CN116826130A - Preparation method of solid oxide fuel cell - Google Patents
Preparation method of solid oxide fuel cell Download PDFInfo
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- CN116826130A CN116826130A CN202310792628.9A CN202310792628A CN116826130A CN 116826130 A CN116826130 A CN 116826130A CN 202310792628 A CN202310792628 A CN 202310792628A CN 116826130 A CN116826130 A CN 116826130A
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- 238000005266 casting Methods 0.000 claims abstract description 60
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2404—Processes or apparatus for grouping fuel cells
Abstract
The invention discloses a preparation method of a solid oxide fuel cell, which specifically comprises the following steps: maintaining the travelling speed of the casting machine to be 0.1-3 cm & s ‑1 The method comprises the steps of carrying out a first treatment on the surface of the Firstly, casting to prepare a fuel electrode layer, then casting an electrolyte layer on the fuel electrode layer, casting an air electrode functional layer on the electrolyte layer, sequentially increasing the height of a scraper of a casting machine between the corresponding functional layers by 10-100 mu m, casting an air electrode support layer to the air electrode functional layer, and increasing the height of the scraper of the casting machine by 300-1000 mu m; then, each functional layer after casting is subjected to lamination hot pressing for 5-10 min at the temperature of 60-80 ℃ and the pressure of 2-5 MPa, so that a complete full-battery biscuit is obtained; finally, the complete full-cell biscuit is put into a high-temperature furnace for sintering, and a solid oxide fuel cell is obtained; the invention ensures that the fuel electrode layer is tightly combined with the electrolyte layer, the electrolyte layer and the air electrode functional layer, and solves the problems of poor interface combination between the fuel electrode layer and the electrolyte layer and the like when the fuel electrode is subjected to tape casting, lamination, hot pressing and sintering and finally silk-screen printing by the traditional manufacturing method.
Description
Technical Field
The invention relates to a battery preparation technology, belongs to the field of fuel cells, and in particular relates to a preparation method of a solid oxide fuel cell.
Background
Compared with other fuel cells such as alkaline fuel cells, phosphoric acid fuel cells and the like, the solid oxide fuel cell (SOFC for short) usually operates in a middle-high temperature range of 600-1000 ℃, has wider fuel adaptability, and can directly use H 2 Besides, the method can also use industrial waste hydrogen and various carbon-based fuels, and has the characteristics of high power generation efficiency (50-60%), low pollution and the like; in addition, the SOFC can also be operated reversely in an electrolysis mode, namely in a Solid Oxide Electrolytic Cell (SOEC) mode, and H is generated by using electric energy and heat energy 2 O or CO 2 Conversion to H 2 Or synthesis gas, has high electrolysis efficiency.
SOEC and SOFC are collectively called solid oxide cell technology (SOC), and when the SOEC and SOFC are operated in a circulating mode, the storage and release of electric energy can be realized; depending on the support, the SOC can be classified into three types of electrolyte support type, electrode support type, and metal-based support type, in which the electrode support type battery can be widely used and studied based on a thin film manufacturing technique to realize a thin film electrolyte;
the electrode-supported cells are classified into fuel electrode-supported cells and air electrode-supported cells. Compared with a fuel electrode support type battery, the air electrode support type battery has the advantages that the air electrode support type battery does not need to face the problem of complex fuel component change, is better in stability, can prepare corresponding optimal fuel electrodes according to different fuels, has wide fuel adaptability in a real sense, but has the problems of thermal matching and chemical compatibility among materials easily caused by the air electrode support type battery, namely, the traditional fuel battery preparation method mainly adopts casting, lamination, hot pressing and sintering, and finally silk-screen printing of the fuel electrode is carried out, and the fuel electrode layer prepared by the method has relatively poor interface combination with an electrolyte layer and is easy to cause layering phenomenon, so that the use effect of the solid oxide fuel battery is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a solid oxide fuel cell, which enables the combination of a fuel electrode layer and an electrolyte layer, and the combination of the electrolyte layer and an air electrode functional layer to be more compact, and solves the problems of poor combination of the interface between the fuel electrode layer and the electrolyte layer and the like when the fuel electrode is subjected to tape casting, lamination, hot pressing and sintering and finally silk-screen printing by the traditional preparation method.
