CN102437358B - Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof - Google Patents
Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof Download PDFInfo
- Publication number
- CN102437358B CN102437358B CN2011103909332A CN201110390933A CN102437358B CN 102437358 B CN102437358 B CN 102437358B CN 2011103909332 A CN2011103909332 A CN 2011103909332A CN 201110390933 A CN201110390933 A CN 201110390933A CN 102437358 B CN102437358 B CN 102437358B
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- powder
- double
- fuel cell
- catalyst
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to solid fuel battery, in particular to a solid oxide fuel cell supported by stainless steel and a preparation method thereof. A cell structure comprises an anode 1, an electrolyte film 3 and a cathode 4; the anode 1 is a porous stainless steel supported body, wherein the pore of the porous stainless steel supported body contains catalyst 2 capable of catalyzing an electrochemical reaction of the solid oxide fuel cell anode; the thickness of the stainless steel supported body is 0.1 mm to 3 mm; the porosity is 10% to 60%, while the thickness of a compact electrolyte film is 2 microns to 80 microns. The solid oxide fuel cell supported by the stainless steel is proved that the cell has good output performance and resistance to oxidization and reduction.
Description
Technical field
The present invention relates to solid fuel cell, be specifically related to Solid Oxide Fuel Cell of a kind of stainless steel support and preparation method thereof.
Background technology
Solid Oxide Fuel Cell (SOFC) is as a kind of novel energy conversion equipment of high-efficiency cleaning, and its various critical materials, preparation technology's research and development and corresponding battery configuration and stack design etc. have been subject to the common concern of whole world researcher and scientific research institution.In general, the configuration of SOFC monocell mainly comprises three kinds of electrolyte-supported (ESC), anode-supported (ASC) and cathode support (CSC).And, for the monocell of these three kinds of configurations, its supporter is all pottery or the cermet material of some fragility on composition, simultaneously also all more or less comprise some precious metal materials.Consider low cost, high conductivity, high strength and easy processing characteristics that some metal materials have, the research and development of metallic support configuration battery (MSC) have received the increasing concern of researchers.
In May, 2007, the permanent brave people of grade of Tu of Shanghai Communications University has applied for patent " preparation method of the low-temperature solid oxide fuel cell that porous metals support " (publication number CN1960047) and " structure of the low-temperature solid oxide fuel cell of porous metals support " (publication number CN1960048).These two pieces of patent Introductions a kind of porous metals that comprise porous stainless steel supporter from bottom to top and reforming catalyst, porous anode film, compact solid electrolyte, reaction barrier layers, activation of cathode layer and cathode contact layer the low temperature SOFC structure and the concrete preparation processes thereof that support.Concrete steps are: (1) adopts porous stainless steel as supporter, deposit successively porous anode film, compact solid electrolytic thin-membrane and reaction barrier layers on the porous stainless steel supporter, using this as half-cell, sintering under reducing atmosphere or inert atmosphere; (2) sintering complete cooling after, continue deposition cathode active layer and cathode contact layer on solid electrolyte film, sintering under air atmosphere, become monocell; (3) flood reforming catalyst in the porous stainless steel supporter, obtain fuel cell, various fuel gas, by the porous stainless steel supporter, are reformatted into the anodic gas that is rich in hydrogen and enter anode, carry out electrochemical reaction.The battery structure made like this is stable, and the electrocatalysis characteristic of anode is improved; The thermal uniformity of whole battery temperature improves, and then the performance of battery and life-span are improved; The whole system structure is compacter, and efficiency is higher.In October, 2009, the people such as the Li Jian of the Central China University of Science and Technology have also applied for the patent of " a kind of preparation method of metallic support type solid oxide fuel cell " by name, and publication number is CN101562255.This invention comprises: (1) prepares the casting slurry step; (2) flow casting molding step; (3) prepare the half-cell step; (4) high temperature sintering step; (5) prepare the monocell step; (6) reduction step.These invention selected materials wide material sources, preparation technology is simple, and cost is lower, and technology of preparing can be used for the preparation of large-area metal support type SOFC.
But, the SOFC of these metallic support configurations structurally at least needs to comprise four layers, i.e. metal support layer, anode layer, dielectric substrate and cathode layer.Between stainless steel supporter and electrolytic thin-membrane, rely on anode functional layer to come catalytic electrochemical reaction, the overall structure of battery and complicated process of preparation.Simultaneously, need nickeliferous anode functional layer and the metal support containing chromium are carried out to high temperature co-firing in preparation process, also likely form NiCr
2o
4deng insulating barrier, reduce the charge-conduction efficiency of battery.
Summary of the invention
For the deficiencies in the prior art, the invention provides Solid Oxide Fuel Cell that a kind of stainless steel of the three-decker that does not need extra anode functional layer supports and preparation method thereof, to simplify battery structure, reduce preparation technology's complexity and preparation cost, and avoid contingent adverse effect in preparation process.
In some embodiments of the present invention, the stainless steel support solid oxide fuel cell comprises anode, fine and close electrolytic thin-membrane and negative electrode three-decker, described anode is porous stainless steel supporter (including the catalyst that the antianode reaction of introducing by the wet-chemical infusion process has catalytic activity), wherein in described porous stainless steel supporter, form on the stainless surface of hole contain can catalytic solid anode of oxide fuel cell electrochemical reaction catalyst, wherein the thickness of stainless steel supporter is 0.1mm to 3mm, preferred 0.2mm to 1.5mm, more preferably 0.4mm to 1.0mm, 0.5mm to 0.8mm most preferably, porosity is 10% to 60%, preferably 20% to 45%, more preferably 25% to 40%, most preferably 30% to 35%, and the thickness of dense electrolyte film is 2 μ m to 80 μ m, preferably 5 μ m to 50 μ m, more preferably 10 μ m to 30 μ m, most preferably 15 μ m to 20 μ m.It is characterized in that, do not comprise special anode functional layer and other supplementary structure such as reaction barrier layers in whole battery structure, the stainless steel supporter, after specific catalyst soakage is modified, is played the part of the role in cell support body and anode function district simultaneously.
