CN102386345A - Sealing gasket for medium-and-low temperature solid oxide fuel cell, and manufacturing method and application of sealing gasket - Google Patents
Sealing gasket for medium-and-low temperature solid oxide fuel cell, and manufacturing method and application of sealing gasket Download PDFInfo
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- CN102386345A CN102386345A CN2011103588204A CN201110358820A CN102386345A CN 102386345 A CN102386345 A CN 102386345A CN 2011103588204 A CN2011103588204 A CN 2011103588204A CN 201110358820 A CN201110358820 A CN 201110358820A CN 102386345 A CN102386345 A CN 102386345A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a sealing gasket for a medium-and-low temperature solid oxide fuel cell, and a manufacturing method and application of the sealing gasket. The sealing gasket comprises sealing glass powder, a dispersant, a plasticizer, a bonding agent and a solvent, and is characterized in that: the sealing glass powder comprises 28 to 38 mol percent of SiO2, 5 to 15 mol percent of B2O3, 30 to 40 mol percent of BaO, 0 to 10 mol percent of Al2O3, 0 to 5 mol percent of ZrO2, 0 to 16 mol percent of CaO, 0 to 15 mol percent of ZnO, 0 to 0.5 mol percent of NiO, 0 to 0.5 mol percent of Cr2O3 and 0 to 0.5 mol percent of Co2O3. Under the working temperature of the medium-and-low temperature solid oxide fuel cell, the coefficient of thermal expansion of the sealing gasket provided by the invention is slightly changeable in long-term thermal treatment, and is stable in the multiple thermal circulation and long-term running of a galvanic pile.
Description
Technical field
The invention belongs to fuel cell field, relate to the sealing gasket that a kind of fuel cell is used, relate in particular to the sealing gasket that contains the glass for sealing powder that is applicable to intermediate temperature solid oxide fuel cell.
Background technology
Fuel cell is the TRT that is converted into chemical energy electric energy, has characteristics such as energy conversion efficiency height, disposal of pollutants be low, meets the growth requirement of 21 century green energy resource.SOFC (SOFC wherein; Solid Oxide Fuel Cell) adopt ceramic material as electrolyte; Have structure of whole solid state, higher energy conversion efficiency, do not adopt noble metal catalyst; Fuel tolerance wide (can directly use hydrocarbon fuel through inside reforming), environmentally friendly (SO like pluralities of fuel gases such as coal gas, natural gas, gasoline, oil liquefied gas
x, NO
xPollute Deng low, the noiselessness of discharging), can realize outstanding feature such as long-life operation, be the efficient green energy of generally acknowledging, can be applied to power plant, decentralized power supply power supply, stand-by power supply, portable power supply etc.
SOFC has four kinds of structures usually, i.e. tubular type, concatenation type, matrix formula and flat, and advantages such as flat solid oxide fuel cell (pSOFC) is simple with its high power density, preparation technology, low production cost become the primary study object of SOFC.Sealing Technology is the application oriented key challenge of pSOFC, because in case sealing goes wrong, will cause fuel gas and oxic gas to mix or leakage, causes battery operated not normal, more serious also possibility explosion caused, brings hidden danger to safety.Therefore the solution of sealing problem also just directly has influence on the commercialization process of SOFC.
The main effect of sealing (sealing-in) is: 1) isolated fuel gas and oxic gas prevent that fuel is (like H
2, CH
4) in battery pile, mix to keep good air-tightness with oxidant (like air); 2) with parts such as the connecting plate in the pile, the battery formation battery pile that links together; 3) with web edge insulation ground separately, prevent the connecting plate short circuit current.Used seal, sealing materials need battery pile oxidation and reducing atmosphere under work long hours, and also to bear the thermal stress of repeatedly thermal cycle process of battery pile.
Therefore, the seal, sealing materials that requires to be adopted satisfies following requirement: 1) will be mated as much as possible by the thermal coefficient of expansion of seal, sealing materials (CET, Coefficient of Thermal Expansion), with relief of thermal stress with each; 2) have higher thermal stability, want stable for extended periods of time, obvious variation should not take place at battery pile run duration thermal coefficient of expansion; 3) have caking property preferably, and had wettability and stronger adhesion preferably by seal, sealing materials; 4) (oxidation and reducing atmosphere) has higher chemical stability under battery pile operation atmosphere; 5) Yu by the material of sealing-in have the good chemical compatibility, significant chemical reaction does not take place.
