CN104183860A - Zirconium oxide plate applied to pressure sintering of plate type anode supporting half SOFC and surface modification method of zirconium oxide plate - Google Patents
Zirconium oxide plate applied to pressure sintering of plate type anode supporting half SOFC and surface modification method of zirconium oxide plate Download PDFInfo
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- CN104183860A CN104183860A CN201410379437.0A CN201410379437A CN104183860A CN 104183860 A CN104183860 A CN 104183860A CN 201410379437 A CN201410379437 A CN 201410379437A CN 104183860 A CN104183860 A CN 104183860A
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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
- 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
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Abstract
The invention relates to a zirconium oxide plate applied to pressure sintering of a plate type anode supporting half SOFC. The zirconium oxide plate is a surface-modified porous zirconium oxide ceramic plate. After surface modification, the upper and lower surfaces of the porous zirconium oxide ceramic plate are coated with porous 3YSZ films which are smooth and flat in surface and are identical with each other in thickness. By carrying out surface modification on a common zirconium oxide plate, the zirconium oxide plate is uniform and consistent in surface component, smooth and fine in surface and free from burr sense, and brown spots (caused by enrichment of Fe and Ti) on local parts of the zirconium oxide plate are completely covered, so that the fatal flaw caused on the surface of an electrolyte of the cell in the half SOFC sintering process when the zirconium oxide plate is used as a pressure plate is avoided. A surface modification method is simple and effective and is easy to be industrially implemented.
Description
Technical field
The present invention relates to a kind of zirconia plate and surface modification method thereof burning of pressing for planar anode-supported type SOFC half-cell, belong to the preparing technical field of planar anode-supported type intermediate temperature solid oxide fuel cell monocell.
Background technology
Solid Oxide Fuel Cell (being called for short SOFC) is the most effective energy conversion apparatus of a kind of novel energy conversion, the chemical energy of fuel is changed into electric energy, its cogeneration can reach more than 80%, due to its fuel can diversity, make it there is huge commercial value and development prospect.
Middle temperature (650～800 ℃) SOFC, because its operating temperature higher temperatures (850～1000 ℃) SOFC is low, is the developing direction of SOFC, is the focus of current commercial development.Intermediate temperature SOFC is that a kind of battery of anode support type forms, according to the shape design of battery, battery can be divided into two large classes is tubular type and flat, tubular type monocell is easy to sealing when group heap, flat have a larger energy density, and most research and development all concentrate on planar cells aspect.The conventional preparation method of flat intermediate temperature SOFC monocell industrialization is the method that adopts anode and electrolytic thin-membrane once to burn altogether, because electrolyte is that 8YSZ material and anode are the material that 8YSZ, NiO and pore creating material mix according to suitable proportioning,, there is the inconsistent situation of shrinking of burning till in the common burning of dissimilar materials.By formula, adjust, the contraction of burning till of general furnishing anode is slightly larger than the electrolytical contraction (contributing to electrolytical densification) of burning till, but the problem of bringing is the cell piece of Bao Er great, and micro-anode direction is crooked, it is not peaceful whole making prepared flat monocell, affects group heap.Generally like this need in sintering process, increase pressing plate, the distortion (microbend) of restriction battery, because the NiO in anode and aluminium oxide at high temperature can kickbacks, so pressing plate should adopt zirconia plate and can not be the plate of alumina plate or other material.Simultaneously, because need to discharge in battery base sheet the organic substances such as binding agent in sintering process, require pressing plate to should be porous, so that organic oxidation and exhaust etc.The porous zirconium plate porous zirconia load bearing board that can buy is in the market mainly zirconia and the stable zirconia of yttrium of calcium stable.The former main component is: ZrO
2>=94.00%, CaO3.50～4.50%, Al
2o
3≤ 0.40%, SiO
2≤ 0.40%, TiO
2≤ 0.20%, Fe
2o
3≤ 0.10%, MgO≤0.10%.Physical state is faint yellow; The latter's main component is: ZrO
2>=91.00, Y
2o
36～8%, Al
2o
3≤ 0.10%, SiO
2≤ 0.30%, TiO
2≤ 0.10%, Fe
2o
3≤ 0.10%, MgO≤0.10%.Physical state is faint yellow.This business-like zirconium plate is generally to use (refractory material), its some burr sense, rough of surface for holding to burn.Integral body is faint yellow, and there is the fleck (due to the enrichment of Fe, Ti) of brown part.Laboratory and suitability for industrialized production be the burning till for SOFC monocell using this zirconium plate as pressing plate generally.Because battery mainly contains two parts composition, be dielectric substrate and anode layer, general electrolytical thickness is only 10～20 μ m, if with the surperficial burr of dielectric substrate close contact zirconium plate and rough or have Fe/Ti fleck (this fleck is during at high temperature with electrolyte close contact, because the material that Fe/Ti oxide is low temperature passes through High temperature diffusion mass transfer to bath surface, make its surface produce fusion hole), probably at bath surface, produce deep pit or fusion hole, this pit and fusion hole penetrate thin layer of electrolyte, make dielectric substrate gas leakage and produce battery performance and decay rapidly, so that cannot use.
