CN105449249A - Chip-type solid oxide fuel cell with quasi-symmetric structure and manufacturing method therefor - Google Patents

Chip-type solid oxide fuel cell with quasi-symmetric structure and manufacturing method therefor Download PDF

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CN105449249A
CN105449249A CN201510946500.9A CN201510946500A CN105449249A CN 105449249 A CN105449249 A CN 105449249A CN 201510946500 A CN201510946500 A CN 201510946500A CN 105449249 A CN105449249 A CN 105449249A
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左艳波
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • 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
    • H01M8/1097—Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
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Abstract

The invention relates to the technical field of a solid oxide fuel cell, and in particular to a chip-type solid oxide fuel cell with a quasi-symmetric structure and a manufacturing method therefor. According to the chip-type solid oxide fuel cell with the quasi-symmetric structure and the manufacturing method therefor, the adoption of the chip-type solid oxide fuel cell with the quasi-symmetric structure solves the problem of unmatched sintering and shrinkage of a conventional nickel-based positive electrode supporting type single battery, the flatness of the single battery is fully ensured, and the sealing success rate in battery stacking is improved; the problem of sudden change of volume of the conventional nickel-based positive electrode supporting type single battery in an oxidation-reduction process is solved, the cold and hot circulation capacity of the battery stack is improved, and the service life of the battery stack is prolonged; and the chemical compatibility between novel electrodes with higher catalytic activity and electrolyte materials is realized, the working temperature of the single battery is reduced, and the power output level of the single battery is improved.

Description

A kind of chip-type solid oxide fuel cell with accurate symmetrical structure and preparation method thereof
Technical field
The present invention relates to and belong to Solid Oxide Fuel Cell technical field, particularly relate to a kind of chip-type solid oxide fuel cell with accurate symmetrical structure and preparation method thereof.
Background technology
Solid Oxide Fuel Cell is all solid state electrochemical appliance that a kind of chemical energy by hydrogen, natural gas and biogas fuel is converted into electric energy.There is the remarkable advantages such as efficient, clean, noiseless.SOFC monocell can be divided into tubular type and the large fundamental type of chip two.Wherein, chip monocell, due to advantages such as the output power density of unit volume are large, dress pile structure is compacter, obtains extensive attention.A developing direction of current chip SOFC monocell is middle low temperature, and reason is, can reducing the seal request of monocell when filling heap, reducing the material requirements to bipolar plates, reduce battery pile production cost, promote the life-span etc. of battery pile.By thinning for dielectric substrate and electrode that is that select catalytic activity higher and electrolyte by low temperature in SOFC effective means.When chip SOFC monocell is filled heap together with other assemblies, must solve the thickness matching sex chromosome mosaicism of each inter-module, therefore this just proposes higher requirement to the evenness of SOFC monocell.The Ni-based anode support type chip SOFC monocell of current routine shrinks unmatched problem because the asymmetry of structural design causes large area chip SOFC monocell to exist in sintering process between each functional layer, and then causes monocell to occur the defects such as bending, distortion.In addition, the volume discontinuities problem of Ni-based anode in oxidation-reduction process, easily causes monocell in oxidation-reduction process, occur cracking, and then causes whole pile seal failure, even occur safety problem.
The electrode that existing a lot of catalytic activity is higher at present and electrolyte are developed.Common are lanthanum strontium gallium magnesium (LSGM), gadolinium doped-ceria (GDC), samarium doping cerium oxide (SDC), lanthanum strontium ferro-cobalt (LSCoF), samarium strontium cobalt (SSC), barium samarium doped strontium cobalt (SBSCO) etc.But these materials are as also there are some problems to be solved when SOFC electrode or electrolyte.Such as within the scope of the nominal sintering temperatures of about 1300-1400 DEG C, the problem of the chemical incompatibility of LSGM and other many typical materials, the problem of the electronic conductivity of GDC in redox condition.There is the problem of high-temperature chemical reaction in LSCoF and YSZ electrolyte, etc.
Based on the problems referred to above that existing technology exists, the invention provides a kind of chip-type solid oxide fuel cell with accurate symmetrical structure and preparation method thereof, this use with the chip-type solid oxide fuel cell of accurate symmetrical structure solves the unmatched problem of sintering shrinkage of conventional Ni-based anode support type monocell, fully ensure that the evenness of monocell, promote battery dress heap time be sealed to power; Solve the volume discontinuities problem of conventional Ni-based anode support type monocell in oxidation-reduction process, improve the cold cycling ability of battery pile, improve cell stack life level; Solve the chemical compatibility issues between the active higher electrode of new catalytic and electrolyte, reduce the working temperature of monocell, promote the power stage level of monocell.
Summary of the invention
In order to overcome the defect existed in background technology, the technical solution adopted for the present invention to solve the technical problems is: a kind of chip-type solid oxide fuel cell with accurate symmetrical structure, described chip-type solid oxide fuel cell is made up of the battery skeleton and the active electrode material be carried in battery skeleton with symmetrical structure, described battery skeleton is three-decker, described battery skeleton forms with the porous electrode casing play being positioned at both sides by being positioned at middle dense electrolyte layer, described active electrode material comprises active material of cathode and active material of positive electrode, described active material of cathode is positioned on the duct inwall of battery skeleton side porous electrode casing play, and the porous electrode casing play being loaded with active material of cathode is called porous cathode layer, described active material of positive electrode is positioned on the duct inwall of the porous electrode casing play of battery skeleton opposite side, and the porous electrode casing play being loaded with active material of positive electrode is called porous anode layer.
The thickness of preferred described dense electrolyte layer is 5-50 micron, and the thickness of described porous electrode casing play is 0.2-2 millimeter, and the open-cell porosity of described porous electrode casing play is 5%-80%.
The material of preferred described dense electrolyte layer is one or more in YSZ, SSZ, GDC and LSGM; Described YSZ is yttrium stable zirconium oxide, and wherein doped yttrium amount is 3%-8%/mol; Described SSZ is scandium stabilizing zirconia, and wherein scandium doping is 3%-10%/mol; Described GDC is gadolinium doped-ceria, and wherein Gd2 O3 amount is 5%-25%/mol; Described LSGM is lanthanum strontium gallium magnesium (La1-xSrxGa1-yMgyO 3-δ, wherein 0<x≤0.8,0<y≤0.8).