In some embodiments of the present invention, the preparation method of the Solid Oxide Fuel Cell that the stainless steel of described three-decker supports, comprise by the double-layer tablet of pressing altogether the co-firing technology preparation to comprise porous stainless steel supporter and dense electrolyte layer, add catalyst granules by the ion infusion process in the porous stainless steel supporter, form half-cell, and thereby coating cathode powder sintering form negative electrode thereon, to complete the preparation of monocell.Wherein, the method for coating cathode comprises silk screen print method, sprayed deposit etc., preferably silk screen print method.
In some embodiments of the present invention, the process of the double-layer tablet that described preparation comprises porous stainless steel supporter and dense electrolyte layer, it is characterized in that utilizing the disposable common preparation that just can complete stainless steel supporter and dielectric substrate of traditional common pressure co-firing technology, technical maturity is simple, single batch of output is large, and can be by the suitable control of pore creating material in sintering procedure and stainless steel supporter, prepare the electrolytic thin-membrane of high-compactness simultaneously and there is the stainless steel supporter of required porosity and pore size distribution.The concrete preparation process of described embodiment comprises:
(1) mix grinding of stainless steel supporter presoma powder: stainless steel powder and polymethyl methacrylate (PMMA) and graphite as pore creating material are mixed together in alcohol solvent, chemical matching and the thermal matching of the electrolyte phase powder that simultaneously also adds the 10-30 % by weight stainless steel supporter and electrolytic thin-membrane when strengthening sintering, then fully grind mixed powder evenly and drying.
(2) compacting of double-layer tablet: take a certain amount of stainless steel supporter precursor powder and pour in compression mold, first be depressed in advance 10MP to 100MPa, preferred 50MP, and then pour appropriate electrolyte powder into and be paved into even thin layer on its surface, be depressed into altogether again 200MPa to 400MPa, preferred 300MPa, pressurize a period of time retreats mill, takes out double-layer tablet.
(3) sintering of double-layer tablet: the double-layer tablet suppressed first is put in Muffle furnace, with the speed of 1-2 ℃/min, is warming up to 400 ℃ to 800 ℃, preferably 600 ℃, burn 10h thoroughly to remove the pore creating material in the stainless steel supporter in air atmosphere.Again double-layer tablet is placed in to atmosphere furnace after cooling, carries out 1200 ℃-1600 ℃ under reducing atmosphere, preferably the high temperature sintering of 1350-1450 ℃.In sintering process, should, in other some titanium valves of placing of double-layer tablet to remove the micro amount of oxygen that may sneak in sintering process, prevent stainless oxidation.Simultaneously, about the setting of sintering procedure, before 550 ℃, heating rate is 0.5 ℃/min to 5 ℃/min, preferred 1 ℃/min, and, at 550 ℃ of insulation 2h, the speed with 2 ℃/min is warmed up to sintering temperature and is incubated 5h afterwards, speed with 2 ℃/min cools to 800 ℃ subsequently, more naturally cools.
In some embodiments of the present invention, also can use the general pore creating material such as graphite or starch to replace polymethyl methacrylate.
In some embodiments of the present invention, also can use propyl alcohol, n-butanol, isobutanol or acetone equal solvent to replace ethanol.
In some embodiments of the present invention, in above-mentioned preparation process, described stainless steel adopts the business powder, as 430 series stainless steel powder (SS430) of business.Described electrolyte is because the high temperature co-firing process need carries out under reducing atmosphere, thus preferably use stable zirconia-based material, as the zirconia (YSZ) of 8mol% stabilized with yttrium oxide.This stable Zirconium powder preferably synthesizes to obtain fluffy powder by glycine method, and wherein the addition of glycine (amount of substance) is half of nitrate ion amount of substance total amount.For two kinds of pore creating materials used in above-mentioned preparation process, the macropore that PMMA produces is mainly for the ease of the gas transport in the stainless steel supporter, and the aperture that graphite is produced is conducive to expand the effective active zone of reaction.
In some embodiments of the present invention, described by the ion infusion process to adding the process of catalyst granules in the porous stainless steel supporter, the catalyst particle size that it is characterized in that preparation is less, substantially be nano shape, more contingent side reactions while also having avoided high-temperature heat treatment simultaneously.The concrete preparation process of described embodiment comprises:
(1) preparation of maceration extract: according to the composition of required catalyst, select suitable metal-nitrate solutions, according to required stoichiometric proportion, be made into the metal ion maceration extract.For example, use Sm
0.2ce
0.8o
1.9(SDC), as catalyst, the nitrate that contains metal ion is Sm (NO
3)
3, Ce (NO
3)
3, and meet amount of substance and compare Sm
3+: Ce
3+=1: 4.During preparation, in maceration extract, also need to add glycine to be stirred complexing, the addition of glycine (amount of substance) is half of nitrate ion amount of substance total amount.
(2) dipping process: porous stainless steel supporter one side of the double-layer tablet for preparing previously is placed in to surface plate upward, in vacuum, the maceration extract prepared is slowly dripped in surface plate until all compressing tablets all are submerged.Continuing in a vacuum standing one littlely takes out compressing tablet after the meeting.
(3) heat treatment: after the compressing tablet that will flood dries, wipe away the bath surface of compressing tablet by the ethanol cotton rub, wiping away may residual maceration extract thereon.Then compressing tablet is placed in to Muffle furnace and carries out the heat treatment of 2 hours, heat treatment temperature approaches with the one-tenth phase temperature of catalyst, is generally 400 ℃ to 800 ℃, and for example, for SDC, this heat treatment temperature is generally 600 ℃.
(4) determining of pickup: after dipping and heat treatment process complete, by the quality of electronic balance weighing compressing tablet, then contrasted with the quality of the front compressing tablet of dipping, the difference of mass change is the pickup of catalyst.Consider that the pickup that each dipping can reach is very limited, thus often need multiple dipping and heat treatment process in preparation process, to reach required catalyst soakage amount.
In some embodiments of the present invention, in the preparation steps of superincumbent (1) maceration extract, catalyst can be also other metal or oxide particles that reaction has catalytic activity to anode of fuel cell arbitrarily, and described metal or oxide particle with catalytic activity comprises Ni, Pt, Pd, Ru, Ag, SDC, CeO
2, GDC etc. and their compound phase.
