CN117497814A - Flat-plate proton ceramic fuel cell large-area single cell and preparation method thereof - Google Patents

Flat-plate proton ceramic fuel cell large-area single cell and preparation method thereof Download PDF

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CN117497814A
CN117497814A CN202311284071.4A CN202311284071A CN117497814A CN 117497814 A CN117497814 A CN 117497814A CN 202311284071 A CN202311284071 A CN 202311284071A CN 117497814 A CN117497814 A CN 117497814A
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electrolyte
anode
value
functional layer
slurry
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邱鹏
涂宝峰
戚惠颖
苏新
吴磊
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Shandong University of Science and Technology
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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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M8/1253—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 zirconium oxide
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a large-area single cell of a flat-plate proton ceramic fuel cell and a preparation method thereof, belonging to the field of proton ceramic fuel cells. Comprises a hot pressing step, an electrolyte slurry spraying step and a high-temperature co-firing step; the hot-pressing step comprises the steps of superposing at least one anode support substrate and at least one anode functional layer substrate together for hot-pressing to obtain an anode support with an anode functional layer; the high-temperature co-firing step includes co-firing two anode supports with anode functional layers and electrolyte layers disposed opposite to each other and embedded in mixed powder of NiO-electrolyte, with the two anode supports with anode functional layers and electrolyte layers in contact with each other. The invention is applied to the aspect of proton ceramic fuel cells, and solves the problems that when the effective area of the single cell of the traditional flat plate type proton ceramic fuel cell is large, the flatness of the flat plate type substrate is poor, the flat plate type substrate is easy to deform, and the sealing of the single cell and the assembly of a galvanic pile are not facilitated. The proton ceramic fuel cell prepared by the invention has the characteristics of high flatness, large effective area and excellent performance.

Description

Flat-plate proton ceramic fuel cell large-area single cell and preparation method thereof
Technical Field
The invention belongs to the field of proton ceramic fuel cells, and particularly relates to a large-area single cell of a flat plate type proton ceramic fuel cell and a preparation method thereof.
Background
The Solid Oxide Fuel Cell (SOFC) can convert chemical energy of fuel into electric energy and heat energy, has the advantages of high efficiency, low noise, low emission, wide fuel selectivity and the like, and has wide application in the fields of distributed power generation, standby power, military and the like. In order to further meet the commercial demands, the future trend of SOFCs is medium-low temperature. The reduction of the working temperature can realize quick start and stop, greatly prolong the service life, enhance the reliability of the galvanic pile and reduce the cost. SOFCs can be further divided into oxygen ion conductive and Proton Ceramic Fuel Cells (PCFCs) depending on the type of electrolyte conductive carrier. The PCFC operates at a lower temperature than conventional oxygen ion conducting SOFCs, which operate at only 400-600 c, due to the lower migration barrier for protons. Therefore, the development and research of PCFC are of great significance for the commercialization development of medium-temperature SOFC.
However, development and research of flat plate type PCFC stacks is still in the beginning. Among them, the preparation of flat plate type large-area single cells for a cell stack is a major factor limiting the development of PCFC cell stacks. When the effective area of the flat plate type PCFC single cell is large, the flatness of the flat plate type substrate is poor and the flat plate type substrate is easy to deform, which is not beneficial to sealing the single cell and assembling a galvanic pile.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to solve the technical problems that when the effective area of the traditional flat plate type PCFC single cell is large, the flatness of the flat plate type substrate is poor and the flat plate type substrate is easy to deform, so that the sealing and the pile assembly of the single cell are not facilitated, and provides a large-area single cell of the flat plate type proton ceramic fuel cell with high flatness, large effective area and excellent performance and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a large-area single cell of a flat-plate proton ceramic fuel cell, which comprises a hot pressing step, an electrolyte slurry spraying step and a high-temperature co-firing step; the hot-pressing step comprises superposing at least one anode support substrate and at least one anode functional layer substrate together for hot-pressing to obtain anode support with anode functional layer, wherein the hot-pressing temperature is any value of 80-150deg.C, and the hot-pressing pressure is 0.5-3t/100cm 2 The hot pressing time is any value in 1-20 min; the step of spraying electrolyte slurry comprises the step of spraying electrolyte slurry on the surface of the anode functional layer of the anode support body with the anode functional layer by adopting an ultrasonic spraying method to obtain the anode support body with the anode functional layer and the electrolyte layer; the high-temperature co-firing step includes co-firing two anode supports with anode functional layers and electrolyte layers disposed opposite to each other and embedded in mixed powder of NiO-electrolyte, with the two anode supports with anode functional layers and electrolyte layers in contact with each other.
