JPH09115544A - Joining method of beta alumina solid electrolytic tube and ceramic insulation ring, and glass ring for joining and cell incorporated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a joining method for a glass solder joining which is reliable and low cost without many man-hours, in the joining method to join a ceramic ring insulating a positive pole chamber and a negative pole chamber in a high temperature type secondary cell and a beta alumina solid electrolyte tube using a glass solder, a glass ring for joining, and also the high temperature type secondary cell incorporated with the glass ring for joining. SOLUTION: This high temperature type secondary cell isolates a positive pole chamber and a negative pole chamber with a beta alumina solid electrolyte tube 3, and the positive pole chamber accommodates a sulfur or a compound of sulfur and sodium, a transition metal, or a halide of an aluminum, and the negative pole chamber accommodates a sodium. In this case, a glass solder joining between a ceramic insulating ring 2 which insulates the positive pole chamber and the negative pole chamber and the beta alumina solid electrolyte pipe 3 is made using a fusion glass ring 1 having at least a slit. Thereby, a joining structure can be obtained at lower cost, eliminating the advanced processing which meets the severe dimension accuracy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high temperature type secondary battery used for electric power storage, electric vehicle battery and the like, and more particularly to a ceramic ring and a beta for insulating a positive electrode chamber and a negative electrode chamber of the high temperature type secondary battery. A method of joining a beta-alumina solid electrolyte tube and a ceramic insulating ring, which can perform glass solder joining of an alumina solid electrolyte tube with high reliability and at low cost without man-hours, a glass ring for joining, and the same. The present invention relates to a built-in high temperature secondary battery.

[0002]

2. Description of the Related Art As shown in FIG. 1, a sodium-sulfur secondary battery, which is a typical high-temperature secondary battery, contains a positive electrode 6 made of sulfur as a positive electrode active material and a current collector, and a positive electrode. A positive electrode container 5, a negative electrode 7 made of metallic sodium, a negative electrode container 4 accommodating the negative electrode, a ceramic insulating material 2 for insulating the positive electrode container 5 and the negative electrode container 4, and a solid for separating the positive electrode 6 and the negative electrode 7 inside the battery. It is composed of an electrolyte tube 3.

The high temperature type secondary battery referred to in the specification of the present application is, in addition to the sodium-sulfur battery, a so-called Na / X battery using a transition metal or aluminum halide as a positive electrode active material, sulfur. Aluminum salt, selenium salt, tellurium salt, and those in which other alkali metal or alkaline earth metal is used instead of sodium. Further, a battery in which the arrangement of the positive electrode active material and the negative electrode active material is reversed from that of FIG. 1 is also included in the scope of the present invention.

In the case of a sodium-sulfur battery, both the positive electrode active material and the negative electrode active material are liquid at the battery operating temperature, and charge / discharge is performed by the following reversible reaction.

[0005]

(Equation 1)

[0006]

(Equation 2)

Here, the value is in the range of 3 ≦ x ≦ 5.

In such a high temperature type secondary battery, due to defects such as voids existing in the glass solder joint portion of the beta-alumina solid electrolyte tube and the ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber, There was a problem that caused a decrease in battery life.

Further, the bonding glass has been used by a method in which glass powder is applied in a paste form or a glass ring is attached to the bonding portion. When the glass powder is applied in a paste form, there is a problem that the solvent or the dispersant for forming the paste causes defects in the joint.
The method of attaching the glass ring to the joint portion is fragile, so that there is a risk of breakage when excessive stress is applied. Therefore, it is important that the accuracy of the glass ring, the ceramic insulating ring, and the beta-alumina-based solid electrolyte tube be within the tolerance range, and the processing cost of each member is high.

[0010]

As described above, in the high temperature type secondary battery, there are many problems in the glass solder joint portion, and therefore many techniques have been disclosed for improvement thereof.

For example, JP-A-1-54672 and JP-A-4-175271
The publication discloses a glass material. In addition, JP-A-3-
No. 291860, Japanese Patent Application Laid-Open No. 5-85844, and the like disclose joining methods.

