CN110759743A - Glass-vermiculite composite sealing material and preparation method and application thereof - Google Patents

Glass-vermiculite composite sealing material and preparation method and application thereof Download PDF

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Publication number
CN110759743A
CN110759743A CN201911157335.3A CN201911157335A CN110759743A CN 110759743 A CN110759743 A CN 110759743A CN 201911157335 A CN201911157335 A CN 201911157335A CN 110759743 A CN110759743 A CN 110759743A
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glass
vermiculite
sealing material
powder
composite sealing
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CN110759743B (en
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杨志宾
郭梦媛
葛奔
雷泽
彭苏萍
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China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/102—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/104—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by structure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/108—Special methods for making a non-metallic packing
    • 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
    • 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

Abstract

The invention provides a glass-vermiculite composite sealing material, a preparation method and application thereof, wherein the composite sealing material is formed by sequentially stacking a glass film blank and a vermiculite film blank, and the condition is that the glass blanks are arranged on two sides of the composite material. The glass and the vermiculite are alternately stacked to obtain the sandwich sealing structure, and at the test temperature, the glass softens and wets the ceramic and the metal, wets the rough surface of the vermiculite layer, and is combined with the ceramic and the metal to more closely prevent the air leakage rate from increasing due to the excessive softening of the glass. The porosity of the heated vermiculite layer is low, and the sealing air tightness is improved. The composite sealing material and the sandwich sealing structure provided by the invention have the advantages of wide application temperature range, low requirement on the thermal expansion coefficient of glass, strong sealing airtightness, and effective improvement on the performance and service life of the battery.

Description

Glass-vermiculite composite sealing material and preparation method and application thereof
Technical Field
The invention relates to a composite material, in particular to a composite sealing material which is formed by overlapping glass-vermiculite and can be used for sealing or other heterogeneous sealing of a solid oxide fuel cell.
Background
The Solid Oxide Fuel Cell (SOFC) is an all-solid-state power generation device which can directly and efficiently convert chemical energy into electric energy, and the process is not influenced by Carnot cycle, so that the power generation efficiency is high, the reaction process is environment-friendly, pollution-free and high in reliability.
The SOFC electric pile mainly comprises an electrode, an electrolyte, a connector and a sealing material. The excellent performance of the sealing material directly influences the performance of the cell stack. In the operation process of the battery, gases such as oxygen, hydrogen and the like need to be respectively introduced into the cathode and the anode, so that the sealing material is required to have the properties of stronger air tightness, proper glass softening temperature (Ts), chemical stability, thermal expansion coefficient matched with the battery material and the like in order to prevent gas leakage and the influence of the mixing of cathode and anode gases on the performance of the battery. In the practical operation of the solid fuel cell, the sealing material is in a high-temperature working environment of 600-850 ℃ for a long time, and meanwhile, the sealing material also has the conditions of humidity and redox atmosphere, so that the sealing material of the SOFC is required to have good high-temperature resistance, moisture resistance and chemical stability. Under the temperature for testing the battery, the sealing material is close to the glass softening state, which is more beneficial to sealing, but the glass sealing material is partially crystallized due to factors such as uneven heating or overlong heating time, the stress is increased, cracks are caused, even the battery piece is broken, or the glass is softened excessively, the air tightness of the sealing material is reduced due to the loss of the glass, and the service life of the battery is seriously influenced.
In the prior art, the sealing of the solid fuel cell adopts the glass with specific components, and the single-phase material is used as the sealing material, so that the thermal expansion coefficient of the sealing material at the working temperature is close to that of the sealed material, the application range of the glass material is limited, and the components and the process of the glass are very strict. For example, CN 102910825 a proposes a bismuthate lead-free sealing glass for solid fuel cell, which is disclosed in the specificationThe composition comprises the following components in percentage by mass: (15-25)% of Bi2O3And (25-55)% SiO2And (0-10)% of Al2O3And (1-16)% TiO2(5-20)% of alkaline earth metal oxide and (5-10)% of alkali metal oxide, the sealing glass meets the high temperature resistance required by the sealing material of the solid fuel cell, and also provides thermal and stable data, but when the sealing glass is practically applied to the solid fuel cell, the airtightness of the glass is reduced after the glass is softened at the working temperature, and the operation efficiency and the service life of the cell are further deteriorated. CN 109841868A proposes a composite sealant for a solid oxide fuel cell, comprising a solid glass component and a liquid glass component; the solid glass component is made of SiO2Is a formed body and contains an alkali metal element and/or an alkaline earth metal element as a modifier. The patent still needs to strictly control the thermal expansion coefficient of the obtained modified sealing material to realize the matching with the cell, and the application of the material in the practical solid fuel cell is limited.
