CN102386345B - 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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- CN102386345B CN102386345B CN2011103588204A CN201110358820A CN102386345B CN 102386345 B CN102386345 B CN 102386345B CN 2011103588204 A CN2011103588204 A CN 2011103588204A CN 201110358820 A CN201110358820 A CN 201110358820A CN 102386345 B CN102386345 B CN 102386345B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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 sealing gasket that contains the glass for sealing powder that is applicable to intermediate temperature solid oxide fuel cell and its preparation method and application.
Background technology
Fuel cell is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that chemical energy is converted into electric energy, has the characteristics such as energy conversion efficiency is high, disposal of pollutants is low, meets the growth requirement of 21 century green energy resource.Solid Oxide Fuel Cell (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 by inside reforming, such as pluralities of fuel gases such as coal gas, natural gas, gasoline, oil liquefied gas), environmentally friendly (SO
x, NO
xPollute Deng low, the noiselessness of discharging), can realize the 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 the 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 Function of sealing (sealing-in) is: 1) isolated fuel gas and oxic gas prevent that fuel is (such as H
2, CH
4) in battery pile, mix the air-tightness that keeps good with oxidant (such as air); 2) parts such as the connecting plate in the pile, battery are linked together formation battery pile; 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 repeatedly thermal stress of Thermal Cycling of battery pile.
Therefore, the seal, sealing materials that requires to adopt 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 at battery pile run duration thermal coefficient of expansion, obvious variation should not occur; 3) have preferably caking property, and had wettability preferably and stronger adhesion 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 good chemical compatibility, significant chemical reaction does not occur.
Present research to the SOFC Sealing Technology both at home and abroad mainly comprises means of press seals and hard sealing.Hard sealing refers to that encapsulant connects (sealing-in) firmly, the seal, sealing materials that adopts mainly contains reactive metal material (such as brazing, silver slurry etc.), glass, devitrified glass, glass ceramics and two or more carries out compound material etc., such as CN1574417A, CN1465647A, CN1929163A, CN1469497A, CN1180493C, CN1599092A, CN1095598C, CN1746252A, CN1660954A etc.Means of press seals mainly adopts the concept 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., such as CN1649186A, CN1454398A, US2005147866-A1, US2005266288-A1, US2005064273-A1 etc.
Glass, devitrified glass class seal, sealing materials are with its technology of preparing maturation, low production cost, it is the main study subject of SOFC sealing always, the at present research of such material mainly concentrates on the sign of material key property, such as 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 such material mainly concentrates on the sign of material key property, such as 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-based seal, sealing materials and have come with some shortcomings: such as the long-term thermal stability of material under serviceability temperature, namely, 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 respectively employing CaO-Al
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 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 the easily temperature of growth of the easy crystallization of glass-based seal, sealing materials and crystalline phase under this temperature.Mention the increase with temperature retention time in a lot of researchs, crystallization constantly occurs in seal, sealing materials, the kind of crystalline phase, quantity, grain size are changing always, cause material thermal expansion coefficient to occur significantly to change, 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, these methods are simple and convenient in the enforcement of little sealing area, such as the test of monolithic baby battery, separately and the sealing-in of electrolyte or connecting plate, but when sealing area increases, when particularly in battery pile, implementing, these methods are used cumbersome, quality control is difficult to, and sealing-in thickness is uncontrollable, this can greatly affect 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 to be applicable to middle low temperature SOFC.
Summary of the invention
In the face of the problems referred to above that prior art exists, a first aspect of the present invention provides a kind of intermediate temperature solid oxide fuel cell 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 processed 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 described sealing gasket, the weight percentage of described glass for sealing powder can be 40～60wt%, the weight percentage of described dispersant can be 0.1～2wt%, the weight percentage of described plasticizer can be 2～8wt%, the weight percentage of described binding agent can be 2～5wt%, and the weight percentage of described solvent can be 30～50wt%.Described dispersant can comprise polymine and/or triethanolamine.Described plasticizer comprises in dibutyl phthalate, polyvinyl alcohol 200 and the olein one or more.Described binding agent comprises in polyvinyl butyral resin, glycerine, ethyl cellulose, the methylcellulose one or more.Described 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 described glass for sealing powder, described 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 described glass for sealing powder, the molar content of described NiO can be 0.2～0.5mol%, described Cr
2O
3Molar content can be 0.2～0.5mol%, described 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, the pre-element of being correlated with and may reacting that adds may have to the reaction at interface the effect of inhibition.
