[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN103928693B - The metal of SOFC supports half-cell and preparation method thereof - Google Patents

The metal of SOFC supports half-cell and preparation method thereof Download PDF

Info

Publication number
CN103928693B
CN103928693B CN201410109806.4A CN201410109806A CN103928693B CN 103928693 B CN103928693 B CN 103928693B CN 201410109806 A CN201410109806 A CN 201410109806A CN 103928693 B CN103928693 B CN 103928693B
Authority
CN
China
Prior art keywords
porous
metal
cell
sofc
film
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.)
Active
Application number
CN201410109806.4A
Other languages
Chinese (zh)
Other versions
CN103928693A (en
Inventor
屠恒勇
余晴春
胡鸣若
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Zhongfu New Energy Technology Co ltd
Zhongfu Wuxi New Energy Co ltd
Original Assignee
Shanghai Jiao Tong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanghai Jiao Tong University filed Critical Shanghai Jiao Tong University
Priority to CN201410109806.4A priority Critical patent/CN103928693B/en
Publication of CN103928693A publication Critical patent/CN103928693A/en
Application granted granted Critical
Publication of CN103928693B publication Critical patent/CN103928693B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0232—Metals or alloys
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0236—Glass; Ceramics; Cermets
    • 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
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Fuel Cell (AREA)

Abstract

The metal that the invention discloses a kind of SOFC supports half-cell and preparation method thereof；Described half-cell includes porous metals supporting layer thick film, porous metalloceramic gradient transition layer film, porous anode layer film and dense electrolyte layer film from bottom to top.The porous gradient transitional lay that the mixed oxide of the present invention forms with fluorite structure oxide can avoid directly contact of porous metals supporting layer and porous anode layer, and reduction is the phase counterdiffusion of Ni element in Fe, Cr element and porous anode layer in metal supporting layer under the conditions of high temperature sintering.Mixed oxide reduces under the working condition of battery and forms alloy；High anode active material is formed at anode-side interface, forming alloy at interface, metal support side is the high-conductivity composite material of principal phase, present higher electrical conductivity, reduce ohmage, and do not reduce electro catalytic activity, guarantee the long-time stability of battery operation, be simultaneously achieved the good combination of porous metals supporting layer and porous anode layer.