The present invention proposes a kind of surface modification technology and technique of the industrial zircite porous ceramic plate generally using, the porousness and the evenness that by this surface, have kept former zirconium plate, simultaneously fully effective surface local injustice, burr or coarse, the local Fe/Ti fleck that has overcome former zirconium plate produces fatal defect to the bath surface of battery while making to be used as pressing plate in SOFC half-cell sintering process.
Summary of the invention
The object of the invention is to overcome the defect of prior art, a kind of zirconia plate and surface modification method thereof burning of pressing for planar anode-supported type SOFC half-cell is provided, the present invention is by carrying out finishing to common zirconia plate, make zirconia plate top layer composition uniformity, smooth surface is fine and smooth, there is no burr sense, and there is to the fleck of brown part (due to Fe, the enrichment of Ti) cover completely, thereby while having avoided being used as pressing plate in SOFC half-cell sintering process, the bath surface of battery is produced to fatal defect, and this surface modification method is simple, effectively, and be easy to industrializing implementation.
The present invention is achieved by the following technical solutions:
For planar anode-supported type SOFC half-cell, press the zirconia plate burning, the smooth porous 3YSZ film of layer of surface that comprises the body of a porous zirconia earthenware slab and cover on the upper and lower surface of described body; And the thickness of the porous 3YSZ film on upper surface is identical with the thickness of the porous 3YSZ film on lower surface.
Wherein, described 3YSZ is for adopting 3mol%Y
2o
3stable ZrO
2; Mol% represents molal weight percentage, the zirconia of the stabilized with yttrium oxide of 3mol% is example, the zirconia (both mole percentage sums are 100%) that the stabilized with yttrium oxide mole that to refer to by mole be 3% is 97%, makes the zirconia of stabilized with yttrium oxide, i.e. 3YSZ.
Preferably, described porous zirconia earthenware slab is commercially available prod, and thickness is 4.0-6.0mm, and porosity is 15vol.%-35vol.%.
Preferably, the thickness of described porous 3YSZ film is 20～50 μ m, and porosity is 15vol.%-25vol.%.In upper and lower surface, the thickness of porous 3YSZ film is identical, can avoid like this single layer coating to burn after a little to the phenomenon of a microbend; If coating is too thick, after burning, the bending of zirconium plate is excessive, its reason is that coated thin layer has certain contraction of burning till, and former zirconium plate has burnt till through high temperature, do not shrink the thicker zirconium plate of 3YSZ layer therefore applying, its inconsistent due to both shrinkages after burning, the zirconium plate that makes to apply 3YSZ is crooked to this face of 3YSZ thin layer, and its crooked degree strengthens because of thickening of 3YSZ thickness.Therefore the thickness of 3YSZ can not be excessive, simultaneously can not be too small, otherwise can not play defects such as covering zirconium plate surface burr, rough and spot (as oxidation iron spot).
The present invention further provides described a kind of surface modification method of pressing the zirconia plate burning for planar anode-supported type SOFC half-cell, is silk screen print method, specifically comprises the following steps:
(1) after in advance binding agent being dissolved in solvent completely, then add 3YSZ powder, ball milling is made 3YSZ slurry;
(2) adopt the mode of silk screen printing, at the upper and lower faces of porous zirconia earthenware slab, print respectively the 3YSZ slurry of same thickness;
(3) sintering;
Wherein,
Preferably, in step (1), the D of described 3YSZ powder
50be 0.3～0.7 μ m, and narrower particle size distribution, D
10be 0.1～0.3 μ m, D
90being 0.5～1.0 μ m, is nearly normal distribution, and specific area is 6～12m
2/ g, powder purity is greater than 99%.If 3YSZ powder granularity is excessive, its film is still more coarse after burning can not play the defect of improving former zirconium plate surface burr; If 3YSZ powder is meticulous, the high cost of this powder, and make to film inhomogeneous because powder easily produces reunion.
Preferably, in step (1), the mass percent example of described 3YSZ powder, binding agent and solvent is respectively 60～75wt%, 1～5wt% and 20～39wt%; Three's sum is 100%.