In the prior art, a sealing material for obtaining a multiphase composite structure is also disclosed, for example, CN 106299399A proposes a composite sealing material for a solid oxide fuel cell, which includes an inner core layer material, a coupling layer material and an outer shell layer material; the inner core layer is made of silver-based adhesive coated on the sealing part of the solid oxide fuel cell device and other components; the coupling layer is made of silver-based I-type glass composite adhesive coated on the periphery of the inner core layer; the shell layer is made of II-type glass-based adhesive coated on the periphery of the coupling layer. The sealing material with the core-shell structure is adopted in the patent, so that the sealing material is favorable for keeping better air tightness in a high-temperature state, but the preparation process is complex, and the sealing performance of the sealing material needs to be further improved.
Therefore, improving the air tightness of the sealing material at high temperature and reducing the porosity and air leakage rate become one of the key technologies for improving the efficiency of the SOFC.
Disclosure of Invention
In order to solve the defect that the sealing material of the solid fuel cell in the prior art has poor air tightness at high temperature, the thermal expansion coefficient of the glass which is the main component of the sealing material needs to be close to that of the sealed material, and the application range of the glass material is limited. The invention provides a glass-vermiculite composite sealing material and a preparation method thereof. The composite sealing material provided by the invention is suitable for heterogeneous sealing, such as solid oxide fuel cells, or ceramic/metal heterogeneous sealing.
The first purpose of the invention is to provide a glass-vermiculite composite sealing material, which is formed by sequentially stacking a glass film blank and a vermiculite film blank, wherein the two sides of the composite material are glass blanks.
The glass- (vermiculite-glass) for the composite sealing materialn-vermiculite-glass stacking order, wherein n is an integer from 0 to 5, preferably an integer from 0 to 3.
The thickness of the whole composite sealing material is 1.5-8.5mm, preferably 1.5-6.2mm, wherein the thickness of the glass film blank and the vermiculite film blank is independently 500-800 μm. The formed blank has good flexibility and compression resistance, and can bear the pressure in the galvanic pile integration process (the pressure in the galvanic pile integration process is 0.1-1kg/cm in general)2)。
The raw material of the vermiculite film embryo body is natural vermiculite powder. Preferably, the vermiculite powder is preheated. The preheating treatment is to heat the vermiculite powder to 600-900 ℃ by microwave; or the sintering temperature is 600-900 ℃.
The glass powder of the glass film blank comprises SiO as the main component2Or BaO and metal oxides, of which SiO is2Or BaO as a former and a metal oxide as a network modifier, the metal oxide comprising K2O、Na2O、CaO、BaO、ZnO、ZrO2、Al2O3、MgO、TiO2、B2O3、La2O3、SrO、Fe2O3At least one of (1).
The main component comprises SiO2And metal oxides, in which SiO2The metal oxide is a network modification for the formation of bodies, said metal oxide comprising K2O、Na2O、CaO、BaO、Al2O3、MgO、TiO2、La2O3、SrO、Fe2O3At least one of; the coefficient of thermal expansion of the glass is 6 to 15 x 10-6K-1Preferably 7 to 13X 10-6K-1。
Preferably, the glass component is SiO260-75wt％，K2O 5-15wt％，Na2O 3-10wt％，CaO 2-8wt％， BaO 0.5-5wt％，MgO 0.5-5wt％、TiO20.3-1.5 wt%, the balance being Fe2O3。
Further preferably, the glass component is SiO265-72wt％，K2O 9-12wt％，Na2O 5-8wt％，CaO 3-6 wt％，BaO 1-3wt％，MgO 1-3wt％、TiO20.5-1 wt%, the balance being Fe2O3。
As a sealing material for solid state fuel cells, the glass used needs to have a good thermal expansion match with the other cell connecting components. Otherwise, the thermal cycle of the solid fuel cell will cause air leakage due to the difference of the thermal expansion coefficients of different materials, the defect of poor air tightness, unstable operation of the cell, low cell efficiency and potential safety hazard in serious cases, so the thermal expansion coefficient of the solid glass component is generally required to be controlled to be 9.0-12.0 multiplied by 10-6K-1But this also limits the kind and range of glass used. The invention adopts the composite sealing material of a sandwich structure overlapped by glass-vermiculite, wherein the thermal expansion coefficient of the glass is 6-15 multiplied by 10-6K-1The requirement of air tightness can be met. At the operating temperature of the battery, the glass firstly softens, has a better wetting angle with the vermiculite layer, the connecting body and the ceramic, does not react with the vermiculite layer, and is tightly combined with the vermiculite layer, the connecting body and the ceramic; meanwhile, the composite structure of the sandwich structure can play a certain role in buffering during thermal expansion. Therefore, the range of the thermal expansion coefficient of the glass material used in the present invention is widened, and the requirement of the thermal expansion coefficient is relaxed compared with the glass of the general sealing material, which means that some excellent properties (corrosion resistance, heat resistance, stability, mechanical strength, etc.) can be adopted) However, special glass with an unsatisfactory thermal expansion coefficient can also be used for sealing materials, in particular for sealing materials of solid fuel cells, and the application fields of various glasses, in particular special glass in the aspect of SOFC (solid oxide fuel cell) are widened.