The present both at home and abroad research to the SOFC Sealing Technology mainly comprises means of press seals and hard sealing.Hard sealing is meant that encapsulant connects (sealing-in) firmly; The seal, sealing materials that is adopted mainly contains reactive metal material (like brazing, silver slurry etc.), glass, devitrified glass, glass ceramics and two or more carries out compound material etc., like CN1574417A, CN1465647A, CN1929163A, CN1469497A, CN1180493C, CN1599092A, CN1095598C, CN1746252A, CN1660954A etc.Means of press seals mainly adopts the notion of " sealing ring " to realize the sealing of SOFC; The dipping of mica, flexible graphite, fibre and above-mentioned material that the employing pressuring method seals is compound etc., like CN1649186A, CN1454398A, US2005147866-A1, US2005266288-A1, US2005064273-A1 etc.
Glass, devitrified glass class seal, sealing materials, low production cost ripe with its technology of preparing; It is the main research object of SOFC sealing always; The research of said material at present mainly concentrates on the sign of material key property; Like the matched coefficients of thermal expansion situation of encapsulant and adjacent component, chemical stability in oxidation and reducing atmosphere, and with the reactivity at battery and connecting plate interface etc.The research of said material mainly concentrates on the sign of material key property, like the matched coefficients of thermal expansion situation of seal, sealing materials and adjacent component, chemical stability in oxidation and reducing atmosphere, and with the reactivity at battery and connecting plate interface etc.
These researchs have disclosed existing glass base seal, sealing materials and have come with some shortcomings: like the long-term thermal stability of material under serviceability temperature; Promptly, often do not consider the thermal stability of glass-based seal, sealing materials under serviceability temperature, especially when being used for the sealing-in of low temperature SOFC.CN1494176A and CN1469497A disclose employing CaO-Al respectively
2O
3-SiO
2-B
2O
3Microcrystalline glass in series, CaO-MgO-SiO
2-Fe
2O
3The microcrystalline glass in series sealing-in is adopted, and it is applicable to that working temperature is 800～1000 ℃ high temperature SOFC.Yet with regard to middle low temperature SOFC, its working temperature is generally below 800 ℃, yet just in time is that the glass-based seal, sealing materials is prone to the temperature that crystallization and crystalline phase are prone to growth under this temperature.Mention increase in a lot of researchs with temperature retention time; Crystallization constantly takes place in seal, sealing materials; The kind of crystalline phase, quantity, grain size are changing always; Cause material thermal expansion coefficient generation obvious variation, and with pile in adjacent component matching variation, greatly reduce thermal circulation performance and fine and close envelope lost efficacy.
In addition, the implementation method of the encapsulant of mentioning in the prior art adopts coating, brushing, injection etc. more, and these methods are simple and convenient in the enforcement of little sealing area; Like the test of monolithic baby battery, separately and the sealing-in of electrolyte or connecting plate; But when the sealing area increase, when particularly in battery pile, implementing, these methods are used cumbersome; Quality control is difficult to; And sealing-in thickness is uncontrollable, and this can greatly influence the electric current collection of battery pile, brings very serious problem to the success rate of pile assembling and the output of power.
Therefore, in the exploitation under the low temperature SOFC sealing gasket of Heat stability is good and method for sealing be still this area problem demanding prompt solution with low temperature SOFC in being applicable to.
