KR102119318B1 - Composition of sealing glass for solid oxide fuel cell and sealing paste comprising the same - Google Patents

Composition of sealing glass for solid oxide fuel cell and sealing paste comprising the same Download PDF

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Publication number
KR102119318B1
KR102119318B1 KR1020180117600A KR20180117600A KR102119318B1 KR 102119318 B1 KR102119318 B1 KR 102119318B1 KR 1020180117600 A KR1020180117600 A KR 1020180117600A KR 20180117600 A KR20180117600 A KR 20180117600A KR 102119318 B1 KR102119318 B1 KR 102119318B1
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South Korea
Prior art keywords
fuel cell
solid oxide
oxide fuel
glass composition
mol
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KR1020180117600A
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Korean (ko)
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KR20200038024A (en
Inventor
정운진
이한솔
김우식
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공주대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders

Abstract

Sealed glass composition for a solid oxide fuel cell according to the present invention includes 20 to 40 mol% of SiO 2 , 15 to 30 mol% of B 2 O 3 and 40 to 60 mol% of BaO, and an average coefficient of thermal expansion measured at room temperature to 600° C. It is characterized in that it is 80 × 10 -7 ℃ or more.

Description

Composition of sealing glass for solid oxide fuel cell and sealing paste comprising the same}

The present invention relates to a sealing glass composition for a solid oxide fuel cell and a sealing paste comprising the same.

Generally, a solid oxide fuel cell (SOFC) is a device that converts chemical energy of a fuel into electrical energy directly in a cell, and is a pollution-free power generation device that has been recently studied with interest as a power source for automobiles.

In such a solid oxide fuel cell, a stack of a fuel cell cell assembly in which a unit cell for producing electricity is stacked and its peripheral parts is supplied with hydrogen as a fuel gas as an anode and oxygen as an oxidant as a cathode to produce electricity.

In such a solid oxide fuel cell, a sealing material that prevents hydrogen or oxygen (air), which is a fuel gas, from being mixed with each other, does not mix or leak between the components, is sealed at the gas sealing portion.

The function of the sealing material used in the gas sealing part in the fuel cell is to prevent the anode, the cathode gas, and the surrounding atmosphere gas from mixing with each other. When gas is mixed with each other, it has a fatal effect on the efficiency of the fuel cell, and also the temperature rises locally, which gives the cell bad results.

As a function of another sealing material, it is flexible enough at the operating temperature, so it can function to reduce the mechanical stress that can occur during unit cell or stack operation.

Sealing materials that can be used in solid oxide fuel cells operating at high temperatures of 700°C or higher must be hermetically sealed with the material to be adhered, and thermal expansion coefficient and heat resistance properties must be able to fully satisfy the conditions of use. Crystallized glass materials have been mainly researched and developed.

Among glass, soda lime silicate glass, which is well known as a general window glass, reacts with the components of the battery or has a very low viscosity of 10 3 Pa·sec or less at 700 to 1000° C., causing a leak of the sealing adhesive.

The glass or crystallized glass composition developed for use as a sealing material for solid oxide fuel cells includes SrO-La 2 O 3 -Al 2 O 3 -B 2 O 3 -SiO 2 -based glass, and BaO- used in TFT-LCD. Al 2 O 3 -B 2 O 3 -SiO 2 -based commercial glass substrates were also used as sealing materials, but in the case of the above-mentioned glass or crystallized glass, it is difficult to obtain a satisfactory effect in preventing gas leakage.

In Korean Patent Publication No. 10-2005-0028069, glass containing oxides of BaO, SiO 2 , B 2 O 3 , ZrO 2 , Al 2 O 3 is a sealed glass composition for solid oxide fuel cells in which the amount of these oxides is adjusted. It is disclosed. However, since the glass composition according to Korean Patent Publication No. 10-2005-0028069 has a low softening temperature of 700° C. or lower, adhesion may be deteriorated when a high temperature solid oxide fuel cell is operated, and alkali group elements, transition metals, etc. Since this is contained, there is a problem of deterioration by reacting with the electrolyte of the solid oxide fuel cell.

Korean Patent Publication No. 10-2005-0028069

The present invention is to solve the above problems, to provide a sealed glass composition for a solid oxide fuel cell having a high thermal expansion coefficient that can be sufficiently used as a sealing material in a high temperature solid oxide fuel cell manufacturing process even with a ternary composition.

