CN107017423B - Low-temperature solid oxide fuel cell and preparation method thereof - Google Patents
Low-temperature solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN107017423B CN107017423B CN201710232995.8A CN201710232995A CN107017423B CN 107017423 B CN107017423 B CN 107017423B CN 201710232995 A CN201710232995 A CN 201710232995A CN 107017423 B CN107017423 B CN 107017423B
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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
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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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- 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
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- 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
Abstract
The invention provides a low-temperature solid oxide fuel cell, which comprises an anode support body; a dense electrolyte layer disposed on the anode support; a bismuth oxide-based dense electrolyte layer disposed on the dense electrolyte layer; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer; and a cathode active layer disposed on the bismuth oxide-based dense electrolyte layer. Compared with the prior art, the compact electrolyte layer is arranged between the bismuth oxide-based compact electrolyte layer and the anode support body, and can effectively protect the bismuth oxide-based compact electrolyte layer, effectively isolate the direct contact between the bismuth oxide-based compact electrolyte layer and a reducing gas, so that the bismuth oxide-based compact electrolyte layer is not decomposed, the normal work of bismuth oxide is ensured, the optimized and efficient use of different electrolytes is realized, the internal resistance of the cell is effectively reduced, and the performance of the cell at a low-temperature section is improved, so that the solid oxide fuel cell can efficiently conduct oxygen ions and efficiently work under the low-temperature working condition.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a low-temperature solid oxide fuel cell and a preparation method thereof.
Background
The fuel cell is a device for directly converting chemical energy stored in fuel into electric energy through an electrochemical process, and has the characteristics of high efficiency, environmental friendliness, continuous operation, modularization, low operation noise, strong fuel applicability and the like, so that the fuel cell is widely concerned. The Solid Oxide Fuel Cell (SOFC) has an all-solid-state structure without a noble metal catalyst, is safe and reliable, has a wide application range, and can be used as a portable mobile power supply, a vehicle auxiliary power supply, a dispersed power station and the like.
At present, one of the main factors limiting the commercial application of the conventional SOFC is its high working temperature, and the high operating temperature causes many problems, such as the requirements of thermal stability, thermal expansion matching, chemical stability, high temperature strength, etc. of each component of the battery are harsh, the operating cost of the system is increased, and the performance decay rate is accelerated, so that it has become a trend in this field to reduce the operating temperature of the SOFC. The technical development of the last decade aims at reducing the operation temperature to an intermediate temperature range (600-800 ℃), but if the operation temperature of the SOFC can be reduced to a low temperature range (300-600 ℃), a wider range of connecting materials and sealing materials can be selected, and the cost of the SOFC system can be greatly reduced.
In the existing electrolyte system, the Bi-based electrolyte system material has the highest oxygen ion conductivity at a low-temperature section, but because the Bi-based electrolyte system material is easy to decompose in a reducing atmosphere and is rarely applied as an SOFC electrolyte, how to apply the Bi-based electrolyte system to the SOFC by adopting a low-cost preparation technology and ensure the high-efficiency operation of the Bi-based electrolyte system in a low-temperature working region is not realized by related technologies.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low temperature solid oxide fuel cell and a method for manufacturing the same, wherein the low temperature solid oxide fuel cell has high performance and mechanical strength at a low temperature.
The invention provides a low-temperature solid oxide fuel cell, which comprises:
an anode support;
a dense electrolyte layer disposed on the anode support; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer;
a bismuth oxide-based dense electrolyte layer disposed on the dense electrolyte layer;
and a cathode active layer disposed on the bismuth oxide-based dense electrolyte layer.
Preferably, the thickness of the anode supporting layer is 500-1500 μm; the anode supporting layer is a two-phase composite anode supporting material layer or a single-phase mixed ion electronic conductor anode supporting material layer.
Preferably, the electron conducting phase in the dual-phase composite anode supporting material layer is selected from one or more of NiO, CuO and ZnO; the ion conducting phase in the two-phase composite anode supporting material layer is selected from one or more of samarium-doped cerium oxide, gadolinium-doped cerium oxide, samarium-neodymium-doped cerium oxide and stable zirconium oxide; the volume fraction of the electronic conducting phase in the two-phase composite anode supporting material layer is 30-70%.
Preferably, the single-phase mixed ion electron conductor in the single-phase mixed ion electron conductor anode supporting material layer is selected from strontium and chromium co-doped lanthanum manganate, lanthanum and transition metal element co-doped calcium titanate, lanthanum-doped strontium titanate and layered perovskite material PrBaMn2O5+One or more of (a).
Preferably, the thickness of the dense electrolyte layer is 5-100 μm; the electrolyte in the compact electrolyte layer is selected from one or more of samarium-doped cerium oxide, gadolinium-doped cerium oxide, samarium-neodymium-doped cerium oxide and stabilized zirconia.
Preferably, the thickness of the bismuth oxide-based dense electrolyte layer is 5-100 μm; the electrolyte in the bismuth oxide-based compact electrolyte layer is selected from erbium-stabilized bismuth oxide, yttrium-stabilized bismuth oxide and Bi2V0.9Cu0.1O5.5-One or more of (a).
