WO2017104960A1

WO2017104960A1 - Glass sealing material for solid oxide fuel cell and sealing method using same

Info

Publication number: WO2017104960A1
Application number: PCT/KR2016/011838
Authority: WO
Inventors: 문지웅; 이성연; 윤종훈
Original assignee: 재단법인 포항산업과학연구원
Priority date: 2015-12-17
Filing date: 2016-10-20
Publication date: 2017-06-22
Also published as: KR20170072640A; KR101782609B1

Abstract

The present invention relates to a glass sealing material for a solid oxide fuel cell and a sealing method using the same. Provided are a glass sealing material for a solid oxide fuel cell and a solid oxide fuel cell sealing method using the same, the glass sealing material for a solid oxide fuel cell comprising reinforcement filling materials on a glass base, wherein the reinforcement filling materials are spherical oxide particles of which the average particle size is greater than 5μm and is equal to or less than 21μm.

Description

【Specification】

[Name of invention]

Glass sealing material for solid oxide fuel cell and sealing method using the same

A glass sealing material for a solid oxide fuel cell and a method for sealing a solid oxide fuel cell using the same.

Background Art

A solid oxide fuel cell (SOFC) is an electrochemical energy converter, and is composed of an oxygen ion conducting solid electrolyte made of an oxide material and an air electrode (anode) and a fuel electrode (cathode) located on both sides thereof. In the cathode, the oxygen ions generated by the reduction reaction of oxygen move to the anode through the electrolyte and react with hydrogen supplied to the anode again to generate water. At this time, since electrons are generated at the anode and electrons are consumed at the cathode, electricity flows when the two electrodes are connected to each other.

However, since the power generated from one unit cell based on the cathode, the electrolyte, and the anode is quite small, a large amount of power can be output by stacking (stacking) several unit cells to form a fuel cell. It is possible to construct a power generation system for various purposes.

A flat solid oxide fuel cell (SOFC) consists of a unit cell in which both the negative electrolyte and the positive electrode are in the form of a flat plate. Several flat unit cells are stacked to form a stack. In order to increase the voltage of the stack, the cathode of one unit cell and the anode of another unit cell must be electrically connected in series. For this, each unit cell needs a structure capable of supplying and separating fuel and air, and a metal separator is used.

In this case, the fuel cell stack seals between the metal separator and the unit cell components to prevent the mixing of hydrogen, which is fuel gas, and air, which is combustion gas, to prevent gas leakage to the outside of the stack, and to insulate the unit cells. It is important. If the sealing material and sealing part of the fuel cell stack are broken, air and fuel meet directly, causing combustion reactions _. Can cause the temperature of the stack to rise Rapid performance deterioration occurs, and in serious cases can lead to safety accidents, it is urgent to improve the reliable sealing technology and the sealing material to support it.

[Detailed Description of the Invention]

Technical problem

A glass sealing material for a solid oxide fuel cell and a method for sealing a solid oxide fuel cell stack using the same are provided.

Technical Solution

One embodiment of the present invention includes a reinforcing filler on a glass substrate, wherein the reinforcing layered material provides a sealing material for a solid oxide fuel cell, wherein the reinforcing layered material is spherical oxide particles having an average particle diameter of more than 5 / zm and less than 21 GPa. .

The content of the reinforcing layer dusting, relative to the total amount of the glass matrix and the reinforcing filler 100% by weight, may be 25% by weight or more and 35% by weight or less.

The reinforcing filler may be one or more of alumina (A1 ₂ 0 ₃ ), or Y ₂ 0 ₃ — doped stabilized Zr¾.

The average particle diameter of the reinforcing filler may be 10 or more and 21 / rni or less.

The reinforcing layer dusting material may be alumina (A1 ₂ 0 ₃ ).

The glass matrix phase may include a Ba0-Al ₂ O ₃ -B ₂ O ₃ Si02-M ₂ O ₃ (M-Zr0 ₂ , ZnO, or a combination thereof) -based glass.

The Ba 0 -Al ₂ 0 ₃ -B ₂ 0 ₃ -Si0 ₂ -M ₂ 0 ₃ (M = Zr0 ₂₎ ZnO, or a combination thereof) is based on BaO: 40- 60 weight%, A1 ₂ 0 ₃ : 3-6 weight ¾>, ¾0 ₃ : 3-8 weight% Si0 ₂ : 30-40 weight%, and M ₂ 0 ₃ : 3-6 weight%. .