Description

The metal of SOFC supports half-cell and preparation method thereof
Technical field
Half-cell that the present invention relates to field of fuel cell technology and preparation method thereof, the metal being specifically related to a kind of SOFC supports half-cell and preparation method thereof.
Background technology
SOFC (Solid Oxide Fuel Cell, SOFC) it is a kind of all solid state power generating device that by electrochemical reaction, the chemical energy in fuel is translates directly into electric energy, it is not required to through the transition process from fuel chemical energy → heat energy → mechanical energy → electric energy, have many advantages, wherein prominent advantage is the broad applicability of fuel, i.e. hydrogen, carbon monoxide and Hydrocarbon all can be as fuel, therefore hydrogen can be widely used, carbon monoxide, natural gas, liquefied gas, coal gas, biogas, the multiple hydrocarbon fuel such as methanol and ethanol.SOFC has a wide range of applications field, and it is mainly applied and includes distributed power station, family power station, vehicle accessory power supply, uninterrupted power source and Military Power etc..The developmental research of SOFC and commercialization, receive the most attention of many countries in the world, the most generally have an optimistic view of the application prospect of SOFC.At present, SOFC enters the major obstacle of commercialized development is the reliability of battery system, life-span and price.Flat solid oxide fuel cell, middle low temperature flat solid oxide fuel cell (500～800 DEG C), it is forward position and the focus of SOFC research the most in the world, its the most prominent advantage is while ensureing high power density, the alloys such as cheap rustless steel can be used as metallic interconnection materials, reduce the requirement to other materials such as sealings, the ceramic preparation technology that can use low cost manufactures, it is expected to material and the manufacturing cost of SOFC are greatly lowered.Conventional middle low temperature flat solid oxide fuel cell uses Ni/YSZ (YSZ: yttrium stable zirconium oxide) anode support structure, excellent stack performance also has been reported, part research and development unit has possessed fairly large production capacity, but the problem relevant to thick anode support is solved at all.Thick anode support comprises more YSZ and Ni so that battery is relatively costly.In redox cycle, metallic nickel in multihole anode support is oxidized to NiO, then NiO is reduced into metallic nickel, multihole anode support experience change in volume, thus cause electrolyte to ftracture, if therefore system malfunctions cause fuel supply discontinuity easily cause because air enter anode chamber and make Ni/YSZ positive electrode support solid oxide fuel cell damage.In view of Ni/YSZ anode support structure exists the problems referred to above, the SOFC research and development unit of recent domestic starts the emphasis of research and development is turned to metal-supported solid oxide fuel cell, the battery of this structure type uses ferritic stainless steel as supporter, thus the price of supporter can be reduced, improve the mechanical strength of battery, reduce the thermograde of inside battery, tolerable battery quickly starts, thermal cycle and redox cycle, also enhance to thermal shock resistance, reduce battery pile simultaneously and seal and connect difficulty.Although metal-supported solid oxide fuel cell shows above-mentioned plurality of advantages, but its preparation is faced with important challenge.Owing to battery at high temperature reducing atmosphere sintering, simultaneously for obtaining fine and close YSZ based solid electrolyte thin film, the sintering temperature of battery is often higher than 1200 DEG C, therefore the Ni in anode can occur crystal grain to grow up, there is phase counterdiffusion with Cr and Fe in rustless steel simultaneously, thus cause cell performance decay.Preparing a difficult problem for solving above-mentioned metal-supported solid oxide fuel cell, domestic and international researcher has carried out much work in terms of battery structure and corresponding battery preparation technology.
Through the literature search of prior art is found, the Chinese invention patent of Patent No. CN200580019112.0 discloses a kind of SOFC, the patent proposes metal as backing material, and provide for stoping metal to support the device of diffusion between active anode, specifically use gradual change, terminate at the metal support of the electron conducting oxide of substantially pure, but these electron conducting oxide present relatively low electrical conductivity under battery operated reducing atmosphere condition, thus for metal, add the ohmage of cell support body, metal support also with the addition of metal-oxide and structure in gradient, which enhance the price of supporter and manufacture complexity.This patent proposes osmotic layer configurations simultaneously, i.e. first at high temperature carry out permeable formation sintering, then use ionic impregnation normal osmosis layer to penetrate into Ni, then be treated with heat such that nitrate decomposes at a lower temperature, thus stop the phase counterdiffusion between Ni and metal support material.On the one hand the prominent shortcoming of ionic impregnation method is multi-step, i.e. needs repeatedly to impregnate and heat treatment, so that the content of Ni reaches the amount needed, thus causes battery preparation technique loaded down with trivial details；On the other hand, owing to the Ni impregnated inevitably directly contacts with metal support, the phase counterdiffusion of easy generating material in the running of battery and make cell performance decay.
The Chinese invention patent of Application No. CN200810129800.8 discloses the SOFC of a kind of metal support, the patent proposes cathode precursor layer and anode precursor Rotating fields, after being at high temperature sintered obtaining multiple structure, wherein use precursor solution or the suspended substance dipping anode precursor layer of anode, and carry out heat treatment subsequently.But its pickling processes needs repeatedly to impregnate and heat treatment, so that the content of material reaches the amount needed, thus cause battery preparation technique loaded down with trivial details.
Summary of the invention
Present invention aims to the weak point of above-mentioned technology, it is proposed that the metal of a kind of SOFC supports half-cell and preparation method thereof；Avoiding between Ni and metal support material while phase counterdiffusion, the internal resistance that the metal making the middle low temperature flat solid oxide fuel cell formed supports half-cell is lower, the electro catalytic activity of anode does not reduces, the long-time stability of battery operation are guaranteed, reduce battery preparation process, it is achieved the flat metal of middle low temperature supports the low cost of half-cell to be prepared.
It is an object of the invention to be achieved through the following technical solutions:
First aspect, the metal that the present invention relates to a kind of SOFC supports half-cell, including the porous metals supporting layer thick film set gradually from bottom to top, porous metalloceramic gradient transition layer film, porous anode layer film and dense electrolyte layer film.
Preferably, described porous metals supporting layer is mainly made up of rustless steel FeCrM alloy；Described M element is one or more in Ni, Ti, Mn, Mo, W, Nb, Co, Cu, V, La, Si, Ce, Al, C, N, P and S.
