CN1872794A - Improved coating method for preparing membrane of oxide ceramics - Google Patents
Improved coating method for preparing membrane of oxide ceramics Download PDFInfo
- Publication number
- CN1872794A CN1872794A CN 200610010218 CN200610010218A CN1872794A CN 1872794 A CN1872794 A CN 1872794A CN 200610010218 CN200610010218 CN 200610010218 CN 200610010218 A CN200610010218 A CN 200610010218A CN 1872794 A CN1872794 A CN 1872794A
- Authority
- CN
- China
- Prior art keywords
- oxide
- slurry
- film
- coating method
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Fuel Cell (AREA)
Abstract
This invention relates to an improved coating method for preparing oxide ceramic membrane. The method comprises: (1) preparing a support; (2) preparing a slurry of the raw materials; (3) coating the slurry onto the support; (4) spin-coating and leveling; (5) drying the membrane blank; (6) repeating the steps 3-5; (7) calcining at a high temperature. The method is convenient and rapid, and has such advantages as high raw materials utility and good membrane quality. The zirconium oxide electrolyte membrane thus prepared can be used to prepare solid oxide cells with high output power density and stable performance.
Description
Technical field
The present invention relates to a kind of preparation method of membrane of oxide ceramics.
Background technology
Usually membrane of oxide ceramics can adopt cladding process, silk screen printing, sol-gel method, electrophoretic deposition, dry pressing, filter to be coated with a lot of method preparations such as method, slurry for rotary coating method.The background technology directly relevant with the present invention is slurry cladding process and slurry for rotary coating method: the slurry cladding process is that the thickness suspension slip that will contain the finite concentration ceramics powder directly is coated in formation film base on the supporter; And being the suspension slurry that will have certain flowability, the slurry for rotary coating method drops on the supporter substrate, the supporter substrate is inhaled on sol evenning machine, sol evenning machine drive substrate and on slurry drop high speed rotating, utilize centrifugal force that drop is launched rapidly on the supporter substrate, after after a while, form certain thickness liquid film, dry back forms the film base.The diaphragm that above-mentioned two kinds of methods are made places high-temperature electric resistance furnace with the supporter substrate, carries out high temperature sintering, and sintering process notes controlling heating schedule, to guarantee film quality.200410044156.6) and " a kind of slurry for rotary coating preparation method of film " (application number: 200510010410.5) above-mentioned two kinds of methods relate separately to " a kind of preparation method of anode support type yttrium oxide stable zirconium oxide electrolyte film " (application number:.
In above-mentioned two kinds of methods, cladding process technology is fairly simple, owing to can use high concentration slurry, so film base initial density is higher, but slurry fluidity is relatively poor, and coating procedure needs the auxiliary armrest industry control system of certain pressure, and the homogeneity of thickness is difficult to control; The slurry for rotary coating method can be made the uniform film of thickness, but slurry concentration can not be feeding-up, otherwise can't drip, and also is difficult to the film forming of outwarding winding, and the slurry that the spin coating process throws away is more, easily causes wastage of material.
Summary of the invention
At the relative merits of above-mentioned two kinds of methods, the invention provides a kind of improvement coating method for preparing membrane of oxide ceramics, this method is in conjunction with above-mentioned two kinds of method advantages, and avoids the shortcoming of the two effectively.