The solid oxide fuel cell sealing material has a maximum thickness strain

It may be 7 or more.

Another embodiment of the present invention, the step of mixing the glass powder and the reinforced layered material; Preparing a paste by adding a binder and a solvent to the mixed glass powder and the reinforced layered material; Applying the paste to a seal of the solid oxide fuel cell stack; And the applied paste And a heat treatment step; wherein the reinforcing layer dusting material may be spherical oxide particles having an average particle diameter of more than 5 // πι and 21 m or less.

In the step of mixing the glass powder and the reinforcing filler; the content of the reinforcing filler may be 25 to 35% by weight based on 100% by weight of the total amount of the glass powder and the reinforced layered filler.

Applying the paste to a seal of the solid oxide fuel cell stack; may be performed by a robot dispensing process.

Heat-treating the applied paste; may be performed ^at 800 ^° C. or more and 900 ^° C. or less.

The reinforcing layer dusting material may be alumina (A1 ₂ 0 ₃ ).

The average particle diameter of the alumina may be 10 / mm or more and 21 or less.

【Effects of the Invention]

One embodiment of the present invention provides a glass sealing material for a solid oxide fuel cell and a method for sealing a stack of a solid oxide fuel cell using the same. Through this, it is possible to manufacture a sealing material having improved durability while maintaining the tolerance absorbing capacity of the sealing material. In addition, durability of the thermal cycle of the solid oxide fuel cell stack may be improved.

[Brief Description of Drawings]

1 is an SEM image of particles of a conventional non-spherical alumina layered material having an average particle diameter of 4.8 mm 3. Of

2 is a SEM photograph of spherical alumina particles having an average particle diameter of 10. 3 is a SEM photograph of spherical alumina particles having an average particle diameter. 4 is a graph comparing the maximum thickness strain according to the content of the reinforcing layered material.

Figure 5 is a photograph of the sealing material made in the form of a strip (str ip) for the maximum thickness strain measurement.

6 is a schematic diagram of the maximum thickness strain measurement experimental configuration.

7 is a photograph of a sealant and a stopper formed on an STS444 plate for gas leak rate measurement experiments.

8 is a schematic diagram of the experimental configuration for measuring gas leakage. 9 is a graph comparing the results of durability according to the heat cycle.

10 is a schematic diagram of a temperature raising and lowering schedule of the heating furnace during the heat cycle.

[Best form for implementation of the invention]

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, "particle diameter" means the diameter of a spherical material unless otherwise defined. If the material is non-spherical, it means the diameter of the sphere calculated by approximating the non-spherical material to the sphere.

As used herein, "average particle diameter" means the average diameter of spherical materials present in a unit of measurement unless otherwise defined. If the material is non-spherical, it means the diameter of the sphere calculated by approximating the non-spherical material to the sphere.

In stacks of solid oxide fuel cells, cracking between metal separators and unit cell components to prevent the mixing of fuel gases and air, such as hydrogen and natural gas, to prevent leakage of gases out of the stack, and to insulate between unit cells It is important. In general, the glass-based sealing material is used to prevent gas leakage due to its excellent interfacial adhesion, as well as long-term durability in a high temperature oxidation and reducing atmosphere. In addition, since the sealing process has a large strain in the thickness direction, thickness variations and warpage occurring during the manufacturing of components such as separators, current collectors and sals, misalignment between components during stack lamination, surface pressure and temperature Tolerances caused by deviations can be absorbed.

However, glass-based sealing material has a disadvantage of low strength and fracture toughness due to the material properties. Therefore, if the thermal and mechanical forces generated during the manufacture and operation of the stack accumulate, brittle fracture of the seal may occur during SOFC operation. In particular, the disadvantage of the glass sealant is that the temperature of the stack due to an external factor such as a thermal cycle such as a load cycle (Load ^' Tr ip) during the operation at 700 to 800 ^° C. Can occur when

In general, in order to improve the strength of the glass-based sealant than glass Oxide particles with high strength and elastic modulus and high fire resistance are added as a filler. Since the crack on the glass matrix is disturbed by the layered particles and the crack direction can be photographed, the robustness of the glass sealing material can be improved by improving the fracture toughness according to the increase of the crack propagation path.