Preferably, the thickness of the cathode active layer is 5-80 μm; the cathode active layer is a two-phase composite cathode active layer; the ion conducting phase in the two-phase composite cathode active layer is selected from erbium-stabilized bismuth oxide and/or yttrium-stabilized bismuth oxide; the electronic conducting phase in the biphase composite cathode active layer is selected from strontium-doped lanthanum manganate, strontium and bismuth-co-doped lanthanum manganate and Pr0.5Ba0.5MnO3-And Bi2Ru2O7One or more of (a).
The invention also provides a preparation method of the low-temperature solid oxide fuel cell, which comprises the following steps:
s1) mixing the anode support material with a pore-forming agent, and performing compression molding to obtain an anode support precursor;
s2) preparing a compact electrolyte layer on the anode support precursor, and sintering at high temperature to obtain the anode support with the compact electrolyte layer; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer;
s3) coating the bismuth oxide-based electrolyte slurry on the compact electrolyte layer of the anode support body provided with the compact electrolyte layer, and after low-temperature co-firing, obtaining the anode support body provided with the bismuth oxide-based compact electrolyte layer and the compact electrolyte layer;
s4) preparing a cathode active layer on the bismuth oxide-based dense electrolyte layer of the anode support body provided with the bismuth oxide-based dense electrolyte layer and the dense electrolyte layer to obtain the low-temperature solid oxide fuel cell.
Preferably, the pore-forming agent is selected from graphite, starch or polymethyl methacrylate; the mass ratio of the pore-forming agent to the anode support material is (1-3): (9-7).
Preferably, the high-temperature sintering temperature is 1200-1400 ℃; the high-temperature sintering time is 5-20 h; the low-temperature co-firing temperature is 700-900 ℃; and the low-temperature co-firing time is 5-30 h.
The invention provides a low-temperature solid oxide fuel cell, which comprises an anode support body; a dense electrolyte layer disposed on the anode support; a bismuth oxide-based dense electrolyte layer disposed on the dense electrolyte layer; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer; and a cathode active layer disposed on the bismuth oxide-based dense electrolyte layer. Compared with the prior art, the compact electrolyte layer is arranged between the bismuth oxide-based compact electrolyte layer and the anode support body to form a double-layer electrolyte structure, the compact electrolyte layer can effectively protect the bismuth oxide-based electrolyte layer, effectively isolate the direct contact between the bismuth oxide-based compact electrolyte layer and a reducing gas, prevent the bismuth oxide-based compact electrolyte layer from being decomposed, ensure the normal work of bismuth oxide, realize the optimized and high-efficiency use of different electrolytes, effectively reduce the internal resistance of the cell and improve the performance of the cell at a low-temperature section, so that the solid oxide fuel cell can also efficiently conduct oxygen ions and efficiently work under the low-temperature working condition, and simultaneously, the low-temperature solid oxide fuel cell provided by the invention has excellent mechanical strength.
Drawings
FIG. 1 is a schematic structural diagram of a low temperature solid oxide fuel cell provided by the present invention;
FIG. 2 is a schematic diagram of a process for preparing a low temperature solid oxide fuel cell according to the present invention;
FIG. 3 is a scanning electron micrograph of a low temperature solid oxide fuel cell obtained in example 1 of the present invention;
FIG. 4 is a P-I, V-I graph of a low temperature solid oxide fuel cell obtained in example 1 of the present invention at different temperatures;
fig. 5 is an ac impedance spectrum of the low-temperature solid oxide fuel cell obtained in example 1 of the present invention at different temperatures;
fig. 6 is a scanning electron micrograph of the low temperature solid oxide fuel cell obtained in example 2 of the present invention;
FIG. 7 is a P-I, V-I graph of a low temperature solid oxide fuel cell obtained in example 2 of the present invention at different temperatures;
fig. 8 is an ac impedance spectrum of the low-temperature solid oxide fuel cell obtained in example 2 of the present invention at different temperatures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a low-temperature solid oxide fuel cell, which comprises: an anode support; a dense electrolyte layer disposed on the anode support; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer; a bismuth oxide-based dense electrolyte layer disposed on the dense electrolyte layer; and a cathode active layer disposed on the bismuth oxide-based dense electrolyte layer.
Referring to fig. 1, fig. 1 is a low-temperature solid oxide fuel cell provided by the present invention, wherein a is a cathode active layer, B is a bismuth oxide-based dense electrolyte layer, C is a dense electrolyte layer, and D is an anode support.