In some embodiments of the present invention, in above-mentioned preparation process, the concentration of the pickup in each dipping cycle and the porosity of stainless steel supporter and maceration extract is closely related.So, can regulate and control by the optimization to them pickup of single impregnation.But, it should be noted that too dense the stable of battery structure that all be unfavorable for of the too high or maceration extract of porosity, so will select suitable porosity and impregnation concentration.In general, the concentration of maceration extract should be 0.1M to 2.0M, preferably 0.3M to 1.5M, more preferably 0.5M to 1.2M, most preferably 0.8M to 1.0M.In addition, also should be noted that the treatment temperature while controlling heat treatment, should guarantee that catalyst can become phase on the one hand, also will avoid on the other hand the too high stainless steel supporter that causes for the treatment of temperature oxidized.
In some embodiments of the present invention, the process of the described coated cathode of the method by silk screen printing and in-situ sintering, it is characterized in that in the sintering process of negative electrode, can avoid the aerial oxidation of stainless steel supporter, can avoid again negative electrode that the reduction of metal occurs under reducing atmosphere, when preparing negative electrode, make the stability of battery fully be ensured simultaneously.The concrete preparation process of described embodiment comprises:
(1) preparation of slurry and coating: to the terpinol that adds the ethyl cellulose that contains 10% mass fraction of its 1.5 times of quality in cathode powder, brush the bath surface of the double-layer tablet of modifying through catalyst after fully grinding evenly by silk screen print method, altogether need to repeat to brush three times and dry under infrared lamp.
(2) in-situ sintering of negative electrode: the logical reducibility gas of double-layer tablet stainless steel supporter one side that brushes negative electrode, cathode side keeps oxidizing atmosphere or air condition, and, by the contact of the isolated both sides of certain sealing device (usually using the testing apparatus of battery) gas, stove is warming up to the temperature required sintering that completes negative electrode.
In some embodiments of the present invention, described cathode material normally is applicable to the lanthanum strontium manganese sill of stable zirconium oxide base electrolyte, as (La
0.85sr
0.15)
0.9srMnO
3-δ(LSM)-YSZ, LSM-SDC, LSM-(Y
0.25bi
0.75)
2o
3(YSB) etc.And the synthetic of LSM, SDC, YSB etc. also all is based on glycine method, and the addition of glycine (amount of substance) is all also nitrate ion amount of substance total amount half.
After the in-situ sintering of negative electrode completes, complete the preparation process of the stainless steel support solid oxide fuel cell of three-decker of the present invention, can test accordingly battery.
To sum up, in some embodiments of stainless steel support solid oxide fuel cell of the present invention, the method of first by bilayer, pressing altogether and burning altogether under reducing atmosphere is prepared the double-layer tablet that comprises porous stainless steel supporter and dense electrolyte film, then by the wet-chemical infusion process, to immersing the antianode reaction in the stainless steel supporter, there is the nano particle of catalytic activity to work as the anode of SOFC, last again by the method coating cathode of silk screen printing and in-situ sintering, complete the preparation of whole monocell.With traditional metallic support SOFC technology, compare, the characteristics of stainless steel support solid oxide fuel cell maximum of the present invention are exactly not need special anode functional layer.In some embodiments of the present invention, the stainless steel supporter of porous, in the supporter solid as whole battery, also can be good at the electronics that the conduction reaction produces; Simultaneously, be added on electrolyte phase powder in the stainless steel supporter when strengthening stainless steel supporter and dense electrolyte layer matching, also make in the stainless steel supporter to have possessed certain ionic conductance, and then the active region of reacting is increased; And the follow-up catalyst granules of introducing by the wet-chemical infusion process has strengthened the catalytic activity in the stainless steel supporter greatly, make stainless steel support the oxidation reaction of physical efficiency catalytic fuel as anode functional layer.On the other hand, the resistances such as good heat resistanceheat resistant circulation that stainless steel has and anti-oxidant reduction cycle, also make that whole battery can be stablized, safe carrying out exported for a long time.
Compared to existing technology, above preparation method also has following advantage:
(1) catalyst in the stainless steel supporter adds by the wet-chemical infusion process, both be conducive to prepare little, the active high catalyst granules of size, side reaction problem simultaneously that also well avoided traditional high temperature preparation process to cause, and also more be conducive to safeguard the stability of whole battery structure during the cycle in the experience redox.Thereby, needn't consider some other complicated factor when selecting catalyst, so long as various anode reactions are had to metal or the oxide particle of stronger catalytic activity, can attempt being applied in the stainless steel support solid oxide fuel cell of described three-decker.
(2) negative electrode can adopt the preparation of the techniques such as silk screen printing and in-situ sintering, can complete the sintering of negative electrode under temperature required, can be good at again guaranteeing that the stainless steel supporter is not oxidized.Thereby, when selecting cathode material, selection face is also comparatively extensive, only need consider emphatically material for the catalytic activity of cathode reaction with and with electrolyte the reactive problem when the sintering temperature.
(3) do not comprise the preparation technology that ESD, PLD etc. are comparatively complicated in whole preparation process, simple, easy row, reproducible, be conducive to large-scale manufacture generally.
Below by embodiment and accompanying drawing, be described further.
The accompanying drawing explanation
The generalized section of the stainless steel support solid oxide fuel cell that Fig. 1 the present invention proposes, this Solid Oxide Fuel Cell comprises negative electrode 4, electrolyte 3, porous stainless steel supporter (anode) 1, at the hole of stainless steel supporter 1, contains catalyst 2.
Fig. 2 is the untreated SS430-YSZ stainless steel supporter skeleton for preparing by the inventive method in embodiment 1 and the scanning electron microscope (SEM) photograph of YSZ dielectric film contact interface.
Fig. 3 be preparation in the embodiment of the present invention 1 convenient test take the SS430 stainless steel support solid oxide fuel cell that (430 series stainless steel powder)-YSZ is the three-decker of supporter skeleton P-V-I curve when 700 ℃ of work in different Ni-SDC catalyst soakage amount situation.
Fig. 4 is that the stainless steel support solid oxide fuel cell that SS430-YSZ is the three-decker of supporter skeleton of take of the convenient test of preparation in the embodiment of the present invention 1 experiences the peak power output variable density situation of repeatedly redox week after date during in 700 ℃ after the Ni-SDC catalyst granules of dipping 6 % by weight.