The present invention prepares membrane of oxide ceramics according to following steps:
One, the preparation of supporter: with transition group metallic oxide, oxide solid solution ionogen and three kinds of raw materials of organic pore-forming agents according to 5: (3～7): after the mass ratio thorough mixing of (0.1～5) grinds, placing mould to be pressed into thickness with 100～500MPa is the thick disk of 0.2～3mm, place high-temperature electric resistance furnace then, temperature rise rate with 0.5 ℃/min～20 ℃/min is warmed up to 900～1200 ℃, sintering 0.5～2 hour promptly obtains being used for the anode support of solid-oxide fuel battery electrolyte film preparation;
Two, the preparation of slurry: granularity is used ball mill ball milling 1～48 hour at the ceramic powder of 0.1～5 micron sosoloid electrolyte, add binding agent then, make ceramic powder account for 1～60% of slurry total mass, the mixed together ball milling is 0.5～10 hour again;
Three, slurry applies: above-mentioned slurry is coated on the one side of anode support sheet, forms the coating of 10～100 micron thickness in its surface;
Four, spin coating leveling: the supporter that will apply the slurry thick film places on the turntable of sol evenning machine, and the rotating speed of control sol evenning machine is 2krpm～10krpm, and the even glue time is 10 seconds～5 minutes, forms the thinner uniform thin film base substrate of thickness in supporting body surface;
Five, film base drying: membrane blank is put in the electric furnace, slowly is warming up to 420 ℃ with the speed of 0.5 ℃/min～100 ℃/min, baking 5～10min obtains exsiccant film base layer;
Six, repeating step three is to step 5, and every thickness that repeats once to survey a film is until obtaining needed film thickness;
Seven, high temperature sintering: place high-temperature electric resistance furnace through applying a spin coating leveling-baking exsiccant multilayer film base repeatedly, speed with 2 ℃/min～10 ℃/min is warming up to 1300～1500 ℃, sintering 1～10h obtains the dense oxide electrolyte ceramics film of anode-supported.
The present invention combines the advantage of slurry coating method and slurry for rotary coating method dexterously, and in this way Zhi Bei zirconia electrolytic thin-membrane is successfully used to the preparation of solid oxide cell, output power density height, stable performance.Prepared film has micron order thickness, can be used for the electrolyte thin membrane prepare of Solid Oxide Fuel Cell (SOFC).That the present invention has is convenient, fast, technology is simple, film thickness is even, film quality is good, raw material availability is high, advantage such as with low cost.
Description of drawings
Fig. 1 is cell output figure as a result.
Embodiment
Embodiment one: present embodiment adopts following technical scheme to prepare membrane of oxide ceramics:
1, the preparation of supporter: supporter is made up of multiple hopcalite, the supporter that is used for the oxide electrolytic film of Solid Oxide Fuel Cell is the powder of transition group metallic oxide micron or submicron particle size and the mixture of another kind of oxide solid solution solid electrolyte powder and organic pore-forming agents.Transition group metallic oxide refers to one or both the mixture in nickel oxide, cobalt oxide, cupric oxide, the ferric oxide; The oxide solid solution ionogen refers to (account for 3～15mol%) and adulteratedly have cube or the zirconium white of tetragonal, or rare earth (one or more among Y, Sm, La, Pr, Nd, the Gd etc.) or alkaline earth (Ca and/or Sr) doped cerium oxide with elements such as yttrium, scandium, calcium or magnesium; Pore-forming material is a particle size at 1～50 micron flour, starch, gac or powdered graphite.With above-mentioned transition group metallic oxide, oxide solid solution ionogen and three kinds of raw materials of organic pore-forming agents according to 5: (3～7): after the mass ratio thorough mixing of (0.1～5) grinds, placing mould to be pressed into thickness with 100～500MPa is the thick disk of 0.2～3mm, place high-temperature electric resistance furnace then, temperature rise rate with 0.5 ℃/min～20 ℃/min is warmed up to 900～1200 ℃, sintering 0.5～2 hour promptly obtains being used for the anode support of solid-oxide fuel battery electrolyte film preparation.
2, preparation applies slurry: the slurry preparation comprised powder processing and with the mixing process of binding agent.The processing of powder be with granularity at the ceramic powder of oxide solid solution electrolytes such as 0.1～5 micron doped zirconia, doped cerium oxide with ball mill ball milling 1～48 hour; Said binding agent is that organic binder bonds such as ethyl cellulose are dissolved in the Terpineol 350, and wherein the content of ethyl cellulose is 1～10%; Add the ceramic powder that accounts for total mass 1～60% in the binding agent, the mixed together ball milling is 0.5～10 hour again.