In addition, the present invention provides a sealed glass composition for a solid oxide fuel cell having excellent heat resistance and chemical resistance at an operating temperature of a high temperature solid oxide fuel cell.

In addition, the present invention provides a sealing paste comprising the sealing glass composition for the solid oxide fuel cell.

On the other hand, other objects not specified in the present invention will be further considered within a range that can be easily deduced from the following detailed description and its effects.

In order to achieve this object, the sealing glass composition for a solid oxide fuel cell according to an embodiment of the present invention includes 20 to 40 mol% of SiO 2 , 15 to 30 mol% of B 2 O 3 and 40 to 60 mol% of BaO. The average thermal expansion coefficient measured at room temperature to 600°C is 80×10 -7 °C or higher.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, the molar ratio of (SiO 2 + B 2 O 3 )/BaO may be 0.6 to 1.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, the molar ratio of SiO 2 /B 2 O 3 may be 0.6 to 2.7.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, the molar ratio of BaO/B 2 O 3 may be 1.3 to 4.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, one or two or more selected from Na 2 O, K 2 O, Al 2 O 3 , WO 3 and La 2 O 3 is greater than 0 and 15 mol % Or less.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, it may include more than 0 and 20 parts by weight or less of a ceramic filler with respect to 100 parts by weight of the sealed glass composition for a solid oxide fuel cell.

In the sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention, the ceramic filler may have an average coefficient of thermal expansion measured at room temperature to 600°C or more and 150×10 -7 °C or higher.

In addition, the present invention is a sealed glass composition for a solid oxide fuel cell described above; And a sealing paste comprising an organic binder.

The sealed glass composition for a solid oxide fuel cell according to the present invention may have an average thermal expansion coefficient of 80×10 -7 °C or higher measured at room temperature to 600°C even with a ternary composition alone, and also operate at a high temperature of about 700 to 800°C. Even in the operating environment of the solid oxide fuel cell, there is an advantage that it can be stably used without cracking or deterioration due to thermal shock.

In addition, the sealed glass composition for a solid oxide fuel cell according to the present invention is rapidly melted at a temperature of about 900 to 1000° C., which is the manufacturing temperature of a solid oxide fuel cell, to give a high bonding strength even with only a ternary composition, thereby improving the speed and efficiency of the process. Can be given.

In addition, the sealed glass composition for a solid oxide fuel cell according to the present invention is chemically stable because it has little reactivity with an electrolyte of a solid oxide fuel cell operating at a high temperature of about 700 to 800°C, and is physically strong due to high adhesion strength, It is possible to manufacture at the same temperature as that of the solid oxide fuel cell.

In addition, the sealing glass composition for a solid oxide fuel cell according to the present invention may further provide a sealing glass having a higher thermal expansion coefficient by further including a ceramic filler.

On the other hand, even if the effects are not explicitly mentioned herein, it is noted that the effects described in the following specification expected by the technical features of the present invention and the potential effects thereof are treated as described in the specification of the present invention.

Hereinafter, the present invention will be described in detail. The following examples and drawings are provided as examples to sufficiently convey the spirit of the present invention to those skilled in the art. In addition, unless otherwise defined in the technical terms and scientific terms used in the present invention, those skilled in the art to which this invention belongs have the meanings commonly understood, and the present invention in the following description and accompanying drawings Descriptions of well-known functions and configurations that may unnecessarily obscure the subject matter are omitted.

In describing the present invention, the term "thermal expansion coefficient" means an average thermal expansion coefficient measured at room temperature to 600°C.

In describing the present invention, the term “fluidity” refers to a state in which the glass can melt and flow when the sealed glass composition is heated at 900° C. for 30 minutes. In addition, when the fluidity of the glass composition is good in the present invention, the sealed glass composition is rapidly melted at a temperature of about 900° C. or higher, which is the manufacturing temperature of the solid oxide fuel cell, and thus gives high bonding strength, thereby improving the speed/efficiency of the process. It can be interpreted as giving.

Unless specifically stated in the present invention, the sealed glass composition means amorphous.

Sealed glass composition for a solid oxide fuel cell according to an embodiment of the present invention comprises 20 to 40 mol% of SiO 2 , 15 to 30 mol% of B 2 O 3 and 40 to 60 mol% of BaO, measured at room temperature to 600° C. It is characterized by an average thermal expansion coefficient of 80 × 10 -7 °C or higher.