Preferably as the supporter of half-cell, the thickness of described porous metals supporting layer thick film is 200～1000 μm, to guarantee that half-cell has enough mechanical strengths.More preferably 600～900 μm.
Preferably, described porous metalloceramic gradient transitional lay is mainly made up of metal A and fluorite structure oxide, and the element of described metal A is selected from the combination in any of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Nb, Mo, Ta, W, La, Si, Ce and Al.
Preferably, described fluorite structure oxide is doped zirconia, cerium oxide or rear-earth-doped oxidation cerium, one or more in YSZ (zirconium oxide of stabilized with yttrium oxide), SSZ (zirconium oxide of scandia stabilized), ScYSZ (Scia and yttrium oxide co-stabilized zirconium oxide), ScCeSZ (Scia and cerium oxide are total to the most stable zirconium oxide) of described doped zirconia；Described rare earth is one or more in Y, La, Pr, Nd, Sm, Gd.
Preferably, the content of described fluorite structure oxide is 0～50wt%.
More preferably, the content of described fluorite structure oxide is 10～50wt%, there is higher anode activity realizing porous metalloceramic gradient transitional lay anode-side after prepared by battery, and there is in supporting layer side high electron conduction and the hot expansibility matched.
Preferably, the thickness of described porous metalloceramic gradient transition layer film is 20～100 μm, to reach to stop between porous metals supporting layer and porous anode layer the thickness needed for metallic element phase counterdiffusion.More preferably 40～70 μm.
Preferably, described porous anode layer is the ceramic metal being made up of electrolyte, TM and conductive oxide.
Preferably, the content of described electrolyte is 30～50wt%, to provide ionic conductivity；The content of described TM is 30～70wt%, to realize high electro catalytic activity and good electric conductivity in the anode；The content of described conductive oxide is 0～20wt%, to improve the electric conductivity of anode.It is further preferred that the content of TM is 50～70wt%.
Preferably, one or more in YSZ (zirconium oxide of stabilized with yttrium oxide), SSZ (zirconium oxide of scandia stabilized), ScYSZ (Scia and yttrium oxide co-stabilized zirconium oxide), ScCeSZ (Scia and cerium oxide are total to the most stable zirconium oxide), GDC (cerium oxide of Gadolinia. doping), SDC (oxidation Sm doped CeO_2), LSGM (Sr-and Mg-doped gallate) and LSGMC (lanthanum gallate of strontium magnesium cobalt doped) of described electrolyte.
Preferably, described TM is selected from one or more of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Nb, Mo, Ta, W.
Preferably, described conductive oxide is selected from CeO2, SrTi0.9Nb0.09O3 ±δ, SrxY0.07TiO3 ±δ(wherein x=0.80～1.02), Sr0.895Y0.07TiyO3 ±δ(wherein y=1.00～1.20) and Sr1-a-bLaaTi1-zNzO3- δ(wherein a=0.1～0.9；B=0.0～0.2；Z=0.0～0.9；N is element or the mixture of these elements such as Mn, Co, Ni, Fe, Cr and Nb) in one or more.δ (0≤δ≤1) represents oxygen content, and its numerical value determines the average valence of Ti and N.
Preferably, the thickness of described porous anode layer film is 10～50 μm, so that anode has high electro catalytic activity and good electric conductivity.More preferably 30～40 μm.
Preferably, one or more in YSZ (zirconium oxide of stabilized with yttrium oxide), SSZ (zirconium oxide of scandia stabilized), ScYSZ (Scia and yttrium oxide co-stabilized zirconium oxide), ScCeSZ (Scia and cerium oxide are total to the most stable zirconium oxide), GDC (cerium oxide of Gadolinia. doping), SDC (oxidation Sm doped CeO_2), LSGM (Sr-and Mg-doped gallate) and LSGMC (lanthanum gallate of strontium magnesium cobalt doped) of described dense electrolyte layer material.
Preferably, the thickness of described dense electrolyte layer film is 5～40 μm, can reduce the thickness of thin film to reduce the ohmage of half-cell under preparation condition.More preferably 10～20 μm.
Second aspect, the metal that the present invention relates to above-mentioned SOFC supports the preparation method of half-cell, said method comprising the steps of:
A, by rustless steel powder body, pore creating material, solvent and dispersant mix；Add binding agent and plasticizer mixing, form casting slurry a；After screen filtration, vacuum degassing process, curtain coating makes porous metals supporting layer thick film biscuit, is dried；
B, by AOxJoin in the terpineol solution of ethyl cellulose that cellulose content is 1～5wt% with the mixed powder of fluorite structure oxide, grind the slurry c obtaining stable uniform, described slurry c silk screen printing is deposited on described porous metals supporting layer thick film biscuit, forms porous metalloceramic gradient transitional lay precursor film；AO in described mixed powderxBeing 90: 10～50: 50 with the weight ratio of fluorite structure oxide, described mixed powder is 15: 85～80: 20 with the weight ratio of terpineol solution of ethyl cellulose；
C, by TMOx, the mixed powder of electrolyte and conductive oxide join in the terpineol solution of ethyl cellulose that cellulose content is 1～5wt%, grind the slurry d obtaining stable uniform, described slurry d silk screen printing is deposited on porous metalloceramic gradient transitional lay precursor film, forms porous anode layer precursor film；TMO in described mixed powderx, the weight ratio of electrolyte and conductive oxide be 70: 30: 0～30: 50: 20, described mixed powder is 15: 85～80: 20 with the weight ratio of terpineol solution of ethyl cellulose；
D, by electrolyte powder body, solvent and dispersant mix；Add binding agent and plastic agent mixing, form casting slurry b；After screen filtration, vacuum degassing process, curtain coating makes dense electrolyte layer film biscuit, is dried；
E, being placed on the porous anode layer precursor film obtained by step C by described dense electrolyte layer film biscuit, carry out isostatic pressed 1～10 minutes under room temperature, pressure is 50～300MP (more preferably 100～300MP), forms multilamellar preform structure；In inert atmosphere or vacuum 300～600 DEG C of plastic removals 2～6 hours, respectively 1000～1200 DEG C and 1150～1300 DEG C of co-sinterings 2～6 hours, controlling to rise gentle rate of temperature fall is 0.5～5 DEG C/min, be cooled to room temperature, both described SOFC metal support half-cell.
Wherein, porous metalloceramic gradient transitional lay predecessor by step E and under battery operating conditions in-situ reducing formed porous metalloceramic gradient transitional lay, porous anode layer predecessor by step E and under battery operating conditions in-situ reducing formed porous anode layer.
Preferably, in step A, rustless steel powder body, pore creating material, solvent and dispersant are with 100～500rpm rotating speed ball millings 4～mixing in 24 hours；Add binding agent and plasticizer, with 100～500rpm rotating speeds ball milling 4 again～mixing in 24 hours.
Preferably, the composition of the casting slurry a of the thick film of porous metals supporting layer described in step A is:
For above-mentioned rustless steel content range, it is difficult to when content is less than 30wt% be prepared into the supporter with sufficient mechanical strength, the supporter porosity then prepared when content is higher than 60wt% is the lowest, and other compositions of casting slurry a are to change with rustless steel content.
Preferably, in step A, one or more in ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, graphite, starch and polymethyl methacrylate of described pore creating material.
Preferably, in step A and D, described solvent is respectively selected from one or more in dehydrated alcohol, isopropanol, n-butyl alcohol, acetone, butanone, Ketohexamethylene, ethyl fat, trichloro ethylene and dimethylbenzene.