Referring to Fig. 1, a lot of discrete being distributed in stainless steel supporter skeleton 1 of catalyst granules 2, electrolytic thin-membrane 3 is attached on the stainless steel supporter skeleton 1 of porous, cathode layer 4 is coated in the surface of electrolytic thin-membrane 3, thereby forms the stainless steel support solid oxide fuel cell of whole three-decker.
Embodiment
The stainless steel of embodiment 1:SS430-YSZ (Ni-SDC)/YSZ/LSM-YSB three-decker supports SOFC
(1) prepare electrolyte YSZ (8mol%Y with glycine-nitrate process
2o
3-ZrO
2) LSM ((La in powder and negative electrode
0.85sr
0.15)
0.9srMnO
3-δ) and YSB ((Y
0.25bi
0.75)
2o
3) powder: with the example that synthesizes of YSZ, the Y (NO demarcated in advance
3)
3, Zr (NO
3)
4mix by stoichiometric proportion, keep Y
3+and Zr
4+the amount of substance ratio be 0.16: 0.92, form nitrate presoma Y
0.16zr
0.92(NO
3)
xsolution, then add glycine as complexing agent, and the amount of substance of required glycine is half of nitrate ion total amount, stirs abundant complexing in 1 hour after glycine dissolves.Then, get the Y of about 0.02mol at every turn
0.16zr
0.92(NO
3)
xprecursor liquid is placed in the beaker of 1000mL, on the electric hot plate of 500W, heats, and boils off unnecessary moisture.Become after thick and continue heating until solution, jelly takes fire, and sprays shallow white powder.These shallow white powders, 700 ℃ of heat treatments 2 hours, are made into to the YSZ electrolyte powder of phase.For LSM and YSB powder, when synthetic, also can use the nitrate solution of its respective metal ion to be mixed into precursor solution by stoichiometric proportion, while adding complexing of glycin, the amount of substance of glycine is also half of nitrate ion total amount.Finally the LSM powder of ejection need be 800 ℃ of heat treatments 2 hours, and the YSB powder need be 600 ℃ of heat treatments 2 hours.
(2) prepare stainless steel supporter precursor powder: YSZ powder prepared by business 430 series stainless steel powders (SS430) and glycine-nitrate process and as the polymethyl acrylate (PMMA) of pore creating material and graphite (C) according to mass ratio SS430: YSZ: PMMA: C=16: in alcohol solvent carry out mix grinding at 4: 1: 2.Until abundant mix grinding evenly after, then polyvinyl alcohol (PVA) solution that adds 5 % by weight by the amount of 2～4 of every grams is as binding agent, further mill is put into the baking oven of 80 ℃ after dry and is dried to drying.
(3) prepare the SS430-YSZ/YSZ double-layer tablet: take dried stainless steel supporter precursor powder 0.5 gram, in the mould that to pour diameter into be 13mm, under 50MPa pressure, single shaft is colded pressing.Subsequently, then pour the YSZ electrolyte powder of 0.025 gram into to its surface, further molded altogether under 300MPa pressure after tiling evenly.The double-layer tablet pressed directly is put in the high alumina porcelain boat, burns 600 ℃/10h thoroughly to remove pore creating material wherein in Muffle furnace.Add a small amount of titanium valve again in porcelain boat after lowering the temperature, burn 1400 ℃/5h and complete sintering under hydrogen atmosphere.High temperature sintering heats up and it should be noted that: 1 ℃/min is raised to 550 ℃, insulation 2h, and then 2 ℃/min is raised to 1400 ℃, is incubated 5 hours, and 2 ℃/min cools to 800 ℃, then natural cooling down.The stainless steel supporter thickness of burned double-layer tablet is 0.970mm, and porosity is that 36%, YSZ dielectric substrate thickness is 49.8 μ m.
(4) flood the NiO-SDC catalyst precursor particles in stainless steel insert: with Ni (NO
3)
2, Sm (NO
3)
3and Ce (NO
3)
3three kinds of metal-nitrate solutions are Ni in molar ratio
2+: Sm
3+: Ce
3+=43: being mixed with the metal ion total concentration at 2: 8 is 1molL
-1mixed solution, add wherein glycine (amount of substance of the glycine added is half of nitrate ion total amount), fully stir complexing and become maceration extract.SS430-YSZ/YSZ double-layer tablet porous stainless steel one side sintered is placed in to surface plate upward, under vacuumizing state, the maceration extract prepared is dropwise dripped to surface plate in until flood all compressing tablets.Continue the maintenance vacuum after a period of time, compressing tablet is taken out and dries, with the ethanol cotton, wipe the maceration extract that the dielectric substrate surface may be remaining away, then compressing tablet is put into to 600 ℃/2h of Muffle furnace burning and made the maceration extract immersed resolve into the NiO-SDC catalyst precursor particles.Because the single impregnation amount is limited, thus need to repeat dipping and sintering process, until reach required catalyst soakage amount.In concrete experimentation, often carry out haply dipping three times, the quality of the Ni-SDC catalyst that finally can immerse is 2% of supporter quality.
(5) coating of LSM-YSB negative electrode and in-situ sintering: the LSM that will prepare with glycine-nitrate process and YSB powder be LSM: YSB=6 in mass ratio: 4 mix grindings, the terpinol that adds subsequently the ethyl cellulose that contains 10% mass fraction of 1.5 times of its gross masses, be coated to the YSZ bath surface of impregnated double-layer tablet, the circle that the negative electrode of coating is diameter 0.8cm after further grinding evenly by silk screen print method.Altogether need to repeat to brush three times and dry under infrared lamp.After negative electrode is dried by cell package to alumina tube, be placed in the stove of setting, in the situation that stainless steel supporter one side is led to hydrogen, negative electrode one side in surrounding air, stove is warmed up to 850 ℃ and be incubated the sintering that completes negative electrode in 2 hours with the speed of 3 ℃/min, during need to be 350 ℃ of insulations 1 hour.In the process of sintering, in the stainless steel supporter, the NiO-SDC catalyst precursor particles of dipping also has been reduced into final Ni-SDC catalyst simultaneously in position, and the preparation of monocell also thoroughly completes.Just can test accordingly battery subsequently.
