CN109841868A - A kind of solid oxide fuel cell compound seal agent and its application - Google Patents
A kind of solid oxide fuel cell compound seal agent and its application Download PDFInfo
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- CN109841868A CN109841868A CN201711203638.5A CN201711203638A CN109841868A CN 109841868 A CN109841868 A CN 109841868A CN 201711203638 A CN201711203638 A CN 201711203638A CN 109841868 A CN109841868 A CN 109841868A
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- fuel cell
- compound seal
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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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Abstract
The invention discloses a kind of solid oxide fuel cell compound seal agent, include solid glass component and liquid glass component, and wherein solid glass components by weight is 50%-80%, and liquid glass components by weight is 20%-50%.The solid glass component is with SiO2To form body, and contain one or more kinds of alkali metal element and alkali earth metal as modifying agent；The liquid glass group is divided into the aqueous solution of glass, and the glass for being used to prepare liquid glass component is with SiO2To form body, and contain one or more kinds of alkali metal element and alkali earth metal.Solid oxide fuel cell compound seal agent of the invention is applied between cell of fuel cell and battery pile other component, has the advantages that good seal, adhesive strength are high.The sealant with higher-density and intensity can be formed after compound seal agent is dry, pressure sintering is not necessarily to, is particularly suitable for the sealing of tubular solid oxide fuel cells.
Description
Technical field
The present invention relates to solid oxide fuel cell more particularly to a kind of compound seals of solid oxide fuel cell
Agent and its application.
Background technique
Solid oxide fuel cell (SOFC) is that a kind of chemical energy by fuel is cleanly and efficiently converted into electricity
The power generator of energy has many advantages, such as to adapt to pluralities of fuel gas extensively and UTILIZATION OF VESIDUAL HEAT IN value is high.SOFC can be provided
One module close to terminal user solves high energy consumption in electric energy transmission process and the problems such as noise, can be applicable to mobile electricity
The fields such as source, distributed generation, embedded power generator and symbiosis power generation, are particularly suitable for important government and military affairs portion
Door.
SOFC is broadly divided into two class of template and cast at present.Wherein template SOFC battery pile be by template battery unit and
Sheet bipolar plate stack is formed, and in order to which anodic gas and cathode gas is isolated, is needed between template battery unit and sheet bipolar plates
Being fully sealed under the conditions of SOFC hot operation is realized, to the thermal expansion matching of sealing material, thermal stability, chemical stability
Equal requirements are very high.Currently, template SOFC battery pile mainly uses the silica glass using alkali and alkaline earth metal ions as modifying agent
Or Pyrex are as sealing material.The CaO-Al as disclosed in patent CN1494176A2O3-B2O3-SiO2Glass, patent
SiO disclosed in CN1746252A2-Al2O3-B2O3-Na2O-CaO glass, BaO-CaO-Al disclosed in patent CN1660954A2O3-
La2O3-B2O3-SiO2Glass, CaO-MgO-B disclosed in patent CN14699497A2O3-SiO2Glass etc..Glass powder or glass
Glass fiber and organic solvent, adhesive are mixed to form glazing compound, are coated on the position for needing to seal, are then heated to sealing
Temperature realizes bonding and sealing.In order to improve the mechanical strength and thermal expansion matching of glass sealing material, above-mentioned glazing compound
In can also add a certain proportion of solid ceramic powder or dystectic glass powder as bone photo, such as patent
CN1884423A, patent 101079476A, glass-sealing agent disclosed in patent CN103570372A and CN106277794A.Generally
In the case of, the seal temperature of SOFC is higher than the softening temperature of glass but lower than glass melting.Glass is viscoelastic body when sealing, because
Need to apply certain pressure in this seal process to promote the flowing and extension of glass, to guarantee sealing effect.
Compared with template SOFC, the cast SOFC sealing structure for stationary electric power plant power supply is relatively easy, general using not
Sealing or endless hermetically sealed technical solution, such as Siemens-Westinghouse Electric cast SOFC battery pile just use not exclusively
Sealing structure (US2002/0110716A1).It is often right in order to meet mobile needs for middle-size and small-size mobile power station or power supply
Sealing has higher requirement.The sealing of cast SOFC battery at present mainly uses inorganic adhesive (silicate adhesive, phosphoric acid
Salt adhesive etc.) etc. be sealed.Inorganic adhesive adhesion strength with higher, however be used to be difficult to when SOFC cell sealing
Meet seal request: on the one hand, porous structure can be showed on microcosmic after inorganic adhesive solidification；On the other hand due to inorganic
The thermal expansion coefficient of adhesive is far below battery material, and the thermal stress in heating and cooling process will lead to sealant removing and either exist
Sealant underbead crack.The reaction gas of anode and cathode two sides can pass through porous sealant or crackle, not only reduce battery
Open-circuit voltage such as also results in the failure of pile or catches fire, explodes at the contingencies when serious.