The glass film blank and the vermiculite film blank are respectively obtained by molding glass powder and vermiculite powder, and the molding method comprises tape casting, spraying or screen printing; casting is preferred.
The casting comprises the steps of dispersing powder (glass powder and vermiculite powder) to be formed and auxiliary materials including a dispersing agent, a plasticizer and a binder in a solvent, carrying out ball milling and mixing uniformly, then carrying out vacuum defoaming on slurry, enabling the slurry to flow onto a film carrier moving forwards from the lower part of a hopper, enabling a blank and the film carrier to enter a drying chamber together after passing through a scraper, drying the blank, and then forming a film, wherein the thickness of the blank is controlled by the height of the scraper.
Further preferably, the dosage ratio of the powder to be molded, the dispersant, the plasticizer and the binder is 100-: 10-15: 10-15: 15-25.
The dispersant is triethanolamine, triammonium citrate, polyacrylic acid phosphate, glyceride, fatty acid amine, sodium silicate, sodium carbonate, ammonium polyphosphate, polyethyleneimine, polymethacrylic acid, polyacrylic acid and the like; and/or the plasticizer is diethyl oxalate, polyethylene glycol, polyglycerol, phthalate octyl ester, phthalate butyl benzyl ester; and/or the binder is selected from polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, acrylic emulsion, polyacrylate, polyvinyl acetate, and the like.
Optionally, other functional aids such as defoaming agents (tributyl phosphate, etc.) may also be added to the raw materials in the casting step. The amounts of the other functional auxiliaries are known to the person skilled in the art and can be selected as appropriate.
The solvent is water or alcohol water solution, and water is not particularly limited, but water with higher purity is preferred, such as ultrapure water, deionized water, purified water and distilled water; the alcohol aqueous solution is 20-50% of lower alcohol, and the lower alcohol is selected from C1-C6 alcohol, specifically at least one of methanol, ethanol, propanol and butanol. The amount of the solvent is not particularly limited as long as the powder to be molded can be sufficiently dispersed, and generally, the mass ratio of the amount of the solvent to the powder to be molded is 1-2: 1-2.
The forming mode can be that the glass powder and the vermiculite powder are separately formed into blanks and then are superposed for use, or the glass or the vermiculite blank is firstly formed to be used as a base layer, then the blank of another material is formed on the base layer, and finally the glass- (vermiculite-glass) is formedn-a vermiculite-glass "sandwich" structure of the composite sealing material.
The second purpose of the invention is to provide a preparation method of the composite sealing material, which comprises the following steps:
(S1) grinding: preparing glass powder and vermiculite powder, grinding the powder respectively, and drying the obtained powder after passing through a 100-mesh and 200-mesh screen for later use;
(S2) molding: respectively forming the glass powder and the vermiculite powder obtained in the step (S1) into film blanks, and then overlapping to form a sandwich composite structure; or a film blank body is obtained by molding firstly and is used as a base layer, and a film blank body made of another material is molded on one side or two sides of the base layer; repeating the above molding operation to obtain glass- (vermiculite-glass)n-a composite sealing blank of sandwich structure in vermiculite-glass stacking order;
(S3) clipping: and (S2) cutting the composite sealing material blank body with the sandwich structure obtained in the step (S2) into a proper annular structure according to the size of the cell stack.
