CN1812159A - Mesotherm hermetic glass and hermetic method for solid oxide fuel cell - Google Patents
Mesotherm hermetic glass and hermetic method for solid oxide fuel cell Download PDFInfo
- Publication number
- CN1812159A CN1812159A CN200510011284.5A CN200510011284A CN1812159A CN 1812159 A CN1812159 A CN 1812159A CN 200510011284 A CN200510011284 A CN 200510011284A CN 1812159 A CN1812159 A CN 1812159A
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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Abstract
This invention relates to a kind of middle temperature sealed glass and sealing method used in solid oxide fuel cell. The component and mole percent of glass are: SiO2 20-40%, B<2O3 5%-40%, BaO 10%-45%, La2O<3 0-11%, Y<2O3 0-10%, ZrO2 1-15%, TiO2 0-10%, ZnO 0-30%. The sealing process is: crush the produced glass and reserve; mix the produces glass powder and dispersing agent, monomer, crosslinking agent and distilled water to form size, after which ball-mill evenly dispersed in ball mill. Then, they are cast into the mould after adding initiator or catalyst. Next, they are put in the oven to solidify. The monomer polymerize to sealed glass base. It is cut into sealing base after drying; the produced sealing base is positioned between pending sealed parts. The sealing of pending sealed parts is achieved during the process of warming, heat preservation, warming again and heat preservation again.
Description
Technical field
The present invention relates to a kind of in warm seal glass and be used for the method for Solid Oxide Fuel Cell (SOFC) sealing.
Background technology
Solid Oxide Fuel Cell (SOFC) has energy conversion efficiency height, environmental friendliness (SO
x, NO
x) discharging is low, noiselessness pollutes), the wide outstanding advantages such as (can directly use by inside reforming and comprise various fuel such as natural gas, gasoline, oil liquefied gas) of fuel tolerance, be the efficient green energy of generally acknowledging.SOFC has board-like and two kinds of structures of tubular type, and board-like SOFC has advantages such as power density height, preparation technology is simple, preparation cost is low, and the board-like SOFC of middle temperature (600-800 ℃) is the focus of current domestic and international SOFC research.One of difficult point of board-like SOFC is to need sealing, though board-like SOFC research has successfully solved a lot of technological challenges, but sealing problem is still unresolved so far, current subject matter is that the long-time stability of " sealing-in " are poor, thermal cycle (starting/stop) operation seldom of only suitable short-term and number of times, can't satisfy the requirement of long-term (as 40000 hours), repeatedly thermal cycle (as 3000 times) stable operation, become one of major obstacle of board-like SOFC development.
The major function of sealing is: (1) prevents that fuel is (as H
2, CH
4Deng) mix in SOFC with oxidant (as air), keep good air-tightness; (2) " anode/negative electrode/connection utmost point " battery unit is combined formation battery pile; (3) will connect utmost point edge insulation ground separately, prevent to form the short circuit of connection electrode current.In the encapsulant of warm SOFC need long-term work under 600～800 ℃ oxidation and reducing atmosphere, and also to bear the thermal stress of battery pile startup/stopped process, the requirement encapsulant satisfies: (1) will be mated as much as possible by the thermal coefficient of expansion of seal, sealing materials (CTE-Coefficient of Thermal Expansion) with each, with relief of thermal stress; (2) have thermal stability preferably, promptly the thermal coefficient of expansion at SOFC run duration encapsulant should not take place to change significantly; (3) have suitable viscosity, guaranteeing the Stability Analysis of Structures of operating temperature lower seal, and guarantee to have suitable sealing temperature simultaneously; (4) Yu by seal, sealing materials have wettability and stronger adhesion preferably; (5) (air, wet fuel gas) has better chemical stability under SOFC operation atmosphere; (6) Yu by seal, sealing materials have good chemical compatibility, significant chemical reaction does not take place.The SOFC encapsulant is carried out a lot of researchs both at home and abroad, proposed hard sealing (Rigid sealing), means of press seals (Compressive sealing) and self-adapting seal three kinds of seal concept such as (Compliant sealing).Self-adapting seal is meant that encapsulant can produce certain plastic deformation under operating temperature, to eliminate the thermal stress that produces because of variations in temperature, avoid the excessive seal failure that causes of thermal stress, this kind sealing is very high to the chemical