CN113937317A - Composite sealing material with directionally-arranged fibers for solid oxide fuel cell and preparation method thereof - Google Patents

Composite sealing material with directionally-arranged fibers for solid oxide fuel cell and preparation method thereof Download PDF

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CN113937317A
CN113937317A CN202010603646.4A CN202010603646A CN113937317A CN 113937317 A CN113937317 A CN 113937317A CN 202010603646 A CN202010603646 A CN 202010603646A CN 113937317 A CN113937317 A CN 113937317A
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glass
sealing material
ceramic
composite sealing
composite
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CN113937317B (en
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任海深
林慧兴
谢天翼
张奕
何飞
姜少虎
赵相毓
姚晓刚
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Shanghai Institute of Ceramics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0282—Inorganic material
    • 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 provides a composite sealing material with directionally-arranged fibers for a solid oxide fuel cell and a preparation method thereof. The composite sealing material is one or more layers, and each layer comprises a fiber network formed by ceramic fibers, a glass phase-ceramic fiber composite layer in which a glass phase is dispersed in gaps of the fiber network, and a glass phase layer coated on the surface of the glass phase-ceramic fiber composite layer; wherein the ceramic fiber is a continuous long fiber with the diameter of 5-20 μm; preferably, the composite sealing material is composed of 50wt% or more and 100wt% or less of a glass phase, and 50wt% or less of ceramic fibers.

Description

Composite sealing material with directionally-arranged fibers for solid oxide fuel cell and preparation method thereof
Technical Field
The invention relates to a composite sealing material with directionally-arranged fibers for a solid oxide fuel cell and a preparation method thereof, which are particularly suitable for sealing between an SOFC cell element and a metal connector and can be used for long-time work at medium and low temperature and frequent thermal cycle.
Background
Solid Oxide Fuel Cells (SOFC) are one of the high-efficiency green energy technologies acknowledged in the 21 st century, and SOFC uses yttria stabilized zirconia-oxygen ceramic material (YSZ for short) as electrolyte, Co-based ceramic material with a layered perovskite structure as cathode, and Ni-based ceramic material as anode, has an all-Solid structure, higher energy conversion efficiency, does not need noble metal catalyst, can directly convert chemical energy in various fuels such as coal gas, natural gas, liquefied petroleum gas and the like into electric energy, has the characteristics of wide Fuel applicability, environmental friendliness, long service life, and the like, and can be applied to power plants, distributed power supplies, standby power supplies, mobile power supplies and the like. Besides the three functional materials of the electrolyte, the cathode and the anode, the structure of the solid oxide fuel cell also comprises two auxiliary materials of a connecting piece and a sealing material, wherein the sealing material is used for isolating fuel gas and oxidizing gas in the cell, thereby ensuring that the fuel gas and oxygen are not contacted to cause danger. In the operation process, the sealing material (also called as "sealing material") is required to have stable performance in all aspects in a high-temperature oxidation-reduction atmosphere and good air tightness and electrical conductivity. The sealing material plays a role in sealing and bonding in the SOFC, and is directly connected with the electrolyte and the connecting body, so that the thermal expansion coefficient of the sealing material is required to be better matched with other parts, and strict requirements are required on important properties such as thermal stability, chemical stability and the like, otherwise, interface cracking is easily caused in the cooling process under the action of high-temperature thermal stress, so that fuel gas leakage is dangerous. Therefore, the preparation of a sealing material having excellent properties is the most effective way to solve the above problems. The sealing materials currently applied to the flat SOFC are mainly divided into three categories: compression sealing material, flexible sealing material, rigid sealing material. Compared with a compression sealing material and a flexible sealing material, the rigid sealing material has more stable performance and is more suitable for sealing fuel cells.
