CN1300275C - Seal agent of medium-temperature solid oxide fuel cell - Google Patents
Seal agent of medium-temperature solid oxide fuel cell Download PDFInfo
- Publication number
- CN1300275C CN1300275C CNB2004100419280A CN200410041928A CN1300275C CN 1300275 C CN1300275 C CN 1300275C CN B2004100419280 A CNB2004100419280 A CN B2004100419280A CN 200410041928 A CN200410041928 A CN 200410041928A CN 1300275 C CN1300275 C CN 1300275C
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- China
- Prior art keywords
- sealing agent
- present
- temperature
- solid oxide
- oxide fuel
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Glass Compositions (AREA)
Abstract
The present invention relates to a glass and ceramic sealing agent, particularly to a sealing agent of medium-temperature solid oxide fuel cells, which comprises glass powder and a binding agent, wherein the binding agent is a binding agent usually used in the prior art. The present invention is characterized in that the glass powder has a formula: 30 to 60 wt% of SiO2, 0 to 10 wt% of Al2O3, 10 to 40 wt% of B2O3, 5 to 10 wt% of Na2O and 5 to 10 wt% of CaO. In the glass powder of the present invention, high SiO2 content can ensure thermal shock resistance; the addition of the Al2O3 and the CaO enhances the mechanical performance of the sealing agent; high B2O3 content and a small amount of Na2O can greatly reduce the melting temperature of the sealing agent, and the softening temperature is about 700 DEG C; thus, the present invention is especially suitable for being used at medium temperature; meanwhile, owing to low Na2O content in the present invention, favorable electric insulation of the sealing agent can be guaranteed during cell operation; a small amount of free Al2O3 is added to form the glass and ceramic sealing agent, and thus, the resistance is further increased; as a result, the present invention has an insulating effect. The sealing agent has the advantages of simple raw materials, convenient manufacture and low cost is suitable for the sealing use of medium-temperature solid oxide fuel cell groups.
Description
Technical field
The present invention relates to the glass to ceramic seal agent, particularly the sealing agent of intermediate temperature solid oxide fuel cell.
Background technology
Solid Oxide Fuel Cell (SOFC) is a kind of all solid state fuel cell, and it combines by two porous ceramic electrodes with between interelectrode solid oxide electrolyte usually.Oxygen obtains electronics at negative electrode and forms oxonium ion, and reacting to anode and fuel through electrolyte diffusion generates electronics, H
2O and CO
2, electronics is got back to negative electrode again through external circuit.The fuel of Solid Oxide Fuel Cell is generally hydrogen, methane, Sweet natural gas etc., and oxygenant is an air, and fuel and air flow in passage separately.Electro-chemical conversion occurs near the triple-phase region, and fuel and air generation electrochemical reaction produce dc electric power output.In the application of actual monocell and battery pile, in order to prevent that oxygen and fuel gas from directly contacting battery efficiency is reduced, and even the danger that sets off an explosion, fuel gas and oxic gas (air) are completely cut off fully open.That is to say, must the different piece of monocell or battery pile be sealed.Sealing method of the prior art mainly contains compression seal and sealing agent two classes.Compression seal easily produces stress concentration, and the height of battery pile and the number of plies are restricted, and therefore adopts sealing agent to realize sealing at present mostly.Sealing agent generally should have suitable softening temperature and temperature of fusion, and according to the difference of service temperature, fuel cell can be divided into low temperature, middle gentle high-temperature fuel cell.This just requires the softening temperature of sealing agent and temperature of fusion to adapt with it.For service temperature is the 600-800 ℃ of intermediate temperature solid oxide fuel cell in the scope, and when using under service temperature and room temperature, sealing agent must have good thermostability and chemical stability and excellent electric insulating etc.; Require the various piece of it and battery that good thermal expansion matching is all arranged simultaneously, general thermal expansivity is 9-15 * 10
-6/ ℃.