Preferably, the method further comprises an anode support substrate preparation step, an anode functional layer substrate preparation step and an anode support substrate and anode functional layer substrate casting step before the hot-pressing step; the preparation step of the anode support substrate comprises the step of preparing the anode support substrate by taking anode support slurry as a raw material through a tape casting process, and the preparation step of the anode functional layer substrate comprises the step of preparing the anode functional layer substrate by taking anode functional layer slurry as a raw material through a tape casting process; the anode support slurry and the anode functional layer slurry comprise NiO, electrolyte powder, starch, fish oil, dimethylbenzene, ethanol, PVB, plasticizer and cyclohexanone; the particle diameters of the NiO and the electrolyte powder for the anode support slurry are any one value of 1 to 10 μm, and the particle diameters of the NiO and the electrolyte powder for the anode functional layer slurry are any one value of 0.1 to 1 μm.
Preferably, the mass ratio of the NiO to the electrolyte powder is 0.5-1.5: 1; the volume ratio of the dimethylbenzene to the ethanol is 5-1: 1.
Preferably, the raw materials adopted in the step of spraying the electrolyte slurry comprise electrolyte materials and binders; the mass ratio of the electrolyte material to the binder is 3-0.5: 1; the particle size of the electrolyte material is any value of 0.1-1 mu m; the thickness of the electrolyte layer is any one value of 5 to 50 μm.
Preferably, the electrolyte is BaZr 0.8-x Ce x Y 0.1 Yb 0.1 O 3-δ ，0.1≤x≤0.7。
Preferably, the ultrasonic frequency in the step of spraying the electrolyte slurry is any value of 30-130 kHz; the spraying flow is any value of 0.1-10 mL/min; the spraying time is any value of 1-10 min.
Preferably, the temperature of the high-temperature co-firing step is any value of 1300-1600 ℃, and the heat preservation time is any value of 1-10 h.
Preferably, the method further comprises a low-temperature degreasing step between the step of spraying the electrolyte slurry and the high-temperature cofiring step, wherein the low-temperature degreasing temperature of the low-temperature degreasing step is any value of 200-400 ℃, the heating speed is any value of 0.5-5 ℃/min, and the heat preservation time is any value of 1-10 h.
Preferably, the method further comprises a step of printing cathode slurry after the high-temperature co-firing step, wherein the step of printing cathode slurry comprises the following steps: printing cathode slurry on the outer surface of an electrolyte layer of an anode support body with an anode functional layer and an electrolyte layer by adopting a screen printing method, drying and sintering the cathode slurry, and forming a cathode layer outside the electrolyte layer to obtain the flat-plate proton ceramic fuel cell large-area single cell; the cathode material is PrBa 1-x Sr x Co 2-y Fe y O 5+δ Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; the sintering temperature is any value of 800-1100 ℃, and the heat preservation time is any value of 1-6 h.
The invention also provides a large-area single cell of the flat plate type proton ceramic fuel cell, which is prepared by the preparation method of the large-area single cell of the flat plate type proton ceramic fuel cell in any one of the technical scheme, wherein the thickness of the single cell is any one of 0.5-3mm, and the side length of the single cell is any one of 5-15 cm.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a large-area single cell of a flat proton ceramic fuel cell, which is characterized in that through a hot pressing step, hot pressing temperature, hot pressing pressure and hot pressing time in the hot pressing step are limited, on one hand, an anode support substrate and an anode functional layer substrate are connected together, and on the other hand, stress in a casting substrate is favorably eliminated under the process condition, so that the substrate is smoother and is not easy to deform, and the problem of local unevenness generated during co-firing of the large-area single cell can be relieved as much as possible; by limiting the high-temperature co-firing step and adopting the buried firing treatment and limiting the opposite firing operation, the element diffusion and the phase structure change in the electrolyte can be greatly avoided, and the electrolyte layer can be effectively prevented from being polluted;
the invention also provides a large-area single cell of the flat-plate proton ceramic fuel cell, which has the characteristic of high flatness and is beneficial to sealing and assembling of a galvanic pile; the effective area is large, and the method can be used for assembling medium-large proton ceramic fuel cell stacks; the anode support has high porosity, is favorable for the diffusion of fuel gas, and has excellent electrochemical performance of single cells; the working temperature is low, the operation can be carried out in a medium temperature stage of 400-600 ℃, and the method has important significance for promoting the commercial development of medium temperature solid oxide fuel cell technology and increasing the application scene.