Wherein, the anode support is a porous anode support known to those skilled in the art, and is not particularly limited; the thickness of the anode support body is preferably 500-1500 μm, more preferably 600-1300 μm, still more preferably 700-1100 μm, and most preferably 800-900 μm; the anode support is preferably a two-phase composite anode support material layer or a single-phase mixed ion electron conductor anode support material layer; when the anode support is a two-phase composite anode support material layer, the two-phase composite anode support material is preferably a two-phase composite anode support material composed of an electron conducting phase and an ion conducting phase, wherein the volume fraction of the electron conducting phase is preferably 30% to 70%, more preferably 40% to 60%, still more preferably 50% to 60%, and most preferably 55% to 60%; the electron-conducting phase is not particularly limited, but is preferably one or more of NiO, CuO, and ZnO; the ion-conducting phase is a technique in the artThe ion conducting phase is not particularly limited, but is preferably one or more of samarium-doped ceria, gadolinium-doped ceria, samarium-neodymium-doped ceria, and stabilized zirconia; when the anode support is a single-phase mixed ion electronic conductor anode support material layer, the unidirectional mixed ion electronic conductor is preferably strontium and chromium co-doped lanthanum manganate, lanthanum and transition metal element co-doped calcium titanate, lanthanum-doped strontium titanate and layered perovskite material PrBaMn2O5+One or more of; the transition metal element is not particularly limited as long as it is known to those skilled in the art, and in the present invention, Mn, Fe, Co, Ni or Cu is preferable; the single-phase mixed ion-electron conductor has the capability of simultaneously conducting electrons and ions.
According to the invention, a dense electrolyte layer is arranged on the anode support; the thickness of the compact electrolyte layer is preferably 5-100 μm, more preferably 5-80 μm, still more preferably 5-60 μm, still more preferably 5-30 μm, and most preferably 5-20 μm; the dense electrolyte layer is not particularly limited as long as it is an electrolyte layer of a bismuth oxide-based electrolyte, which is well known to those skilled in the art, and in the present invention, one or more of samarium-doped ceria, gadolinium-doped ceria, samarium-neodymium-co-doped ceria, and stabilized zirconia are preferred; when the electrolyte of the compact electrolyte layer is doped cerium oxide, namely the doped cerium oxide is used for protecting the bismuth oxide-based compact electrolyte layer to form a double-layer electrolyte, the bismuth oxide film in the bismuth oxide-based compact electrolyte layer can also block the electronic conductance generated by the cerium oxide layer in a reducing atmosphere, and the open-circuit voltage of the battery is ensured not to be reduced due to internal short circuit.
According to the invention, a bismuth oxide-based dense electrolyte layer is arranged on the dense electrolyte layer; the thickness of the bismuth oxide-based dense electrolyte layer is preferably 5-100 μm, more preferably 5-80 μm, still more preferably 5-60 μm, still more preferably 5-30 μm, and most preferably 5-20 μm; the bismuth oxide-based dense electrolyte layer may be any bismuth oxide-based electrolyte known to those skilled in the art, and is not particularly limited, and the electrolyte in the present invention is preferably erbium-stabilized bismuth oxide or yttrium-stabilized bismuth oxideBismuth and Bi2V0.9Cu0.1O5.5-One or more of (a).
According to the invention, a cathode active layer is arranged on the bismuth oxide-based compact electrolyte layer; the thickness of the cathode active layer is preferably 5-80 μm, more preferably 10-60 μm, still more preferably 10-40 μm, and most preferably 10-30 μm; the cathode active layer is not particularly limited as long as it is known to those skilled in the art, and a two-phase composite cathode active layer is preferred in the present invention; the two-phase composite cathode active layer consists of an electronic conducting phase and an ionic conducting phase; the volume fraction of the electron conducting phase is preferably 35 to 65%, more preferably 40 to 60%, and still more preferably 45 to 65%; most preferably 45 to 50 percent; the ion-conducting phase is not particularly limited as long as it is well known to those skilled in the art, and in view of the strong reactivity of bismuth oxide, erbium-stabilized bismuth oxide and/or yttrium-stabilized bismuth oxide are preferred in the present invention; the electron conducting phase is not particularly limited as long as it is an electron conductor or mixed ion electron conductor material with good compatibility with the bismuth oxide electrolyte material, which is well known to those skilled in the art, and in the present invention, strontium-doped lanthanum manganate, strontium-bismuth co-doped lanthanum manganate, Pr are preferred0.5Ba0.5MnO3-And Bi2Ru2O7One or more of (a).
The compact electrolyte layer is arranged between the bismuth oxide-based compact electrolyte layer and the anode support body to form a double-layer electrolyte structure, the compact electrolyte layer can effectively protect the bismuth oxide-based compact electrolyte layer, effectively isolate the direct contact between the bismuth oxide-based compact electrolyte layer and a reducing gas, prevent the bismuth oxide-based compact electrolyte layer from being decomposed, ensure the normal work of bismuth oxide, realize the optimized high-efficiency use of different electrolytes, effectively reduce the internal resistance of the cell and improve the performance of the cell at a low-temperature section, so that the solid oxide fuel cell can also efficiently conduct oxygen ions and efficiently work under the low-temperature working condition, and simultaneously, the low-temperature solid oxide fuel cell provided by the invention has excellent mechanical strength, is a flat plate type anode-supported bismuth oxide-based double-layer electrolyte solid oxide fuel cell, and has a fine microstructure.
