JPH0214885A - Jointing of beta-alumina bag tube and alpha-alumina ring - Google Patents
Jointing of beta-alumina bag tube and alpha-alumina ringInfo
- Publication number
- JPH0214885A JPH0214885A JP63139033A JP13903388A JPH0214885A JP H0214885 A JPH0214885 A JP H0214885A JP 63139033 A JP63139033 A JP 63139033A JP 13903388 A JP13903388 A JP 13903388A JP H0214885 A JPH0214885 A JP H0214885A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- temperature
- bag tube
- glass composition
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 title claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 9
- 238000010309 melting process Methods 0.000 claims abstract description 3
- 230000007423 decrease Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 abstract description 11
- 230000035939 shock Effects 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020275 Na2Sx Inorganic materials 0.000 description 1
- JYGRFALVSCHYEX-UHFFFAOYSA-N [Th]=S Chemical class [Th]=S JYGRFALVSCHYEX-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- JLQNHALFVCURHW-UHFFFAOYSA-N cyclooctasulfur Chemical compound S1SSSSSSS1 JLQNHALFVCURHW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Ceramic Products (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はナトリウム−硫黄電池のβ−アルミナ袋管とα
−アルミナリングの接合方法に係わり、さらに詳しくは
β−アルミナ袋管とα−アルミナリングの接合強度、耐
熱衝撃性及び高温状態での劣化特性を向上することがで
きるβ−アルミナ袋管とα−アルミナリングの接合方法
に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a β-alumina bag tube and an α-sulfur battery for sodium-sulfur batteries.
- Concerning the method of joining alumina rings, more specifically, β-alumina bag tubes and α-alumina rings that can improve the bonding strength, thermal shock resistance, and deterioration characteristics under high temperature conditions. This invention relates to a method for joining alumina rings.
（従来の技術）
最近、電気自動車用、夜間電力貯蔵用の二次電池として
性能面及び経済面の両面において優れ、３００〜３５０
℃で作動する高温型のナトリウム−硫黄電池の研究開発
が進められている。(Prior art) Recently, as a secondary battery for electric vehicles and nighttime power storage, it has been developed to be excellent in both performance and economical aspects.
Research and development is progressing on high-temperature sodium-sulfur batteries that operate at ℃.
このすトリウム−硫黄電池として、従来、第４図に示す
ように陽極活物質である溶融硫黄Ｓを含浸したカーボン
マント等の陽極用導電材Ｍを収納する円筒状の陽極容器
１と、該陽極容器１の上端部に対し、α−アルミナリン
グ２を介して連結され、かつ溶融金属ナトリウムＮａを
貯留する陰極容器３と、前記α−アルミナリング２の内
周部に固着され、かつ陰極活物質であるナトリウムイオ
ンＮａ＋を選択的に透過させる機能を有した下方へ延び
る円筒状の多結晶β−アルミナ袋管４とからなっている
。As shown in FIG. 4, this thorium-sulfur battery conventionally includes a cylindrical anode container 1 that houses a conductive material M for the anode, such as a carbon cloak impregnated with molten sulfur S, which is an anode active material, and A cathode container 3 is connected to the upper end of the container 1 via an α-alumina ring 2 and stores molten metal Na, and a cathode active material is fixed to the inner circumference of the α-alumina ring 2. It consists of a cylindrical polycrystalline β-alumina bag tube 4 extending downward and having a function of selectively transmitting sodium ions Na+.
又、陰極容器３の上部蓋の中央部には、該陰極容器３を
貫通してβ−アルミナ袋管４底部まで延びた細長い陰極
管５が貫通支持されている。Further, an elongated cathode tube 5 is supported through the center of the upper lid of the cathode container 3, and extends through the cathode container 3 to the bottom of the β-alumina bag tube 4.
そして、放電時には次のような反応によってナトリウム
イオンがβ−アルミナ袋管４を透過して陽極容器１内の
硫黄Ｓと反応し、多硫化すｌ−ＩＪウムを生成する。During discharge, sodium ions pass through the β-alumina bag tube 4 and react with the sulfur S in the anode container 1 through the following reaction, producing l-IJium polysulfide.
２Ｎａ＋ＸＳ→Ｎａ２ Ｓｘ
又、充電時には放電時とは逆の反応が起こり、ナトリウ
ムＮａび硫黄Ｓが生成される。2Na+XS→Na2Sx Also, during charging, a reaction opposite to that during discharging occurs, and sodium Na and sulfur S are generated.
上記のように構成されたナトリウム−硫黄電池のβ−ア
ルミナ袋管４は、α−アルミナリングと無機質のガラス
により接合固定され、その接合強度及び気密性を向上す
るようにしていた。The β-alumina bag tube 4 of the sodium-sulfur battery configured as described above is bonded and fixed to the α-alumina ring and inorganic glass to improve the bonding strength and airtightness.