Detailed Description
The technical scheme in the specific embodiment of the invention will be fully described in detail. It is apparent that the described embodiments are only some specific implementations, but not all implementations, of the general technical solution of the present invention. All other embodiments, which are obtained by those skilled in the art based on the general inventive concept, fall within the scope of the present invention.
The invention provides a preparation method of a large-area single cell of a flat-plate proton ceramic fuel cell, which comprises a hot pressing step, an electrolyte slurry spraying step and a high-temperature co-firing step; the hot-pressing step includes laminating at least one anode support substrate and at least one anode functional layerThe substrates are overlapped together to be hot-pressed to obtain the anode support body with the anode functional layer, the hot-pressing temperature is any value of 80-150 ℃, and the hot-pressing pressure is 0.5-3t/100cm 2 The hot pressing time is any value in 1-20 min; the step of spraying electrolyte slurry comprises the step of spraying electrolyte slurry on the surface of the anode functional layer of the anode support body with the anode functional layer by adopting an ultrasonic spraying method to obtain the anode support body with the anode functional layer and the electrolyte layer; the high-temperature co-firing step includes co-firing two anode supports with anode functional layers and electrolyte layers disposed opposite to each other and embedded in mixed powder of NiO-electrolyte, with the two anode supports with anode functional layers and electrolyte layers in contact with each other. According to the preparation method of the large-area single cell of the flat proton ceramic fuel cell, through the hot pressing step, the hot pressing temperature, the hot pressing pressure and the hot pressing time in the hot pressing step are limited, on one hand, the anode support substrate and the anode functional layer substrate are connected together, and on the other hand, the stress in the casting substrate is favorably eliminated under the process condition, so that the substrate is smoother and is not easy to deform, and the problem of local unevenness generated during co-firing of the large-area single cell can be relieved as much as possible; by limiting the high-temperature co-firing step, the buried firing treatment is adopted, and the opposite firing operation is simultaneously limited, so that the element diffusion and the phase structure change in the electrolyte can be greatly avoided, and the electrolyte layer can be effectively prevented from being polluted, specifically, the BaZr 0.8-x Ce x Y 0.1 Yb 0.1 O 3-δ The electrolyte can be seriously diffused with the crucible container during high-temperature cofiring, and can be directly contacted with high-temperature air to cause the phase structure of the electrolyte to change, thereby influencing the proton conductivity of the electrolyte, and when the support embryo is buried and burned by the powder with the same components, the BaZr can be greatly avoided 0.8-x Ce x Y 0.1 Yb 0.1 O 3-δ Besides the burial firing, the technical scheme also limits the butt firing, namely the surface sprayed with electrolyte slurry is contacted with the electrolyte surface of the other battery, so that the electrolyte layer can be prevented from being polluted. The number of anode support substrates in the hot pressing step is any one of 1 to 10 sheets,the number of anode functional layer substrates is any one value of 1 to 5 sheets, wherein the thicknesses of the anode support substrate and the anode functional layer substrate after drying are any one value of 0.1 to 0.5 mm. The technical proposal specifically limits the hot pressing temperature, the hot pressing pressure and the hot pressing time, and it can be understood that the hot pressing temperature can be any value within the range of 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the hot pressing pressure can be 1.0t/100cm 2 、1.5t/100cm 2 、2.0t/100cm 2 、2.5t/100cm 2 And any value within the range thereof, the hot pressing time may be 5min, 10min, 15min or any point value within the range thereof.