The invention also provides a preparation method of the low-temperature solid oxide fuel cell, which comprises the following steps: s1) mixing the anode support material with a pore-forming agent, and performing compression molding to obtain an anode support precursor; s2) preparing a compact electrolyte layer on the anode support precursor, and sintering at high temperature to obtain the anode support with the compact electrolyte layer; the compact electrolyte layer is a cerium-based electrolyte layer or a zirconium-based electrolyte layer; s3) coating the bismuth oxide-based electrolyte slurry on the compact electrolyte layer of the anode support body provided with the compact electrolyte layer, and after low-temperature co-firing, obtaining the anode support body provided with the bismuth oxide-based compact electrolyte layer and the compact electrolyte layer; s4) preparing a cathode active layer on the bismuth oxide-based dense electrolyte layer of the anode support body provided with the bismuth oxide-based dense electrolyte layer and the dense electrolyte layer to obtain the low-temperature solid oxide fuel cell.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
Mixing an anode support material with a pore-forming agent; the anode support material is the same as that described above, and is not described in detail herein; the pore-forming agent is a pore-forming agent well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of graphite, starch, and polymethyl methacrylate (PMMA) are preferred; the mass ratio of the pore-forming agent to the anode support material is preferably (1-3): (9-7), more preferably (1.5-3): (8.5-7), preferably (1.5-2.5): (8.5-7.5), most preferably (1.5-2): (8.5-8); in accordance with the present invention, it is preferred to mix the anode support material with the pore-forming agent in an alcohol solvent; the alcohol solvent may be one known to those skilled in the art, and is not particularly limited, and ethanol is preferred in the present invention.
After mixing, preferably ball milling, obtaining an anode support material dispersion liquid; the ball milling time is preferably 5-48 h; the solid content of the anode supporting material dispersion liquid is preferably 20-50%; then drying the anode support material dispersion liquid to obtain anode support powder; the drying temperature is preferably 50-100 ℃; the drying time is preferably 12-48 h; the drying is preferably carried out in flowing air.
Pressing and molding the anode support body powder to obtain an anode support body precursor; the press forming preferably adopts a dry pressing method.
Preparing a compact electrolyte layer on the anode support precursor, and sintering at a high temperature to obtain the anode support provided with the compact electrolyte layer; the compact electrolyte layer is the same as the above, and is not described in detail herein; the present invention preferably produces a dense electrolyte layer according to the following method: dispersing electrolyte materials of the compact electrolyte layer on a precursor of an anode support body, and co-pressing and forming to obtain a single-layer electrolyte half-cell ceramic green sheet; sintering the single-layer electrolyte half-cell ceramic green sheet at high temperature to obtain an anode support body provided with a compact electrolyte layer; the high-temperature sintering temperature is preferably 1200-1400 ℃; the high-temperature sintering time is preferably 5-20 h.
Coating bismuth oxide-based electrolyte slurry on the compact electrolyte layer of the anode support provided with the compact electrolyte layer; the bismuth oxide-based electrolyte slurry is not particularly limited as long as it is well known to those skilled in the art, and preferably includes a bismuth oxide-based electrolyte and an organic component in the present invention; the organic component comprises a binder, a dispersant, a plasticizer and an organic solvent; the solid content of the bismuth oxide-based electrolyte slurry is preferably 10 to 30 percent; the bismuth oxide-based electrolyte is the same as described above and is not described in detail herein; the binder is not particularly limited as long as it is well known to those skilled in the art, and in the present invention, polyvinyl butyral (PVB) and/or polyether sulfone (PESf) are preferred; the mass of the binder is preferably 4.3-11% of that of the organic component; the dispersant is not particularly limited as long as it is well known to those skilled in the art, and in the present invention, polyvinylpyrrolidone (PVP) and/or Triethanolamine (TEA) are preferable; the mass of the dispersing agent is preferably 1.3-3% of that of the organic component; the plasticizer is a plasticizer well known to those skilled in the art, and is not particularly limited, and polyethylene glycol and/or dibutyl phthalate (DBP) are preferable in the present invention; the mass of the plasticizer is preferably 0.2 to 1.6 percent of the mass of the organic component; the organic solvent is not particularly limited as long as it is well known to those skilled in the art, and in the present invention, one or more of ethanol, 2-butanone and 1-methyl-2-pyrrolidone (NMP) are preferable. In the present invention, the organic component preferably includes 0.3 to 1 wt% of polyvinyl butyral, 4 to 10 wt% of polyethersulfone, 1 to 2 wt% of polyvinylpyrrolidone, 0.3 to 1 wt% of triethanolamine, 0.1 to 0.8 wt% of polyethylene glycol, 0.1 to 0.8 wt% of dibutyl phthalate, 20 to 40 wt% of ethanol, 40 to 70 wt% of 2-butanone, and 20 to 40 wt% of 1-methyl-2-pyrrolidone (NMP).
The preparation method of the bismuth oxide-based electrolyte slurry is a preparation method well known to those skilled in the art, and is not particularly limited, and in the present invention, the bismuth oxide-based electrolyte slurry is preferably prepared according to the following method: dispersing a binder, a dispersing agent and a plasticizer into an organic solvent, ball-milling for 1-5 h, and standing for 10-50 h to obtain an organic component; and mixing the bismuth oxide-based electrolyte with the organic components, and performing ball milling for 20-100 hours to obtain bismuth oxide-based electrolyte slurry.