Preferably, in step A and D, described dispersant is respectively selected from one or more in herring oil, triethanolamine, triethyl phosphate, Span-80, tributyl phosphate, terpineol, glycerol trioleate, polyacrylic acid and ethoxy compound.
Preferably, in step A and D, described binding agent one or more in polyvinyl alcohol, polyvinyl butyral resin, polymethyl acrylate, polymethylacrylic acid and ethyl cellulose respectively.
Preferably, in step A and D, described plasticizer is respectively selected from one or more in ethylene glycol, Polyethylene Glycol, dibutyl phthalate, dioctyl phthalate, diethyl oxalate ester and glycerol.
Preferably, in step D, by electrolyte powder body, solvent and dispersant with 100～500rpm rotating speed ball millings 4～mixing in 24 hours；Add binding agent and plastic agent, with 100～500rpm rotating speeds ball milling 4 again～mixing in 48 hours.
Preferably, the composition of the casting slurry b of dense electrolyte layer film described in step D is:
For above-mentioned electrolyte content scope, being difficult to be prepared into thin dense electrolyte film when content is less than 40wt%, be then difficult to when content is higher than 70wt% prepare the slurry being suitable for curtain coating, other compositions of casting slurry b are to change with electrolyte content.
Preferably, in step C and D, described electrolyte is respectively selected from one or more in YSZ, SSZ, ScYSZ, ScCeSZ, GDC, SDC, LSGM and LSGMC.
Preferably, in step E, described inert atmosphere is selected from nitrogen or argon.
Compared with prior art, there is advantages that
1, the metal at SOFC supports in half-cell preparation process, adding the porous gradient transitional lay that form with fluorite structure oxide of mixed oxide between porous metals supporting layer and porous anode layer and can avoid directly contacting of porous metals supporting layer and porous anode layer, reduction is the phase counterdiffusion of Ni element in Fe and Cr element and porous anode layer in metal supporting layer under the conditions of high temperature sintering.Mixed oxide reduces under the working condition of battery and forms alloy, formed at the interface of anode-side and there is high anode active material, the high-conductivity composite material with alloy as principal phase is then formed at the interface of metal support side, thus present higher electrical conductivity relative to electron conducting oxide, reduce the ohmage of half-cell, the most do not reduce the electro catalytic activity of anode, ensure that the long-time stability of battery operation, also achieve the good combination of porous metals supporting layer and porous anode layer simultaneously.
2, due to the TMO in anode layerxComposite oxides carry out high temperature sintering in an inert atmosphere and are not reduced, then under battery operating conditions, in-situ reducing becomes metal eelctro-catalyst, therefore avoid the crystal grain of metal eelctro-catalyst in cell manufacturing process to grow up, the preparation method of anode layer is not required to use ionic impregnation method simultaneously, greatly reduces preparation process.
3, half-cell simple in construction of the present invention; it is easy to use cheap preparation technology; it is suitable for co-sintering and reduces preparation process; can be amplified and scale manufacture; use inert atmosphere or vacuum and non-reducing atmosphere avoids a large amount of uses of hydrogen; reduce the manufacturing cost of half-cell, be with a wide range of applications.
Accompanying drawing explanation
The detailed description with reference to the following drawings, non-limiting example made by reading, the other features, objects and advantages of the present invention will become more apparent upon:
Fig. 1 is that the metal of the SOFC of the present invention supports half-cell structural representation；
Fig. 2 is the micro-structure diagram of the half-cell section of embodiment 1 preparation；
Fig. 3 is the micro-structure diagram of the YSZ bath surface of embodiment 1 preparation；
Wherein, 1 is porous metals supporting layer thick films, and 2 is porous metalloceramic gradient transition layer film, and 3 is porous anode layer film, and 4 is dense electrolyte layer film.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art and are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improve these and broadly fall into protection scope of the present invention.
Embodiment 1
The present embodiment relates to the metal of a kind of SOFC and supports half-cell；This metal supports half-cell structure as it is shown in figure 1, include porous metals supporting layer thick film 1, porous metalloceramic gradient transition layer film 2, porous anode layer film 3 and the dense electrolyte layer film 4 set gradually from bottom to top.Its preparation technology comprises the steps:
A, porous metals supporting layer thick film biscuit and the preparation of dense electrolyte layer film biscuit；
Respectively by 90 grams of rustless steel AM-1 (composition is as shown in table 1) powder body, 10 grams of fecula pore creating materials, by 82 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 2 grams of triethyl phosphate dispersants, with planetary ball mill with the mixing in 8 hours of 300rpm rotating speed ball milling.12 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 6 grams of dibutyl phthalates and 6 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 16 hours again of 300rpm rotating speed.Respectively by 80 grams of YSZ powder body, by 60 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 5 grams of triethyl phosphate dispersants, with planetary ball mill with the mixing in 24 hours of 300rpm rotating speed ball milling.3 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 3 grams of dibutyl phthalates and 3 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 24 hours again of 300rpm rotating speed.The slurry of above-mentioned 2 kinds of last ball millings mixing is carried out vacuum degassing process 30 minutes, casting machine carry out flow casting molding and is dried, preparing the porous metals supporting layer thick film biscuit that thickness is 600 μm and the dense electrolyte layer film biscuit that thickness is 40 μm respectively.
B, ethyl cellulose is dissolved in terpineol, make the terpineol solution of ethyl cellulose that cellulose content is 2wt%, to be applied to porous metalloceramic gradient transitional lay precursor film and the deposition of porous anode layer precursor film as silk screen printing binding agent.
C, by 3.5 grams of Fe2O3Powder body and 0.4 gram of fluorite structure oxide GDC mixed powder join in 12 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 40 μm.
D, 3 grams of NiO and 2 grams of YSZ mixed powders are joined in 18 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 30 μm.
E, the dense electrolyte layer film biscuit obtained by step A is placed on the porous anode layer precursor film obtained by step D, at room temperature carry out isostatic pressed 3 minutes, pressure is 200MP, and being formed is porous metals supporting layer thick film, porous metalloceramic gradient transitional lay precursor film, porous anode layer precursor film and the multilamellar preform structure of dense electrolyte layer film from bottom to top.
F, this multilamellar biscuit being cut into square piece, plastic removal 2 hours at a temperature of 400 DEG C in nitrogen atmosphere, controlling to rise a gentle rate of temperature fall is 1 DEG C/min；Then by difference co-sintering 4 hours at a temperature of the half-cell after plastic removal in a vacuum 1100 DEG C and 1200 DEG C, controlling to rise gentle rate of temperature fall is 3 DEG C/min, is cooled to room temperature and obtains smooth, to have dense electrolyte layer film porous metals and support SOFC half-cell.And, porous metalloceramic gradient transitional lay by porous metalloceramic gradient transitional lay predecessor by step F and under battery operating conditions in-situ reducing is formed, porous anode layer by porous anode layer predecessor pass through step F and under battery operating conditions in-situ reducing formed.
