CN101562255A - Method for preparing metallic support type solid oxide fuel cell - Google Patents

Method for preparing metallic support type solid oxide fuel cell Download PDF

Info

Publication number
CN101562255A
CN101562255A CNA2009100621646A CN200910062164A CN101562255A CN 101562255 A CN101562255 A CN 101562255A CN A2009100621646 A CNA2009100621646 A CN A2009100621646A CN 200910062164 A CN200910062164 A CN 200910062164A CN 101562255 A CN101562255 A CN 101562255A
Authority
CN
China
Prior art keywords
ysz
mol
solid oxide
oxide fuel
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2009100621646A
Other languages
Chinese (zh)
Other versions
CN101562255B (en
Inventor
李箭
孔永红
华斌
蒲健
颜冬
池波
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.)
Yizheng Boyuan in Amperex Technology Limited
Original Assignee
Huazhong University of Science and Technology
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 Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN2009100621646A priority Critical patent/CN101562255B/en
Publication of CN101562255A publication Critical patent/CN101562255A/en
Application granted granted Critical
Publication of CN101562255B publication Critical patent/CN101562255B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a method for preparing a metallic support type solid oxide fuel cell, and belongs to a method for preparing a solid oxide fuel cell (SOFC). The invention aims to simplify process, lower cost and prepare the fuel cell with excellent electric property. The method comprises the following steps: (1) a tape casting slurry preparation step; (2) a tape casting formation step; (3) a half cell preparation step; (4) a high-temperature sintering step; (5) a monocell preparation step; and (6) a reducing step. The method has the advantages of wide raw material source, simple preparation process and low cost; and the open-circuit voltage of the prepared SOFC, which is measured at a temperature of 750 DEG C, is 1.01V, the maximum power density is 0.64w/cm<2>, so that the SOFC can be applied to the preparation of the large-area metallic support type solid oxide fuel cell.

