CN117457952A - Preparation method of solid oxide fuel cell - Google Patents
Preparation method of solid oxide fuel cell Download PDFInfo
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- CN117457952A CN117457952A CN202311545777.1A CN202311545777A CN117457952A CN 117457952 A CN117457952 A CN 117457952A CN 202311545777 A CN202311545777 A CN 202311545777A CN 117457952 A CN117457952 A CN 117457952A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000446 fuel Substances 0.000 title claims abstract description 13
- 239000007787 solid Substances 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000005266 casting Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 238000007650 screen-printing Methods 0.000 claims description 9
- 229940116411 terpineol Drugs 0.000 claims description 9
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 6
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 claims description 3
- 229920002799 BoPET Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention discloses a preparation method of a solid oxide fuel cell, which comprises the following steps: step 1: preparing electrolyte casting slurry; step 2: and preparing the SOFC full cell. The invention provides a preparation process suitable for an SOFC, which comprises the following steps: a preparation method of a solid oxide fuel cell comprises casting and sintering processes of electrolyte, coating of electrodes and sintering processes of the cell, and can prepare an SOFC with high mechanical strength and high performance.
Description
Technical Field
The invention relates to a preparation method of a solid oxide fuel cell, and belongs to the technical field of fuel cells.
Background
A Solid Oxide Fuel Cell (SOFC) is an energy conversion device that directly converts chemical energy of fuel gas into electric energy, and has high efficiency and no net emission of greenhouse gases. The basic component of a SOFC is a dense electrolyte with high ionic conductivity at the SOFC operating temperature, sandwiched by porous electrodes with mixed electronic and ionic conductivity. Due to the all-solid-state ceramic structure, SOFCs can be supported by any structural component and have different properties. Electrolyte supported SOFCs are considered the most stable SOFC type compared to the other three types because of less volume change of the electrolyte during operation and because of the higher strength of fluorite structured ceramics. As hydrocarbon fuels are used as one of the trends in SOFCs, electrolyte supported SOFCs are more suitable for hydrocarbon fuels than other supported cells. The preparation process of the electrolyte supported SOFC generally comprises the steps of preparing a supporting body electrolyte, sintering at high temperature, printing electrodes on two sides, and sintering to obtain the complete cell. While high manufacturing costs are one of the biggest challenges that prevent sofc from dominating in the power generation industry. As a solution, cast molding processes have been widely used to manufacture low cost, uniform and thin SOFC electrolytes. According to the different solvents and organic reagents selected for preparing the slurry, the common casting molding process comprises an organic base and a water base, and the organic base casting molding is more mature than the water base casting molding. In the SOFC preparation process, the organic system is similar to the dielectric constant of the ceramic powder material, so that the uniform organic slurry is easier to obtain by selecting an organic tape casting process.
The existing electrolyte with mechanical strength meeting the requirement of SOFC support basically has the thickness of more than 200 mu m, and has high ohmic resistance because the electrolyte is thicker and the distance for ions to move is longer. One of the solutions is to reduce the thickness of the electrolyte to reduce the impedance caused by the electrolyte portion, but if the electrolyte material used in the SOFC is too thin, the mechanical stability of the unit cell is reduced, and the unit cell is easily brittle, so that the stack assembly is difficult and the shock resistance is weak. The overall thickness of the cell is typically greater than 250 μm due to the thicker support electrolyte thickness of the electrolyte supported SOFC, which typically does not perform very well due to the excessive ohmic resistance of the electrolyte. And thus high strength and high performance are substantially difficult to meet at the same time.
