CN114094123A - Anode/electrolyte half cell, anode-supported solid oxide fuel cell and method for manufacturing the same - Google Patents
Anode/electrolyte half cell, anode-supported solid oxide fuel cell and method for manufacturing the same Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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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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- 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
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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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Abstract
The invention provides an anode/electrolyte half cell, an anode supporting type solid oxide fuel cell and a manufacturing method thereof, wherein the manufacturing method of the anode/electrolyte half cell comprises the steps of preparing a NiO-YSZ anode supporting body tape casting sheet; micro-processing the surface of one side of the NiO-YSZ anode support body tape-casting sheet to form a special orthogonal net structure on the surface; pre-sintering the treated NiO-YSZ anode support body tape-casting sheet; coating nano powder slurry on the surface of the pre-sintered anode support body, and drying to form an anode functional layer; and coating a YSZ electrolyte layer on the anode functional layer and then sintering at high temperature. The anode-supported solid oxide fuel cell comprises an anode/electrolyte half cell and an LSM-YSZ composite cathode layer coated on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell. The anode-supported solid oxide fuel cell has excellent structural stability, activity and electrochemical performance.
Description
Technical Field
The invention relates to an anode/electrolyte half cell, an anode-supported solid oxide fuel cell and a preparation method thereof, belonging to the technical field of solid oxide fuel cells.
Background
A Solid Oxide Fuel Cell (SOFC) is an energy conversion device that can directly convert chemical energy of fuel (combustible gas such as hydrogen and methane) into electric energy, and has the advantages of strong fuel applicability, high energy conversion efficiency, and little environmental pollution. However, conventional SOFCs need to operate at high temperatures (-800 ℃) in order to ensure sufficiently high ionic conductivity of the solid electrolyte. This presents a number of problems, such as: the thermal expansion rates of different materials are difficult to match, the long-term stability of each part at high temperature is difficult to guarantee, the manufacturing cost of the cell is high, and the problems hinder the rapid development of the SOFC. Therefore, lowering the operating temperature of SOFCs is one of the key ways to accelerate their marketability. The operating temperature of the SOFC can be reduced by two strategies. On the one hand, the performance of the anode, cathode and electrolyte materials can be improved. For example, the use of high ionic conductivity materials instead of traditional YSZ electrolytes reduces the ohmic losses of the cell. On the other hand, the electrochemical performance of the SOFC at low and medium temperature can be improved by optimizing the cell structure. Such as electrode surface and microstructure, electrode-electrolyte interface modification, and the like.
Therefore, it is an urgent technical problem in the art to provide a novel anode/electrolyte half cell, an anode-supported solid oxide fuel cell and a method for manufacturing the same.
Disclosure of Invention
To address the above-described shortcomings and drawbacks, it is an object of the present invention to provide a method of making an anode/electrolyte half cell.
It is also an object of the present invention to provide an anode/electrolyte half-cell made by the above-described method of making an anode/electrolyte half-cell.
It is still another object of the present invention to provide an anode-supported solid oxide fuel cell.
Still another object of the present invention is to provide a method for manufacturing the anode-supported solid oxide fuel cell as described above. The invention can improve the electrode/electrolyte interface of the anode-supported solid oxide fuel cell, thereby leading the anode-supported solid oxide fuel cell to have excellent structural stability, activity and electrochemical performance.
In order to achieve the above object, in one aspect, the present invention provides a method of fabricating an anode/electrolyte half cell, wherein the method of fabricating comprises:
(1) dissolving NiO powder, YSZ powder, a pore-forming agent and a dispersing agent in a solvent, ball-milling the obtained mixture, adding a binder and a plasticizer into the obtained slurry after uniformly mixing, continuing ball-milling, carrying out vacuum pumping treatment on the uniformly mixed slurry, then casting the slurry onto a polyester film, and drying to obtain a NiO (nickel oxide) -YSZ (yttria-stabilized zirconia) anode support body casting sheet;
(2) cutting the NiO-YSZ anode support body cast sheet, and then carrying out micro-processing treatment on one side surface of the NiO-YSZ anode support body cast sheet to enable the surface of the NiO-YSZ anode support body cast sheet to be in an orthogonal net-shaped structure;
(3) pre-sintering the NiO-YSZ anode support body tape-casting sheet after surface treatment obtained in the step (2);
(4) coating nano powder slurry on the modifying surface (namely the surface on the surface treated side) of the pre-sintered NiO-YSZ anode support body obtained in the step (3), and drying to form an anode functional layer;
(5) and coating a YSZ electrolyte layer on the surface of the anode functional layer, and drying and roasting to obtain the anode/electrolyte half cell.
The method for manufacturing the anode/electrolyte half-cell comprises the step (1) of mixing NiO powder and YSZ powder in a mass ratio of 3: 7-7: 3.
In the method for manufacturing the anode/electrolyte half-cell, the amount of the pore-forming agent is 5-30% of the total mass of the NiO powder and the YSZ powder in step (1).
In the method for manufacturing the anode/electrolyte half-cell, the pore-forming agent is one or more selected from polymer material microsphere pore-forming agents in step (1).