However, in order to obtain a highly reliable glass bonded portion at a low cost, even if the materials and the bonding technology according to the disclosed technology are used, there remains a problem in the reliability of the bonded portion or the bonding processing cost. . In particular, many problems remain in the joining technology. Therefore, there is a problem that the battery is damaged and the battery life is shortened. Further, it has been one of the causes for increasing the manufacturing cost of the battery.

The present invention has been made in view of such circumstances, and it is possible to solve the above-mentioned problems, improve the reliability and life of a high temperature secondary battery, and reduce the manufacturing cost. An object of the present invention is to provide a method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring, a glass ring for joining, and a high temperature secondary battery incorporating the same.

[0014]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the invention described in claims 1 and 7 uses a beta-alumina solid electrolyte tube composed of β "-alumina and / or β-alumina to form a positive electrode chamber. In a high-temperature secondary battery in which the negative electrode chamber is isolated, the positive electrode chamber contains sulfur or a compound of sulfur and sodium, a transition metal or a halide of aluminum, and the negative electrode chamber contains sodium. Beta-alumina solid electrolyte obtained by using a glass ring having a slit formed in at least one position along the axial direction for glass-solder bonding of a ceramic insulating ring for insulating a chamber from a beta-alumina-based solid electrolyte tube The present invention relates to a method of joining a tube and a ceramic insulating ring, and a glass ring for joining the same. The glass ring having slits is used for the glass solder joining of the beta-alumina-based solid electrolyte tube of the high temperature secondary battery and the ceramic insulating ring.

In the prior art, since glass soldering was performed with a glass ring having a shape without a slit as shown in FIG. 2, the accuracy of the three members of the glass ring, the ceramic insulating ring, and the beta-alumina solid electrolyte tube was improved. If it was not within the tolerance range, it was impossible to wear the three. Particularly fragile glass rings were often broken during installation. Therefore, each member is processed by a high-level processing technique so that the accuracy of the three members falls within the tolerance range, resulting in a high cost.

The present invention avoids the above-mentioned problems of the prior art by forming a slit in the glass ring.

The inventions of claims 2 and 8 are shown in FIG.
As shown in (b) and (c), the slits of the glass ring are formed in parallel with the axis of the ring or at an angle (θ) formed with the axis of less than 20 degrees, and the glass rings are laminated by shifting the positions of the slits. The present invention relates to a method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring, which is characterized by performing glass solder joining, and the joined glass ring. Inserting the slits is simple, but if the slits are a single layer, the reliability of the joining of the slits is not sufficient. Therefore, stack glass rings as shown in Fig. 4, and shift the slits of each glass ring. Are laminated and joined together.

According to the third and ninth aspects of the invention, as shown in FIG. 5, the slits of the glass ring are formed with an angle of 20 degrees or more with respect to the axis of the ring. The present invention relates to a method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring and a glass ring for joining, which is characterized by performing glass solder joining.

According to the fourth and tenth aspects of the invention, the angle (θ) formed by the slit and the axis of the ring is less than 20 degrees and 20 degrees or more.
The present invention relates to a bonding method for bonding a glass ring for bonding, a beta-alumina-based solid electrolyte tube, and a ceramic insulating ring having a temperature of less than 100 degrees. When the angle formed by the slit formed with the axis of the glass ring is less than 20 degrees, there is a risk of continuous pores remaining in the slit portion when the glass melts, so the slit portion is a staggered laminated glass ring. There is a need.

The materials of the laminated glass rings may be the same or different. The characteristics required for glass are different between the positive electrode chamber side and the negative electrode chamber side of the battery, that is, since the negative electrode chamber side is exposed to Na atmosphere, Na corrosion resistance and the positive electrode chamber side are required to have mechanical strength. However, it may be effective to use different materials.

If the angle is in the range of 20 degrees to 80 degrees, the risk of continuous pores remaining is reduced, and it is not necessary to stack glass rings. In this case as well, the glass rings may be laminated and used.

