |
| CN112164814B (en) * | 2020-09-29 | 2021-11-30 | 清华大学 | Preparation method of composite electrolyte layer of solid oxide fuel cell and solid oxide fuel cell |
| CN112687928A (en) * | 2020-12-25 | 2021-04-20 | 中国科学院上海应用物理研究所 | Preparation method of solid oxide battery and solid oxide battery obtained by preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932368A (en) * | 1996-02-02 | 1999-08-03 | Sulzer Innotec Ag | High temperature fuel cell with a thin film electrolyte |
| CN1244050A (en) * | 1998-08-05 | 2000-02-09 | 日本电池株式会社 | Polymer dielectric membrne, electrochemical unit and manufacture of polymer dielectric membrane |
| CN1438722A (en) * | 2003-03-21 | 2003-08-27 | 西安交通大学 | Method for making tubelike high-temp. solid oxide fuel battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932368A (en) * | 1996-02-02 | 1999-08-03 | Sulzer Innotec Ag | High temperature fuel cell with a thin film electrolyte |
| CN1244050A (en) * | 1998-08-05 | 2000-02-09 | 日本电池株式会社 | Polymer dielectric membrne, electrochemical unit and manufacture of polymer dielectric membrane |
| CN1438722A (en) * | 2003-03-21 | 2003-08-27 | 西安交通大学 | Method for making tubelike high-temp. solid oxide fuel battery |
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