Summary of the invention
In the face of the problems referred to above that prior art exists, first aspect of the present invention provides a kind of intermediate temperature solid oxide fuel cell to use sealing gasket, comprises glass for sealing powder, dispersant, plasticizer, binding agent and solvent; Wherein said glass for sealing powder comprises 28～38mol%SiO by the mole percentage composition
2, 5～15mol%B
2O
3, 30～40mol%BaO, 0～10mol%Al
2O
3, 0～5mol%ZrO
2, 0～16mol%CaO, 0～15mol%ZnO, 0～0.5%mol NiO, 0～0.5mol%Cr
2O
3And 0～0.5mol%Co
2O
3
Sealing gasket of the present invention is applicable to intermediate temperature solid oxide fuel cell, its under the working temperature of intermediate temperature solid oxide fuel cell, in long term thermal is handled thermal coefficient of expansion change little, repeatedly all highly stable in thermal cycle and the long-time running at pile.
In the present invention; In said sealing gasket; The weight percentage of said glass for sealing powder can be 40～60wt%, and the weight percentage of said dispersant can be 0.1～2wt%, and the weight percentage of said plasticizer can be 2～8wt%; The weight percentage of said binding agent can be 2～5wt%, and the weight percentage of said solvent can be 30～50wt%.Said dispersant can comprise polymine and/or triethanolamine.Said plasticizer comprises in dibutyl phthalate, polyvinyl alcohol 200 and the olein one or more.Said binding agent comprises in polyvinyl butyral resin, glycerine, ethyl cellulose, the methylcellulose one or more.Said solvent comprises in butanone, ethanol, cyclohexanone, n-butanol, butyl acetate and the deionized water one or more.
The filler (dispersant, plasticizer, binding agent and solvent) that the present invention adopts is cheap and easy to get, and cost is low, be easy to industrial applications.
In a preferred embodiment, in said glass for sealing powder, said ZrO
2Molar content can be 2～5mol%.Introduce ZrO
2(0～5mol%) can increase the chemical stability of glass, improves and electrolytical compatibility.
In yet another preferred embodiment, in said glass for sealing powder, the molar content of said NiO can be 0.2～0.5mol%, said Cr
2O
3Molar content can be 0.2～0.5mol%, said Co
2O
3Molar content can be 0.2～0.5mol%.Add NiO, the Cr of trace
2O
3, Co
2O
3Can be used to regulate the wettability of encapsulant, the reactivity of reduction and metal, and the crystallization property that improves material.
In the present invention, NiO, the ZrO in the battery material of introducing trace in the glass for sealing powder
2With the Cr in the connecting plate material
2O
3, like this, add the relevant element that possibly react in advance, the effect of inhibition may be arranged the reaction at interface.
In yet another preferred embodiment, in said glass for sealing powder, said Al
2O
3Molar content can be 4～10mol%, the molar content of said ZnO can be 4～15mol%.A small amount of Al that adds
2O
3Can improve the thermal coefficient of expansion of glass, increase thermal stability, add Al in right amount
2O
3But, help stablizing in anode high humidity atmosphere with the resistance to water of ZnO reinforcing glass.
In yet another preferred embodiment, in said glass for sealing powder, the molar content of said CaO can be 12～16mol%.Add CaO and can reduce the glass high temperature viscosity, increase low temperature viscosity, help founding and sealing-in under suitable temperature of glass.
In yet another preferred embodiment, said glass for sealing powder alkali-free metal oxide.Be not contained in conductivity height under the high temperature, can corrode the alkali metal oxide of pile assembly, improved the stability of pile operation.
In the present invention, the mean thermal expansion coefficients of said glass for sealing powder can be 10.4～11.5 * 10
-6/ k.
Glass for sealing powder of the present invention through 550～600 ℃ (preferred 600 ℃) down coring handle 0.5～2 hour (for example 1 hour) and can be 10.5～12 * 10 at 800～850 ℃ (preferred 850 ℃) mean thermal expansion coefficients after crystallization is handled 0.5～2 hour (for example 70 minutes) down
-6/ k, preferred 11.5～11.8 * 10
-6/ k.
The said sealing-in of handling through coring and crystallization with sealing gasket 750 ℃ of following heat treatments after 200 hours, after 2300 hours in the amplitude of variation of its mean thermal expansion coefficients in 6%.The sealing gasket of handling system through preferred coring and crystallization is 750 ℃ of following heat treatments after 100 hours, after 2400 hours in the amplitude of variation of its mean thermal expansion coefficients in 2%.