The rigid sealing material is usually made of glass or microcrystalline glass material and is positioned between the cell piece and the connecting piece to realize mutual isolation between fuel gas and oxidizing gas and isolation between the fuel gas and the oxidizing gas and the outside. In order to avoid thermal stress during the operation of the SOFC, the thermal expansion coefficient of the sealing glass should be between the two, otherwise the sealing glass and the sealing glass will "pull" each other at high temperature due to the inconsistent thermal expansion degree of the connecting plate, the cell slice and the sealing ring, and therefore the cell may have faults such as leakage, rupture and the like, and in severe cases, the cell may explode. In addition, the sealing material can be subjected to tests of humid, oxidizing and reducing atmospheres under the working environment of 700-850 ℃ for a long time, so that the design and the manufacture of the sealing ring are one of the key technologies of the solid oxide fuel cell. The sealing ring made of the rigid sealing material by adopting a tape casting process is the most common sealing mode of the SOFC at present, and the process is approximately as follows: mixing the glass powder and an organic solvent to form slurry with certain viscosity; casting into a film tape with appropriate strength and toughness; then laminating, hot-pressing and cutting the membrane tape into the designed shape and size; and finally, laminating the battery piece and the connecting piece together and sintering the battery piece and the connecting piece to form the galvanic pile. The glass-based sealing ring has to have a certain thickness (1.5-3 mm) to reach a certain strength to ensure that the glass sealing ring can be used for processing and battery assembly, but the thicker sealing material has larger deformation caused by temperature change in the process of temperature change from high working temperature to room temperature, and the larger deformation is easy to crack the glass sealing ring and thus cause sealing failure of the sealing ring.
In the research of the SOFC sealing material at the present stage, the properties such as the thermal expansion coefficient, the mechanical strength and the like of the glass can be improved by preparing the glass-based composite sealing material. EP-A-1010675 discloses glass powders and fillers suitable for use in solid oxide fuel cellsThe composite sealing material is prepared, and the filler can improve the glass powder with low expansion coefficient to be in the range of (9-13) from 7.5. The Chinese invention patent CN103570372A discloses a low-boron, Ba-free glass and ceramic powder composite sealing material which does not crystallize in the working temperature range, the glass phase has the sealing effect, the ceramic powder dispersion effect can improve the mechanical strength and expansion coefficient of the sealing material, and the compatibility of the sealing material and a battery element is enhanced. The disordered ceramic phase powder is used as a rigidity reinforcing phase, the mechanical property is not obviously improved when the adding amount is too small, and the viscosity of a glass phase is increased easily when the adding amount is too high, so that the sealing temperature is increased or the air tightness is reduced. In addition, in the casting process of the sealing element, the ideal biscuit with uniform components and uniform size can be obtained only by controlling the powder within a certain particle size range, and the disordered distribution of the ceramic phase often causes agglomeration in the glass phase due to the undersize particle size of the ceramic powder, thereby causing the deterioration of the sealing effect and the mechanical property. Taniguchi S et al, Japan, SiO2-Al2O3Addition of ceramic fibers to SiO2-BaO-B2O3-Al2O3The ceramic fiber/glass composite sealing material is prepared from glass, so that the thermal stress generated in the operation process of the battery is relieved, and the thermal cycle performance and sealing airtightness of the battery are improved. In order to realize the ordered distribution of the ceramic reinforcing phase in the sealing glass, the Chinese invention patent CN1649186A discloses that SiO with the length-diameter ratio of 10-2002-Al2O3The method is characterized in that ceramic chopped fibers and glass phases are compounded, and a sealing material is prepared through a spray granulation-hot press molding process (50-200 ℃), although the method realizes the directional distribution of the fibers in a certain range, the possibility of uneven distribution of the fibers still exists in the spray process, and the method is not easily applicable to fiber ceramic phases with larger length-diameter ratio (more than 200). Therefore, how to mix the fibers and the glass powder uniformly avoids the problem of failure of toughening effect caused by long fiber agglomeration or short fiber and whisker breaking in the mixing process, and the sealing ring manufacturing completed by the tape casting process is the main reason for limiting the application of the fiber/glass composite sealing material in the aspect of SOFC.
Disclosure of Invention
Based on the existing problems, the invention provides a composite sealing material with fibers capable of being directionally arranged for a solid oxide fuel cell and a preparation method thereof, and aims to solve the problems that the glass sealing ring is broken and the sealing ring is failed due to large deformation caused by temperature change in the temperature change process of the sealing material from high working temperature to room temperature; and the problems of uneven mixing and easy fiber agglomeration existing in the preparation process of the fiber and glass composite sealing material are also solved.