Disclosure of Invention
The invention provides a preparation process suitable for an SOFC, which comprises the following steps: a preparation method of a solid oxide fuel cell comprises casting and sintering processes of electrolyte, coating of electrodes and sintering processes of the cell, and can prepare an SOFC with high mechanical strength and high performance.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method of making a solid oxide fuel cell, the method comprising:
step 1: preparation of electrolyte casting slurry
Step (1.1): electrolyte powder with 37-60wt% of specific surface area of 5-16m2/g, D50 of 0.2-1 mu m, 28-55wt% of organic solvent and 2-10wt% of dispersing agent are uniformly mixed in a ball mill, wherein the electrolyte powder comprises but is not limited to yttria-stabilized zirconia series: 3YSZ, 5YSZ, 8YSZ; scandium stabilized zirconia series: scSZ, ceScSZ, ybCeScSZ, gdCeScSZ, YCeScSZ; the organic solvent comprises absolute ethyl alcohol and butyl carbitol in a mass ratio of 2 to 1, and the dispersing agent is in a mass ratio of 1:9, ball milling the mixture of triethanolamine and polyacrylic acid for 12-18h at a rotating speed of 200-350r/min;
step (1.2): adding 3-8wt% of plasticizer, 3-8wt% of binder, 0.1-1wt% of flatting agent and 0.1-0.5wt% of defoaming agent into the slurry after ball milling in the step (1.1), and continuing ball milling, wherein the plasticizer is as follows: the mass ratio is 1: butyl benzyl phthalate and polyethylene glycol 400 of 1.2; the binder is polyvinyl butyral, and the leveling agent is: the fluorine-containing acrylic acid and the defoamer are as follows: commercially available non-silicon defoamer, wherein the ball milling time is 12-18h, and the rotating speed is 200-350r/min;
step (1.3): casting the slurry obtained in the step (1.2) on a PET film through an adjustable scraper, wherein the height of the scraper is 100 mu m, the casting width is 15cm, the length is 2m, and drying is carried out at room temperature for 24 hours to obtain a film belt;
step (1.4): cutting the film strip into squares of 13 x 13cm by a cutting machine, stacking 6 pieces, placing the squares into a vacuum bag for vacuumizing, placing the squares into a warm isostatic pressing machine, and pressing the films into a film without layering at 80 ℃ under 10Mpa for 2 min;
step (1.5): placing the membrane into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the heat at the room temperature of 2 ℃/min to 250 ℃ for 1h, preserving the heat at the room temperature of 2 ℃/min to 370 ℃ for 1h, preserving the heat at the temperature of 2 ℃/min to 450 ℃ for 2h, preserving the heat at the temperature of 3 ℃/min to 1150 ℃ for 2h, pressing and burning by using a porous burning plate after the temperature of 2 ℃/min to room temperature, preserving the heat of yttria-stabilized zirconia series from 3 ℃/min to 1450 ℃ for 4h, preserving the heat of scandia-stabilized zirconia series from 3 ℃/min to 1550 ℃ for 8h, cooling the temperature of 2 ℃/min to 500 ℃ and naturally cooling the temperature to the room temperature to obtain an electrolyte sheet with the thickness of about 150 mu m, wherein the size of 10 x 10cm is obtained;
step 2: preparation of SOFC full cell
Step (2.1): uniformly mixing 55wt% of GDC powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on two sides of an electrolyte through a screen printing process, and drying at 120 ℃ for 1 h;
step (2.2): uniformly mixing NiO and GDC powder with the mass ratio of 55 to 45, uniformly mixing 65wt% of d NiO-GDC mixed powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on one side of an electrolyte through a screen printing process, and drying at 120 ℃ for 1h to obtain a half cell; the half-cell is put into a high temperature furnace for sintering, and the sintering procedure is as follows: preserving heat for 2 hours at the temperature of 2 ℃/min to 450 ℃ at room temperature, preserving heat for 2 hours at the temperature of 3 ℃/min to 1250 ℃, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain a half-cell after sintering;
step (2.3): uniformly mixing LSCF and GDC powder with the mass ratio of 6 to 4, uniformly mixing 70wt% of dLSCF-GDC mixed powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on the other side of the electrolyte through a screen printing process, and drying at 120 ℃ for 1h. Obtaining a full battery; placing the whole battery into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the temperature at the room temperature of 2 ℃/min to 450 ℃ for 2 hours, preserving the temperature at the temperature of 3 ℃/min to 1050 ℃ for 2 hours, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain the sintered full battery.
Compared with the prior art, the invention has the following implementation effects:
the electrolyte sheet prepared by the tape casting method has high mechanical strength, thin thickness and low resistance; the SOFC prepared by the electrolyte support has high mechanical strength and good performance. When the thickness is less than 150 mu m, the bending strength can reach more than 250 MPa.
Drawings
FIG. 1 is an ionic conductivity of a CeScSZ electrolyte sheet cast sintered in step (1.1) according to the present invention;
fig. 2 is an SEM image of a CeScSZ electrolyte sheet prepared according to the method of the present invention.