Description

A kind of preparation method of metallic support type solid oxide fuel cell
Technical field
The invention belongs to the preparation method of Solid Oxide Fuel Cell (SOFC), be specifically related to a kind of preparation method of metallic support type solid oxide fuel cell.
Background technology
According to the difference of supporter type, traditional Solid Oxide Fuel Cell (SOFC) can be divided into electrolyte-supporting type Solid Oxide Fuel Cell, anode supporting type solid oxide fuel cell and cathode support type Solid Oxide Fuel Cell.In the Solid Oxide Fuel Cell that all kinds support, support body material all belongs to ceramic material or ceramic-metal composite.Because ceramic material is difficult for processing, thermal-shock resistance and weldability are poor, cause monocell to increase in pile assembling process difficulty, break easily.
The exploitation of electrolyte thin membranization and low temperature novel electrolytes material, effectively reduce the working temperature (600～800 ℃) of Solid Oxide Fuel Cell, thereby enlarged the range of choice of Solid Oxide Fuel Cell material, made the application of metal material in Solid Oxide Fuel Cell become possibility.In recent years, select the support body material of metal material as Solid Oxide Fuel Cell for use, the research of preparation metallic support type solid oxide fuel cell receives much concern.With respect to pottery or cermet material, metal material has advantages such as high electronic conductance, high heat conductance, good ductility and easy machine-shaping, low cost, make metallic support type solid oxide fuel cell have advantage such as mechanical strength, electric conductivity preferably, therefore become a Solid Oxide Fuel Cell developing direction in future.
Than traditional electrode-supported Solid Oxide Fuel Cell or electrolyte-supporting type Solid Oxide Fuel Cell, metallic support type solid oxide fuel cell has more advantage.Because the densification sintering temperature generally higher (＞1300 ℃) of solid-oxide fuel battery electrolyte, and high temperature like this is easy to cause the oxidation of metal material, therefore, in the preparation of metallic support type solid oxide fuel cell, electrolytical densification sintering becomes current difficult point.According to electrolytical forming method, the preparation of metal current support type solid oxide fuel cell mainly is divided into two classes: a class is the low temperature moulding preparation method, as pulsed laser deposition, chemical vapour deposition (CVD), suspension plasma spraying etc., prepared electrolyte is comparatively fine and close, and sintering temperature is low, can effectively suppress the oxidation of metal, but these class methods is higher to equipment requirements, complex process, thus high preparation cost caused; See Shiqiang Hui, Dongfang Yang, Zhenwei Wang, et al. " 400-600 ℃ of Metal-supported solid oxide fuel cell operated at " (Journal ofPower Sources, 2007,167:336-339).Another kind of then is the method that adopts high temperature co-firing in reducing atmosphere, high temperature co-firing in reducing atmosphere, though can simplify moulding process, and can use the wet method ceramic molding to prepare electrolyte to reduce production costs, but high temperature co-firing is easy to cause the counterdiffusion mutually of metallic element between metal support and the anode functional layer in reducing atmosphere, thereby reduces battery performance; For example in Fe-Cr base support type SOFC, Cr Elements Diffusion in the supporter enters anode functional layer and easily causes declining to a great extent of battery performance, metallic element in the anode layer such as Ni are diffused into the variation that then can cause the supporter thermal coefficient of expansion in the Fe-Cr supporter, cause the cracking of dielectric substrate; See Michael C.Tucker, Grace Y.Lau, C P.Jacobson. " Performance of metal-supported SOFCs with infiltrated electrodes " (Journal of power sources, 2007,171:477-482).
Summary of the invention
The invention provides a kind of preparation method of metallic support type solid oxide fuel cell, purpose is to simplify technology, reduces cost, and prepares the fuel cell with excellent electrical.
The preparation method of a kind of metallic support type solid oxide fuel cell of the present invention comprises the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 20～23, pore creating material 1～1.5, binding agent 2.2～2.5, plasticizer 2.2～2.5, dispersant 0.3～0.4, organic solvent 96～104, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 4～7 of defrothers, ball milling is made casting slurry;
(2) flow casting molding step: the casting slurry flow casting molding with obtaining obtains the nickel oxide base substrate after the air dry; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that meets dimensional requirement;
(3) preparation half-cell step: adopt silk-screen printing technique printed anode functional layer material and dielectric substrate material successively on nickel oxide supporter base substrate, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, carry out high temperature sintering under 1370～1450 ℃, realize electrolytical densification, exerting pressure during sintering is 650～750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer material on the solid oxide fuel half-cell after the densification, and under 1100～1300 ℃ of temperature, carry out sintering, realize the sintering of cathode layer and dielectric substrate, the solid oxide fuel monocell;
(6) reduction step: under 700～800 ℃ of temperature, the solid oxide fuel monocell is placed reducing atmosphere,, prepare the metallic nickel supporter of porous, obtain the metallic nickel support type solid oxide fuel cell by reduction to nickel oxide.
Described preparation method is characterized in that, in the described preparation casting slurry step:
Described pore creating material is a kind of in starch, the carbon dust;
Described binding agent is a kind of in polyvinyl butyral resin, polyacrylate, the methylcellulose; Described plasticizer is one or more in phthalic acid fourth benzyl fat, ployalkylene glycol, phosphate toluene diphenyl ester, the adipic acid propylene glycol polyester;
Described dispersant is a kind of in fatty acid polyethylene glycol ester, glyceryl tristearate, the fish oil;
Described organic solvent is one or more in triethanolamine, styrene, dimethylbenzene, the absolute ethyl alcohol.
Described preparation method is characterized in that:
In the described preparation half-cell step, described anode function layer material is a kind of among NiO-YSZ, NiO-GDC or the NiO-SDC, and among the NiO-YSZ, the weight ratio of NiO and YSZ is: 64～70: 36～30, and YSZ is 8～10%mol Y 2O 3Doping ZrO 2Among the NiO-GDC, the weight ratio of NiO and GDC is: 64～70: 36～30, and GDC is the CeO that 10～20%mol Gd mixes 2Among the NiO-SDC, the weight ratio of NiO and SDC is: 64～70: 36～30, and SDC is the CeO that 10～20%mol Sm mixes 2
In the described preparation half-cell step, described dielectric substrate material is a kind of among GDC, YSZ, LSGM or the SDC, and wherein, GDC is the CeO that 10～20%mol Gd mixes 2YSZ is 8～10%mol Y 2O 3Doping ZrO 2LSGM is the LaGaO that 10～15%mol Sr and 20～25%mol Mg mix 3SDC is the CeO that 10～20%mol Sm mixes 2
In the described preparation monocell step, described cathode function layer material is a kind of among LSCN, Pd-YSZ, LSCF-GDC or the LSCN-YSZ, and LSCN is the LaCoO that 10～30%mol Sr and 10～30%mol Ni mix 3Among the Pd-YSZ, the weight ratio of Pd and YSZ is 6.6～7: 94～93, and YSZ is 8～10%mol Y 2O 3Doping ZrO 2Among the LSCF-GDC, the weight ratio of LSCF and GDC is 2～6: 98～94, and LSCF is the LaFeO that 30～50%mol Sr and 10～30%molCo mix 3, GDC is the CeO that 10～20%mol Gd mixes 2Among the LSCN-YSZ, the weight ratio of LSCN and YSZ is 4～8: 96～92, and LSCN is the LaCoO that 10～30%mol Sr and 10～30%mol Ni mix 3, YSZ is 8～10%mol Y 2O 3Doping ZrO 2