3, coating procedure: apply spin coating and prepare YSZ (Tosoh) film: from storage receptacle, transfer on the anode support earlier slurry, with instruments such as scraper plate, blade or hairbrush slurry is coated with out, make its one side that intactly covers the supporter sheet, form slurry film base with tens of approximately micron thickness.If slurry is denseer, viscosity is bigger, then the thickness of film base may be uneven.
4, spin coating leveling: the supporter that will apply the slurry thick film places on the turntable of sol evenning machine, start vacuum pump and inhale sheet, the rotating speed of setting sol evenning machine then is 2krpm～10krpm, setting the even glue time is 10 seconds～5 minutes, start sol evenning machine, it is whole that film base surface is flattened under centrifugal action, makes redundant sizing agent be thrown away supporter by centrifugal force simultaneously, forms the thinner uniform thin film base substrate of thickness in supporting body surface.
5, the drying of film base: the certain thickness film base of making attached on the supporter is put in the electric furnace, speed with 0.5 ℃/min～100 ℃/min slowly is warming up to 420 ℃, baking 5～10min vapors away organic solvent and binding agent in the film base, obtains exsiccant film base layer.
6, step 3 to step 5 is carried out repeatedly, and every thickness that repeats once to survey a film is until obtaining needed film thickness.
7, high temperature sintering: place high-temperature electric resistance furnace through coating-spin coating leveling-baking exsiccant multilayer film base repeatedly, speed with 2 ℃/min～10 ℃/min is warming up to 1300～1500 ℃, sintering 1～10h obtains the dense oxide electrolyte ceramics film of anode-supported.
Embodiment two: present embodiment is with the example that is made as of the supporter of the oxide electrolytic film that is used for Solid Oxide Fuel Cell.Raw material uses glycine-nitrate process synthetic nickel oxide (NiO) nano-powder and yttria-stabilized zirconia (YSZ) electrolyte ceramics powder, pore-forming material flour, these three kinds of raw materials are prepared burden according to 5: 5: 1.7 mass ratio, after thorough mixing grinds, placing mould to be pressed into thickness with 150～200MPa is the thick disk of 0.6mm, place high-temperature electric resistance furnace then, temperature rise rate with 2 ℃/min～10 ℃/min is warmed up to 1000 ℃, sintering 2 hours promptly obtains being used for the NiO-YSZ anode support of solid-oxide fuel battery electrolyte film preparation.
Embodiment three: present embodiment is with the example that is made as of the supporter of the oxide electrolytic film that is used for Solid Oxide Fuel Cell.Raw material uses precipitator method synthetic nickel oxide nano powder and Samarium trioxide doped cerium oxide (SDC) electrolyte ceramics powder, pore-forming material flour, these three kinds of raw materials are prepared burden according to 5: 5: 2 mass ratio, after thorough mixing grinds, placing mould to be pressed into thickness with 150～200MPa is the thick disk of 0.5mm, place high-temperature electric resistance furnace then, temperature rise rate with 2 ℃/min～10 ℃/min is warmed up to 1000 ℃, sintering 2 hours promptly obtains being used for the NiO-SDC anode support of solid-oxide fuel battery electrolyte film preparation.
Embodiment four: present embodiment applies slurry according to following method preparation: yttria-stabilized zirconia (YSZ) ceramic powder is placed aluminum oxide mill jar, add zirconium white (ZrO
2) porcelain ball and alcohol solvent, use planetary ball mill ball milling 24 hours.The ethyl cellulose organic binder bond is dissolved in the Terpineol 350, and wherein the content of ethyl cellulose is 4%.In dissolving good binding agent, add the YSZ ceramic powder that accounts for total mass 30%, pack into the zirconium oxide porcelain ball and grind in the jar, use ball mill ball milling 2 hours.
