CN116666683A - Ceramic-based powder grading type sealing material for medium-temperature flat plate type solid oxide fuel cell and preparation method thereof - Google Patents
Ceramic-based powder grading type sealing material for medium-temperature flat plate type solid oxide fuel cell and preparation method thereof Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 73
- 239000007787 solid Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 20
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
-
- 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
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a ceramic-based powder grading type sealing material for a medium-temperature plate type solid oxide fuel cell, which fills fine ceramic powder particles between gaps of coarse ceramic powder particles by a powder particle grading method, improves the stacking density and reduces the porosity, thereby improving the air tightness of the ceramic-based powder grading type sealing material, improving the heat stability and the sealing performance of the ceramic-based powder grading type sealing material and further providing excellent sealing effect. The ceramic-based powder grading type sealing material provided by the invention has smaller air tightness difference in the temperature range of 600-800 ℃ and is less affected by temperature; in a thermal shock cycle test of rapid temperature change, the air tightness is increased to a certain extent in the initial 4 times of cycles, and then the air tightness is basically kept stable, so that the sealing requirement of the medium-temperature flat plate type solid oxide fuel cell is met; the high-temperature insulating material has the characteristics of good high-temperature insulating property, simple manufacturing method, low cost, stable quality and the like, and is suitable for commercial mass production.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a ceramic-based powder grading type sealing material for a medium-temperature plate type solid oxide fuel cell and a preparation method thereof.
Background
A solid oxide fuel cell is an energy conversion device that can directly convert chemical energy in fuel into electrical energy. Compared with the traditional power generation mode, the solid oxide fuel cell has the characteristics of high energy conversion efficiency, low environmental pollution, low working noise and the like. Regarding the research trend at home and abroad, the medium temperature plate type solid oxide fuel cell is the main stream of the current research, and has the advantages of high single cell power density, low production cost, easy assembly and the like. The medium temperature plate type solid oxide fuel cell stack is mainly formed by connecting single cells with a connector in series, and the working temperature is generally 600-850 ℃. The sealing material is a key component for realizing large-scale application of the medium-temperature plate type solid oxide fuel cell stack, and the sealing material with good sealing performance can ensure the output performance and long-term stability of the stack. During the actual operation of the stack, air is introduced into the cathode side of the cell and fuel gas is introduced into the anode side. The sealing material needs to provide sufficient air tightness to isolate the reaction gas between the single cells and the connector and between the single cells and the stack clamp, and prevent the rapid deterioration of the electrochemical performance of the stack and even safety accidents caused by gas mixing. The sealing material also needs to isolate the inside and outside atmosphere of the stack and prevent leakage of the stack reactant gas at the main gas path. Besides good air tightness, the sealing material also needs to have the characteristics of insulativity, good chemical compatibility with adjacent components, certain mechanical strength, long-term stability, thermal cycle stability, low manufacturing cost, easy mass production, short production period, easy processing, simple assembly and the like.
Sealing materials commonly used for the current flat plate type solid oxide fuel cell can be classified into two types according to sealing modes: rigid sealing material and compression sealing material. Rigid sealing materials have high requirements for matching thermal expansion coefficients, and common rigid sealing materials are generally classified into metal brazing sealing materials and glass-based sealing materials. The metal brazing type sealing material has good plastic deformation capability, can better release thermal stress and mechanical stress, but has certain conductivity and is easy to oxidize in a high-temperature oxidation-reduction environment. The glass-based sealing material has the advantages of low manufacturing cost, simple sealing mode and good sealing performance, but has the defects that the glass raw material is relatively difficult to prepare, the glass characteristics are difficult to control, and the glass transition temperature and the softening temperature of the glass-based sealing material limit the application temperature range of the glass-based sealing material. The removal of the stack is very difficult due to the nature of the glass infiltration related components. In addition, the chemical stability of the glass is not good enough. The brittleness is high, and the service life is short.
The compression type sealing material is tightly attached to the single cell/connector by applying a certain load pressure to realize the sealing effect. Therefore, the compression type sealing material has lower requirement on the matching performance of the thermal expansion coefficient between the adjacent components, and can effectively reduce the damage to the battery components in the thermal cycle process.