Described preparation method is characterized in that:
In the described reduction step, described reducing atmosphere is H 2And N 2Mist or H 2With the Ar mist; H 2And N 2Mist is percent by volume: 4%～20%H 2, 96%～80%N 2H 2With the Ar mist be percent by volume: 4%～20%H 2, 96%～80%Ar.
The present invention selects for use nickel oxide as support body material, nickel oxide belongs to ceramic material, can realize the high temperature co-firing knot with other assemblies of battery, and have suitable thermal coefficient of expansion, avoid the defectives such as dielectric substrate cracking that do not match and cause because of thermal coefficient of expansion in the high temperature sintering; Adopt cost silk-screen printing technique lower, that efficient is higher to prepare electrolyte and electrode function layer; Electrolytical densification realizes that by high temperature sintering in air atmosphere equipment needed thereby is simple, work simplification; Dielectric substrate promptly reaches complete densification through high temperature co-firing, and has realized good the contact with anode support.In the high temperature co-firing process, there are not the counterdiffusion mutually of element or bad reaction to take place between anode functional layer and the nickel oxide supporter; Subsequently by the silk screen printing cathode functional, and can select sintering temperature voluntarily, avoid the too high reduction that causes cathode activity of sintering temperature.The metallic nickel supporter for preparing porous among the present invention by reduction-oxidation nickel is effectively simple.Nickel oxide in supporter and the anode layer all can present loose structure through after the reduction reaction, to satisfy the requirement in gas transmission and anode layer phase reaction district.
Compared with prior art, selected materials wide material sources of the present invention, preparation technology is simple, and cost is lower, and prepared SOFC measured open circuit voltage under 750 ℃ is 1.01V, and maximum power density is 0.64w/cm 2, can be used for the preparation of large-area metal support type solid oxide fuel cell.
Description of drawings
Fig. 1 is a process chart of the present invention;
Fig. 2 is that embodiment 1 prepared metallic nickel support type solid oxide fuel cell cross section ESEM (SEM) is schemed;
Fig. 3 is prepared metallic nickel support type solid oxide fuel cell anode layer X-ray diffraction (XRD) collection of illustrative plates of embodiment 1;
Fig. 4 is that the prepared metallic nickel support type solid oxide fuel cell of embodiment 1 is at 650-800 ℃ of measured voltage-to-current density curve (V-I) and power density-current density curve (P-I);
Fig. 5 is that embodiment 2 prepared metallic support type solid oxide fuel cell cross section surface sweeping Electronic Speculum (SEM) are schemed.
Embodiment
Fig. 1 is a flow chart of the present invention, below in conjunction with embodiment the present invention is specified.
Embodiment 1: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material carbon dust 15g, binding agent polyvinyl butyral resin (PVB) 25g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fish oil 4g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1450 ℃ of sintering 2 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printing Pd-YSZ cathode functional on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 6.6: 94, YSZ is 8%mol Y 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 11 hours, obtain the metallic nickel support type solid oxide fuel cell.
Fig. 2 is the SEM sectional view of embodiment 1 prepared metallic nickel support type SOFC, as can be seen from the figure, behind high temperature sintering, these other assemblies of cell support body and battery contact well, do not have layering or crackle at the interface and occur, dielectric substrate is very fine and close, no significant defect, and supporter and anode functional layer all present loose structure, help the gas transmission.
Fig. 3 is the X ray diffracting spectrum of embodiment 1 prepared metallic nickel support type SOFC anode layer, as can be seen, the basic Restore All of nickel oxide is a nickel, thus show the nickel oxide supporter 750 ℃ after 11 hours reduction reaction, can be reduced to the metallic nickel supporter of porous.
Fig. 4 be embodiment 1 prepared metallic nickel support type SOFC at 650-800 ℃ of measured V-I curve and P-I curve, test result shows, this battery is respectively 0.23,0.38,0.64 and 0.81w/cm at 650,700,750,800 ℃ maximum power density 2The result shows that the metallic nickel support type SOFC of the present invention's preparation possesses excellent electric performance.
Embodiment 2: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material carbon dust 10g, binding agent polyvinyl butyral resin (PVB) 22g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant fish oil 3g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 4 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique printed anode functional layer NiO-YSZ and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 650Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 7: 93, YSZ is 8%mol Y 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(4%H in the mist reducing atmosphere 2+ 96%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Fig. 5 is the SEM sectional view of embodiment 2 prepared metallic nickel support type SOFC, as can be seen, when sintering temperature is 1370 ℃, the dielectric substrate of sintering is just very fine and close, the reduction of sintering temperature can prevent that not only supporter is too fine and close when burning altogether, increase reduction difficulty subsequently, and can avoid growing up of anode layer particle, reduce battery performance.
Embodiment 3: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent methylcellulose 22g, plasticizer adipic acid propylene glycol polyester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant glyceryl tristearate 3g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix 3, YSZ is 8%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (10%H in the Ar mist reducing atmosphere 2+ 90%Ar vol.%), to the reduction of nickel oxide through 7 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 4: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent methylcellulose 22g, plasticizer adipic acid propylene glycol polyester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant glyceryl tristearate 3g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix 3, YSZ is 8%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (10%H in the Ar mist reducing atmosphere 2+ 90%Ar vol.%), to the reduction of nickel oxide through 7 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 5: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix 3, YSZ is 8%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (4%H in the Ar mist reducing atmosphere 2+ 96%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 6: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix 3, YSZ is 8%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 7: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 200g, pore creating material starch 10g, binding agent polyacrylate 22g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 22g, dispersant fatty acid polyethylene glycol ester 3g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 96g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix 3, YSZ is 10%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1150 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (6%H in the Ar mist reducing atmosphere 2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 8: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 70: 30, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 30%mol Sr and 30%mol Ni mix 3, YSZ is 10%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (6%H2+94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell in the Ar mist reducing atmosphere.