The sealed glass composition having the above composition ratio and the coefficient of thermal expansion exhibits excellent fluidity at 850°C or higher, so it can be manufactured at the same temperature as that of the solid oxide fuel cell, and is physically strong due to its high bonding strength. . In addition, the sealed glass composition does not soften at about 700° C., which is the operating temperature of the solid oxide fuel cell, and has little reactivity with the electrolyte, and thus has physical and chemical stability.

Looking specifically at each component constituting the sealed glass composition for a solid oxide fuel cell according to the present invention, the SiO 2 is an oxide forming a network structure as a main component of the glass to increase the heat resistance and heat shock resistance , When the content is high, the melting point of the glass is increased, while the content of SiO 2 can also increase the thermal conductivity. Therefore, the content of SiO 2 is preferably in the range of 20 to 40 mol%, preferably 20 to 30 mol%. According to an embodiment of the present invention, when the content of SiO 2 is less than 20 mol% or exceeds 40 mol%, phase separation may occur during glass production, and the sealing glass composition may not melt. have.

The B 2 O 3 acts as a network forming agent similar to SiO 2 but has a two-dimensional structure, thereby increasing glass stability of the glass material and contributing to viscosity reduction. However, if the content of B 2 O 3 exceeds 30 mol%, the thermal expansion coefficient decreases and phase separation may occur. In addition, if the content of B 2 O 3 is less than 15 mol%, there is a problem in that phase separation occurs easily and melting and glass formation are difficult. Therefore, it is preferable that the content of B 2 O 3 satisfies the range of 15 to 30 mol%, or 15 to 25 mol%.

The BaO is a major component that forms a glass structure as a network modifier, and serves to increase chemical durability and thermal conductivity. However, when the BaO is contained too high, phase separation phenomenon easily occurs, and melting and glass formation are difficult, or the devitrification characteristics and chemical resistance may be reduced and the viscosity may be increased. When the BaO is contained too low, the thermal conductivity may be lowered. Can be. Therefore, the content of BaO is preferably in the range of 40 to 60 mol%, or 50 to 60 mol%. According to an embodiment of the present invention, when the content of BaO is less than 40 mol% or exceeds 60 mol%, phase separation may occur during glass production, and the sealing glass composition may not melt. have.

Meanwhile, in the sealed glass composition for a solid oxide fuel cell according to another embodiment of the present invention, the molar ratio of (SiO 2 + B 2 O 3 )/BaO may be 0.6 to 1. When the molar ratio of (SiO 2 + B 2 O 3 )/BaO is less than 0.6, a phenomenon in which the sealed glass composition does not melt may occur, and when the molar ratio of (SiO 2 + B 2 O 3 )/BaO is greater than 1 The thermal expansion coefficient of the prepared glass may be lowered to less than 80×10 -7 /℃. In addition, when the molar ratio of (SiO 2 + B 2 O 3 )/BaO is less than 0.6 or exceeds 1.2, the fluidity rapidly decreases, so the molar ratio of (SiO 2 + B 2 O 3 )/BaO is 0.6 to 1, preferably It is good to satisfy the range of 0.7 to 1.

In addition, in the sealed glass composition for a solid oxide fuel cell according to another embodiment of the present invention, the molar ratio of SiO 2 /B 2 O 3 may be 0.6 to 2.7. When the molar ratio of SiO 2 /B 2 O 3 is less than 0.6, the thermal expansion coefficient may be lowered to less than 80×10 -7 /°C, and when the molar ratio of SiO 2 /B 2 O 3 exceeds 2.7, the sealed glass composition This non-melting phenomenon may occur. In addition, when the molar ratio of SiO 2 /B 2 O 3 is less than 0.6 or exceeds 2.7, fluidity rapidly decreases, so the molar ratio of (SiO 2 + B 2 O 3 )/BaO is 0.6 to 2.7, preferably 0.8 to It is good to satisfy the range of 2.0.

In addition, in the sealed glass composition for a solid oxide fuel cell according to another embodiment of the present invention, the molar ratio of BaO/B 2 O 3 may be 1.3 to 4. When the molar ratio of BaO/B 2 O 3 is less than 1.3, the thermal expansion coefficient of the prepared glass may be lowered to less than 80×10 -7 /°C, and when the molar ratio of BaO/B 2 O 3 is greater than 4 A phenomenon that the sealing glass composition does not melt may occur. In addition, when the molar ratio of BaO/B 2 O 3 is less than 1.3 or exceeds 2.75, the fluidity rapidly decreases, so the molar ratio of BaO/B 2 O 3 satisfies the range of 1.3 to 4, preferably 2 to 4 It is good.

