CN114349349B - Medium-high temperature SOFC sealing microcrystalline glass, sealing material, preparation method and use method - Google Patents

Medium-high temperature SOFC sealing microcrystalline glass, sealing material, preparation method and use method Download PDF

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CN114349349B
CN114349349B CN202210263805.XA CN202210263805A CN114349349B CN 114349349 B CN114349349 B CN 114349349B CN 202210263805 A CN202210263805 A CN 202210263805A CN 114349349 B CN114349349 B CN 114349349B
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王兵兵
袁坚
信彩丽
马利特
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Glass Technology Research Institute Of Shahe City Of Hebei Province
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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

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Abstract

The invention discloses sealing microcrystalline glass with high thermal stability in a medium-high temperature SOFC working environment, a sealing material, a preparation method and a use method thereof, wherein the sealing microcrystalline glass comprises the raw materials of SiO2, Al2O3, MO and an additive. The glass system of the invention does not contain B, thus completely solving the problem of volatilization of B-containing substances in the sealing glass in a working environment, greatly improving the thermal stability of the sealing glass and the chemical compatibility with a cathode, ensuring that the thermal expansion coefficient after sealing is more than 10.5 multiplied by 10 < -6 >/DEG C, and ensuring that the crystal phase is stable, the preparation raw materials are simple, the cost is low, the method is easy to obtain, the process is stable, and the practical and industrialized conditions are achieved.

Description

Medium-high temperature SOFC sealing microcrystalline glass, sealing material, preparation method and use method
Technical Field
The invention belongs to the field of solid oxide fuel cells, and particularly relates to sealing glass ceramics and a sealing material with high thermal stability in a medium-high temperature S0FC working environment, a preparation method and a use method.
Background
The Solid Oxide Fuel Cell (SOFC) adopts solid oxide (ceramic) electrolyte, operates at high temperature, and has the advantages of high power generation efficiency, low material cost, strong fuel adaptability (such as methane, coal gas, methanol, alcohol, liquefied petroleum gas and the like). The major problem faced in developing SOFCs, however, is how to effectively isolate and seal the fuel and oxidant gases at high temperatures and how the seal material interacts with the cathode. Due to the fact that the working temperature of the battery is high (700-850 ℃), selection of a proper sealing material becomes a key for restricting the development of the flat SOFC.
Because B203 can adjust the characteristic temperature, the thermal expansion coefficient, the crystallization temperature and the like of the glass, and the existence of B203 can improve the wettability of the sealing glass during sealing and increase the sealing strength and the sealing performance of the glass, the existing microcrystalline glass sealing material is added with B.
The prior art shows that the common SOFC sealing glass mainly comprises four systems of silicate sealing glass, borosilicate sealing glass, aluminosilicate sealing glass and boroaluminosilicate sealing glass, such as MgO-BaO-SiO researched by Pascual2Glass ceramics, MaO-BaO-SiO by Christian research2Glass ceramics, Sasweti research BaO-CaO-Al2O3-SiO2Glass ceramics, Na from Krainova research2O-ZrO2-CaO-Al2O3-SiO2Glass, La studied by Wang2O3-Al2O3-SiO2The microcrystalline glass is researched and found that the required glass transition point and glass softening point can be obtained by reasonably regulating the proportion of MgO, CaO, SrO and BaO, for example, Chinese patent document CN 103739201A. Thus, borosilicate has become the most promising type of sealing glass.
However, the research of the subject group finds that the boron silicate glass sealing material seriously reduces the thermal stability of the glass itself due to the volatilization of boron-containing substances (j. Am. center. soc., 2008, Volume 91, Issue 8, P2564-2569) in the SOFC operation environment, and meanwhile, the volatilization of the boron-containing substances can also cause the generation of a large number of holes in the sealing glass, which affects the air tightness of the sealing material; in addition, recent related studies have also found that boron-containing substances in borosilicate glass sealing materials are vigorously volatilized during the operation of SOFC, and then deposited on and react with the cathode, resulting in severe degradation of catalytic performance of the cathode (j. electrochem. so. 2013, Volume 160, Issue 3, PF 301-F308).