Preferably, described solvent is selected from terpinol, polyethylene glycol, ethyl acetate etc.Preferably, described binding agent is selected from second
Base cellulose, polyvinyl butyral resin etc.
Preferably, described ethyl cellulose is ethyl cellulose M70.
Preferably, the molecular weight distribution of described polyvinyl butyral resin (MW) is 40000-80000.
Preferably, in step (1), described rotational speed of ball-mill is 50～100 revs/min, and Ball-milling Time is 24～48 hours.
Preferably, in step (1), making the viscosity of 3YSZ slurry under room temperature (25 ℃) is 10～80Pa.s.
Preferably, in step (2), the meshcount of described silk screen printing is 100～200 orders, and during printing, the distance of silk screen and described zirconia ceramics flat board is 3～5mm, brush and silk screen angle at 45 °; After every printing once, 100-150 ℃ of oven dry, so repeats; General about 0.5 hour of described oven dry.
Preferably, in step (2), the thickness of the 3YSZ slurry printing on upper and lower faces is 30-60 μ m.
Preferably, in step (3), the temperature of described sintering is 1380～1420 ℃, and the time of sintering is 2-4h.Burn till rear porous zirconium plate and still keep original evenness and porousness, but smooth surface, without any burr with hide Fe or the Ti spot on former zirconium plate completely.
When prepared by commercially available porous zirconia earthenware slab, the grain diameters that adopt are tens microns of even powder preparations of hundreds of micron more, and the purity of this kind of powder is also lower simultaneously, as contained Fe, Ti oxide.Fe on zirconium plate Ti fleck easily make bath surface produce fusion hole, electrolytic thin-membrane is penetrated, battery performance decay is serious.If adopt fine powder (and the higher powder of purity) preparation, its cost of material and preparation cost all obviously increase.The present invention is from being down to cost consideration, and the porous zirconia earthenware slab that the commercially available price of take is comparatively cheap is base material, by finishing, makes its naturally smooth exquisiteness in surface, can overcome the above problems well.
The present invention adopts submicron order 3YSZ powder, and diameter of particle is concentrated, purity is greater than 99%, adopt silk screen print method to carry out finishing on commercialization zirconium plate, sintering forms one deck 3YSZ film, its naturally smooth exquisiteness in surface and top layer composition uniformity, hide completely Fe on former zirconium plate Ti spot, while therefore pressing as planar anode-supported type SOFC half-cell the pressing plate burning, can effectively avoid the bath surface of battery to produce fatal defect, and this surface modification method is simple, effective, and is easy to industrializing implementation.
Accompanying drawing explanation
The commercially available porous zirconia ceramic wafer of Fig. 1 surface topography map
Porous zirconia ceramic wafer surface topography map after Fig. 2 surface modification
Embodiment
By specific instantiation, technical scheme of the present invention is described below.Should be understood that one or more method steps that the present invention mentions do not repel between the step that also has additive method step or clearly mention at these before and after described combination step can also insert additive method step; Should also be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, without essence change technology contents in the situation that, when being also considered as the enforceable category of the present invention.
Embodiment 1
Prepare a kind of zirconia plate burning of pressing for planar anode-supported type SOFC half-cell:
(1) screen printing sizing agent of standby 3YSZ:
Batching specification: 3YSZ powder, D
50be 0.52 μ m, its distribution of particles is D
10be 0.15 μ m; D
90be 0.91 μ m, powder specific-surface area detection is 6.2m
2/ g powder, purity is for being greater than 99.5%; Purchased from Jiangxi Wei Yi hitech materials Co., Ltd;
Formula: 3YSZ:75wt%; Terpinol: 23.5wt%; Ethyl cellulose: 1.5wt%.
Slurrying: in advance ethyl cellulose is dissolved in terpinol completely, then adds 3YSZ powder, be placed in ball grinder ball milling and disperse, ball milling speed is 80 turn/min, ball milling 24h, makes the screen printing sizing agent of 3YSZ, and range of viscosities is at normal temperatures 20Pa.s;
(2) silk screen printing: (it is of a size of: length * wide * thick=158cm * 158cm * 4mm at business porous zirconia earthenware slab, percent opening is 33vol.%, screen printing is carried out on upper and lower surface as shown in Figure 1), meshcount is 100 orders, during printing, silk screen and zirconia plate distance are 5mm, brush and silk screen angle at 45 °; In upper and lower surface, respectively brush 6 times, every seal brushes one times, and the baking oven that is placed in 120 ℃ is dried 0.5 hour, so repeats, and upper and lower surface respectively forms the 3YSZ pasty film that thickness is 40 μ m;
(3) burn till: at 1400 ℃, sintering is 2.5 hours, on zirconium plate, form porous 3YSZ film (percent opening is 23vol.%), after burning, thickness is 27 μ m, is closely as one with former zirconium plate surface, and the zirconium plate after modification keeps evenness and the porous breathable of former zirconium plate.But smooth surface, there is no burr sense and color by the original faint yellow white (because the 3YSZ layer covering is white) that become, hide Fe/Ti spot local on former zirconium plate simultaneously completely.As shown in Figure 2.