compatibility and the viscosity control requirement of encapsulant, only limits to the experimental exploring stage at present.Means of press seals adopts the notion of " sealing ring " to realize the sealing of SOFC, what only " sealing ring " adopted is high temperature resistant, sludge proof inorganic layered compounds (as mica), the sealing ring that is filled in the SOFC inter-module by compacting reaches the purpose of sealing, interlayer faults can take place to eliminate the thermal stress that variations in temperature produces in use laminate sealing ring, and the part that fracture does not meanwhile take place can provide sealing.At present this kind encapsulating method still is in the exploratory stage, has only the research report of minority, and sealing effectiveness is not ideal enough when using separately.Hard sealing is meant that encapsulant is connected firmly with the SOFC inter-module, can not produce plastic deformation after the sealing-in, the sealing that can not do relative motion.Hard encapsulant mainly contains metal material (as brazing, silver slurry etc.), glass, glass ceramics etc., and wherein metal sealing material is not subjected to paying attention to widely because of problems such as high-temperature oxydations.Glass and glass ceramics (hereinafter to be referred as seal glass) have low, the easy sealing-in of cost, are easy to advantages such as large-scale production; be the SOFC seal, sealing materials of domestic and international broad research and employing, carried out comparatively extensive studies, as CN1469497A; CN1234617A; CN1414646A, CN1465647A, CN02147179.7; US6475938; US6291092, US6541146, the seal glass that US5453331 etc. are disclosed.These researchs mainly concentrate on glass and the chemical stability of glass-ceramic seal materials under oxidation and reducing atmosphere, with the matching of other storeroom thermal coefficient of expansion of SOFC, and the aspects such as viscosity under operating temperature.
Yet also there is tangible deficiency in existing seal glass: promptly do not consider the thermal stability of seal glass under serviceability temperature.The serviceability temperature of seal glass is generally at 600～800 ℃, this temperature range just in time is between easy crystallization of seal glass and the easy vitellarium of crystalline phase, as article " Alternative planar SOFC sealingconcepts " (Fuel Cells Bulletin, 2004, May, " existing seal glass just begins crystallization at high temperature initial several hours, makes CTE that marked change take place " of pp11-16) being commented.People such as Sohn are at research SiO
2-B
2O
3-BaO-Al
2O
3Be that the thermal coefficient of expansion of seal glass is found during with the variation of heat treatment time, behind 800 ℃ of insulation 100h, preferably the thermal coefficient of expansion of glass is just from initial 11.2 * 10
-6K
-1Change to 10.8 * 10
-6K
-1, and behind 800 ℃ of insulation 500h, the thermal coefficient of expansion of glass further drops to 9.9 * 10
-6K
-1, the variation of thermal coefficient of expansion surpasses 10%, and the variation of the thermal coefficient of expansion of poor glass even reach 35%.Its reason is two kinds of crystalline phase: celsian and the hexacelsian that has separated out baryta fledspar in 800 ℃ of lower-glass, and their thermal coefficient of expansion is respectively 2.0 * 10
-6K
-1With 8.0 * 10
-6K
-1, and along with the prolongation of heat treatment time, metastable hexacelsian can be finally converted into stable celsian, therefore (the Journalof the American Ceramic Society that caused the thermal coefficient of expansion prolongation in time of glass progressively to reduce, 2004,87,254-260).
Present seal glass patent about SOFC, CN1469497A As mentioned above, CN1234617A, CN1414646A, CN1465647A, CN02147179.7, US6475938, US6291092, US6541146, US5453331 etc. do not relate to the thermal stability of seal glass.Therefore, in the exploitation temperature down the SOFC seal glass of Heat stability is good remain one of subject matter that this area faces.
Summary of the invention
The object of the present invention is to provide a kind of middle temperature seal glass of using at the solid oxide fuel cell seal of 8mol% yttria-stabilized zirconia (8YSZ) electrolyte, should in warm seal glass have extraordinary in warm stability, after using (heat treatment) for a long time under the middle temperature, there is not tangible crystallization, can devitrification, thermal coefficient of expansion changes very little after the heat treatment.
Another purpose of the present invention be to provide a kind of described in the method that is used for Solid Oxide Fuel Cell (its electrolyte is 8mol% yttria-stabilized zirconia (8YSZ)) sealing of warm seal glass.