G, on dense electrolyte layer film, prepare Ce respectively0.8Gd0.2O2- δBarrier layer and La0.6Sr0.4CoO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.107V.
Porous metals prepared by the present embodiment support the micro-structure diagram of SOFC half-cell section as shown in Figure 2, prepared as shown in Figure 2 metal supporting layer thick film, metal ceramic gradient transition zone precursor film and anode layer precursor film are all in loose structure, it is ensured that battery descends the transmission of fuel gas in working order；From Fig. 2 and Fig. 3, dielectric substrate thin film is the finest and close, consistent with measured battery open circuit voltage result, it is ensured that being effectively isolated of fuel gas and oxic gas；Meanwhile, and each Coating combination is good.
The composition (wt%) of table 1. rustless steel AM-1
Cr Fe Si Mn C
34.00 63.24 2.60 0.12 0.04
Embodiment 2
It is as follows that the metal of the SOFC that the present embodiment relates to supports preparing of half-cell:
A, porous metals supporting layer thick film biscuit and the preparation of dense electrolyte layer film biscuit；
Respectively by 85 grams of rustless steel AM-1 powder body, 15 grams of fecula pore creating materials, by 90 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 3 grams of triethanolamine dispersant, with planetary ball mill with the mixing in 8 hours of 300rpm rotating speed ball milling.13 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 7 grams of dibutyl phthalates and 7 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 16 hours again of 300rpm rotating speed.Respectively by 85 grams of ScCeSZ powder body, by 70 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 4 grams of triethanolamine dispersant, with planetary ball mill with the mixing in 24 hours of 300rpm rotating speed ball milling.4 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 4 grams of dibutyl phthalates and 4 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 24 hours again of 300rpm rotating speed.The slurry of above-mentioned 2 kinds of last ball millings mixing is carried out vacuum degassing process 30 minutes, casting machine carry out flow casting molding and is dried, preparing the porous metals supporting layer thick film biscuit that thickness is 700 μm and the dense electrolyte layer film biscuit that thickness is 30 μm respectively.
B, ethyl cellulose is dissolved in terpineol, make the terpineol solution of ethyl cellulose that cellulose content is 5wt%, to be applied to porous metalloceramic gradient transitional lay precursor film and the deposition of porous anode layer precursor film as silk screen printing binding agent.
C, by 4 grams of Co2O3Powder body and 1 gram of fluorite structure oxide YSZ mixed powder join in 14 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 50 μm.
D, 3 grams of NiO and 2 grams of GDC mixed powders are joined in 18 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 40 μm.
E, the dense electrolyte layer film biscuit obtained by step A is placed on the porous anode layer precursor film obtained by step D, at room temperature carry out isostatic pressed 10 minutes, pressure is 100MP, and being formed is porous metals supporting layer thick film, porous metalloceramic gradient transitional lay precursor film, porous anode layer precursor film and the multilamellar preform structure of dense electrolyte layer film from bottom to top.
F, this multilamellar biscuit being cut into square piece, plastic removal 2 hours at a temperature of 400 DEG C in nitrogen atmosphere, controlling to rise a gentle rate of temperature fall is 0.5 DEG C/min；Then by respectively co-sintering 4 hours at a temperature of 1050 DEG C and 1180 DEG C in argon of the half-cell after plastic removal, controlling to rise gentle rate of temperature fall is 5 DEG C/min, is cooled to room temperature and obtains smooth, to have dense electrolyte layer film porous metals and support SOFC half-cell.And, porous metalloceramic gradient transitional lay by porous metalloceramic gradient transitional lay predecessor by step F and under battery operating conditions in-situ reducing is formed, porous anode layer by porous anode layer predecessor pass through step F and under battery operating conditions in-situ reducing formed.
G, on dense electrolyte layer film, prepare Ce respectively0.8Sm0.2O2- δBarrier layer and Sm0.5Sr0.5CoO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.072V.
Embodiment 3
It is as follows that the metal of the SOFC that the present embodiment relates to supports preparing of half-cell:
A, porous metals supporting layer thick film biscuit and the preparation of dense electrolyte layer film biscuit；
Respectively by 80 grams of rustless steel AM-1 powder body, 20 grams of fecula pore creating materials, by 100 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 4 grams of Span-80 dispersants, with planetary ball mill with the mixing in 8 hours of 300rpm rotating speed ball milling.14 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 8 grams of dibutyl phthalates and 8 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 16 hours again of 300rpm rotating speed.Respectively by 90 grams of SSZ powder body, by 80 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 6 grams of Span-80 dispersants, with planetary ball mill with the mixing in 24 hours of 300rpm rotating speed ball milling.5 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 5 grams of dibutyl phthalates and 5 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 24 hours again of 300rpm rotating speed.The slurry of above-mentioned 2 kinds of last ball millings mixing is carried out vacuum degassing process 30 minutes, casting machine carry out flow casting molding and is dried, preparing the porous metals supporting layer thick film biscuit that thickness is 800 μm and the dense electrolyte layer film biscuit that thickness is 35 μm respectively.
B, ethyl cellulose is dissolved in terpineol, make the terpineol solution of ethyl cellulose that cellulose content is 3wt%, to be applied to porous metalloceramic gradient transitional lay precursor film and the deposition of porous anode layer precursor film as silk screen printing binding agent.
C, by 4 grams of MoO3Powder body and 1 gram of fluorite structure oxide CeO2Mixed powder joins in 14 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 50 μm.
D, by 1.8 grams of NiO, 3 grams of GDC and 1.2 grams of La0.2Sr0.7TiO3Mixed powder join in 20 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 40 μm.
E, the dense electrolyte layer film biscuit obtained by step A is placed on the porous anode layer precursor film obtained by step D, at room temperature carry out isostatic pressed 2 minutes, pressure is 300MP, and being formed is porous metals supporting layer thick film, porous metalloceramic gradient transitional lay precursor film, porous anode layer precursor film and the multilamellar preform structure of dense electrolyte layer film from bottom to top.