In the present invention, through the control crystallization, can obtain in the long term thermal processing procedure sealing gasket that the kind of thermal coefficient of expansion, crystalline phase and the sealing-in of grain size stabilized are used.
The glass transition temperature of glass for sealing powder of the present invention can be 580～680 ℃, and the glass softening point temperature can be 630～730 ℃.
The preferred average grain diameter of glass for sealing powder of the present invention is the glass dust about 20 μ m.
On the other hand; The present invention provides a kind of method for preparing above-mentioned intermediate temperature solid oxide fuel cell with sealing gasket; It is characterized in that; Said method comprises: with said glass for sealing powder and dispersant, plasticizer, binding agent and solvent by the proportioning ball mill mixing of regulation evenly, curtain coating, drying, hot pressing, be cut into the sealing gasket of regulation shape.
On the one hand; The present invention provides above-mentioned intermediate temperature solid oxide fuel cell to use with sealing gasket, it is characterized in that, places said intermediate temperature solid oxide fuel cell to need the position of sealing-in on said sealing gasket pad; Be warmed up to 550～600 ℃ of insulations 0.5～2 hour with 2～5 ℃/min; Carry out organic eliminating and coring and handle, be warmed up to 800～850 ℃ of insulations 0.5～2 hour then, carry out sealing-in and crystallization and handle.
Preparation method provided by the invention and application process, simple, with low cost, be fit to large-scale production.And the mean thermal expansion coefficients of the sealing gasket that makes is good with the member matching of the sealing-in of wanting, and Heat stability is good, is fit to be widely used in the sealing of fuel cell, low-temperature solid fuel cell in being particularly useful for.
Description of drawings
Fig. 1 illustrates the example seal pad that is used for sealing-in SOFC of the present invention;
Fig. 2 illustrates the example seal, sealing materials of the SOFC of being used for of the present invention, 750 ℃ of following heat treatments, with the variation of heat treatment time mean thermal expansion coefficients;
Fig. 3 illustrates the example seal, sealing materials of the SOFC of being used for of the present invention, and 750 ℃ of following heat treatments, with the variation of heat treatment time crystalline phase, among the figure, 1 is Ba
1.31Ca
0.69SiO
42 is Ba
1.3Ca
0.7SiO
44 is Ca
5Ba
2B
10O
225 is SiO
2(Quartz Low); 6 is BaAl
2SiO
8
Fig. 4 illustrates the thermal cycle and the medium-term and long-term operation test of the example battery heap that adopts 3 battery pile formation of seal, sealing materials sealing-in of the present invention.
Embodiment
With reference to Figure of description, and combine following execution mode to further specify the present invention, should be understood that Figure of description and following execution mode only are used to explain the present invention, and unrestricted the present invention.
Seal, sealing materials provided by the invention is with BaO, B
2O
3, SiO
2Be nucleus, can obtain thermal coefficient of expansion and target, be suitable for the sealing-in thermal coefficient of expansion 10～12.5 * 10 near reaching the suitable material of viscosity
-6Material between the/k is like (YSZ) electrolyte of cubic zirconia among the SOFC and metallic interconnect materials.
SiO wherein
2Be that main glass in the glass forms agent, its molar content can be 28～38mol%, and it can also reinforcing glass and intermetallic bond strength except that thermal stability that can reinforcing glass, chemical stability, the raising air-tightness.
B
2O
3Molar content can be 5～15mol%, its adds can regulate glass viscosity, and and SiO
2Improve the stability of glass together as the network organizator of glass, in addition B
2O
3As surface reactive material, can significantly reduce the surface tension of glass, help glass and sprawl in the infiltration of metal surface.
The BaO molar content can be 30～40mol%, is used for improving the thermal coefficient of expansion of glass, because Ba
2+Ionic radius bigger, activity is relatively poor in the glass network structure, this will greatly increase resistivity, can make glass have the excellent electric insulating ability.