Embodiment 9: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 15g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant fatty acid polyethylene glycol ester 4g, organic solvent triethanolamine/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 8: 92, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix 3, YSZ is 10%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2With (6%H in the Ar mist reducing atmosphere 2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 10: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 230g, pore creating material starch 13g, binding agent polyacrylate 25g, plasticizer phosphate toluene diphenyl ester/ployalkylene glycol (PAG) (weight ratio, 1: 1) 25g, dispersant glycerine tristearate 4g, organic solvent styrene/absolute ethyl alcohol (weight ratio, 1: 1) 104g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 7 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN-YSZ on the solid oxide fuel half-cell after the densification, LSCN and YSZ weight ratio are 4: 96, LSCN is the LaCoO that 10%mol Sr and 10%mol Ni mix 3, YSZ is 10%molY 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2With (6%H in the Ar mist reducing atmosphere 2+ 94%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 11: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 50: 50, and YSZ is 8%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN on the solid oxide fuel half-cell after the densification, LSCN are the LaCoO that 10%mol Sr and 10%molNi mix 3, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2With (4%H in the Ar mist reducing atmosphere 2+ 96%Ar vol.%), to the reduction of nickel oxide through 9 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 12: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and YSZ dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 40: 60, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCN on the solid oxide fuel half-cell after the densification, LSCN are the LaCoO that 30%mol Sr and 30%molNi mix 3, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2With (5%H in the Ar mist reducing atmosphere 2+ 95%Ar vol.%), to the reduction of nickel oxide through 10 hours, prepares the metallic nickel supporter of porous, obtains the metallic nickel support type solid oxide fuel cell.
Embodiment 13: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 64: 36, and GDC is the CeO that the Gd of 20%mol mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol 3, GDC is the CeO that the Gd of 20%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 14: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 70: 30, and GDC is the CeO that the Gd of 20%mol mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol 3, GDC is the CeO that the Gd of 20%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 15: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 220g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 64: 36, and GDC is the CeO that the Gd of 10%mol mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1380 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol 3, GDC is the CeO that the Gd of 10%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 16: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-GDC anode functional layer and GDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and GDC weight ratio are 70: 30, and GDC is the CeO that the Gd of 10%mol mixes 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 30%mol and 10%mol 3, GDC is the CeO that the Gd of 10%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 17: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 10%mol Sm 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol 3, GDC is the CeO that the Gd of 10%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 750 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 18: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 70: 30, the CeO that SDC mixes for 10%mol Sm 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol 3, GDC is the CeO that the Gd of 10%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 19: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 20%mol Sm 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1370 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 6: 94, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol 3, GDC is the CeO that the Gd of 20%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1100 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(5%H in the mist reducing atmosphere 2+ 95%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 20: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-SDC anode functional layer and SDC dielectric substrate successively on nickel oxide supporter base substrate, NiO and SDC weight ratio are 64: 36, the CeO that SDC mixes for 20%mol Sm 2, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 700Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer LSCF-GDC on the solid oxide fuel half-cell after the densification, LSCF and GDC weight ratio are 2: 98, LSCF is the LaFeO of the Co doping of the Sr of 50%mol and 30%mol 3, GDC is the CeO that the Gd of 20%mol mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1200 ℃ of sintering temperatures 2 hours, make the solid oxide fuel monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed H 2And N 2(6%H in the mist reducing atmosphere 2+ 94%N 2, vol.%),, prepare the metallic nickel supporter of porous to the reduction of nickel oxide through 9 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 21: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and LSGM dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, LSGM is the LaGaO that 10%mol Sr and 20%mol Mg mix 3, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1390 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 7: 93, YSZ is 10%mol Y 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the soild oxide monocell;
(6) reduction step: under 700 ℃ of temperature, the soild oxide monocell is placed reducing atmosphere (5%H 2+ 95%N 2, vol.%) in, to the reduction of nickel oxide, prepare the metallic nickel supporter of porous through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.
Embodiment 22: comprise the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 210g, pore creating material carbon dust 12g, binding agent polyvinyl butyral resin (PVB) 24g, plasticizer phthalic acid fourth benzyl fat (BBP)/ployalkylene glycol (PAG) (weight ratio, 1: 1) 24g, dispersant fish oil 5g, organic solvent dimethylbenzene/absolute ethyl alcohol (weight ratio, 1: 1) 101g, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 6 of defrother cyclohexanone, ball milling is made casting slurry;
(2) flow casting molding step:, obtain the nickel oxide base substrate that thickness is about 1mm after the air dry with the casting slurry flow casting molding that obtains; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that diameter is 26mm;
(3) preparation half-cell step: adopt silk-screen printing technique to print NiO-YSZ anode functional layer and LSGM dielectric substrate successively on nickel oxide supporter base substrate, the weight ratio of NiO and YSZ is 64: 36, and YSZ is 10%mol Y 2O 3The ZrO that mixes 2, LSGM is the LaGaO that 15%mol Sr and 25%mol Mg mix 3, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, 1400 ℃ of sintering 3 hours, realize electrolytical densification, exerting pressure during sintering is 750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer Pd-YSZ on the solid oxide fuel half-cell after the densification, the weight ratio of Pd and YSZ 6.6: 94, YSZ is 10%mol Y 2O 3The ZrO that mixes 2, and, realize the sintering of cathode layer and dielectric substrate 1300 ℃ of sintering temperatures 2 hours, make the soild oxide monocell;
(6) reduction step: under 800 ℃ of temperature, the soild oxide monocell is placed reducing atmosphere (5%H 2+ 95%N 2, vol.%) in, to the reduction of nickel oxide, prepare the metallic nickel supporter of porous through 10 hours, obtain the metallic nickel support type solid oxide fuel cell.