In order to achieve the above object, the present invention provides a composite sealing material in which fibers for a solid oxide fuel cell can be aligned. The composite sealing material is one or more layers, and each layer comprises a fiber network formed by ceramic fibers, a glass phase-ceramic fiber composite layer in which a glass phase is dispersed in gaps of the fiber network, and a glass phase layer coated on the surface of the glass phase-ceramic fiber composite layer; wherein the ceramic fiber is continuous long fiber with the diameter of 5-20 μm.
Wherein the ceramic fibers form a fiber network structure in the composite sealing material in an oriented distribution mode. The mechanical strength of the composite sealing material is improved by utilizing the unique one-dimensional mechanical characteristics of the fibers, and the problems that the glass sealing ring is broken and the sealing ring is failed due to large deformation caused by temperature change in the temperature change process of the sealing material from high working temperature to room temperature are solved.
The composite sealing material is composed of 50wt% or more and 100wt% or less of a glass phase and 50wt% or less of ceramic fibers. Therefore, the glass phase can be ensured to be softened at a certain temperature to fill gaps among ceramic fibers and seal other parts, and the ceramic fibers can be directionally distributed in the glass phase to adjust the thermal expansion coefficient and the mechanical property of the sealing material, but the content of the ceramic fibers is not too high, otherwise, the high-temperature viscosity of the glass is reduced, and the sealing property is influenced. Preferably, the composite sealing material consists of 60-90 wt% of glass phase and 10-40 wt% of ceramic fiber.
In some embodiments, the composite sealing material is formed by ceramic fiber pre-fixing, tape casting and hot isostatic pressing lamination (low-temperature hot isostatic pressing, 50-80 ℃) so as to realize the oriented distribution of the ceramic fibers in the composite sealing material. The composite sealing material is a multilayer composite sealing material with a criss-cross fiber network structure. On one hand, the tape-casting green body shows good toughness and strength, so that the tape-casting green body can be processed into a desired shape and size by adopting a cutting machine, a punching machine and other process equipment, on the other hand, the organic matter in the green body can realize the lamination of multiple layers of green bodies through hot isostatic pressing to form sealing green bodies with different thicknesses, and in addition, the orientation arrangement of ceramic fibers is realized by controlling the lamination direction of the green bodies containing the ceramic fibers.
In the composite sealing material, the length-diameter ratio of the ceramic fibers is not limited, and the blank after casting molding can be cut to be adaptively changed.
Preferably, the glass phase composition comprises 20-40 wt% of SiO 22 to 8wt% of Al2O320 to 60wt% of alkaline earth metal oxide, 0 to 5wt% of alkali metal oxide, and B less than 10wt% in total2O3And Bi2O3。
Preferably, the glass phase also comprises 2-15 wt% of one or more additives of transition metal oxides and rare earth metal oxides except harmful heavy metals such as Cr, Pb, V and the like; preferably the additive is selected from one or more of Co-based oxide, Fe-based oxide and Ni-based oxide.
Preferably, the ceramic long fiber is selected to have an expansion coefficient of 8 × 10-6/K～15×10-6At least one or more of Al2O3 base, ZrO2, mullite, yttrium aluminum garnet and MgO ceramic fiber between/K, wherein the diameter of the fiber is between 5 and 20 mu m.
In a second aspect, the present invention also provides a method for preparing the composite sealing material with directionally arranged fibers for the solid oxide fuel cell, which comprises the following steps:
s1, preparing raw materials corresponding to the proportion of the glass phase according to a stoichiometric ratio, melting the raw materials at 1350-1550 ℃ for 1-4 hours to prepare glass powder, sieving the glass powder, and preparing the glass powder into glass powder slurry containing 50-65 wt% of glass powder and 15-40 wt% of solvent;
s2, after ceramic fiber raw materials are uniformly distributed on a bottom film, spraying the glass powder slurry on the bottom film on which the ceramic fibers are distributed in the process that the bottom film moves forwards, and drying to fix the ceramic fibers on the bottom film to form the glass phase-ceramic fiber composite layer;
s3, carrying out tape casting on the glass powder slurry on the surface of the glass phase-ceramic fiber composite layer to form the glass phase layer, wherein the thickness of the dried glass phase layer is 100-300 mu m;
and S4, removing the bottom film to obtain the composite sealing material biscuit.
The composite sealing material biscuit can be subjected to cutting, punching, laminating and other processing according to the actual application requirements.