Therefore, the invention specially improves the microcrystalline glass system and eliminates the harm of boron element to sealing glass.
Disclosure of Invention
In order to solve the problems, the invention provides a medium-high temperature SOFC sealing microcrystalline glass, a sealing material prepared from the microcrystalline glass, and a preparation and use method of the sealing material, wherein the sealing microcrystalline glass does not contain B, the volatilization of B-containing substances in the sealing glass in a working environment is thoroughly solved, so that the thermal stability of the sealing glass and the chemical compatibility of the sealing glass and a cathode are greatly improved, and meanwhile, Ca (Mg, Al) (Si, Al) in a microcrystalline glass matrix prepared by the invention2O6The formation of crystals also helps to improve the matching of the thermal expansion coefficients of the sealing glass and other components of the SOFC.
The invention is implemented by the following technical scheme:
in one aspectThe invention provides a middle-high temperature SOFC sealing microcrystalline glass, which has the raw material composition of SiO2、Al2O3MO and an additive in a molar ratio of 25-60: 1-5: 38-50: 0-5, wherein the MO is selected from MgO, CaO, SrO and BaO and at least comprises MgO and CaO;
the additive is TiO2、LaO、SnO2One or a mixture of several of them;
formation of Ca (Mg, Al) (Si, Al) in a glass-ceramic matrix2O6And (4) crystals.
On the other hand, the invention provides a preparation method for preparing a sealing material by using the medium-high temperature SOFC sealing microcrystalline glass, which comprises the following steps:
1) uniformly mixing the microcrystalline glass raw materials, melting at 1250-; quenching the melted glass liquid to obtain glass frit, crushing, grinding or ball-milling the glass frit, and sieving to obtain glass powder;
2) mixing glass powder with a binder, a dispersant and a solvent to form slurry, ball-milling in a ball mill to uniformly disperse, tape-casting to form, naturally drying, and cutting into a blank body with a required shape to prepare the glass sealing material.
Preferably, the binder in step 2) is one or a mixture of several of epoxy resin, methyl cellulose and polyvinyl alcohol.
The method for preparing a sealing material by using the medium-high temperature SOFC sealing microcrystalline glass of claim 1, wherein the dispersant in the step 2) is one or a mixture of polyacrylic acid, polyvinyl alcohol and polyacrylamide.
The preparation method for preparing the sealing material by using the medium-high temperature SOFC sealing microcrystalline glass of claim 1, wherein in the step 2), the solvent is one or a mixture of more of terpineol, ethanol, isopropanol and n-butanol.
In a third aspect, the invention provides a sealing material prepared by the above preparation method.
The invention has the following remarkable advantages:
(1) the sealing glass ceramics containing B has low thermal stability, the weight loss rate is up to 4 percent, the sealing glass ceramics without B has high thermal stability, and the weight loss rate can be controlled at 0.5 percent. Moreover, the sealing glass-ceramic contains no boron, so that the problem of volatilization of B-containing substances in the sealing glass in a working environment can be perfectly solved, and the thermal stability of the sealing glass and the chemical compatibility of the sealing glass and a cathode are improved;
(2) thermal expansion coefficient after sealing is more than 10.5 multiplied by 10-6The temperature per DEG C meets the requirement of the SOFC on the expansion coefficient of the sealing material (10-12 multiplied by 10)-6/° c) and stable crystalline phase;
(3) the wetting contact angle theta of the sealing microcrystalline glass is 30-60 degrees during sealing, the sealing microcrystalline glass has good wetting sealing performance, the wetting contact angle is too low (theta is less than 30 degrees), and glass liquid flows out of a sealing area during sealing, so that the pollution to an SOFC battery is caused, and the performance of the SOFC battery is influenced; the wetting contact angle is too high (theta is more than 60 degrees), and when the sealing is carried out, the wetting effect of the glass liquid is general, so that the sealing strength and the air tightness of the battery can be greatly reduced;
(4) the preparation raw materials selected by the invention are simple, the cost is low, the raw materials are easy to obtain, and the process is stable. The corresponding oxides are selected as source substances, so that the oxides are uniformly mixed, and the high-proportion mixing and distributing state is always kept in the melting and subsequent heat treatment, so that the process is simple and feasible, and the practical and industrialized conditions are achieved.