Detailed Description
The present invention will now be described in detail with reference to specific embodiments thereof, and it should be apparent that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without undue burden are within the scope of the invention
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method of making a solid oxide fuel cell, the method comprising:
step 1: preparation of electrolyte casting slurry
Step (1.1): electrolyte powder with 37-60wt% of specific surface area of 5-16m2/g, D50 of 0.2-1 mu m, 28-55wt% of organic solvent and 2-10wt% of dispersing agent are uniformly mixed in a ball mill, wherein the electrolyte powder comprises but is not limited to yttria-stabilized zirconia series: 3YSZ, 5YSZ, 8YSZ; scandium stabilized zirconia series: scSZ, ceScSZ, ybCeScSZ, gdCeScSZ, YCeScSZ; the organic solvent comprises absolute ethyl alcohol and butyl carbitol in a mass ratio of 2 to 1, and the dispersing agent is in a mass ratio of 1:9, ball milling for 12-18h at 200-350r/min (shown in figure 1);
step (1.2): adding 3-8wt% of plasticizer, 3-8wt% of binder, 0.1-1wt% of flatting agent and 0.1-0.5wt% of defoaming agent into the slurry after ball milling in the step (1.1), and continuing ball milling, wherein the plasticizer is as follows: the mass ratio is 1: butyl benzyl phthalate and polyethylene glycol 400 of 1.2; the binder is polyvinyl butyral, and the leveling agent is: the fluorine-containing acrylic acid and the defoamer are as follows: commercially available non-silicon defoamer, wherein the ball milling time is 12-18h, and the rotating speed is 200-350r/min;
step (1.3): casting the slurry obtained in the step (1.2) on a PET film through an adjustable scraper, wherein the height of the scraper is 100 mu m, the casting width is 15cm, the length is 2m, and drying is carried out at room temperature for 24 hours to obtain a film belt;
step (1.4): cutting the film strip into squares of 13 x 13cm by a cutting machine, stacking 6 pieces, placing the squares into a vacuum bag for vacuumizing, placing the squares into a warm isostatic pressing machine, and pressing the films into a film without layering at 80 ℃ under 10Mpa for 2 min;
step (1.5): placing the membrane into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the heat at the room temperature of 2 ℃/min to 250 ℃ for 1h, preserving the heat at the room temperature of 2 ℃/min to 370 ℃ for 1h, preserving the heat at the temperature of 2 ℃/min to 450 ℃ for 2h, preserving the heat at the temperature of 3 ℃/min to 1150 ℃ for 2h, pressing and burning by using a porous burning plate after the temperature of 2 ℃/min to room temperature, preserving the heat of yttria-stabilized zirconia series from 3 ℃/min to 1450 ℃ for 4h, preserving the heat of scandia-stabilized zirconia series from 3 ℃/min to 1550 ℃ for 8h, cooling the temperature of 2 ℃/min to 500 ℃ and naturally cooling the temperature to the room temperature to obtain an electrolyte sheet with the thickness of about 150 mu m, wherein the size of 10 x 10cm is obtained;
step 2: preparation of SOFC full cell
Step (2.1): uniformly mixing 55wt% of GDC powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on two sides of an electrolyte through a screen printing process, and drying at 120 ℃ for 1 h;
step (2.2): uniformly mixing NiO and GDC powder with the mass ratio of 55 to 45, uniformly mixing 65wt% of d NiO-GDC mixed powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on one side of an electrolyte through a screen printing process, and drying at 120 ℃ for 1h to obtain a half cell; the half-cell is put into a high temperature furnace for sintering, and the sintering procedure is as follows: preserving heat for 2 hours at the temperature of 2 ℃/min to 450 ℃ at room temperature, preserving heat for 2 hours at the temperature of 3 ℃/min to 1250 ℃, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain a half-cell after sintering;
step (2.3): uniformly mixing LSCF and GDC powder with the mass ratio of 6 to 4, uniformly mixing 70wt% of dLSCF-GDC mixed powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on the other side of the electrolyte through a screen printing process, and drying at 120 ℃ for 1h. Obtaining a full battery; placing the whole battery into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the temperature at the room temperature of 2 ℃/min to 450 ℃ for 2 hours, preserving the temperature at the temperature of 3 ℃/min to 1050 ℃ for 2 hours, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain the sintered full battery.