Preferably, in the preparation process of the sealing material, the ceramic long fibers are fixed on the PCB film in advance, and then the glass slurry is used for casting to complete compounding, so that the problem that the long fibers are easy to agglomerate in the traditional ball-milling mixing method is solved, the uniformity of fiber distribution is improved, and meanwhile, a fiber network structure can be formed in the composite sealing material by a biscuit dislocation hot isostatic pressing lamination method, so that the thermal shock resistance and the mechanical property of the sealing material are improved.
Preferably, the composite sealing material biscuit is cut into a specified shape, the number of lamination layers is selected according to the requirement, hot isostatic pressing lamination is carried out, wherein the pressure is controlled to be 20-40 MPa, the temperature is 50-80 ℃, and the pressure maintaining time is 5-40 min.
Preferably, in order to improve the binding force between the ceramic fiber and the glass casting slurry in the process and keep the ceramic fiber and the glass casting slurry fixed on a PCB bottom die, 0-100 wt% of solvent is added into the glass powder slurry for dilution and then sprayed on the basement membrane distributed with the ceramic fiber, wherein the spraying amount is that the solid content in the glass powder slurry accounts for 1-10 wt% of the ceramic fiber; preferably, the solvent is an alcohol.
Preferably, the directional alignment of the ceramic fibers is achieved by controlling the direction of the stack of ceramic fiber-containing greensheets.
Preferably, the mass percentage of the ceramic fiber can be controlled by the uniformly distributed ceramic fiber density and the coating thickness of the glass slurry on the base film.
Preferably, the lamination is obtained by stacking the biscuit in staggered position, with the aim of improving the mechanical properties thereof in order to form a criss-cross fiber network structure in the sealing material. The angle of the staggered lamination can be any angle between 0 and 180 degrees.
Preferably, the biscuit in the lamination process can comprise ceramic fibers of the same type with different mass ratios, ceramic fibers of different types with the same mass ratio and ceramic fibers of different types with different mass ratios.
Preferably, the particle diameter D of the glass powder50＝2～4μm。
Preferably, the glass frit paste further comprises: 2-10 wt% of binder, 2-10 wt% of dispersant and 2-10 wt% of plasticizer. Preferably, the solvent comprises one or more of ethanol, benzene solvent, ketone solvent and ether organic solvent, the binder comprises cellulose binder and polyvinyl alcohol binder, the dispersant comprises fish oil and linseed oil, and the plasticizer is benzoic acid plasticizer and glycol plasticizer. More preferably, in the glass powder slurry, the solvent is 5-10 wt%, the binder is 3-10 wt%, and the plasticizer is 3-10 wt%.
Preferably, the basement membrane is a PCB basement membrane and/or a PET basement membrane of which the surfaces are modified by silicone oil, and the peeling force is controlled to be 5-100N/m.
The invention has the following remarkable advantages:
(1) the sealing glass material is used as a matrix, and ceramic fibers which can be directionally arranged are used as a mechanical reinforcing agent, so that the requirement of high-reliability sealing of the SOFC is met;
(2) the method adopts the method of ceramic long fiber fixation in advance, traditional tape casting molding and low-temperature hot isostatic pressing (50-80 ℃) lamination molding to realize the directional distribution of the long fiber in the composite sealing material, and the preparation method is simple, economic and environment-friendly;
(3) the composite sealing material composition can greatly increase the content of ceramic fibers in the composite material, thereby improving the mechanical strength of glass, enhancing the thermomechanical stability of the glass and simultaneously not influencing the air tightness of the glass.
Drawings
FIG. 1 is a schematic view of a composite sealant green body malposed lamination;
FIG. 2 is a schematic view of the modified ceramic long fiber tape casting;
FIG. 3 the thermal expansion coefficient of the composite sealing material of example 3 varies with operating time;
FIG. 4V-I-t curves before and after thermal cycling of the composite sealing material of example 3 into a 5-cell stack;
figure 5 example 3V-P-t curves for long term stability operation of composite sealing materials assembled into 5 cell stacks.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The present disclosure provides a fiber/glass composite sealing material for SOFC, which is composed of 50 to 100wt% of a glass phase or a glass-ceramic phase, and 50wt% or less of a ceramic fiber. The glass phase or glass-ceramic phase in the composite sealing material can be prepared by molding and sintering glass powder in a tape casting way.