Typical compression type sealing materials are mica-based sealing materials and ceramic-based sealing materials. Mica-based sealing materials consist of parallel sheets of silicate tetrahedra, which makes them able to accommodate very large thermal stresses, but require a sufficiently large loading pressure to be applied during operation to achieve a good sealing effect, but excessive compressive stresses can lead to cell rupture. In addition, the mica-based sealing material has poor thermal cycle performance, and potassium element in mica is easy to poison an electrode. In contrast, ceramic-based sealing materials prepared by a tape casting process have the characteristics of controllable thickness, sufficient toughness and easy processing energy, and have been successfully applied to flat-plate solid oxide fuel cells.
Ceramic-based sealing materials generally have good mechanical stability and chemical compatibility. With Al 2 O 3 For example, a single-size Al is used as the base sealing material 2 O 3 Pure Al produced by powder 2 O 3 The base sealing material can ensure the sealing of the solid oxide fuel cell stack under low air pressure difference, but can generate air leakage phenomenon in the process of high air pressure difference and long-term operation. Al added with Al powder 2 O 3 The base sealing material is compared with pure Al 2 O 3 The base sealing material has better sealing performance and thermal stability, but during the temperature rising process, al powder in the sealing material is oxidized to cause a thickening phenomenon of the material, which is disadvantageous to the contact between battery components and easily causes electrochemical performance loss. As noted above, the existing ceramic-based sealing materials have shortcomings in sealing performance, thermal stability and the like, and therefore, providing a ceramic-based sealing material with high sealing performance and good thermal stability is a problem to be solved in the prior art.
Disclosure of Invention
The ceramic-based powder graded sealing material for the medium-temperature plate type solid oxide fuel cell, which is prepared by the method, has high sealing performance and excellent thermal stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a ceramic-based powder grading sealing material for a medium-temperature plate type solid oxide fuel cell, which is prepared from 50-90 parts of coarse ceramic powder and 10-50 parts of fine ceramic powder;
the average grain diameter of the coarse ceramic powder is 0.5-12 mu m, and the average grain diameter of the fine ceramic powder is 90-900 nm;
the thickness of the ceramic-based powder grading type sealing material is 0.20-0.70 mm.
Preferably, the ceramic-based powder grading type sealing material is prepared from 60-80 parts of coarse ceramic powder and 20-40 parts of fine ceramic powder;
preferably, the coarse ceramic powder has an average particle diameter of 1 to 10 μm, and the fine ceramic powder has an average particle diameter of 100 to 800nm
Preferably, the thickness of the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell is 0.25-0.60 mm
The invention also provides a preparation method of the ceramic-based powder grading type sealing material, which comprises the following steps:
(1) Uniformly mixing absolute ethyl alcohol, dimethylbenzene and a dispersing agent to obtain a mixed solvent;
(2) Mixing the mixed solvent obtained in the step (1) with coarse ceramic powder and fine ceramic powder, and performing first ball milling to obtain slurry;
(3) Mixing the slurry obtained in the step (2) with a binder, a plasticizer and a defoaming agent, and performing second ball milling to obtain second ball milled slurry;
(4) And (3) carrying out tape casting molding on the slurry obtained in the step (3) after the second ball milling to obtain the ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell.
Preferably, the dispersing agent in the step (1) is at least one of KD24, herring oil and castor oil.
Preferably, the first ball milling time in the step (1) is 14-18 h, and the medium of the first ball milling is zirconia ball milling beads.
Preferably, the binder in the step (3) is at least one of polyvinyl butyral (PVB) with a brand number of B76 or B98.
Preferably, the second ball milling time in the step (3) is 25-30 h.
The invention also provides the application of the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell or the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell prepared by the preparation method in the medium-temperature solid oxide fuel cell stack.