A kind of sealing glass compositions is disclosed in the Chinese patent application 91101165, comprising 18-70wt% plumbous oxide, 18-60wt% vanadium oxide, 1-10wt% phosphorus oxide, 0-30wt% bismuth oxide, at least a oxide compound and the 0.5-5wt% niobium oxides that is selected from weisspiessglanz and selenium oxide of 1-15wt%.The sealing agent can only be issued to gratifying cohesive strength in the sintering temperature that is lower than 400 ℃, because of its use temperature is too low, is unsuitable for intermediate temperature solid oxide fuel cell.Disclose a kind of ceramic high temperature sealing adhering method in the Chinese patent application 96115217, it adopts weight ratio is (0.1-0.3) K
2O: (0.1-0.3) Na
2O: (0.2-0.5) PbO
2: (0.2-0.5) CaO: (0.2-0.5) Al
2O
3: (2.0-2.3) SiO
2Proportioning carry out synthetic glaze, temperature 800-1300 ℃, contain under the atmosphere that oxygen is 4-25% roast make carry out between pottery, porous ceramics or combination bonding.It is suitable for high temperature solid oxide fuel cell.Carry out bonding between pottery or combination.It is suitable for high temperature solid oxide fuel cell.
Disclosed among the EP0982274A2 is the glass-sealing agent that is used for intermediate temperature solid oxide fuel cell, and its two assembly side is as follows: (1) 55-65wt%SiO
2, 0-3wt%Al
2O
3, 0-4wt%Li2O, 6-12wt%K
2O, 2-8wt%Na
2O, 0-5wt%BaO, 0-6wt%ZrO
2, 15-20wt%ZnO, 0-5wt%TiO
2(2) 50-70wt%SiO
2, 0-5wt%Al
2O
3, 0-6wt%Li
2O, 5-15wt%K
2O, 2-10wt%Na
2O, 0-10wt%BaO, 0-10wt%ZrO
2, 10-25wt%ZnO, 0-5wt%TiO
2From its prescription, they have mainly adopted the zinc silicon alkali glass mixture of high yield strength or high expansion coefficient.Because it contains a large amount of alkalimetal oxides, therefore can not guarantee that good electrical isolation is arranged when battery-operated.
Also disclose a kind of sealing agent that is used for intermediate temperature solid oxide fuel cell among the US6271158, it makes matrix by the 40-90wt% frit, and filler is chosen from metallic substance and stupalith in the sealing agent, accounts for 10-60wt%, and sealing agent can seal the slit of 3mm.Glass transition temp is 500-800 ℃, and thermal expansivity is 8-13 * 10
-6/ ℃.The frit main component is: 50-70wt%SiO
2, 10-25wt%ZnO, 5-20wt%K
2O, 0-15wt%Na
2O, 0-8wt%Li
2O, 0-8wt%BaO, 0-5wt%ZrO
2, 0-3wt%CaO, 0-2wt%MgO.The filler main component is: 12-77wt%Ni, 3-65wt%Fe, 16-23wt%Cr, 0-15wt%W, 0-6wt%Co, 0-5wt%Al etc.Also contain a large amount of alkalimetal oxides in the sealing agent, and filler also is all-metal material, so it can produce electronic conduction when using equally, fully electrical isolation.
Summary of the invention
The objective of the invention is to,, provide the sealing agent of the intermediate temperature solid oxide fuel cell that a kind of resistivity is big, insulation effect is good at the deficiencies in the prior art.
Purpose of the present invention realizes in the following manner.
The sealing agent of intermediate temperature solid oxide fuel cell of the present invention comprises glass powder and cakingagent, and described cakingagent is cakingagent, for example water or Na commonly used in the prior art
2SiO
39H
2O (0-10wt%) or (0-10wt%) Al
2O
3Deng, it is characterized in that the prescription of described glass powder is: 30-60wt%SiO
2, 0-10wt%Al
2O
3, 10-40wt%B
2O
3, 5-10wt%Na
2O, 5-10wt%CaO.
The preparation process of described glass powder is: the proportioning according to above-mentioned glass ingredient takes by weighing raw material, mixes the back ball mill mixing, puts into muffle furnace in the Stainless Steel Crucible of packing into, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend becomes glass then, oven dry, and glass powder is worn in crushing.