Technical scheme of the present invention is as follows:
Warm seal glass in provided by the invention, its contained component comprises SiO
2, B
2O
3, BaO, La
2O
3, Y
2O
3, ZrO
2, TiO
2And ZnO, the molar content of each component is: SiO
220～40%, B
2O
35%～40%, BaO 10%～45%, La
2 O
30～11%, Y
2O
30～10%, ZrO
21～15%, TiO
20～10%, ZnO 0～30%; Warm seal glass has the thermal coefficient of expansion close with 8YSZ in of the present invention, 8.5～11.1 * 10
-6K
-1Between (room temperature～transition temperature), in this warm seal glass 700 ℃ handle 500 hours after thermal coefficient of expansion still 8.5～11.1 * 10
-6K
-1Between (room temperature～transition temperature).
The feature of the warm seal glass of the 8mol% of being used for yttria-stabilized zirconia provided by the invention (8YSZ) electrolyte is not contain Al in its component
2O
3Because Al
2O
3Containing SiO
2With the baryta fledspar that forms low thermal coefficient of expansion in the glass system of BaO easily mutually, do not contain Al so the present invention adopts
2O
3, mainly be based on SiO
2-B
2O
3-BaO-ZrO
2-Y
2O
3-La
2O
3-TiO
2-ZnO system, wherein B
2O
3Be used to regulate the viscosity of glass, and and SiO
2Improve the stability of glass together as the network organizator of glass, BaO is used for improving the thermal coefficient of expansion of glass, Y
2O
3And ZrO
2Be used for improving the electrolytical chemical compatibility of glass and 8YSZ, La
2O
3, TiO
2Be used for improving the stability of glass with ZnO.
Provided by the invention described in warm seal glass be used for the method for solid oxide fuel cell seal, may further comprise the steps:
(1) preparation of warm seal glass in: with contained component S iO
2, B
2O
3, BaO, La
2O
3, Y
2O
3, ZrO
2, TiO
2And ZnO, by the molar content of each component be: SiO
220～40%, B
2O
35%～40%, BaO 10%～45%, La
2O
30～11%, Y
2O
30～10%, ZrO
21～15%, TiO
20～10%, after ZnO 0～30% weighs and mixes, be heated to 1300～1500 ℃ of insulations 1～5 hour, Quench obtains glass then; The glass that makes is pulverized, and it is standby to cross 50～500 mesh sieves;
(2) preparation sealing-in base substrate: the middle temperature seal glass powder that step (1) is made mixes the formation slurry with dispersant, monomer, crosslinking agent and distilled water, place the ball mill ball milling to evenly disperseing in slurry, water in the mould that casts from customization after adding initator or catalyst, mould is put into baking oven to be solidified 10-60 minute or dry under field conditions (factors) 10-60 minute, monomer polymerization forms the seal glass base substrate in the slurry, again the seal glass base substrate is carried out drying, afterwards, carry out cutting, obtain the sealing-in base substrate.Each components contents (weight percentage) is: 20%-65% glass dust; 1%-5% dispersant, dispersant are gum arabic, polyacrylamide or polyvinyl alcohol; 12%-30% monomer, monomer are acrylamide or Methacrylamide; 1%-10% crosslinking agent, crosslinking agent are nitrogen nitrogen dimethyl bisacrylamide or many ethyleneglycol dimethacrylates; 0.1%-0.5% initator or catalyst, initator are ammonium persulfate, and catalyst is a tetramethylethylenediamine; 15%-35% distilled water;
(3) sealing-in: the sealing-in base substrate that makes in (2) is placed between the material for the treatment of sealing-in, in electric furnace, temperature is slowly risen to 550～650 ℃ and be incubated 20～40 minutes, slowly rise to 750～850 ℃ of insulations 10～30 minutes then, i.e. the sealing-in between the sealing-in parts is treated in realization.
Description of drawings
Fig. 1 is the sealing schematic diagram of solid-oxide fuel cell stack;
Fig. 2 be among the embodiment a kind of in warm seal glass under 700 ℃, before and after the 500h heat treatment with the contrast of the unit thermal expansion amount of 8YSZ;
Fig. 3 be among the embodiment a kind of in the CTE (room temperature～transition temperature) of warm seal glass under 700 ℃ with the variation of heat treatment time;
Fig. 4 be among the embodiment a kind of in the CTE (room temperature～transition temperature) of warm seal glass under 800 ℃ with the variation of heat treatment time;
Fig. 5 A is the sealing-in base substrate that is placed between connecting plate and the anode;
Fig. 5 B is the sealing-in base substrate between connecting plate and the connecting plate.