The glass phase can be composed of 25-50 wt% of glass network forming body, 25-65 wt% of glass network modifying body, 2-8 wt% of glass network intermediate, 2-15 wt% of additive and the like. The glass can be in a non-microcrystalline glass state or a microcrystalline glass state in the working process.
Preferably, the glass network former is 20-40 wt% SiO2B, in total, less than 10wt%2O3And Bi2O3. In order to ensure the chemical stability, thermal stability and mechanical property of the glass in the long-time high-temperature working process, SiO in the glass network forming body2The content is not less than 20 wt%, and when it exceeds 40wt%, the sealing temperature may be excessively high and the thermal expansion coefficient may be excessively low due to an excessively large content. Low melting point network former B2O3And Bi2O3Can reduce glass melting temperature and sealing temperature, and increase thermal expansionCoefficients, but low melting point network formers (especially B)2O3) The sealing agent is unstable under high temperature and high humidity conditions, is very volatile to form air holes, and causes sealing failure, so the content of the sealing agent is controlled to be less than 10 wt%.
Preferably, the glass network modifier is selected from one or more of alkaline earth metal oxide and alkali metal oxide, so that the glass can keep the property of high thermal expansion coefficient and can be matched with the expansion coefficient of SOFC cell elements and connectors. In addition, the alkali metal oxide also has the effects of reducing the melting temperature of the glass material and improving the rheological property in the glass sealing process, but has the problems that the components are easily volatilized at high temperature and cause the reduction of the resistivity, so that the content is not suitable to be excessively high. Preferably, the content of the alkaline earth metal oxide is 20 to 60wt%, and the content of the alkali metal oxide is 0 to 5 wt%. The alkaline earth metal oxide RO, R may be Mg, Ca, Ba or Sr. Alkali metal oxide R2O and R can be Na or K.
Al2O3The glass is a glass network intermediate in the composite sealing material, can improve the chemical stability and the thermal stability of the glass, and influences the crystallization behavior of the glass. In order to avoid a decrease in the coefficient of thermal expansion of the sealing glass, it is not desirable to use a glass phase in an excessively high amount. Preferably, Al2O3The content is 2-8 wt%.
Preferably, the additive is one or more of transition metal oxide and rare earth metal oxide except harmful heavy metals such as Cr, Pb, V, etc., such as Co-based oxide, Fe-based oxide and Ni-based oxide for improving sealing interface between the sealing material and the metal connecting member, such as TiO2、ZrO2、ZnO、Y2O3、La2O3And the like can influence the crystallization behavior of the glass, adjust the fluidity in the sealing process and improve the problem of component volatilization in the working process. Preferably, the additive is present in an amount of 2 to 15 wt%.
The expansion coefficient of the ceramic fiber is 8-15 x 10-6Al between/K2O3ZrO based2At least one or more of mullite, yttrium aluminum garnet and MgO ceramic fiber, wherein the diameter of the fiber is 5-20 mu m.
As shown in table 1, the selected ceramic fibers have high thermal expansion, excellent mechanical properties, a service temperature much higher than the SOFC operating temperature, and stable chemical properties, and do not react with the cell elements during long-term operation. The ceramic fibers with high tensile strength can form a fiber network in the sealing material in a directional distribution mode, so that the mechanical strength of the glass is improved, and the problems that the glass sealing ring is broken and the sealing ring fails due to large deformation caused by temperature change in the temperature change process of the sealing material from high working temperature to room temperature can be solved.
TABLE 1 Properties of selected ceramic fibers
Figure BDA0002560073180000071
The following is an exemplary description of the method for producing the composite sealing material in which fibers for a solid oxide fuel cell according to the present invention can be aligned (may also be referred to as "fiber/glass composite sealing material for SOFC").
(1) Respectively weighing raw materials corresponding to the components, grinding the raw materials into balls: alcohol: the mass ratio of the materials is (1-3): (2-3): (1) ball milling is carried out for 6-12 h at 100-300 r/min, and the mixture is uniformly mixed and dried at 100-120 ℃.
(2) Melting the mixture obtained in the step (1) at 1350-1550 ℃ for 1-4 hours, and quenching the melted glass liquid to obtain glass fragments or broken slag; the melting temperature is preferably 1400-1550 ℃; in some embodiments, the temperature is maintained at 800 ℃ for 4 hours before melting at 1350-1550 ℃.