The invention provides a ceramic-based powder grading sealing material for a medium-temperature plate type solid oxide fuel cell, which is prepared from 50-90 parts of coarse ceramic powder and 10-50 parts of fine ceramic powder; the average grain diameter of the coarse ceramic powder is 0.5-12 mu m, and the average grain diameter of the fine ceramic powder is 90-900 nm; the thickness of the ceramic-based powder grading type sealing material is 0.20-0.70 mm. According to the invention, ceramic powder combinations with different grading proportions are designed through a powder grading method, coarse ceramic powder is used as a main body of the sealing material, fine ceramic powder is filled between gaps of coarse ceramic powder particles, the stacking density of the ceramic-based powder grading type sealing material is improved, the porosity of the ceramic-based powder grading type sealing material is reduced, and therefore the air tightness of the ceramic-based powder grading type sealing material is improved, the thermal stability and sealing performance of the ceramic-based powder grading type sealing material are improved, and further an excellent sealing effect is provided. The ceramic-based powder grading type sealing material provided by the invention has smaller air tightness difference in the temperature range of 600-800 ℃ and is less affected by temperature; in a thermal shock cycle test of rapid temperature change, the air tightness is increased to a certain extent in the initial 4 times of cycles, and then the air tightness is basically kept stable, so that the sealing requirement of the medium-temperature flat plate type solid oxide fuel cell is met; the high-temperature insulating material has the characteristics of good high-temperature insulating property, simple manufacturing method, low cost, stable quality and the like, and is suitable for commercial mass production. The results of the examples show that the ceramic-based powder grading sealing material for the medium-temperature flat-plate type solid oxide fuel cell prepared in the example 1 of the invention maintains good air tightness in the temperature range of 650-800 ℃ and under the maximum ventilation pressure of 20kPa, and maintains good air tightness when the rapid temperature cycle is carried out between 300-750 ℃; when the sealing material is applied to a galvanic pile, the sealing performance is still excellent.
Drawings
FIG. 1 shows the Al used in example 1 of the present invention 2 O 3 Coarse ceramic powder and Al 2 O 3 Microcosmic morphology map of fine ceramic powder;
FIG. 2 is a graph showing the thermal weight loss of the ceramic-based powder grading seal material for a medium temperature plate type solid oxide fuel cell prepared in example 1 of the present invention;
FIG. 3 is a graph showing the change of gas leakage rate of the ceramic-based powder graded sealing material for a medium temperature plate type solid oxide fuel cell prepared in example 1 of the present invention at different temperatures and different ventilation pressures;
FIG. 4 is a graph showing the change of gas leakage rate of the ceramic-based powder graded sealing material for a solid oxide fuel cell of a medium temperature plate type prepared in example 1 according to the present invention under different load pressures;
FIG. 5 is an XRD pattern of the ceramic-based powder grading seal material for a medium temperature plate type solid oxide fuel cell prepared in example 1 after thermal shock cycle test at a final temperature of 750℃and a loading pressure of 0.2 MPa;
fig. 6 is a graph showing current-voltage-power density at 750 c of a cell stack assembled from a ceramic-based powder grading type sealing material for a solid oxide fuel cell of a medium temperature plate type prepared in example 1 according to the present invention.
Detailed Description
The invention provides a ceramic-based powder grading sealing material for a medium-temperature plate type solid oxide fuel cell, which is prepared from 50-90 parts of coarse ceramic powder and 10-50 parts of fine ceramic powder; the average grain diameter of the coarse ceramic powder is 0.5-12 mu m, and the average grain diameter of the fine ceramic powder is 90-900 nm; the thickness of the ceramic-based powder grading type sealing material is 0.20-0.70 mm.
In the present invention, the ceramic-based powder graded sealing material is preferably prepared from a ceramic powder comprising 60 to 80 parts of a coarse ceramic powder and 20 to 40 parts of a fine ceramic powder.