In yet another preferred embodiment, in described glass for sealing powder, described Al
2O
3Molar content can be 4～10mol%, the molar content of described 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 in right amount Al
2O
3But with the resistance to water of ZnO reinforcing glass, be conducive to stablizing in anode high humidity atmosphere.
In yet another preferred embodiment, in described glass for sealing powder, the molar content of described CaO can be 12～16mol%.Add CaO and can reduce the glass high temperature viscosity, increase low temperature viscosity, be conducive to founding and sealing-in under suitable temperature of glass.
In yet another preferred embodiment, described glass for sealing powder alkali-free metal oxide.Do not contain that at high temperature conductivity is high, 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 described glass for sealing powder can be 10.4～11.5 * 10
-6/ k.
Glass for sealing powder of the present invention is through processing 0.5～2 hour (for example 1 hour) in 550～600 ℃ (preferred 600 ℃) lower coring and the mean thermal expansion coefficients after 800～850 ℃ (preferred 850 ℃) lower crystallization is processed 0.5～2 hour (for example 70 minutes) can be 10.5～12 * 10
-6/ k, preferred 11.5～11.8 * 10
-6/ k.
The described sealing-in of processing through coring and crystallization with sealing gasket 750 ℃ of lower heat treatments after 200 hours, after 2300 hours in the amplitude of variation of its mean thermal expansion coefficients in 6%.Through the sealing gasket of preferred coring and crystallization resolving system 750 ℃ of lower 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, by 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 invention provides a kind of method that above-mentioned intermediate temperature solid oxide fuel cell is used sealing gasket for preparing, it is characterized in that, described method comprises: with described glass for sealing powder and dispersant, plasticizer, binding agent and solvent proportioning ball milling in accordance with regulations mix, curtain coating, drying, hot pressing, be cut into the sealing gasket of regulation shape.
On the one hand, the invention provides above-mentioned intermediate temperature solid oxide fuel cell uses with sealing gasket, it is characterized in that, place described intermediate temperature solid oxide fuel cell to need the position of sealing-in on described 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 process, then be warmed up to 800～850 ℃ of insulations 0.5～2 hour, carry out sealing-in and crystallization and process.
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 Components Matching of the sealing-in of wanting, and Heat stability is good, is fit to be widely used in the sealing of fuel cell, is particularly useful for middle low-temperature solid fuel cell.
Description of drawings
Fig. 1 illustrates the example seal pad for sealing-in SOFC of the present invention;
Fig. 2 illustrates the example seal, sealing materials for SOFC of the present invention, 750 ℃ of lower heat treatments, with the variation of heat treatment time mean thermal expansion coefficients;
Fig. 3 illustrates the example seal, sealing materials for SOFC of the present invention, and 750 ℃ of lower 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 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 further specify with the following embodiments the present invention, should be understood that Figure of description and following execution mode only are used for explanation 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 and approach and the suitable material of viscosity, be suitable for the sealing-in thermal coefficient of expansion 10～12.5 * 10
-6Material between the/k is such as (YSZ) electrolyte of cubic zirconia among the SOFC and metallic interconnect materials.
SiO wherein
2Be the main glass forming agent in the glass, its molar content can be 28～38mol%, and it can also reinforcing glass and intermetallic bond strength except thermal stability that can reinforcing glass, chemical stability, improves air-tightness.
B
2O
3Molar content can be 5～15mol%, its adds can regulate glass viscosity, and and SiO
2Improve together the stability of glass as the Network former of glass, in addition B
2O
3As surface reactive material, can significantly reduce the surface tension of glass, be conducive to 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 larger, activity is relatively poor in the glass network structure, this will greatly increase resistivity, can make glass have good electrical insulation capability.
A small amount of Al that adds
2O
3(0～10mol%) can improve the thermal coefficient of expansion of glass, increases thermal stability, adds in right amount Al
2O
3And ZnO (but the resistance to water of 0～15mol%) reinforcing glass is conducive to stable in anode high humidity atmosphere; (0～16mol%) can reduce the glass high temperature viscosity to CaO, increases low temperature viscosity, is conducive to 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, the pre-element of being correlated with and may reacting that adds may have to the reaction at interface the effect of inhibition.In addition, seal, sealing materials does not contain that at high temperature conductivity is high, 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 made specific annular, square, bar shaped etc., are preferably glass dust, for the preparation of sealing-in base substrate (sealing gasket).