The foregoing is a detailed description of the invention with reference to specific embodiments, and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (1)
1. A method for preparing a solid oxide fuel cell, characterized by: the preparation method comprises the following steps:
step 1: preparation of electrolyte casting slurry
Step (1.1): electrolyte powder with 37-60wt% of specific surface area of 5-16m2/g, D50 of 0.2-1 mu m, 28-55wt% of organic solvent and 2-10wt% of dispersing agent are uniformly mixed in a ball mill, wherein the electrolyte powder comprises but is not limited to yttria-stabilized zirconia series: 3YSZ, 5YSZ, 8YSZ; scandium stabilized zirconia series: scSZ, ceScSZ, ybCeScSZ, gdCeScSZ, YCeScSZ; the organic solvent comprises absolute ethyl alcohol and butyl carbitol in a mass ratio of 2 to 1, and the dispersing agent is in a mass ratio of 1:9, ball milling the mixture of triethanolamine and polyacrylic acid for 12-18h at a rotating speed of 200-350r/min;
step (1.2): adding 3-8wt% of plasticizer, 3-8wt% of binder, 0.1-1wt% of flatting agent and 0.1-0.5wt% of defoaming agent into the slurry after ball milling in the step (1.1), and continuing ball milling, wherein the plasticizer is as follows: the mass ratio is 1: butyl benzyl phthalate and polyethylene glycol 400 of 1.2; the binder is polyvinyl butyral, and the leveling agent is: the fluorine-containing acrylic acid and the defoamer are as follows: commercially available non-silicon defoamer, wherein the ball milling time is 12-18h, and the rotating speed is 200-350r/min;
step (1.3): casting the slurry obtained in the step (1.2) on a PET film through an adjustable scraper, wherein the height of the scraper is 100 mu m, the casting width is 15cm, the length is 2m, and drying is carried out at room temperature for 24 hours to obtain a film belt;
step (1.4): cutting the film strip into squares of 13 x 13cm by a cutting machine, stacking 6 pieces, placing the squares into a vacuum bag for vacuumizing, placing the squares into a warm isostatic pressing machine, and pressing the films into a film without layering at 80 ℃ under 10Mpa for 2 min;
step (1.5): placing the membrane into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the heat at the room temperature of 2 ℃/min to 250 ℃ for 1h, preserving the heat at the room temperature of 2 ℃/min to 370 ℃ for 1h, preserving the heat at the temperature of 2 ℃/min to 450 ℃ for 2h, preserving the heat at the temperature of 3 ℃/min to 1150 ℃ for 2h, pressing and burning by using a porous burning plate after the temperature of 2 ℃/min to room temperature, preserving the heat of yttria-stabilized zirconia series from 3 ℃/min to 1450 ℃ for 4h, preserving the heat of scandia-stabilized zirconia series from 3 ℃/min to 1550 ℃ for 8h, cooling the temperature of 2 ℃/min to 500 ℃ and naturally cooling the temperature to the room temperature to obtain an electrolyte sheet with the thickness of about 150 mu m, wherein the size of 10 x 10cm is obtained;
step 2: preparation of SOFC full cell
Step (2.1): uniformly mixing 55wt% of GDC powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on two sides of an electrolyte through a screen printing process, and drying at 120 ℃ for 1 h;
step (2.2): uniformly mixing NiO and GDC powder with the mass ratio of 55 to 45, uniformly mixing 65wt% of d NiO-GDC mixed powder with 4wt% of ethyl cellulose-terpineol solution, uniformly printing on one side of an electrolyte through a screen printing process, and drying at 120 ℃ for 1h to obtain a half cell; the half-cell is put into a high temperature furnace for sintering, and the sintering procedure is as follows: preserving heat for 2 hours at the temperature of 2 ℃/min to 450 ℃ at room temperature, preserving heat for 2 hours at the temperature of 3 ℃/min to 1250 ℃, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain a half-cell after sintering;
step (2.3): uniformly mixing LSCF and GDC powder with the mass ratio of 6 to 4, uniformly mixing 70wt% of mixed powder of d LSCF-GDC and 4wt% of ethyl cellulose-terpineol solution, uniformly printing on the other side of the electrolyte through a screen printing process, and drying at 120 ℃ for 1h. Obtaining a full battery; placing the whole battery into a high-temperature furnace for sintering, wherein the sintering procedure is as follows: preserving the temperature at the room temperature of 2 ℃/min to 450 ℃ for 2 hours, preserving the temperature at the temperature of 3 ℃/min to 1050 ℃ for 2 hours, and naturally cooling to the room temperature after 2 ℃/min to 450 ℃ to obtain the sintered full battery.
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| CN202311545777.1A CN117457952A (en) | 2023-12-26 | 2023-12-26 | Preparation method of solid oxide fuel cell |
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| CN202311545777.1A CN117457952A (en) | 2023-12-26 | 2023-12-26 | Preparation method of solid oxide fuel cell |
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2023
- 2023-12-26 CN CN202311545777.1A patent/CN117457952A/en active Pending
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