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the pore-forming agent is polymethyl methacrylate (PMMA) and/or Polystyrene (PS).
In the method for manufacturing the anode/electrolyte half-cell, the amount of the dispersant used in the step (1) is 0.5-5% of the total mass of the NiO powder and the YSZ powder.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the dispersant is one or more selected from amine dispersants.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the dispersant is triethanolamine and/or 2-amino-2-methyl-1-propanol (AMP).
In the method for manufacturing the anode/electrolyte half-cell, the amount of the solvent used in the step (1) is 1 to 20 times of the total mass of the NiO powder and the YSZ powder.
The method for manufacturing an anode/electrolyte half-cell according to the present invention is characterized in that, in the step (1), the solvent is one or more selected from organic solvents.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the organic solvent is one or more of ethanol, xylene, and trichloroethylene.
In the method for manufacturing the anode/electrolyte half-cell, the binder is used in an amount of 1-20% of the total mass of the NiO powder and the YSZ powder in step (1).
The method for manufacturing an anode/electrolyte half cell according to the present invention is characterized in that, in the step (1), the binder is one or more selected from non-water-based binders.
In the method for manufacturing an anode/electrolyte half-cell according to the present invention, in the step (1), the binder is one or more of polyvinyl butyral, polymethyl acrylate, and ethyl cellulose.
In the method for manufacturing the anode/electrolyte half-cell, the plasticizer is used in an amount of 1-20% of the total mass of the NiO powder and the YSZ powder in step (1).
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the plasticizer is one or more selected from polyethylene glycol, dibutyl phthalate, and ethylene glycol.
The manufacturing method of the anode/electrolyte half-cell is characterized in that in the step (1), the ball milling time is 12-24 hours, and the ball milling time is 12-24 hours. Wherein the ball milling is carried out in a high energy ball mill.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (1), the uniformly mixed slurry is vacuumized in the vacuum chamber, and the bubbles in the slurry can be removed by vacuuming the uniformly mixed slurry.
In the method for manufacturing the anode/electrolyte half-cell, the thickness of the NiO-YSZ anode support tape casting sheet in the step (1) is 1-10 mm.
In the method for manufacturing an anode/electrolyte half-cell according to the present invention, in the step (1), the drying is performed at room temperature.
In the method for manufacturing the anode/electrolyte half-cell, the NiO-YSZ anode support tape casting sheet is cut into small round sheets in the step (2), and the diameter of each small round sheet is 10-50 mm.
In the method for manufacturing the anode/electrolyte half-cell, a pulse fiber laser is adopted to perform micro-processing treatment on one side surface of the cut NiO-YSZ anode support body tape-casting sheet in the step (2), wherein the pulse fiber laser is used at a power of 1-10W, a frequency of 20-50 Hz, and a scanning speed of 100-500 mm/s.
In the method for manufacturing an anode/electrolyte half cell according to the present invention, in the step (2), the micro-machining, i.e., the laser micro-machining, is performed by performing laser etching according to a predetermined pattern under the control of computer aided design software (CAD).
In the step (2) of the method for manufacturing the anode/electrolyte half-cell, the cast sheet of the NiO-YSZ anode support body is cut, and then micro-processing is carried out on one side surface of the cast sheet, so that the surface of the cast sheet presents an orthogonal net structure along with thermal ablation of organic matter components and fragmentation of ceramic particles in the cast sheet; and the forming of the orthogonal net structure on the surface of the NiO-YSZ anode support casting sheet has the highest efficiency and is most easily realized.
In the method for manufacturing the anode/electrolyte half-cell, in the step (2), the distance between two adjacent parallel lines in the orthogonal net structure is 10 to 100 μm.
The manufacturing method of the anode/electrolyte half-cell is characterized in that in the step (3), the pre-sintering temperature is 900-1300 ℃, and the time is 1-5 hours.
And (3) pre-sintering the NiO-YSZ anode support casting sheet after surface treatment obtained in the step (2) so as to enable the NiO-YSZ anode support casting sheet to have certain mechanical strength. And (4) performing presintering in the step (3) in a medium-temperature furnace.
The method for manufacturing the anode/electrolyte half-cell comprises the step (4) of dropping the nano powder slurry in an amount of 0.1-1 mL/cm2The dripping area is 1-10 cm2。
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, in the step (4), the nano powder slurry is coated on the modification surface (i.e., the surface on the surface-treated side) of the pre-sintered NiO-YSZ anode support obtained in the step (3) by using a spin-on-drop coating method.
In the method for manufacturing the anode/electrolyte half-cell, in the step (4), the nano powder in the nano powder slurry is high-activity nano powder, such as NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7-7: 3. The invention does not make specific requirements on the specific size of the used nano powder, and can be reasonably set according to actual operation needs as long as the nano size is ensured.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, the drying in the step (4) is performed at room temperature for 30-120 min.
In the method for manufacturing an anode/electrolyte half cell according to the present invention, in the step (5), the dropping amount of the YSZ electrolyte paste used for coating the YSZ electrolyte layer is 0.1 to 2mL/cm2The dripping area is 1-10 cm2。
As the method for manufacturing the anode/electrolyte half cell, in the step (5), a YSZ electrolyte slurry is applied to the surface of the anode functional layer by a spin-on-dip method to form a YSZ electrolyte layer.