The material of preferred described porous electrode casing play is one or more in LSCrF-YSZ, LSCrF-SSZ, LSCrF-GDC and LSCrF-LSGM; Described LSCrF is lanthanum strontium ferrochrome (La1-xSrxCr1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8); Described LSCrF-YSZ is that LSCrF and YSZ is composited in proportion, and ratio is wherein LSCrF:YSZ=20-80:80-20 (volume ratio); Described LSCrF-SSZ is that LSCrF and SSZ is composited in proportion, and ratio is wherein LSCrF:SSZ=20-80:80-20 (volume ratio); Described LSCrF-GDC is that LSCrF and GDC is composited in proportion, and ratio is wherein LSCrF:GDC=20-80:80-20 (volume ratio); Described LSCrF-LSGM is that LSCrF and LSGM is composited in proportion, and ratio is wherein LSCrF:LSGM=20-80:80-20 (volume ratio).
Preferred described active material of cathode is one or more in LSCoF-SDC, LSCoF-GDC, SSC and SBSCO; Described LSCoF is lanthanum strontium ferro-cobalt (La1-xSrxCo1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8); Described SDC is samarium doping cerium oxide, and wherein samarium doping amount is 5%-25%/mol; Described SSC is SmSrCo 2o 5; Described SBSCO is SmBaxSr1-xCo 2o 5, wherein 0<x≤0.8; Described LSCoF-SDC is that LSCoF and SDC is composited in proportion, and ratio is wherein LSCoF:SDC=20-80:80-20 (volume ratio); Described LSCoF-GDC is that LSCoF and GDC is composited in proportion, and ratio is wherein LSCoF:GDC=20-80:80-20 (volume ratio).
Preferred described active material of positive electrode is Ni-SDC, Ni-GDC and LNF (LaNixFe1-xO 3-δ) one or more wherein in 0<x≤0.8; Described Ni-SDC is that nickel and SDC are composited in proportion, wherein Ni; SDC=20-80:80-20 (volume ratio); Described Ni-GDC is that nickel and GDC are composited in proportion, wherein Ni; GDC=20-80:80-20 (volume ratio).
Described a kind of manufacture method with the chip-type solid oxide fuel cell of accurate symmetrical structure, the steps include:
(1), with one or more in YSZ, SSZ, GDC and LSGM powder for raw material, fully mix with dispersant, binding agent, plasticiser and solvent, described dispersant weight percentage is 0.5-10wt%, described weight of binder percentage is 0.5-10wt%, and described plasticiser percentage by weight is 0.5-10wt%.Described solvent weight percent is 0.5-40wt%, is made into slurry one;
(2), by slurry one described in step (1) by flow casting molding and the obtained electrolyte laminin embryo of oven dry, and cutting is carried out in order to using according to dimensional requirement;
(3), one or more in YSZ, SSZ, GDC and LSGM powder are mixed with LSCrF powder, fully mix with dispersant, pore creating material, binding agent, plasticiser and solvent again, described dispersant weight percentage is 0.5-10wt%, described pore creating material percentage by weight is 5-50wt%, described weight of binder percentage is 0.5-10wt%, described plasticiser percentage by weight is 0.5-10wt%, described solvent weight percent is 0.5-40wt%, is made into slurry two;
(4), by slurry two-way described in step (3) cross flow casting molding and dry obtained electrode laminin embryo, and carry out cutting in order to using according to dimensional requirement;
(5), according to battery size requirement, electrolyte laminin embryo described in step (2) and step (4) and electrode laminin embryo are carried out lamination alignment according to the order of " M layer electrode laminin embryo | N layer electrolyte laminin embryo | M ' layer electrode laminin embryo ", wherein 1≤M=M '≤20,1≤N≤10;
(6), by the plain embryo described in step (5) after lamination alignment carry out lamination, in pressure layer process, temperature is 25-85 DEG C, and pressure is 10-50MPa, and the dwell time is 10-30 minute, obtains battery skeleton element embryo;
(7), by the element of battery skeleton described in step (6) embryo put into sintering furnace high temperature sintering, high temperature sintering heating step is: rise to 750-800 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 0.5-2h; Then be warming up to 1300-1450 DEG C with the heating rate of 2-5 DEG C/min from 750-800 DEG C, and be incubated 2-10h; Then be cooled to 800 DEG C with the rate of temperature fall of 3-5 DEG C/min from 1300-1450 DEG C after, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 800 DEG C, obtain battery skeleton;
(8), lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate and deionized water and citric acid are made into LSCoF solution; Samaric nitrate and cerous nitrate and deionized water and citric acid are made into SDC solution; Gadolinium nitrate and cerous nitrate and deionized water and citric acid are made into GDC solution; Samaric nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SSC solution; Samaric nitrate, barium nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SBSCO solution; LSCoF solution and SDC solution are mixed and obtains LSCoF-SDC mixed solution; LSCoF solution and GDC solution are mixed and obtains LSCoF-GDC mixed solution, above solution or mixed solution are referred to as cathode dipping solution;
(9), with cathode dipping solution described in liquid shifting equipment aspiration step (8), be arranged in the cathode porous layer of battery skeleton side uniformly on the surface, immerse behind cathode porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60-85 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 2-3h; Then be warming up to 600-900 DEG C with the heating rate of 2-5 DEG C/min from 60-85 DEG C, and be incubated 2-10h; Then be cooled to 200 DEG C with the rate of temperature fall of 2-5 DEG C/min from 600-900 DEG C, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in cathode dipping solution become cathode active material;
(10) step (9), is repeated until the cathode active material of cathode porous layer load reaches required amount;
(11), SDC solution described in nickel nitrate solution and step (8) is mixed obtain Ni-SDC mixed solution; GDC solution described in nickel nitrate solution and step (8) is mixed and obtains Ni-GDC mixed solution; Lanthanum nitrate, nickel nitrate and ferric nitrate and deionized water and citric acid are made into LNF solution, above solution or mixed solution are referred to as anode pickling solution;
(12), anode pickling solution described in appropriate step (11) is drawn with liquid shifting equipment, be arranged in the anodic porous layer of the other side of battery skeleton uniformly on the surface, immerse behind anodic porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60-85 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 2-3h; Then be warming up to 600-900 DEG C with the heating rate of 2-5 DEG C/min from 60-85 DEG C, and be incubated 2-10h; Then be cooled to 200 DEG C with the rate of temperature fall of 2-5 DEG C/min from 600-900 DEG C, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in anode pickling solution become anode active material;
(13) step 12, is repeated until the anode active material of anodic porous layer load reaches required amount;
(14), with cutting equipment there is the battery skeleton of anode active material and cathode active material to carry out cutting processing according to required size load, obtain the chip-type solid oxide fuel cell finished product with accurate symmetrical structure.