On the other hand, the sealing glass composition for a solid oxide fuel cell according to an embodiment of the present invention is one or two or more selected from Na 2 O, K 2 O, Al 2 O 3 , WO 3 and La 2 O 3 greater than 0 and 15 mol % Or less. Na 2 O, K 2 O, Al 2 O 3 , WO 3 and La 2 O 3 can improve the stability of the glass, and when included in the above category, the average thermal expansion coefficient of the sealed glass composition is about 120×10 -7. Although it can be raised above ℃ (measured at room temperature to 600 ℃), the present invention is not limited thereto. If one or more substances selected from Na 2 O, K 2 O, Al 2 O 3 , WO 3 and La 2 O 3 are contained in the sealed glass composition in an amount of more than 15% by weight, crystallization of the glass occurs. Liquidity may deteriorate.

In addition, the sealing glass composition for a solid oxide fuel cell according to another embodiment of the present invention may further include a ceramic filler.

The ceramic filler is sufficient if the average thermal expansion coefficient measured at room temperature to 600°C is 150×10 -7 °C or higher, and a preferred example is KAlSiO 4 .

In one embodiment of the present invention, when the filler contains more than 0 and 20 parts by weight or less of a ceramic filler with respect to 100 parts by weight of the sealed glass composition for a solid oxide fuel cell, the average thermal expansion coefficient of the sealed glass composition for a solid oxide fuel cell is about 110Х10. It can be raised above -7 °C.

In addition, the present invention is a sealed glass composition for a solid oxide fuel cell described above; And a sealing paste comprising an organic binder.

In the sealing paste according to an embodiment of the present invention, the organic binder may be a thermoplastic resin. As a specific and non-limiting example, the organic binder may include ethyl cellulose, an acrylate-based polymer, and the like.

Hereinafter, for the detailed description of the present invention, the following examples will be described in detail, but the present invention is not limited to the following examples.

(Examples 1 to 4, Comparative Examples 1 to 7)

The sealed glass composition for a solid oxide fuel cell according to the present invention is weighed by composition according to each example as shown in Table 1 below. Thereafter, the mixture mixed with the composition of Table 1 was melted at 1400°C for 1 hour, quenched on a copper plate at room temperature, immediately transferred to a heat treatment furnace, annealed at 550°C for 2 hours, and then cooled by furnace to prepare a final sealed glass composition.

In addition, the prepared sealed glass composition classified the glass formed transparently and the glass where phase separation occurred, and the transparent glass was processed into a glass specimen of a certain standard to measure the coefficient of thermal expansion. The specifications for processing were set to 5 mm (W) x 5 mm (D) x 10 to 15 mm (H), and after processing with a diamond cutter, the surface was optically polished to minimize surface roughness.

SiO 2
(mol%)
B 2 O 3
(mol%)
BaO
(mol%)
Coefficient of thermal expansion
(10 -7 /℃)
Remark
Comparative Example 1
(KRS-30)
15 35 50 - Phase separation
Example 1 (KRS-13) 20 20 60 96.1 Example 2
(KRS-22)
25 35 40 91.1
Example 3
(KRS-28)
35 20 45 80.6
Example 4 (KRS-3) 40 15 45 80.2 Comparative Example 2 (KRS-9) 35 10 55 - Beauty Jung Comparative Example 3
(KRS-15)
35 5 60 - Beauty Jung
Comparative Example 4
(KRS-16)
25 10 65 - Beauty Jung
Comparative Example 5 (KRS-19) 45 15 40 72.1 Comparative Example 6 (KRS-23) 20 40 40 66.2 Comparative Example 7
(KRS-26)
20 15 65 - Beauty Jung

In Table 1, "unmelted" refers to a sealed glass composition that is not melted after heat-treating a mixture having the composition of Table 1 at 1400°C for 1 hour.