(3) Grinding with a grinding ball: alcohol: the mass ratio of the materials is (2-4): (1-3): (1) performing planetary ball milling on the glass fragments or the crushed slag in the step (2) at 300-600 r/min for 1-3 hours to obtain glass powder, drying at 100-120 ℃ for 6-12 hours, and sieving with a 200-mesh sieve to obtain glass powder with the particle size of D50＝2-4μm。
(4) And (3) ball-milling the glass powder in the step (3), 10-30 wt% of solvent and 3-10 wt% of dispersant for 0.5-3 h at the rotating speed of 300-500 r/min, and then adding 5-10 wt% of solvent, 3-10 wt% of binder and 3-10 wt% of plasticizer for ball-milling for 2-5 h at the rotating speed of 150-350 r/min.
(5) And filtering and separating the slurry and the grinding balls through a 60-200-mesh sieve, and performing vacuum defoaming treatment.
(6) After the ceramic fibers are uniformly distributed in parallel to the running direction of the PCB film, the ceramic fibers are sprayed by glass powder slurry with the dilution amount of 0-100% in the forward process of the PCB film, and then the ceramic fibers enter a thermostatic chamber with the temperature controlled at 50-90 ℃ to be fixed on the PCB film. For example, the ceramic fibers can be uniformly distributed parallel to the running direction of the PCB film by a special separation device.
(7) Pouring the slurry onto a PET bottom die attached with ceramic fibers for tape casting, driving the PET bottom die to move forwards at the speed of 0.3-1 m/min, controlling the thickness of the slurry at 100-300 mu m by a scraper, controlling the temperature in a tape casting chamber at 50-90 ℃, and removing the bottom die after the slurry is formed into a film tape to obtain a blank.
(8) And cutting the green body, stacking the green body in a staggered way, and laminating the green body by hot isostatic pressing to obtain the composite sealing material with directionally-arranged fibers for the solid oxide fuel cell. The preparation method further comprises the following steps: the offset lamination angle in step S5 is any angle below 180 °. The angle of the staggered lamination is any angle between 0 and 180 degrees. The lamination process may include different mass ratios of the same type of ceramic fibers, the same mass ratio of different types of ceramic fibers, and different mass ratios of different types of ceramic fibers. The number of the laminated layers is selected according to actual use conditions. And in the hot isostatic pressing lamination process, the pressure is controlled to be 20-40 MPa, the temperature is 50-80 ℃, and the pressure maintaining time is 5-40 min. The above method can achieve the directional arrangement of ceramic fibers by controlling the direction of lamination of a biscuit containing ceramic fibers.
(9) And cutting the multilayer biscuit subjected to the hot isostatic pressing into a certain size and shape according to the actual sealing requirement to obtain the sealing gasket.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) According to the glass mixture ratio of example 1 in table 2, the total mass is 1000 g, and the corresponding raw materials are calculated and weighed: SiO 22256.5 g, Bi2O321.72 g, H3BO353.43 g, Al2O362.66 g of BaCO3425.82 g SrCO395.23 g, Na2CO342.86 g, La2O333.42 g, Ni2O34.18 g, Fe2O34.18 grams, with grinding ball: alcohol: the mass of the raw materials is 2000 g: 2000 g: 1000 g, ball-milling in a nylon tank for 6 hours, discharging, and drying in a constant-temperature drying oven at 110 ℃ for 12 hours to obtain a mixture;
(2) placing the mixture in the step (1) in a platinum crucible, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 4 hours, heating to 1450 ℃ at the speed of 3 ℃/min, melting for 2 hours, and water-quenching the uniformly melted glass to obtain glass slag;
(3) grinding the crushed glass slag obtained in the step (3) by using grinding balls: alcohol: the mass ratio of the materials is 1000 g: 500 g: 500 g, ball-milling at 500r/min for 2 hours, drying at 100-120 ℃ for 8 hours, and sieving with a 200-mesh sieve to obtain glass powder;