Furthermore, the slit of the glass ring must be at least at one position as shown in FIG.
This may be in multiple places. When the angle is 80 degrees or more, it is difficult to process the slit in the glass ring and there is a risk that the end portion of the slit is easily damaged.

Claims 5 and 11 relate to the width of the slit and provide a molten glass ring having a width of 0.03 mm to 2 mm. When the slit width is 0.03 mm or less, it is not industrial because the cutting blade for forming the slit is limited.

On the other hand, if it is 2 mm or more, the slit width becomes too large, and there is a risk of residual pores in the slit portion.

The surface of the slit portion of the glass ring may or may not be a smooth surface.

[0026] Claims 6 and 12 relate to a method for joining a beta-alumina-based solid electrolyte tube using a colored glass ring and a ceramic insulating ring, and a joining glass ring.

A thirteenth aspect of the present invention relates to a high temperature secondary battery incorporating a joining body in which the joining glass ring and the beta-alumina solid electrolyte tube and the ceramic insulating ring are joined by the joining method of the present invention.

In the prior art, the glass ring, the ceramic ring, and the beta-alumina-based solid electrolyte tube were handled as an integral glass ring without slits. It was impossible to do. Therefore, each member is processed by a high-level processing technique so that the accuracy of the three members falls within the tolerance range, resulting in a high cost.

On the other hand, the glass ring and the ceramic ring which are slit as in the present invention and the glass ring are bonded to each other by performing glass bonding between the beta-alumina solid electrolyte tube and the ceramic ring. It is not necessary to improve the processing accuracy of the three parties of the beta-alumina solid electrolyte tube, and it is possible to significantly reduce the bonding cost.

When the slit of the glass ring is parallel to the axis of the ring or the angle formed with the axis is less than 20 degrees, the rings are laminated by shifting the positions of the slits and bonded by glass soldering. This glass ring has the effect that the method of forming the slit is simple and the processing is simple, but if the slit is a single layer, the reliability of the joining of the slit part is not sufficient, so the glass with the slit part shifted Join by stacking rings. This makes it possible to obtain a highly reliable joint at low cost.

In the case of a glass ring in which the slit makes an angle of 20 degrees or more and 80 degrees or less with the axis of the ring, the angle formed by the slit is parallel to the axis of the ring or is 20 degrees.
The processing becomes complicated as compared with the case where it is formed so as to be less than 100 degrees.

However, in this case, since the continuous pores do not remain there when the slit portion is melted, there is no need to stack glass rings, and there is an effect that the bonding work can be simplified.

The glass material that can be used in the present invention has a coefficient of thermal expansion adjusted between the beta-alumina-based solid electrolyte tube and the ceramic ring, and is electrically, chemically, and chemically controlled under the operating environment of the high temperature secondary battery. There is no particular limitation as long as it can ensure mechanical durability.

Further, in the present invention, when glass rings having different characteristics are laminated and used, it is effective to use colored glass so that the order of laminating the glass is not mistaken. Coloring of glass is obtained by adding transition metal elements such as Co, Fe and Cr or rare earth elements such as Er, Y, Th, Pr, Nd and Eu to glass. Add a few pp
The effect can be obtained with a minute amount of m to 1 mass%.

The characteristics of the glass containing 50 ppm of Co are the same as those of the glass without addition.

On the other hand, its color tone was blue, which was clearly distinguishable from glass without addition of Co. The strength of the glass containing 1.0 mass% Er was 1.2 times that of the glass containing no Er, and the color tone was pink with the effect of increasing the strength, and it was clearly distinguishable from the glass without Er addition by the color tone.

The effect of adding a coloring agent to glass is
In addition to the above effects, when glass adheres to the battery member, the adhered state can be easily detected by its color,
There is also an effect that the risk of causing battery contamination can be prevented.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to embodiments of the invention.