Coating the bismuth oxide-based electrolyte slurry on the compact electrolyte layer, preferably naturally curing and then coating until the thickness of the bismuth oxide-based dot matrix layer is reached, drying the bismuth oxide-based dot matrix layer in flowing air at the temperature of between 30 and 50 ℃ for 1 to 5 hours, and then carrying out low-temperature co-firing to obtain an anode support body provided with the bismuth oxide-based compact electrolyte layer and the compact electrolyte layer; the low-temperature co-firing temperature is preferably 700-900 ℃; the low-temperature co-firing time is preferably 5-30 h.
And preparing a cathode active layer on the bismuth oxide-based compact electrolyte layer of the anode support body provided with the bismuth oxide-based compact electrolyte layer and the compact electrolyte layer to obtain the low-temperature solid oxide fuel cell. The preparation method of the cathode active layer is a preparation method well known to those skilled in the art, and is not particularly limited, and the cathode active layer is preferably prepared according to the following method in the present invention: mixing a cathode active material with a terpineol solution of ethyl cellulose to obtain cathode slurry; the cathode active material is the same as described above and is not described in detail herein; the mass fraction of the ethyl cellulose in the terpineol solution of the ethyl cellulose is preferably 5-30%; the solid content of the cathode slurry is preferably 40-60%; preparing a cathode active layer on the bismuth oxide-based compact electrolyte layer by adopting a screen printing technology; after obtaining the cathode active layer, preferably co-firing at a low temperature to obtain a low-temperature solid oxide fuel cell; the low temperature is preferably 600-800 ℃; the co-firing time is preferably 1-30 hours, more preferably 1-20 hours, still more preferably 1-15 hours, still more preferably 3-10 hours, and most preferably 3-5 hours.
Fig. 2 is a schematic diagram of a process for preparing a low-temperature solid oxide fuel cell according to the present invention.
The preparation method disclosed by the invention combines the co-pressing and slurry coating technologies, is simple, high in efficiency, low in cost, suitable for industrial production, and has important significance on the bismuth oxide-based low-temperature solid oxide fuel cell.
In order to further illustrate the present invention, a low temperature solid oxide fuel cell and a method for manufacturing the same according to the present invention are described in detail with reference to the following examples.
Example 1
The electronic conducting phase NiO powder of the anode supporting layer is obtained by decomposing basic nickel carbonate at 600 ℃, the grain diameter D50 of the electronic conducting phase NiO powder is 0.4 mu m, and the ionic conducting phase Sm is0.075Nd0.075Ce0.85O2-Obtained by citrate combustion method (SNDC, powder treated in air at 700 ℃ for 3 hours), and the particle diameter D50 was 0.4 μm.
And (3) preparing the mixed powder of the NiO and the SNDC of the anode supporting layer according to the volume ratio of 60:40, adding 20% of starch by mass, ball-milling in ethanol for 10 hours, uniformly mixing, and drying to obtain the NiO-SNDC mixed powder containing the starch.
Taking a proper amount of NiO-SNDC mixed powder containing starch, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of about 900 microns; taking a proper amount of loose SNDC powder obtained by a citrate combustion method by the same method, preparing an SNDC film with the thickness of about 20 mu m by a co-pressing method to obtain a NiO-SNDC | SNDC double-layer half-cell green body, and co-firing the NiO-SNDC | SNDC double-layer half-cell green body at 1400 ℃ for 5h to obtain a single-layer electrolyte anode support body half-cell ceramic sintered body.
Uniformly dispersing 0.5g of polyvinyl butyral (PVB) and 5g of polyether sulfone (PESf) as a binder, 1.6g of polyvinylpyrrolidone (PVP) and 0.4g of Triethanolamine (TEA) as a dispersant, 0.3g of polyethylene glycol as a plasticizer and 0.2g of dibutyl phthalate (DBP) into 20g of ethanol, 50g of 2-butanone and 22g of 1-methyl-2-pyrrolidone (NMP) as three solvents, carrying out ball milling for 1h, and standing for 10h to obtain an organic component for preparing the Bi-based slurry suspension after uniformly mixing; 10g of citrate is taken for combustion to obtain Er with uniform particles0.4Bi1.6O3(ESB, the powder is processed in air at 600 ℃ for 5h, and the particle size D50 is 0.45 mu m), added into a prepared organic solvent, and subjected to ball milling for 24h to obtain ESB electrolyte powder slurry with the solid content of 10%.
The ESB slurry is uniformly coated on the electrolyte surface of the single-layer electrolyte anode support half-cell ceramic sintered body, placed in the air for natural curing for 30min, and after the ESB slurry is cured, the slurry coating operation is repeated to obtain the desired ESB electrolyte thickness (about 20 μm).
The cured ESB electrolyte membrane green body was dried in flowing air at 40 ℃ for 1 h.
And (3) placing the dried ESB electrolyte film green body in a muffle furnace for low-temperature co-firing at 800 ℃ for 10h to obtain the anode-supported double-layer electrolyte semi-cell pre-sintered body.