Embodiment
Further describe the present invention below in conjunction with embodiment and accompanying drawing.
The preparation of warm seal glass among the embodiment 1～11
Molar content according to each component of listed each embodiment in the table 1 takes by weighing a certain amount of analytically pure SiO respectively
2, B
2O
3, BaCO
3, La
2O
3, Y
2O
3, ZrO
2, TiO
2And ZnO, respectively with behind the abundant mix grinding of planetary ball mill, take out oven dry; Respectively powder is placed on platinum alloy and does in the pot, place chamber type electric resistance furnace, be warming up to 1300 ℃～1500 ℃ under the air atmosphere, constant temperature 2～4 hours takes out down at 1100 ℃ then and pours cooling fast in the cold water into, forms warm seal glass grog in the fritter; After the pulverizing, cross the 50-500 mesh standard sieve, warm seal glass sealing-in powder is stand-by in making.
Warm seal glass component table (molar content) in the table 1.
| SiO 2 | B 2O 3 | BaO | La 2O 3 | Y 2O 3 | ZrO 2 | TiO 2 | ZnO | |
| Embodiment 1 | 33.2 | 28.4 | 12.2 | 10.8 | 6.2 | 4.7 | 4.5 | 0 |
| Embodiment 2 | 25.0 | 10.7 | 20.3 | 3.3 | 5.7 | 4.4 | 4.0 | 26.6 |
| Embodiment 3 | 22.9 | 23.8 | 18.6 | 3.0 | 2.2 | 1.6 | 3.7 | 24.2 |
| Embodiment 4 | 24.2 | 14.8 | 24.4 | 3.2 | 2.3 | 1.7 | 3.9 | 25.5 |
| | 25.2 | 7.7 | 28.9 | 3.3 | 2.4 | 1.7 | 4.1 | 26.7 |
| Embodiment 6 | 22.1 | 23.1 | 24.8 | 0.6 | 0.8 | 1.5 | 3.6 | 23.5 |
| Embodiment 7 | 22.3 | 16.4 | 25.0 | 0.6 | 0.8 | 1.6 | 9.6 | 23.7 |
| | 30.7 | 34.6 | 31.7 | 0.6 | 0.8 | 1.6 | 0 | 0 |
| Embodiment 9 | 24.8 | 28.3 | 41.6 | 0.7 | 0.9 | 3.7 | 0 | 0 |
| | 38.3 | 27.4 | 31.3 | 0.6 | 0.8 | 1.6 | 0 | 0 |
| Embodiment 11 | 30.1 | 30.9 | 23.0 | 0.6 | 0.8 | 14.6 | 0 | 0 |
The test of embodiment 12 long-term thermal stabilities:
After making glass under 1300 ℃, allow the glass that is in molten state reduce to heat treatment temperature (700 ℃ and 800 ℃) with furnace temperature, and under heat treatment temperature, be incubated 100h respectively, 300h and 500h, with the thermal coefficient of expansion of research glass with the variation of heat treatment time: with the glass-cutting 15mm that grows up, the cuboid of wide 4mm is with elevated temperature heat dilatometer (L75/1550, LINSEIS, Germany) thermal coefficient of expansion of glass before and after the test heat treatment.Fig. 2 is warm seal glass contrast with the unit thermal expansion amount of 8YSZ 700 ℃ of following heat treatment 500h front and back among prepare among the embodiment a kind of, as can be seen, heat treatment through 500h, obvious variation does not take place in the unit length swell increment of warm seal glass in being somebody's turn to do, and all approaching with the unit length swell increment of 8YSZ.Fig. 3 be the CTE (room temperature～transition temperature) of warm seal glass among prepare among the embodiment a kind of under 700 ℃ with the variation of heat treatment time, CTE of warm seal glass is 9.8 * 10 in this
-6/ K, through 100h, the CTE after 300h and the 500h heat treatment is respectively 9.8 * 10
-6/ K, 10.05 * 10
-6/ K, 9.95 * 10
-6/ K is with the CTE (10.0 * 10 of 8YSZ in room temperature to 700 ℃
-6/ K) very approaching.Fig. 4 be among prepare among the embodiment a kind of warm seal glass at 800 ℃ of following heat treatment 100h, the variation of CTE behind 200h and the 300h, the CTE of warm seal glass variation with heat treatment time under 800 ℃ is very little in this kind, the thermal coefficient of expansion variation is 1% only behind the heat treatment 300h, shows that the thermal stability of warm seal glass under middle temperature is very good in this.
