CN103553334B - A kind of containing MnO 2glass sealing material and using method - Google Patents
A kind of containing MnO 2glass sealing material and using method Download PDFInfo
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- CN103553334B CN103553334B CN201310501671.1A CN201310501671A CN103553334B CN 103553334 B CN103553334 B CN 103553334B CN 201310501671 A CN201310501671 A CN 201310501671A CN 103553334 B CN103553334 B CN 103553334B
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Abstract
The invention discloses a kind of containing MnO
2glass sealing material and preparation and application, raw material consists of B
2o
3, Al
2o
3, SiO
2, the mixture of one or more in RO(MgO, CaO, SrO, BaO) and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.By adding MnO
2mn ion (the Mn of mixed valence is introduced in seal glass
2+with Mn
3+, and different valence state Mn ion relative content and MnO
2addition closely related), from thermodynamics, regulation and control are realized to the stability at elevated temperature of seal glass; Meanwhile, MnO
2add the softening temperature that can also reduce seal glass, improve its coking property.Raw materials of the present invention is simple, be easy to get, and process stabilizing, obtains with SiO
2for the inverse glass network structure of main body, cost is low, and technique is simple, feasible, reaches practical and industrialized condition.
Description
Technical field
The invention belongs to field of solid oxide fuel, be specifically related to a kind of containing MnO
2glass sealing material and preparation and application.
Background technology
The advantages such as Solid Oxide Fuel Cell (SOFC) adopts soild oxide (pottery) ionogen, and at high temperature run, have generating efficiency high, the cost of material is low, fuel tolerance strong (as methane, coal gas, methyl alcohol, alcohol, oil liquefied gas etc.).But the subject matter that exploitation SOFC faces is that at high temperature how fuel gas and oxic gas effectively completely cut off and sealing-in.Due to the working temperature of battery high (700 ~ 750 DEG C), suitable seal, sealing materials and sealing technology is selected to become the key of restriction planar SOFC development.For solving seal, sealing materials and containing the stainless sealing-in Problem of Failure of Cr, domestic and international investigator have employed:
1. preoxidation is carried out to containing Cr alloy linker, to reduce seal, sealing materials and the surface reaction containing Cr alloy;
2. to armor coated containing Cr alloy linker, to limit the diffusion of Cr;
3. by improving the uniform recipe design surface reaction of seal glass, the Loehman as Sandia National Laboratory of the U.S. also attempts the Cr adding saturation concentration to glass basis
2o
3to suppress the diffusion of Cr;
4. utilize alkalimetal oxide (as Na
2o and K
2o) replace the methods such as the alkaline earth metal oxide that easily reacts, but above method all fails to satisfactorily resolve the sealing-in Problem of Failure that surface reaction causes.
On seal, sealing materials, the glass system of research mainly concentrates on phosphorus system, boron system and silicate.(1) series of phosphate: under SOFC working temperature, phosphoric acid salt volatilizees easily and anode generation surface reaction, forms nickelous phosphate and zirconium phosphate etc., reduces anode active.Meanwhile, the stability of crystal in the fuel atmosphere of humidity of phosphate glass formation is also very undesirable.(2) borate salt system: B
2o
3interpolation can promote the reduction of glass transition point, improve the Forming ability of glass, but B
2o
3remarkable volatilization under the high temperature conditions governs the application of borate-based glass in SOFC seal, sealing materials.Research finds that this is that glass causes obvious weightlessness owing to volatilizing, and the reaction at the interface occurred also clearly.(3) silicate systems: comparatively speaking, the volatility of silicate-based glasses material is more weak, has stronger sealing-in stability.In order to obtain the mobility of enough materials, people attempt employing and add various additive to improve sealing-in effect.In recent years, it is found that employing mixed type glass is a direction that can obtain better sealing-in effect.Wherein borosilicate is the system that people comparatively pay close attention to, by regulation and control B
2o
3/ SiO
2ratio can obtain required glass transition point and glass softening point.