Embodiment five: present embodiment prepares the coating slurry according to following method: nitrate citric acid method synthetic SDC powder is placed aluminum oxide mill jar, add zirconium oxide porcelain ball and alcohol solvent, use planetary ball mill ball milling 36 hours.The ethyl cellulose organic binder bond is dissolved in the Terpineol 350, and wherein the content of ethyl cellulose is 6%.In dissolving good binding agent, add the SDC ceramic powder that accounts for total mass 40%, pack into the zirconium oxide porcelain ball and grind in the jar, use ball mill ball milling 4 hours.
Embodiment six: will transfer on the one side of the supporter sheet for preparing according to embodiment two described methods according to embodiment four prepared slurry, implement to apply with scraper plate, form the coating of 10～50 micron thickness in its surface, cover this surface of supporter fully.The supporter ceramic plate of coating is transferred to rapidly on the sample table of sol evenning machine, start vacuum pump and inhale sheet, the rotating speed of setting sol evenning machine then is 6krpm, setting the even glue time is 30 seconds, start sol evenning machine, it is whole that film base surface is flattened under centrifugal action, makes redundant sizing agent be thrown away supporter by centrifugal force simultaneously, forms the thinner uniform thin film base substrate of thickness in supporting body surface.Formed certain thickness film base and supporter thereof are put in the electric furnace together, are warming up to 420 ℃, toasted 5 minutes, organic solvent and binding agent in the film base are vapored away, obtain exsiccant film base layer with the speed of 5 ℃/min.Coating-spin coating leveling-film base drying process is carried out 3 times repeatedly, and acquisition thickness is 10～15 microns YSZ film.
Embodiment seven: will transfer on the one side of the supporter sheet for preparing according to embodiment three described methods according to embodiment five prepared slurry, implement to apply with blade, form the coating of 10～50 micron thickness in its surface, cover this surface of supporter fully.The supporter ceramic plate of coating is transferred to rapidly on the sample table of sol evenning machine, start vacuum pump and inhale sheet, the rotating speed of setting sol evenning machine then is 10krpm, setting the even glue time is 1 minute, start sol evenning machine, it is whole that film base surface is flattened under centrifugal action, makes redundant sizing agent be thrown away supporter by centrifugal force simultaneously, forms the thinner uniform thin film base substrate of thickness in supporting body surface.Formed certain thickness film base and supporter thereof are put in the electric furnace together, are warming up to 420 ℃, toasted 10 minutes, organic solvent and binding agent in the film base are vapored away, obtain exsiccant film base layer with the speed of 3 ℃/min.Coating-spin coating leveling-film base drying process is carried out 5 times repeatedly, and acquisition thickness is 10～20 microns SDC film.
Embodiment eight: high temperature sintering.The zirconium oxide film base of the dried NiO-YSZ anode-supported that will make according to embodiment six places high-temperature electric resistance furnace, is warming up to 1400 ℃ with the speed of 5 ℃/min, and sintering 4h obtains the compact YSZ electrolyte ceramics film of NiO-YSZ anode-supported.
Embodiment nine: high temperature sintering.The zirconium oxide film base of the dried NiO-SDC anode-supported that will make according to embodiment seven places high-temperature electric resistance furnace, is warming up to 1350 ℃ with the speed of 3 ℃/min, and sintering 8h obtains the fine and close SDC electrolyte ceramics film of NiO-SDC anode-supported.