Embodiment 2
Prepare a kind of zirconia plate burning of pressing for planar anode-supported type SOFC half-cell:
(1) prepare the screen printing sizing agent of 3YSZ:
Batching specification: 3YSZ powder, D
50be 0.31 μ m, its distribution of particles is D
10be 0.17 μ m; D
90be 0.83 μ m, powder specific-surface area detection is 10m
2/ g powder, purity is for being greater than 99.5%; Purchased from Jiangxi Wei Yi hitech materials Co., Ltd;
Formula: 3YSZ:64wt%; Terpinol: 34wt%; Polyvinyl butyral resin (MW40000-80000): 2wt%.
Slurry preparation: in advance polyvinyl butyral resin is dissolved in terpinol completely, then adds 3YSZ powder, be placed in ball grinder ball milling and disperse, ball milling speed is 100 turn/min, ball milling 48h, makes the screen printing sizing agent of 3YSZ;
(2) silk screen printing: (it is of a size of: length * wide * thick=158cm * 158cm * 5mm at business porous zirconia earthenware slab, percent opening is 25vol.%) screen printing sizing agent of upper silk screen printing 3YSZ, meshcount is 200 orders, during printing, silk screen and zirconia plate distance are 5mm, brush and silk screen angle at 45 °; In upper and lower surface, respectively brush 5 times, every seal brushes one times, and the baking oven that is placed in 150 ℃ is dried 0.5 hour, so repeats, and upper and lower surface respectively forms the 3YSZ pasty film that thickness is 50 μ m;
(3) burn till: at 1380 ℃, sintering is 4 hours, on zirconium plate, form porous 3YSZ film (porosity is 17vol.%), after burning, thickness is that (thickness after burning has relation because of print thickness to 38 μ m, also differently from temperature, powdery pulp there is a minor variations), be closely as one with former zirconium plate surface, the zirconium plate after modification keeps evenness and the porous breathable of former zirconium plate.But smooth surface, there is no burr sense and color by the original faint yellow white (because the 3YSZ layer covering is white) that become, hide Fe/Ti spot local on former zirconium plate simultaneously completely.
Embodiment 3
Prepare a kind of zirconia plate burning of pressing for planar anode-supported type SOFC half-cell:
(1) prepare the screen printing sizing agent of 3YSZ:
Batching specification: 3YSZ powder, D
50be 0.7 μ m, its distribution of particles is D
10be 0.3 μ m; D
90be 0.95 μ m, powder specific-surface area detection is 8m
2/ g powder, purity is for being greater than 99.5%; Purchased from Jiangxi Wei Yi hitech materials Co., Ltd;
Formula: 3YSZ:68.5wt%; Polyethylene glycol: 27.5wt%; Ethyl cellulose: 4wt%;
Slurry preparation: in advance ethyl cellulose is dissolved in polyethylene glycol completely, then adds 3YSZ powder, be placed in ball grinder ball milling and disperse, ball milling speed is 60 turn/min, ball milling 36h, makes the screen printing sizing agent of YSZ;
(2) silk screen printing: (it is of a size of: length * wide * thick=158cm * 158cm * 6mm at business porous zirconia earthenware slab, percent opening is 18vol.%) upper and lower surface on the screen printing sizing agent of silk screen printing 3YSZ, meshcount is 150 orders, during printing, silk screen and zirconia plate distance are 4mm, brush and silk screen angle at 45 °; In upper and lower surface, respectively brush 5 times, every seal brushes one times, and the baking oven that is placed in 120 ℃ is dried 0.5 hour, so repeats, and upper and lower surface respectively forms the 3YSZ pasty film that thickness is 30 μ m;
(3) burn till: at 1420 ℃, sintering is 2 hours, on zirconium plate, form porous 3YSZ film (porosity 20vol.%), after burning, thickness is 22 μ m, is closely as one with former zirconium plate surface, and the zirconium plate after modification keeps evenness and the porous breathable of former zirconium plate.But smooth surface, there is no burr sense and color by the original faint yellow white (because the 3YSZ layer covering is white) that become, hide Fe/Ti spot local on former zirconium plate simultaneously completely.