Drawings
FIG. 1 is a DSC thermogram of four example sealed glass-ceramics.
FIG. 2 is a graph of the contact angle of an example of a sealed glass-ceramic measured at a sealing temperature under an ultra-high temperature.
FIG. 3 is a graph showing the thermal expansion coefficient of two sealing microcrystalline glasses of the example after sealing and heat preservation for 500 hours after sealing.
FIG. 4 is an XRD diffraction pattern of two sealing microcrystalline glasses of the example after sealing and after heat preservation for 500 h.
Fig. 5 is a microstructure of an example tri-seal glass ceramic sealed to the SOFC electrolyte.
Fig. 6 is a microscopic topography of the example four-seal glass ceramic after sealing with the SOFC anode cell sheet.
FIG. 7 is a comparison of the heat stability (weight loss) of the sealing glass-ceramics of the four-sealing glass-ceramics of example with a B content of 0% at operating temperature (850 ℃).
FIG. 8 is a comparison of the thermal stability (weight loss) of the sealing glass-ceramics of example V, which contains 15% B, at operating temperature (850 ℃ C.).
FIG. 9 is a comparison of the heat stability (weight loss) of the sealing glass-ceramics of example six-sealing glass-ceramics containing 7.5% of B at operating temperature (850 ℃ C.).
Detailed Description
The material composition of the medium-high temperature SOFC sealing microcrystalline glass is SiO2、Al2O3MO and an additive in a molar ratio of 25-60: 1-5: 38-50: 0-5, wherein the MO is selected from MgO, CaO, SrO and BaO and at least comprises MgO and CaO.
The preparation method for preparing the sealing material by using the medium-high temperature SOFC sealing microcrystalline glass comprises the following steps:
1) uniformly mixing the microcrystalline glass raw materials, melting at 1250-; quenching the melted glass liquid to obtain glass frit, then crushing, grinding or ball-milling the glass frit, and sieving to obtain glass powder;
2) mixing glass powder with a binder, a dispersant and a solvent to form slurry, ball-milling in a ball mill to uniformly disperse, tape-casting to form, naturally drying, and cutting into a blank body with a required shape to prepare the glass sealing material.
TABLE 1 composition table (mol ratio) of sealing glass ceramics in examples
Figure 438987DEST_PATH_IMAGE001
Example one
Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the table 1, and ball-milling the raw materials for 1 hour by using a planetary ball mill to uniformly mix the raw materials; then putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a high-temperature lifting furnace, heating to 1450 ℃ at the temperature of 5 ℃ per minute, and preserving heat for 1.5 hours; then, taking out the crucible, pouring the melt into deionized water for water quenching, and drying to obtain fragments of the glass melt; grinding, and sieving with a 200-mesh sieve to obtain the glass powder. Mixing glass powder with epoxy resin, terpineol and polyvinyl alcohol (weight ratio is 80%, 3%, 2% and 15% in sequence) to form slurry, and performing ball milling in a ball mill to uniformly disperse the slurry; tape casting, natural drying, and cutting into a blank body with a required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 8 ℃/min, preserving the heat at 900 ℃ for 30min, and then naturally cooling to 850 ℃ for crystallization treatment for 2 hours to finish sealing. FIG. 1 shows that the glass transition point of the sealing glass of this example is 730.7 ℃ and the maximum devitrification peak is 926.5 ℃. It can be seen from FIG. 2 that the seal wetting angle is 38.7, which is an example of excellent sealing performance.