For seal, sealing materials and other interelements because coefficient of thermal expansion mismatch is (as seal glass 11 ~ 13 × 10
-6/ K, chromium stainless steel alloy linker ~ 13 × 10
-6/ K) cause the generation of thermal stresses, and then bring out the initiation and propogation of crackle, so that the defect of sealing-in ultimate failure, domestic and international research drops into great effort exploitation at high temperature can the self-healing seal, sealing materials of long term maintenance vitreous state, attempts the thermal stresses of the viscous flow release seal interface accumulation by glassy phase.But, easily react under SOFC working temperature with containing Cr alloy linker for the network ligand ion (as IIA race) improving seal glass viscosity, generate as BaCrO
4, SrCrO
4and CaCrO
4etc. having high thermal expansivity (18 ~ 20 × 10
-6/ K) product, again cause the coefficient of thermal expansion mismatch with other elements of seal interface, destroy sealing-in bonding force, the work-ing life of serious restriction seal, sealing materials and SOFC, especially in the stability of Thermal Cycling.
Summary of the invention
In order to solve the problem, the invention provides a kind of containing MnO
2glass sealing material and preparation and application, by add MnO
2mn ion (the Mn of mixed valence is introduced in seal glass
2+with Mn
3+, and different valence state Mn ion relative content and MnO
2addition closely related), from thermodynamics, regulation and control are realized to the stability at elevated temperature of seal glass; Meanwhile, MnO
2add the softening temperature that can also reduce seal glass, improve its coking property.
For achieving the above object, the present invention adopts following technical scheme:
A kind of containing MnO
2the raw material of glass sealing material consist of B
2o
3, Al
2o
3, SiO
2, RO and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30; Wherein RO is the mixture of one or more in MgO, CaO, SrO, BaO.
Preparation method comprises the following steps:
(1) raw material is mixed by proportioning ball milling; Carry out carbonate decomposition at 1100 DEG C after, found at 1400-1500 DEG C, insulation 2-5 hour; The glass metal melted is poured in cold water and carries out quenching, obtain glass frit; Pulverized by glass frit, grinding or ball milling, obtain glass powder after sieving;
(2) glass powder of step (1) is incubated 2-5 hour, to regulate Mn at 700-750 DEG C
2+with Mn
3+relative content;
(3) by the glass powder of step (2) and dispersion agent, binding agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape, makes glass sealing material.
Described binding agent comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more of polyvinyl alcohol.
Described dispersion agent comprises the mixture of one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
Described solvent comprises the mixture of one or more of water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
Glass sealing material is placed in and treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, at 400-500 DEG C of insulation 0.5-2 hour, 700-750 DEG C of Crystallizing treatment 2-5 hour is heated to again with 3 DEG C/min, again with the ramp of 1-3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.
Remarkable advantage of the present invention is:
(1) by adding MnO
2mn ion (the Mn of mixed valence is introduced in seal glass
2+with Mn
3+, and different valence state Mn ion relative content and MnO
2addition closely related), from thermodynamics, regulation and control are realized to the stability at elevated temperature of seal glass;
(2) MnO
2add the softening temperature that can also reduce seal glass, improve its coking property;
(3) raw materials of the present invention's selection is cheap, and sources is various, process stabilizing.Select corresponding oxide compound to be source material, make their Homogeneous phase mixing, remain a high proportion of mixing and distribution state in fusing and subsequent heat treatment, can prepare with SiO
2for the inverse glass network structure of main body, and excellent performance, be applicable to Solid Oxide Fuel Cells sealing-in, reach practical and industrialized condition.
Accompanying drawing explanation
Fig. 1 is that traditional borosilicate system seal glass (does not contain MnO
2) and Cr
2o
3powder carries out the ultraviolet spectrogram of the reaction product of solid state reaction after 24 hours at 750 DEG C.
Fig. 2 is interpolation 5% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 3 is interpolation 10% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 4 is for adding 20%MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 5 is interpolation 25% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 6 is interpolation 30% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.