In general, however, the oxide layering material f i ller having high modulus, hardness, and fire resistance prevents densification of glass particles by viscous flow. Accordingly, gas leakage may occur due to an increase in residual pores or a decrease in bonding strength of the seal. In addition, by increasing the content of the oxide layered material, the maximum thickness strain of the sealing material can be reduced because the deformation on the glass matrix is suppressed.

In addition, when the content of the oxide filler is increased, the contact area of the glass phase at the interface between the metal separator and the sealing material is relatively reduced, and thus the contact area of the oxide particles is relatively increased, thereby causing gas leakage.

The commercialization of S0FC requires the development of large area stacks. However, the higher stacking area of S0FC stack, the more the stacking tolerances or deformation due to local unevenness of surface pressure and silver are accumulated due to the quality deviation of each component. .

The tolerance absorbency of the seal can be expressed as the maximum thickness strain of the seal. Therefore, if the maximum thickness strain of the sealant is greatly reduced in the process of improving the durability of the sealant, it is difficult to apply to the high-laminate large area stack. The present invention provides a glass sealing material for a solid oxide fuel cell that can obtain a strengthening effect by increasing the content of the reinforcing layered material without causing the above problems.

In one embodiment of the present invention includes a reinforcing filler on a glass substrate, the reinforcing filler provides a sealing material for a solid oxide fuel cell that is a spherical oxide particles having an average particle diameter of more than 5 21mm or less.

Sealing material for a solid oxide fuel cell containing the reinforced layer of the present invention, the content of the reinforced layer can be increased compared to the conventional sealant mentioned above Because of this, the durability of the sealing material can be improved. In addition, despite the increased content of the reinforced layered material, it maintains a high maximum thickness deformation and is applicable to a large area stack.

The reinforced layered material may be spherical. In this case, the shape of the spherical particles, the shape of the real sphere with the longest diameter ratio (short-to-short ratio) to the shortest diameter, is most ideal.

When the reinforcing filler is spherical, the area where the components of the solid oxide fuel cell SOFC, for example, the metal separator and the reinforcing layered material contact at the interface can be minimized.

As the reinforcing filler content is increased, the fraction of reinforcing fillers that do not contribute to securing the gas tightness of the interface of the joint increases, and if a network between the reinforcing layer is formed, gas leakage may occur along the interface.

When the content of the reinforcing layering material in the sealant is the same, when the shape of the reinforcing layering material is spherical, the contact area of the filler at the interface can be minimized by forming point contact at the interface of the joint, thereby preventing gas leakage at the interface. can do.

The average-particle diameter of the spherical reinforcing filler may be more than 5 and less than 21. have. More specifically greater than 5 μs and less than 21; 8 or more and 21 or less; 10 or more and 20 or less; Or 10 or more and 21 or less.

If the average particle diameter of the reinforcing layered material is too large, it is difficult to uniformly disperse the particles in the glass matrix, so the durability of the sealing material may be lowered due to the nonuniformity of the structure. If the particle diameter of the layered material is too small, the contact between the reinforced layered material and the glass powder particles increases. However, when the contact area of the reinforcing layer material and the glass powder particles and the number of contact points increase, the effect of suppressing the viscous flow of the glass powder increases, which causes the densification of the glass-based sealing material due to the viscous flow. As a result, residual pores may be generated around the reinforcement layer. In addition, the maximum thickness strain of the seal can also be reduced.

The spherical reinforcing filler content may be 25% by weight or more and 35% by weight or less with respect to 100% by weight of the total sealant. More specifically 25% by weight or more 33 weight% or less, 27 weight% or more, 33 weight% or less, 29 weight% or more, 31 weight% or less, or 30 weight%.

In general, single phase glass is a material having a very low fracture toughness compared to a polycrystalline oxide material. Therefore, oxide-based reinforcing fillers having superior strength, hardness, elastic modulus, and fracture toughness as compared to glass have a greater effect of suppressing crack growth of known glass as the added amount increases.

Thus, when the content of the reinforcing layer is too small, the durability of the sealing material can not be significantly improved. On the other hand, when the content of the reinforced layered material is too much, the maximum thickness strain may be reduced to 70% or less, so that it may be difficult to secure the maximum thickness deformation. In general, in order to sufficiently absorb the tolerances of stack components such as sal and separator in large area stacks, the maximum thickness deformation of the sealant must be 70% or more to ensure sufficient reliability.