In the method for manufacturing the anode/electrolyte half-cell according to the present invention, the drying in the step (5) is performed at room temperature for 30 to 120 min.
The manufacturing method of the anode/electrolyte half-cell is characterized in that in the step (5), the roasting temperature is 1200-1500 ℃, and the roasting time is 1-5 hours.
The concentration of the nano powder slurry used in the step (4) and the concentration of the YSZ electrolyte slurry used in the step (5) are not specifically required, and the nano powder slurry and the YSZ electrolyte slurry can be reasonably set according to actual operation requirements.
In another aspect, the present invention also provides an anode/electrolyte half-cell made by the above-described method of making an anode/electrolyte half-cell.
In yet another aspect, the present invention also provides an anode-supported solid oxide fuel cell, wherein the anode-supported solid oxide fuel cell comprises the anode/electrolyte half cell described above and an LSM-YSZ composite cathode layer coated on the surface of the YSZ electrolyte layer of the anode/electrolyte half cell.
In the anode-supported solid oxide fuel cell provided by the invention, the contact area between the electrolyte and the electrode material is larger, the polarization of the cell is reduced, and more active sites can be provided for electrochemical reaction, so that the electrochemical performance of the cell is improved.
In another aspect, the present invention also provides a method for manufacturing the anode-supported solid oxide fuel cell, wherein the method comprises:
1) mixing YSZ powder, LSM (lanthanum strontium manganate) powder, a binder and an organic solvent to obtain LSM-YSZ slurry;
2) and coating the LSM-YSZ slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell, and calcining after drying the slurry to obtain the anode-supported solid oxide fuel cell.
The method for manufacturing the anode-supported solid oxide fuel cell comprises the step 1) of mixing YSZ powder and LSM powder in a mass ratio of 3: 7-7: 3.
The manufacturing method of the anode-supported solid oxide fuel cell comprises the step 1), wherein the amount of the organic solvent is 1-10 times of the total mass of the YSZ powder and the LSM powder.
In the method for manufacturing the anode-supported solid oxide fuel cell according to the present invention, in step 1), the organic solvent is one or more selected from alcohol organic solvents.
In the method for manufacturing the anode-supported solid oxide fuel cell according to the present invention, in step 1), the organic solvent is one or more selected from terpineol, ethanol, and isopropanol.
The manufacturing method of the anode-supported solid oxide fuel cell comprises the step 1), wherein the usage amount of the binder is 0.1-1% of the total mass of the YSZ powder and the LSM powder.
The method for manufacturing the anode-supported solid oxide fuel cell according to the present invention is characterized in that, in step 1), the binder is selected from one or more of non-water-based binders.
In the method for manufacturing an anode-supported solid oxide fuel cell according to the present invention, in step 1), the binder is one or more selected from the group consisting of polyvinyl butyral, polymethyl acrylate, and ethyl cellulose.
The method for manufacturing the anode-supported solid oxide fuel cell comprises the step 2) of coating the LSM-YSZ slurry in an amount of 0.1-3 mL/cm2The coating area is 1-10 cm2。
As the method for manufacturing the anode-supported solid oxide fuel cell of the present invention, in step 2), the coating is performed by screen printing.
The manufacturing method of the anode-supported solid oxide fuel cell is characterized in that in the step 2), the drying temperature is 25-50 ℃ and the drying time is 30-60 min.
The manufacturing method of the anode-supported solid oxide fuel cell is characterized in that in the step 2), the calcining temperature is 800-1200 ℃ and the time is 1-5 hours. Wherein, in the step 2), the calcination is carried out in a high-temperature furnace.
According to the invention, one side surface of the NiO-YSZ anode support tape casting sheet is subjected to micro-processing treatment so as to enable the surface of the NiO-YSZ anode support tape casting sheet to present an orthogonal net-shaped structure, so that an electrolyte membrane of the anode support type solid oxide fuel cell can be better attached to the surface of an anode support to form a compact stable structure, and the cell has excellent structural stability; meanwhile, the three-phase reaction interface of the battery is greatly increased, the polarization resistance of the battery is reduced, and the reaction efficiency is improved; in addition, the nanometer anode functional layer is introduced, so that the activity of the cell can be greatly improved, and the electrochemical performance of the SOFC is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic diagram of products obtained in each step of the method for manufacturing an anode/electrolyte half cell provided in example 1 of the present invention.
FIG. 2 is a schematic representation of a cast sheet of NiO-YSZ anode support made in step (1) of example 1 of the present invention.
Fig. 3 is a schematic diagram of the NiO-YSZ anode support tape casting surface micro-processed in step (2) of example 1 of the present invention and then a special orthogonal network structure is formed on the surface.
FIG. 4 is a schematic view showing the structure of an anode-supported solid oxide fuel cell provided in example 1-1 of the present invention.
FIG. 5 is an AC impedance spectrum of Cell 0, Cell 1, Cell 2 and Cell 3 in the open circuit state at 800 ℃ in test example 1 of the present invention.