[First Embodiment] SiO2: 19.6 mass%, B2O3: 4
2.1mass%, Al2O3: 13.1mass%, BaO: 16.2mass%, ZrO2: 3.4
Glass ring with an inner diameter of 43 mm, an outer diameter of 45 mm, and a height of 3 mm obtained by melting glass having a composition of mass%, MgO: 5.6 mass%
Prepared (A). A glass ring (A) with a slit of 0.5 mm in width in a plane parallel to the axis of the ring (B), and a glass ring (A) with a surface having an angle of 45 degrees to the axis of the ring. A glass ring (C) having a slit of mm was similarly prepared. These glass rings have an outer diameter of 42.8 mm,
Set between the solid electrolyte tube manufactured with the indicated dimensions of inner diameter 38.8mm and length 380mm and the ceramic insulating ring manufactured with the indicated dimensions of inner diameter 47.2mm, outer diameter 63.2mm, and thickness 8mm, up to 950 ℃ The glass was heated to melt and bond the glass.

The joint portion between the solid electrolyte tube and the ceramic insulating ring should be subjected to a cantilever bending test in which the insulating ring 2 of the joined body shown in FIG. 7 is held and a load is applied to the side surface of the solid electrolyte tube 3. Evaluated by The cantilever bending load is shown in Table 1.

In the case of the glass ring A, some of the glass rings cannot be attached to the solid electrolyte tube due to dimensional errors between the members and deformation of the members. Sometimes it was damaged.

In the case of the glass ring B, there was no problem when the glass ring was attached, but the strength evaluation after joining resulted in variation in strength. Those with low strength were found to have residual pores in the slits. It was confirmed that when the C glass ring was used, there was no problem when the ring was attached and the strength was stable.

[0043]

[Table 1]

[Embodiment 2] Two glass rings of B of Embodiment 1 were laminated, and the slit portions were set out of phase with each other and set and joined. The joining conditions were the same as in the first embodiment. Table 2 shows the results.

There was no generation of a low-strength bonded body, and the glass bonded portion was thickened by laminating two rings, so that the overall strength was high.

[0046]

[Table 2]

[0047]

The glass solder joint of the beta-alumina-based solid electrolyte tube is performed by using a molten glass ring having a slit formed in at least one position. As a result, in the conventional technology in which a single ring is handled, it is not possible to mount the glass ring, the ceramic insulating ring, and the beta-alumina-based solid electrolyte tube unless the accuracy of the three is within the tolerance range. It was possible. Therefore, each member was processed by advanced processing technology so that the accuracy of the three members was within the tolerance range, resulting in high cost.

According to the present invention, by forming a slit in at least one place of the glass ring, the above-mentioned problems of the prior art can be avoided and a bonded body can be obtained at low cost.

[Brief description of the drawings]

FIG. 1 is a sectional view showing the overall structure of a sodium-sulfur battery to which the present invention is applied.

FIG. 2 is a perspective view showing a conventional glass ring shape.

FIG. 3 is a perspective view showing an external shape of a glass ring for bonding according to the present invention.

FIG. 4 is a perspective view showing a state in which the glass rings for bonding according to the present invention are laminated at the time of bonding.

FIG. 5 is a perspective view showing an external shape of a glass ring for joining according to the present invention.

FIG. 6 is a perspective view showing the outer shape of the glass ring for bonding according to the present invention.

FIG. 7 is an explanatory diagram showing a strength evaluation method of a glass solder joint portion of a sodium-sulfur battery to which the present invention is applied.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass solder joint part 2 Ceramic insulating ring 3 Solid electrolyte tube 4 Negative electrode container 5 Positive electrode container 6 Positive electrode 7 consisting of sulfur and current collector 7 Negative electrode

Front Page Continuation (72) Inventor Takashi Namerikawa 1-1-1 Omika-cho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Hiroki Yamamoto 7-1-1 Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd., Hitachi Research Laboratory

Claims (13)