The reinforcing filler may be at least one of alumina (A1 ₂ 0 ₃ ) or Y ₂ 0 ₃ -doped Zr0 ₂ . However, this kind is only an example and is not limited thereto. More specifically, it may be alumina (A1 ₂ 0 ₃ ).

The glass matrix of the present invention may comprise BaO—Al ₂ O ₃ —B ₂ O ₃ —SiO ₂ —M ₂ O ₃ (M = ZrO ₂ , ZnO, or a combination thereof) based glass. Castle ^"The content of each component of the group BaO glass for the glass the total amount of 100 parts by weight): 40-60% by weight, A1 ₂ 0 _3: 3-6% by weight, ¾0 _3: 3-8 wt.% Si0 _2: 30- 40 weight%, M ₂ 0 ₃ : 3-6 weight ¾ may be included.

In another embodiment of the present invention, the step of mixing the glass powder and the reinforcing filler; Preparing a paste by adding a binder and a solvent to the mixed glass powder and the reinforced layered material; Applying the paste to a seal of the solid oxide fuel cell stack; And heat-treating the applied paste. The reinforcing layer dusting material provides a sealing method of a solid oxide fuel cell in which spherical oxide particles having an average particle diameter of more than 5 and 21 or less.

Mixing the glass powder and the reinforcing layered material; the content of the reinforcing filler is based on the total weight of the glass powder and the reinforcing layered material »100

25 weight ¾ or more may be 35 weight% or less. More specifically, 25% by weight ¾ »or more, 33% by weight or less, 27% by weight or more, 33% by weight or less, 29% by weight or more and 31% by weight Or less than or equal to 30% by weight.

Applying the paste to a seal of the solid oxide fuel cell stack; may be performed by a dispensing process. However, the present invention is not limited thereto, and any method may be used as long as it is possible to prepare a paste or slurry of a sealing material such as tape casting, tape calendering, extrusion, screen printing, and bar coating to a desired thickness and width. 열처리 heat-treating the introduced paste; the heat treatment temperature may be 800 ^° C or more and 90 CTC or less. If the heat treatment temperature is lower than 800 ^° C, the sealing material may not be sufficiently densified. If the heat treatment temperature is higher than 900 ^° C, oxidation and deformation of the metal material among the stack components may occur severely.

During the pretreatment and operation of the solid oxide fuel cell stack, a surface pressure is applied to the entire stack to apply a constant compressive force to the sealing portion to secure the adhesion of the sealing interface and to prevent thermomechanical damage. Range of the compressive force is 0.5kgf / cm ² is at least 4kgf / cm ² or less.

[Form for implementation of invention]

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples. Examples and Comparative Examples

Example 1

_{_{P5 (BaO- Al 2 0 3 -¾0}} 3 -Si0 2 eu _{_{M 2 0 3 (M = Zr0}} 2, and ZnO) based, content of each component contained in the glass powder is _{BaO:. 40 ~ 60wt, A1} 2 0 ₃ : 3 ~ 6wt%, B ₂ 0 ₃ : 3 ~ 8wt% Si0 ₂ : 30 ~ 40wt, M ₂ 0 ₃ : 3 ~ 6), glass and spherical alumina powder (average particle size 10, Showa Denko, CB- A10S).

The average particle diameter of the spherical alumina powder used in this example is the D50 reference average particle diameter suggested by the manufacturer, and CB-A10S of Showa Denko is measured by Coullter Counter Methode.

2 is a SEM photograph of the spherical alumina.

After mixing 70 g of the glass powder, and 30 g of the spherical alumina powder, R910 (Winner Tech) was mixed with a vacuum conditioning mixer (Musashi Engineer Ing, A-MV310) as a binder to prepare a paste for robot dispensing.

Example 2

In Example 1, except that the glass powder was changed to 90g, a spherical alumina powder 10 _{_g.} In the same manner as in Example 1, a sealing test sample was prepared.

Example 3

In Example 1, a sealing test sample was prepared in the same manner as in Example 1, except that 80 g of glass powder and 20 g of spherical alumina powder were changed.

Example 4

In Example 1, except for changing to 60 g of the glass powder and 40 g of the spherical alumina powder, a sealing test sample was prepared in the same manner as in Example 1 _. Prepared.