Claims (4)

1. the preparation method of a metallic support type solid oxide fuel cell comprises the steps:
(1) preparation casting slurry step: according to weight ratio: nickel oxide 20～23, pore creating material 1～1.5, binding agent 2.2～2.5, plasticizer 2.2～2.5, dispersant 0.3～0.4, organic solvent 96～104, nickel oxide, pore creating material, binding agent, plasticizer and dispersant are dissolved in the organic solvent, add 4～7 of defrothers, ball milling is made casting slurry;
(2) flow casting molding step: the casting slurry flow casting molding with obtaining obtains the nickel oxide base substrate after the air dry; The nickel oxide base substrate is cut into the nickel oxide supporter base substrate that meets dimensional requirement;
(3) preparation half-cell step: adopt silk-screen printing technique printed anode functional layer material and dielectric substrate material successively on nickel oxide supporter base substrate, prepare the solid oxide fuel half-cell;
(4) high temperature sintering step: after the solid oxide fuel half-cell carried out degreasing and presintering, carry out high temperature sintering under 1370～1450 ℃, realize electrolytical densification, exerting pressure during sintering is 650～750Pa;
(5) preparation monocell step: adopt silk-screen printing technique, printed cathode functional layer material on the solid oxide fuel half-cell after the densification, and under 1100～1300 ℃ of temperature, carry out sintering, and realize the sintering of cathode layer and dielectric substrate, make the solid oxide fuel monocell;
(6) reduction step: under 700～800 ℃ of temperature, the solid oxide fuel monocell is placed reducing atmosphere,, prepare the metallic nickel supporter of porous, obtain the metallic nickel support type solid oxide fuel cell by reduction to nickel oxide.
2. preparation method as claimed in claim 1 is characterized in that, in the described preparation casting slurry step:
Described pore creating material is a kind of in starch, the carbon dust;
Described binding agent is a kind of in polyvinyl butyral resin, polyacrylate, the methylcellulose; Described plasticizer is one or more in phthalic acid fourth benzyl fat, ployalkylene glycol, phosphate toluene diphenyl ester, the adipic acid propylene glycol polyester;
Described dispersant is a kind of in fatty acid polyethylene glycol ester, glyceryl tristearate, the fish oil;
Described organic solvent is one or more in triethanolamine, styrene, dimethylbenzene, the absolute ethyl alcohol.
3. preparation method as claimed in claim 1 or 2 is characterized in that:
In the described preparation half-cell step, described anode function layer material is a kind of among NiO-YSZ, NiO-GDC or the NiO-SDC, and among the NiO-YSZ, the weight ratio of NiO and YSZ is: 64～70: 36～30, and YSZ is 8～10%mol Y 2O 3Doping ZrO 2Among the NiO-GDC, the weight ratio of NiO and GDC is: 64～70: 36～30, and GDC is the CeO that 10～20%mol Gd mixes 2Among the NiO-SDC, the weight ratio of NiO and SDC is: 64～70: 36～30, and SDC is the CeO that 10～20%mol Sm mixes 2
In the described preparation half-cell step, described dielectric substrate material is a kind of among GDC, YSZ, LSGM or the SDC, and wherein, GDC is the CeO that 10～20%mol Gd mixes 2YSZ is 8～10%mol Y 2O 3Doping ZrO 2LSGM is the LaGaO that 10～15%mol Sr and 20～25%mol Mg mix 3SDC is the CeO that 10～20%mol Sm mixes 2
In the described preparation monocell step, described cathode function layer material is a kind of among LSCN, Pd-YSZ, LSCF-GDC or the LSCN-YSZ, and LSCN is the LaCoO that 10～30%mol Sr and 10～30%mol Ni mix 3Among the Pd-YSZ, the weight ratio of Pd and YSZ is 6.6～7: 94～93, and YSZ is 8～10%mol Y 2O 3Doping ZrO 2Among the LSCF-GDC, the weight ratio of LSCF and GDC is 2～6: 98～94, and LSCF is the LaFeO that 30～50%mol Sr and 10～30%molCo mix 3, GDC is the CeO that 10～20%mol Gd mixes 2Among the LSCN-YSZ, the weight ratio of LSCN and YSZ is 4～8: 96～92, and LSCN is the LaCoO that 10～30%mol Sr and 10～30%mol Ni mix 3, YSZ is 8～10%mol Y 2O 3Doping ZrO 2
4. preparation method as claimed in claim 3 is characterized in that:
In the described reduction step, described reducing atmosphere is H 2And N 2Mist or H 2With the Ar mist; H 2And N 2Mist is percent by volume: 4%～20%H 2, 96%～80%N 2H 2With the Ar mist be percent by volume: 4%～20%H 2, 96%～80%Ar.
CN2009100621646A 2009-05-19 2009-05-19 Method for preparing metallic support type solid oxide fuel cell Expired - Fee Related CN101562255B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100621646A CN101562255B (en) 2009-05-19 2009-05-19 Method for preparing metallic support type solid oxide fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100621646A CN101562255B (en) 2009-05-19 2009-05-19 Method for preparing metallic support type solid oxide fuel cell