In a preferred embodiment, the method further comprises an anode support substrate preparation step, an anode functional layer substrate preparation step, and an anode support substrate and anode functional layer substrate casting step prior to the hot pressing step; the preparation step of the anode support substrate comprises the step of preparing the anode support substrate by taking anode support slurry as a raw material through a tape casting process, and the preparation step of the anode functional layer substrate comprises the step of preparing the anode functional layer substrate by taking anode functional layer slurry as a raw material through a tape casting process; the anode support slurry and the anode functional layer slurry comprise NiO, electrolyte powder, starch, fish oil, dimethylbenzene, ethanol, PVB, plasticizer and cyclohexanone; the particle diameters of the NiO and the electrolyte powder for the anode support slurry are any one value of 1 to 10 μm, and the particle diameters of the NiO and the electrolyte powder for the anode functional layer slurry are any one value of 0.1 to 1 μm. The present technical solution specifically defines particle diameters of the NiO and the electrolyte powder for the anode support slurry, and particle diameters of the NiO and the electrolyte powder for the anode functional layer slurry, preferably, particle diameters of the NiO and the electrolyte powder for the anode support slurry are 10 times larger than those of the NiO and the electrolyte powder for the anode functional layer slurry, the former being larger than the latter in that one of requirements of the anode support is to have larger pores to allow fuel gas to rapidly reach the electrochemical active region, and thus it is required that particle diameters of the NiO and electrolyte powder in the anode support slurry be larger, and particle diameters of the NiO and electrolyte powder in the anode functional layer slurry be smaller, so that it is advantageous to increase a specific surface area of the reaction active region as much as possible, while the smaller pores can prevent infiltration of the electrolyte slurry when the electrolyte slurry is sprayed by ultrasonic waves.
In a preferred embodiment, the mass ratio of the NiO to the electrolyte powder is 0.5-1.5: 1; the volume ratio of the dimethylbenzene to the ethanol is 5-1: 1. Specifically, the anode support substrate preparation steps include: adding NiO and electrolyte powder into a dimethylbenzene-ethanol-fish oil solvent, performing ball milling, gradually adding PVB, a plasticizer and cyclohexanone, performing secondary ball milling, and performing vacuum defoaming to obtain anode support slurry; the preparation steps of the anode functional layer substrate comprise: adding NiO and electrolyte powder into a dimethylbenzene-ethanol-fish oil solvent, ball milling, gradually adding PVB, a plasticizer and cyclohexanone, performing secondary ball milling, and performing vacuum defoaming to obtain anode functional layer slurry.
In a preferred embodiment, the raw materials used in the step of spraying the electrolyte slurry include an electrolyte material and a binder; the mass ratio of the electrolyte material to the binder is 3-0.5: 1; the particle size of the electrolyte material is any value of 0.1-1 mu m; the thickness of the electrolyte layer is any one value of 5 to 50 μm. In a preferred embodiment, the electrolyte is BaZr 0.8-x Ce x Y 0.1 Yb 0.1 O 3-δ ，0.1≤x≤0.7。
In a preferred embodiment, the ultrasonic frequency in the step of spraying the electrolyte slurry is any one of 30-130 kHz; the spraying flow is any value of 0.1-10 mL/min; the spraying time is any value of 1-10 min. The technical scheme specifically limits the technological parameters of ultrasonic spraying, is favorable for saving slurry, and meets the requirements of uniform spraying and thin electrolyte of the flat-plate proton ceramic fuel cell.
In a preferred embodiment, the temperature of the high temperature co-firing step is any value from 1300 ℃ to 1600 ℃ and the holding time is any value from 1 to 10 hours. It is understood that the temperature of the high temperature cofiring step can be 1400 ℃, 1500 ℃ and any point value in the range of the same, and the heat preservation time can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and any point value in the range of the same.
In a preferred embodiment, the method further comprises a low-temperature degreasing step between the step of spraying the electrolyte slurry and the high-temperature cofiring step, wherein the low-temperature degreasing temperature of the low-temperature degreasing step is any value of 200-400 ℃, the heating speed is any value of 0.5-5 ℃/min, and the heat preservation time is any value of 1-10 h.