Use the seal process of this sealing agent to be: (1) element is handled.The stainless steel part sand papering that will seal is cleaned with cotton ball soaked in alcohol, and cleans ceramic surface; (2) get in a certain amount of glass powder and to add furnishing pasty state behind the cakingagent mixed grinding, and select the usage quantity of different cakingagents according to different use occasions, with the required denseness that obtains sticking with paste, described cakingagent is water or Na
2SiO
39H
2O (0-10wt%) or (0-10wt%) Al
2O
3Deng; (3) sealing agent with pasty state evenly is coated on sealing place, dries in the shade 24 hours after making it tight.(4) sealing element is risen to 180 ℃ from room temperature with 0.5 ℃/min, insulation 30min; Rise to more than the glass melting point insulation 30min with 1 ℃/min; Reduce to following about 50 ℃ of glass transition temperature with 1 ℃/min again, constant temperature uses.
Compare with the sealing agent of existing Solid Oxide Fuel Cell, in the glass powder of sealing agent of the present invention, a large amount of SiO
2The heat-shock resistance that can guarantee; Al
2O
3Can improve its mechanical property with the adding of CaO; Big content B is arranged
2O
3With minor N a
2O can reduce the temperature of fusion of sealing agent greatly, makes its softening temperature about 700 ℃, and temperature is used down in being particularly suitable for; Simultaneously because Na wherein
2The content of O is lower, can guarantee enough big of when the battery-operated resistance of sealing agent; And can add a spot of Al
2O
3Powder forms glass to ceramic seal, further increases resistance, reaches high insulating effect.
In actual use, sealing agent of the present invention can also be by adjusting B
2O
3And SiO
2Consumption adjust the softening temperature and the temperature of fusion of sealing agent.
The raw material that sealing agent of the present invention adopted is simple, and manufacture craft is simple, and cost is low, is suitable for battery pile and uses.
Embodiment
Embodiment 1
(1) with 30wt%SiO
2, 10wt%Al
2O
3, 40wt%B
2O
3, 10wt%Na
2O, the proportioning of 1Owt%CaO takes by weighing each component, puts into the ball mill ball milling 24 hours after placing ball grinder to mix.
(2) pack into and put into muffle furnace in the Stainless Steel Crucible, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend became glass then, oven dry, and glass powder is worn in crushing.
(3) add entry furnishing pasty state after, in order to sealing stainless steel tube and YSZ ceramic plate.After pressing the seal process operation, rise to 180 ℃ with 0.5 ℃/min, insulation 30min from room temperature; Rise to 730 ℃ and be incubated 30min with 1 ℃/min then; Reduce to 700 ℃ and be incubated 120min with 1 ℃/min again.After testing, sealing agent melts fully, flows, uniform distribution, and all fine bonding with stainless steel and YSZ, it is fine to record resistance to air loss.When being used to seal YSZ ionogen monocell, on one side logical hydrogen, lead to oxygen on one side, recording battery open circuit voltage in the time of 450 ℃ is 1.12v, near theoretical value, this illustrates that its sealing effectiveness and electric insulating effect are all better.
Embodiment 2.
(1) with 45wt%SiO
2, 1wt%Al
2O
3, 38wt%B
2O
3, 8wt%Na
2O, the proportioning of 8wt%CaO takes by weighing each component, puts into the ball mill ball milling 24 hours after placing ball grinder to mix.
(2) pack into and put into muffle furnace in the Stainless Steel Crucible, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend became glass then, oven dry, and glass powder is worn in crushing.
(3) behind the adding cakingagent water furnishing pasty state, in order to sealing stainless steel tube and YSZ ceramic plate.After pressing the seal process operation, rise to 180 ℃ with 0.5 ℃/min, insulation 30min from room temperature; Rise to 750 ℃ with 1 ℃/min, insulation 30min; Reduce to 700 ℃ with 1 ℃/min again, insulation 120min, after testing, sealing agent melts fully, flows, uniform distribution, and is all fine bonding with stainless steel and YSZ.When being used to seal the YSZ monocell, on one side logical hydrogen, lead to oxygen on one side, recording open circuit voltage in the time of 450 ℃ is 1.16v, near theoretical value, this illustrates that its sealing effectiveness and electric insulating effect are all better.