As can be seen in Table 1, the sealing glass compositions prepared in Examples 1 to 4 include 20 to 40 mol% of SiO 2 , 15 to 30 mol% of B 2 O 3, and 40 to 60 mol% of BaO. , Transparent glass can be produced, phase separation of the prepared glass can be prevented, and especially, the coefficient of thermal expansion is 80×10 −7 /℃ or higher. As described above, the sealed glass composition having a coefficient of thermal expansion of 80×10 −7 /°C or higher improves the bonding strength in a high-temperature solid oxide fuel cell manufacturing process, and thus can be used as a sealing material for solid oxide fuel cell manufacturing.

However, as can be seen in Comparative Examples 1 to 7, SiO 2 20 to 40 mol%, B 2 O 3 15 to 30 mol% and BaO 40 to 60 mol% of at least one of the glass composition consisting of, if it deviates, It is difficult to use as a sealing material in a solid oxide fuel cell manufacturing process because a phase separation or unmelted state occurs or the thermal expansion coefficient is greatly reduced to less than 80×10 −7 /℃.

(Examples 5 to 9)

It was carried out in the same manner as in Example 1, but was prepared by adjusting the molar ratio of (SiO 2 + B 2 O 3 )/BaO, the molar ratio of SiO 2 /B 2 O 3 , and the molar ratio of BaO/B 2 O 3 .

Table 2 shows the results of measuring the thermal conductivity and fluidity of the sealed glass compositions according to Examples 1 to 9.

For the measurement of fluidity, after forming the molded body of the sealed glass composition with a diameter of 12 mm × 20 mm in height, the molded body is placed on a ceramic substrate used in a solid oxide fuel cell stack, and then heated at 900° C. for 30 minutes in air. The flow size adhered to the ceramic substrate as it melted and flowed down was measured and then denoted by A to D below.

-A: more than 20 mm,

-B: 16~20 mm,

-C: 13~16 mm,

-D: less than 13 mm

-E: does not melt

SiO 2
(mol%)
B 2 O 3
(mol%)
BaO
(mol%)
(SiO 2 + B 2 O 3 )
/BaO
SiO 2 /B 2 O 3 BaO/B 2 O 3 Coefficient of thermal expansion
(10 -7 /℃)
liquidity Remark
Example 1
(KRS-13)
20 20 60 0.7 1.0 3.0 96.1 A
Example 2
(KRS-22)
25 35 40 1.5 0.7 1.1 91.1 D
Example 3
(KRS-28)
35 20 45 1.2 1.8 2.3 80.6 D
Example 4 (KRS-3) 40 15 45 1.2 2.7 3.0 80.2 D Example 5
(KRS-14)
20 30 50 1.0 0.7 1.7 83.6 B
Example 6
(KRS-25)
20 25 55 0.8 0.8 2.2 84.2 A
Example 7 (KRS-12) 25 20 55 0.8 1.3 2.8 84.4 A Example 8 (KRS-11) 30 15 55 0.8 2.0 3.7 89.2 A Example 9
(KRS-17)
25 15 60 0.7 1.7 4.0 102.6 A
Comparative Example 8 (KRS-33) 15 20 65 0.5 0.8 3.3 - - Phase separation Comparative Example 9 (KRS-31) 15 30 55 0.8 0.5 1.8 - - Phase separation Comparative Example 2 (KRS-9) 35 10 55 0.8 3.8 5.5 - - Beauty Jung Comparative Example 7 (KRS-26) 20 15 65 0.5 1.3 4.3 - - Beauty Jung

As shown in Table 2, the sealing glass compositions of Examples 1 and 5 to 9 satisfy the composition range of the sealing glass composition described above, and the molar ratio of (SiO 2 + B 2 O 3 )/BaO is 0.6 to 1 , SiO 2 /B 2 O 3 Since the molar ratio of 0.6 to 2.7, and BaO/B 2 O 3 molar ratio of 1.3 to 4 satisfies the numerical range, the thermal expansion coefficient is not only excellent at 80×10 -7 /℃ or higher, , It also shows excellent results in fluidity characteristics.

However, in Examples 2 to 4, it can be seen that despite having a thermal expansion coefficient of 80×10 −7 /°C or higher, the fluidity characteristics were insufficient. The D grade is considered to be partially melted because the flow size is less than 13 mm, but is insufficient because it is an additional flow within 1 mm of the initial molded diameter because it reflects the molded body diameter (12 mm).

It can be seen that these fluidity results are related to the molar ratio values between the compositions listed in Table 2 above.