Example 5

In Example 1, a sealing test sample was prepared in the same manner as in Example 1, except that 50 g of glass powder and 50 g of spherical alumina powder were changed.

Example 6

In Example 1, the spherical alumina powder having an average particle diameter of 21 (Showa

Seal test samples were prepared in the same manner as in Example 1, except that Denko CB-A20S) was used. The average particle diameter of the spherical alumina powder used in this example is the D50 reference average particle diameter suggested by the manufacturer, and in the case of CB-A20S of Showa Denko, measured by Coulter Counter Methode.

3 is a SEM photograph of the spherical alumina.

Example 7

In Example 6, a sealing test sample was prepared in the same manner as in Example 1, except that 90 g of glass powder and 10 g of spherical alumina powder were changed.

Example 8 In Example 6, a sealing test sample was prepared in the same manner as in Example 1, except that 80 _{g of} glass powder and 20 _g of spherical alumina powder were changed.

Example 9

In Example 6, a sealing test sample was prepared in the same manner as in Example 1, except that 60 g of glass powder and 40 g of spherical alumina powder were changed.

Example 10

In Example 6, a sealing test sample was prepared in the same manner as in Example 1, except that 50 g of glass powder and 50 g of spherical alumina powder were changed.

Comparative Example 1

In Example 1, except that a spherical alumina powder (Showa Denko, CB-A05S) having an average particle diameter of 5 was used, a sealing test sample was prepared in the same manner as in Example 1. The average particle diameter of the spherical alumina powder used in this comparative example is the D50 reference average particle diameter suggested by the manufacturer, and CB-A05S manufactured by Showa Denko is measured by the Coulter Counter Methode.

Comparative Example 2

In Comparative Example 1, a sealing test sample was prepared in the same manner as in Comparative Example 1, except that 90 g of glass powder and 10 g of spherical alumina powder were changed.

Comparative Example 3

In Comparative Example 1, a sealing test sample was prepared in the same manner as in Comparative Example 1, except that 90 g of glass powder and spherical alumina powder ^' lOg were changed.

Comparative Example 4

In Comparative Example 1, 80 g of glass powder, 20 g of spherical alumina powder. Except having changed, the sealing test sample was produced by the same method as the comparative example 1. ^'

Comparative Example 5 In Comparative Example 1, except for changing to 60 g of the glass powder and 40 g of the spherical alumina powder, a sealing test sample was prepared in the same manner as in Example 1.

Comparative Example 6

In Example 1, a sealing test sample was prepared in the same manner as in Example 1, except that a non-spherical alumina powder (AM21, average particle size of 4.8 1, Sumi tomo) that had been used in the past was used. The average particle diameter of the non-spherical alumina powder used in this comparative example is the D50 reference average particle diameter suggested by the manufacturer, and measured by Laser Di fract ion (MT3300) in the case of 崖 21 sumi tomo.

1 is a SEM photograph of the non-spherical alumina. As can be seen in Figure 1, it consists of a conventional plate and polyhedral form.

Comparative Example 7

In Comparative Example 6, a sealing test sample was prepared in the same manner as in Comparative Example 6, except that 90 g of glass powder and 10 g of non-spherical alumina powder were changed.

Comparative Example 8

In Comparative Example 6, except that 80 g of glass powder and 20 g of non-spherical alumina powder were changed, a sealing test sample was prepared in the same manner as in Comparative Example 6.

Comparative Example 9

In Comparative Example 6, a sealing test sample was prepared in the same manner as in Comparative Example 6, except that 75 g of the glass powder and 25 g of the non-spherical alumina powder were changed.

Comparative Example 10

In Comparative Example 6, 50 g of glass powder and 50 g of non-spherical alumina powder were changed. Except for the sealing experiment sample was prepared in the same manner as in Comparative Example 6.

Experimental Example

Experimental Example 1 Measurement of Maximum Thickness Strain The maximum thickness strain is the thickness strain at the sealing temperature and the surface pressure in the absence of a component that acts as a stopper to stop the deformation of the sealing material, such as a cell or a current collector, and when stacking a solid oxide fuel cell stack. Tolerance of each component is an indicator of the ability of the sealant to absorb.