In order to achieve the above object, the present invention provides a method for preparing a solid oxide fuel cell, comprising the steps of:
s1, maintaining the travelling speed of the casting machine to be 0.1-3 cm & S -1 ；
Firstly, casting to prepare a fuel electrode layer, then casting an electrolyte layer on the fuel electrode layer, casting an air electrode functional layer on the electrolyte layer, sequentially increasing the height of a scraper of a casting machine between the corresponding functional layers by 10-100 mu m,
s2, casting the air electrode support layer to the air electrode functional layer in the step S1, wherein the height of a scraper of the casting machine is increased by 300-1000 mu m;
s3, carrying out lamination hot pressing on each functional layer after casting at the temperature of 60-80 ℃ and the pressure of 2-5 MPa for 5-10 min to obtain a complete full-battery biscuit;
s4, finally, putting the complete full-cell biscuit into a high-temperature furnace, and obtaining the solid oxide fuel cell at a heating rate of 0.25-3 ℃/min, a sintering temperature of 1100-1300 ℃ and a sintering time of 3-5 hours;
the electrolyte layer is selected from: fluorite type Y x Zr 1-x O 2-α 、Sc x Zr 1-x O 2-α Wherein x is more than or equal to 0.03 and less than or equal to 0.2; or Sm y Ce 1-y O 2-α 、Gd y Ce 1-y O 2-α Wherein y is more than or equal to 0.1 and less than or equal to 0.3;
the air electrode is selected from: (La, sr) MnO having perovskite structure 3-δ 、(La，Sr)FeO 3-δ 、(La，Sr)CoO 3-δ One or more of,Then forming a composite cathode with the mixture of the electrolyte;
the fuel electrode layer is selected from: niO, cuO, (La, Y) z Sr 1-z TiO 3-β 、(La，Sr)(Cr，Mn)O 3-β And then with electrolyte, wherein z is more than or equal to 0 and less than or equal to 0.6;
alpha, beta, delta represent the number of oxygen vacancies ranging from 0< alpha <2, 0< beta <3, 0< delta <3.
Further, the fuel electrode layer is composed of NiO and SSZ, and the mass ratio of the NiO to the SSZ is 5: 1-5, the thickness of the fuel electrode layer is 10-100 mu m;
the electrolyte layer consists of SSZ, and the thickness of the electrolyte layer is 5-30 mu m;
the air electrode functional layer consists of LSM98 and SSZ, and the mass ratio is 5: 1-5, the thickness is 10-100 mu m;
the air electrode supporting layer consists of LSM95 and 3YSZ, and the mass ratio is 5: 2-5, the thickness of which is 300-1000 mu m;
LSM95 has the molecular formula (La) 0.8 Sr 0.2 ) 0.95 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the 3YSZ is 3% Y 2 O 3 Stabilized ZrO 2 The molecular formula is Y 0.058 Zr 0.942 O 1.971 The method comprises the steps of carrying out a first treatment on the surface of the LSM98 has the molecular formula (La) 0.8 Sr 0.2 ) 0.98 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the SSZ is Sc stabilized ZrO 2 Has a molecular formula (Sc) 2 O 3 ) 0.1 (CeO 2 ) 0.01 (ZrO 2 ) 0.89 ，Sc 0.18 Zr 0.82 O 1.91 。
Further, the fuel polar layer flow preparation method specifically comprises the following steps:
5-10 g of dispersing agent DM-55 is dissolved in 50-150 g of butyl acetate solvent, 100-300 g of NiO and SSZ powder are added, wherein the mass ratio of NiO to SSZ is 5: 1-5, adding PMMA accounting for 0% -10% of the total mass of NiO and SSZ powder as a pore-forming agent, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting to obtain the fuel electrode layer.