Stainless steel support solid oxide fuel cell to the SS430-YSZ (Ni-SDC) of above-mentioned preparation/YSZ/LSM-YSB three-decker carries out the properties test:
Output performance and the redox cycle resistance test of the battery of different Ni-SDC pickup when 700 ℃ of work.With silver slurry and filamentary silver collected current, stainless steel supporter one side atmosphere is wet hydrogen (3%H
2o), negative electrode one side atmosphere is surrounding air.Output performance with ZAHNER IM6eX electrochemical workstation test battery at 700 ℃.When measurement redox cycle resistance, first the atmosphere of stainless steel supporter is switched to argon gas, be cut to again subsequently air.After keeping 30min, then switch back argon gas, then continue the variation of logical wet hydrogen atmosphere test battery performance.Altogether carried out the test in five cycles.
Fig. 2 is the scanning electron microscope (SEM) photograph of untreated SS430-YSZ stainless steel supporter skeleton and YSZ dielectric film contact interface.The stainless steel supporter is very good with contacting of YSZ dielectric substrate as can be seen from Figure, and electrolyte density after sintering is higher simultaneously.
Fig. 3 has shown the P-V-I curve of battery when 700 ℃ of work in different Ni-SDC catalyst soakage amount situation.From scheming, can find out, while flooding any catalyst, the open circuit voltage of battery does not just have 1.001V, shows that stainless steel itself has certain catalytic activity for the oxidation reaction of hydrogen; But, the maximum power density of battery only has 36mWcm
-2, the catalytic activity of stainless steel supporter or on the low side is described.After the Ni-SDC catalyst soakage, the output performance of battery is improved significantly, and when pickup reaches 6 % by weight of measuring in skeleton, the maximum power density of battery has reached 246mWcm
-2, approach very much the performance level that the stainless steel that uses the supplementary anode functional layer in bibliographical information supports SOFC.
Fig. 4 reflection be the situation of change that the monocell of 6 % by weight Ni-SDC dippings experience the peak power output density of all after dates of five redox in the time of 700 ℃.Can find out, redox period treatment does not repeatedly cause too large impact to battery performance, and after the circulation in five cycles of experience, the maximum power density of battery still has 220mWcm
-2, than initial value 10% left and right that only descended.
Embodiment 2:SS430-YSZ (Ni-CeO
2the stainless steel of)/YSZ/LSM-YSB three-decker supports SOFC
(1) prepare electrolyte YSZ (8mol%Y with glycine-nitrate process
2o
3-ZrO
2) LSM ((La in powder and negative electrode
0.85sr
0.15)
0.9mnO
3-δ) and YSB ((Y
0.25bi
0.75)
2o
3) powder: with the example that synthesizes of LSM, the La (NO demarcated in advance
3)
3, Sr (NO
3)
2and Mn (NO
3)
2mix by stoichiometric proportion, keep La
3+, Sr
2+and Mn
2+the amount of substance ratio be 0.765: 0.135: 1, form nitrate presoma La
0.765sr
0.135mn (NO
3) x solution, then add glycine as complexing agent, the amount of substance of required glycine is half of nitrate ion total amount, stirs abundant complexing in 1 hour after glycine dissolves.Then, get the La of about 0.02mol at every turn
0.765sr
0.135mn (NO
3) the x precursor liquid is placed in the beaker of 1000mL, on the electric hot plate of 500W, heats, and boils off unnecessary moisture.Become after thick and continue heating until solution, jelly takes fire, and ejection grey powder.These grey powders, 800 ℃ of heat treatments 2 hours, are made into to the LSM powder of phase.For YSZ and YSB powder, when synthetic, also use the nitrate solution of its respective metal ion to be mixed into precursor solution by stoichiometric proportion, while adding complexing of glycin, the amount of substance of glycine is also half of nitrate ion total amount.Finally the YSZ powder of ejection need be 700 ℃ of heat treatments 2 hours, and the YSB powder need be 600 ℃ of heat treatments 2 hours.
(2) prepare stainless steel supporter precursor powder: YSZ powder prepared by business 430 series stainless steel powders (SS430) and glycine-nitrate process and as the polymethyl acrylate (PMMA) of pore creating material and graphite (C) according to mass ratio SS430: YSZ: PMMA: C=17: in alcohol solvent carry out mix grinding at 3: 1: 2.Until abundant mix grinding evenly after, then polyvinyl alcohol (PVA) solution that adds 5 % by weight by the amount of 2～4 of every grams is as binding agent, further mill is put into the baking oven of 80 ℃ after dry and is dried to drying.
(3) prepare the SS430-YSZ/YSZ double-layer tablet: take dried stainless steel supporter precursor powder 0.4 gram, in the mould that to pour diameter into be 13mm, under 50MPa pressure, single shaft is colded pressing.Subsequently, then pour the YSZ electrolyte powder of 0.02 gram into to its surface, further molded altogether under 300MPa pressure after tiling evenly.The double-layer tablet pressed directly is put in the high alumina porcelain boat, burns 600 ℃/10h thoroughly to remove pore creating material wherein in Muffle furnace.Add a small amount of titanium valve again in porcelain boat after lowering the temperature, burn 1400 ℃/5h and complete sintering under hydrogen atmosphere.High temperature sintering heats up and it should be noted that: 1 ℃/min is raised to 550 ℃, insulation 2h, and then 2 ℃/min is raised to 1400 ℃, is incubated 5 hours, and 2 ℃/min cools to 800 ℃, then natural cooling down.The stainless steel supporter thickness of burned double-layer tablet is 0.786mm, and porosity is that 34%, YSZ dielectric substrate thickness is 39.6 μ m.
(4) flood NiO-CeO in stainless steel insert
2catalyst precursor particles: with Ni (NO
3)
2and Ce (NO
3)
3two kinds of metal-nitrate solutions are Ni in molar ratio
2+: Ce
3+=43: 10 to be mixed with the metal ion total concentration be 1molL
-1mixed solution, add wherein glycine (amount of substance of the glycine added is half of nitrate ion total amount), fully stir complexing and become maceration extract.SS430-YSZ/YSZ double-layer tablet porous stainless steel one side sintered is placed in to surface plate upward, under vacuumizing state, the maceration extract prepared is dropwise dripped to surface plate in until flood all double-layer tablet.Continue the maintenance vacuum after a period of time, double-layer tablet is taken out and dried, with the ethanol cotton, wipe the maceration extract that the dielectric substrate surface may be remaining away, then double-layer tablet is put into to 600 ℃/2h of Muffle furnace burning and made the maceration extract immersed resolve into NiO-CeO
2catalyst precursor particles.Because the single impregnation amount is limited, thus need to repeat dipping and sintering process, until reach required catalyst soakage amount.In concrete experimentation, often carry out haply dipping three times, the Ni-CeO that finally can immerse
2the quality of catalyst is 2% of supporter quality.