Fig. 7 is different MnO
2the Mn of seal glass under parallel laboratory test condition added
3+/ (Mn
2++ Mn
3+).
Fig. 8 is different MnO
2the thermal dilatometry of seal glass under parallel laboratory test condition added.
Embodiment
A kind of containing MnO
2the raw material of seal glass consist of B
2o
3, Al
2o
3, SiO
2, the mixture of one or more in MO(MgO, CaO, SrO, BaO) and MnO
2, its mol ratio is 0 ~ 10:0 ~ 5:25 ~ 60:20 ~ 50:5 ~ 30.
Said method comprising the steps of:
(1) preparation of seal glass: raw material is mixed; Carry out carbonate decomposition at 1100 DEG C, found at 1400 ~ 1500 DEG C, soaking time 2-5 hour; Pour in stainless steel mould by the glass metal part melted, obtain the right cylinder glass of certain size, a remaining part is poured in cold water and is carried out quenching, obtains glass frit; Then, pulverized by glass frit, grinding or ball milling, obtain glass powder after sieving;
(2) glass powder of above-mentioned acquisition is incubated 2-5 hour at 700-750 DEG C, obtains the glass system of different Mn ionic valence condition mixing;
(3) preparation of glass idiosome: the glass powder that step (2) was processed and binding agent, dispersion agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape, makes glass sealing material.
The binding agent of described step (3) comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, one or more of polyvinyl alcohol.The dispersion agent of described step (3) comprise fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide one or more.The solvent of described step (3) be water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone one or more.
The using method of glass sealing material, glass sealing material is placed in treat sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, at 400-500 DEG C of insulation 0.5-2 hour, 700-750 DEG C of Crystallizing treatment 2-5 hour is heated to again with 3 DEG C/min, again with the ramp of 1-3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.
Table 1 is the sealing glass composition table (molecular fraction) in embodiment 1-5
Embodiment 1: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, MnO
2), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1500 DEG C with 3 DEG C/min, be incubated 2 hours; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves.Glass powder and polyvinyl alcohol, fish oil, ethanol and toluene (weight ratio is followed successively by 80%, 6%, 2%, 10%, 2%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 450 DEG C of insulations 1 hour, then be heated to 750 DEG C of Crystallizing treatment 2 hours with 3 DEG C/min, be warming up to the working temperature of Solid Oxide Fuel Cell again with the speed of 3 DEG C/min, namely complete sealing-in.Fig. 2 shows, adds 5% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for corresponding not containing MnO at 750 DEG C
2seal glass 35%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, adds 5%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.6.Fig. 8 shows, adds 5%MnO
2the glass transition point Tg of seal glass be 664 DEG C, softening temperature is 729 DEG C.
Embodiment 2: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, MnO
2), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into platinum crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1450 DEG C with 3 DEG C/min, be incubated 2 hours; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves.Obtained glass powder and methylcellulose gum, polyvinyl alcohol, propyl carbinol and acetone (weight ratio is followed successively by 84%, 3%, 1%, 8%, 4%) are mixed into slurry by this glass powder, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 500 DEG C of insulations 1 hour, be heated to 730 DEG C of Crystallizing treatment 2 hours with 3 DEG C/min, again with the ramp of 3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.This example is preferably form.Fig. 3 shows, adds 10% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for corresponding not containing MnO at 750 DEG C
2seal glass 42%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, adds 10%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.4.Fig. 8 shows, adds 10%MnO
2the glass transition point Tg of seal glass be 657 DEG C, softening temperature is 717 DEG C.