The invention provides a kind of chip-type solid oxide fuel cell with accurate symmetrical structure and preparation method thereof, this use with the chip-type solid oxide fuel cell of accurate symmetrical structure solves the unmatched problem of sintering shrinkage of conventional Ni-based anode support type monocell, fully ensure that the evenness of monocell, promote battery dress heap time be sealed to power; Solve the volume discontinuities problem of conventional Ni-based anode support type monocell in oxidation-reduction process, improve the cold cycling ability of battery pile, improve cell stack life level; Solve the chemical compatibility issues between the active higher electrode of new catalytic and electrolyte, reduce the working temperature of monocell, promote the power stage level of monocell.
Embodiment
Specific embodiment one, a kind of chip-type solid oxide fuel cell with accurate symmetrical structure, it is characterized in that: described chip-type solid oxide fuel cell is made up of the battery skeleton and the active electrode material be carried in battery skeleton with symmetrical structure, described battery skeleton is three-decker, described battery skeleton forms with the porous electrode casing play being positioned at both sides by being positioned at middle dense electrolyte layer, described active electrode material comprises active material of cathode and active material of positive electrode, described active material of cathode is positioned on the duct inwall of battery skeleton side porous electrode casing play, and the porous electrode casing play being loaded with active material of cathode is called porous cathode layer, described active material of positive electrode is positioned on the duct inwall of the porous electrode casing play of battery skeleton opposite side, and the porous electrode casing play being loaded with active material of positive electrode is called porous anode layer, the thickness of described dense electrolyte layer is 5 microns, the thickness of described porous electrode casing play is 0.2 millimeter, the open-cell porosity of described porous electrode casing play is 5%, the material of described dense electrolyte layer is YSZ, SSZ, one or more in GDC and LSGM, described YSZ is yttrium stable zirconium oxide, and wherein doped yttrium amount is 3%/mol, described SSZ is scandium stabilizing zirconia, and wherein scandium doping is 3%/mol, described GDC is gadolinium doped-ceria, and wherein Gd2 O3 amount is 5%/mol, described LSGM is lanthanum strontium gallium magnesium (La1-xSrxGa1-yMgyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), the material of described porous electrode casing play is one or more in LSCrF-YSZ, LSCrF-SSZ, LSCrF-GDC and LSCrF-LSGM, described LSCrF is lanthanum strontium ferrochrome (La1-xSrxCr1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described LSCrF-YSZ is that LSCrF and YSZ is composited in proportion, and ratio is wherein LSCrF:YSZ=1:4 (volume ratio), described LSCrF-SSZ is that LSCrF and SSZ is composited in proportion, and ratio is wherein LSCrF:SSZ=1:4 (volume ratio), described LSCrF-GDC is that LSCrF and GDC is composited in proportion, and ratio is wherein LSCrF:GDC=1:4 (volume ratio), described LSCrF-LSGM is that LSCrF and LSGM is composited in proportion, and ratio is wherein LSCrF:LSGM=1:4 (volume ratio), and described active material of cathode is one or more in LSCoF-SDC, LSCoF-GDC, SSC and SBSCO, described LSCoF is lanthanum strontium ferro-cobalt (La1-xSrxCo1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described SDC is samarium doping cerium oxide, and wherein samarium doping amount is 5%/mol, described SSC is SmSrCo 2o 5, described SBSCO is SmBaxSr1-xCo 2o 5, wherein 0<x≤0.8, described LSCoF-SDC is that LSCoF and SDC is composited in proportion, and ratio is wherein LSCoF:SDC=1:4 (volume ratio), described LSCoF-GDC is that LSCoF and GDC is composited in proportion, and ratio is wherein LSCoF:GDC=1:4 (volume ratio), and described active material of positive electrode is Ni-SDC, Ni-GDC and LNF (LaNixFe1-xO 3-δ) one or more wherein in 0<x≤0.8, described Ni-SDC is that nickel and SDC are composited in proportion, wherein Ni, SDC=1:4 (volume ratio), described Ni-GDC is that nickel and GDC are composited in proportion, wherein Ni, GDC=1:4 (volume ratio).