F, this multilamellar biscuit being cut into square piece, plastic removal 2 hours at a temperature of 600 DEG C in nitrogen atmosphere, controlling to rise a gentle rate of temperature fall is 5 DEG C/min；Then by respectively co-sintering 6 hours at a temperature of 1000 DEG C and 1150 DEG C in nitrogen of the half-cell after plastic removal, controlling to rise gentle rate of temperature fall is 4 DEG C/min, is cooled to room temperature and obtains smooth, to have dense electrolyte layer film porous metals and support SOFC half-cell.And, porous metalloceramic gradient transitional lay by porous metalloceramic gradient transitional lay predecessor by step F and under battery operating conditions in-situ reducing is formed, porous anode layer by porous anode layer predecessor pass through step F and under battery operating conditions in-situ reducing formed.
G, on dense electrolyte layer film prepare La0.8Sr0.2MnO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.085V.
Embodiment 4
It is as follows that the metal of the SOFC that the present embodiment relates to supports preparing of half-cell:
A, porous metals supporting layer thick film biscuit and the preparation of dense electrolyte layer film biscuit；
Respectively by 80 grams of rustless steel 430L powder body, 20 grams of fecula pore creating materials, by 100 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 4 grams of Span-80 dispersants, with planetary ball mill with the mixing in 10 hours of 300rpm rotating speed ball milling.14 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 8 grams of dibutyl phthalates and 8 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 14 hours again of 300rpm rotating speed.Respectively by 90 grams of SDC powder body, by 80 grams of butanone of 2: 1 weight ratios and alcohol mixed solvent and 6 grams of Span-80 dispersants, with planetary ball mill with the mixing in 24 hours of 300rpm rotating speed ball milling.5 grams of polyvinylbutyral binder it are equipped with the most again in the slurry that above-mentioned ball milling mixes, and 5 grams of dibutyl phthalates and 5 grams of polyethylene glycol 200 mixed plasticizers, with planetary ball mill with the ball milling mixing in 24 hours again of 300rpm rotating speed.The slurry of above-mentioned 2 kinds of last ball millings mixing is carried out vacuum degassing process 30 minutes, casting machine carry out flow casting molding and is dried, preparing the porous metals supporting layer thick film biscuit that thickness is 900 μm and the dense electrolyte layer film biscuit that thickness is 40 μm respectively.
B, ethyl cellulose is dissolved in terpineol, make the terpineol solution of ethyl cellulose that cellulose content is 4wt%, to be applied to porous metalloceramic gradient transitional lay precursor film and the deposition of porous anode layer precursor film as silk screen printing binding agent.
C, by 4 grams of MnO2Powder body and 1 gram of fluorite structure oxide LDC (Ce0.8La0.2O2- δ) mixed powder joins in 14 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 50 μm.
D, by 3 grams of NiO, 2.4 grams of SSZ and 0.6 gram of Sr0.895Y0.07TiO3- δMixed powder join in 20 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 40 μm.
E, the dense electrolyte layer film biscuit obtained by step A is placed on the porous anode layer precursor film obtained by step D, at room temperature carry out isostatic pressed 1.5 minutes, pressure is 300MP, and being formed is porous metals supporting layer thick film, porous metalloceramic gradient transitional lay precursor film, porous anode layer precursor film and the multilamellar preform structure of dense electrolyte layer film from bottom to top.
F, this multilamellar biscuit being cut into square piece, plastic removal 6 hours at a temperature of 300 DEG C in nitrogen atmosphere, controlling to rise a gentle rate of temperature fall is 1.5 DEG C/min；Then by difference co-sintering 2 hours at a temperature of the half-cell after plastic removal in a vacuum 1150 DEG C and 1300 DEG C, controlling to rise gentle rate of temperature fall is 4 DEG C/min, is cooled to room temperature and obtains smooth, to have dense electrolyte layer film porous metals and support SOFC half-cell.And, porous metalloceramic gradient transitional lay by porous metalloceramic gradient transitional lay predecessor by step F and under battery operating conditions in-situ reducing is formed, porous anode layer by porous anode layer predecessor pass through step F and under battery operating conditions in-situ reducing formed.
G, on dense electrolyte layer film prepare Sm0.5Sr0.5CoO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 0.902V.
Embodiment 5
The metal of the SOFC that the present embodiment relates to supports step A in the preparation of half-cell, B, D, E, F with embodiment 3.Institute's difference is step C, G:
C, by 4 grams of WO3Powder body and 1 gram of fluorite structure oxide S cCeSZ mixed powder join in 15 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 60 μm.
G, on dense electrolyte layer film prepare Ce0.8Gd0.2O2- δBarrier layer and La0.6Sr0.4Co0.2Fe0.8O3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.084V.
Embodiment 6
The metal of the SOFC that the present embodiment relates to supports step A in the preparation of half-cell, B, D, E, F with embodiment 4, and institute's difference is step C, G:
C, by 5 grams of V2O5Powder body and 1 gram of fluorite structure oxide Ce0.8Nd0.2O2- δMixed powder joins in 16 milliliters of terpineol solution of ethyl cellulose, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metals supporting layer thick film biscuit, the porous metalloceramic gradient transitional lay precursor film that thickness is 70 μm.
G, on dense electrolyte layer film prepare PrBaCo2O5- δ+Sm0.2Ce0.8O2- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 0.913V.
Embodiment 7
The metal of the SOFC that the present embodiment relates to supports step A in the preparation of half-cell, B, C, E, F with embodiment 1；Institute's difference is step D, G:
D, by 2 grams of NiO, 1 gram of Co2O3Join in 18 milliliters of terpineol solution of ethyl cellulose with 2 grams of YSZ mixed powders, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 30 μm.
G, on dense electrolyte layer film, prepare Ce respectively0.8Gd0.2O2Barrier layer and La0.6Sr0.4CoO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.111V.
Embodiment 8
The metal of the SOFC that the present embodiment relates to supports step A in the preparation of half-cell, B, C, E, F with embodiment 2；Institute's difference is step D, G:
D, by 2 grams of Co2O3, 1 gram of MoO3Join in 18 milliliters of terpineol solution of ethyl cellulose with 2 grams of SDC mixed powders, grind the slurry obtaining stable uniform for 2 hours, the slurry prepared is uniformly deposited on by screen process press and forms, on porous metalloceramic gradient transitional lay precursor film, the porous anode layer precursor film that thickness is 40 μm.
G, on dense electrolyte layer film, prepare Ce respectively0.8Sm0.2O2Barrier layer and Sm0.5Sr0.5CoO3- δCathode layer and formed porous metals support SOFC monocell, measured battery open circuit voltage is 1.067V.
Above the specific embodiment of the present invention is described.It will be appreciated that, although embodiment only gives the application examples of the porous gradient transitional lay of several metal A and the formation of fluorite structure oxide, but due in the preparation and running of SOFC monocell, metal A metal in the interface of anode-side with anode forms alloy and has high anode active material, the high-conductivity composite material with alloy as principal phase is then formed with Cr and Fe in metal support at the interface of metal support side, the porous gradient transitional lay that several metal A the most similarly enumerated in claim are formed with fluorite structure oxide the most necessarily possesses similar effect.Therefore, the invention is not limited in above-mentioned particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, and this has no effect on the flesh and blood of the present invention.