Further, the electrolyte layer casting preparation method specifically comprises the following steps:
5-10 g of dispersing agent DM-55 is dissolved in 50-150 g of butyl acetate solvent, 100-300 g of SSZ powder is added, ball milling is carried out for 12-24 hours, then 10-50 g of plasticizing agent B50 and 10-50 g of binding agent B72 are sequentially added, ball milling is continued for 12-24 hours, slurry is taken out, vacuum defoaming is carried out, air in the slurry is removed, and then an electrolyte layer is cast on a fuel electrode layer.
Further, in step S1, the air electrode function layer casting preparation method specifically includes:
dissolving 5-10 g of dispersing agent DM-55 in 50-150 g of butyl acetate solvent, and adding 100-300 g of LSM98 and SSZ powder, wherein the mass ratio of the LSM to the SSZ is 5: 1-5, adding PAMMA accounting for 10% -30% of the total mass of LSM98 and SSZ powder as a pore-forming agent, ball-milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball-milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode functional layer on an electrolyte layer.
Further, in step S2, the preparation method of the air electrode support layer comprises the following steps:
dissolving 5-10 g of dispersing agent DM-55 into 50-150 g of butyl acetate solvent, adding 100-300 g of LSM95 and 3YSZ, wherein the mass ratio of the LSM95 to the 3YSZ is 5:2-5, adding PMMA accounting for 10-30% of the total mass of the LSM95 and the 3YSZ as a pore-forming agent, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode support layer on an air electrode functional layer.
Further, in step S1, the doctor blade height of the casting machine between the corresponding functional layers is sequentially increased by 50 μm, 100 μm, 150 μm;
in step S2, the doctor blade height of the casting machine is increased by 950. Mu.m.
In the step S3, the full-cell blank is maintained at 75 ℃ and 3MPa for 10min, and then is cut into a wafer with the diameter of 20 mm;
and then placing the cut full-cell biscuit into a high-temperature furnace, and preserving the temperature for 4 hours at 1250 ℃ at a heating rate of 3 ℃/min to obtain the solid oxide fuel cell.
Compared with the prior art, the preparation method of the solid oxide fuel cell sequentially carries out tape casting treatment on the fuel electrode layer, the electrolyte layer, the air electrode functional layer and the air electrode supporting layer, and then carries out hot pressing and one-step co-sintering to prepare the air electrode supporting solid oxide fuel cell, so that the combination of the fuel electrode layer and the electrolyte layer, the electrolyte layer and the air electrode functional layer is tighter, the thermal cycle performance is good, the forward/reverse operation can be realized, the problems that the interface combination of the fuel electrode layer and the electrolyte layer is poor and the like when the fuel electrode is tape-cast, laminated, hot pressed and sintered and finally silk-screened by the traditional preparation method are solved, the method is simpler, the energy consumption is lower, and the cost is effectively reduced.
Drawings
FIG. 1 is a cross-sectional view SEM of a solid oxide fuel cell made in accordance with the present invention;
FIG. 2 is a fragmentary enlarged cross-sectional view SEM of a solid oxide fuel cell made in accordance with the present invention;
FIG. 3 is a graph of I-V-P test results for a solid oxide fuel cell made in accordance with the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1 and 2, the solid oxide fuel cell is sequentially composed of four layers, namely a fuel electrode layer, an electrolyte layer, an air electrode functional layer and an air electrode supporting layer, and the preparation method comprises the following steps: each functional layer is prepared by tape casting, laminated and hot pressed to obtain a complete full-cell biscuit, and finally the full-cell biscuit is sintered to obtain a solid oxide fuel cell;
specifically, the travelling speed of the casting machine is kept between 0.1 and 3 cm.s -1 Firstly, casting to prepare a fuel electrode layer, then casting an electrolyte layer on the fuel electrode layer, casting an air electrode functional layer on the electrolyte layer, sequentially increasing the height of a scraper of a casting machine between the corresponding functional layers by 10-100 mu m, casting an air electrode support layer to the air electrode functional layer, increasing the height of the scraper of the casting machine by 300-1000 mu m, and carrying out lamination hot pressing on each cast functional layer at the temperature of 60-80 ℃ and the pressure of 2-5 MPa for 5-10 min to obtain a complete full-cell biscuit; finally, putting the complete full-cell biscuit into a high-temperature furnace for sintering treatment, wherein the sintering temperature is 1100-1300 ℃ at a heating rate of 0.25-3 ℃/min, the sintering time is 3-5 hours, and the solid oxide fuel cell is obtained, and the sintering temperature is preferably kept at 1250 ℃ for 4 hours;