Described a kind of manufacture method with the chip-type solid oxide fuel cell of accurate symmetrical structure, is characterized in that the steps include:
(1), with one or more in YSZ, SSZ, GDC and LSGM powder for raw material, fully mix with dispersant, binding agent, plasticiser and solvent, described dispersant weight percentage is 0.5wt%, described weight of binder percentage is 0.5wt%, and described plasticiser percentage by weight is 0.5wt%.Described solvent weight percent is 0.5wt%, is made into slurry one;
(2), by slurry one described in step (1) by flow casting molding and the obtained electrolyte laminin embryo of oven dry, and cutting is carried out in order to using according to dimensional requirement;
(3), one or more in YSZ, SSZ, GDC and LSGM powder are mixed with LSCrF powder, fully mix with dispersant, pore creating material, binding agent, plasticiser and solvent again, described dispersant weight percentage is 0.5%, described pore creating material percentage by weight is 5wt%, described weight of binder percentage is 0.5wt%, described plasticiser percentage by weight is 0.5wt%, and described solvent weight percent is 0.5wt%, is made into slurry two;
(4), by slurry two-way described in step (3) cross flow casting molding and dry obtained electrode laminin embryo, and carry out cutting in order to using according to dimensional requirement;
(5), according to battery size requirement, electrolyte laminin embryo described in step (2) and step (4) and electrode laminin embryo are carried out lamination alignment according to the order of " M layer electrode laminin embryo | N layer electrolyte laminin embryo | M ' layer electrode laminin embryo ", wherein 1≤M=M '≤20,1≤N≤10;
(6), by the plain embryo described in step (5) after lamination alignment carry out lamination, in pressure layer process, temperature is 25 DEG C, and pressure is 10MPa, and the dwell time is 10 minutes, obtains battery skeleton element embryo;
(7), by the element of battery skeleton described in step (6) embryo put into sintering furnace high temperature sintering, high temperature sintering heating step is: rise to 750 DEG C with the heating rate of 1 DEG C/min from room temperature, and be incubated 0.5h; Then be warming up to 1300 DEG C with the heating rate of 2 DEG C/min from 750 DEG C, and be incubated 2h; Then be cooled to 800 DEG C with the rate of temperature fall of 3 DEG C/min from 1300 DEG C after, be finally down to room temperature with the rate of temperature fall of 5 DEG C/min from 800 DEG C, obtain battery skeleton;
(8), lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate and deionized water and citric acid are made into LSCoF solution; Samaric nitrate and cerous nitrate and deionized water and citric acid are made into SDC solution; Gadolinium nitrate and cerous nitrate and deionized water and citric acid are made into GDC solution; Samaric nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SSC solution; Samaric nitrate, barium nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SBSCO solution; LSCoF solution and SDC solution are mixed and obtains LSCoF-SDC mixed solution; LSCoF solution and GDC solution are mixed and obtains LSCoF-GDC mixed solution, above solution or mixed solution are referred to as cathode dipping solution;
(9), with cathode dipping solution described in liquid shifting equipment aspiration step (8), be arranged in the cathode porous layer of battery skeleton side uniformly on the surface, immerse behind cathode porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60 DEG C with the heating rate of 1 DEG C/min from room temperature, and be incubated 2h; Then be warming up to 600 DEG C with the heating rate of 2 DEG C/min from 60 DEG C, and be incubated 2h; Then be cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min from 600 DEG C, be finally down to room temperature with the rate of temperature fall of 5 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in cathode dipping solution become cathode active material;
(10) step (9), is repeated until the cathode active material of cathode porous layer load reaches required amount;
(11), SDC solution described in nickel nitrate solution and step (8) is mixed obtain Ni-SDC mixed solution; GDC solution described in nickel nitrate solution and step (8) is mixed and obtains Ni-GDC mixed solution; Lanthanum nitrate, nickel nitrate and ferric nitrate and deionized water and citric acid are made into LNF solution, above solution or mixed solution are referred to as anode pickling solution;
(12), anode pickling solution described in appropriate step (11) is drawn with liquid shifting equipment, be arranged in the anodic porous layer of the other side of battery skeleton uniformly on the surface, immerse behind anodic porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60 DEG C with the heating rate of 1 DEG C/min from room temperature, and be incubated 2h; Then be warming up to 600 DEG C with the heating rate of 2 DEG C/min from 60 DEG C, and be incubated 2h; Then be cooled to 200 DEG C with the rate of temperature fall of 2 DEG C/min from 600 DEG C, be finally down to room temperature with the rate of temperature fall of 5 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in anode pickling solution become anode active material;
(13) step 12, is repeated until the anode active material of anodic porous layer load reaches required amount;
(14), with cutting equipment there is the battery skeleton of anode active material and cathode active material to carry out cutting processing according to required size load, obtain the chip-type solid oxide fuel cell finished product with accurate symmetrical structure.
Specific embodiment two, a kind of chip-type solid oxide fuel cell with accurate symmetrical structure, it is characterized in that: described chip-type solid oxide fuel cell is made up of the battery skeleton and the active electrode material be carried in battery skeleton with symmetrical structure, described battery skeleton is three-decker, described battery skeleton forms with the porous electrode casing play being positioned at both sides by being positioned at middle dense electrolyte layer, described active electrode material comprises active material of cathode and active material of positive electrode, described active material of cathode is positioned on the duct inwall of battery skeleton side porous electrode casing play, and the porous electrode casing play being loaded with active material of cathode is called porous cathode layer, described active material of positive electrode is positioned on the duct inwall of the porous electrode casing play of battery skeleton opposite side, and the porous electrode casing play being loaded with active material of positive electrode is called porous anode layer, the thickness of described dense electrolyte layer is 35 microns, the thickness of described porous electrode casing play is 1 millimeter, the open-cell porosity of described porous electrode casing play is 55%, the material of described dense electrolyte layer is YSZ, SSZ, one or more in GDC and LSGM, described YSZ is yttrium stable zirconium oxide, and wherein doped yttrium amount is, 6%/mol, described SSZ is scandium stabilizing zirconia, and wherein scandium doping is 7%/mol, described GDC is gadolinium doped-ceria, and wherein Gd2 O3 amount is 18%/mol, described LSGM is lanthanum strontium gallium magnesium (La1-xSrxGa1-yMgyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), the material of described porous electrode casing play is one or more in LSCrF-YSZ, LSCrF-SSZ, LSCrF-GDC and LSCrF-LSGM, described LSCrF is lanthanum strontium ferrochrome (La1-xSrxCr1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described LSCrF-YSZ is that LSCrF and YSZ is composited in proportion, and ratio is wherein LSCrF:YSZ=, 1:1 (volume ratio), described LSCrF-SSZ is that LSCrF and SSZ is composited in proportion, and ratio is wherein LSCrF:SSZ=1:1 (volume ratio), described LSCrF-GDC is that LSCrF and GDC is composited in proportion, and ratio is wherein LSCrF:GDC=20-80:80-20 (volume ratio), described LSCrF-LSGM is that LSCrF and LSGM is composited in proportion, and ratio is wherein LSCrF:LSGM=1:1 (volume ratio), and described active material of cathode is one or more in LSCoF-SDC, LSCoF-GDC, SSC and SBSCO, described LSCoF is lanthanum strontium ferro-cobalt (La1-xSrxCo1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described SDC is samarium doping cerium oxide, and wherein samarium doping amount is, 17%/mol, described SSC is SmSrCo 2o 5, described SBSCO is SmBaxSr1-xCo 2o 5, wherein 0<x≤0.8, described LSCoF-SDC is that LSCoF and SDC is composited in proportion, and ratio is wherein LSCoF:SDC=20-80:80-20 (volume ratio), described LSCoF-GDC is that LSCoF and GDC is composited in proportion, and ratio is wherein LSCoF:GDC=1:1 (volume ratio), and described active material of positive electrode is Ni-SDC, Ni-GDC and LNF (LaNixFe1-xO 3-δ) one or more wherein in 0<x≤0.8, described Ni-SDC is that nickel and SDC are composited in proportion, wherein Ni, SDC=, 1:1 (volume ratio), described Ni-GDC is that nickel and GDC are composited in proportion, wherein Ni, GDC=1:1 (volume ratio).