With inorganic adhesive ratio, SOFC glass sealing material thermal expansion matching and with good sealing performance, however by
Glass is in viscoelastic state when sealing, and needing to pressurize promotes glass extension to realize sealing.In tubular cells, it is difficult to realize this
Pressurization limits glass sealing material and applies in cast SOFC battery pile.
Summary of the invention
The purpose of the present invention is to provide a kind of glass-sealing agent without pressurization, with realize cast SOFC or other
The excellent sealing of type SOFC battery.
Solid oxide fuel cell compound seal agent of the invention, include solid glass component and liquid glass component,
The solid glass component is with SiO2To form body, and contain one or more kinds of alkali metal element and/or alkaline-earth metal
Element is as modifying agent；The liquid glass group is divided into the basic aqueous solution of glass, used to be used to prepare liquid glass component
Glass with SiO2To form body, and contain one or more kinds of alkali metal element and/or alkali earth metal.
Described to be used in solid glass component and liquid glass component, the alkali metal element as modifying agent includes K or Na
One or both of, the alkali earth metal as modifying agent includes one or more of Mg, Ca, Sr or Ba.Institute
Stating solid glass component includes glass intermediate and glass modifier, and the glass intermediate is Al2O3, in solid glass group
Mass percentage in point is 1-10%.The glass modifier is one or more of rare earth oxide.Pass through
Modifying agent and intermediates content are controlled, controls the thermal expansion coefficient of solid glass component between 9.0-12.0, it is close to realize
Good thermal expansion matching between closure material and battery.It is viscous that other adjustment glass can also be added in glass according to actual needs
The additive of the physical characteristics such as degree, mobility, glass transition temperature.
The liquid glass group is divided into the basic aqueous solution of glass, passes through the alkalinity of initial glass and K, Na, Ba or Sr
The reaction of solution obtains；The initial glass glass is with SiO2To form body, and contain one or more kinds of alkali metal elements
And/or alkali earth metal is as modifying agent.
In the compound seal agent of the solid oxide fuel cell, as liquid glass component ratio increases, compound glass
The mobility of glass sealant is more excellent, but sealing intensity and high-temperature stability can a degree of decline, in actual use
The viscosity and mobility that can according to need are adjusted.Solid glass in technical solution of the present invention, in compound seal agent
The optimization weight ratio of component is 50%-80%, and the optimization weight ratio of liquid glass component is 20%-50%.Within this range, glass
Glass sealant can realize good sealing effect, be able to satisfy general SOFC sealing and intensity requirement.
In the compound seal agent of the solid oxide fuel cell, the solid glass component contains one or two
Above solid phase glass powder or fiber.When solid glass component contains two or more solid phase glass powder and fiber
When, the mean thermal expansion coefficients of two kinds of glass should be 9.0-12.0 × 10-6Between/K.
In the compound seal agent of the solid oxide fuel cell of any of the above-described, can be used for SOFC cell of fuel cell and
Sealing bonding in pile between other component.In specific application, compound seal agent of the invention can use different
Technical solution forms sealant.The solid glass component of scheme one, the compound seal agent is uniformly mixed with liquid glass component
Afterwards, it is directly coated at and needs between the solid oxide fuel cell unit sealed and battery pile other component, formed after dry
Glass seal layer.Scheme two, in the be scattered in organic solution of solid glass component of the compound seal agent, be coated on need it is close
Between the solid oxide fuel cell unit and battery pile other component of envelope, pre-burning is carried out at 400-800 DEG C after dry and is obtained
Obtain porous glass skeleton；Liquid glass component is filled in the hole of the porous glass skeleton, forms glass after dry
Sealant.Liquid glass component after drying forms glass gels around solid glass component, ensure that the airtight of sealant
Property.When SOFC pile is increased to running temperature, the glass gels and solid glass component formed after dry are in viscoelastic state,
And it merges and to form uniform glass seal layer.In order to further increase the intensity of sealant in assembling process, need to seal consolidates
After oxide body cell of fuel cell and battery pile other component are bonded and are sealed using the compound seal agent, after dry
Heat at 600-900 DEG C, the battery unit and other component after heat treatment are placed in battery pile again to be assembled.