Embodiment ten: fuel battery performance test.Apply on the surface of the YSZ film of the NiO-YSZ anode-supported that will make according to embodiment eight and prepare La with sol-gel method
0.7Sr
0.3MnO
3(LSM) negative electrode (at 1000 ℃ of calcining 2h) then at 1100 ℃ of sintering 2h, with cerous nitrate and samaric nitrate mixing solutions dipping LSM negative electrode, subsequently at 850 ℃ of sintering 1h, is made anode-ionogen-cathodic coating electrode assemblie (MEA) of SOFC then.MEA is encapsulated in an end of alumina ceramic tube, and wherein the NiO-YSZ anode is in pipe, and the LSM negative electrode is exposed to outside the pipe, each electrode respectively connects the lead-in wire of 2 filamentary silvers as electrode, anode in the pipe feeds nitrogen purging to 700 ℃, feeds hydrogen reducing, and negative electrode is directly exposed in the air.At 700 ℃～800 ℃ volt-ampere and the power density curves that discharge with Solartron SI 1287 electrochemical interface test batteries with four electrode method, the cell output result who obtains as shown in Figure 1.More than 1V, the power density of 700 ℃, 750 ℃ and 800 ℃ is respectively 0.671W/cm to monocell at the open circuit voltage of this warm area
2, 0.958W/cm
2And 1.643W/cm
2
Claims (9)
1, a kind of improvement coating method for preparing membrane of oxide ceramics is characterized in that described method is:
One, the preparation of supporter: with transition group metallic oxide, oxide solid solution ionogen and three kinds of raw materials of organic pore-forming agents according to 5: (3～7): after the mass ratio thorough mixing of (0.1～5) grinds, placing mould to be pressed into thickness with 100～500MPa is the thick disk of 0.2～3mm, place high-temperature electric resistance furnace then, temperature rise rate with 0.5 ℃/min～20 ℃/min is warmed up to 900～1200 ℃, sintering 0.5～2 hour promptly obtains being used for the anode support of solid-oxide fuel battery electrolyte film preparation;
Two, the preparation of slurry: granularity is used ball mill ball milling 1～48 hour at the ceramic powder of 0.1～5 micron sosoloid electrolyte, add binding agent then, make ceramic powder account for 1～60% of slurry total mass, the mixed together ball milling is 0.5～10 hour again;
Three, slurry applies: above-mentioned slurry is coated on the one side of anode support sheet, forms the coating of 10～100 micron thickness in its surface;
Four, spin coating leveling: the supporter that will apply the slurry thick film places on the turntable of sol evenning machine, and the rotating speed of control sol evenning machine is 2krpm～10krpm, and the even glue time is 10 seconds～5 minutes, forms the thinner uniform thin film base substrate of thickness in supporting body surface;
Five, film base drying: membrane blank is put in the electric furnace, slowly is warming up to 420 ℃ with the speed of 0.5 ℃/min～100 ℃/min, baking 5～10min obtains exsiccant film base layer;
Six, repeating step three is to step 5, and every thickness that repeats once to survey a film is until obtaining needed film thickness;
Seven, high temperature sintering: place high-temperature electric resistance furnace through coating-spin coating leveling-baking exsiccant multilayer film base repeatedly, speed with 2 ℃/min～10 ℃/min is warming up to 1300～1500 ℃, sintering 1～10 hour obtains the dense oxide electrolyte ceramics film of anode-supported.
2, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 1 is characterized in that the powder of described transition group metallic oxide for micron or submicron particle size.
3, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 1 and 2 is characterized in that described transition group metallic oxide refers to one or both the mixture in nickel oxide, cobalt oxide, cupric oxide, the ferric oxide.
4, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 1, it is characterized in that described oxide solid solution ionogen refers to have cube or the zirconium white of tetragonal with yttrium, scandium, calcium or magnesium are adulterated, or rare earth or alkaline earth doping of cerium oxide.
5, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 4 is characterized in that described rare earth is one or more the mixture among Y, Sm, La, Pr, Nd, the Gd.
6, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 4 is characterized in that described alkaline earth is Ca and/or Sr.
7, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 1 is characterized in that described pore-forming material is flour, starch, gac or powdered graphite.
8, according to claim 1 or 7 described a kind of improvement coating methods that prepare membrane of oxide ceramics, the particle size that it is characterized in that described pore-forming material is 1～50 micron.