the solid oxide fuel cell adopts the steps that a fuel electrode layer, an electrolyte layer, an air electrode functional layer and an air electrode supporting layer are sequentially cast and then directly hot-pressed and sintered in one step, so that the phenomenon that the interface combination of the fuel electrode layer and the electrolyte layer is relatively poor and layering easily occurs in the preparation process of the traditional fuel cell is avoided;
the electrolyte in the electrolyte layer is selected from one or more of fluorite type, namely Y x Zr 1-x O 2-α 、Sc x Zr 1-x O 2-α Wherein x is more than or equal to 0.03 and less than or equal to 0.2; or Sm y Ce 1-y O 2-α 、Gd y Ce 1-y O 2-α Wherein y is more than or equal to 0.1 and less than or equal to 0.3;
the air electrode is selected from: (La, sr) MnO having perovskite structure 3-δ 、(La，Sr)FeO 3-δ 、(La，Sr)CoO 3-δ One or more of which are then mixed with electrolyte to form a composite cathode;
the fuel electrode layer is selected from: niO, cuO, (La, Y) z Sr 1-z TiO 3-β 、(La，Sr)(Cr，Mn)O 3-β And then with electrolyte, wherein z is more than or equal to 0 and less than or equal to 0.6;
the α, β, δ represent the number of oxygen vacancies, and the ranges are 0< α <2, 0< β <3, 0< δ <3;
preferably, the fuel electrode layer consists of NiO and SSZ, and the thickness of the fuel electrode layer is 10-100 mu m;
the electrolyte layer consists of SSZ, and the thickness of the electrolyte layer is 5-30 mu m;
the air electrode functional layer consists of LSM98 and SSZ, and the thickness of the air electrode functional layer is 10-100 mu m;
the air electrode supporting layer consists of LSM95 and 3YSZ, and the thickness of the air electrode supporting layer is 300-1000 mu m;
wherein LSM95 has the formula (La 0.8 Sr 0.2 ) 0.95 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the 3YSZ is 3% Y 2 O 3 Stabilized ZrO 2 The molecular formula is Y 0.058 Zr 0.942 O 1.971 The method comprises the steps of carrying out a first treatment on the surface of the LSM98 has the molecular formula (La) 0.8 Sr 0.2 ) 0.98 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the SSZ is Sc stabilized ZrO 2 Molecular formula is Sc 0.18 Zr 0.82 O 1.91 。
As a preferred embodiment, the specific method of fuel polar layer casting preparation comprises:
5-10 g of dispersing agent DM-55 is dissolved in 50-150 g of butyl acetate solvent, 100-300 g of NiO and SSZ powder are added, wherein the mass ratio of NiO to SSZ is 5: 1-5, adding PMMA accounting for 0% -10% of the total mass of NiO and SSZ powder as a pore-forming agent, ball-milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuously ball-milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting to prepare a fuel electrode layer, wherein the purity of the related raw materials and reagents is analytically pure;
as a preferred embodiment, the specific method of electrolyte layer casting preparation includes:
dissolving 5-10 g of dispersing agent DM-55 in 50-150 g of butyl acetate solvent, adding 100-300 g of SSZ powder, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an electrolyte layer on a fuel electrode layer;
as a preferred embodiment, the specific method for preparing the air electrode functional layer comprises the following steps:
dissolving 5-10 g of dispersing agent DM-55 in 50-150 g of butyl acetate solvent, and adding 100-300 g of LSM98 and SSZ powder, wherein the mass ratio of the LSM to the SSZ is 5: 1-5, adding PAMMA accounting for 10% -30% of the total mass of LSM98 and SSZ powder as a pore-forming agent, ball-milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball-milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode functional layer on an electrolyte layer;
as a preferred embodiment, the specific method for preparing the air electrode support layer comprises the following steps:
dissolving 5-10 g of dispersing agent DM-55 in 50-150 g of butyl acetate solvent, adding 200-220g of LSM95 and 3YSZ, wherein the mass ratio of the LSM95 to the 3YSZ is 5:2-5, adding PMMA accounting for 10-30% of the total mass of the LSM95 and 3YSZ powder as a pore-forming agent, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode support layer on an air electrode functional layer;
in addition, in the embodiment of the preparation of each functional layer, the binder may be PVB or B72, the dispersing agent is TEA or DM55, the plasticizer is PEG, DOP or B50, ethanol, butanone, butyl acetate are used as solvents, preferably, B72 is used as the binder, DM55 is used as the dispersing agent, B50 is used as the plasticizer, and butyl acetate is used as the solvent;
as a preferred embodiment, the present solid oxide fuel cell manufacturing method includes the steps of:
according to the preparation method of the fuel electrode layer, the electrolyte layer, the air electrode functional layer and the air electrode support layer, a complete full-cell blank A is obtained;
specifically, 4g of dispersing agent DM-55 is dissolved in 100g of butyl acetate solvent, 60g of NiO and 40g of SSZ powder are added, 10g of PMMA is added as a pore-forming agent, ball milling is carried out for 24 hours, and then 9g of plasticizer is added in sequenceB50 and 9g of binder B72, continuing ball milling for 12 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and setting the travelling speed of a casting machine to be 1cm & s -1 The height of the scraper is 50 mu m, and casting is carried out on the polymer film strip to obtain a fuel electrode layer;
dissolving 4g of dispersing agent DM-55 (acrylic resin) in 100g of butyl acetate solvent, adding 100g of SSZ powder, ball milling for 24 hours, sequentially adding 9g of plasticizer B50 and 9g of binder B72, ball milling for 12 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and setting the travelling speed of a casting machine to be 1cm & s -1 The doctor blade height was 100 μm, casting an electrolyte layer on the fuel electrode layer;
dissolving 4g of dispersing agent DM-55 (acrylic resin) in 100g of butyl acetate solvent, adding 60g of LSM98 and 40g of SSZ powder, adding 20g of PMMA as a pore-forming agent, ball milling for 24 hours, sequentially adding 9g of plasticizer B50 and 9g of binder B72, ball milling for 12 hours, taking out slurry, vacuum defoaming, removing air inside, and setting the travelling speed of a casting machine to be 1cm & s -1 The height of the scraper is 150 mu m, and an air electrode functional layer is cast on the electrolyte layer;
dissolving 4g of dispersing agent DM-55 (acrylic resin) in 100g of butyl acetate solvent, adding 60g of LSM95 and 40g of 3YSZ powder, adding 30g of PMMA as a pore-forming agent, ball milling for 24 hours, sequentially adding 9g of plasticizer B50 and 9g of binder B72, continuing ball milling for 12 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and setting the travelling speed of a casting machine to be 1cm & s -1 The height of the scraper is 950 mu m, and the air electrode supporting layer is cast on the air electrode functional layer;
thus obtaining the complete full cell embryo A; maintaining the pressure of the full-cell biscuit A at 75 ℃ and 3MPa for 10min by using a hot press, and then cutting into wafers with the diameter of 20mm to obtain a full-cell biscuit B;
then placing the full-cell biscuit B in a high-temperature furnace, and preserving heat for 4 hours at 1250 ℃ at a heating rate of 3 ℃/min to obtain a solid oxide fuel cell;
the current-voltage (I-U) curve test of the fuel cell adopts hydrogen as fuel gas, air as oxidizing gas, the hydrogen flow is controlled by a mass flowmeter, silver conductive glue is used as a current collector, ceramic glue is used for sealing and isolating air and hydrogen, the test range is 650-800 ℃, the test is carried out once at intervals of 50 ℃, and the test result is shown in figure 3;
the solid oxide fuel cell preparation method adopts co-casting, hot pressing and one-step co-sintering to prepare the air electrode support solid oxide cell, so that the fuel electrode layer and the electrolyte layer, the electrolyte layer and the air electrode functional layer are combined more tightly, the thermal cycle performance is good, the forward/reverse operation can be realized, the problems of poor interface combination between the fuel electrode layer and the electrolyte layer and the like when the fuel electrode is subjected to casting, lamination, hot pressing and sintering in the final silk screen printing in the traditional preparation method are solved, the method is simpler, the energy consumption is lower, and the cost is effectively reduced.