Claims (14)

1. the metal of a SOFC supports half-cell, it is characterised in that include the most successively Porous metals supporting layer thick film, porous metalloceramic gradient transition layer film, porous anode layer film and the densification electricity arranged Solve matter layer film；
Described porous metalloceramic gradient transitional lay is mainly made up of metal A and fluorite structure oxide, and described fluorite is tied The content of structure oxide is 10～50wt%；The element of described metal A selected from Ni, Ti, V, Cr, Mn, Fe, Co, The combination in any of Cu, Zn, Nb, Mo, Ta, W, La, Si, Ce and Al；Described fluorite structure oxide is for mixing Miscellaneous zirconium oxide, cerium oxide or rear-earth-doped oxidation cerium, described doped zirconia is selected from YSZ, SSZ, ScYSZ, ScCeSZ, Described rare earth is one or more in Y, La, Pr, Nd, Sm, Gd；
The thickness of described porous metals supporting layer thick film is 200～1000 μm；
The thickness of described porous metalloceramic gradient transition layer film is 20～100 μm；
The thickness of described porous anode layer film is 10～50 μm；
The thickness of described dense electrolyte layer film is 5～40 μm；
The metal of described SOFC supports the preparation method of half-cell, comprises the following steps:
A, by rustless steel powder body, pore creating material, solvent and dispersant mix；Add binding agent and plasticizer mixing, shape Become casting slurry a；After screen filtration, vacuum degassing process, curtain coating makes porous metals supporting layer thick film biscuit, is dried ?；
B, by AO that weight ratio is 90:10～50:50xEthyl cellulose is joined with the mixed powder of fluorite structure oxide Cellulose content is in the terpineol solution of ethyl cellulose of 1～5wt%, grinds the slurry c obtaining stable uniform, by described slurry Material c silk screen printing is deposited on described porous metals supporting layer thick film biscuit, before forming porous metalloceramic gradient transitional lay Drive thing thin film；Described mixed powder is 15:85～80:20 with the weight ratio of terpineol solution of ethyl cellulose；
C, by TMO that weight ratio is 70:30:0～30:50:20x, the mixed powder of electrolyte and conductive oxide adds In the terpineol solution of ethyl cellulose that cellulose content is 1～5wt%, grind the slurry d obtaining stable uniform, Described slurry d silk screen printing is deposited on porous metalloceramic gradient transitional lay precursor film, forms porous anode layer Precursor film；Described mixed powder is 15:85～80:20 with the weight ratio of terpineol solution of ethyl cellulose；Described TM is selected from one or more of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Nb, Mo, Ta, W；
D, by electrolyte powder body, solvent and dispersant mix；Add binding agent and plastic agent mixing, form curtain coating slurry Material b；After screen filtration, vacuum degassing process, curtain coating makes dense electrolyte layer film biscuit, is dried；
E, described dense electrolyte layer film biscuit is placed on the porous anode layer precursor film obtained by step C, Carrying out isostatic pressed 1～10 minutes under room temperature, pressure is 50～300MP, forms multilamellar preform structure；At inert atmosphere Or 300～600 DEG C of plastic removals 2～6 hours in vacuum, respectively at 1000～1200 DEG C and 1150～1300 DEG C of co-sinterings 2～ 6 hours, controlling to rise gentle rate of temperature fall was 0.5～5 DEG C/min, is cooled to room temperature, obtains described solid oxide fuel The metal of battery supports half-cell.
2. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that institute The porous metals supporting layer stated mainly is made up of rustless steel FeCrM alloy；Described M element is Ni, Ti, Mn, Mo, One or more in W, Nb, Co, Cu, V, La, Si, Ce, Al, C, N, P and S.
3. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that institute Stating porous anode layer is the ceramic metal being made up of electrolyte, TM and conductive oxide；Described electrolyte selects One or more in YSZ, SSZ, ScYSZ, ScCeSZ, GDC, SDC, LSGM and LSGMC；Institute State TM selected from one or more of Ni, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Nb, Mo, Ta, W； Described conductive oxide is selected from CeO2、SrTi0.9Nb0.09O3±δ、SrxY0.07TiO3±δ、Sr0.895Y0.07TiyO3±δWith Sr1-a-bLaaTi1-zNzO3+δIn one or more；Wherein, 0≤δ≤1, x=0.80～1.02, y=1.00～1.20, a=0.1～ 0.9, b=0.0～0.2, z=0.0～0.9, N is one or more in Mn, Co, Ni, Fe, Cr and Nb.
4. the metal of SOFC as claimed in claim 3 supports half-cell, it is characterised in that institute The content stating electrolyte is 30～50wt%, and the content of described TM is 30～70wt%, described conductive oxide Content be 0～20wt%.
5. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that institute State the electrolyte of dense electrolyte layer selected from YSZ, SSZ, ScYSZ, ScCeSZ, GDC, SDC, LSGM With one or more in LSGMC.
6. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that system The composition of the casting slurry a of porous metals supporting layer thick film described in step A of Preparation Method is:
7. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that system In step A of Preparation Method, described pore creating material is selected from ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, graphite, starch and poly-first One or more in base acrylic acid methyl ester..
8. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that preparation In step A of method and D, described solvent be respectively selected from dehydrated alcohol, isopropanol, n-butyl alcohol, acetone, butanone, One or more in Ketohexamethylene, ethyl fat, trichloro ethylene and dimethylbenzene.
9. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that system In step A of Preparation Method and D, described dispersant is respectively selected from herring oil, triethanolamine, triethyl phosphate, this dish -80, one or more in tributyl phosphate, terpineol, glycerol trioleate, polyacrylic acid and ethoxy compound.
10. the metal of SOFC as claimed in claim 1 supports half-cell, it is characterised in that preparation In step A of method and D, described binding agent is respectively selected from polyvinyl alcohol, polyvinyl butyral resin, polyacrylic acid first One or more in ester, polymethylacrylic acid and ethyl cellulose.
The metal of 11. SOFCs as claimed in claim 1 supports half-cell, it is characterised in that system In step A of Preparation Method and D, described plasticizer be respectively selected from ethylene glycol, Polyethylene Glycol, dibutyl phthalate, One or more in dioctyl phthalate, diethyl oxalate ester and glycerol.
The metal of 12. SOFCs as claimed in claim 1 supports half-cell, it is characterised in that system The composition of the casting slurry b of dense electrolyte layer film described in step D of Preparation Method is:
The metal of 13. SOFCs as claimed in claim 1 supports half-cell, it is characterised in that system In step C of Preparation Method and D, described electrolyte be respectively selected from YSZ, SSZ, ScYSZ, ScCeSZ, GDC, One or more in SDC, LSGM and LSGMC.
The metal of 14. SOFCs as claimed in claim 1 supports half-cell, it is characterised in that system In step E of Preparation Method, described inert atmosphere is selected from nitrogen or argon.
CN201410109806.4A 2014-03-21 2014-03-21 The metal of SOFC supports half-cell and preparation method thereof Active CN103928693B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410109806.4A CN103928693B (en) 2014-03-21 2014-03-21 The metal of SOFC supports half-cell and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410109806.4A CN103928693B (en) 2014-03-21 2014-03-21 The metal of SOFC supports half-cell and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103928693A CN103928693A (en) 2014-07-16
CN103928693B true CN103928693B (en) 2016-09-28