9, a kind of improvement coating method for preparing membrane of oxide ceramics according to claim 1 is characterized in that described binding agent is the terpineol solution of ethyl cellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100102180A CN100500615C (en) | 2006-06-27 | 2006-06-27 | Improved coating method for preparing membrane of oxide ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100102180A CN100500615C (en) | 2006-06-27 | 2006-06-27 | Improved coating method for preparing membrane of oxide ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1872794A true CN1872794A (en) | 2006-12-06 |
| CN100500615C CN100500615C (en) | 2009-06-17 |
Family
ID=37483419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100102180A Expired - Fee Related CN100500615C (en) | 2006-06-27 | 2006-06-27 | Improved coating method for preparing membrane of oxide ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100500615C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102322550A (en) * | 2011-06-15 | 2012-01-18 | 新兴铸管股份有限公司 | Preparation method of ceramic coating for replacing refractory coating produced by using centrifugal cast iron pipe heated mould method |
| CN103682406A (en) * | 2013-12-14 | 2014-03-26 | 济南开发区星火科学技术研究院 | Solid oxide fuel cell employing natural gas |
| CN104103873A (en) * | 2014-06-25 | 2014-10-15 | 华中科技大学 | Solid electrolyte film, and preparation method and application of solid electrolyte film |
| CN106147300A (en) * | 2015-04-09 | 2016-11-23 | 广州市劲业节能技术有限公司 | A kind of anticorrosive wear-resistant rare earth composite coating |
| CN106631044A (en) * | 2016-09-19 | 2017-05-10 | 武汉大学 | Method for shaping gradient-straight-hole double-layer asymmetric ceramic oxygen separation membrane |
| CN107354479A (en) * | 2017-07-26 | 2017-11-17 | 合肥工业大学 | A kind of anode preparation method suitable for high-temperature electrochemistry hydrogen pump |
| CN110436889A (en) * | 2019-07-09 | 2019-11-12 | 太原理工大学 | A method of based on both hand in clear opening ceramic surface plated film |
| WO2020191829A1 (en) * | 2019-03-27 | 2020-10-01 | 景德镇陶瓷大学 | Preparation method for sofc anti-carbon-deposition ni-ysz anode material |
| CN114751725A (en) * | 2022-04-26 | 2022-07-15 | 景德镇陶瓷大学 | Preparation and application method of embedded flat ceramic membrane layer slurry |
| CN115557789A (en) * | 2022-10-25 | 2023-01-03 | 安徽工业大学 | Preparation method and application of flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film |
-
2006
- 2006-06-27 CN CNB2006100102180A patent/CN100500615C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102322550A (en) * | 2011-06-15 | 2012-01-18 | 新兴铸管股份有限公司 | Preparation method of ceramic coating for replacing refractory coating produced by using centrifugal cast iron pipe heated mould method |
| CN103682406A (en) * | 2013-12-14 | 2014-03-26 | 济南开发区星火科学技术研究院 | Solid oxide fuel cell employing natural gas |
| CN103682406B (en) * | 2013-12-14 | 2015-11-18 | 济南开发区星火科学技术研究院 | Utilize the Solid Oxide Fuel Cell of natural gas |
| CN104103873A (en) * | 2014-06-25 | 2014-10-15 | 华中科技大学 | Solid electrolyte film, and preparation method and application of solid electrolyte film |
| CN106147300A (en) * | 2015-04-09 | 2016-11-23 | 广州市劲业节能技术有限公司 | A kind of anticorrosive wear-resistant rare earth composite coating |
| CN106631044A (en) * | 2016-09-19 | 2017-05-10 | 武汉大学 | Method for shaping gradient-straight-hole double-layer asymmetric ceramic oxygen separation membrane |
| CN107354479A (en) * | 2017-07-26 | 2017-11-17 | 合肥工业大学 | A kind of anode preparation method suitable for high-temperature electrochemistry hydrogen pump |
| CN107354479B (en) * | 2017-07-26 | 2019-04-05 | 合肥工业大学 | A kind of anode preparation method suitable for high-temperature electrochemistry hydrogen pump |