In the present invention, the coarse ceramic powder preferably has an average particle diameter of 1 to 10. Mu.m. In the present invention, the fine ceramic powder preferably has an average particle diameter of 100 to 800nm
In the invention, the thickness of the ceramic-based powder grading sealing material for the medium temperature plate type solid oxide fuel cell is preferably 0.25-0.60 mm
The invention also provides a preparation method of the ceramic-based powder grading type sealing material, which comprises the following steps:
(1) Uniformly mixing absolute ethyl alcohol, dimethylbenzene and a dispersing agent to obtain a mixed solvent;
(2) Mixing the mixed solvent obtained in the step (1) with coarse ceramic powder and fine ceramic powder, and performing first ball milling to obtain slurry;
(3) Mixing the slurry obtained in the step (2) with a binder, a plasticizer and a defoaming agent, and performing second ball milling to obtain second ball milled slurry;
(4) And (3) carrying out tape casting molding on the slurry obtained in the step (3) after the second ball milling to obtain the ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
The invention mixes absolute ethyl alcohol, dimethylbenzene and dispersing agent uniformly to obtain mixed solvent.
In the present invention, the volume ratio of the absolute ethanol to the xylene is preferably 7:3.
In the present invention, the dispersant is preferably at least one of KD24, herring oil and castor oil. In the present invention, the concentration of the dispersant in the mixed solvent is preferably 57 to 75g/L, more preferably 62.5 to 70g/L.
After the mixed solvent is obtained, the mixed solvent is mixed with the coarse ceramic powder and the fine ceramic powder, and then the first ball milling is carried out to obtain slurry.
In the present invention, the mixed solvent is preferably mixed with the coarse ceramic powder and the fine ceramic powder by sequentially adding the fine ceramic powder and the coarse ceramic powder to the mixed solvent. In the present invention, the ratio of the volume of the mixed solvent to the total mass of the fine ceramic powder and the coarse ceramic powder is preferably 1L: (1.5-2) kg, more preferably 1L: (1.66-1.87) kg. In the present invention, the time of the first ball milling is preferably 14 to 18 hours, more preferably 15 to 17 hours. In the present invention, the medium for the first ball milling is preferably zirconia ball milling beads. The invention promotes the uniform mixing of the components through the first ball milling.
After the slurry is obtained, the slurry is mixed with a binder, a plasticizer and a defoaming agent, and then subjected to second ball milling to obtain the slurry after the second ball milling.
In the present invention, the binder is at least one of polyvinyl butyral (PVB) having the designation B76 or B98. In the present invention, the plasticizer is at least one of butyl benzyl ester (PAG) or polyalkyl glycol (BBP). In the invention, the foam remover is at least one of cyclohexanone foam remover or silicon-based foam remover. In the invention, the mass ratio of the slurry to the binder, the plasticizer and the foam remover is preferably 1000: (36.51-38.68): (48.18-51.01): (0.44-0.47).
In the present invention, the time of the second ball milling is preferably 25 to 30 hours, more preferably 26 to 28 hours. The sealing material formed by the method has enough strength and good flexibility through the second ball milling.
After the second ball-milled slurry is obtained, the second ball-milled slurry is subjected to tape casting and molding to obtain the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell.
In the present invention, the second ball-milled slurry is preferably subjected to vacuum defoaming before the casting molding is performed. The method for removing bubbles in vacuum is not particularly limited, and the technical scheme well known in the art can be adopted. The invention removes the slurry bubbles after the second ball milling through vacuum bubble removal, which is favorable for obtaining the ceramic-based powder grading sealing material with good compactness, flatness and smooth surface for the medium temperature plate type solid oxide fuel cell and good comprehensive performance.
The method for casting and forming is not particularly limited, and the method can adopt the technical scheme well known in the art.
After casting, the invention dries the casting product to obtain the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell.
In the present invention, the drying time is preferably 22 to 26 hours; the drying temperature is preferably 25 to 30 ℃.
The preparation method of the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell is simple to operate, mild in reaction condition and suitable for large-scale production.
The invention also provides the application of the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell or the ceramic-based powder grading sealing material for the medium-temperature plate type solid oxide fuel cell prepared by the preparation method in the medium-temperature solid oxide fuel cell stack.