The apparatus used for the grinding in the step (S1) is not particularly limited as long as the raw material is ground to a specified particle size, such as a planetary ball mill.
The method for forming the film blank in the step (S2) includes tape casting, spraying or silk-screen printing, and the finally obtained green blank is flat after being dried, uniform in thickness and stable in placement and is not easy to crack.
The preparation method of the glass-vermiculite composite sealing material provided by the invention is simple, and the two materials of glass and vermiculite are crossly stacked to form a multi-layer sandwich structure.
The third purpose of the invention is to provide the application of the composite sealing material in heterogeneous sealing, such as solid oxide fuel cells, ceramic and metal heterogeneous sealing. Particularly, when the sealing ring is used for a solid oxide fuel cell, the sealing ring is arranged between a single cell layer and a connector layer of a cell stack component, and is fixed by screws and then subjected to a pressure test, so that tight combination of the cell components is ensured, gas introduced into the cell stack is prevented from leaking, the effect of the sealing material can be effectively exerted, the sealing ring is excellent in airtightness, the cell is ensured to stably run at high temperature for a long time, and the open-circuit voltage is not attenuated for a long time.
For the glass sealing material in the prior art, the invention has the following beneficial effects:
firstly, creatively, a glass-vermiculite-glass sandwich structure is prepared by a simple method, at the operation temperature of the solid fuel cell, glass is firstly softened, and a closed layered structure is formed inside a vermiculite layer at the test temperature. The softened glass has a better wetting angle with the vermiculite layer, the connector and the ceramic, does not react with the vermiculite layer and is tightly combined with the vermiculite layer, excellent air tightness is obtained, and stable and safe operation of the solid fuel cell is ensured.
And the softened glass can fill the rough surface of the vermiculite layer, so that the air tightness reduction caused by excessive softening of the glass is prevented.
And thirdly, the sandwich composite structure of the sealing material can play a certain buffering role. Compared with the glass of the common sealing material, the glass material as the sealing material has wider application range and glass application range.
The sandwich structure composite sealing material prepared by the invention has good sealing effect and high thermal cycle efficiency, can improve the power generation efficiency and prolong the service life of the cell stack, and has high application value in solid oxide fuel cell stacks and other heterogeneous sealing.
Drawings
Fig. 1 is an assembly view showing a sealing structure of a solid fuel cell using the sealing material of the present invention.
FIG. 2 shows the linear thermal expansion of the glass used in example 1 from 30 to 600 ℃.
FIG. 3 is the cross-sectional morphology of the vermiculite layer after testing of the cell of example 1.
Fig. 4 is a cross-sectional view of the glass layer in combination with the vermiculite layer after testing of the cell of example 1.
FIG. 5 is a cross-sectional view of the glass to interconnect bonding after testing of the cell of example 1.
FIG. 6 is the cross-sectional profile of the combination of glass and ceramic Ni-YSZ anodes after the cell of example 1 has been tested.
Fig. 7 is the stability of the open circuit voltage when the cell of example 2 was tested.
Detailed Description
The composite sealing material of the present invention will be further described with reference to the drawings and specific examples, but it should be understood that the present invention is not limited to the following examples.
The invention is simple and convenient, and adopts the following terms: YSZ-yttria stabilized zirconia; GDC-gadolinium oxide doped ceria; LSCF-lanthanum strontium cobalt iron.