| WO2020191829A1 (en) * | 2019-03-27 | 2020-10-01 | 景德镇陶瓷大学 | Preparation method for sofc anti-carbon-deposition ni-ysz anode material |
| CN110436889A (en) * | 2019-07-09 | 2019-11-12 | 太原理工大学 | A method of based on both hand in clear opening ceramic surface plated film |
| CN110436889B (en) * | 2019-07-09 | 2022-04-22 | 太原理工大学 | Method for coating film on surface of straight-through hole ceramic based on manual coating method |
| CN114751725A (en) * | 2022-04-26 | 2022-07-15 | 景德镇陶瓷大学 | Preparation and application method of embedded flat ceramic membrane layer slurry |
| CN115557789A (en) * | 2022-10-25 | 2023-01-03 | 安徽工业大学 | Preparation method and application of flexible transition metal oxide lanthanum strontium manganese oxygen ferromagnetism thick film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100500615C (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100500615C (en) | Improved coating method for preparing membrane of oxide ceramics | |
| JP5469795B2 (en) | Anode-supported solid oxide fuel cell using cermet electrolyte | |
| JP6437821B2 (en) | Composite anode for solid oxide fuel cells with improved mechanical integrity and efficiency | |
| JP2007529852A5 (en) | ||
| JPWO2006101136A1 (en) | Fuel electrode material for solid oxide fuel cell, fuel electrode using the same, and fuel cell | |
| CN104779409A (en) | Solid oxide fuel cell and preparation method thereof | |
| KR20100041348A (en) | Method of preparing a metal oxide sol, method of manufacturing a metal oxide thin film structure using the method and solid oxide fuel cell comprising a metal oxide thin film structure manufactured by the method | |
| US9318766B2 (en) | Technique for designing and manufacturing solid oxide fuel cell having improved output capability in mid to low temperature | |
| JP5615771B2 (en) | Solid oxide fuel cell system and conductive bonding material | |
| CN113337834B (en) | Asymmetric-structure electrolytic cell made of symmetric materials and preparation method thereof | |
| Ai et al. | Preparation of Sm0. 2Ce0. 8O1. 9 membranes on porous substrates by a slurry spin coating method and its application in IT-SOFC | |
| CN111009675B (en) | Solid oxide fuel cell and preparation method thereof | |
| Hongyan et al. | Preparation and characterization of La0. 8Sr0. 04Ca0. 16Co0. 6Fe0. 4O3-δ-La0. 9Sr0. 1 Ga0. 8Mg0. 2O3 composite cathode thin film for SOFC by slurry spin coating | |
| CN101222050A (en) | Anti-carbon deposition anode film material and method for producing the same | |
| JP2007200664A (en) | Method of manufacturing solid oxide fuel cell | |
| US8158304B2 (en) | Formulation of nano-scale electrolyte suspensions and its application process for fabrication of solid oxide fuel cell-membrane electrode assembly (SOFC-MEA) | |
| EP2166602B1 (en) | Fabrication of solid oxide fuel cell-membrane electrode assembly (SOFC-MEA) | |
| CN1320677C (en) | Method of preparing yttrium oxide stable zirconium oxide electrolyte film | |
| KR101146349B1 (en) | Fabrication Method of Metal Supported Solid Oxide Fuel Cell | |
| CN111416138A (en) | Proton ceramic membrane fuel cell and preparation method thereof | |
| JPH09171830A (en) | Cell of solid electrolytic fuel cell | |
| CN100363116C (en) | Process for preparing film slurry for rotary coating | |
| CN108598540A (en) | Solid oxide fuel cell and preparation method thereof | |
| JP2006059611A (en) | Ceria based solid electrolyte fuel cell and its manufacturing method | |
| US20150147677A1 (en) | FABRICATION OF SOLID OXIDE FUEL CELLS WITH A THIN (LA0.9SR0.1)0.98(GA0.8MG0.2)O3-delta ELECTROLYTE ON A SR0.8LA0.2TIO3 SUPPORT |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090617 Termination date: 20100627 |