In this experimental example, the maximum thickness strain test of the sealing material in the stack surface pressure 3kgf / cm ² stack was carried out. As shown in FIG. 5, a strip material having a thickness of 1.0 隱 and a width of 5.5 str is formed by a robot dispensing process on a metal plate made of Ferr itic Stainless Steel (STS 444) having a thickness of 2 醒 and 150 讓 X 150 mm. It was. In general, due to the stack surface pressure is [sealant later area (~ design area) + cell area)] x 3kgf / cm ^2, the present experiment, the initial area of the sealing material in the example of the stack contact pressure actual stack of 3kgf / cm ^² 250cm ² of In the case of reflecting the application of a surface pressure of about 3, 000 kgf, the maximum thickness deformation is increased to 1 ⁰ C per minute up to 850 ^o C with a surface pressure of the initial area X 12 kgf / cm ² of the test seal at the same rate for 4 hours. The maximum thickness shrinkage was evaluated by holding it for a while and then cooling to room temperature at 1 ⁰ C per minute. At this time, the maximum thickness deformation was calculated as [(initial thickness-later thickness) / initial thickness] X 100 (%) by measuring the later height relative to the initial height of the sealing material. The maximum thickness deformation of the sealing material was measured through the experiments of Examples 1 to 10 and Comparative Examples 1 to 10. The measurement results are shown in FIG. 4. Referring to FIG. 4, as a result of measuring the maximum thickness strain according to the layered ash content, it was confirmed that the addition of spherical alumina particles having an average particle diameter of 10 or 73 maintains a 73% thickness strain even at 30 wt%. In addition, it shows a maximum thickness strain of more than 70% up to a content of about 35 weight ¾.

The effect of increasing the maximum thickness strain tended to saturate at the average particle diameter of 21 of spherical alumina. When the size of the layered particles is too large, it is difficult to uniformly disperse the particles, and since the thickness strain enhancing effect reaches a saturation state, it was determined that it is not necessary to add alumina particles having a larger average particle size.

On the other hand, when the average particle size of 4.8 zm non-spherical alumina particles used and the average particle size m-spherical particles are added, the maximum thickness strain is 70 at the point where the filler content is about 25% by weight. Below% The decrease was found to be unsuitable for application to solid oxide fuel cell stacks.

Experimental Example 2 Evaluation of gas leak rate (density) and heat cycle durability

The gas leak rate and durability of the sealing test samples of Example 1, Example 6 and Comparative Example 1 were evaluated. Specifically, using a stainless steel plate (STS444) metal plate as shown in the left photo of FIG. 7 and a leak rate measurement replica plate (material Crofer 22APU) as shown in the schematic diagram of FIG. Whether the airtightness of the sealing material of 6 was secured and the leakage rate change according to the heat cycle were measured to compare the heat cycle durability of each sealing material.

Apply a surface pressure of 3.0 kgf / cm ² to the sum of the final area of the sealant (~ design area) and the stopper area on the leak rate evaluation plate, and raise the temperature to 850 ^° C at rc / min and hold for 4 hours. Malbong was formed. In the process of heating up to the sealing temperature, the sealing material is densified by the viscous flow of the glass powder and decreases in thickness, and when the height of the stopper reaches the height of the stopper, the change in height is no longer possible, so the thickness change is stopped.

In this experiment, 0.5 mm3 alumina substrate was used as a stopper based on a 1 mm thick 5.5 mm thick encapsulant. After the sealing is formed, the temperature of the heating furnace is cooled to 700 ^° C, which is the evaluation temperature of operation. At this time, N ₂ gas is injected into the leak rate evaluation plate, which is blocked from the outside with the sealing material, and when the pressure reaches 1 atm, the gas supply is cut off. Then, the pressure change over time was checked for 10 minutes, and the pressure decrease was recorded over time, and the leakage rate was measured (sccm / cm) as the amount of gas leaked per unit time per unit length of the sealant at 0 ° C.

In general, it can be said that the gas leakage through the sealing material has sufficient airtightness as the back surface solid oxide fuel cell (S0FC) sealing material of 0.01 sccm / cm or less.

As a result of the experiment, as shown in FIG. 9, immediately after the seal formation, Comparative Example 1 using the conventional non-spherical alumina having an average particle diameter of 4.8 as a layering material, and an example using spherical alumina particles having an average particle diameter of 10 and an average particle diameter of 21 卿 as the layering material It was confirmed that no gas leakage occurred in the samples of 1 and 6, either. In order to compare the durability of the samples of Example 1 and Comparative Example 1, the leak rate was evaluated by applying a heat cycle of the type shown in FIG. Experimental results are shown in

9 is shown.