A small amount of Al that adds
2O
3(0～10mol%) can improve the thermal coefficient of expansion of glass, increases thermal stability, adds Al in right amount
2O
3And ZnO (but the resistance to water of 0～15mol%) reinforcing glass helps stable in anode high humidity atmosphere; (0～16mol%) can reduce the glass high temperature viscosity to CaO, increases low temperature viscosity, helps founding and sealing-in under suitable temperature of glass; Introduce ZrO
2(0～5mol%) can increase the chemical stability of glass, improves and electrolytical compatibility; And add trace NiO (0～0.5mol%), Cr
2O
3(0～0.5mol%), Co
2O
3(0～0.5mol%) can be used to regulate the wettability of encapsulant, the reactivity of reduction and metal, and the crystallization property that improves material.
In the present invention, NiO, the ZrO in the battery material of introducing trace in seal, sealing materials
2With the Cr in the connecting plate material
2O
3, like this, add the relevant element that possibly react in advance, the effect of inhibition may be arranged the reaction at interface.In addition, seal, sealing materials is not contained in conductivity height under the high temperature, can corrode the alkali metal oxide of pile assembly, has improved the stability of pile.
Seal, sealing materials of the present invention can have various forms, and for example bulk, sheet, graininess or Powdered are perhaps processed specific annular, square, bar shaped etc., are preferably glass dust, are used to prepare sealing-in base substrate (sealing gasket).
Above-mentioned seal, sealing materials and and dispersant, plasticizer, binding agent and solvent be by certain proportioning, ball mill mixing evenly, curtain coating, drying, hot pressing, be cut into the suitable sealing gasket of shape as required.The sealing gasket of preparation places the position that needs sealing-in, carries out sealing-in and crystallization and handles, and can realize sealing-in.Seal, sealing materials is converted into the lower crystallite attitude of activation energy from the higher glassy state of activation energy in the sealing-in process, had higher intensity, and has greatly reduced the diffusion mobility and the interfacial reaction of ion.
Through the control crystallization, can obtain in the long term thermal processing procedure kind of thermal coefficient of expansion, crystalline phase and the seal, sealing materials of grain size stabilized.The seal, sealing materials mean thermal expansion coefficients of process crystallization processing is not 10.4～11.5 * 10
-6Between/the k (room temperature～550 ℃); The seal, sealing materials mean thermal expansion coefficients of process crystallization and thermal treatment is 10.5～12 * 10
-6Between/the k (room temperature～600 ℃); The sample that preferred crystallization is handled system is at 750 ℃, and during the 2500h long-time stability were investigated, mean thermal expansion coefficients was stabilized in 11.5～11.8 * 10
-6Between/the k (room temperature～750 ℃), in pile, can realize repeatedly thermal cycle, operation steady in a long-term.
Below, be that example further specifies the present invention with the preparation of seal, sealing materials, sealing gasket and to the sealing-in of battery pile:
One, the preparation of glass-based seal, sealing materials:
According to each components contents in listed each sample in the following table 1, take by weighing a certain amount of SiO respectively
2, B
2O
3, BaCO
3, Al
2O
3, ZrO
2, CaCO
3, ZnO, NiO, Cr
2O
3And Co
2O
3, carry out sufficient mixing with batch mixer after, powder is put into crucible; Place the high temperature elevator furnace, be heated to 1300～1500 ℃, preferred 1350～1450 ℃; Be incubated 2～4 hours, preferred 1～3 hour, taking-up was poured on the corrosion resistant plate then; Put into Muffle furnace 400～500 ℃ of annealing 0.5～2 hour, obtain block glass, the molar content of each component that it contains is seen and is seen the following form 1.With block glass is broken, grinding, sieving to obtain the glass dust that sealing-in is used.
Table 1: each components contents in the seal, sealing materials (molar content, mol%)
Also can take by weighing a certain amount of SiO respectively according to each components contents in listed each sample in the last table 1
2, B
2O
3, BaCO
3, Al
2O
3, ZrO
2, CaCO
3, ZnO, NiO, Cr
2O
3And Co
2O
3, carry out sufficient mixing with batch mixer after, place the high temperature elevator furnace; Be heated to 1300～1500 ℃, preferred 1350～1450 ℃, be incubated 2～4 hours; Preferred 1～3 hour, directly topple over the stainless steel cask that cold water into is housed again, shrend obtains undersized glass particle; Ball milling sieves then, obtains the subsequent use glass dust of sealing-in, and the particle diameter of glass dust is about 20 μ m.