In the present invention, a method for assembling the above ceramic-based powder gradation sealing material for a medium temperature plate type solid oxide fuel cell into a solid oxide fuel cell stack comprises the steps of:
(S1) cutting the ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell according to the required size to obtain a sealing frame;
(S2) coating an adhesive on one side surface of the sealing frame obtained in the step (S1), and then placing the sealing frame between each solid oxide fuel cell and a corresponding connector to obtain a placed sealing frame;
(S3) applying a load pressure of about 0.2 to 0.4MPa in a direction perpendicular to the placed sealing frame obtained in the step (S2) outside the solid oxide fuel cell stack, and raising the temperature of the stack to an operating temperature of 500 to 800 ℃, thereby completing the sealing of the solid oxide fuel cell stack or the assembly of the ceramic-based powder gradation sealing material for a medium temperature plate type solid oxide fuel cell.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
The ceramic-based powder grading type sealing material for medium temperature plate type solid oxide fuel cell consists of Al with average grain size of 2-3 microns in 80 portions 2 O 3 Coarse ceramic powder and 20 parts of Al with average grain diameter of 100-200 nm 2 O 3 Preparing fine ceramic powder; the saidThe thickness of the ceramic-based powder graded sealing material is 0.23mm.
The preparation method of the ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell comprises the following steps:
(1) Uniformly mixing 0.048L of absolute ethyl alcohol, 0.112L of dimethylbenzene and 11gKD of dispersing agent to obtain a mixed solvent; the concentration of the dispersing agent in the mixed solvent is 68.75g/L;
(2) Sequentially adding 250g of the mixed solvent with the average particle size of 2-3 mu mAl into the mixed solvent obtained in the step (1) 2 O 3 Coarse ceramic powder and 50g of ceramic powder with average grain size of 100-200 nmAl 2 O 3 Mixing fine ceramic powder in a ball milling tank, adding 900g of zirconia ball milling beads as a ball milling medium, and performing first ball milling for 16 hours to obtain slurry;
(3) Mixing the slurry obtained in the step (2) with 16.44g of polyvinyl butyral binder with the brand number of B76, 21.68g of plasticizer and 0.2g of cyclohexanone foam remover in a ball milling tank, and performing second ball milling for 28 hours to obtain second ball-milled slurry;
the plasticizer is butyl benzyl ester (PAG) and polyalkyl glycol (BBP) with the mass ratio of 1:1; the mass ratio of the sizing agent to the binder, the plasticizer and the foam remover is 1000:36.92:48.69:0.45;
(4) And (3) carrying out vacuum bubble removal on the slurry obtained in the step (3), carrying out tape casting molding, and drying at 25 ℃ for 24 hours to obtain the ceramic-based powder grading sealing material for the medium-temperature flat-plate type solid oxide fuel cell, wherein the thickness of the ceramic-based powder grading sealing material is uniform, and the surface of the ceramic-based powder grading sealing material is flat and smooth.
FIG. 1 shows the Al used in example 1 of the present invention 2 O 3 Coarse ceramic powder and Al 2 O 3 Microcosmic topography of fine ceramic powder, wherein Al in FIG. 1 (a) 2 O 3 The average particle diameter of the coarse ceramic powder is 2 to 3 μm, and Al in FIG. 1 (b) 2 O 3 The average grain diameter of the fine ceramic powder is 100-200 nm.
Thermogravimetric testing: the ceramic base powder graded sealing material for a solid oxide fuel cell prepared in example 1 was subjected to thermogravimetry, the temperature elevation program was from room temperature to 800 ℃ at an elevation rate of 10 ℃/min, and a graph of thermal weight loss of the ceramic base powder graded sealing material for a solid oxide fuel cell prepared in example 1 was obtained as shown in fig. 2. As can be seen from fig. 2, the ceramic-based powder grading type sealing material for solid oxide fuel cell prepared in example 1 has a rapid decrease in weight with an increase in temperature between 200 ℃ and 420 ℃, a gradual weight loss of the material after 400 ℃, a very small weight change, a weight loss within 2% in a temperature range between 420 ℃ and 800 ℃, and a maximum weight loss of all the materials of not more than 15%. This shows that the organic matters in the ceramic-based powder graded sealing material for a medium temperature plate type solid oxide fuel cell prepared in example 1 are almost all substantially volatilized between 200 and 420 ℃. The temperature rise curve process for the sealing material air tightness test is set according to the thermal weight loss curve: heating to 200 ℃ at 2 ℃/min, then preserving heat for 1h, then slowly heating to 500 ℃ at a speed of 1 ℃/min, preserving heat for 1h, and finally heating to different test temperatures (650-800 ℃) at 1 ℃/min, preserving heat for 1h, and testing.