Example 1
(1) Grinding: the glass component and the content thereof are respectively SiO270.4wt％，K2O 10.5wt％，Na2O6.5wt％， CaO 4.3wt％，BaO 2.2wt％，MgO 1.3wt％、TiO21.2 wt% and the balance Fe2O3The softening temperature of the glass is lower than 650 ℃, the thermal expansion is shown in figure 2, and the thermal expansion coefficient of the glass is (8.4-11.2) multiplied by 10 at the temperature of 30-600 DEG C-6K-1(ii) a Calcining glass powder at high temperature to form a molten mass, quenching, crushing and grinding, adding ethanol and zirconia balls, performing ball milling for more than 12 hours, drying after ball milling, sieving with a 200-mesh sieve to obtain glass powder, primarily crushing vermiculite, adding ethanol and zirconia balls, grinding for more than 18 hours, drying, and sieving with a 200-mesh sieve to obtain vermiculite powder;
(2) molding: respectively casting glass powder and vermiculite powder obtained in the step (1), specifically mixing 6g of triethanolamine and 50g of ultrapure water, ball-milling for 30min, adding 50g of powder to be formed, ball-milling for 12h, adding 6.3g of glycerol, 52.5g of 15 wt% polyvinyl alcohol and 1g of tributyl phosphate, ball-milling for a certain time again, uniformly mixing, respectively casting to form a glass blank and a vermiculite film blank, drying, wherein the surface of the obtained film blank is flat, smooth and free of gaps, the thickness of the glass film blank is 650 micrometers, the thickness of the vermiculite film blank is 610 micrometers, stacking the obtained film blanks, and finally obtaining the glass-vermiculite-glass three-layer composite sealing material, wherein the thickness is about 1.9 mm.
(3) Cutting: cutting the composite sealing material into square rings with the outer side length of 10cm and the inner side length of 9cm for use;
(4) assembling: placing the cut annular sealing material between the anode-electrolyte-cathode three-in-one single cell and the alloy connector, fixing the single cell by using a screw, and performing pressure test;
and (3) carrying out an open-circuit voltage stability test by using the NiO-YSZ | YSZ | GDC | LSCF-GDC | LSCF of the anode-supported battery, heating to 200 ℃ at a speed of 2 ℃/min in the test process, preserving heat for 1h to remove glue, and then heating to 750 ℃ for testing. The Open Circuit Voltage (OCV) of the single cell tested at 750 ℃ has no obvious attenuation in the heat cycle test of more than 6 times of raising the temperature to 750 ℃ and reducing the temperature to 100 ℃, the accumulated test time exceeds 2300min, and the OCV is kept to be more than 1.05V.
The tested sealing material is observed by an electron microscope, and fig. 3 shows the cross section appearance of a vermiculite layer after the battery is tested, and shows that the section of the vermiculite layer is layered, the glass layer has individual gaps which are not communicated, the glass layer is tightly connected with the connecting body, the ceramic and the vermiculite layer, and the connecting part has no gap, which shows that the battery using the sealing material of the embodiment 1 has low air leakage rate and good air tightness.
FIG. 4 is a cross-sectional view of a glass layer in combination with a vermiculite layer after testing of the cell; FIG. 5 is a cross-sectional view of the bonding of glass to a connector after battery testing; FIG. 6 is the cross-sectional profile of the combination of glass and ceramic Ni-YSZ anode after cell testing. Through the electron microscope photos, the softened glass, the vermiculite layer, the connector and the ceramic interface are tightly combined and have no crack and peeling phenomena after the battery is tested, and the wetting effect of the glass and the materials is good at the test temperature, so that the sealing performance of the sealing material is improved.
Example 2
The other steps are the same as the example 1, except that the vermiculite powder used in the step (2) is subjected to preheating treatment, specifically, the pretreatment is that the vermiculite powder is heated to 900 ℃ by a muffle furnace at a speed of 2 ℃/min and is kept for 60min, and then the temperature is reduced to room temperature at a speed of 2 ℃/min.
The obtained composite sealing material ring is cut according to the same method of the embodiment 1, placed and tested under the same battery test condition, fig. 7 shows the stability of the open-circuit voltage when the battery is tested in the embodiment 2, the open-circuit voltage (OCV) of a single cell tested at 750 ℃ has no obvious attenuation in the OCV of the battery when the OCV is subjected to 6 thermal cycle tests of raising the temperature to 750 ℃ and reducing the temperature to 100 ℃, the cumulative test time exceeds 2500min, and the OCV is kept to be more than 1.05V.
Example 3
The other steps are the same as example 2, except that a five-layer composite sealing material of glass-vermiculite-glass is finally obtained, and the thickness of the composite sealing material is about 3.1 mm.
The obtained composite sealing material ring is cut according to the same method of the embodiment 1, placed and tested under the same battery test conditions, the Open Circuit Voltage (OCV) of a single cell tested at 750 ℃ has no obvious attenuation in 8 thermal cycle tests when the OCV is heated to 750 ℃ and cooled to 100 ℃, the cumulative test time exceeds 3000min, and the OCV is kept to be more than 1.05V.