Example two
Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the table 1, and ball-milling the raw materials for 1.5 hours by using a planetary ball mill to uniformly mix the raw materials; then putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1400 ℃ at the speed of 4 ℃/min, and preserving heat for 2 hours; then, taking out the crucible, pouring the melt into deionized water for quenching, and drying to obtain fragments of the glass melt; grinding, and sieving with a 200-mesh sieve to obtain the glass powder. Mixing glass powder with methylcellulose, polyvinyl alcohol, n-butanol and ethanol (weight ratio is 81%, 3%, 8% and 5% in sequence) to obtain slurry, and ball-milling in a ball mill for uniform dispersion; tape casting, natural drying, and cutting into a blank body with a required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 10 ℃/min, preserving the heat at 850 ℃ for 40min, and then naturally cooling the blank body to 800 ℃ for crystallization treatment for 3 hours to finish sealing. This example is the preferred composition. FIG. 1 shows that the glass transition point of the sealing glass of this example is 743.2 ℃ and the maximum devitrification peak is 920.8 ℃. FIGS. 3 and 4 show that the coefficient of thermal expansion of this example is 11X 10-6The temperature per DEG C meets the requirement of the SOFC on the expansion coefficient of the sealing material (10-12 multiplied by 10)-6V. C), the main crystal precipitated during the sealing process is Ca (Mg, Al) (Si, Al)2O6After the temperature is kept for 500 hours, the thermal expansion coefficient and the precipitated main crystal phase of the sealed microcrystalline glass sample of the example have no obvious change, and the example is proved to be thermally stableThe properties are excellent.
EXAMPLE III
Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the table 1, and ball-milling the raw materials for 30min by using a planetary ball mill to uniformly mix the raw materials; then putting the powder into a platinum crucible, putting the platinum crucible into a high-temperature lifting furnace, heating to 1420 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; and then, taking out the crucible, pouring the melt into deionized water for water quenching, drying to obtain glass melt fragments, and sieving through a 250-mesh sieve after grinding to obtain glass powder. Mixing glass powder with epoxy resin, polyacrylamide and n-butyl alcohol (the weight ratio is 84%, 1.5%, 2.5% and 12% in sequence) to form slurry, and performing ball milling in a ball mill to uniformly disperse the slurry; tape casting, natural drying, and cutting into a blank body with a required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 10 ℃/min, preserving the heat for 40min at 880 ℃, and then naturally cooling the blank body to 800 ℃ for crystallization treatment for 4 hours to finish sealing. This example is the preferred composition. FIG. 1 shows that the glass transition point of the sealing glass of this example is 702.0 ℃ and the maximum devitrification peak is 903.3 ℃. Fig. 5 shows that the sealed microcrystalline glass of the embodiment is tightly combined with the electrolyte sheet after being sealed, and the whole sealed glass layer has fewer bubbles and is independent, so that the requirement of the sealing material on air tightness is met.
Example four
Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the table 1, and ball-milling for 2 hours by using a planetary ball mill to uniformly mix; then putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1280 ℃ at the speed of 10 ℃/min, and preserving heat for 2.5 hours; then taking out the crucible, pouring the melt into deionized water for water quenching, and drying to obtain fragments of the glass melt; grinding and sieving with a 300-mesh sieve to obtain the glass powder. Mixing glass powder with polyvinyl butyral, polyacrylic acid, terpineol and ethanol (in weight ratio of 84%, 2%, 1%, 8% and 5%) to obtain slurry, and ball-milling in a ball mill for uniform dispersion; tape casting, natural drying, and cutting into a blank body with a required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 10 ℃/min, preserving the heat for 40min at 880 ℃, and then naturally cooling the blank body to 800 ℃ for crystallization treatment for 4 hours to finish sealing. This example is the preferred composition. FIG. 1 shows that the glass transition point of the sealing glass of this example is 747.0 ℃ and the maximum devitrification peak is 927.6 ℃. Fig. 6 shows that the sealed microcrystalline glass of the embodiment is tightly bonded with the anode cell after being sealed, and the whole sealed glass layer has fewer bubbles and is independent, so that the requirement of the sealing material on air tightness is met. FIG. 7 shows the heat stability (weight loss) of the sealing glass containing 0% of B at the working temperature (850 ℃), and FIG. 7 shows that the heat stability of the glass without B is high and the weight loss rate is controlled within 0.5%.