Described a kind of manufacture method with the chip-type solid oxide fuel cell of accurate symmetrical structure, the steps include:
(1), with one or more in YSZ, SSZ, GDC and LSGM powder for raw material, fully mix with dispersant, binding agent, plasticiser and solvent, described dispersant weight percentage is 6wt%, described weight of binder percentage is 6wt%, and described plasticiser percentage by weight is 6wt%.Described solvent weight percent is 20wt%, is made into slurry one;
(2), by slurry one described in step (1) by flow casting molding and the obtained electrolyte laminin embryo of oven dry, and cutting is carried out in order to using according to dimensional requirement;
(3), one or more in YSZ, SSZ, GDC and LSGM powder are mixed with LSCrF powder, fully mix with dispersant, pore creating material, binding agent, plasticiser and solvent again, described dispersant weight percentage is 6wt%, described pore creating material percentage by weight is 25wt%, described weight of binder percentage is 6wt%, described plasticiser percentage by weight is 6wt%, and described solvent weight percent is 20wt%, is made into slurry two;
(4), by slurry two-way described in step (3) cross flow casting molding and dry obtained electrode laminin embryo, and carry out cutting in order to using according to dimensional requirement;
(5), according to battery size requirement, electrolyte laminin embryo described in step (2) and step (4) and electrode laminin embryo are carried out lamination alignment according to the order of " M layer electrode laminin embryo | N layer electrolyte laminin embryo | M ' layer electrode laminin embryo ", wherein 1≤M=M '≤20,1≤N≤10;
(6), by the plain embryo described in step (5) after lamination alignment carry out lamination, in pressure layer process, temperature is 25-85 DEG C, and pressure is 30MPa, and the dwell time is 20 minutes, obtains battery skeleton element embryo;
(7), by the element of battery skeleton described in step (6) embryo put into sintering furnace high temperature sintering, high temperature sintering heating step is: rise to 760 DEG C with the heating rate of 1.5 DEG C/min from room temperature, and be incubated 1h; Then be warming up to 1400 DEG C with the heating rate of 3 DEG C/min from 760 DEG C, and be incubated 7h; Then be cooled to 800 DEG C with the rate of temperature fall of 4 DEG C/min from 1400 DEG C after, be finally down to room temperature with the rate of temperature fall of 8 DEG C/min from 800 DEG C, obtain battery skeleton;
(8), lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate and deionized water and citric acid are made into LSCoF solution; Samaric nitrate and cerous nitrate and deionized water and citric acid are made into SDC solution; Gadolinium nitrate and cerous nitrate and deionized water and citric acid are made into GDC solution; Samaric nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SSC solution; Samaric nitrate, barium nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SBSCO solution; LSCoF solution and SDC solution are mixed and obtains LSCoF-SDC mixed solution; LSCoF solution and GDC solution are mixed and obtains LSCoF-GDC mixed solution, above solution or mixed solution are referred to as cathode dipping solution;
(9), with cathode dipping solution described in liquid shifting equipment aspiration step (8), be arranged in the cathode porous layer of battery skeleton side uniformly on the surface, immerse behind cathode porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 75 DEG C with the heating rate of 1.5 DEG C/min from room temperature, and be incubated 2.5h; Then be warming up to 800 DEG C with the heating rate of 3 DEG C/min from 75 DEG C, and be incubated 6h; Then be cooled to 200 DEG C with the rate of temperature fall of 3 DEG C/min from 800 DEG C, be finally down to room temperature with the rate of temperature fall of 7 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in cathode dipping solution become cathode active material;
(10) step (9), is repeated until the cathode active material of cathode porous layer load reaches required amount;
(11), SDC solution described in nickel nitrate solution and step (8) is mixed obtain Ni-SDC mixed solution; GDC solution described in nickel nitrate solution and step (8) is mixed and obtains Ni-GDC mixed solution; Lanthanum nitrate, nickel nitrate and ferric nitrate and deionized water and citric acid are made into LNF solution, above solution or mixed solution are referred to as anode pickling solution;
(12), anode pickling solution described in appropriate step (11) is drawn with liquid shifting equipment, be arranged in the anodic porous layer of the other side of battery skeleton uniformly on the surface, immerse behind anodic porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 75 DEG C with the heating rate of 1.5 DEG C/min from room temperature, and be incubated 2.5h; Then be warming up to 800 DEG C with the heating rate of 3 DEG C/min from 75 DEG C, and be incubated 6h; Then be cooled to 200 DEG C with the rate of temperature fall of 3 DEG C/min from 800 DEG C, be finally down to room temperature with the rate of temperature fall of 7 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in anode pickling solution become anode active material;
(13) step 12, is repeated until the anode active material of anodic porous layer load reaches required amount;
(14), with cutting equipment there is the battery skeleton of anode active material and cathode active material to carry out cutting processing according to required size load, obtain the chip-type solid oxide fuel cell finished product with accurate symmetrical structure.