Compound seal agent of the invention can be applied to the Leakless sealing between SOFC battery unit and other component, have
The high advantage of good seal, adhesive strength.It can be formed after compound seal agent is sufficiently dry with higher-density and intensity
Sealant is not necessarily to pressure sintering, is particularly suitable for the sealing of tubular solid oxide fuel cells.
Detailed description of the invention
Fig. 1 is the composition schematic diagram of solid oxide fuel cell compound seal agent of the present invention.
A1 in figure, A2 represent solid glass component, and B represents liquid glass component
Fig. 2 is the stereoscan photograph after compound seal agent of the present invention is sealed and heated.
Fig. 3 is the schematic diagram that compound seal agent of the present invention is applied to the sealing of tubular cells unit.
1 represents the solid oxide fuel cell unit for needing to seal in figure, and 2 represent metal termination, and 3 represent glass capsulation
Layer
Fig. 4 is compared using the battery performance of compound seal agent of the present invention and the sealing of Conventional Portland adhesive.
Specific embodiment
The present invention can be there are many embodiment, and as shown in the figure and following specific descriptions is some embodiment party of the invention
Formula and embodiment are not to limit the present invention.
Embodiment 1
Tubular solid oxide fuel cells compound seal agent, including solid glass component (as shown in figure 1 shown in A1 and A2)
With liquid glass component (as shown in figure 1 shown in B).
In the present embodiment, solid glass component A1 is SrO-Al2O3-SiO2Glass powder.A2 is SrO-K2O-Al2O3-
SiO2Glass powder.Glass preparation uses traditional fusion method.The oxide raw material mixed in proportion melts at 1300-1500 DEG C
Quenching obtains glass frit after system, obtains glass powder after drying is broken.Liquid glass component B is that the glass containing Sr, K is water-soluble
Liquid heats pressurized hydrolysis by silicate glass and obtains in the alkaline solution containing Sr and K.
In the present embodiment, the weight ratio of solid glass component is 80%, and the weight ratio of liquid glass component is 20%.Solid-state
It is spread evenly across the position for needing to seal after glass ingredient and the mixing of liquid glass component, dries 12h or more at room temperature, at room temperature
Dry 12-18h, carries out heat-agglomerating processing at 900 DEG C.In order to accelerate rate of drying, 4-6h can also be dried at 60 DEG C.
Fig. 2 is the stereoscan photograph of sealant after heat treatment, it can be seen that after compound seal agent is used for sealing-in, sealing
The reacted formation of two kinds of components integrally, can be obtained fine and close sealant under the air-proof condition that pressure is not added in agent.
Embodiment 2
Difference from Example 1 is that the solid glass group of compound seal agent is divided into BaO-Al2O3-SiO2Glass powder
End, liquid glass group are divided into the silicate glass aqueous solution containing Na, Ba.In the present embodiment, the weight ratio of solid glass component
It is 50%, the weight ratio of liquid glass component is 50%.It is uniformly distributed on foot after solid glass component and the mixing of liquid glass component
Heated at 600 DEG C sufficiently after drying at the position for needing to seal.
Embodiment 3
Difference from Example 2 is that the solid glass group of compound seal agent is divided into BaO-Al2O3-SiO2Glass powder
With the mixture of fiber.The mixture of the glass powder and fiber is scattered in the organic solution of PVB, is coated on and is needed to seal
Solid oxide fuel cell unit 1 and metal termination 2 between (as shown in Figure 3), carry out pre-burning at 800 DEG C after dry and obtain
Porous glass skeleton is obtained, then liquid glass component is filled in formation glass seal layer 3 in the hole of glass skeleton, it is dry
After use.
Fig. 4 is using the tubular cells performance after compound seal agent sealing of the invention.With use Conventional Portland gluing
The battery of agent (high-temp glue) sealing is compared, and since sealing performance is promoted, the open circuit potential and power density of battery are significantly improved.
Claims (9)
1. a kind of solid oxide fuel cell compound seal agent, it is characterised in that:
The solid oxide fuel cell compound seal agent includes solid glass component and liquid glass component；
The solid glass component is with SiO2To form body, and contain one or more kinds of alkali metal element and/or alkaline earth gold
Belong to element as modifying agent；
The liquid glass group is divided into the aqueous solution of glass, and the glass for being used to prepare liquid glass component is with SiO2For shape
Adult, and contain one or more kinds of alkali metal element and/or alkali earth metal.
2. compound seal agent according to claim 1, it is characterised in that: the weight ratio of the solid glass component is
50%-80%, the weight ratio of the liquid glass component are 20%-50%.