Publications (2)

Publication Number Publication Date
CN101562255A true CN101562255A (en) 2009-10-21
CN101562255B CN101562255B (en) 2010-12-01

Family

ID=41220950

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100621646A Expired - Fee Related CN101562255B (en) 2009-05-19 2009-05-19 Method for preparing metallic support type solid oxide fuel cell

Country Status (1)

Country Link
CN (1) CN101562255B (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101894956A (en) * 2010-08-17 2010-11-24 哈尔滨工业大学 Method for preparing anode support with columnar orientation pores
CN102437358A (en) * 2011-11-30 2012-05-02 中国科学技术大学 Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof
CN102593478A (en) * 2012-01-18 2012-07-18 苏州华清京昆新能源科技有限公司 Method for manufacturing multilayer thin-film solid oxide fuel cell
CN103165903A (en) * 2011-12-15 2013-06-19 江苏超洁绿色能源科技有限公司 Anti-carbon-deposition, high-performance and functionally-graded anode composite film of solid oxide fuel cells and preparation method thereof
CN103613105A (en) * 2013-11-25 2014-03-05 中国科学院宁波材料技术与工程研究所 Single cell as well as preparation method and application thereof
CN103682406A (en) * 2013-12-14 2014-03-26 济南开发区星火科学技术研究院 Solid oxide fuel cell employing natural gas
CN103872366A (en) * 2012-12-12 2014-06-18 中国科学院上海硅酸盐研究所 Metal-supported solid oxide fuel cell and preparation method thereof
CN104364425A (en) * 2012-06-18 2015-02-18 旭化成株式会社 Bipolar alkaline water electrolysis unit and electrolytic cell
CN104638287A (en) * 2015-01-28 2015-05-20 潮州三环（集团）股份有限公司 Method for preparing anode-supported type solid oxide fuel battery
CN104916857A (en) * 2015-06-16 2015-09-16 华中科技大学 Planar solid oxide fuel cell
EP2660918A4 (en) * 2010-12-28 2016-08-10 Posco Solid oxide fule cell, method for manufacturing same, and tape casting device for manufacturing a fuel electrode
CN109904497A (en) * 2019-01-09 2019-06-18 华中科技大学 A kind of anti-carbon metal-supported solid oxide fuel cell and preparation method thereof
CN110224146A (en) * 2019-05-23 2019-09-10 湖北大学 A kind of online densifying method of fuel-cell electrolyte low temperature
CN110676480A (en) * 2019-09-29 2020-01-10 武汉华科福赛新能源有限责任公司 Porous tubular support body and preparation method thereof, and preparation method of composite cathode support body
CN111276705A (en) * 2020-01-06 2020-06-12 南京理工大学 Preparation method of metal-supported oxide fuel cell half cell
CN112448010A (en) * 2020-11-25 2021-03-05 广东石油化工学院 Preparation method of multi-layer structure composite block with porous sub-millimeter layer connected with high-compactness composite micron layer
CN112768704A (en) * 2021-01-12 2021-05-07 万华化学(四川)有限公司 Solid oxide fuel cell based on proton conduction type electrolyte and preparation method
CN113258112A (en) * 2021-07-16 2021-08-13 北京思伟特新能源科技有限公司 Preparation method of metal-supported solid oxide fuel cell and fuel cell
CN114530610A (en) * 2021-12-31 2022-05-24 浙江氢邦科技有限公司 Anode current collecting layer slurry and preparation method thereof, support body, solid oxide fuel cell and preparation method thereof
CN114914507A (en) * 2022-05-26 2022-08-16 西安交通大学 Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure
CN116813309A (en) * 2022-12-30 2023-09-29 安徽壹石通材料科技股份有限公司 Method for improving porosity of Ni-YSZ anode material
CN116845309A (en) * 2023-08-31 2023-10-03 中石油深圳新能源研究院有限公司 Solid oxide fuel cell and method for producing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3734027B2 (en) * 2001-11-30 2006-01-11 日産自動車株式会社 Single cell for solid oxide fuel cell
CN1588682A (en) * 2004-10-15 2005-03-02 华中科技大学 Plate type solid oxide fuel cell
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