Burning ESB powder and citrate to obtain La0.74Bi0.1Sr0.16MnO3-(LBSM) is evenly mixed according to the volume ratio of 1:1, ball milling is carried out for 2h to obtain cathode active layer composite ceramic powder ESB-LBSM, the ESB-LBSM is evenly dispersed into terpineol solution with 10% of ethyl cellulose by mass fraction, and ball milling is carried out for 5h to obtain cathode slurry with 50% of solid content; preparing a cathode active layer ESB-LBSM (the thickness is about 20 mu m) on the surface of an ESB electrolyte of an anode-supported double-layer electrolyte half-cell pre-sintering body by adopting a screen printing technology, and co-firing for 3h at 750 ℃ to obtain a single-cell NiO-SNDC | SNDC | ESB | ESB-LBSM (low-temperature solid oxide fuel cell) with a four-layer structure of an anode support body, an anode-side compact electrolyte, a bismuth oxide compact electrolyte layer and a cathode active layer.
A scanning electron microscope was used to analyze the low-temperature solid oxide fuel cell obtained in example 1, and a scanning electron micrograph of the entire cross section was obtained, as shown in fig. 3.
The performance of the low-temperature solid oxide fuel cell obtained in example 1 is tested, and cell performance graphs at different temperatures are obtained, as shown in fig. 4 and 5, wherein fig. 4 is a P-I, V-I curve at different temperatures; FIG. 5 is an AC impedance spectrum at different temperatures.
Example 2
The preparation method of the electronic conducting phase NiO powder of the anode supporting layer is the same as that of example 1, and the ion conducting phase G0.1Ce0.9O2-Obtained by citrate combustion method (GDC, powder treated in air at 800 ℃ for 3 hours, particle diameter D50 ═ 0.5 μm).
And (3) preparing the mixed powder of the NiO and the GDC of the anode supporting layer according to the volume ratio of 60:40, adding 20% of starch by mass, ball-milling in ethanol for 10 hours, uniformly mixing, and drying to obtain the NiO-GDC mixed powder containing the starch.
Taking a proper amount of mixed powder containing the starch NiO-GDC, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of about 900 microns; taking a proper amount of loose GDC powder obtained by a citrate combustion method, preparing a GDC film with the thickness of about 15 mu m by a co-pressing method to obtain a NiO-GDC | GDC double-layer half-cell green body, and co-firing the NiO-GDC | GDC double-layer half-cell green body at 1400 ℃ for 5 hours to obtain a single-layer electrolyte anode support body half-cell ceramic sintered body.
Er is adopted as the bismuth oxide electrolyte layer0.4Bi1.6O3The ESB electrolyte powder preparation, slurry preparation and film preparation methods were the same as example 1, and the ESB thickness obtained in this example was about 15 μm.
Burning ESB powder and citrate to obtain La0.8Sr0.2MnO3-(LSM) is uniformly mixed according to the volume ratio of 1:1, and ball milling is carried out for 2h to obtain cathode active layer composite ceramic powder ESB-LSM, the ESB-LSM is uniformly dispersed into terpineol solution with 10% of ethyl cellulose by mass fraction, and ball milling is carried out for 5h to obtain cathode slurry with 50% of solid content; preparing a cathode active layer ESB-LSM on the surface of an ESB electrolyte of an anode-supported double-layer electrolyte semi-cell pre-sintered body by adopting a screen printing technology, and co-firing at 750 ℃ for 3 hours to obtain an anode support body single-electrode with a four-layer structureNiO-GDC/ESB/LSM (low temperature solid oxide fuel cell) cell slice
A scanning electron microscope was used to analyze the low-temperature solid oxide fuel cell obtained in example 2, and a scanning electron micrograph of the entire cross section was obtained, as shown in fig. 6.
The performance of the low-temperature solid oxide fuel cell obtained in example 2 was tested to obtain cell performance graphs at different temperatures, as shown in fig. 7 and 8, wherein fig. 7 is a P-I, V-I curve at different temperatures; FIG. 8 is an AC impedance spectrum at different temperatures.
Example 3
The preparation method of the electronic conducting phase NiO powder of the anode supporting layer is the same as that of the example 1, and the ionic conducting phase Sm is0.2Ce0.8O2-Obtained by citrate combustion (SDC, powder treated in air at 600 ℃ for 3h), and having a particle size D50 of 0.4 μm.
And (3) mixing the NiO and SDC mixed powder of the anode supporting layer according to the volume ratio of 60:40, adding 20% of starch by mass, ball-milling in ethanol for 10 hours, uniformly mixing, and drying to obtain the NiO-SDC mixed powder containing the starch.
Taking a proper amount of mixed powder containing NiO-SDC starch, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of about 900 microns; taking a proper amount of loose SDC powder obtained by a citrate combustion method by the same method, preparing an SDC film with the thickness of about 20 mu m by a co-pressing method to obtain a NiO-SDC | SDC double-layer half-cell green body, and co-firing the NiO-SDC | SDC double-layer half-cell green body at 1400 ℃ for 5h to obtain a single-layer electrolyte anode support body half-cell ceramic sintered body.
The bismuth oxide electrolyte layer adopts Y0.5Bi1.5O3(YSB, the powder obtained by the citrate method is processed in the air at 700 ℃ for 5h, and the grain diameter D50 is 0.45 mu m), and the preparation method of the YSB electrolyte powder, the preparation method of the slurry and the preparation method of the film are the same as the example 1.