FIG. 6 is an I-V-P curve at 800 ℃ of Cell 0, Cell 1, Cell 2 and Cell 3 in test example 2 of the present invention.
The main reference numbers illustrate:
1. NiO-YSZ anode support tape-cast sheet.
2. An orthogonal mesh structure.
3. NiO-YSZ anode functional layer.
4. YSZ electrolyte layer.
5. An LSM-YSZ composite cathode layer.
Detailed Description
The "ranges" disclosed herein are given as lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges defined in this manner are combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for particular parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Further, if the minimum range values listed are 1 and 2 and the maximum range values listed are 3, 4, and 5, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed throughout this disclosure, and "0 to 5" is only a shorthand representation of the combination of these numbers.
In the present invention, all the embodiments and preferred embodiments mentioned in the present invention may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned in the present invention and preferred features may be combined with each other to form a new technical solution, if not specifically stated
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. The following described embodiments are some, but not all embodiments of the present invention, and are merely illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The methods for fabricating the anode/electrolyte half cell and the anode-supported solid oxide fuel cell described in the following examples, that is, the method for improving the electrode/electrolyte interface of the anode-supported solid oxide fuel cell, mainly include: firstly preparing an anode support body casting sheet, then forming a special orthogonal net-shaped structure on one side surface of the anode support body casting sheet by a micromachining technology of laser etching, and then coating an anode functional layer, an electrolyte layer and a composite cathode layer on the surface of the modified anode support body in sequence to obtain the anode support type solid oxide fuel cell. The improved electrode-electrolyte interface provided by the invention can enable an electrolyte membrane to be better attached to the surface of an anode support body, and meanwhile, the contact area between the electrolyte and an electrode material can be greatly increased, the polarization of a battery is reduced, more active sites are provided for electrochemical reaction, and the electrochemical performance of the battery is improved.
Example 1
This example provides an anode/electrolyte half cell, the schematic diagram of the product obtained in each step of the manufacturing method is shown in fig. 1, and as can be seen from fig. 1, the manufacturing method includes the following specific steps:
step (1): preparing a NiO-YSZ anode support body tape casting sheet by adopting a tape casting method:
6g of NiO, 4g of YSZ powder, 0.6g of PMMA and 0.05g of triethanolamine are respectively weighed and dissolved in 100g of mixed solvent of ethanol and xylene, and the obtained mixed solution is ball-milled for 24 hours on a high-energy ball mill. After being mixed evenly, 0.2g of polyvinyl butyral, 0.2g of polymethyl acrylate and 0.5g of ethyl cellulose are added into the obtained slurry, and the ball milling is continued for 12 hours. And then, placing the uniformly mixed slurry in a vacuum cavity for vacuumizing treatment to remove air bubbles in the slurry. Finally, casting the slurry onto a polyester film, and drying at room temperature to obtain a NiO-YSZ anode support casting sheet 1, wherein the thickness of the NiO-YSZ anode support casting sheet 1 is 5mm as shown in FIG. 2;
step (2): micro-processing the surface of the cast sheet of the NiO-YSZ anode support body to form a special orthogonal net structure 2 on the surface, as shown in FIG. 3:
firstly, cutting a NiO-YSZ anode support body casting sheet into small sheets with the diameter of 40mm, and performing micro-processing treatment on the surface (single surface) of the casting sheet by adopting a pulse optical fiber laser, wherein the processing pattern is orthogonal net-shaped, the distance between adjacent lines is 80 mu m, the using power of the pulse optical fiber laser is 3W, the frequency is 50Hz, and the scanning speed is 300 mm/s;
and (3): pre-sintering the NiO-YSZ anode support body tape-casting sheet treated in the step (2):
putting the NiO-YSZ anode support body tape-casting sheet subjected to surface treatment in the step (2) into a medium-temperature furnace, and calcining for 2 hours at 1050 ℃;
and (4): coating a high-activity anode functional layer on the surface of the pre-sintered NiO-YSZ anode support:
coating high-activity nano powder slurry on the modification surface of the pre-sintered NiO-YSZ anode support body by adopting a rotary drop coating method, wherein the drop coating amount is 0.3mL, and forming a high-activity anode functional layer after the nano powder slurry is dried at room temperature for 60min, namely forming a NiO-YSZ anode functional layer 3;
wherein the nano powder in the high-activity nano powder slurry is NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7;
and (5): coating a YSZ electrolyte layer on the anode functional layer, and sintering at high temperature:
and coating YSZ electrolyte slurry on the surface of the high-activity anode functional layer by adopting a rotary drop coating method to form a YSZ electrolyte layer 4, wherein the drop coating amount of the YSZ electrolyte slurry is 0.5mL, and after drying the YSZ electrolyte slurry at room temperature for 30min, calcining at 1450 ℃ for 2h to obtain the anode/electrolyte half cell.