(4) placing 100 g of glass powder, 21 g of alcohol, 21 g of xylene and 4 g of herring oil dispersing agent into a nylon tank, carrying out planetary ball milling for 2 hours at the rotating speed of 450r/min, and then adding 4.14 g of alcohol, 4.14 g of xylene, 10 g of PVB 98 binding agent and 6.8 g of S160 plasticizer, carrying out planetary ball milling for 2 hours at the rotating speed of 300r/min to obtain glass slurry;
(5) filtering and separating the glass slurry and the grinding balls through a 100-mesh sieve, and performing vacuum defoaming treatment;
(6) taking out 30 g of the slurry after the vacuum defoaming treatment, diluting the slurry with 6.24 g of alcohol and 6.24 g of xylene, spraying the diluted slurry on a PCB film uniformly distributed with mullite ceramic fibers with the diameter of 10 mu m, and fixing the fibers on the PCB film in a constant temperature room at 80 ℃;
(7) pouring the slurry on a PCB bottom die with fixed fibers for tape casting, and driving the PCB bottom die to move forwards at the speed of 0.5 m/min, wherein the thickness of the slurry is controlled at 100 mu m by a scraper, the temperature in a tape casting chamber is controlled at 75 ℃, and after the slurry is formed into a film tape, removing the bottom die to obtain a blank;
(8) simply cutting the biscuit, selecting the number of lamination layers according to the actual use condition, and carrying out hot isostatic pressing lamination, wherein the pressure is controlled at 35MPa, the temperature is 70 ℃, and the pressure maintaining time is 20 min;
(9) and cutting the multilayer biscuit subjected to the hot isostatic pressing into a certain size and shape according to the actual sealing requirement to obtain the sealing gasket.
TABLE 2 glass phase component content (unit: mass%) of examples 1 to 5
Figure BDA0002560073180000091
Examples 2-5 are essentially the same as example 1, except that: the raw materials in step (1) were adaptively replaced with the corresponding components and contents according to table 2.
As can be seen from fig. 2, the ceramic fibers are linearly distributed in the glass frit, and no agglomerated fibers are present.
As can be seen from fig. 3, 4, and 5, the composite sealing material has excellent thermal stability and sealing performance during long-term stable operation and thermal cycling.

Claims (12)

1. The composite sealing material with the fibers capable of being directionally arranged for the solid oxide fuel cell is characterized by comprising one or more layers, wherein each layer comprises a fiber network formed by ceramic fibers, a glass phase-ceramic fiber composite layer with glass phases dispersed in gaps of the fiber network, and a glass phase layer coated on the surface of the glass phase-ceramic fiber composite layer; wherein the ceramic fiber is a continuous long fiber with the diameter of 5-20 μm; preferably, the composite sealing material is composed of 50wt% or more and 100wt% or less of a glass phase, and 50wt% or less of ceramic fibers.
2. The composite sealing material according to claim 1, wherein the ceramic fibers form a fiber network structure in the composite sealing material by way of directional distribution.
3. The composite sealing material according to claim 1 or 2, wherein the composite sealing material is pre-consolidated with ceramic fibers, tape casting and hot isostatic pressing lamination to achieve an oriented distribution of the ceramic fibers in the composite sealing material.
4. The composite sealing material according to any one of claims 1 to 3, wherein the composition of the glass phase comprises 20 to 40wt% SiO22 to 8wt% of Al2O320-60 wt% of alkaline earth metal oxide, 0-5 wt% of alkali metal oxide and B with the mass percentage sum of less than 10wt%2O3And Bi2O3。
5. The composite sealing material according to claim 4, wherein the glass phase further comprises 2 to 15wt% of an additive of one or more of transition metal oxides and rare earth metal oxides other than harmful heavy metals; preferably the additive is selected from one or more of Co-based oxide, Fe-based oxide and Ni-based oxide.
6. The composite sealing material according to any one of claims 1 to 5, wherein the ceramic fibers are selected from fibers having a coefficient of expansion between 8
Figure 559841DEST_PATH_IMAGE001
10-6/K ~15
Figure 476982DEST_PATH_IMAGE001
10-6Al between/K2O3ZrO based2Mo, MoAt least one of mullite, yttrium aluminum garnet and MgO ceramic fiber.