Above-mentioned seal, sealing materials and and dispersant, plasticizer, binding agent and solvent be by certain proportioning, ball milling mixes, curtain coating, drying, hot pressing, is cut into as required the suitable sealing gasket of shape.The sealing gasket of preparation places the position that needs sealing-in, carries out sealing-in and crystallization and processes, and can realize sealing-in.Seal, sealing materials is the lower crystallite attitude of activation energy from the higher glass transition of activation energy in the sealing-in process, has had higher intensity, and has greatly reduced diffusion mobility and the interfacial reaction of ion.
By 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 of preferred crystallization resolving 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, further specify the present invention take the preparation of seal, sealing materials, sealing gasket and to the sealing-in of battery pile as example:
One, the preparation of glass-based seal, sealing materials:
Content according to each component in listed each sample in the following table 1 takes by weighing respectively a certain amount of SiO
2, B
2O
3, BaCO
3, Al
2O
3, ZrO
2, CaCO
3, ZnO, NiO, Cr
2O
3And Co
2O
3After carrying out sufficient mixing with batch mixer, 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, then take out and be poured on the corrosion resistant plate, 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 breaking, grinding, sieving to obtain the glass dust that sealing-in is used.
Table 1: the content of each component in the seal, sealing materials (molar content, mol%)
Also can according to the content of each component in listed each sample in the upper table 1, take by weighing respectively a certain amount of SiO
2, B
2O
3, BaCO
3, Al
2O
3, ZrO
2, CaCO
3, ZnO, NiO, Cr
2O
3And Co
2O
3After carrying out sufficient mixing with batch mixer, 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 again into the stainless steel cask that cold water is housed, shrend obtains undersized glass particle, then ball milling sieves, and obtains sealing-in glass dust for subsequent use, 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 above-described embodiment 1～9 preparation must be become 5 * 5 * 20mm's is rectangular, with the high temperature thermal 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
Ginseng sees the above table 2 as can be known, and the thermal coefficient of expansion of the seal, sealing materials of the present invention's preparation and the thermal coefficient of expansion of the 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, carry out curtain coating and drying at casting machine, then hot pressing under 50～100 ℃, the pressure condition of 5～20Mpa is cut into the suitable sealing gasket of size on demand during use.Following table 3 illustrates the content of each component among three embodiment of the standby sealing gasket of this legal system.
Table 3: the tape casting prepares the content (g) of each component 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 |
| |
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:
Be the rectangular of size 3mm * 5mm * 30mm with the casting films cutting, lamination, the hot pressing that prepare, place electric tube furnace, heat up with 2～5 ℃/min, the crystallization system of according to the form below 4 is heat-treated, then with the embodiment 13 that obtains and 14 sample.
Table 4: the heat of crystallization resolving system 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 process, 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
Can find out embodiment 13 samples from upper table 5 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); The thermal coefficient of expansion of adjacent component approaching very in the thermal coefficient of expansion of two embodiment samples and the pile is substantially 10.6～12 * 10
-6Between/the k.The sample (embodiment 14) that preferred heat of crystallization resolving system 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.The above-mentioned data of mentioning and caption this seal, sealing materials be highly suitable for the sealing of Solid Oxide Fuel Cell (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 processes, then be warmed up to 800～850 ℃ of insulations 0.5～2 hour, carry out sealing-in and crystallization and process, realize sealing-in.
Adopt above-mentioned seal, sealing materials and method for sealing assembled battery heap, the battery pile of assembling 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, the second connecting plate, sealing gasket, battery unit thereon ... by that analogy, form battery pile structure, then as above-mentioned organic eliminating and coring processing, sealing-in and the crystallization of carrying out process, 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 adopts said method to form seal between solid electrolyte, negative electrode, anode, connector.
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 take Ni-YSZ as anode, La
0.7Sr
0.3MnO
3Be negative electrode, effective area is 49cm
2The anode-supported cells unit.
This battery pile is carried out the test (referring to Fig. 4) of thermal cycle and medium-term and long-term discharge with act as a fuel gas and oxic gas of hydrogen and oxygen 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 batch production, and quality controllable, for reliable sealing-in and the stable operation of battery pile provides sound assurance.