Specific embodiment three, a kind of chip-type solid oxide fuel cell with accurate symmetrical structure, it is characterized in that: described chip-type solid oxide fuel cell is made up of the battery skeleton and the active electrode material be carried in battery skeleton with symmetrical structure, described battery skeleton is three-decker, described battery skeleton forms with the porous electrode casing play being positioned at both sides by being positioned at middle dense electrolyte layer, described active electrode material comprises active material of cathode and active material of positive electrode, described active material of cathode is positioned on the duct inwall of battery skeleton side porous electrode casing play, and the porous electrode casing play being loaded with active material of cathode is called porous cathode layer, described active material of positive electrode is positioned on the duct inwall of the porous electrode casing play of battery skeleton opposite side, and the porous electrode casing play being loaded with active material of positive electrode is called porous anode layer, the thickness of described dense electrolyte layer is 50 microns, the thickness of described porous electrode casing play is 2 millimeters, the open-cell porosity of described porous electrode casing play is 80%, the material of described dense electrolyte layer is YSZ, SSZ, one or more in GDC and LSGM, described YSZ is yttrium stable zirconium oxide, and wherein doped yttrium amount is 8%/mol, described SSZ is scandium stabilizing zirconia, and wherein scandium doping is 10%/mol, described GDC is gadolinium doped-ceria, and wherein Gd2 O3 amount is 25%/mol, described LSGM is lanthanum strontium gallium magnesium (La1-xSrxGa1-yMgyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), the material of described porous electrode casing play is one or more in LSCrF-YSZ, LSCrF-SSZ, LSCrF-GDC and LSCrF-LSGM, described LSCrF is lanthanum strontium ferrochrome (La1-xSrxCr1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described LSCrF-YSZ is that LSCrF and YSZ is composited in proportion, and ratio is wherein LSCrF:YSZ=4:1 (volume ratio), described LSCrF-SSZ is that LSCrF and SSZ is composited in proportion, and ratio is wherein LSCrF:SSZ=4:1 (volume ratio), described LSCrF-GDC is that LSCrF and GDC is composited in proportion, and ratio is wherein LSCrF:GDC=20-80:80-20 (volume ratio), described LSCrF-LSGM is that LSCrF and LSGM is composited in proportion, and ratio is wherein LSCrF:LSGM=4:1 (volume ratio), and described active material of cathode is one or more in LSCoF-SDC, LSCoF-GDC, SSC and SBSCO, described LSCoF is lanthanum strontium ferro-cobalt (La1-xSrxCo1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8), described SDC is samarium doping cerium oxide, and wherein samarium doping amount is 5%-25%/mol, described SSC is SmSrCo 2o 5, described SBSCO is SmBaxSr1-xCo 2o 5, wherein 0<x≤0.8, described LSCoF-SDC is that LSCoF and SDC is composited in proportion, and ratio is wherein LSCoF:SDC=4:1 (volume ratio), described LSCoF-GDC is that LSCoF and GDC is composited in proportion, and ratio is wherein LSCoF:GDC=4:1 (volume ratio), and described active material of positive electrode is Ni-SDC, Ni-GDC and LNF (LaNixFe1-xO 3-δ) one or more wherein in 0<x≤0.8, described Ni-SDC is that nickel and SDC are composited in proportion, wherein Ni, SDC=, 4:1 (volume ratio), described Ni-GDC is that nickel and GDC are composited in proportion, wherein Ni, GDC=4:1 (volume ratio).
Described a kind of manufacture method with the chip-type solid oxide fuel cell of accurate symmetrical structure, the steps include:
(1), with one or more in YSZ, SSZ, GDC and LSGM powder for raw material, fully mix with dispersant, binding agent, plasticiser and solvent, described dispersant weight percentage is 10wt%, described weight of binder percentage is 10wt%, and described plasticiser percentage by weight is 10wt%.Described solvent weight percent is 40wt%, is made into slurry one;
(2), by slurry one described in step (1) by flow casting molding and the obtained electrolyte laminin embryo of oven dry, and cutting is carried out in order to using according to dimensional requirement;
(3), one or more in YSZ, SSZ, GDC and LSGM powder are mixed with LSCrF powder, fully mix with dispersant, pore creating material, binding agent, plasticiser and solvent again, described dispersant weight percentage is 10wt%, described pore creating material percentage by weight is 35wt%, described weight of binder percentage is 10wt%, described plasticiser percentage by weight is 10wt%, and described solvent weight percent is 20wt%, is made into slurry two;
(4), by slurry two-way described in step (3) cross flow casting molding and dry obtained electrode laminin embryo, and carry out cutting in order to using according to dimensional requirement;
(5), according to battery size requirement, electrolyte laminin embryo described in step (2) and step (4) and electrode laminin embryo are carried out lamination alignment according to the order of " M layer electrode laminin embryo | N layer electrolyte laminin embryo | M ' layer electrode laminin embryo ", wherein 1≤M=M '≤20,1≤N≤10;
(6), by the plain embryo described in step (5) after lamination alignment carry out lamination, in pressure layer process, temperature is 85 DEG C, and pressure is 50MPa, and the dwell time is 30 minutes, obtains battery skeleton element embryo;
(7), by the element of battery skeleton described in step (6) embryo put into sintering furnace high temperature sintering, high temperature sintering heating step is: rise to 800 DEG C with the heating rate of 2 DEG C/min from room temperature, and be incubated 2h; Then be warming up to 1450 DEG C with the heating rate of 5 DEG C/min from 800 DEG C, and be incubated 10h; Then be cooled to 800 DEG C with the rate of temperature fall of 5 DEG C/min from 1450 DEG C after, be finally down to room temperature with the rate of temperature fall of 10 DEG C/min from 800 DEG C, obtain battery skeleton;
(8), lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate and deionized water and citric acid are made into LSCoF solution; Samaric nitrate and cerous nitrate and deionized water and citric acid are made into SDC solution; Gadolinium nitrate and cerous nitrate and deionized water and citric acid are made into GDC solution; Samaric nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SSC solution; Samaric nitrate, barium nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SBSCO solution; LSCoF solution and SDC solution are mixed and obtains LSCoF-SDC mixed solution; LSCoF solution and GDC solution are mixed and obtains LSCoF-GDC mixed solution, above solution or mixed solution are referred to as cathode dipping solution;
(9), with cathode dipping solution described in liquid shifting equipment aspiration step (8), be arranged in the cathode porous layer of battery skeleton side uniformly on the surface, immerse behind cathode porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 85 DEG C with the heating rate of 2 DEG C/min from room temperature, and be incubated 3h; Then be warming up to 900 DEG C with the heating rate of 5 DEG C/min from 85 DEG C, and be incubated 2-10h; Then be cooled to 200 DEG C with the rate of temperature fall of 5 DEG C/min from 900 DEG C, be finally down to room temperature with the rate of temperature fall of 10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in cathode dipping solution become cathode active material;
(10) step (9), is repeated until the cathode active material of cathode porous layer load reaches required amount;
(11), SDC solution described in nickel nitrate solution and step (8) is mixed obtain Ni-SDC mixed solution; GDC solution described in nickel nitrate solution and step (8) is mixed and obtains Ni-GDC mixed solution; Lanthanum nitrate, nickel nitrate and ferric nitrate and deionized water and citric acid are made into LNF solution, above solution or mixed solution are referred to as anode pickling solution;
(12), anode pickling solution described in appropriate step (11) is drawn with liquid shifting equipment, be arranged in the anodic porous layer of the other side of battery skeleton uniformly on the surface, immerse behind anodic porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 85 DEG C with the heating rate of 2 DEG C/min from room temperature, and be incubated 3h; Then be warming up to 900 DEG C with the heating rate of 5 DEG C/min from 85 DEG C, and be incubated 10h; Then be cooled to 200 DEG C with the rate of temperature fall of 5 DEG C/min from 900 DEG C, be finally down to room temperature with the rate of temperature fall of 10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in anode pickling solution become anode active material;
(13) step 12, is repeated until the anode active material of anodic porous layer load reaches required amount;
(14), with cutting equipment there is the battery skeleton of anode active material and cathode active material to carry out cutting processing according to required size load, obtain the chip-type solid oxide fuel cell finished product with accurate symmetrical structure.