Embodiment 3: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, MnO
2), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1450 DEG C with 3 DEG C/min, be incubated 2 hours; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves.Obtained glass powder and methylcellulose gum, polyvinyl alcohol, propyl carbinol and acetone (weight ratio is followed successively by 81%, 4%, 2%, 9%, 4%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 3 DEG C/min in electric furnace, 450 DEG C of insulations 1 hour, then be heated to 720 DEG C of Crystallizing treatment 2 hours with 3 DEG C/min, again with the ramp of 3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.Fig. 4 shows, adds 20% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for corresponding not containing MnO at 750 DEG C
2seal glass 60%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, adds 20%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.2.Fig. 8 shows, adds 20%MnO
2the glass transition point Tg of seal glass be 651 DEG C, softening temperature is 704 DEG C.
Embodiment 4: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, MnO
2), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1400 DEG C with 3 DEG C/min, be incubated 2 hours; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Obtained glass powder and epoxy resin, polyacrylamide, Virahol and toluene (weight ratio is followed successively by 81%, 3%, 2%, 10%, 4%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 500 DEG C of insulations 1 hour, then be heated to 700 DEG C of Crystallizing treatment 2 hours with 3 DEG C/min, again with the ramp of 3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.This example is preferably form.Fig. 5 shows, adds 25% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for corresponding not containing MnO at 750 DEG C
2seal glass 31%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain glass transition point and softening temperature.Fig. 7 shows, adds 25%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.8.Fig. 8 shows, adds 25%MnO
2the glass transition point T of seal glass
gbe 650 DEG C, softening temperature is 688 DEG C.
Embodiment 5: the preparation of material and sealing-in
According to the proportioning of each component of table 1, take a certain amount of analytical pure raw material (CaO, SrO, SiO
2, Al
2o
3, B
2o
3, MnO
2), within 24 hours, mix with planetary ball mill ball milling; Then powder is put into crucible, be placed in the air atmosphere of chamber type electric resistance furnace, be heated to 1400 DEG C with 3 DEG C/min, be incubated 2 hours; Then, take out crucible, melt is poured into chilling in deionized water, the dry fragment obtaining glass melt; Grinding, crosses 100 mesh sieves, obtains glass powder.Obtained glass powder and polyvinyl butyral acetal, polyacrylic acid, Virahol and acetone (weight ratio is followed successively by 82%, 2%, 2%, 10%, 4%) are mixed into slurry, and in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape; Idiosome is placed in and treats sealing-in position, with the ramp of 2 DEG C/min in electric furnace, 480 DEG C of insulations 1 hour, then be heated to 700 DEG C of Crystallizing treatment 2 hours with 3 DEG C/min, again with the ramp of 3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.Fig. 6 shows, adds 30% MnO
2seal glass and Cr
2o
3powder carries out the reactivity of solid state reaction after 24 hours for corresponding not containing MnO at 750 DEG C
2seal glass 26%.Melt after insulation is poured in the stainless steel grinding tool after preheating, obtains the glass cylinder of Φ=10mm, d=25mm, with the test of the heating rate of 10 DEG C/min on NETZSCH DIL 402EP thermal dilatometer, obtain thermal expansivity and softening temperature.Fig. 7 shows, adds 30%MnO
2the Mn of seal glass
3+/ (Mn
2++ Mn
3+) be 0.9.Fig. 8 shows, adds 30%MnO
2the glass transition point T of seal glass
gbe 645 DEG C, softening temperature is 683 DEG C.