Claims (19)
1. intermediate temperature solid oxide fuel cell sealing gasket, described sealing gasket be by glass for sealing powder, dispersant, plasticizer, binding agent and solvent proportioning ball milling is in accordance with regulations mixed, curtain coating, drying, hot pressing, be cut into the sealing gasket of regulation shape; It is characterized in that, described 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, 0.2～0.5mol%NiO, 0.2～0.5mol%Cr
2O
3And 0.2～0.5mol%Co
2O
3
2. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1, it is characterized in that, the weight percentage of described glass for sealing powder is 40～60wt%, the weight percentage of described dispersant is 0.1～2wt%, the weight percentage of described plasticizer is 2～8wt%, the weight percentage of described binding agent is 2～5wt%, and the weight percentage of described solvent is 30～50wt%.
3. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described dispersant comprises polymine or triethanolamine.
4. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described plasticizer comprises in dibutyl phthalate, polyvinyl alcohol 200 and the olein one or more.
5. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described binding agent comprises in polyvinyl butyral resin, glycerine, ethyl cellulose, the methylcellulose one or more.
6. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described solvent comprises in butanone, ethanol, cyclohexanone, n-butanol, butyl acetate and the deionized water one or more.
7. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described ZrO
2Molar content be 2～5mol%.
8. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described Al
2O
3Molar content be 4～10mol%, the molar content of described ZnO is 4～15mol%.
9. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, the molar content of described CaO is 12～16mol%.
10. intermediate temperature solid oxide fuel cell sealing gasket according to claim 1 is characterized in that, described glass for sealing powder alkali-free metal oxide.
11. each described intermediate temperature solid oxide fuel cell sealing gasket is characterized in that according to claim 1～10, the mean thermal expansion coefficients of described glass for sealing powder is 10.4～11.5 * 10
-6/ k.
12. intermediate temperature solid oxide fuel cell sealing gasket according to claim 11, it is characterized in that, described glass for sealing powder is 10.5～12 * 10 through processing the mean thermal expansion coefficients that reached in 0.5～2 hour after 800～850 ℃ of lower crystallization are processed 0.5～2 hour 550～600 ℃ of lower coring
-6/ k.
13. intermediate temperature solid oxide fuel cell sealing gasket according to claim 12, it is characterized in that, described glass for sealing powder is 750 ℃ of lower heat treatments after 200 hours, after 2300 hours in the amplitude of variation of its mean thermal expansion coefficients in 6%.
14. intermediate temperature solid oxide fuel cell sealing gasket according to claim 12, it is characterized in that, described glass for sealing powder is 11.5～11.8 * 10 through processing the mean thermal expansion coefficients that reached in 1 hour after 850 ℃ of lower crystallization are processed 70 minutes 600 ℃ of lower coring
-6/ k.
15. intermediate temperature solid oxide fuel cell sealing gasket according to claim 14, it is characterized in that, described glass for sealing powder is 750 ℃ of lower heat treatments after 100 hours, after 2400 hours in the amplitude of variation of its mean thermal expansion coefficients in 2%.
16. each described intermediate temperature solid oxide fuel cell sealing gasket is characterized in that according to claim 1～10, the glass transition temperature of described glass for sealing powder is 580～680 ℃, and the glass softening point temperature is 630～730 ℃.
17. described intermediate temperature solid oxide fuel cell sealing gasket is characterized in that according to claim 1～10, the average grain diameter of described glass for sealing powder is 20 μ m.
18. method for preparing each described intermediate temperature solid oxide fuel cell usefulness sealing gasket in the claims 1～17, it is characterized in that, described method comprises: with described glass for sealing powder and dispersant, plasticizer, binding agent and solvent proportioning ball milling in accordance with regulations mix, curtain coating, drying, hot pressing, be cut into the sealing gasket of regulation shape.
19. each described intermediate temperature solid oxide fuel cell is with the using method of sealing gasket in the claims 1～17, it is characterized in that, place described intermediate temperature solid oxide fuel cell to need the position of sealing-in on described sealing gasket pad, be warmed up to 550～600 ℃ of insulations 0.5～2 hour with 2～5 ℃/min, carrying out organic eliminating and coring processes, then be warmed up to 800～850 ℃ of insulations 0.5～2 hour, carry out sealing-in and crystallization and process.
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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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| EP3985767A1 (en) * | 2020-10-13 | 2022-04-20 | Instytut Energetyki - Instytut Badawczy | Method of preparation of an intermediate product, intermediate product, and method of manufacturing a gasket |
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