Family

ID=51146834

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410109806.4A Active CN103928693B (en) 2014-03-21 2014-03-21 The metal of SOFC supports half-cell and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103928693B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269563A (en) * 2014-09-17 2015-01-07 上海交通大学 Preparation method of cathode barrier layer of metallic-propping solid oxide fuel cell
CN104332635B (en) * 2014-11-17 2017-03-08 安徽中科新研陶瓷科技有限公司 A kind of SOFC and preparation method thereof
EP3276721B1 (en) * 2015-03-26 2019-08-21 NGK Spark Plug Co., Ltd. Electrochemical reaction unit and fuel cell stack
KR102072875B1 (en) 2015-06-11 2020-02-03 주식회사 엘지화학 Sheet laminate for solid oxide fuel cell, precursor of solid oxide fuel cell comprising the same, manufacturing device of sheet laminate for solid oxide fuel cell and manufacturing method of sheet laminate for solid oxide fuel cell
JP6667238B2 (en) * 2015-09-18 2020-03-18 大阪瓦斯株式会社 Metal-supported electrochemical device, solid oxide fuel cell, and method of manufacturing metal-supported electrochemical device
CN107305953B (en) * 2016-04-18 2019-10-25 汕头大学 A kind of solid oxide fuel cell composite substrate and its preparation process
CN105967689B (en) * 2016-05-04 2019-04-02 内蒙古科技大学 A kind of preparation method of electrolyte film material
CN107845822B (en) * 2017-11-03 2020-08-28 广东康荣高科新材料股份有限公司 Fuel cell anode support extrusion pug and preparation method thereof
CN108154950A (en) * 2017-12-01 2018-06-12 北京有色金属研究总院 A kind of NiO/ proton electrolytes composite film electrode structure and preparation method thereof
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
CN111403762B (en) * 2020-03-31 2021-05-18 西安交通大学 Ceramic and metal common support flat tube, battery/electrolytic cell and battery stack structure
CN112647089B (en) * 2020-12-15 2021-12-07 中国科学院大连化学物理研究所 Preparation method of ternary composite anode of solid oxide electrolytic cell
CN113506905A (en) * 2021-07-14 2021-10-15 清华四川能源互联网研究院 Proton conduction type half cell, proton conduction type solid oxide cell, and preparation method and application thereof
CN114335640B (en) * 2021-12-27 2023-06-02 安徽壹石通材料科学研究院有限公司 Sintering method of anode support type SOFC half-cell
CN114315377B (en) * 2022-01-12 2022-11-08 东莞富瑟尔科技有限公司 Rapid mass production method of multilayer structure composite functional ceramic

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985397A (en) * 2004-06-10 2007-06-20 丹麦科技大学 Solid oxide fuel cell
CN102760896A (en) * 2011-04-29 2012-10-31 中国科学院大连化学物理研究所 Current collection component of anode supporting tube type solid oxide fuel cell and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985397A (en) * 2004-06-10 2007-06-20 丹麦科技大学 Solid oxide fuel cell
CN102760896A (en) * 2011-04-29 2012-10-31 中国科学院大连化学物理研究所 Current collection component of anode supporting tube type solid oxide fuel cell and application thereof

Also Published As

Publication number Publication date
CN103928693A (en) 2014-07-16

Similar Documents

Publication Publication Date Title
CN103928693B (en) The metal of SOFC supports half-cell and preparation method thereof
CN102082284B (en) Method for preparing anode supporting type intermediate-temperate solid oxide fuel cell (SOFC)
Fan et al. Electrochemical stability of La0. 6Sr0. 4Co0. 2Fe0. 8O3− δ-infiltrated YSZ oxygen electrode for reversible solid oxide fuel cells
JP6398647B2 (en) Method for producing anode for solid oxide fuel cell and method for producing electrolyte layer-electrode assembly for fuel cell
CN104779409B (en) A kind of solid oxide fuel cell and preparation method thereof
US10050295B2 (en) Solid electrolyte laminate, method for manufacturing solid electrolyte laminate, and fuel cell
EP2833452A1 (en) Solid electrolyte, manufacturing method for solid electrolyte, solid electrolyte laminate, manufacturing method for solid electrolyte laminate, and fuel cell
CN104269563A (en) Preparation method of cathode barrier layer of metallic-propping solid oxide fuel cell
Dayaghi et al. Stainless steel-supported solid oxide fuel cell with La0. 2Sr0. 8Ti0. 9Ni0. 1O3− δ/yttria-stabilized zirconia composite anode
CN102881929B (en) Structure of flat-plate type metal-support solid oxide fuel cell for immersing electrodes
CN101485018A (en) Ceramic material combination for an anode of a high-temperature fuel cell
CN102593480B (en) Mixed titanate support solid electrolyte multilayer film of solid oxide fuel cell and manufacturing method thereof
CN103811789A (en) Solid oxide fuel cell with symmetrical electrodes, and preparation method and application thereof
EP3430661B1 (en) Alternative anode material for solid oxide fuel cells
CN102290580A (en) Solid oxide fuel cell anode/electrolyte double-layered membrane and preparation method thereof
Zhou et al. Long-term stability of metal-supported solid oxide fuel cells employing infiltrated electrodes
CN107017423A (en) A kind of low-temperature solid oxide fuel cell and preparation method thereof
Liu et al. Fabrication and characterization of a co-fired La0. 6Sr0. 4Co0. 2Fe0. 8O3− δ cathode-supported Ce0. 9Gd0. 1O1. 95 thin-film for IT-SOFCs
CN103219525A (en) Low-temperature solid oxide fuel cell and making method thereof
CN102738492A (en) Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the same
JP6573243B2 (en) Air electrode composition, air electrode and fuel cell including the same
CN101521282A (en) Metal electrode catalyst and preparation method thereof
JP6152171B2 (en) Powder mixture for layers in solid oxide fuel cells
CN101222050A (en) Anti-carbon deposition anode film material and method for producing the same
CN104037425A (en) Medium-temperature SOFC (solid oxide fuel cell) flat-plate anode-supported monocell anode structure 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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20170720

Address after: 200241, room three, building 555, Dongchuan Road, Minhang District, Shanghai,

Patentee after: SHANGHAI ZHONGFU NEW ENERGY TECHNOLOGY CO.,LTD.

Address before: 200240 Dongchuan Road, Shanghai, No. 800, No.

Patentee before: Shanghai Jiao Tong University

CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: Room 1188, C Building, 555 Dongchuan Road, Minhang District, Shanghai, 200241

Patentee after: Shanghai Zhongfu New Energy Technology Co.,Ltd.

Address before: Room 103A, Building 3, 555 Dongchuan Road, Minhang District, Shanghai, 200241

Patentee before: SHANGHAI ZHONGFU NEW ENERGY TECHNOLOGY CO.,LTD.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190304

Address after: 214000 Donggang Zhenyuan South Road, Xishan District, Wuxi City, Jiangsu Province, 28

Patentee after: Zhongfu (Wuxi) New Energy Co.,Ltd.

Address before: Room 1188, C Building, 555 Dongchuan Road, Minhang District, Shanghai, 200241

Patentee before: Shanghai Zhongfu New Energy Technology Co.,Ltd.