The temperature rise program for the thermal shock cycle test is as follows: and (3) heating the test furnace to 750 ℃ according to a heating process set by a thermogravimetric test, preserving heat for 1h, then rapidly reducing the furnace temperature from 750 ℃ to 300 ℃ (the average cooling rate is about 7 ℃/min), preserving heat for 0.5h, heating to 750 ℃ at 3 ℃/min, preserving heat for 1h again, completing a thermal shock cycle test, and then carrying out the thermal shock cycle test under the same conditions.
Cutting the ceramic-based powder grading type sealing material for the medium temperature plate type solid oxide fuel cell prepared in the embodiment 1 to obtain a ' reverse ' -shaped sealing frame, placing the reverse ' -shaped sealing frame in a sealing test furnace, applying a load pressure of 0.2MPa, and heating to different test temperatures according to the heating curve process of the sealing material air tightness test set by a thermogravimetric test to obtain a graph of changing gas leakage rate of the ceramic-based powder grading type sealing material for the medium temperature plate type solid oxide fuel cell prepared in the embodiment 1 at different temperatures and different ventilation pressures, wherein as shown in fig. 3, the ceramic-based powder grading type sealing material for the medium temperature plate type solid oxide fuel cell prepared in the embodiment 1 maintains good air tightness at a temperature range of 650-800 ℃ and a maximum ventilation pressure of 20kPa as shown in fig. 3.
The ceramic base powder graded sealing material for a solid oxide fuel cell of example 1 was subjected to a thermal shock cycle test, and the final temperature was set to 750 ℃, the loading pressure was 0.2MPa, and the ventilation pressures were 2.5kPa, 5kPa, 7.5kPa, 10kPa, 12.5kPa, 15kPa, 17.5kPa, and 20kPa, respectively, to obtain a graph showing the change in gas leakage rate at different ventilation pressures for the ceramic base powder graded sealing material for a solid oxide fuel cell of example 1, as shown in fig. 4. As can be seen from fig. 4, the ceramic-based powder grading type sealing material for a medium temperature plate type solid oxide fuel cell prepared in example 1 maintains excellent air tightness when rapid temperature cycling is performed between 300 and 750 ℃.
XRD testing is carried out on the sealing material subjected to thermal shock cycle testing at the final temperature of 750 ℃ and the loading pressure of 0.2MPa, so that the XRD diagram of the ceramic-based powder grading sealing material for the medium-temperature flat plate type solid oxide fuel cell, which is prepared in example 1 and is subjected to thermal shock cycle testing at the final temperature of 750 ℃ and the loading pressure of 0.2MPa, is shown in figure 5. As is clear from FIG. 5, the ceramic-based powder graded sealing material for a medium temperature plate type solid oxide fuel cell prepared in example 1, which was subjected to a thermal shock cycle test at a final temperature of 750℃and a load pressure of 0.2MPa, had only Al 2 O 3 And (3) phase (C).
The ceramic-based powder gradation sealing material for a medium temperature plate type solid oxide fuel cell prepared in example 1 was assembled into a single cell stack, and the specific assembly procedure was as follows: a single cell with an effective area of 13×13cm was selected, and the sealing material prepared in example 1 was cut into a 14×14cm "back" type sealing frame, with a width of 1cm maintained; placing a 'back' type sealing frame at a specific position of a single cell clamp, enabling the periphery of a single cell to be just pressed on the sealing frame, and then assembling the single cell clamp; and (3) applying a load pressure of 0.2-0.3 MPa in the vertical direction of the single cell clamp, heating from room temperature to 500 ℃ according to an average heating rate of 1.5 ℃/min, and then heating to a working temperature according to 1 ℃/min to realize sealing of a single cell stack or assembling of the ceramic-based powder grading sealing material for the medium-temperature flat-plate type solid oxide fuel cell prepared in the embodiment 1.