In the description of the present invention, it should be understood that the terms "center," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Claims (8)
1. A method for preparing a solid oxide fuel cell is characterized in that,
the method specifically comprises the following steps:
s1, maintaining the travelling speed of the casting machine to be 0.1-3 cm & S -1 ；
Firstly, casting to prepare a fuel electrode layer, then casting an electrolyte layer on the fuel electrode layer, casting an air electrode functional layer on the electrolyte layer, sequentially increasing the height of a scraper of a casting machine between the corresponding functional layers by 10-100 mu m,
s2, casting the air electrode support layer to the air electrode functional layer in the step S1, wherein the height of a scraper of the casting machine is increased by 300-1000 mu m;
s3, carrying out lamination hot pressing on each functional layer after casting at the temperature of 60-80 ℃ and the pressure of 2-5 MPa for 5-10 min to obtain a complete full-battery biscuit;
s4, finally, putting the complete full-cell biscuit into a high-temperature furnace, and obtaining the solid oxide fuel cell at a heating rate of 0.25-3 ℃/min, a sintering temperature of 1100-1300 ℃ and a sintering time of 3-5 hours;
the electrolyte layer is selected from: fluorite type Y x Zr 1-x O 2-α 、Sc x Zr 1-x O 2-α Wherein x is more than or equal to 0.03 and less than or equal to 0.2; or Sm y Ce 1-y O 2-α 、Gd y Ce 1-y O 2-α Wherein y is more than or equal to 0.1 and less than or equal to 0.3;
the air electrode is selected from: (La, sr) MnO having perovskite structure 3-δ 、(La，Sr)FeO 3-δ 、(La，Sr)CoO 3-δ One or more of which are then mixed with electrolyte to form a composite cathode;
the fuel electrode layer is selected from: niO, cuO, (La, Y) z Sr 1-z TiO 3-β 、(La，Sr)(Cr，Mn)O 3-β And then with electrolyte, wherein z is more than or equal to 0 and less than or equal to 0.6;
alpha, beta, delta represent the number of oxygen vacancies ranging from 0< alpha <2, 0< beta <3, 0< delta <3.
2. The method for preparing a solid oxide fuel cell according to claim 1, wherein the fuel electrode layer is composed of NiO and SSZ in a mass ratio of 5: 1-5, the thickness of the fuel electrode layer is 10-100 mu m;
the electrolyte layer consists of SSZ, and the thickness of the electrolyte layer is 5-30 mu m;
the air electrode functional layer consists of LSM98 and SSZ, and the mass ratio is 5: 1-5, the thickness is 10-100 mu m;
the air electrode supporting layer consists of LSM95 and 3YSZ, and the mass ratio is 5: 2-5, the thickness of which is 300-1000 mu m;
LSM95 has the molecular formula (La) 0.8 Sr 0.2 ) 0.95 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the 3YSZ is 3% Y 2 O 3 Stabilized ZrO 2 The molecular formula is Y 0.058 Zr 0.942 O 1.971 The method comprises the steps of carrying out a first treatment on the surface of the LSM98 has the molecular formula (La) 0.8 Sr 0.2 ) 0.98 MnO 3-δ The method comprises the steps of carrying out a first treatment on the surface of the SSZ is Sc stabilized ZrO 2 Molecular formula is Sc 0.18 Zr 0.82 O 1.91 。
3. The method for producing a solid oxide fuel cell according to claim 1 or 2, characterized in that in step S1, the fuel electrode layer casting production method specifically comprises:
5-10 g of dispersing agent DM-55 is dissolved in 50-150 g of butyl acetate solvent, 100-300 g of NiO and SSZ powder are added, wherein the mass ratio of NiO to SSZ is 5: 1-5, adding PMMA accounting for 0% -0% of the total mass of NiO and SSZ powder as a pore-forming agent, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting to obtain the fuel electrode layer.