The present invention obtains the seal glass with stability at elevated temperature and sealing property by above-mentioned enforcement.Its significant effect embodies a concentrated reflection of the raising aspect of stability at elevated temperature, its principle to be in seal glass mixed valence ion especially lower valency ion in surface reaction process, serve as the role of competing reaction, effectively reduce the reaction of network part and metallic matrix from thermodynamics aspect.To seal, sealing materials and Cr
2o
3the product of powder at high temperature solid state reaction is by ultraviolet spectroscopy Cr(VI) absorption intensity, can the chemical stability of quantitative evaluation material, the number of pages being published in " Journal of Power Sources " see this seminar in 2010 6795 to 6797 article.Reactivity is lower, shows that the stability at elevated temperature of seal, sealing materials is better.In addition, this seminar recent work finds, with traditional borosilicate system seal glass (not containing MnO
2) compare, add MnO
2glass present unique reaction mechanism in surface reaction process.Fig. 1 is that traditional borosilicate system seal glass (does not contain MnO
2) and Cr
2o
3the ultraviolet spectrogram of powder at high temperature solid state reaction product.Fig. 2 is interpolation 5% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 3 is interpolation 10% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 4 is interpolation 20% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 5 is interpolation 25% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Fig. 6 is interpolation 30% MnO
2the ultraviolet spectrogram of seal glass under parallel laboratory test condition.Can see from the contrast of five figure, the chemical stability of seal glass and MnO
2addition is closely related.Fig. 7 is different MnO
2the Mn of seal glass under parallel laboratory test condition added
3+/ (Mn
2++ Mn
3+).Mn can be found out by the contrast of Fig. 6 and Fig. 7
3+/ (Mn
2++ Mn
3+) with the corresponding relation of seal glass chemical stability.Fig. 8 is different MnO
2the Alysis of Thermal Exponsion Coefficient figure of seal glass under parallel laboratory test condition added.As shown in Figure 8, the softening temperature of sealing-in seal glass and glass transition point are with MnO
2the raising of addition and reducing, is applicable to the operating temperature range of intermediate temperature fuel cell.
The present invention relates generally to Solid Oxide Fuel Cell (SOFC) field, but is not limited to SOFC, can also be used for the sealing-in between metalloid and pottery.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. one kind contains MnO
2glass sealing material, it is characterized in that: raw material consists of B
2o
3, Al
2o
3, SiO
2, RO and MnO
2, its mol ratio is 5 ~ 10:0 ~ 5:40 ~ 60:25 ~ 40:10 ~ 25; Wherein RO is the mixture of one or more in MgO, CaO, SrO, BaO;
Preparation method comprises the following steps:
(1) raw material is mixed by proportioning ball milling; Carry out carbonate decomposition at 1100 DEG C after, found at 1400-1500 DEG C, insulation 2-5 hour; The glass metal melted is poured in cold water and carries out quenching, obtain glass frit; Pulverized by glass frit, grinding or ball milling, obtain glass powder after sieving;
(2) glass powder of step (1) is incubated 2-5 hour, to regulate Mn at 700-750 DEG C
2+with Mn
3+relative content;
(3) by the glass powder of step (2) and dispersion agent, binding agent and solvent form slurry, in ball mill, ball milling is dispersed; Flow casting molding, seasoning, is then cut into the idiosome of desired shape, makes glass sealing material.
2. according to claim 1 containing MnO
2glass sealing material, it is characterized in that: the binding agent of described step (3) comprises epoxy resin, methylcellulose gum, polyvinyl butyral acetal, the mixture of one or more of polyvinyl alcohol.
3. according to claim 1 containing MnO
2glass sealing material, it is characterized in that: the dispersion agent of described step (3) comprises the mixture of one or more of fish oil, polyacrylic acid, polyvinyl alcohol, polyacrylamide.
4. according to claim 1 containing MnO
2glass sealing material, it is characterized in that: the solvent of described step (3) comprises the mixture of one or more of water, ethanol, Virahol, propyl carbinol, toluene, dimethylbenzene, acetone.
5. one kind contains MnO as claimed in claim 1
2the using method of glass sealing material, it is characterized in that: glass sealing material is placed in and treats sealing-in position, with the ramp of 1-5 DEG C/min in electric furnace, at 400-500 DEG C of insulation 0.5-2 hour, 700-750 DEG C of Crystallizing treatment 2-5 hour is heated to again with 3 DEG C/min, again with the ramp of 1-3 DEG C/min to the working temperature of Solid Oxide Fuel Cell, namely complete sealing-in.
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|---|---|---|---|
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|---|---|---|---|
| CN201310501671.1A CN103553334B (en) | 2013-10-23 | 2013-10-23 | A kind of containing MnO 2glass sealing material and using method |
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