Embodiment 3.
(1) with 60wt%SiO
2, 8wt%Al
2O
3, 12wt%B
2O
3, 10wt%Na
2O, the proportioning of 10wt%CaO takes by weighing each component, puts into the ball mill ball milling 24 hours after placing ball grinder to mix.
(2) pack into and put into muffle furnace in the Stainless Steel Crucible, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend became glass then, oven dry, and glass powder is worn in crushing.
(3) behind the adding cakingagent water furnishing pasty state, in order to sealing stainless steel tube and YSZ ceramic plate.After pressing the seal process operation, rise to 180 ℃ with 0.5 ℃/min, insulation 30min from room temperature; Rise to 800 ℃ with 1 ℃/min, insulation 30min; Reduce to 700 ℃ with 1 ℃/min again, insulation 120min, after testing, sealing agent melts fully, flows, uniform distribution, and is all fine bonding with stainless steel and YSZ.When being used to seal the YSZ monocell, on one side logical hydrogen, lead to oxygen on one side, recording open circuit voltage in the time of 450 ℃ is 1.07v, this illustrates that its sealing effectiveness and electric insulating effect are all better.
Embodiment 4.
(1) with 52wt%SiO
2, 5wt%Al
2O
3, 28wt%B
2O
3, 5wt%Na
2O, the proportioning of 10wt%CaO takes by weighing each component, puts into the ball mill ball milling 24 hours after placing ball grinder to mix.
(2) pack into and put into muffle furnace in the Stainless Steel Crucible, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend became glass then, oven dry, and glass powder is worn in crushing.
(3) behind the adding cakingagent water furnishing pasty state, in order to sealing stainless steel tube and YSZ ceramic plate.After pressing the seal process operation, rise to 180 ℃ with 0.5 ℃/min, insulation 30min from room temperature; Rise to 750 ℃ with 1 ℃/min, insulation 30min; Reduce to 700 ℃ with 1 ℃/min again, insulation 120min, after testing, sealing agent melts fully, flows, uniform distribution, and is all fine bonding with stainless steel and YSZ.When being used to seal the YSZ monocell, on one side logical hydrogen, lead to oxygen on one side, recording open circuit voltage in the time of 450 ℃ is 1.11v, this illustrates that its sealing effectiveness and electric insulating effect are all better.
Embodiment 5.
(1) with 42wt%SiO
2, 8wt%Al
2O
3, 37wt%B
2O
3-, 8wt%Na
2O, the proportioning of 5wt%CaO takes by weighing each component, puts into the ball mill ball milling 24 hours after placing ball grinder to mix.
(2) pack into and put into muffle furnace in the Stainless Steel Crucible, 1000 ℃ (or 900 ℃) insulation 2 hours, shrend became glass then, oven dry, and glass powder is worn in crushing.
(3) behind the adding cakingagent water furnishing pasty state, in order to sealing stainless steel tube and YSZ ceramic plate.After pressing the seal process operation, rise to 180 ℃ with 0.5 ℃/min, insulation 30min from room temperature; Rise to 750 ℃ with 1 ℃/min, insulation 30min; Reduce to 700 ℃ with 1 ℃/min again, insulation 120min, after testing, sealing agent melts fully, flows, uniform distribution, and is all fine bonding with stainless steel and YSZ.When being used to seal the YSZ monocell, on one side logical hydrogen, lead to oxygen on one side, recording open circuit voltage in the time of 450 ℃ is 1.17v, near theoretical value, this illustrates that its sealing effectiveness and electric insulating effect are all better.