Two, the mensuration of the fundamental performance parameter of glass-based seal, sealing materials:
The block glass-cutting of the foregoing description 1～9 preparation must be become 5 * 5 * 20mm's is rectangular; With the elevated temperature heat dilatometer in air atmosphere; Thermal expansion curve with the heating rate tested glass of 5 ℃/min; Analyze glass transition temperature (Tg) that data obtain each sample, glass softening point temperature (Tf), mean thermal expansion coefficients (CTE) (room temperature～550 ℃), see the following form 2.
Table 2: the fundamental performance parameter of seal, sealing materials
Can know that referring to last table 2 thermal coefficient of expansion of the seal, sealing materials of the present invention's preparation and the thermal coefficient of expansion of electrolyte in the battery pile and metallic interconnect materials are very approaching.
Three, the preparation of sealing gasket:
(wt%) glass dust and the dispersant of 0.1～2wt%, the plasticizer of 2～8wt%, the binding agent of 2～5wt% and solvent ball milling of 30～50wt% of taking by weighing the above-mentioned preparation of 40～60wt% mixed in 1～3 hour by weight percentage; On casting machine, carry out curtain coating and drying; Hot pressing under 50～100 ℃, the pressure condition of 5～20Mpa is cut into the suitable sealing gasket of size on demand during use then.Following table 3 illustrates each components contents among three embodiment of sealing gasket of this method preparation.
Table 3: The tape casting prepares each components contents (g) in the sealing gasket
| Glass dust | Dispersant | Plasticizer | Binding agent | Solvent | |
| |
50 | 0.5 | 4.2 | 2.5 | 50 |
| |
50 | 0.8 | 7 | 3.6 | 33 |
| Embodiment 12 | 50 | 1.7 | 8.5 | 5 | 45 |
In the present invention, the dispersant of employing can be polymine or triethanolamine; Plasticizer can be in dibutyl phthalate, polyvinyl alcohol 200 and the olein one or more; Binding agent can be in polyvinyl butyral resin, glycerine, ethyl cellulose, the methylcellulose one or more; Solvent can be in butanone, ethanol, cyclohexanone, n-butanol, butyl acetate and the deionized water one or more.
The sealing gasket of embodiment 11 is cut into suitable shape, sees Fig. 1.
Four, the control crystallization of seal, sealing materials and long-term thermal stability test:
With the casting films cutting for preparing, lamination, hot pressing is the rectangular of size 3mm * 5mm * 30mm, places electric tube furnace, heats up with 2～5 ℃/min, and the crystallization system of according to the form below 4 is heat-treated, then with the sample of the embodiment that obtains 13 and 14.
Table 4: the crystallization heat treating regime of seal, sealing materials
The sample of above-mentioned preparation is respectively at 750 ℃ of insulation 0h, 100h, 200h, 500h, 1000h and 2500h, and the mean thermal expansion coefficients of seal, sealing materials and crystalline phase are with the situation of change of heat treatment time behind the investigation control crystallization.Following table 5 is after to be seal, sealing materials through two kinds of crystallization systems shown in the table 4 handle, and its mean thermal expansion coefficients (room temperature～600 ℃) is with the delta data of heat treatment time.
Table 5: the CTE of seal, sealing materials (room temperature～600 ℃) is with the variation of heat treatment time
From last table 5, can find out embodiment 13 samples after heat treatment surpasses 200h, in 2300h afterwards, the thermal coefficient of expansion amplitude of variation is in 6%; And embodiment 14 samples are after heat treatment surpasses 100h, and in 2400h afterwards, the thermal coefficient of expansion amplitude of variation is in 2%, and crystalline phase stable (as shown in Figure 3); Very approaching of the thermal coefficient of expansion of adjacent component in the thermal coefficient of expansion of two embodiment samples and the pile is basically 10.6～12 * 10
-6Between/the k.The sample (embodiment 14) that preferred crystallization heat treating regime obtains is in the 2500h long-time stability are investigated, and mean thermal expansion coefficients remains on 11.5～11.8 * 10
-6Between/the k (room temperature～750 ℃) (as shown in Figure 2), shown that the thermal stability of this seal, sealing materials under the working temperature of middle low temperature SOFC is very good.Above-mentioned data of mentioning and caption this seal, sealing materials be highly suitable for the sealing of SOFC (especially in low temperature SOFC); And the seal, sealing materials behind the process control crystallization is so stable, and moving for the long-term stability of battery pile provides powerful guarantee.