Example 4
The other steps are the same as example 2, except that seven layers of the composite sealing material of glass-vermiculite-glass are finally obtained, and the thickness of the composite sealing material is about 4.3 mm.
The obtained composite sealing material ring is cut according to the same method of the embodiment 1, placed and tested under the same battery test condition, the Open Circuit Voltage (OCV) of a single cell tested at 750 ℃ has no obvious attenuation in 8 thermal cycle tests when the OCV is heated to 750 ℃ and cooled to 100 ℃, the cumulative test time exceeds 3200min, and the OCV is kept to be more than 1.05V.
Example 5
The other steps are the same as example 3, except that the single cell is tested at 800 ℃, the OCV of the cell is not obviously attenuated in 6 thermal cycle tests of raising the temperature to 800 ℃ and reducing the temperature to 100 ℃, the cumulative test time exceeds 2200min, and the OCV is kept above 1.05V.
Example 6
The other steps are the same as example 3, except that the single cell is tested at 820 ℃, the OCV of the cell is not obviously attenuated in 6 thermal cycle tests of raising the temperature to 820 ℃ and reducing the temperature to 100 ℃, the cumulative test time exceeds 1900min, and the OCV is kept above 1.0V.
Example 7
The other steps are the same as those in example 3 except that a glass of BaO 63 wt% and SiO was used217 wt%, CaO6.0 wt%, ZnO 6.5 wt%, B2O 35 wt wt%, the balance being TiO2The coefficient of thermal expansion (30-650 ℃) thereof is (7-8.5) x 10- 6K-1。
The obtained composite sealing material ring is cut according to the same method of the embodiment 1, placed and tested under the same battery test conditions, the Open Circuit Voltage (OCV) of a single cell tested at 750 ℃ has no obvious attenuation in 6 thermal cycle tests when the single cell is subjected to temperature rise of 750 ℃ and temperature drop of 100 ℃, the cumulative test time exceeds 2600min, and the OCV is kept above 1.05V.
Example 8
The other steps are the same as in example 3, except that SiO is used as the glass245wt％，BaO 40wt％，CaO 12wt％，Al2O34wt％，La2O33 wt% and the balance ZrO2And TiO2The coefficient of thermal expansion (30-500 ℃) is (11-16) x 10-6K-1。
The obtained composite sealing material ring is cut according to the same method of the embodiment 1, placed and tested under the same battery test conditions, the Open Circuit Voltage (OCV) of a single cell tested at 750 ℃ has no obvious attenuation in 6 thermal cycle tests when the OCV is heated to 750 ℃ and cooled to 100 ℃, the cumulative test time exceeds 2700min, and the OCV is kept to be more than 1.05V.
Example 9
The other steps are the same as the embodiment 2, except that the forming step is to form a vermiculite blank film firstly, and then form glass blanks on two sides of the vermiculite blank film to obtain the glass-vermiculite-glass three-layer composite sealing material with a sandwich structure, and the thickness of the glass-vermiculite-glass three-layer composite sealing material is 1.9 mm. And testing under the same battery testing condition, the Open Circuit Voltage (OCV) of the single cell tested at 750 ℃ has no obvious attenuation in 6 thermal cycle tests of raising the temperature to 750 ℃ and reducing the temperature to 100 ℃, the cumulative testing time exceeds 2800min, and the OCV is kept above 1.05V.
Example 10
The other steps are the same as the embodiment 2, and the vermiculite powder is preheated, which is characterized in that the forming step comprises the steps of firstly forming to obtain a vermiculite embryo body film, then forming glass embryo bodies on two sides of the vermiculite embryo body film, and then continuously forming on the glass embryo body on one side according to the sequence of glass, vermiculite and glass. Finally, the composite sealing material with a five-layer sandwich structure of glass-vermiculite-glass is obtained, and the thickness of the composite sealing material with five layers is 3.0 mm. And testing under the same battery testing condition, the Open Circuit Voltage (OCV) of the single battery tested at 750 ℃ has no obvious attenuation in the 8 thermal cycle tests of raising the temperature to 750 ℃ and reducing the temperature to 100 ℃, the cumulative testing time exceeds 3100min, and the OCV is kept above 1.05V.
When the single cell is tested under the same cell test condition, the Open Circuit Voltage (OCV) of the single cell tested at 820 ℃ has no obvious attenuation in 6 thermal cycle tests of raising the temperature to 820 ℃ and reducing the temperature to 100 ℃, the accumulated test time exceeds 2200min, and the OCV is kept above 1.0V.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.