(5) coating of LSM-YSB negative electrode and in-situ sintering: the LSM that will prepare with glycine-nitrate process and YSB powder be LSM: YSB=6 in mass ratio: 4 mix grindings, the terpinol that adds subsequently the ethyl cellulose that contains 10% mass fraction of 1.5 times of its gross masses, be coated to the YSZ bath surface of impregnated double-layer tablet, the circle that the negative electrode of coating is diameter 0.8cm after further grinding evenly by silk screen print method.Altogether need to repeat to brush three times and dry under infrared lamp.After negative electrode is dried by cell package to alumina tube, be placed in the stove of setting, in the situation that stainless steel supporter one side is led to hydrogen, negative electrode one side in surrounding air, stove is warmed up to 850 ℃ and be incubated the sintering that completes negative electrode in 2 hours with the speed of 3 ℃/min, during need to be 350 ℃ of insulations 1 hour.In position in the process of sintering, the NiO-CeO of dipping in the stainless steel supporter
2catalyst precursor particles also has been reduced into final Ni-CeO simultaneously
2catalyst, the preparation of monocell also finally completes.Just can test accordingly battery subsequently.
SS430-YSZ (Ni-CeO to above-mentioned preparation
2the stainless steel support solid oxide fuel cell of)/YSZ/LSM-YSB three-decker carries out electrochemical property test, finds: at the Ni-CeO of dipping 6 % by weight
2after catalyst, the maximum power density of battery is by untreated 40mWcm
-2bring up to 304mWcm
-2, and experiencing the also not significantly decay of repeatedly redox week after date.The performance of battery even is better than the situation of SS430-YSZ in embodiment 1 (Ni-SDC)/YSZ/LSM-YSB, and this is because further reduced the thickness of YSZ dielectric substrate in embodiment 2 on the one hand, is also because the CeO flooded on the other hand
2have the catalytic activity that more is better than SDC, this point also is confirmed in the document in many SOFC field.
The stainless steel of embodiment 3:SS430-YSZ (Ni-SDC)/YSZ/LSM-SDC three-decker supports SOFC
(1) prepare electrolyte YSZ (8mol%Y with glycine-nitrate process
2o
3-ZrO
2) LSM ((La in powder and negative electrode
0.85sr
0.15)
0.9srMnO
3-δ) and SDC (Sm
0.2ce
0.8o
1.9) powder: with the example that synthesizes of SDC, the Sm (NO demarcated in advance
3)
3, Ce (NH
4)
2(NO
3)
6(annotate: practice finds to use Ce (NH here
4)
2(NO
3)
6the SDC powder characteristic ratio of making for raw material is used Ce (NO
3)
3the time performance better) by stoichiometric proportion, mix, keep Sm
3+and Ce
4+the amount of substance ratio be 0.2: 0.8, form nitrate presoma Sm
0.2ce
0.8(NH
4)
1.6(NO
3)
xsolution, then add glycine as complexing agent, half (notes: need button to remove NH here that the amount of substance of required glycine is the nitrate ion total amount
4 +consumable NO
3 -, each NH
4 +consume a NO
3 -), after dissolving, stirs glycine abundant complexing in 1 hour.Then, get the Sm of about 0.02mol at every turn
0.2ce
0.8(NH
4)
1.6(NO
3)
xprecursor liquid is placed in the beaker of 1000mL, on the electric hot plate of 500W, heats, and boils off unnecessary moisture.Become after thick and continue heating until solution, jelly takes fire, and sprays light yellow powder.These yellow powder, 600 ℃ of heat treatments 2 hours, are made into to the SDC powder of phase.For YSZ and LSM powder, when synthetic, also use the nitrate solution of its respective metal ion to be mixed into precursor solution by stoichiometric proportion, while adding complexing of glycin, the amount of substance of glycine is also half of nitrate ion total amount.Finally the YSZ powder of ejection need be 700 ℃ of heat treatments 2 hours, and the LSM powder need be 800 ℃ of heat treatments 2 hours.
(2) prepare stainless steel supporter precursor powder: YSZ powder prepared by business 430 series stainless steel powders (SS430) and glycine-nitrate process and as the polymethyl acrylate (PMMA) of pore creating material and graphite (C) according to mass ratio SS430: YSZ: PMMA: C=15: in alcohol solvent carry out mix grinding at 5: 1: 2.Until abundant mix grinding evenly after, then polyvinyl alcohol (PVA) solution that adds 5 % by weight by the amount of 2～4 of every grams is as binding agent, further mill is put into the baking oven of 80 ℃ after dry and is dried to drying.
(3) prepare the SS430-YSZ/YSZ double-layer tablet: take dried stainless steel supporter precursor powder 0.6 gram, in the mould that to pour diameter into be 13mm, under 50MPa pressure, single shaft is colded pressing.Subsequently, then pour the YSZ electrolyte powder of 0.025 gram into to its surface, further molded altogether under 300MPa pressure after tiling evenly.The double-layer tablet pressed directly is put in the high alumina porcelain boat, burns 600 ℃/10h thoroughly to remove pore creating material wherein in Muffle furnace.Add a small amount of titanium valve again in porcelain boat after lowering the temperature, burn 1400 ℃/5h and complete sintering under hydrogen atmosphere.High temperature sintering heats up and it should be noted that: 1 ℃/min is raised to 550 ℃, insulation 2h, and then 2 ℃/min is raised to 1400 ℃, is incubated 5 hours, and 2 ℃/min cools to 800 ℃, then natural cooling down.The stainless steel supporter thickness of burned double-layer tablet is 1.180mm, and porosity is that 39%, YSZ dielectric substrate thickness is 49.4 μ m.
