CN109524675A - A kind of solid oxide fuel cell and preparation method thereof - Google Patents

A kind of solid oxide fuel cell and preparation method thereof Download PDF

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CN109524675A
CN109524675A CN201811359657.1A CN201811359657A CN109524675A CN 109524675 A CN109524675 A CN 109524675A CN 201811359657 A CN201811359657 A CN 201811359657A CN 109524675 A CN109524675 A CN 109524675A
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functional
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宋昭远
许星光
龙文
张雷
张磊磊
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Liaoning Shihua University
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Liaoning Shihua University
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8864—Extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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

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Abstract

The invention discloses a kind of solid oxide fuel cell and preparation method thereof, the following steps are included: S1: weighing the nickel oxide for accounting for 55% specific gravity in blank sample, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, S2: precision electronic balance is selected to weigh 0.5~1.0g of ceria rare earth oxide, then the cermet material containing cobalt that mass ratio is 45~65% in blank material is weighed, S3: the cathode functional raw material of preparation is weighed, S4: 0.3~0.8g of ceria base oxide is weighed, then the trivalent rare earth metals oxide that mass ratio 30~45% is accounted in blank material is weighed, S5: by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode layer, it carries out plastic removal and carries out multilayer co-firing processing, obtain solid combustion Expect battery, to the preparation method of solid fuel cell, increases the stability of battery preparation, improve the conductivity of fuel cell, also ensure the service performance of solid oxide fuel cell.

Description

A kind of solid oxide fuel cell and preparation method thereof
Technical field
The present invention relates to field of fuel cell technology more particularly to a kind of solid oxide fuel cell and its preparation sides Method.
Background technique
Solid oxide fuel cell (SOFC) is high with generating efficiency, discharge is low, is adapted to extensively pluralities of fuel gas And UTILIZATION OF VESIDUAL HEAT IN is worth the advantages that high, is to provide the energy of clean and effective, alleviates the energy and environmental crisis, realizes that China can be held One of the grand strategy technology of supervention exhibition.According to operating temperature height, solid oxide fuel cell (SOFC) usually can be with It is divided into high temperature SOFC, intermediate temperature SOFC and tri- kinds of low temperature SOFC.Solid oxide fuel cell (SOFC) is one kind in high temperature (500 ~1000 °C) under directly convert chemical energy in the device of electric energy.
Compared to other fuel cells, SOFC has the advantages that energy conversion efficiency height；Fuel wide adaptation range, It can be directly using small molecule hydrocarbon as fuel；Without noble metal catalyst；All solid state mounting structure, securely and reliably；Using Range is wide, can be used as Portable mobile power source, vehicle accessory power supply, dispersion power station etc..
With the development of solid oxide fuel cell technology, the thin-film electrolyte SOFC of electrode supporting has become master Stream, wherein the plate SOFC of electrode supporting, cell stack power density are high.The preparation of planar electrode support SOFC mostly uses The technologies such as curtain coating, dry pressing.Dry pressing is unsuitable for preparing large-sized monocell.Traditional curtain coating technology of preparing, pore creating material and Powder granule natural packing formed porous supporting body, the diffusion admittance of electrode reaction gas is winding, often result in compared with Big concentration polarization, influences battery performance.
Therefore, we have proposed a kind of solid oxide fuel cell and preparation method thereof for solving the above problems.
Summary of the invention
The purpose of the present invention is to solve traditional curtain coating technology of preparing, pore creating material and powder exists in the prior art The porous supporting body that grain natural packing is formed, the diffusion admittance of electrode reaction gas is winding, often results in biggish dense The shortcomings that difference polarizes, and influences battery performance, and a kind of solid oxide fuel cell and preparation method thereof proposed.
To achieve the goals above, present invention employs following technical solutions:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
The anode support structure layer and the structure for supporting of cathode layer are made of yttrium stable zirconium oxide and nickel oxide, and the sun The content of nickel is between 30%~70% in pole support structure layers and the structure for supporting of cathode layer, and mesh number is 220~250 mesh；
The anode functional layer in the cermet containing cobalt and ceria rare earth oxide by forming, mesh number 220-200 Mesh, and the anode functional layer with a thickness of 5~100 μm；
The electrolyte layer selection ceria base oxide mixes trivalent rare earth metals oxide；
The cathode functional selection perovskite structure type cobalt base oxide, perovskite structure sections base oxide or perovskite knot One of configuration nickel-based oxide.