Claims (10)

1. A glass-vermiculite composite sealing material is formed by sequentially stacking a glass film blank and a vermiculite film blank, wherein the glass blanks are arranged on two sides of the composite material.
2. The composite sealing material according to claim 1, wherein the glass- (vermiculite-glass) for composite sealing materialn-vermiculite-glass stacking order, wherein n is an integer from 0 to 5, preferably an integer from 0 to 3.
3. A composite sealing material according to claim 1, wherein the thickness of the composite sealing material as a whole is 1.5-8.5mm, preferably 1.5-6.2mm, wherein the thickness of the glass film blank and the vermiculite film blank is independently 500-.
4. The composite sealing material according to claim 1, wherein the glass powder as a main component of the glass thin film green body comprises SiO2And metal oxides, in which SiO2The metal oxide is a network modification for the formation of bodies, said metal oxide comprising K2O、Na2O、CaO、BaO、Al2O3、MgO、TiO2、Fe2O3At least one of; the coefficient of thermal expansion of the glass is 6 to 15 x 10-6K-1Preferably 7 to 13X 10-6K-1。
5. A composite sealing material according to claim 1, wherein the raw material of the vermiculite film blank is selected from natural vermiculite ore, preferably natural vermiculite powder which has been subjected to a preheating treatment; the preheating treatment is to heat natural vermiculite by microwave at the temperature of 500-800 ℃; or sintered at 800 ℃ and 500 ℃.
6. The composite sealing material according to claim 1, wherein the glass film blank and the vermiculite film blank are respectively formed by glass powder and vermiculite powder, and the forming method comprises tape casting, spraying or silk-screen printing; casting is preferred.
7. The composite sealing material according to claim 6, wherein the casting is performed by dispersing the powder to be molded (glass powder, vermiculite powder) and auxiliary materials including a dispersant, a plasticizer and a binder in a solvent, performing ball milling and mixing uniformly, and then performing casting; the dosage ratio of the powder to be molded, the dispersant, the plasticizer and the binder is 100-130: 10-15: 10-15: 15-25.
8. The composite sealing material according to claim 6, wherein the glass powder and the vermiculite powder are separately molded into an embryo and then stacked; or forming a glass or vermiculite blank as a base layer, and forming a blank of another material on the base layer to finally form the glass- (vermiculite-glass)n-a vermiculite-glass "sandwich" structure of the composite sealing material.
9. A method of making a composite sealing material according to any of claims 1 to 8, comprising the steps of:
(S1) grinding: preparing glass powder and crushing vermiculite, respectively grinding the powder, and drying the obtained powder after passing through a 100-one 200-mesh screen for later use;
(S2) molding: respectively forming the glass powder and the vermiculite powder obtained in the step (S1) into film blanks, and then overlapping to form a sandwich composite structure; or a film blank body is obtained by molding firstly and is used as a base layer, and a film blank body made of another material is molded on one side or two sides of the base layer; repeating the above molding operation to obtain glass- (vermiculite-glass)n-a composite sealing blank of sandwich structure in vermiculite-glass stacking order;
(S3) clipping: and (S2) cutting the composite sealing material blank body with the sandwich structure obtained in the step (S2) into a proper annular structure according to the size of the cell stack.
10. Use of a composite sealing material according to any of claims 1 to 8 in heterogeneous sealing, for solid oxide fuel cells, ceramic and metal heterogeneous sealing.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1884423A (en) * 2006-05-19 2006-12-27 中国矿业大学(北京) Complex phase seal material for solid oxide fuel cell and its preparation method
CN105051959A (en) * 2013-01-21 2015-11-11 福莱西投资公司 Gasket for fuel cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1884423A (en) * 2006-05-19 2006-12-27 中国矿业大学(北京) Complex phase seal material for solid oxide fuel cell and its preparation method
CN105051959A (en) * 2013-01-21 2015-11-11 福莱西投资公司 Gasket for fuel cells
US20150372324A1 (en) * 2013-01-21 2015-12-24 Flexitallic Investments, Inc. Gasket for fuel cells

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
于立安等: "玻璃和云母复合封接SOFC电池堆性能", 《材料科学与工程学报》 *
萧继枬: "《蛭石》", 31 August 1958, 建筑工程出版社 *

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