(4) flood the NiO-SDC catalyst precursor particles in stainless steel insert: with Ni (NO
3)
2, Sm (NO
3)
3and Ce (NO
3)
3three kinds of metal-nitrate solutions are Ni in molar ratio
2+: Sm
3+: Ce
3+=43: being mixed with the metal ion total concentration at 2: 8 is 1molL
-1mixed solution, add wherein glycine (amount of substance of the glycine added is half of nitrate ion total amount), fully stir complexing and become maceration extract.SS430-YSZ/YSZ double-layer tablet porous stainless steel one side sintered is placed in to surface plate upward, under vacuumizing state, the maceration extract prepared is dropwise dripped to surface plate in until flood all double-layer tablet.Continue to keep vacuum after a period of time, double-layer tablet is taken out and dried, wipe with the ethanol cotton maceration extract that the dielectric substrate surface may be remaining away, then double-layer tablet is put into to 600 ℃/2h of Muffle furnace burning and made the maceration extract immersed resolve into the NiO-SDC catalyst precursor particles.Because the single impregnation amount is limited, thus need to repeat dipping and sintering process, until reach required catalyst soakage amount.In concrete experimentation, often carry out haply dipping three times, the quality of the Ni-SDC catalyst that finally can immerse is 2% of supporter quality.
(5) coating of LSM-SDC negative electrode and in-situ sintering: the LSM that will prepare with glycine-nitrate process and YSB powder be LSM: SDC=7 in mass ratio: 3 mix grindings, the terpinol that adds subsequently the ethyl cellulose that contains 10% mass fraction of 1.5 times of its gross masses, be coated to the YSZ bath surface of impregnated double-layer tablet, the circle that the negative electrode of coating is diameter 0.8cm after further grinding evenly by silk screen print method.Altogether need to repeat to brush three times and dry under infrared lamp.After negative electrode is dried by cell package to alumina tube, be placed in the stove of setting, in the situation that stainless steel supporter one side is led to hydrogen, negative electrode one side in surrounding air, stove is warmed up to 850 ℃ and be incubated the sintering that completes negative electrode in 2 hours with the speed of 3 ℃/min, during need to be 350 ℃ of insulations 1 hour.In the process of sintering, in the stainless steel supporter, the NiO-SDC catalyst precursor particles of dipping also has been reduced into final Ni-SDC catalyst simultaneously in position, and the preparation of monocell also thoroughly completes.Just can test accordingly battery subsequently.
Stainless steel support solid oxide fuel cell to the SS430-YSZ (Ni-SDC) of above-mentioned preparation/YSZ/LSM-SDC three-decker carries out electrochemical property test, has also obtained comparatively satisfied result.After the Ni-SDC catalyst of dipping 6 % by weight, the maximum power density of battery is by untreated 34mWcm
-2bring up to 230mWcm
-2, also in higher level.And the battery of preparation still demonstrates good redox resistance.
Claims (7)
1. a Solid Oxide Fuel Cell, described Solid Oxide Fuel Cell comprises anode, electrolytic thin-membrane and negative electrode, wherein said anode is the porous stainless steel supporter, the hole of described porous stainless steel supporter contain can catalytic solid anode of oxide fuel cell electrochemical reaction catalyst, wherein said catalyst is metal or the oxide particle with catalytic activity, and described metal or oxide particle with catalytic activity is Pt, Pd, Ru, Ag, Sm
0.2ce
0.8o
1.9,ceO
2, Gd
0.2ce
0.8o
1.9or their compound phase, the thickness of wherein said porous stainless steel supporter is 0.1mm to 3mm, porosity is 10% to 60%.
2. a method for preparing Solid Oxide Fuel Cell claimed in claim 1 said method comprising the steps of:
(1) porous stainless steel supporter precursor powder preparation process is wherein mixed stainless steel powder, pore creating material and electrolyte powder in solvent, afterwards mixed powder is ground and drying;
(2) double-layer tablet pressing step, wherein, at first by the precompressed of porous stainless steel supporter precursor powder, be placed in the electrolyte powder on the compressing tablet surface of porous stainless steel supporter presoma afterwards, carries out afterwards common pressure to form double-layer tablet;
(3) double-layer tablet sintering step, wherein by presintering at the temperature of double-layer tablet pore creating material in can removing the porous stainless steel supporter in air of obtaining in step (2) to remove pore creating material; The double-layer tablet that to remove afterwards after pore creating material is cooling; Sintering under reducing atmosphere afterwards, thus double-deck sintered body obtained;
(4) catalyst soakage and heat treatment step, the catalyst impregnating solution of the anode electrochemical reaction in wherein can the catalytic solid fuel cell drops to stainless steel supporter one side of the double-deck sintered body obtained in step (3), maceration extract is entered in the hole of porous stainless steel supporter, afterwards double-deck sintered body is heat-treated, obtain the interior sintered body with catalyst of hole;
(5) cathode slurry preparation and applying step, wherein cathode powder is dispersed in liquid and obtains cathode slurry, these slurries are coated on the sintered body with catalyst obtained in step (4) again, to apply the sintered body drying of cathode slurry, obtained the sintered body that is coated with cathode powder;
(6) negative electrode sintering step, sintering again after wherein the sintered body that is coated with cathode powder obtained in step (5) being heated up.
3. method as claimed in claim 2, wherein the pore creating material described in step (1) is polymethyl methacrylate, graphite or starch, or wherein the solvent described in step (1) is ethanol, propyl alcohol, n-butanol, isobutanol or acetone.
4. method as claimed in claim 2, the electrolyte powder wherein added in step (1) is the 10-30 % by weight with respect to stainless steel powder.
5. method as claimed in claim 2, the pressure wherein used in the process by porous stainless steel supporter precursor powder compressing tablet in step (2) is 10MPa to 100MPa, or wherein in step (2), in common swaging, to become the pressure used in the process of double-layer tablet be 200MPa to 400MPa.
6. method as claimed in claim 2, wherein in step (3), the presintering under air completes at the temperature of 400 ℃ to 800 ℃, or wherein in step (3) sintering under reducing atmosphere at the temperature of 1200 ℃ to 1600 ℃, complete.