Claims (13)
1. for planar anode-supported type SOFC half-cell, press the zirconia plate burning, the smooth porous 3YSZ film of layer of surface that comprises the body of a porous zirconia earthenware slab and cover on the upper and lower surface of described body; And the thickness of the porous 3YSZ film on upper surface is identical with the thickness of the porous 3YSZ film on lower surface.
2. a kind of zirconia plate burning of pressing for planar anode-supported type SOFC half-cell as claimed in claim 1, is characterized in that, the thickness of described porous zirconia earthenware slab is 4.0-6.0mm, and porosity is 15vol.%-35vol.%.
3. a kind of zirconia plate burning of pressing for planar anode-supported type SOFC half-cell as claimed in claim 1, is characterized in that, the thickness of described porous 3YSZ film is 20～50 μ m, and porosity is 15vol.%-25vol.%.
4. for planar anode-supported type SOFC half-cell, press a surface modification method for the zirconia plate burning, specifically comprise the following steps:
(1) after in advance binding agent being dissolved in solvent completely, then add 3YSZ powder, ball milling is made 3YSZ slurry;
(2) adopt the mode of silk screen printing, at the upper and lower faces of porous zirconia earthenware slab, print respectively the 3YSZ slurry of same thickness;
(3) sintering.
5. surface modification method as claimed in claim 4, is characterized in that, in step (1), and the D of described 3YSZ powder
50be 0.3～0.7 μ m, and narrower particle size distribution, D
10be 0.1～0.3 μ m, D
90being 0.5～1.0 μ m, is nearly normal distribution, and specific area is 6～12m
2/ g, powder purity is greater than 99%.
6. surface modification method as claimed in claim 4, is characterized in that, in step (1), the mass percent example of described 3YSZ powder, binding agent and solvent is respectively 60～75wt%, 1～5wt% and 20～39wt%.
7. surface modification method as claimed in claim 4, is characterized in that, described solvent is selected from terpinol, polyethylene glycol and ethyl acetate.
8. surface modification method as claimed in claim 4, is characterized in that, described binding agent is selected from ethyl cellulose and polyvinyl butyral resin.
9. surface modification method as claimed in claim 4, is characterized in that, in step (1), described rotational speed of ball-mill is 50～100 revs/min, and Ball-milling Time is 24～48 hours.
10. surface modification method as claimed in claim 4, is characterized in that, in step (1), making 3YSZ slurry viscosity is at room temperature 10～80Pa.s.
11. surface modification methods as claimed in claim 4, is characterized in that, in step (2), the meshcount of described silk screen printing is 100～200 orders, and during printing, the distance of silk screen and described zirconia ceramics flat board is 3～5mm, brush and silk screen angle at 45 °; After every printing once, 100-150 ℃ of oven dry, so repeats.
12. surface modification methods as claimed in claim 4, is characterized in that, in step (2), the thickness of the 3YSZ slurry printing on upper and lower faces is 30-60 μ m.
13. surface modification methods as claimed in claim 4, is characterized in that, in step (3), described sintering temperature is 1380～1420 ℃, and the time of sintering is 2-4h.
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|---|---|---|---|
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|---|---|---|---|
| CN201410379437.0A CN104183860B (en) | 2014-08-04 | 2014-08-04 | A kind of zirconium oxide plate burnt for planar anode-supported type SOFC half-cell pressure and surface modification method thereof |
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Citations (3)
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|---|---|---|---|---|
| CN1877895A (en) * | 2006-06-29 | 2006-12-13 | 哈尔滨工业大学 | Method for reducing deformation of solid oxide fuel cell electrolyte film |
| CN1925200A (en) * | 2006-08-18 | 2007-03-07 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| CN103086737A (en) * | 2013-02-25 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Large-area ceramic porous burning plate and preparation method thereof |
-
2014
- 2014-08-04 CN CN201410379437.0A patent/CN104183860B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1877895A (en) * | 2006-06-29 | 2006-12-13 | 哈尔滨工业大学 | Method for reducing deformation of solid oxide fuel cell electrolyte film |
| CN1925200A (en) * | 2006-08-18 | 2007-03-07 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| CN103086737A (en) * | 2013-02-25 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | Large-area ceramic porous burning plate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YEN-YU CHEN，ET AL.: "Processing and characterization of ultra-thin yttria-stabilized zirconia (YSZ) electrolytic films for SOFC", 《SOLID STATE IONICS》 * |
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