Example 2
The embodiment provides an anode/electrolyte half cell, and a manufacturing method thereof comprises the following specific steps:
step (1): preparing a NiO-YSZ anode support body tape casting sheet by adopting a tape casting method:
6g of NiO, 4g of YSZ powder, 0.6g of PMMA and 0.05g of triethanolamine are respectively weighed and dissolved in 100g of mixed solvent of ethanol and xylene, and the mixture is ball-milled for 24 hours on a high-energy ball mill. After being mixed evenly, 0.2g of polyvinyl butyral, 0.2g of polymethyl acrylate and 0.5g of ethyl cellulose are added into the obtained slurry, and the ball milling is continued for 12 hours. Subsequently, the uniformly mixed slurry is placed in a vacuum chamber for vacuum pumping treatment to remove air bubbles in the slurry. Finally, casting the slurry onto a polyester film, and drying at room temperature to obtain a NiO-YSZ anode support casting sheet, wherein the thickness of the NiO-YSZ anode support casting sheet is 5 mm;
step (2): micro-processing one side surface of the NiO-YSZ anode support body tape casting sheet to form a special orthogonal net structure on the surface:
firstly, cutting a NiO-YSZ anode support body casting sheet into small sheets with the diameter of 40mm, and performing micro-processing treatment on the surface (single surface) of the casting sheet by adopting a pulse optical fiber laser, wherein the processing pattern is orthogonal net-shaped, the distance between adjacent lines is 50 mu m, the using power of the pulse optical fiber laser is 3W, the frequency is 50Hz, and the scanning speed is 300 mm/s;
and (3): pre-sintering the NiO-YSZ anode support body tape-casting sheet treated in the step (2):
putting the NiO-YSZ anode support body tape-casting sheet subjected to the surface treatment in the step (2) into a medium-temperature furnace, and calcining for 2 hours at 1050 ℃;
and (4): coating a high-activity anode functional layer on the surface of the NiO-YSZ anode support tape casting sheet pre-sintered in the step (3):
coating a layer of high-activity nano powder slurry on the modification surface of the NiO-YSZ anode support body pre-sintered in the step (3) by adopting a rotary drop coating method, wherein the drop coating amount is 0.3mL, and after the nano powder slurry is dried at room temperature for 60min, forming a high-activity anode functional layer, namely forming the NiO-YSZ anode functional layer;
wherein the nano powder in the high-activity nano powder slurry is NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7;
and (5): coating a layer of YSZ electrolyte layer on the surface of the NiO-YSZ anode functional layer, and sintering at high temperature:
and coating YSZ electrolyte slurry on the surface of the NiO-YSZ anode functional layer by adopting a rotary dropping coating method to form a YSZ electrolyte layer, wherein the dropping coating amount of the YSZ electrolyte slurry is 0.5mL, and after drying the YSZ electrolyte slurry at room temperature for 30min, calcining at 1450 ℃ for 2h to obtain the anode/electrolyte half cell.
Example 3
The embodiment provides an anode/electrolyte half cell, and a manufacturing method thereof comprises the following specific steps:
step (1): preparing a NiO-YSZ anode support body tape casting sheet by adopting a tape casting method:
6g of NiO, 4g of YSZ powder, 0.6g of PMMA and 0.05g of triethanolamine are respectively weighed and dissolved in 100g of mixed solvent of ethanol and xylene, and the mixture is ball-milled for 24 hours on a high-energy ball mill. After being mixed evenly, 0.2g of polyvinyl butyral, 0.2g of polymethyl acrylate and 0.5g of ethyl cellulose are added into the slurry, and the ball milling is continued for 12 hours. Subsequently, the uniformly mixed slurry is placed in a vacuum chamber for vacuum pumping treatment to remove air bubbles in the slurry. Finally, casting the slurry onto a polyester film, and drying at room temperature to obtain a NiO-YSZ anode support casting sheet, wherein the thickness of the NiO-YSZ anode support casting sheet is 5 mm;
step (2): micro-processing one side surface of the NiO-YSZ anode support body tape-casting sheet to form a special orthogonal net structure on the surface:
firstly, cutting a NiO-YSZ anode support body casting sheet into small round sheets with the diameter of 40mm, and performing micro-processing treatment on the surface (single surface) of the NiO-YSZ anode support body casting sheet by adopting a pulse optical fiber laser, wherein the processing pattern is orthogonal net-shaped, the distance between adjacent lines and lines is 20 mu m, the using power of the pulse optical fiber laser is 3W, the frequency is 50Hz, and the scanning speed is 300 mm/s;
and (3): pre-sintering the NiO-YSZ anode support body tape-casting sheet treated in the step (2):
placing the NiO-YSZ anode support body tape-casting sheet subjected to surface treatment in the step (2) into a medium-temperature furnace, and calcining for 2 hours at 1050 ℃;
and (4): coating a layer of high-activity anode functional layer on the surface of the NiO-YSZ anode support body tape casting sheet pre-sintered in the step (3):
coating a layer of high-activity nano powder slurry on the modification surface of the NiO-YSZ anode support body pre-sintered in the step (3) by adopting a rotary dropping coating method, wherein the dropping coating amount is 0.3mL, and forming a high-activity anode functional layer after the nano powder slurry is dried at room temperature for 60min, namely forming the NiO-YSZ anode functional layer;
wherein the nano powder in the high-activity nano powder slurry is NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7;
and (5): coating a layer of YSZ electrolyte layer on the surface of the NiO-YSZ anode functional layer, and sintering at high temperature:
and coating YSZ electrolyte slurry on the surface of the NiO-YSZ anode functional layer by adopting a rotary dropping coating method to form a YSZ electrolyte layer, wherein the dropping coating amount of the YSZ electrolyte slurry is 0.5mL, and after drying the YSZ electrolyte slurry at room temperature for 30min, calcining at 1450 ℃ for 2h to obtain the anode/electrolyte half cell.