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101894956B (en) * 2010-08-17 2012-10-03 哈尔滨工业大学 Method for preparing anode support with columnar orientation pores
CN101894956A (en) * 2010-08-17 2010-11-24 哈尔滨工业大学 Method for preparing anode support with columnar orientation pores
EP2660918A4 (en) * 2010-12-28 2016-08-10 Posco Solid oxide fule cell, method for manufacturing same, and tape casting device for manufacturing a fuel electrode
CN102437358A (en) * 2011-11-30 2012-05-02 中国科学技术大学 Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof
CN102437358B (en) * 2011-11-30 2013-12-11 中国科学技术大学 Three-layered structured oxide fuel cell supported by stainless steel and preparation method thereof
CN103165903A (en) * 2011-12-15 2013-06-19 江苏超洁绿色能源科技有限公司 Anti-carbon-deposition, high-performance and functionally-graded anode composite film of solid oxide fuel cells and preparation method thereof
CN102593478A (en) * 2012-01-18 2012-07-18 苏州华清京昆新能源科技有限公司 Method for manufacturing multilayer thin-film solid oxide fuel cell
CN102593478B (en) * 2012-01-18 2014-12-24 苏州华清京昆新能源科技有限公司 Method for manufacturing multilayer thin-film solid oxide fuel cell
CN104364425A (en) * 2012-06-18 2015-02-18 旭化成株式会社 Bipolar alkaline water electrolysis unit and electrolytic cell
US9683300B2 (en) 2012-06-18 2017-06-20 Asahi Kasei Kabushiki Kaisha Bipolar alkaline water electrolysis unit and electrolytic cell
CN103872366A (en) * 2012-12-12 2014-06-18 中国科学院上海硅酸盐研究所 Metal-supported solid oxide fuel cell and preparation method thereof
CN103613105B (en) * 2013-11-25 2016-01-06 中国科学院宁波材料技术与工程研究所 Monocell, its preparation method and application
CN103613105A (en) * 2013-11-25 2014-03-05 中国科学院宁波材料技术与工程研究所 Single cell as well as preparation method and application thereof
CN103682406B (en) * 2013-12-14 2015-11-18 济南开发区星火科学技术研究院 Utilize the Solid Oxide Fuel Cell of natural gas
CN103682406A (en) * 2013-12-14 2014-03-26 济南开发区星火科学技术研究院 Solid oxide fuel cell employing natural gas
CN104638287A (en) * 2015-01-28 2015-05-20 潮州三环（集团）股份有限公司 Method for preparing anode-supported type solid oxide fuel battery
CN104916857A (en) * 2015-06-16 2015-09-16 华中科技大学 Planar solid oxide fuel cell
CN104916857B (en) * 2015-06-16 2017-12-22 华中科技大学 A kind of flat solid oxide fuel cell
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
CN109904497A (en) * 2019-01-09 2019-06-18 华中科技大学 A kind of anti-carbon metal-supported solid oxide fuel cell and preparation method thereof
CN110224146A (en) * 2019-05-23 2019-09-10 湖北大学 A kind of online densifying method of fuel-cell electrolyte low temperature
CN110676480A (en) * 2019-09-29 2020-01-10 武汉华科福赛新能源有限责任公司 Porous tubular support body and preparation method thereof, and preparation method of composite cathode support body
CN111276705A (en) * 2020-01-06 2020-06-12 南京理工大学 Preparation method of metal-supported oxide fuel cell half cell
CN111276705B (en) * 2020-01-06 2021-01-26 南京理工大学 Preparation method of metal-supported oxide fuel cell half cell
CN112448010A (en) * 2020-11-25 2021-03-05 广东石油化工学院 Preparation method of multi-layer structure composite block with porous sub-millimeter layer connected with high-compactness composite micron layer
CN112448010B (en) * 2020-11-25 2021-08-10 广东石油化工学院 Preparation method of multi-layer structure composite block with porous sub-millimeter layer connected with high-compactness composite micron layer
WO2022110566A1 (en) * 2020-11-25 2022-06-02 广东石油化工学院 Preparation method for multi-layer composite block material with porous sub-millimeter layer connected to high-compactness composite micron layer
CN112768704A (en) * 2021-01-12 2021-05-07 万华化学(四川)有限公司 Solid oxide fuel cell based on proton conduction type electrolyte and preparation method
CN113258112A (en) * 2021-07-16 2021-08-13 北京思伟特新能源科技有限公司 Preparation method of metal-supported solid oxide fuel cell and fuel cell
CN114530610A (en) * 2021-12-31 2022-05-24 浙江氢邦科技有限公司 Anode current collecting layer slurry and preparation method thereof, support body, solid oxide fuel cell and preparation method thereof
CN114914507A (en) * 2022-05-26 2022-08-16 西安交通大学 Conductive flat tube support type solid oxide fuel cell/electrolytic cell, preparation method thereof and cell stack structure
CN116813309A (en) * 2022-12-30 2023-09-29 安徽壹石通材料科技股份有限公司 Method for improving porosity of Ni-YSZ anode material
CN116845309A (en) * 2023-08-31 2023-10-03 中石油深圳新能源研究院有限公司 Solid oxide fuel cell and method for producing the same