The preparation of embodiment 13 sealing-in base substrates
The middle temperature seal glass powder for preparing among the 30.0g embodiment 1-11 is joined in the solution of being made up of 8.0g Methacrylamide, 0.8g nitrogen nitrogen dimethyl bisacrylamide, 0.8g gum arabic and 15g distilled water, form slurry; Place ball mill fully to grind in slurry, the ammonium persulfate that adds 0.1g, slurry is watered in the mould that casts from customization again, mould is put into 60 ℃ of baking ovens solidify 30min, treat behind the monomer polymerization in the slurry seal glass base substrate that forms to be carried out drying, the base substrate of drying is cut into seals required form as shown in Figure 5, can obtain the sealing-in base substrate.Other embodiment sees Table 2.
Embodiment 14-16: prepare the sealing-in base substrate by the listed proportioning of table 2;
Each components contents (weight percentage) in the table 2. sealing-in body preparation
| Glass dust | Monomer | Crosslinking agent | Dispersant | Catalyst | Distilled water | |
| Embodiment 14 | 22.8 | 28.8 | 9.8 | 4.6 | 0.4 | 33.6 |
| Embodiment 15 | 48.2 | 20.2 | 6.4 | 2.9 | 0.2 | 22.1 |
| Embodiment 16 | 62.6 | 16.3 | 3.3 | 1.2 | 0.2 | 16.4 |
Monomer described in the table 2 is an acrylamide; Described crosslinking agent is many ethyleneglycol dimethacrylates; Described dispersant is polyacrylamide or polyvinyl alcohol; Described catalyst is a tetramethylethylenediamine.
Embodiment 17: use any sealing-in base substrate of the foregoing description 14-16 preparation to carry out the sealing-in of battery pack
The connecting plate that has gas passage of Solid Oxide Fuel Cell is placed ground floor (as Fig. 1 1), put one deck seal glass base substrate (as among Fig. 1 2) in the above, put one deck connecting plate (as among Fig. 1 3) again, locate to put to comprise negative electrode in the centre, electrolyte, the single cell units of the three-in-one structure that anode is combined with each other (as among Fig. 1 4), again the sealing-in base substrate is placed single cell units periphery (as Fig. 1 5), on connecting plate, put sealing-in base substrate (as among Fig. 1 6) then, put second layer connecting plate (as among Fig. 1 7) again, the rest may be inferred, form battery pile, tighten together with the screw pressurization at last; The battery pile that will tighten together is put in the high temperature furnace, slowly is warmed up to 600 ℃ of insulations 30 minutes, slowly rises to 750～850 ℃ of insulation 10min then, can realize the sealing-in of storeroom.The battery pack working temperature is 600～800 ℃.
Claims (3)
1, warm seal glass in a kind of, its contained component comprises SiO
2, B
2O
3, BaO, La
2O
3, Y
2O
3, ZrO
2, TiO
2And ZnO, the molar content of each component is: SiO
220～40%, B
2O
35%～40%, BaO10%～45%, La
2O
30～11%, Y
2O
30～10%, ZrO
21～15%, TiO
20～10%, ZnO0～30%.
2, by claim 1 described in warm seal glass, it is characterized in that the thermal coefficient of expansion of warm seal glass from room temperature to glass transformation temperature is 8.5～11.1 * 10 in this
-6K
-1Between, behind 700～800 ℃ of following heat treatment 300～500h, its thermal coefficient of expansion is still 8.5～11.1 * 10
-6K
-1Between.