Comparative example 1
The present comparative example provides an anode/electrolyte half cell, the method of making comprising the specific steps of:
step (1): preparing a NiO-YSZ anode support body tape casting sheet by adopting a tape casting method:
6g of NiO, 4g of YSZ powder, 0.6g of PMMA and 0.05g of triethanolamine are respectively weighed and dissolved in 100g of mixed solvent of ethanol and xylene, and the mixture is ball-milled for 24 hours on a high-energy ball mill. After being mixed evenly, 0.2g of polyvinyl butyral, 0.2g of polymethyl acrylate and 0.5g of ethyl cellulose are added into the slurry, and the ball milling is continued for 12 hours. And then, placing the uniformly mixed slurry in a vacuum cavity for vacuumizing treatment to remove air bubbles in the slurry. Finally, casting the slurry onto a polyester film, and drying at room temperature to obtain a NiO-YSZ anode support casting sheet, wherein the thickness of the NiO-YSZ anode support casting sheet is 5 mm;
step (2): pre-sintering the NiO-YSZ anode support body tape-casting sheet treated in the step (1):
cutting the NiO-YSZ anode support body cast sheet prepared in the step (1) into small round sheets with the diameter of 40mm, and then putting the cast sheet into a medium-temperature furnace to calcine for 2 hours at 1050 ℃;
and (3): coating a layer of high-activity anode functional layer on the surface of the NiO-YSZ anode support body tape casting sheet pre-sintered in the step (2):
coating a layer of high-activity nano powder slurry on the modification surface of the NiO-YSZ anode support body tape casting sheet pre-sintered in the step (2) by adopting a rotary dropping coating method, wherein the dropping coating amount is 0.3mL, and forming a NiO-YSZ anode functional layer after the nano powder slurry is dried at room temperature for 60 min;
wherein the nano powder in the high-activity nano powder slurry is NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7;
and (4): coating a layer of YSZ electrolyte layer on the surface of the NiO-YSZ anode functional layer, and sintering at high temperature:
and coating YSZ electrolyte slurry on the surface of the NiO-YSZ anode functional layer by adopting a rotary dropping coating method to form a YSZ electrolyte layer, wherein the dropping coating amount of the YSZ electrolyte slurry is 0.5mL, and after drying the YSZ electrolyte slurry at room temperature for 30min, calcining at 1450 ℃ for 2h to obtain the anode/electrolyte half cell.
Examples 1 to 1
This embodiment provides an anode-supported solid oxide fuel cell, whose schematic structural diagram is shown in fig. 4, wherein the anode-supported solid oxide fuel cell includes the anode/electrolyte half cell of embodiment 1 and an LSM-YSZ composite cathode layer 5 coated on the surface of the YSZ electrolyte layer of the anode/electrolyte half cell, and its manufacturing method includes the following specific steps:
weighing 4g of YSZ and LSM powder according to the mass ratio of 7:3, dissolving the powder into a mixed solvent of terpineol, ethanol and isopropanol, wherein the mass of the solvent is 10g, adding 0.01g of polyvinyl butyral, 0.01g of polymethyl acrylate and 0.02g of ethyl cellulose, uniformly mixing, and coating the obtained slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell by adopting a screen printing method, wherein the coating amount is 0.5 mL; and after the slurry is dried at 25 ℃ for 30min, calcining at 1100 ℃ for 2h to prepare the NiO-YSZ/YSZ/LSM-YSZ single Cell which is marked as Cell 1.
Example 2-1
The present embodiment provides an anode-supported solid oxide fuel cell, wherein the anode-supported solid oxide fuel cell includes the anode/electrolyte half cell of embodiment 2 and an LSM-YSZ composite cathode layer coated on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell, and the manufacturing method includes the following specific steps:
weighing 4g of YSZ and LSM powder according to the mass ratio of 7:3, dissolving the powder into a mixed solvent of terpineol, ethanol and isopropanol, wherein the mass of the solvent is 10g, adding 0.01g of polyvinyl butyral, 0.01g of polymethyl acrylate and 0.02g of ethyl cellulose, uniformly mixing, and coating the obtained slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell by adopting a screen printing method, wherein the coating amount is 0.5 mL; and after the slurry is dried at 25 ℃ for 30min, calcining at 1100 ℃ for 2h to prepare the NiO-YSZ/YSZ/LSM-YSZ single Cell which is marked as Cell 2.