Preferably, the overall thickness of the anode support structure layer and the anode functional layer is 800~1500 μm, the electricity Solve matter layer with a thickness of 5~30 μm, the overall thickness of the cathode functional and the structure for supporting of cathode layer is 10~120 μm.
Preferably, the position A of the perovskite in the cathode functional is the Ln system metal of alkaline earth oxide and doping Ion, B are transition metal ions, and the operating temperature of cathode functional is at 600 DEG C~800 DEG C.
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 2~6% diatomite, is mixing it It is sufficiently mixed in machine, by red light irradiation drying and processing after material grinding 10min, column then is made in blank material using tablet press machine Then shape sample is sintered manufactured blank sample, obtain anode support structure layer and the preparation of structure for supporting of cathode layer Blank sample；
S2: the blank preparation of anode functional layer: selecting precision electronic balance to weigh ceria 0.5~1.0g of rare earth oxide, Then the cermet material containing cobalt that mass ratio is 45~65% in blank material is weighed, by weighed blank material mixed It is sufficiently mixed in conjunction machine, and does mixed base liquid using alcohol, after the completion of blank material mixing, material is ground into 20min Then cylindrical sample is made using tablet press machine in blank material by red light irradiation drying and processing afterwards, then to manufactured blank sample into Row sintering processes obtain anode functional layer and prepare blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria 0.3~0.8g of base oxide is weighed, is then weighed in blank material The trivalent rare earth metals oxide for accounting for mass ratio 30~45% makes blank material in mixing machine using alcohol as basic mixed liquor It is sufficiently mixed, obtains electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, obtains solid fuel cell.
Preferably, the operating pressure of tablet press machine is set as 180~300MPa in the S1 and S2, and is arranged in S1 and S2 and burns The temperature of knot is at 1200~1500 DEG C, and sintering time is 8~12h.
Preferably, the sintering temperature being arranged in the S5 is 750~900 DEG C, and sintering time is 2~4h.
The beneficial effects of the present invention are:
1, of the invention, a small amount of diatomite is mixed in anode support structure layer and structure for supporting of cathode layer as pore former, is mentioned The high compactness of fuel cell supporting body structure, can reduce the thermal expansion coefficient of anode material, and can prevent the burning of nickel Conglomeration is poly-, improves the conductivity of anode functional layer, increases the stability of solid oxide fuel cell, also improve fuel The mechanical strength and chemical property of battery.
2, of the invention, anode functional layer includes the cermet containing cobalt, because cobalt can keep in a reducing environment stable, It is not easy to be oxidized, while cobalt has good tolerance level to sulphur, it may have good catalytic performance improves the steady of fuel cell It is qualitative.
3, of the invention, by mixing trivalent rare earth metals oxide in electrolyte layer, the conductance of oxonium ion can be improved Electric rate, improves the stability of electrolyte, and ensure that the service efficiency of battery.
In conclusion increasing the stability of battery preparation to the preparation method of solid fuel cell, fuel electricity is improved The conductivity in pond also ensures the service performance of solid oxide fuel cell.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment one:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 2% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 180MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1200 DEG C, sintering time 8h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.5g, then claims The cermet material containing cobalt that mass ratio is 45% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 180MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1200 DEG C, and sintering time 8h obtains anode function Ergosphere prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.3g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 30% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 750 DEG C, and sintering time is 2h, obtains solid fuel Battery.
The solid oxide fuel cell prepared according to above-mentioned steps, anode support structure layer and anode functional layer it is total With a thickness of 1000 μm, electrolyte layer with a thickness of 20 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 30 μm.
Embodiment two:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 3% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 180MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1200 DEG C, sintering time 8h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.6g, then claims The cermet material containing cobalt that mass ratio is 50% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 180MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1200 DEG C, and sintering time 8h obtains anode function Ergosphere prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.5g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 35% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 800 DEG C, and sintering time is 3h, obtains solid fuel Battery.