In a preferred embodiment, the method further comprises a step of printing cathode paste after the high temperature co-firing step, the step of printing cathode paste comprising: printing cathode slurry on the outer surface of an electrolyte layer of an anode support body with an anode functional layer and an electrolyte layer by adopting a screen printing method, drying and sintering the cathode slurry, and forming a cathode layer outside the electrolyte layer to obtain the flat-plate proton ceramic fuel cell large-area single cell; the cathode material is PrBa 1-x Sr x Co 2-y Fe y O 5+δ Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; the sintering temperature is any value of 800-1100 ℃, and the heat preservation time is any value of 1-6 h.
The invention also provides a large-area single cell of the flat plate type proton ceramic fuel cell, which is prepared by the preparation method of the large-area single cell of the flat plate type proton ceramic fuel cell in any one of the technical scheme, wherein the thickness of the single cell is any one of 0.5-3mm, and the side length of the single cell is any one of 5-15 cm.
In order to more clearly and in detail describe the large-area single cell of the flat plate type proton ceramic fuel cell and the preparation method thereof provided by the embodiment of the invention, the following description will be made with reference to specific embodiments.
Example 1
And (3) preparing anode support slurry. Anode support slurry comprises NiO, electrolyte powder, starch, fish oil, xylene, ethanol, PVB, plasticizer, cyclohexanone. Wherein the electrolyte material is BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ . Specifically, niO and electrolyte powder each having a particle diameter of 5 μm were added to xylene-ethanol-in a fish oil solvent, wherein the volume ratio of xylene to ethanol is 1.5:1, a step of; after ball milling for 24 hours, PVB, plasticizer and cyclohexanone are gradually added, and the second ball milling is carried out for 24 hours; and (5) removing bubbles in vacuum to obtain anode support slurry.
And (3) preparing anode functional layer slurry. Anode support slurry comprises NiO, electrolyte powder, starch, fish oil, xylene, ethanol, PVB, plasticizer, cyclohexanone. Wherein the electrolyte material is BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ . Specifically, niO and electrolyte powders, each having a particle size of 0.5 μm, were added to a xylene-ethanol-fish oil solvent, wherein the volume ratio of xylene to ethanol was 2:1, a step of; after ball milling for 24 hours, PVB, plasticizer and cyclohexanone are gradually added, and the second ball milling is carried out for 24 hours; and (5) removing bubbles in vacuum to obtain anode functional layer slurry.
And (3) casting and hot-pressing the anode support substrate and the anode functional layer substrate. And (3) casting the anode support slurry and the anode functional layer slurry after bubble removal, and drying to obtain an anode support substrate and an anode functional layer substrate with the thickness of 0.3 mm. And then stacking 3 anode support substrates and 1 anode functional layer substrate together for hot pressing, wherein the hot pressing temperature is 200 ℃, and the hot pressing time is 10min.
And uniformly spraying electrolyte slurry on the outer surface of the anode functional layer of the anode support body with the anode functional layer by adopting an ultrasonic spraying method. The electrolyte slurry comprises electrolyte powder and a binder, wherein the mass ratio is 1:1. wherein the electrolyte material is BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ The particle size was 300nm. The electrolyte layer prepared had a thickness of 15 μm.
The anode support substrate with the anode functional layer and the electrolyte layer is subjected to low-temperature degreasing. Wherein the degreasing temperature is 240 ℃, the heating speed is 0.5 ℃/min, and the heat preservation time is 2h.
And (3) performing high-temperature cofiring on the degreased anode support substrate. Wherein the high-temperature cofiring temperature is 1450 ℃, and the heat preservation time is 6 hours; at the time of high-temperature cofiring, the anode with the surface covered with electrolyte materialThe support body is embedded in NiO-BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ Is added to the mixed powder of (a) and (b).
A cathode material is printed on the outer surface of an electrolyte layer of an anode support having an anode functional layer and an electrolyte layer by screen printing, dried and sintered. Wherein the cathode material is PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ The cathode is prepared by adopting a coprecipitation method, the calcining temperature of the cathode is 1000 ℃, and the calcining time is 3 hours.
Finally, the length and side length are 10cm, the thickness is 1mm, and the effective area of the cathode is 64cm 2 A proton ceramic fuel cell of a flat plate structure.