Example 3-1
The present embodiment provides an anode-supported solid oxide fuel cell, wherein the anode-supported solid oxide fuel cell includes the anode/electrolyte half cell of embodiment 3 and an LSM-YSZ composite cathode layer coated on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell, and the manufacturing method includes the following specific steps:
weighing 4g of YSZ and LSM powder according to the mass ratio of 7:3, dissolving the powder into a mixed solvent of terpineol, ethanol and isopropanol, wherein the mass of the solvent is 10g, adding 0.01g of polyvinyl butyral, 0.01g of polymethyl acrylate and 0.02g of ethyl cellulose, uniformly mixing, and coating the obtained slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell by adopting a screen printing method, wherein the coating amount is 0.5 mL; and after the slurry is dried at 25 ℃ for 30min, calcining at 1100 ℃ for 2h to prepare the NiO-YSZ/YSZ/LSM-YSZ single Cell which is marked as Cell 3.
Comparative examples 1 to 1
The present comparative example provides an anode-supported solid oxide fuel cell, wherein the anode-supported solid oxide fuel cell comprises the anode/electrolyte half cell of comparative example 1 and an LSM-YSZ composite cathode layer coated on the surface of the YSZ electrolyte layer of the anode/electrolyte half cell, and the manufacturing method comprises the following specific steps:
weighing 4g of YSZ and LSM powder according to the mass ratio of 7:3, dissolving the powder into a mixed solvent of terpineol, ethanol and isopropanol, wherein the mass of the solvent is 10g, adding 0.01g of polyvinyl butyral, 0.01g of polymethyl acrylate and 0.02g of ethyl cellulose, uniformly mixing, and coating the obtained slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell by adopting a screen printing method, wherein the coating amount is 0.5 mL; and after the slurry is dried at 25 ℃ for 30min, calcining at 1100 ℃ for 2h to prepare the NiO-YSZ/YSZ/LSM-YSZ single Cell, and marking as Cell 0.
Test example 1
In this test example, an ac impedance spectrum test was performed on Cell 0, Cell 1, Cell 2, and Cell 3 at an open circuit state at 800 ℃, and the ac impedance spectrum obtained is shown in fig. 5, and it can be seen from fig. 5 that, compared to a control sample (Cell 0) without surface modification, the polarization resistance of Cell 1 at an open circuit state at 800 ℃ is reduced by 17.8%, the polarization resistance of Cell 2 at an open circuit state at 800 ℃ is reduced by 22.3%, and the polarization resistance of Cell 3 at an open circuit state at 800 ℃ is reduced by 44.6%.
Further, comparing polarization resistance data of Cell 1, Cell 2, and Cell 3 at 800 ℃, it is seen that the smaller the pitch between adjacent lines of the orthogonal network structure in the anode-supported solid oxide fuel Cell, the lower the polarization resistance of the anode-supported solid oxide fuel Cell, and the more excellent the electrochemical performance of the Cell.
Test example 2
In this test example, Cell 0, Cell 1, Cell 2, and Cell 3 were subjected to an I-V-P test at 800 ℃, and the obtained I-V-P curve is shown in fig. 6, and it can be seen from fig. 6 that the maximum power density of Cell 1 at 800 ℃ is increased by 30%, the maximum power density of Cell 2 at 800 ℃ is increased by 36%, and the maximum power density of Cell 3 at 800 ℃ is increased by 60%, compared with the control sample (Cell 0) in which no surface modification is performed.
Further, comparing the maximum power density data of Cell 1, Cell 2, and Cell 3 at 800 ℃, it is found that the smaller the pitch between adjacent lines of the orthogonal mesh structure in the anode-supported solid oxide fuel Cell, the larger the maximum power density of the anode-supported solid oxide fuel Cell.
The above description is only exemplary of the invention and should not be taken as limiting the scope of the invention, so that the invention is intended to cover all modifications and equivalents of the embodiments described herein. In addition, the technical features and the technical inventions of the present invention, the technical features and the technical inventions, and the technical inventions can be freely combined and used.
Claims (10)
1. A method of making an anode/electrolyte half cell comprising:
(1) dissolving NiO powder, YSZ powder, a pore-forming agent and a dispersing agent in a solvent, ball-milling the obtained mixture, adding a binder and a plasticizer into the obtained slurry after uniformly mixing, continuing ball-milling, carrying out vacuum pumping treatment on the uniformly mixed slurry, casting the slurry onto a polyester film, and drying to obtain a NiO-YSZ anode support body casting sheet;
(2) cutting the NiO-YSZ anode support body cast sheet, and then carrying out micro-processing treatment on one side surface of the NiO-YSZ anode support body cast sheet to enable the surface of the NiO-YSZ anode support body cast sheet to be in an orthogonal net-shaped structure;
(3) pre-sintering the NiO-YSZ anode support body tape-casting sheet after surface treatment obtained in the step (2);
(4) coating nano powder slurry on the decorative surface of the pre-sintered NiO-YSZ anode support body obtained in the step (3), and drying to form an anode functional layer;
(5) and coating a YSZ electrolyte layer on the surface of the anode functional layer, and drying and roasting to obtain the anode/electrolyte half cell.