The solid oxide fuel cell prepared according to above-mentioned steps, anode support structure layer and anode functional layer it is total With a thickness of 800 μm, electrolyte layer with a thickness of 15 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 50 μm.
Embodiment three:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 4% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 200MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1400 DEG C, sintering time 10h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.7g, then claims The cermet material containing cobalt that mass ratio is 55% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 200MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1400 DEG C, and sintering time 10h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.7g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 55% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 850 DEG C, and sintering time is 3h, obtains solid fuel Battery.
The solid oxide fuel cell prepared according to above-mentioned steps, anode support structure layer and anode functional layer it is total With a thickness of 1200 μm, electrolyte layer with a thickness of 20 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 80 μm.
Example IV:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 3% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 180MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1500 DEG C, sintering time 12h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.8g, then claims The cermet material containing cobalt that mass ratio is 60% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 300MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1500 DEG C, and sintering time 12h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.8g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 45% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 900 DEG C, and sintering time is 4h, obtains solid fuel Battery.
The solid oxide fuel cell prepared according to above-mentioned steps, anode support structure layer and anode functional layer it is total With a thickness of 900 μm, electrolyte layer with a thickness of 15 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 60 μm.
Embodiment five:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 6% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 300MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1200 DEG C, sintering time 12h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 1.0g, then claims The cermet material containing cobalt that mass ratio is 65% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 300MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1500 DEG C, and sintering time 10h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.6g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 45% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 900 DEG C, and sintering time is 4h, obtains solid fuel Battery.
The solid oxide fuel cell prepared according to above-mentioned steps, anode support structure layer and anode functional layer it is total With a thickness of 1300 μm, electrolyte layer with a thickness of 25 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 80 μm.
Comparative example one:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
Anode support structure layer and structure for supporting of cathode layer are made of yttrium stable zirconium oxide and nickel oxide, and anode support structure layer Content with nickel in structure for supporting of cathode layer is 30%；
Cathode functional selects perovskite structure type cobalt base oxide.
A kind of preparation method of solid oxide fuel cell, comprising the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 4% diatomite, makes it in mixing machine In be sufficiently mixed, by material grind 10min after red light irradiation drying and processing, column then is made in blank material using tablet press machine Sample, the operating pressure of tablet press machine are set as 200MPa, are then sintered to manufactured blank sample, the temperature of sintering is arranged Degree is to obtain the blank sample of anode support structure layer and the preparation of structure for supporting of cathode layer at 1400 DEG C, sintering time 10h；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.7g, then claims The cermet material containing cobalt that mass ratio is 55% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 200MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1400 DEG C, and sintering time 10h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.7g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 40% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 850 DEG C, and sintering time is 4h, obtains solid fuel Battery.
According to above-mentioned steps, the solid oxide fuel cell obtained, anode support structure layer and anode functional layer are prepared Overall thickness be 1500 μm, electrolyte layer with a thickness of 30 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 120 μm。
Comparative example two:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
Anode support structure layer and structure for supporting of cathode layer are made of yttrium stable zirconium oxide and nickel oxide, and anode support structure layer And the content of nickel is between 55% in structure for supporting of cathode layer；
Cathode functional selects perovskite structure sections base oxide.
S1: it the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: weighs and accounts for 55% specific gravity in blank sample Nickel oxide, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes to weigh Blank material be sufficiently mixed in mixing machine, diatomite of the content control 4% is then added into mixing machine, makes it mixed It is sufficiently mixed in conjunction machine, then red light irradiation drying and processing after material grinding 10min blank material is made using tablet press machine Cylindrical sample, the operating pressure of tablet press machine are set as 200MPa, are then sintered to manufactured blank sample, setting sintering Temperature be at 1400 DEG C, sintering time 10h, obtain anode support structure layer and structure for supporting of cathode layer preparation blank Sample；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.7g, then claims The cermet material containing cobalt that mass ratio is 55% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 200MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1400 DEG C, and sintering time 10h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.7g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 40% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 850 DEG C, and sintering time is 4h, obtains solid fuel Battery.