EXAMPLE five
According to the mixture ratio of the components in the table 1 (containing B15%, reducing the content of alkaline earth metal on the basis of the fourth embodiment, and substituting boron for some alkaline earth metal), weighing a certain amount of analytically pure raw materials, ball-milling for 2 hours by using a planetary ball mill, and uniformly mixing; then putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1280 ℃ at the speed of 10 ℃/min, and preserving heat for 2.5 hours; then taking out the crucible, pouring the melt into deionized water for water quenching, and drying to obtain fragments of the glass melt; grinding and sieving with a 300-mesh sieve to obtain the glass powder. Mixing glass powder with polyvinyl butyral, polyacrylic acid, terpineol and ethanol (in weight ratio of 84%, 2%, 1%, 8% and 5%) to obtain slurry, and ball-milling in a ball mill for uniform dispersion; tape casting, natural drying, and cutting into a blank body with a required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 10 ℃/min, preserving the heat for 40min at 880 ℃, and then naturally cooling the blank body to 800 ℃ for crystallization treatment for 4 hours to finish sealing. This example is the preferred composition. FIG. 1 shows that the glass transition point of the sealing glass of this example is 747.0 ℃ and the maximum devitrification peak is 927.6 ℃. Fig. 6 shows that the sealed microcrystalline glass of the embodiment is tightly bonded with the anode cell after being sealed, and the whole sealed glass layer has fewer bubbles and is independent, so that the requirement of the sealing material on air tightness is met. Fig. 8 shows a graph of the heat preservation thermal stability (weight loss) of the sealing glass containing 15% of B at the working temperature (850 ℃), and fig. 7 shows that the glass containing B15% has high thermal stability, and the weight loss rate reaches 4%, which is significantly higher than that of the glass ceramics without B.
EXAMPLE six
Weighing a certain amount of analytically pure raw materials according to the mixture ratio of the components in the table 1 (containing 7.5% of B, reducing the content of alkaline earth metal on the basis of the fourth embodiment, and substituting boron for some alkaline earth metal), and ball-milling for 2 hours by using a planetary ball mill to uniformly mix; then putting the powder into a platinum crucible, placing the platinum crucible in the air atmosphere of a box-type resistance furnace, heating to 1280 ℃ at the speed of 10 ℃/min, and preserving heat for 2.5 hours; then taking out the crucible, pouring the melt into deionized water for water quenching, and drying to obtain fragments of the glass melt; grinding and sieving with a 300-mesh sieve to obtain the glass powder. Mixing glass powder with polyvinyl butyral, polyacrylic acid, terpineol and ethanol (the weight ratio is 84%, 2%, 1%, 8% and 5% in sequence) to form slurry, and performing ball milling in a ball mill to uniformly disperse the slurry; tape casting, natural drying, and cutting into blank with required shape; and placing the blank body on a part to be sealed, heating the blank body in an electric furnace at the speed of 10 ℃/min, preserving the heat for 40min at 880 ℃, and then naturally cooling the blank body to 800 ℃ for crystallization treatment for 4 hours to finish sealing. This example is the preferred composition. FIG. 1 shows that the glass transition point of the sealing glass of this example is 747.0 ℃ and the maximum devitrification peak is 927.6 ℃. Fig. 6 shows that the sealed microcrystalline glass of the embodiment is tightly bonded with the anode cell after being sealed, and the whole sealed glass layer has fewer bubbles and is independent, so that the requirement of the sealing material on air tightness is met. Fig. 8 shows the heat stability (weight loss) of the sealing glass containing 15% of B at operating temperature (850 ℃), and fig. 8 shows that the glass containing 7.5% of B has high heat stability, and the weight loss rate reaches 3%, which is significantly higher than that of the glass-ceramic without B.