2. The manufacturing method according to claim 1, wherein in the step (1), the mass ratio of the NiO powder to the YSZ powder is 3: 7-7: 3;
preferably, the amount of the pore-forming agent is 5-30% of the total mass of the NiO powder and the YSZ powder; more preferably, the pore-forming agent is selected from one or more of polymer material microsphere pore-forming agents; further preferably, the pore-forming agent is polymethyl methacrylate and/or polystyrene;
preferably, the using amount of the dispersing agent is 0.5-5% of the total mass of the NiO powder and the YSZ powder; still more preferably, the dispersant is selected from one or more of amine dispersants; still further preferably, the dispersant is triethanolamine and/or 2-amino-2-methyl-1-propanol;
preferably, the amount of the solvent is 1-20 times of the total mass of the NiO powder and the YSZ powder; still more preferably, the solvent is selected from one or more of organic solvents; still further preferably, the organic solvent is one or more of ethanol, xylene and trichloroethylene;
preferably, the amount of the binder is 1-20% of the total mass of the NiO powder and the YSZ powder; still more preferably, the binder is selected from one or more of non-water based binders; still further preferably, the binder is one or more of polyvinyl butyral, polymethyl acrylate, and ethyl cellulose;
preferably, the amount of the plasticizer is 1-20% of the total mass of the NiO powder and the YSZ powder; still more preferably, the plasticizer is selected from one or more of polyethylene glycol, dibutyl phthalate, ethylene glycol;
still preferably, in the step (1), the ball milling time is 12-24 h, and the ball milling time is 12-24 h;
preferably, in the step (1), the thickness of the NiO-YSZ anode support casting sheet is 1-10 mm;
also preferably, the drying in step (1) is drying at room temperature.
3. The manufacturing method according to claim 1 or 2, wherein in the step (2), the NiO-YSZ anode support cast sheet is cut into small round sheets, and the diameter of each small round sheet is 10-50 mm;
preferably, in the step (2), a pulse fiber laser is adopted to perform micro-processing treatment on one side surface of the cut NiO-YSZ anode support body casting sheet, the power of the pulse fiber laser is 1-10W, the frequency is 20-50 Hz, and the scanning speed is 100-500 mm/s;
preferably, the distance between two adjacent parallel lines in the orthogonal net structure is 10-100 μm.
4. The method according to claim 1 or 2, wherein in the step (3), the pre-sintering temperature is 900 to 1300 ℃ and the time is 1 to 5 hours.
5. The method according to claim 1 or 2, wherein in the step (4), the amount of the nano-powder slurry to be dropped is 0.1 to 1mL/cm2The dripping area is 1-10 cm2；
Preferably, the nano powder in the nano powder slurry is NiO nano powder and YSZ nano powder, and the mass ratio of the NiO nano powder to the YSZ nano powder is 3: 7-7: 3;
preferably, the drying in the step (4) is performed at room temperature, and the drying time is 30-120 min.
6. The method of claim 1 or 2, wherein in step (5), the YSZ electrolyte slurry is applied in an amount of 0.1-2 mL/cm2The dripping area is 1-10 cm2；
Preferably, the drying in the step (5) is drying at room temperature, and the drying time is 30-120 min;
preferably, in the step (5), the roasting temperature is 1200-1500 ℃ and the roasting time is 1-5 h.
7. An anode/electrolyte half-cell made by the method of making an anode/electrolyte half-cell of any one of claims 1-6.
8. An anode-supported solid oxide fuel cell comprising the anode/electrolyte half cell of claim 7 and a LSM-YSZ composite cathode layer coated on the surface of the YSZ electrolyte layer of the anode/electrolyte half cell.
9. The method of manufacturing an anode-supported solid oxide fuel cell according to claim 8, comprising:
1) mixing YSZ powder, LSM powder, a binder and an organic solvent to obtain LSM-YSZ slurry;
2) and coating the LSM-YSZ slurry on the surface of a YSZ electrolyte layer of the anode/electrolyte half cell, and calcining after drying the slurry to obtain the anode-supported solid oxide fuel cell.
10. The manufacturing method of claim 9, wherein in the step 1), the mass ratio of the YSZ powder to the LSM powder is 3: 7-7: 3;
preferably, in the step 1), the amount of the organic solvent is 1-10 times of the total mass of the YSZ powder and the LSM powder; more preferably, the organic solvent is selected from one or more of alcoholic organic solvents; further preferably, the organic solvent is selected from one or more of terpineol, ethanol, isopropanol;
still preferably, in the step 1), the usage amount of the binder is 0.1-1% of the total mass of the YSZ powder and the LSM powder; still more preferably, the binder is selected from one or more of non-water based binders; still further preferably, the binder is selected from one or more of polyvinyl butyral, polymethyl acrylate, ethyl cellulose;
preferably, in the step 2), the coating amount of the LSM-YSZ slurry is 0.1-3 mL/cm2The coating area is 1-10 cm2；
Preferably, in the step 2), the drying temperature is 25-50 ℃ and the drying time is 30-60 min;
still preferably, in the step 2), the calcining temperature is 800-1200 ℃ and the time is 1-5 h.
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