According to above-mentioned steps, the solid oxide fuel cell obtained, anode support structure layer and anode functional layer are prepared Overall thickness be 1200 μm, electrolyte layer with a thickness of 20 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 80 μ m。
Comparative example three:
A kind of solid oxide fuel cell proposed by the present invention, including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
Anode support structure layer and structure for supporting of cathode layer are made of yttrium stable zirconium oxide and nickel oxide, and anode support structure layer And the content of nickel is between 70% in structure for supporting of cathode layer；
Cathode functional selects perovskite structure type nickel-based oxide.
S1: it the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: weighs and accounts for 55% specific gravity in blank sample Nickel oxide, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes to weigh Blank material be sufficiently mixed in mixing machine, diatomite of the content control 4% is then added into mixing machine, makes it mixed It is sufficiently mixed in conjunction machine, then red light irradiation drying and processing after material grinding 10min blank material is made using tablet press machine Cylindrical sample, the operating pressure of tablet press machine are set as 200MPa, are then sintered to manufactured blank sample, setting sintering Temperature be at 1400 DEG C, sintering time 10h, obtain anode support structure layer and structure for supporting of cathode layer preparation blank Sample；
S2: it the blank preparation of anode functional layer: selects precision electronic balance to weigh ceria rare earth oxide 0.7g, then claims The cermet material containing cobalt that mass ratio is 55% in blank material is taken, in mixing machine sufficiently by weighed blank material Mixing, and mixed base liquid is done using alcohol, after the completion of blank material mixing, by red light irradiation after material grinding 20min Then cylindrical sample is made using tablet press machine in blank material by drying and processing, the operating pressure of tablet press machine is set as 200MPa, so Manufactured blank sample is sintered afterwards, the temperature that sintering is arranged is at 1400 DEG C, and sintering time 10h obtains anode Functional layer prepares blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria base oxide 0.7g is weighed, the Zhan Zhiliang in blank material is then weighed Trivalent rare earth metals oxide than 40% is sufficiently mixed blank material in mixing machine using alcohol as basic mixed liquor, Obtain electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode Layer carries out plastic removal and carries out multilayer co-firing processing, and the sintering temperature of setting is 850 DEG C, and sintering time is 4h, obtains solid fuel Battery.
According to above-mentioned steps, the solid oxide fuel cell obtained, anode support structure layer and anode functional layer are prepared Overall thickness be 1000 μm, electrolyte layer with a thickness of 10 μm, the overall thickness of cathode functional and structure for supporting of cathode layer is 60 μ m。
More than, it is merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, it is any Those familiar with the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its invents Design is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (6)

1. a kind of solid oxide fuel cell, which is characterized in that including anode support structure layer, anode functional layer, electrolyte Layer, cathode functional and structure for supporting of cathode layer；
The anode support structure layer and the structure for supporting of cathode layer are made of yttrium stable zirconium oxide and nickel oxide, and the sun The content of nickel is between 30%~70% in pole support structure layers and the structure for supporting of cathode layer, and mesh number is 220~250 mesh；
The anode functional layer in the cermet containing cobalt and ceria rare earth oxide by forming, mesh number 220-200 Mesh, and the anode functional layer with a thickness of 5~100 μm；
The electrolyte layer selection ceria base oxide mixes trivalent rare earth metals oxide；
The cathode functional selection perovskite structure type cobalt base oxide, perovskite structure sections base oxide or perovskite knot One of configuration nickel-based oxide.
2. a kind of solid oxide fuel cell according to claim 1 and preparation method thereof, which is characterized in that the sun The overall thickness of pole support structure layers and the anode functional layer be 800~1500 μm, the electrolyte layer with a thickness of 5~30 μ The overall thickness of m, the cathode functional and the structure for supporting of cathode layer is 10~120 μm.
3. a kind of solid oxide fuel cell according to claim 1 and preparation method thereof, which is characterized in that the yin The position A of perovskite in the functional layer of pole be alkaline earth oxide and doping Ln system metal ion, B be transition metal from Son, and the operating temperature of cathode functional is at 600 DEG C~800 DEG C.