The invention provides a kind of chip-type solid oxide fuel cell with accurate symmetrical structure and preparation method thereof, this use with the chip-type solid oxide fuel cell of accurate symmetrical structure solves the unmatched problem of sintering shrinkage of conventional Ni-based anode support type monocell, fully ensure that the evenness of monocell, promote battery dress heap time be sealed to power; Solve the volume discontinuities problem of conventional Ni-based anode support type monocell in oxidation-reduction process, improve the cold cycling ability of battery pile, improve cell stack life level; Solve the chemical compatibility issues between the active higher electrode of new catalytic and electrolyte, reduce the working temperature of monocell, promote the power stage level of monocell.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all execution modes.And thus the apparent change of extending out or variation be still among the protection range of the invention.

Claims (7)

1. one kind has the chip-type solid oxide fuel cell of accurate symmetrical structure, it is characterized in that: described chip-type solid oxide fuel cell is made up of the battery skeleton and the active electrode material be carried in battery skeleton with symmetrical structure, described battery skeleton is three-decker, described battery skeleton forms with the porous electrode casing play being positioned at both sides by being positioned at middle dense electrolyte layer, described active electrode material comprises active material of cathode and active material of positive electrode, described active material of cathode is positioned on the duct inwall of battery skeleton side porous electrode casing play, and the porous electrode casing play being loaded with active material of cathode is called porous cathode layer, described active material of positive electrode is positioned on the duct inwall of the porous electrode casing play of battery skeleton opposite side, and the porous electrode casing play being loaded with active material of positive electrode is called porous anode layer.
2. a kind of chip-type solid oxide fuel cell with accurate symmetrical structure according to claim 1, it is characterized in that: the thickness of described dense electrolyte layer is 5-50 micron, the thickness of described porous electrode casing play is 0.2-2 millimeter, and the open-cell porosity of described porous electrode casing play is 5%-80%.
3. a kind of chip-type solid oxide fuel cell with accurate symmetrical structure according to claim 1, is characterized in that: the material of described dense electrolyte layer is one or more in YSZ, SSZ, GDC and LSGM; Described YSZ is yttrium stable zirconium oxide, and wherein doped yttrium amount is 3%-8%/mol; Described SSZ is scandium stabilizing zirconia, and wherein scandium doping is 3%-10%/mol; Described GDC is gadolinium doped-ceria, and wherein Gd2 O3 amount is 5%-25%/mol; Described LSGM is lanthanum strontium gallium magnesium (La1-xSrxGa1-yMgyO 3-δ, wherein 0<x≤0.8,0<y≤0.8).
4. a kind of chip-type solid oxide fuel cell with accurate symmetrical structure according to claim 1, is characterized in that: the material of described porous electrode casing play is one or more in LSCrF-YSZ, LSCrF-SSZ, LSCrF-GDC and LSCrF-LSGM; Described LSCrF is lanthanum strontium ferrochrome (La1-xSrxCr1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8); Described LSCrF-YSZ is that LSCrF and YSZ is composited in proportion, and ratio is wherein LSCrF:YSZ=20-80:80-20 (volume ratio); Described LSCrF-SSZ is that LSCrF and SSZ is composited in proportion, and ratio is wherein LSCrF:SSZ=20-80:80-20 (volume ratio); Described LSCrF-GDC is that LSCrF and GDC is composited in proportion, and ratio is wherein LSCrF:GDC=20-80:80-20 (volume ratio); Described LSCrF-LSGM is that LSCrF and LSGM is composited in proportion, and ratio is wherein LSCrF:LSGM=20-80:80-20 (volume ratio).
5. a kind of chip-type solid oxide fuel cell with accurate symmetrical structure according to claim 1, is characterized in that: described active material of cathode is one or more in LSCoF-SDC, LSCoF-GDC, SSC and SBSCO; Described LSCoF is lanthanum strontium ferro-cobalt (La1-xSrxCo1-yFeyO 3-δ, wherein 0<x≤0.8,0<y≤0.8); Described SDC is samarium doping cerium oxide, and wherein samarium doping amount is 5%-25%/mol; Described SSC is SmSrCo 2o 5; Described SBSCO is SmBaxSr1-xCo 2o 5, wherein 0<x≤0.8; Described LSCoF-SDC is that LSCoF and SDC is composited in proportion, and ratio is wherein LSCoF:SDC=20-80:80-20 (volume ratio); Described LSCoF-GDC is that LSCoF and GDC is composited in proportion, and ratio is wherein LSCoF:GDC=20-80:80-20 (volume ratio).
6. a kind of chip-type solid oxide fuel cell with accurate symmetrical structure according to claim 1, is characterized in that: described active material of positive electrode is Ni-SDC, Ni-GDC and LNF (LaNixFe1-xO 3-δ) one or more wherein in 0<x≤0.8; Described Ni-SDC is that nickel and SDC are composited in proportion, wherein Ni; SDC=20-80:80-20 (volume ratio); Described Ni-GDC is that nickel and GDC are composited in proportion, wherein Ni; GDC=20-80:80-20 (volume ratio).