4. The method for producing a solid oxide fuel cell according to claim 1 or 2, characterized in that in step S1, the electrolyte layer casting production method specifically comprises:
5-10 g of dispersing agent DM-55 is dissolved in 50-150 g of butyl acetate solvent, 100-300 g of SSZ powder is added, ball milling is carried out for 12-24 hours, then 10-50 g of plasticizing agent B50 and 10-50 g of binding agent B72 are sequentially added, ball milling is continued for 12-24 hours, slurry is taken out, vacuum defoaming is carried out, air in the slurry is removed, and then an electrolyte layer is cast on a fuel electrode layer.
5. The method for preparing a solid oxide fuel cell according to claim 1 or 2, wherein in step S1, the air electrode function layer is prepared by a method comprising:
dissolving 5-10 g of dispersing agent DM-55 in 50-150 g of butyl acetate solvent, and adding 100-300 g of LSM98 and SSZ powder, wherein the mass ratio of the LSM to the SSZ is 5: 1-5, adding PAMMA accounting for 10% -30% of the total mass of LSM98 and SSZ powder as a pore-forming agent, ball-milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball-milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode functional layer on an electrolyte layer.
6. The method for producing a solid oxide fuel cell according to claim 1 or 2, characterized in that in step S2, the method for producing an air electrode support layer is specifically comprised of:
dissolving 5-10 g of dispersing agent DM-55 into 50-150 g of butyl acetate solvent, adding 100-300 g of LSM95 and 3YSZ, wherein the mass ratio of the LSM95 to the 3YSZ is 5:2-5, adding PMMA accounting for 10-30% of the total mass of the LSM95 and the 3YSZ as a pore-forming agent, ball milling for 12-24 hours, sequentially adding 10-50 g of plasticizer B50 and 10-50 g of binder B72, continuing ball milling for 12-24 hours, taking out slurry, vacuum defoaming, removing air in the slurry, and casting an air electrode support layer on an air electrode functional layer.
7. A method for producing a solid oxide fuel cell according to claim 1 or 2, characterized in that,
in the step S1, the heights of the scrapers of the casting machine between the corresponding functional layers are sequentially increased by 50 mu m, 100 mu m and 150 mu m;
in step S2, the doctor blade height of the casting machine is increased by 950. Mu.m.
8. A method for producing a solid oxide fuel cell according to claim 7, wherein,
in the step S3, the full cell blank is maintained at 75 ℃ and 3MPa for 10min, and then is cut into a wafer with the diameter of 20 mm;
and then placing the cut full-cell biscuit into a high-temperature furnace, and preserving the temperature for 4 hours at 1250 ℃ at a heating rate of 3 ℃/min to obtain the solid oxide fuel cell.
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| CN1925200A (en) * | 2006-08-18 | 2007-03-07 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| CN113346118A (en) * | 2021-08-05 | 2021-09-03 | 北京思伟特新能源科技有限公司 | Method for preparing metal support monomer by adopting co-casting method |
| CN114890787A (en) * | 2022-05-31 | 2022-08-12 | 南京理工大学 | Oxygen electrode supporting type solid oxide electrolytic cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1925200A (en) * | 2006-08-18 | 2007-03-07 | 中国科学院上海硅酸盐研究所 | Anode supporting solid electrolyte compound film for solid oxide fuel battery and its preparing method |
| CN113346118A (en) * | 2021-08-05 | 2021-09-03 | 北京思伟特新能源科技有限公司 | Method for preparing metal support monomer by adopting co-casting method |
| CN114890787A (en) * | 2022-05-31 | 2022-08-12 | 南京理工大学 | Oxygen electrode supporting type solid oxide electrolytic cell and preparation method thereof |
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