4. a kind of preparation method of solid oxide fuel cell, which comprises the following steps:
S1: the preparation of the blank of anode support structure layer and structure for supporting of cathode layer: the oxygen that 55% specific gravity is accounted in blank sample is weighed Change nickel, then weigh accounted in blank sample 45% yttrium stable zirconium oxide, mixed base liquid is done with alcohol, makes weighed hair Blank material material is sufficiently mixed in mixing machine, and content control is then added into mixing machine in 2~6% diatomite, is mixing it It is sufficiently mixed in machine, by red light irradiation drying and processing after material grinding 10min, column then is made in blank material using tablet press machine Then shape sample is sintered manufactured blank sample, obtain anode support structure layer and the preparation of structure for supporting of cathode layer Blank sample；
S2: the blank preparation of anode functional layer: selecting precision electronic balance to weigh ceria 0.5~1.0g of rare earth oxide, Then the cermet material containing cobalt that mass ratio is 45~65% in blank material is weighed, by weighed blank material mixed It is sufficiently mixed in conjunction machine, and does mixed base liquid using alcohol, after the completion of blank material mixing, material is ground into 20min Then cylindrical sample is made using tablet press machine in blank material by red light irradiation drying and processing afterwards, then to manufactured blank sample into Row sintering processes obtain anode functional layer and prepare blank sample；
S3: the preparation of cathode functional blank: the cathode functional raw material of preparation is weighed, then raw material is added to alcohol In mixing machine as basic solution, raw material is sufficiently stirred, is done at red light irradiation drying after raw material is then ground 15min again Then blank is pressed into cylindrical sample using tablet press machine, then does sintering processes to blank sample by reason, sintering temperature is 1400 DEG C, It is sintered 10h, obtains cathode functional blank sample；
S4: the preparation of electrolyte layer slurry: ceria 0.3~0.8g of base oxide is weighed, is then weighed in blank material The trivalent rare earth metals oxide for accounting for mass ratio 30~45% makes blank material in mixing machine using alcohol as basic mixed liquor It is sufficiently mixed, obtains electrolyte slurry；
S5: the preparation of battery: electrolyte slurry is uniformly deposited on to the surface of anode functional layer, then in cathode functional Surface deposition electrolyte slurry, then by anode support structure layer, anode functional layer, cathode functional and structure for supporting of cathode layer Plastic removal carries out multilayer co-firing processing, obtains solid fuel cell.
5. a kind of preparation method of solid oxide fuel cell according to claim 4, which is characterized in that the S1 and The operating pressure of tablet press machine is set as 180~300MPa in S2, and the temperature that sintering is arranged in S1 and S2 is 1200~1500 DEG C, sintering time is 8~12h.
6. a kind of preparation method of solid oxide fuel cell according to claim 4, which is characterized in that in the S5 The sintering temperature of setting is 750~900 DEG C, and sintering time is 2~4h.
CN201811359657.1A 2018-11-15 2018-11-15 A kind of solid oxide fuel cell and preparation method thereof Pending CN109524675A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN105932304A (en) * 2016-05-20 2016-09-07 辽宁石油化工大学 Preparation method for solid oxide fuel cell anode
JP2017123231A (en) * 2016-01-05 2017-07-13 株式会社日本触媒 Single cell for solid oxide fuel cell and method for manufacturing the same, and cathode for solid oxide fuel cell and method for manufacturing the same
CN107195938A (en) * 2017-06-30 2017-09-22 哈尔滨工业大学 A kind of simple SOFC preparation method
CN107768690A (en) * 2017-08-29 2018-03-06 湖北大学 A kind of semiconductive thin film Electrolyte type fuel cell and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104157893A (en) * 2013-05-13 2014-11-19 中国科学院大连化学物理研究所 Low temperature solid oxide fuel cell supported by porous metal and preparation method thereof
JP2017123231A (en) * 2016-01-05 2017-07-13 株式会社日本触媒 Single cell for solid oxide fuel cell and method for manufacturing the same, and cathode for solid oxide fuel cell and method for manufacturing the same
CN105932304A (en) * 2016-05-20 2016-09-07 辽宁石油化工大学 Preparation method for solid oxide fuel cell anode
CN107195938A (en) * 2017-06-30 2017-09-22 哈尔滨工业大学 A kind of simple SOFC preparation method
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