[Claims] 1. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina-based solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide or the like and containing sodium in the negative electrode chamber, a ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina-based solid electrolyte tube are axially arranged. A method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring, characterized by performing glass solder joining through a glass ring having a slit formed at least at one position along the tube. 2. A positive electrode chamber and a negative electrode chamber are separated by a β-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is separated in the positive electrode chamber. In a high-temperature secondary battery containing a halide or the like and containing sodium in the negative electrode chamber, at least one ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are provided. A plurality of glass rings having slits formed in parallel with the axis of the ring or at an angle with the axis of less than 20 degrees are laminated by shifting the positions of the slits, and the glass is laminated via the laminated glass rings. A method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring, which is characterized by soldering. 3. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide or the like and containing sodium in the negative electrode chamber, at least one ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are provided. Beta-alumina-based solid electrolyte tube and ceramic made by glass-solder-bonding a glass ring having slits formed at an angle of 20 degrees or more at a position of the ring at a single point or by laminating a plurality of glass rings Insulation ring joining method. 4. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide or the like and containing sodium in the negative electrode chamber, at least one ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are provided. Beta-alumina-based solid electrolyte tube characterized by glass-solder-bonding glass rings having slits formed at an angle of 20 degrees or more and 80 degrees or less on the axis of the ring at a single position or by laminating a plurality of glass rings And the method of joining the ceramic insulating ring. 5. The width of the slit of the glass ring is 0.03.
mm to 2 mm. 5.
7. A method for joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring according to any one of 1. 6. The method of joining a beta-alumina-based solid electrolyte tube and a ceramic insulating ring according to claim 1, wherein the glass ring is colored. 7. A positive electrode chamber and a negative electrode chamber are separated by a β-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is separated in the positive electrode chamber. In a high-temperature secondary battery containing a halide and the like and sodium contained in the negative electrode chamber, a ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are joined by glass soldering. A glass ring for bonding, wherein a slit is formed at least at one position along the axial direction of the glass ring for bonding by. 8. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide and the like and sodium contained in the negative electrode chamber, a ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are joined by glass soldering. A slit is formed in the glass ring for bonding by at least one position parallel to the axis or at an angle with the axis of less than 20 degrees,
A glass ring for joining, characterized in that a plurality of the glass rings are laminated with the slits displaced to be used for the glass solder joining. 9. A positive electrode chamber and a negative electrode chamber are separated by a β-alumina-based solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide and the like and sodium contained in the negative electrode chamber, a ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are joined by glass soldering. A slit is formed in at least one position on the axis of the glass ring to be joined by the above method at an angle of 20 degrees or more, and this glass ring is used alone or in a plurality of layers for the solder joining. Glass ring for. 10. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina-based solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is placed in the positive electrode chamber. In a high-temperature secondary battery containing a halide and the like and sodium contained in the negative electrode chamber, a ceramic insulating ring for insulating the positive electrode chamber and the negative electrode chamber and a beta-alumina solid electrolyte tube are joined by glass soldering. A slit is formed in at least one position on the axis of the glass ring to be joined by the method at an angle of 20 degrees or more and 80 degrees or less, and the glass ring is used alone or in a plurality of layers for the solder joining. A glass ring for joining. 11. The width of the slit is 0.03 mm to 2 m
The glass ring for bonding according to any one of claims 7 to 10, wherein m is m. 12. The bonding glass ring according to claim 7, which is colored. 13. A positive electrode chamber and a negative electrode chamber are separated by a beta-alumina solid electrolyte tube made of β "-alumina and / or β-alumina, and sulfur or a compound of sulfur and sodium or a transition metal or aluminum is separated in the positive electrode chamber. In a high-temperature secondary battery containing a halide or the like and sodium contained in the negative electrode chamber, for glass solder bonding of a ceramic insulating ring and a beta-alumina solid electrolyte tube for insulating the positive electrode chamber and the negative electrode chamber. A high-temperature secondary battery, characterized by incorporating a glass bonded body bonded by the bonding method according to any one of claims 1 to 6 using the bonding glass ring according to any one of claims 7 to 12. .