3. compound seal agent according to claim 1, it is characterised in that: the solid glass component contains one or two
Above solid phase glass powder and/or fiber.
4. compound seal agent according to claim 1, it is characterised in that: in the solid glass component modification agent, alkali gold
Belonging to element includes one or both of K or Na, and alkali earth metal includes one or more of Mg, Ca, Sr or Ba.
5. compound seal agent according to claim 1, it is characterised in that: the solid glass component includes Al2O3As glass
The intermediate of glass, the mass percentage in solid glass component are 1-10%.
6. compound seal agent according to claim 1, it is characterised in that: be divided into the alkali of glass for the liquid glass group
Property aqueous solution reacts acquisition by initial glass and the alkaline solution of K, Na, Ba or Sr；The initial glass glass is with SiO2
To form body, and contain one or more kinds of alkali metal element and/or alkali earth metal as modifying agent.
7. a kind of a kind of application of solid oxide fuel cell compound seal agent described in claim 1, it is characterised in that: institute
It states solid glass component and liquid glass component after evenly mixing, is coated on the solid oxide fuel cell unit for needing to seal
Between battery pile other component, glass seal layer is formed after dry.
8. a kind of a kind of application of solid oxide fuel cell compound seal agent described in claim 1, it is characterised in that: institute
Solid glass component is stated to be scattered in organic or inorganic solution, be coated on need the solid oxide fuel cell unit that seals and
Between battery pile other component, pre-burning is carried out at 400-800 DEG C after dry and obtains porous glass skeleton；Liquid glass component
It is filled in the hole of the porous glass skeleton, forms glass seal layer after dry.
9. a kind of application of any one of claim 7-8 compound seal agent, it is characterised in that: the solid oxidation for needing to seal
After object cell of fuel cell and battery pile other component are bonded and are sealed using the compound seal agent, at 600-900 DEG C
Lower heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711203638.5A CN109841868B (en) | 2017-11-27 | 2017-11-27 | Solid oxide fuel cell composite sealant and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711203638.5A CN109841868B (en) | 2017-11-27 | 2017-11-27 | Solid oxide fuel cell composite sealant and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109841868A true CN109841868A (en) | 2019-06-04 |
| CN109841868B CN109841868B (en) | 2021-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711203638.5A Active CN109841868B (en) | 2017-11-27 | 2017-11-27 | Solid oxide fuel cell composite sealant and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063867A (en) * | 2022-12-28 | 2023-05-05 | 中国科学院青岛生物能源与过程研究所 | Wide-temperature-range composite sealing material and application thereof |
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| JP2001319670A (en) * | 2000-05-11 | 2001-11-16 | Mitsubishi Heavy Ind Ltd | Cell seal structure for fuel cell |
| CN101072676A (en) * | 2004-10-15 | 2007-11-14 | 密苏里大学董事会 | Glass and glass-ceramic sealant compositions |
| KR101457614B1 (en) * | 2013-05-31 | 2014-11-10 | 한국세라믹기술원 | Glass composition for solid oxide fuel cell sealant, sealant and the manufacturing method using the same |
| JP2014220093A (en) * | 2013-05-08 | 2014-11-20 | 日本電信電話株式会社 | Gas seal structure and solid oxide type fuel cell |
| CN106277794A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Glass-glass composite seal and its preparation method and application |
| CN106795038A (en) * | 2014-07-23 | 2017-05-31 | 福莱西投资公司 | Glass coating composition |
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2017
- 2017-11-27 CN CN201711203638.5A patent/CN109841868B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001319670A (en) * | 2000-05-11 | 2001-11-16 | Mitsubishi Heavy Ind Ltd | Cell seal structure for fuel cell |
| CN101072676A (en) * | 2004-10-15 | 2007-11-14 | 密苏里大学董事会 | Glass and glass-ceramic sealant compositions |
| JP2014220093A (en) * | 2013-05-08 | 2014-11-20 | 日本電信電話株式会社 | Gas seal structure and solid oxide type fuel cell |
| KR101457614B1 (en) * | 2013-05-31 | 2014-11-10 | 한국세라믹기술원 | Glass composition for solid oxide fuel cell sealant, sealant and the manufacturing method using the same |
| CN106795038A (en) * | 2014-07-23 | 2017-05-31 | 福莱西投资公司 | Glass coating composition |
| CN106277794A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Glass-glass composite seal and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063867A (en) * | 2022-12-28 | 2023-05-05 | 中国科学院青岛生物能源与过程研究所 | Wide-temperature-range composite sealing material and application thereof |
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| CN109841868B (en) | 2021-06-18 |
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