Example 2
And (3) preparing anode support slurry. Anode support slurry comprises NiO, electrolyte powder, starch, fish oil, xylene, ethanol, PVB, plasticizer, cyclohexanone. Wherein the electrolyte material is BaZr 0.5 Ce 0.3 Y 0.1 Yb 0.1 O 3-δ . Specifically, niO and electrolyte powders, each having a particle size of 10 μm, were added to a xylene-ethanol-fish oil solvent, wherein the volume ratio of xylene to ethanol was 2:1, a step of; after ball milling for 20 hours, PVB, plasticizer and cyclohexanone are gradually added, and the second ball milling is carried out for 20 hours; and (5) removing bubbles in vacuum to obtain anode support slurry.
And (3) preparing anode functional layer slurry. Anode support slurry comprises NiO, electrolyte powder, starch, fish oil, xylene, ethanol, PVB, plasticizer, cyclohexanone. Wherein the electrolyte material is BaZr 0.5 Ce 0.3 Y 0.1 Yb 0.1 O 3-δ . Specifically, niO and electrolyte powders, each having a particle size of 1 μm, were added to a xylene-ethanol-fish oil solvent, wherein the volume ratio of xylene to ethanol was 2:1, a step of; after ball milling for 20 hours, PVB, plasticizer and cyclohexanone are gradually added, and the second ball milling is carried out for 20 hours; and (5) removing bubbles in vacuum to obtain anode functional layer slurry.
And (3) casting and hot-pressing the anode support substrate and the anode functional layer substrate. And (3) casting the anode support slurry and the anode functional layer slurry after bubble removal, and drying to obtain an anode support substrate and an anode functional layer substrate with the thickness of 0.3 mm. And then, superposing 4 support substrates and 1 functional layer substrate together for hot pressing, wherein the hot pressing temperature is 150 ℃, and the hot pressing time is 15min.
And uniformly spraying electrolyte slurry on the outer surface of the anode functional layer of the anode support body with the anode functional layer by adopting an ultrasonic spraying method. The electrolyte slurry comprises electrolyte powder and a binder, wherein the mass ratio is 1:1. wherein the electrolyte material is BaZr 0.5 Ce 0.3 Y 0.1 Yb 0.1 O 3-δ The particle size was 300nm. The electrolyte layer prepared had a thickness of 20. Mu.m.
The anode support substrate with the anode functional layer and the electrolyte layer is subjected to low-temperature degreasing. Wherein the degreasing temperature is 240 ℃, the heating speed is 1 ℃/min, and the heat preservation time is 3h.
And (3) performing high-temperature cofiring on the degreased anode support substrate. Wherein the high-temperature cofiring temperature is 1430 ℃, and the heat preservation time is 8 hours; during high-temperature cofiring, an anode support body with an electrolyte material coated on the surface is embedded in NiO-BaZr 0.5 Ce 0.3 Y 0.1 Yb 0.1 O 3-δ Is added to the mixed powder of (a) and (b).
A cathode material is printed on the outer surface of an electrolyte layer of an anode support having an anode functional layer and an electrolyte layer by screen printing, dried and sintered. Wherein the cathode material is PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ The cathode is prepared by adopting a coprecipitation method, the calcination temperature of the cathode is 1100 ℃, and the calcination time is 2 hours.
Finally, the length side length is 12cm, the thickness is 1.2mm, and the effective area of the cathode is 100cm 2 A proton ceramic fuel cell of a flat plate structure.

Claims (10)

1. The preparation method of the large-area single cell of the flat-plate proton ceramic fuel cell is characterized by comprising the following steps:
a hot pressing step, including at least one ofThe anode support substrate and at least one anode functional layer substrate are overlapped together for hot pressing to obtain anode support with anode functional layer, the hot pressing temperature is any value of 80-150deg.C, and the hot pressing pressure is 0.5-3t/100cm 2 The hot pressing time is any value in 1-20 min;
spraying electrolyte slurry on the surface of the anode functional layer of the anode support body with the anode functional layer by adopting an ultrasonic spraying method to obtain the anode support body with the anode functional layer and the electrolyte layer;
and a high-temperature co-firing step comprising co-firing two anode supports with anode functional layers and electrolyte layers disposed opposite to each other and embedded in mixed powder of NiO-electrolyte, and contacting the two electrolyte layers of the anode supports with anode functional layers and electrolyte layers.