Claims (1)
1. the sealing agent of an intermediate temperature solid oxide fuel cell comprises glass powder and cakingagent, and described cakingagent is a cakingagent commonly used in the prior art, it is characterized in that the prescription of described glass powder is: 30-60wt%SiO
2, 0-10wt%Al
2O
3, 10-40wt%B
2O
3, 5-10wt%Na
2O, 5-10wt%CaO.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100419280A CN1300275C (en) | 2004-09-06 | 2004-09-06 | Seal agent of medium-temperature solid oxide fuel cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2004100419280A CN1300275C (en) | 2004-09-06 | 2004-09-06 | Seal agent of medium-temperature solid oxide fuel cell |
Publications (2)
Publication Number | Publication Date |
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CN1746252A CN1746252A (en) | 2006-03-15 |
CN1300275C true CN1300275C (en) | 2007-02-14 |
Family
ID=36165972
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CNB2004100419280A Expired - Fee Related CN1300275C (en) | 2004-09-06 | 2004-09-06 | Seal agent of medium-temperature solid oxide fuel cell |
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Cited By (1)
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CN100448066C (en) * | 2007-06-20 | 2008-12-31 | 华中科技大学 | A sealing material of solid oxide fuel cell and its sealing method |
CN101577318B (en) * | 2008-05-05 | 2012-05-30 | 中国科学院宁波材料技术与工程研究所 | Making method of sealing material for cell stack sealing structure |
CN101777662B (en) * | 2009-01-08 | 2012-02-22 | 中国科学院宁波材料技术与工程研究所 | Cell stack device of flat solid oxide fuel cell |
CN102713012B (en) * | 2009-10-06 | 2016-02-10 | 托普索公司 | For the sealing glass that solid oxide electrolysis cell (SOEC) is piled |
FR2958283B1 (en) * | 2010-04-01 | 2014-07-04 | Commissariat Energie Atomique | VITROCERAMIC GLASS COMPOSITIONS FOR JOINTS OF APPLIANCES OPERATING AT HIGH TEMPERATURES AND METHOD OF ASSEMBLY USING SAME. |
CN103443978A (en) * | 2011-03-24 | 2013-12-11 | 株式会社村田制作所 | Bonding material for solid oxide fuel cell, solid oxide fuel cell and solid oxide fuel cell module |
CN102244214A (en) * | 2011-06-09 | 2011-11-16 | 中国华能集团清洁能源技术研究院有限公司 | Sealing material of molten carbonate fuel cell and preparation method thereof |
CN103137985B (en) * | 2013-03-19 | 2015-11-25 | 中国科学院宁波材料技术与工程研究所 | The sealing and connecting device of plate type solid-oxide fuel battery pile |
KR20170032856A (en) * | 2015-09-15 | 2017-03-23 | 주식회사 엘지화학 | Composition for solid oxide fuel cell sealant, sealant using the same and method for manufacturing the same |
CN116218298B (en) * | 2022-12-29 | 2024-05-07 | 上海交通大学 | Seal coating and sealing method for solid oxide fuel cell stack |
Citations (5)
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---|---|---|---|---|
US4405722A (en) * | 1979-01-23 | 1983-09-20 | Asahi Glass Company Ltd. | Sealing glass compositions |
JPS609085A (en) * | 1983-06-29 | 1985-01-18 | 株式会社日立製作所 | Ceramic heater |
CN1007276B (en) * | 1987-02-27 | 1990-03-21 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Walking ballast-tamping and track-lifting machine, especially suitable for operating at switch and crossing area |
CN1214355A (en) * | 1997-10-14 | 1999-04-21 | 旭硝子株式会社 | Hermetic sealing composition |
CN1284528A (en) * | 1999-08-13 | 2001-02-21 | 旭硝子株式会社 | Sealing composition |
-
2004
- 2004-09-06 CN CNB2004100419280A patent/CN1300275C/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4405722A (en) * | 1979-01-23 | 1983-09-20 | Asahi Glass Company Ltd. | Sealing glass compositions |
JPS609085A (en) * | 1983-06-29 | 1985-01-18 | 株式会社日立製作所 | Ceramic heater |
CN1007276B (en) * | 1987-02-27 | 1990-03-21 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Walking ballast-tamping and track-lifting machine, especially suitable for operating at switch and crossing area |
CN1214355A (en) * | 1997-10-14 | 1999-04-21 | 旭硝子株式会社 | Hermetic sealing composition |
CN1284528A (en) * | 1999-08-13 | 2001-02-21 | 旭硝子株式会社 | Sealing composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104733657A (en) * | 2015-03-31 | 2015-06-24 | 昆山艾可芬能源科技有限公司 | Sealing material for solid oxide fuel battery stack |
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