7. a kind of manufacture method with the chip-type solid oxide fuel cell of accurate symmetrical structure according to claim 1, is characterized in that the steps include:
(1), with one or more in YSZ, SSZ, GDC and LSGM powder for raw material, fully mix with dispersant, binding agent, plasticiser and solvent, described dispersant weight percentage is 0.5-10wt%, described weight of binder percentage is 0.5-10wt%, and described plasticiser percentage by weight is 0.5-10wt%.Described solvent weight percent is 0.5-40wt%, is made into slurry one;
(2), by slurry one described in step (1) by flow casting molding and the obtained electrolyte laminin embryo of oven dry, and cutting is carried out in order to using according to dimensional requirement;
(3), one or more in YSZ, SSZ, GDC and LSGM powder are mixed with LSCrF powder, fully mix with dispersant, pore creating material, binding agent, plasticiser and solvent again, described dispersant weight percentage is 0.5-10wt%, described pore creating material percentage by weight is 5-50wt%, described weight of binder percentage is 0.5-10wt%, described plasticiser percentage by weight is 0.5-10wt%, described solvent weight percent is 0.5-40wt%, is made into slurry two;
(4), by slurry two-way described in step (3) cross flow casting molding and dry obtained electrode laminin embryo, and carry out cutting in order to using according to dimensional requirement;
(5), according to battery size requirement, electrolyte laminin embryo described in step (2) and step (4) and electrode laminin embryo are carried out lamination alignment according to the order of " M layer electrode laminin embryo | N layer electrolyte laminin embryo | M ' layer electrode laminin embryo ", wherein 1≤M=M '≤20,1≤N≤10;
(6), by the plain embryo described in step (5) after lamination alignment carry out lamination, in pressure layer process, temperature is 25-85 DEG C, and pressure is 10-50MPa, and the dwell time is 10-30 minute, obtains battery skeleton element embryo;
(7), by the element of battery skeleton described in step (6) embryo put into sintering furnace high temperature sintering, high temperature sintering heating step is: rise to 750-800 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 0.5-2h; Then be warming up to 1300-1450 DEG C with the heating rate of 2-5 DEG C/min from 750-800 DEG C, and be incubated 2-10h; Then be cooled to 800 DEG C with the rate of temperature fall of 3-5 DEG C/min from 1300-1450 DEG C after, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 800 DEG C, obtain battery skeleton;
(8), lanthanum nitrate, strontium nitrate, cobalt nitrate and ferric nitrate and deionized water and citric acid are made into LSCoF solution; Samaric nitrate and cerous nitrate and deionized water and citric acid are made into SDC solution; Gadolinium nitrate and cerous nitrate and deionized water and citric acid are made into GDC solution; Samaric nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SSC solution; Samaric nitrate, barium nitrate, strontium nitrate and cobalt nitrate and deionized water and citric acid are made into SBSCO solution; LSCoF solution and SDC solution are mixed and obtains LSCoF-SDC mixed solution; LSCoF solution and GDC solution are mixed and obtains LSCoF-GDC mixed solution, above solution or mixed solution are referred to as cathode dipping solution;
(9), with cathode dipping solution described in liquid shifting equipment aspiration step (8), be arranged in the cathode porous layer of battery skeleton side uniformly on the surface, immerse behind cathode porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60-85 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 2-3h; Then be warming up to 600-900 DEG C with the heating rate of 2-5 DEG C/min from 60-85 DEG C, and be incubated 2-10h; Then be cooled to 200 DEG C with the rate of temperature fall of 2-5 DEG C/min from 600-900 DEG C, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in cathode dipping solution become cathode active material;
(10) step (9), is repeated until the cathode active material of cathode porous layer load reaches required amount;
(11), SDC solution described in nickel nitrate solution and step (8) is mixed obtain Ni-SDC mixed solution; GDC solution described in nickel nitrate solution and step (8) is mixed and obtains Ni-GDC mixed solution; Lanthanum nitrate, nickel nitrate and ferric nitrate and deionized water and citric acid are made into LNF solution, above solution or mixed solution are referred to as anode pickling solution;
(12), anode pickling solution described in appropriate step (11) is drawn with liquid shifting equipment, be arranged in the anodic porous layer of the other side of battery skeleton uniformly on the surface, immerse behind anodic porous layer inside completely until solution, battery skeleton is carried out high-temperature heat treatment, the heating step of high-temperature heat treatment is: rise to 60-85 DEG C with the heating rate of 1-2 DEG C/min from room temperature, and be incubated 2-3h; Then be warming up to 600-900 DEG C with the heating rate of 2-5 DEG C/min from 60-85 DEG C, and be incubated 2-10h; Then be cooled to 200 DEG C with the rate of temperature fall of 2-5 DEG C/min from 600-900 DEG C, be finally down to room temperature with the rate of temperature fall of 5-10 DEG C/min from 200 DEG C, make the chemical composition Substance Transformation in anode pickling solution become anode active material;
(13) step 12, is repeated until the anode active material of anodic porous layer load reaches required amount;
(14), with cutting equipment there is the battery skeleton of anode active material and cathode active material to carry out cutting processing according to required size load, obtain the chip-type solid oxide fuel cell finished product with accurate symmetrical structure.
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Publication number Priority date Publication date Assignee Title
CN107819131A (en) * 2017-10-27 2018-03-20 深圳大学 A kind of low-resistivity solid oxide fuel cell electrode and preparation method thereof
CN110429285A (en) * 2019-07-15 2019-11-08 合肥国轩高科动力能源有限公司 SOFC anode electrode with sulfur resistance and preparation method thereof
CN111384421A (en) * 2020-03-17 2020-07-07 江西赛瓷材料有限公司 Five-layer structure single cell, preparation method thereof and prepared product
CN116217216A (en) * 2023-02-28 2023-06-06 上海交通大学 Lanthanum ferrite ceramic powder with variable solar absorptivity, and preparation method and application thereof

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US20110189582A1 (en) * 2010-02-03 2011-08-04 University Of South Carolina Mixed Ionic and Electronic Conductor Based on Sr2Fe2-x MoXO6 Perovskite
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Publication number Priority date Publication date Assignee Title
CN107819131A (en) * 2017-10-27 2018-03-20 深圳大学 A kind of low-resistivity solid oxide fuel cell electrode and preparation method thereof
CN110429285A (en) * 2019-07-15 2019-11-08 合肥国轩高科动力能源有限公司 SOFC anode electrode with sulfur resistance and preparation method thereof
CN111384421A (en) * 2020-03-17 2020-07-07 江西赛瓷材料有限公司 Five-layer structure single cell, preparation method thereof and prepared product
CN116217216A (en) * 2023-02-28 2023-06-06 上海交通大学 Lanthanum ferrite ceramic powder with variable solar absorptivity, and preparation method and application thereof
CN116217216B (en) * 2023-02-28 2024-05-14 上海交通大学 Lanthanum ferrite ceramic powder with variable solar absorptivity, and preparation method and application thereof

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