Also Published As

Publication number Publication date
CN101562255B (en) 2010-12-01

Similar Documents

Publication Publication Date Title
CN101562255B (en) Method for preparing metallic support type solid oxide fuel cell
Wang et al. A study of multilayer tape casting method for anode-supported planar type solid oxide fuel cells (SOFCs)
Xia et al. Microstructures, conductivities, and electrochemical properties of Ce0. 9Gd0. 1O2 and GDC–Ni anodes for low-temperature SOFCs
Basu et al. Processing of high-performance anode-supported planar solid oxide fuel cell
EP2380231B1 (en) Thermal shock-tolerant solid oxide fuel cell stack
EP1768208A2 (en) High performance anode-supported solid oxide fuel cell
CA2844311C (en) Composite anode for a solid oxide fuel cell with improved mechanical integrity and increased efficiency
CN101577340B (en) Method for preparing cathode-supported tubular solid oxide fuel cells
US20080193803A1 (en) Precursor Infiltration and Coating Method
Dayaghi et al. Stainless steel-supported solid oxide fuel cell with La0. 2Sr0. 8Ti0. 9Ni0. 1O3− δ/yttria-stabilized zirconia composite anode
JP6658754B2 (en) Solid oxide fuel cell and method for producing electrolyte layer-anode assembly
CN102903945A (en) Method for preparing large-size flat plate type metal supporting solid oxide fuel cell
CN107017423B (en) Low-temperature solid oxide fuel cell and preparation method thereof
Kong et al. A cost-effective process for fabrication of metal-supported solid oxide fuel cells
Wang et al. Effects of bi-layer La0. 6Sr0. 4Co0. 2Fe0. 8O3− δ-based cathodes on characteristics of intermediate temperature solid oxide fuel cells
JP6370696B2 (en) Cell structure, electrolyte membrane-electrode assembly, and fuel cell
Zhou et al. Metal-supported solid oxide fuel cells with in-situ sintered (Bi2O3) 0.7 (Er2O3) 0.3–Ag composite cathode
Ye et al. Use of La0. 75Sr0. 25Cr0. 5Mn0. 5O3 materials in composite anodes for direct ethanol solid oxide fuel cells
Zhao et al. Fabrication and characterization of a cathode-supported tubular solid oxide fuel cell
Timurkutluk et al. Fabrication and optimization of LSM infiltrated cathode electrode for anode supported microtubular solid oxide fuel cells
KR101680626B1 (en) protonic ceramic fuel cells and manufacturing method thereof
Han et al. Fabrication and properties of anode-supported solid oxide fuel cell
EP3343682B1 (en) Flat plate-shaped solid oxide fuel cell and cell module comprising same
AU2009298955B2 (en) Optimized cell configurations for stable LSCF-based solid oxide fuel cells
ur Rehman et al. Fabrication and characterization of La0. 65Sr0. 3MnO3− δ/(Y2O3) 0.08 (ZrO2) 0.92/Gd0. 1Ce0. 9O2− δ tri-composite cathode-supported tubular direct carbon solid oxide fuel cell

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
ASS Succession or assignment of patent right

Owner name: SHENZHEN CHINA SOFC LTD.

Free format text: FORMER OWNER: HUAZHONG SCINECE AND TECHNOLOGY UNIV

Effective date: 20110513

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 430074 NO. 1037, LUOYU ROAD, HONGSHAN DISTRICT, WUHAN CITY, HUBEI PROVINCE TO: 518033 37/F, INTERNATIONAL SCIENCE AND TECHNOLOGY BUILDING, MIDDLE ROAD, SHENNAN AVENUE, FUTIAN DISTRICT, SHENZHEN CITY, GUANGDONG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20110513

Address after: 37, 518033 floor, international science and technology building, Shennan Road, Shenzhen, Guangdong, Futian District

Patentee after: China SOFC Ltd.

Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037

Patentee before: Huazhong University of Science and Technology

ASS Succession or assignment of patent right

Owner name: CHINA SOFC LTD.

Free format text: FORMER OWNER: SHENZHEN CHINA SOFC, LTD.

Effective date: 20111123

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 518033 SHENZHEN, GUANGDONG PROVINCE TO: 211400 YANGZHOU, JIANGSU PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20111123

Address after: 211400, No. 2, Tai Tai Road, Yizheng Economic Development Zone, Yangzhou, Jiangsu

Patentee after: Yizheng Boyuan in Amperex Technology Limited

Address before: 37, 518033 floor, international science and technology building, Shennan Road, Shenzhen, Guangdong, Futian District

Patentee before: China SOFC Ltd.

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: 20101201

Termination date: 20190519