7. The composite sealing material according to any one of claims 1 to 6, wherein the glass transition temperature of the composite sealing material is 600 to 700 ℃, the glass softening temperature is 650 to 750 ℃, and the thermal expansion coefficient is 9 to 12
Figure 256719DEST_PATH_IMAGE001
10-6/K。
8. The method of making a composite seal material with orientable fibers for a solid oxide fuel cell according to any of claims 1 to 7, comprising the steps of:
s1, preparing raw materials corresponding to the proportion of the glass phase according to the stoichiometric ratio, melting the raw materials at 1350-1550 ℃ for 1-4 hours to prepare glass powder, sieving the glass powder, and preparing the glass powder into glass powder slurry containing 50-65 wt% of glass powder and 15-40 wt% of solvent;
s2, after the ceramic fiber raw materials are uniformly distributed on the basement membrane, the glass powder slurry is sprayed on the basement membrane distributed with the ceramic fibers in the process that the basement membrane moves forwards, and the ceramic fibers are fixed on the basement membrane to form the glass phase-ceramic fiber composite layer after drying;
s3, carrying out tape casting on the glass powder slurry on the surface of the glass phase-ceramic fiber composite layer to form the glass phase layer, and drying the glass phase layer to obtain a glass phase layer with a thickness of 100-300 mu m;
and S4, removing the bottom film to obtain the composite sealing material biscuit.
9. The method of manufacturing according to claim 8, further comprising: cutting the composite sealing material biscuit into a specified shape, selecting the number of laminated layers according to the requirement, and carrying out hot isostatic pressing lamination, wherein the pressure is controlled to be 20-40 MPa, the temperature is 50-80 ℃, and the pressure maintaining time is 5-40 min.
10. The preparation method according to claim 8 or 9, wherein 0 to 100wt% of solvent is added to the glass powder slurry to dilute the glass powder slurry, and then the glass powder slurry is sprayed on the basement membrane on which the ceramic fibers are distributed, wherein the spraying amount is such that the solid content in the glass powder slurry accounts for 1 to 10wt% of the ceramic fibers; preferably, the solvent is an alcohol.
11. The preparation method of claim 9, wherein the directional arrangement of the ceramic fibers is realized by controlling the direction of the composite sealing material biscuit dislocation lamination, and the dislocation lamination angle is any angle between 0 and 180 degrees.
12. The production method according to any one of claims 8 to 11, characterized in that the glass frit paste further comprises: 2-10 wt% of binder, 2-10 wt% of dispersant and 2-10 wt% of plasticizer; preferably, the solvent in the glass powder slurry comprises one or more of ethanol, benzene solvents, ketone solvents and ether organic solvents, the binder comprises cellulose binders and polyvinyl alcohol binders, the dispersing agent comprises fish oil and linseed oil, and the plasticizer is benzoic acid plasticizer and glycol plasticizer.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649186A (en) * 2004-01-05 2005-08-03 现代自动车株式会社 Solid oxide fuel cell sealant comprising glass matrix and ceramic fiber and method of manufacturing the same
JP2006185775A (en) * 2004-12-28 2006-07-13 Nippon Telegr & Teleph Corp <Ntt> Seal material for solid oxide fuel cell, and method of manufacturing seal material for solid oxide fuel cell
CN101174677A (en) * 2007-10-31 2008-05-07 中国科学院上海硅酸盐研究所 Sealing ring for solid-oxide fuel battery and production method thereof
JP2012036283A (en) * 2010-08-05 2012-02-23 Toshiba Corp Ceramic seal material and method of using the same
CN103332942A (en) * 2013-06-20 2013-10-02 汕头大学 Low temperature sintered Ni metal fiber composite ceramic substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649186A (en) * 2004-01-05 2005-08-03 现代自动车株式会社 Solid oxide fuel cell sealant comprising glass matrix and ceramic fiber and method of manufacturing the same
JP2006185775A (en) * 2004-12-28 2006-07-13 Nippon Telegr & Teleph Corp <Ntt> Seal material for solid oxide fuel cell, and method of manufacturing seal material for solid oxide fuel cell
CN101174677A (en) * 2007-10-31 2008-05-07 中国科学院上海硅酸盐研究所 Sealing ring for solid-oxide fuel battery and production method thereof
JP2012036283A (en) * 2010-08-05 2012-02-23 Toshiba Corp Ceramic seal material and method of using the same
CN103332942A (en) * 2013-06-20 2013-10-02 汕头大学 Low temperature sintered Ni metal fiber composite ceramic substrate

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