2. The method for manufacturing a flat-plate proton ceramic fuel cell large-area unit cell according to claim 1, further comprising an anode support substrate manufacturing step, an anode functional layer substrate manufacturing step, and an anode support substrate and anode functional layer substrate casting step before the hot pressing step;
the preparation step of the anode support substrate comprises the step of preparing the anode support substrate by taking anode support slurry as a raw material through a tape casting process, and the preparation step of the anode functional layer substrate comprises the step of preparing the anode functional layer substrate by taking anode functional layer slurry as a raw material through a tape casting process;
the anode support slurry and the anode functional layer slurry comprise NiO, electrolyte powder, starch, fish oil, dimethylbenzene, ethanol, PVB, plasticizer and cyclohexanone; the particle diameters of the NiO and the electrolyte powder for the anode support slurry are any one value of 1 to 10 μm, and the particle diameters of the NiO and the electrolyte powder for the anode functional layer slurry are any one value of 0.1 to 1 μm.
3. The method for preparing a large-area single cell of a flat plate type proton ceramic fuel cell according to claim 2, wherein the mass ratio of the NiO to the electrolyte powder is 0.5-1.5: 1; the volume ratio of the dimethylbenzene to the ethanol is 5-1: 1.
4. The method for manufacturing a large-area single cell of a flat-plate proton ceramic fuel cell according to claim 1, wherein the raw materials adopted in the step of spraying the electrolyte slurry include an electrolyte material and a binder; the mass ratio of the electrolyte material to the binder is 3-0.5: 1; the particle size of the electrolyte material is any value of 0.1-1 mu m; the thickness of the electrolyte layer is any one value of 5 to 50 μm.
5. The method for preparing a large-area single cell of a flat-plate proton ceramic fuel cell as claimed in claim 2, wherein the electrolyte material is BaZr 0.8-x Ce x Y 0.1 Yb 0.1 O 3-δ ，0.1≤x≤0.7。
6. The method for manufacturing a large-area single cell of a flat-plate proton ceramic fuel cell according to claim 1, wherein the ultrasonic frequency in the step of spraying the electrolyte slurry is any value of 30-130 kHz; the spraying flow is any value of 0.1-10 mL/min; the spraying time is any value of 1-10 min.
7. The method for preparing a large-area single cell of a flat-plate proton ceramic fuel cell according to claim 1, wherein the temperature of the high-temperature co-firing step is any value of 1300-1600 ℃, and the heat preservation time is any value of 1-10 h.
8. The method for manufacturing a flat plate type proton ceramic fuel cell large area single cell according to claim 1, further comprising a low temperature degreasing step between the step of spraying electrolyte slurry and the high temperature co-firing step, wherein the low temperature degreasing temperature of the low temperature degreasing step is any value of 200-400 ℃, the heating rate is any value of 0.5-5 ℃/min, and the holding time is any value of 1-10 h.
9. The method of claim 1, further comprising a step of printing a cathode paste after the high temperature co-firing step, the step of printing a cathode paste comprising: printing cathode slurry on the outer surface of an electrolyte layer of an anode support body with an anode functional layer and an electrolyte layer by adopting a screen printing method, drying and sintering the cathode slurry, and forming a cathode layer outside the electrolyte layer to obtain the flat-plate proton ceramic fuel cell large-area single cell; the cathode material is PrBa 1-x Sr x Co 2-y Fe y O 5+δ Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; the sintering temperature is any value of 800-1100 ℃, and the heat preservation time is any value of 1-6 h.
10. A flat-plate proton ceramic fuel cell large-area single cell prepared by the preparation method of the flat-plate proton ceramic fuel cell large-area single cell as claimed in any one of claims 1 to 9, wherein the thickness is any one value of 0.5 to 3mm, and the side length is any one value of 5 to 15 cm.
CN202311284071.4A 2023-10-07 2023-10-07 Flat-plate proton ceramic fuel cell large-area single cell and preparation method thereof Pending CN117497814A (en)

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