Five, the application of seal, sealing materials in battery pile:
The sealing gasket (for example Fig. 1 illustrates the example seal pad that the sealing-in battery is used) of the above-mentioned preparation of the present invention is placed the position that needs sealing-in; Be warmed up to 550～600 ℃ of insulations 0.5～2 hour with 2～5 ℃/min; Carrying out organic eliminating and coring handles; Be warmed up to 800～850 ℃ of insulations 0.5～2 hour then, carry out sealing-in and crystallization and handle, realize sealing-in.
Adopt above-mentioned seal, sealing materials and method for sealing assembled battery heap, cell stack assembled comprises battery unit, connector and above-mentioned sealing gasket.Between adjacent battery unit and connector, can adopt said method sealing-in sealing gasket to form hermetically-sealed construction.For example; In one embodiment, the connecting plate of SOFC is placed bottom, put one deck sealing gasket of the present invention, battery unit, another layer sealing gasket of the present invention, second connecting plate, sealing gasket, battery unit above that ... by that analogy; Form battery pile structure; Then as above-mentioned organic eliminating and coring processing, sealing-in and the crystallization of carrying out handle, realize sealing-in, obtain the battery pile after the sealing-in.Wherein battery unit also can comprise between the adjacent component of above-mentioned seal, sealing materials in battery unit and forms hermetically-sealed construction, for example between solid electrolyte, negative electrode, anode, connector, adopts said method to form seal.
Six, the thermal cycle of battery pile and medium-term and long-term discharge test:
In one example, the battery pile that adopts said method to assemble 3 100 * 100mm, the battery unit that comprises is for being anode with Ni-YSZ, La
0.7Sr
0.3MnO
3Be negative electrode, effective area is 49cm
2The anode-supported cells unit.
With act as a fuel gas and oxic gas of hydrogen and oxygen this battery pile is carried out the test (referring to Fig. 4) of thermal cycle and medium-term and long-term discharge respectively, these three battery pile thermal cycles 7 times, each open circuit voltage all is stabilized in about 3.25V; Battery pile is carried out about 5A constant-current discharge test 300h after the thermal cycle, voltage is stabilized in about 2.7V always, shows this battery pile in experiencing repeatedly thermal cycle and constant-current discharge test process again, and sealing effectiveness is all very good.
Industrial applicability: the present invention can provide in the long term thermal processing procedure, the kind of thermal coefficient of expansion, crystalline phase and the seal, sealing materials of grain size stabilized, and it can realize repeatedly thermal cycle in pile, operation steady in a long-term.In addition, the preparation method of seal, sealing materials of the present invention and in solid-oxide fuel cell stack application process, simple, can realize producing in batches, and quality controllable, for the reliable sealing-in and the stable operation of battery pile provides sound assurance.
Claims (20)
1. an intermediate temperature solid oxide fuel cell is used sealing gasket, comprises glass for sealing powder, dispersant, plasticizer, binding agent and solvent; It is characterized in that said glass for sealing powder comprises 28～38mol%SiO by the mole percentage composition
2, 5～15mol%B
2O
3, 30～40mol%BaO, 0～10mol%Al
2O
3, 0～5mol%ZrO
2, 0～16mol%CaO, 0～15mol%ZnO, 0～0.5%mol NiO, 0～0.5mol%Cr
2O
3And 0～0.5mol%Co
2O
3
2. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket; It is characterized in that; The weight percentage of said glass for sealing powder is 40～60wt%, and the weight percentage of said dispersant is 0.1～2wt%, and the weight percentage of said plasticizer is 2～8wt%; The weight percentage of said binding agent is 2～5wt%, and the weight percentage of said solvent is 30～50wt%.
3. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, said dispersant comprises polymine and/or triethanolamine.
4. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, said plasticizer comprises in dibutyl phthalate, polyvinyl alcohol 200 and the olein one or more.
5. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, said binding agent comprises in polyvinyl butyral resin, glycerine, ethyl cellulose, the methylcellulose one or more.
6. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, said solvent comprises in butanone, ethanol, cyclohexanone, n-butanol, butyl acetate and the deionized water one or more.
7. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that said ZrO
2Molar content be 2～5mol%.
8. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, the molar content of said NiO is 0.2～0.5mol%, said Cr
2O
3Molar content be 0.2～0.5mol%, said Co
2O
3Molar content be 0.2～0.5mol%.
9. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that said Al
2O
3Molar content be 4～10mol%, the molar content of said ZnO is 4～15mol%.
10. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, the molar content of said CaO is 12～16mol%.
11. intermediate temperature solid oxide fuel cell according to claim 1 is used sealing gasket, it is characterized in that, said glass for sealing powder alkali-free metal oxide.
12. use sealing gasket, it is characterized in that the mean thermal expansion coefficients of said glass for sealing powder is 10.4～11.5 * 10 according to each described intermediate temperature solid oxide fuel cell in the claim 1～11
-6/ k.
13. intermediate temperature solid oxide fuel cell according to claim 12 is used sealing gasket; It is characterized in that said glass for sealing powder is 10.5～12 * 10 through handling the mean thermal expansion coefficients that reached in 0.5～2 hour after 800～850 ℃ of following crystallization are handled 0.5～2 hour 550～600 ℃ of following coring
-6/ k.
14. intermediate temperature solid oxide fuel cell according to claim 13 is used sealing gasket; It is characterized in that; Said glass for sealing powder is 750 ℃ of following heat treatments after 200 hours, after 2300 hours in the amplitude of variation of its mean thermal expansion coefficients in 6%.
15. intermediate temperature solid oxide fuel cell according to claim 13 is used sealing gasket; It is characterized in that said glass for sealing powder is 11.5～11.8 * 10 through handling the mean thermal expansion coefficients that reached in 1 hour after 850 ℃ of following crystallization are handled 70 minutes 600 ℃ of following coring
-6/ k.
16. intermediate temperature solid oxide fuel cell according to claim 15 is used sealing gasket; It is characterized in that; Said glass for sealing powder is 750 ℃ of following heat treatments after 100 hours, after 2400 hours in the amplitude of variation of its mean thermal expansion coefficients in 2%.
17. use sealing gasket according to each described intermediate temperature solid oxide fuel cell in the claim 1～11, it is characterized in that the glass transition temperature of said glass for sealing powder is 580～680 ℃, the glass softening point temperature is 630～730 ℃.
18. use sealing gasket, it is characterized in that the average grain diameter of said glass for sealing powder is 20 μ m according to the described intermediate temperature solid oxide fuel cell of claim 1～11.
19. one kind prepares in the aforesaid right requirement 1～18 each described intermediate temperature solid oxide fuel cell with the method for sealing gasket; It is characterized in that; Said method comprises: with said glass for sealing powder and dispersant, plasticizer, binding agent and solvent by the proportioning ball mill mixing of regulation evenly, curtain coating, drying, hot pressing, be cut into the sealing gasket of regulation shape.
20. an aforesaid right requires in 1～18 each described intermediate temperature solid oxide fuel cell with the application of sealing gasket; It is characterized in that; Place said intermediate temperature solid oxide fuel cell to need the position of sealing-in on said sealing gasket pad, be warmed up to 550～600 ℃ of insulations 0.5～2 hour, carry out organic eliminating and coring and handle with 2～5 ℃/min; Be warmed up to 800～850 ℃ of insulations 0.5～2 hour then, carry out sealing-in and crystallization and handle.
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| CN2011103588204A CN102386345B (en) | 2011-11-14 | 2011-11-14 | Sealing gasket for medium-and-low temperature solid oxide fuel cell, and manufacturing method and application of sealing gasket |
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