Uniformly mixing YSB powder with LSM obtained by a citrate combustion method in a volume ratio of 1:1, carrying out ball milling for 2 hours to obtain cathode active layer composite ceramic powder YSB-LSM, uniformly dispersing the YSB-LSM into terpineol solution of ethyl cellulose with the mass fraction of 10%, and carrying out ball milling for 5 hours to obtain cathode slurry with the solid content of 50%; and preparing a cathode active layer YSB-LSM on the surface of an anode-supported double-layer electrolyte semi-cell pre-sintered body YSB electrolyte by adopting a screen printing technology, and co-firing at 750 ℃ for 3 hours to obtain a single cell NiO-SDC | SDC | YSB | YSB-LSM with an anode-supported four-layer structure, namely the low-temperature solid oxide fuel cell.
Example 4
The anode support adopts a single-phase mixed ionic electronic conductor layered perovskite material PrBaMn2O5+(PBMO), Pr obtained from the citrate process0.5Ba0.5MnO3-(PBM, 1000 ℃ air treatment for 5H) in 5% H2And the particle diameter D50 is 0.25 mu m.
Adding starch with the mass fraction of 10% into the PBMO ceramic powder, ball-milling in ethanol for 10 hours, uniformly mixing, and drying to obtain the PBMO powder containing starch.
Taking a proper amount of PBMO powder containing starch, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of 800 microns; an appropriate amount of GDC (the powder preparation method was the same as that of example 2, and the particle size D50 was 0.5 μm) powder was taken in the same manner, and a GDC thin film having a thickness of about 20 μm was prepared by co-pressing to obtain a PBMO | GDC two-layer half-cell green compact, which was co-fired at 1200 ℃ for 5 hours to obtain a single-layer electrolyte anode support half-cell ceramic sintered body.
The bismuth oxide electrolyte layer is prepared by YSB, YSB electrolyte powder, slurry preparation and film preparation methods are the same as example 3.
YSB-LSM cathode active layer ceramic powder, cathode slurry with 50% solid content, and method for preparing cathode active layer example 3, finally obtaining anode support four-layer structure single cell piece PBMO | GDC | YSB-LSM, i.e. low temperature solid oxide fuel cell.
Example 5
The method of example 4 was used to change GDC to SNDC (powder preparation method same as example 1, D50 ═ 0.4 μm), and PBMO | SNDC double-layer half-cells were obtained.
The bismuth oxide electrolyte layer adopts ESB, and the preparation methods of bismuth oxide electrolyte powder, slurry preparation and film preparation are the same as those of example 1.
Uniformly mixing ESB powder and PBM (the particle size D50 is 0.25 mu m) obtained by a citrate method in a volume ratio of 1:1, carrying out ball milling for 2h to obtain cathode active layer composite ceramic powder ESB-PBM, uniformly dispersing the ESB-PBM into terpineol solution with 10% of ethyl cellulose by mass fraction, and carrying out ball milling for 5h to obtain cathode slurry with 50% of solid content; preparing a cathode active layer ESB-PBM on the ESB electrolyte surface of the anode-supported double-layer electrolyte semi-cell pre-sintered body by adopting a screen printing technology, and co-firing for 3 hours at 750 ℃ to obtain a single cell PBMO | SNDC | ESB | ESB-PBM with an anode-supported four-layer structure, namely the low-temperature solid oxide fuel cell.
Claims (2)
1. A preparation method of a low-temperature solid oxide fuel cell is characterized by comprising the following steps:
the electronic conducting phase NiO powder of the anode supporting layer is obtained by decomposing basic nickel carbonate at 600 ℃, the grain diameter D50 of the electronic conducting phase NiO powder is 0.4 mu m, and the ionic conducting phase Sm is0.075Nd0.075Ce0.85O2-SNDC, abbreviated to SNDC, obtained by citrate combustion, with a particle size D50 ═ 0.4 μm;
the mixed powder of the NiO and the SNDC of the anode supporting layer is prepared according to the volume ratio of 60:40, starch with the mass fraction of 20% is added, the mixture is evenly mixed in ethanol by ball milling for 10 hours, and the NiO-SNDC mixed powder containing the starch is obtained after drying;
taking a proper amount of NiO-SNDC mixed powder containing starch, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of 900 microns; taking a proper amount of loose SNDC powder obtained by a citrate combustion method by adopting the same method, preparing an SNDC film with the thickness of 20 mu m by a co-pressing method to obtain a NiO-SNDC | SNDC double-layer half-cell green body, and co-firing the NiO-SNDC | SNDC double-layer half-cell green body at 1400 ℃ for 5 hours to obtain a single-layer electrolyte anode support body half-cell ceramic sintered body;
uniformly dispersing 0.5g of polyvinyl butyral and 5g of polyether sulfone as a binder, 1.6g of polyvinylpyrrolidone and 0.4g of triethanolamine as a dispersant, 0.3g of polyethylene glycol as a plasticizer and 0.2g of dibutyl phthalate into 20g of ethanol, 50g of 2-butanone and 22g of 1-methyl-2-pyrrolidone as three solvents, carrying out ball milling for 1h, standing for 10h, and mixing uniformly to obtain an organic component for preparing the Bi-based slurry suspension; 10g of citrate is taken for combustion to obtain Er with uniform particle size D50-0.45 mu m0.4Bi1.6O3Adding ESB (abbreviation: ESB) into the prepared organic component, and performing ball milling for 24 hours to obtain ESB electrolyte powder slurry with the solid content of 10%;