In detail, when the molar ratio of (SiO 2 + B 2 O 3 )/BaO exceeds 1, the fluidity appears as a D grade (Examples 2, 3, 4), and (SiO 2 + B 2 O 3 )/BaO When the molar ratio was less than 0.6, a phenomenon of unmelting occurred during glass production (Comparative Example 8).

In addition, when the SiO 2 /B 2 O 3 molar ratio was less than 0.6, phase separation occurred (Comparative Example 9), and when the SiO 2 /B 2 O 3 molar ratio exceeded 2.7, a phenomenon of unmelting occurred during glass production (Comparative Example 2). ).

In addition, when the molar ratio of BaO/B 2 O 3 was less than 1.3, fluidity appeared as a D grade (Example 2), and when the molar ratio of BaO/B 2 O 3 was greater than 4, a phenomenon of unmelting occurred during glass production (Comparative Example 7 ).

(Examples 10 to 13, Comparative Example 8)

It was carried out in the same manner as in Example 9, except that a mixture of 5, 10, 15, 20, and 25 parts by weight of a ceramic filler was added to 100 parts by weight of the sealed glass composition for a solid oxide fuel cell of Example 9 above. KAlSiO 4 was used as the ceramic filler.

The results of measuring the thermal conductivity and fluidity of the sealed glass compositions according to Examples 9 to 13 and Comparative Example 8 are listed in Table 3.

SiO 2
(mol%)
B 2 O 3
(mol%)
BaO
(mol%)
Ceramic filler Coefficient of thermal expansion
(10 -7 /℃)
liquidity Remark
Example 9
(KRS-17)
25 15 60 - 102.6 A
Example 10 25 15 60 5 111.5 B Example 11 25 15 60 10 115.1 B Example 12 25 15 60 15 118.6 B Example 13 25 15 60 20 121.3 B Comparative Example 10 25 15 60 25 - E Densification

In Table 3, "densification" means that the powder is not re-vitrified and sintered when measuring fluidity.

As shown in Table 3, it can be seen that the sealing glass compositions of Examples 10 to 13 further include the ceramic filler, thereby improving the thermal expansion coefficient by about 10 to 20% compared to Example 9. However, it was confirmed that the sealing glass composition according to Comparative Example 10 showed crystallization during glass production due to the excessive addition amount of the ceramic filler.

As described above, the present invention has been described by specific matters and limited embodiments and drawings, but it is provided to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Various modifications and variations can be made by those skilled in the art.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the spirit of the invention. .

Claims (8)

  1. SiO 2 20 to 40 mol%, B 2 O 3 15 to 30 mol% and BaO 40 to 60 mol%,
    The average thermal expansion coefficient measured at room temperature to 600°C is 80×10 -7 °C or higher,
    The molar ratio of (SiO 2 + B 2 O 3 )/BaO is 0.6 to 0.8, and the sealed glass composition for an amorphous solid oxide fuel cell.
  2. delete
  3. According to claim 1,
    A sealed glass composition for a solid oxide fuel cell having a molar ratio of SiO 2 /B 2 O 3 of 0.7 to 2.0.
  4. According to claim 1,
    A sealed glass composition for a solid oxide fuel cell having a molar ratio of BaO/B 2 O 3 of 1.7 to 4.
  5. According to claim 1,
    A sealed glass composition for a solid oxide fuel cell comprising one or more selected from Na 2 O, K 2 O, Al 2 O 3 , WO 3 and La 2 O 3 in an amount of more than 0 and 15 mol% or less.
  6. According to claim 1,
    A sealed glass composition for a solid oxide fuel cell comprising 0 to 20 parts by weight of a ceramic filler with respect to 100 parts by weight of the sealed glass composition for a solid oxide fuel cell.
  7. The method of claim 6,
    The ceramic filler is a sealed glass composition for a solid oxide fuel cell having an average coefficient of thermal expansion measured at room temperature to 600°C of 150×10 -7 °C or higher.
  8. A sealed glass composition for a solid oxide fuel cell according to any one of claims 1 to 3 to 7; And an organic binder.
KR1020180117600A 2018-10-02 2018-10-02 Composition of sealing glass for solid oxide fuel cell and sealing paste comprising the same KR102119318B1 (en)

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JP2012162445A (en) 2011-01-18 2012-08-30 Nippon Electric Glass Co Ltd High-expansive crystalline glass composition
JP2013056795A (en) 2011-09-08 2013-03-28 Nippon Electric Glass Co Ltd Crystalline glass composition and adhesive material using the same
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