After reaching the operating temperature, the open circuit voltage of the cell stack was tested, followed by testing the discharge performance of the cells. The current-voltage-power density curve of the resulting cell stack at 750 c is shown in fig. 6. As can be seen from fig. 6, the open circuit voltage of the cell stack assembled from the ceramic-based powder gradation sealing material for a solid oxide fuel cell of example 1 reached 1.14V and reached the performance of 53W as the highest output, indicating that the ceramic-based powder gradation sealing material for a solid oxide fuel cell of example 1 maintains excellent sealing performance when applied to the stack.
In conclusion, the ceramic-based powder grading sealing material for the medium-temperature flat plate type solid oxide fuel cell prepared in the embodiment 1 of the invention maintains good air tightness in the temperature range of 650-800 ℃ and under the maximum ventilation pressure of 20kPa, and maintains good air tightness when the ceramic-based powder grading sealing material is subjected to rapid temperature circulation at the temperature of 300-750 ℃; when the sealing material is applied to a galvanic pile, the sealing performance is still excellent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell is prepared from 50-90 parts of coarse ceramic powder and 10-50 parts of fine ceramic powder;
the average grain diameter of the coarse ceramic powder is 0.5-12 mu m, and the average grain diameter of the fine ceramic powder is 90-900 nm;
the thickness of the ceramic-based powder grading type sealing material is 0.20-0.70 mm.
2. The ceramic-based powder grading seal material according to claim 1, wherein the ceramic-based powder grading seal material is prepared from a ceramic powder comprising 60 to 80 parts of coarse ceramic powder and 20 to 40 parts of fine ceramic powder.
3. The ceramic-based powder grading seal material according to claim 1, wherein the average particle size of the coarse ceramic powder is 1 to 10 μm and the average particle size of the fine ceramic powder is 100 to 800nm.
4. The ceramic-based powder grading seal material according to claim 1, wherein the thickness of the ceramic-based powder grading seal material for a medium temperature plate type solid oxide fuel cell is 0.25 to 0.60mm.
5. The method for preparing a ceramic-based powder grading type sealing material according to any one of claims 1 to 4, comprising the steps of:
(1) Uniformly mixing absolute ethyl alcohol, dimethylbenzene and a dispersing agent to obtain a mixed solvent;
(2) Mixing the mixed solvent obtained in the step (1) with coarse ceramic powder and fine ceramic powder, and performing first ball milling to obtain slurry;
(3) Mixing the slurry obtained in the step (2) with a binder, a plasticizer and a defoaming agent, and performing second ball milling to obtain second ball milled slurry;
(4) And (3) carrying out tape casting molding on the slurry obtained in the step (3) after the second ball milling to obtain the ceramic-based powder grading type sealing material for the medium-temperature plate type solid oxide fuel cell.
6. The method according to claim 5, wherein the dispersant in the step (1) is at least one of KD24, herring oil and castor oil.
7. The method according to claim 1, wherein the first ball milling in the step (1) is performed for 14 to 18 hours, and the first ball milling medium is zirconia ball milling beads.
8. The method of claim 1, wherein the binder in step (3) is at least one of polyvinyl butyral (PVB) having a designation B76 or B98.
9. The method according to claim 1, wherein the second ball milling time in the step (3) is 25 to 30 hours.
10. Use of the ceramic-based powder grading seal material for a medium-temperature plate type solid oxide fuel cell according to any one of claims 1 to 4 or the ceramic-based powder grading seal material for a medium-temperature plate type solid oxide fuel cell prepared by the preparation method according to any one of claims 5 to 9 in a medium-temperature solid oxide fuel cell stack.
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