7. method as claimed in claim 2, wherein in step (4), heat treatment temperature used is 400 ℃ to 800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103909332A CN102437358B (en) | 2011-11-30 | 2011-11-30 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103909332A CN102437358B (en) | 2011-11-30 | 2011-11-30 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102437358A CN102437358A (en) | 2012-05-02 |
| CN102437358B true CN102437358B (en) | 2013-12-11 |
Family
ID=45985317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103909332A Expired - Fee Related CN102437358B (en) | 2011-11-30 | 2011-11-30 | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102437358B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150032284A (en) * | 2012-06-11 | 2015-03-25 | 바스프 에스이 | Electrode unit |
| CN102881930A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Method for preparing flat-plate type metal-support solid oxide fuel cell |
| CN103872366B (en) * | 2012-12-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of metal-supported solid oxide fuel cell and preparation method thereof |
| CN103985888B (en) * | 2014-04-15 | 2017-08-15 | 淮南师范学院 | The preparation method of ceramic membrane fuel cells connecting material film and electrolytic thin-membrane |
| CN104156539B (en) * | 2014-08-22 | 2017-07-14 | 江苏科技大学 | Solid oxide fuel cell electrode gas transport Curvature factor Forecasting Methodology |
| CN109904497B (en) * | 2019-01-09 | 2020-07-10 | 华中科技大学 | Anti-carbon-deposition metal-supported solid oxide fuel cell and preparation method thereof |
| CN112072137B (en) * | 2020-08-31 | 2022-03-25 | 佛山科学技术学院 | Anode catalysis layer support body of SOFC (solid oxide Fuel cell), preparation method and application thereof |
| CN112582713B (en) * | 2020-12-11 | 2022-09-06 | 北京国家新能源汽车技术创新中心有限公司 | Electrolyte and electrode integrated three-layer composite ceramic and preparation method thereof, and all-solid-state lithium-air battery and preparation method thereof |
| CN113140771B (en) * | 2021-03-29 | 2022-05-17 | 西安交通大学 | Method for preparing electrolyte film by pre-pressing auxiliary sintering and battery/electrolytic cell |
| CN113937355B (en) * | 2021-08-31 | 2023-08-22 | 河北光兴半导体技术有限公司 | Solid electrolyte sheet, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960047A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Method for preparing low temperature solid oxide fuel cell supported by porous metal |
| CN1960048A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Structure of low temperature solid oxide fuel cell supported by porous metal |
| CN101562255A (en) * | 2009-05-19 | 2009-10-21 | 华中科技大学 | Method for preparing metallic support type solid oxide fuel cell |
| WO2010130692A1 (en) * | 2009-05-11 | 2010-11-18 | Commissariat à l'énergie atomique et aux énergies alternatives | Cell for a high-temperature fuel cell with internal hydrocarbon reforming |
| CN102185148A (en) * | 2011-04-01 | 2011-09-14 | 景德镇陶瓷学院 | NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof |
-
2011
- 2011-11-30 CN CN2011103909332A patent/CN102437358B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960047A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Method for preparing low temperature solid oxide fuel cell supported by porous metal |
| CN1960048A (en) * | 2006-11-23 | 2007-05-09 | 上海交通大学 | Structure of low temperature solid oxide fuel cell supported by porous metal |
| WO2010130692A1 (en) * | 2009-05-11 | 2010-11-18 | Commissariat à l'énergie atomique et aux énergies alternatives | Cell for a high-temperature fuel cell with internal hydrocarbon reforming |
| CN101562255A (en) * | 2009-05-19 | 2009-10-21 | 华中科技大学 | Method for preparing metallic support type solid oxide fuel cell |
| CN102185148A (en) * | 2011-04-01 | 2011-09-14 | 景德镇陶瓷学院 | NiO-based SOFC (Solid Oxide Fuel Cell) composite anode film material with nano-sheet microcellular structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102437358A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102437358B (en) | Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof | |
| RU2342740C2 (en) | Solid oxide fuel cells with bearing anode and cermet ionogen | |
| Jiang | A review of wet impregnation—an alternative method for the fabrication of high performance and nano-structured electrodes of solid oxide fuel cells | |
| CN101485018B (en) | Ceramic material combination for an anode of a high-temperature fuel cell | |
| CN101359746B (en) | Large size tubular solid oxide fuel cell and preparation thereof | |
| Ma et al. | Electrochemical performances of solid oxide fuel cells based on Y-substituted SrTiO3 ceramic anode materials | |
| AU778854B2 (en) | Method of fabricating an assembly comprising an anode-supported electrolyte, and ceramic cell comprising such an assembly | |
| JP2004055326A (en) | Unit cell of solid oxide fuel cell and solid oxide fuel cell using the unit cell | |
| CN103887549B (en) | A kind of Solid Oxide Fuel Cell composite electrolyte film and preparation thereof | |
| JP2007172846A (en) | Tube type electrochemical reactor cell and electrochemical reaction system composed by it | |
| CN107017423B (en) | Low-temperature solid oxide fuel cell and preparation method thereof | |
| KR20130047534A (en) | Solid oxide fuel cell and solid oxide electrolysis cell including ni-ysz fuel(hydrogen) electrode, and fabrication method thereof | |
| CN108461759A (en) | A kind of method of the nano combined cathode material of infusion process preparation solid oxide fuel cell | |
| CN102332588A (en) | Method for preparing anode of solid oxide fuel cell by using immersion method | |
| CN109768292A (en) | A kind of method that anode is prepared in situ in solid oxide fuel cell activation polarization | |
| CN112687929A (en) | Lithium oxide electrode micro-molten salt ceramic fuel cell and preparation method thereof | |
| CN1279643C (en) | Method for preparing anode-support type yttrium oxide stable zirconium oxide electrolyte membrane | |
| CN103985888B (en) | The preparation method of ceramic membrane fuel cells connecting material film and electrolytic thin-membrane | |
| CN103887548B (en) | A kind of ceria-based electrolyte film and Synthesis and applications thereof with preferred orientation | |
| Zhang et al. | Effect of impregnation of Sm-doped CeO2 in NiO/YSZ anode substrate prepared by gelcasting for tubular solid oxide fuel cell | |
| CN101222050A (en) | Anti-carbon deposition anode film material and method for producing the same | |
| JP4534188B2 (en) | Fuel cell electrode material and solid oxide fuel cell using the same | |
| CN112250437B (en) | Solid oxide electrolytic cell supported by oxygen electrode and preparation method thereof | |
| CN101510612B (en) | Method for preparing stephanoporate anode support body using paper fabric a pore-forming agent | |
| CN111416138A (en) | Proton ceramic membrane fuel cell and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131211 Termination date: 20161130 |