3, a kind of claim 1 described in warm seal glass be used for the method for solid oxide fuel cell seal, may further comprise the steps:
(1) warm seal glass in the preparation: with contained component be: SiO by the molar content of each component
220～40%, B
2O
35%～40%, BaO10%～45%, La
2O
30～11%, Y
2O
30～10%, ZrO
21～15%, TiO
20～10%, ZnO0～30% is weighed, and after mixing, is heated to 1300～1500 ℃ of insulations 1～5 hour, then it is carried out Quench, warm seal glass in obtaining; The middle temperature seal glass that makes is pulverized, crossed 50～500 mesh sieves, standby;
(2) preparation sealing-in base substrate: the middle temperature seal glass powder that step (1) is made mixes the formation slurry with dispersant, monomer, crosslinking agent and distilled water, place the ball mill ball milling to evenly disperseing in slurry, water in the mould that casts from customization after adding initator or catalyst, mould is put into baking oven to be solidified 10-60 minute or dry under field conditions (factors) 10-60 minute, monomer polymerization forms the seal glass base substrate in the slurry, again the seal glass base substrate is carried out drying, afterwards, carry out cutting, obtain the sealing-in base substrate; Each components contents (weight percentage) is: 20%-65% glass dust; 1%-5% dispersant, dispersant are gum arabic, polyacrylamide or polyvinyl alcohol; 12%-30% monomer, monomer are acrylamide or Methacrylamide; 1%-10% crosslinking agent, crosslinking agent are nitrogen nitrogen dimethyl bisacrylamide or many ethyleneglycol dimethacrylates; 0.1%-0.5% initator or catalyst, initator are ammonium persulfate, and catalyst is a tetramethylethylenediamine; 15%-35% distilled water;
(3) sealing-in: the sealing-in base substrate that makes in (2) placed treat between the sealing-in parts, in electric furnace, temperature is slowly risen to 550～650 ℃ and be incubated 20～40 minutes, slowly rise to 750～850 ℃ of insulations 10～30 minutes then, i.e. the sealing-in between the sealing-in parts is treated in realization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100112845A CN100376046C (en) | 2005-01-28 | 2005-01-28 | Mesotherm hermetic glass and hermetic method for solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100112845A CN100376046C (en) | 2005-01-28 | 2005-01-28 | Mesotherm hermetic glass and hermetic method for solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1812159A true CN1812159A (en) | 2006-08-02 |
| CN100376046C CN100376046C (en) | 2008-03-19 |
Family
ID=36844918
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100112845A Expired - Fee Related CN100376046C (en) | 2005-01-28 | 2005-01-28 | Mesotherm hermetic glass and hermetic method for solid oxide fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100376046C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684034B (en) * | 2008-09-26 | 2011-07-27 | 中国科学院过程工程研究所 | Sealing glass powder, sealing glass ceramic powder and application |
| CN102593384A (en) * | 2011-01-12 | 2012-07-18 | 三星电机株式会社 | Sealing member for solid oxide fuel cell and solid oxide fuel cell employing the same |
| CN102856572A (en) * | 2012-09-05 | 2013-01-02 | 北京斯塔能源科技有限公司 | Glass sealing method for flat plate type solid oxide fuel cell |
| CN103855414A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Preparation method of solid oxide fuel cell seal gasket |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI458692B (en) * | 2012-10-17 | 2014-11-01 | Univ Nat Taipei Technology | Composite packaging materials |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1421888C3 (en) * | 1960-07-23 | 1973-10-25 | Ernst Leitz Gmbh, 6330 Wetzlar. | Optical Sihko Boiat glass of great chemical resistance with a high refractive index and relatively small dispersion, which is equal to or greater than 218 100 n deep |
| US6541146B1 (en) * | 2000-11-07 | 2003-04-01 | Hybrid Power Generation Systems, Llc | Composite sealant materials based on reacting fillers for solid oxide fuel cells |
| JP4266109B2 (en) * | 2002-10-07 | 2009-05-20 | 日本板硝子株式会社 | Glass frit for sealing |
-
2005
- 2005-01-28 CN CNB2005100112845A patent/CN100376046C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684034B (en) * | 2008-09-26 | 2011-07-27 | 中国科学院过程工程研究所 | Sealing glass powder, sealing glass ceramic powder and application |
| CN102593384A (en) * | 2011-01-12 | 2012-07-18 | 三星电机株式会社 | Sealing member for solid oxide fuel cell and solid oxide fuel cell employing the same |
| CN102856572A (en) * | 2012-09-05 | 2013-01-02 | 北京斯塔能源科技有限公司 | Glass sealing method for flat plate type solid oxide fuel cell |
| CN103855414A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海硅酸盐研究所 | Preparation method of solid oxide fuel cell seal gasket |
| CN103855414B (en) * | 2012-12-05 | 2016-01-13 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of solid oxide fuel cell seal pad |
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| CN100376046C (en) | 2008-03-19 |
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