uniformly coating the ESB slurry on the electrolyte surface of the single-layer electrolyte anode support body half-cell ceramic sintered body, placing the single-layer electrolyte anode support body half-cell ceramic sintered body dielectric slurry, and repeating slurry coating operation after the;
drying the solidified ESB electrolyte film green body in flowing air at 40 ℃ for 1 h;
placing the dried ESB electrolyte film green body in a muffle furnace for low-temperature co-firing at 800 ℃ for 10h to obtain an anode-supported double-layer electrolyte semi-cell pre-sintered body;
burning ESB powder and citrate to obtain La0.74Bi0.1Sr0.16MnO3-Namely LBSM, uniformly mixing the components in a volume ratio of 1:1, performing ball milling for 2 hours to obtain cathode active layer composite ceramic powder ESB-LBSM, uniformly dispersing the ESB-LBSM into terpineol solution with 10% of ethyl cellulose by mass fraction, and performing ball milling for 5 hours to obtain cathode slurry with 50% of solid content; preparing a cathode active layer ESB-LBSM with the thickness of 20 mu m on the ESB electrolyte surface of an anode-supported double-layer electrolyte half-cell pre-sintering body by adopting a screen printing technology, and co-firing for 3h at 750 ℃ to obtain an anode support body, anode side dense electrolyte, a bismuth oxide dense electrolyte layer and a cathode active layer four-layer structure single cell NiO-SNDC | SNDC | ESB | ESB-LBSM, namely the low-temperature solid oxide fuel cell.
2. A preparation method of a low-temperature solid oxide fuel cell is characterized by comprising the following steps:
the electronic conducting phase NiO powder of the anode supporting layer is obtained by decomposing basic nickel carbonate at 600 ℃, the particle diameter D50 of the electronic conducting phase NiO powder is 0.4 mu m, and the ionic conducting phase Gd is0.1Ce0.9O2-Abbreviated GDC, obtained by citrate combustion, with a particle size D50 ═ 0.5 μm;
the mixed powder of the NiO and the GDC of the anode supporting layer is prepared according to the volume ratio of 60:40, starch with the mass fraction of 20% is added, the mixture is evenly mixed in ethanol by ball milling for 10 hours, and the NiO-GDC mixed powder containing the starch is obtained after drying;
taking a proper amount of NiO-GDC mixed powder containing starch, and pressing by a dry pressing method to obtain an anode support body ceramic green compact with the thickness of 900 microns; taking loose GDC powder obtained by a proper amount of citrate combustion method, preparing a GDC film with the thickness of 15 microns by a co-pressing method to obtain a NiO-GDC | GDC double-layer half-cell green body, and co-firing the NiO-GDC | GDC double-layer half-cell green body at 1400 ℃ for 5 hours to obtain a single-layer electrolyte anode support body half-cell ceramic sintered body;
er is adopted as the bismuth oxide electrolyte layer0.4Bi1.6O3Uniformly dispersing 0.5g of polyvinyl butyral and 5g of polyether sulfone as a binder, 1.6g of polyvinylpyrrolidone and 0.4g of triethanolamine as a dispersant, 0.3g of polyethylene glycol as a plasticizer and 0.2g of dibutyl phthalate into 20g of ethanol, 50g of 2-butanone and 22g of 1-methyl-2-pyrrolidone as three solvents, carrying out ball milling for 1h, standing for 10h, and mixing uniformly to obtain an organic component for preparing the Bi-based slurry suspension; 10g of citrate is taken for combustion to obtain Er with uniform particle size D50-0.45 mu m0.4Bi1.6O3Adding ESB (abbreviation: ESB) into the prepared organic component, and performing ball milling for 24 hours to obtain ESB electrolyte powder slurry with the solid content of 10%;
uniformly coating the ESB slurry on the electrolyte surface of the single-layer electrolyte anode support body half-cell ceramic sintered body, placing the single-layer electrolyte anode support body half-cell ceramic sintered body dielectric slurry in the air for natural curing for 30min, and;
burning ESB powder and citrate to obtain La0.8Sr0.2MnO3-Namely LSM, is uniformly mixed according to the volume ratio of 1:1, and is ball-milled for 2 hours to obtain cathode active layer composite ceramic powder ESB-LSM, which is uniformly dispersed into terpineol solution with 10% of ethyl cellulose by mass fraction, and is ball-milled for 5 hours to obtain cathode slurry with 50% of solid content; and preparing a cathode active layer ESB-LSM on the ESB electrolyte surface of the anode-supported double-layer electrolyte semi-cell pre-sintered body by adopting a screen printing technology, and co-firing for 3 hours at 750 ℃ to obtain a single cell NiO-GDC | GDC | ESB | ESB-LSM with an anode-supported four-layer structure, namely the low-temperature solid oxide fuel cell.
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