In Comparative Example 1, in which a non-spherical alumina powder having an average particle diameter of 4.8, which has been conventionally used, was added to the sealing glass, it was observed that the leakage rate increased with the heat cycle and the leakage reached the limit after 13 times. On the other hand provided by the present invention

It was confirmed that Example 1 which added 30 weight% of 10 spherical aluminas, and Example 2 which added 30 weight% of 10 spherical alumina did not generate gas leakage until 13 times.

Through this, it could be confirmed that the present invention provides a sealing material having greatly improved durability by using a reinforcing filler having a larger particle size and a spherical shape than the existing glass powder.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

[Explanation of code]

21 ： Upper plate

22 ： Sealant

23 ： Leak evaluation simulation board

24 ： Stopper

25 ： Lower pressure plate

Claims

[Claim]

[Claim 1]

Including reinforcing layered material on the glass base ，

The reinforcing layer isolation material is a solid oxide fuel cell sealing material, which is a spherical oxide particle having an average particle diameter of more than 21 m.

[Claim 2]

In claim 1, ■ The content of the reinforcing layered material,

For glass base and tempered layered materials and total weight 100

Sealing material for a solid oxide fuel cell that is 25% by weight or more and 35% by weight or less. -

[Claim 3]

In paragraph 1,

The reinforcing filler is,

Sealing material for a solid oxide fuel cell, which is at least one of alumina (A1 ₂ 0 ₃ ) or Y ₂ 0 ₃ -doped stabilized Zr.

[Claim 4]

In claim 3,

The average particle diameter of the reinforcing filler is

A sealing material for a solid oxide fuel cell that is at least lOfm and not more than 21.

[Claim 5]

In paragraph 4,

The reinforcing filler is,

A sealing material for a solid oxide fuel cell, which is alumina (A1 ₂ 0 ₃ ).

[Claim 6]

In paragraph 1,

The glass matrix phase is Ba () -Al ₂ 0 ₃ -B ₂ 0 ₃ -Si0 ₂ -M ₂ 0 ₃ (M = Zr0 ₂ , ZnO, or a combination thereof) based glass for a solid oxide fuel cell Sealant.

[Claim 7]

In claim 6,

The Ba0-A l ₂ 0 ₃ -B ₂ 0 ₃ -Si0 ₂ -M ₂ 0 ₃ (M = Zr0 ₂₎ ZnO, or a combination thereof is based glass, BaO: 4 ()-60% by weight, A1 ₂ 0 ₃ : 3-6% by weight, 0 ₃ : 3-8% by weight Si0 ₂ : 30-40% by weight, and M ₂ relative to 100% by weight of the total glass. 0 ₃ : A sealing material for a solid oxide fuel cell containing 3-6% by weight.

[Claim 8]

In paragraph 1,

The solid oxide fuel cell sealing material,

Sealant for solid oxide fuel cells, with a maximum thickness deformation of more than 70%.

[Claim 9]

Mixing the glass powder and the reinforced layered material;

Preparing a paste by adding a binder and a solvent to the mixed glass powder and the reinforced layer dust;

Applying the paste to a seal of the solid oxide fuel cell stack; And heat treating the applied paste.

And the reinforcing filler is a spherical oxide particle having an average particle diameter of more than 5 and 21 or less.

[Claim 10]

In claim 9,

Mixing the glass powder and reinforcing filler;

The content of the reinforcing filler is a solid oxide fuel cell sealing method of 25% by weight ¾> 35% by weight, based on 100% by weight of the total amount of the glass powder and the reinforced layered material.

[Claim 11]

In paragraph 10,

Applying the paste to a sealing portion of a solid oxide fuel cell stack; is performed by a robot dispensing process.

[Claim 12]

In paragraph 10,

Heat-treating the applied paste;

Of the solid oxide fuel cell that is carried out at a temperature of 800 ^° C or more and 900 ^° C or less. Sealing method.

[Claim 13]

In paragraph 10,

The reinforcement layered material,

A method of sealing a solid oxide fuel cell which is alumina (A1 ₂ 0 ₃ ).

[Claim 14]

Clause 13

The average particle diameter of the alumina is

A sealing method for a solid oxide fuel cell that is more than lO ^ m and less than 21.