Example four, example five and example six confirm that:
the sealing glass ceramics containing B has low thermal stability, the weight loss rate is up to 4 percent, the sealing glass ceramics without B has high thermal stability, and the weight loss rate can be controlled at 0.5 percent.
The sealing glass-ceramic provided by the embodiment does not contain boron, and the problem of volatilization of a B-containing substance in the sealing glass in a working environment can be perfectly solved, so that the thermal stability of the sealing glass and the chemical compatibility of the sealing glass and a cathode are improved;
thermal expansion coefficient after sealing is more than 10.5 multiplied by 10-6V DEG C, meet SOFC to sealThe requirement of the expansion coefficient of the material (10-12 multiplied by 10)-6/° c) and stable crystalline phase;
the wetting contact angle theta of the sealing microcrystalline glass is 30-60 degrees during sealing, the sealing microcrystalline glass has good wetting sealing performance, the wetting contact angle is too low (theta is less than 30 degrees), and glass liquid flows out of a sealing area during sealing, so that the pollution to an SOFC battery is caused, and the performance of the SOFC battery is influenced; the wetting contact angle is too high (theta is more than 60 degrees), and when the sealing is carried out, the wetting effect of the glass liquid is general, so that the sealing strength and the airtightness of the battery can be greatly reduced;
the sealing glass suitable for being used in the medium-temperature SOFC operation environment is obtained through the implementation, and the remarkable effect of the sealing glass is concentrated on the aspect of improving the thermal stability of the sealing material.
The present invention relates generally to the field of intermediate temperature Solid Oxide Fuel Cells (SOFC), but is not limited to SOFC and can also be used for sealing between similar metals and ceramics.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. The medium-high temperature SOFC sealing microcrystalline glass is characterized in that the raw material composition is SiO2、Al2O3MO and an additive in a molar ratio of 25-60: 1-5: 38-50: 0-5, wherein the MO is a mixture of MgO, CaO, SrO and BaO; the additive is TiO2、La2O3、SnO2A mixture of (a);
formation of Ca (Mg, Al) (Si, Al) in a glass-ceramic matrix2O6A crystal; the amount of each raw material added is not 0.
2. The method for preparing the sealing material by using the medium-high temperature SOFC sealing microcrystalline glass as described in claim 1, which comprises the following steps:
1) uniformly mixing the microcrystalline glass raw materials, melting at 1250-; quenching the melted glass liquid to obtain glass frit, then crushing, grinding or ball-milling the glass frit, and sieving to obtain glass powder;
2) mixing glass powder with a binder, a dispersant and a solvent to form slurry, ball-milling in a ball mill to uniformly disperse, tape-casting to form, naturally drying, and cutting into a blank body with a required shape to prepare the glass sealing material.
3. The preparation method of claim 2, wherein the binder in step 2) is one or more of epoxy resin, methyl cellulose and polyvinyl alcohol.
4. The preparation method of claim 3, wherein the dispersant in step 2) is one or more selected from polyacrylic acid, polyvinyl alcohol, and polyacrylamide.
5. The preparation method according to claim 4, wherein the solvent in step 2) is one or more of terpineol, ethanol, isopropanol, and n-butanol.
6. A sealing material produced by the production method according to any one of claims 2 to 5.
7. The method of using a sealing material according to claim 6, comprising the steps of: placing the sealing material at a part to be sealed, applying a certain pressure, placing the sealing material in an electric furnace, raising the temperature at the speed of 5-10 ℃/min, preserving the temperature at 1000 ℃ of 800-plus-materials for 20-60 min, then reducing the temperature to 900 ℃ of 700-plus-materials, preserving the temperature for 0.5-2 h, and completing the sealing.
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CN111785989B (en) * 2020-06-29 2023-03-07 中国科学院上海硅酸盐研究所 Sealing material for solid oxide fuel cell using blast furnace slag as main raw material, and preparation method and use method thereof
CN112521011B (en) * 2020-11-04 2022-03-08 中国科学院上海硅酸盐研究所 Solid oxide fuel cell composite sealing material and preparation method and application thereof

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