（発明が解決しようとする課題）
ところが、上記従来のガラス接着方法においては、最高
温度に加熱してガラスを溶融してから冷却しながら凝固
する過程において、軟化温度とほぼ同温度の６００°Ｃ
で１５分間程度保持し、以降３００°Ｃ／ ｈ ｒで冷
却しているため、第２図に示ず熱膨脂曲線より示される
軟化温度６００℃から室温までのガラスとα−アルミナ
やβ−アルミナとの間の熱膨張差により残留応力が発生
すると考えられる。従って、冷却過程において、ガラス
内部に残留する応力が大きくなり、β−アルミナ袋管と
α−アルミナリングの接合強度を低下し、ナトリウム−
硫黄電池の作動に伴う昇降温時に、βアルミナ袋管のガ
ラス接合端部に作用する片持ち曲げ応用によって、β−
アルミナ袋管が破損することが多かった。(Problems to be Solved by the Invention) However, in the above-mentioned conventional glass bonding method, in the process of heating the glass to the highest temperature to melt it and then solidifying it while cooling, the temperature is 600°C, which is approximately the same temperature as the softening temperature.
It was held for about 15 minutes and then cooled at 300°C/hr, so that the glass, α-alumina, and β- It is thought that residual stress is generated due to the difference in thermal expansion with alumina. Therefore, during the cooling process, the stress remaining inside the glass increases, reducing the bonding strength between the β-alumina bag tube and the α-alumina ring, and
When the temperature rises and falls associated with the operation of a sulfur battery, the β-
Alumina bag tubes were often damaged.
本発明の目的はβ−アルミナ袋管とα−アルミナリング
の接合強度を向上することができるとともに、耐熱衝撃
性及び高温使用状態での劣化特性や・＼リウムリーク特
性を向上することができるとともに、ナトリウム−硫黄
電池の作動に伴う昇降温時のβ−アルミナ袋管のガラス
接合端の破損を防止することができるナトリウム−硫黄
電池におけるβ−アルミナ袋管とα−アルミナリングと
の接合方法を提供することにある。The purpose of the present invention is to improve the bonding strength between a β-alumina bag tube and an α-alumina ring, as well as improve thermal shock resistance, deterioration characteristics under high-temperature usage conditions, and \lium leak characteristics. Provided is a method for joining a β-alumina bag tube and an α-alumina ring in a sodium-sulfur battery that can prevent damage to the glass joint end of the β-alumina bag tube during temperature increases and decreases associated with the operation of a sodium-sulfur battery. It's about doing.
（課題を解決するための手段）
請求項１記載のナトリウム−硫黄電池のβ−アルミナ袋
管とα−アルミナリングの接合方法は、上記目的を達成
するため、β−アルミナ袋管とα−アルミナリングとの
接合面に好ましくはペースト状のガラス組成物を介在さ
せた状態で、前記接合面を加熱し、常温から最高温度ま
での加熱溶融過程において所定温度に一定時間保持し、
最高温度から冷却過程において前記ガラス組成物の転移
温度とほぼ同温度に１０〜２０分間保持し、その後冷却
するという方法を採用している。(Means for Solving the Problems) In order to achieve the above object, a method for joining a β-alumina bag tube and an α-alumina ring of a sodium-sulfur battery according to claim 1 is provided. Heating the bonding surface with preferably a paste-like glass composition interposed on the bonding surface with the ring, and maintaining it at a predetermined temperature for a certain period of time during the heating and melting process from room temperature to the maximum temperature,
In the cooling process from the maximum temperature, a method is adopted in which the glass composition is held at approximately the same temperature as the transition temperature for 10 to 20 minutes, and then cooled.
（作用）
請求項１記載のナトリウム−硫黄電池のβ−アルミナ袋
管とα−アルミナリングの接着方法は、接着用ガラスの
加熱溶融状態から冷却凝固過程において、ガラス組成物
の熱膨脂率が転移温度ではα−アルミナに近く、β−ア
ルミナとの差も大きくないので、転移温度付近での所定
時間の除歪によりガラス内部の残留応力が減少し、接合
強度が向上するとともに、耐熱衝撃性、高温状態での劣
化特性及び電池としての昇降温時の片持ち曲げ応力に対
する耐性が向上することが確認された。(Function) The method for bonding a β-alumina bag tube and an α-alumina ring of a sodium-sulfur battery according to claim 1 is such that the coefficient of thermal expansion of the glass composition is increased in the process of cooling and solidifying the bonding glass from a heated molten state. The transition temperature is close to α-alumina and the difference from β-alumina is not large, so removing strain for a specified period of time near the transition temperature reduces residual stress inside the glass, improving bonding strength and improving thermal shock resistance. It was confirmed that the deterioration characteristics at high temperatures and the resistance to cantilever bending stress during temperature rise and fall as a battery were improved.
（実施例）
次に、本発明のナトリウム−硫黄電池のβ−アルミナ袋
管４とα−アルミナリング２の接合方法の一実施例につ
いて説明する。(Example) Next, an example of a method for joining the β-alumina bag tube 4 and the α-alumina ring 2 of the sodium-sulfur battery of the present invention will be described.
最初に、例えば５８〜６７重量部の５ｉ０２と、８〜１
７重量部のＡｇ２Ｏ３と、８〜１７重量部の８２０３
と、８〜１５重量部のＮ ａ ？０とからなる粉末状の
ガラス組成物を例えば５ｇ秤量する。First, for example, 58-67 parts by weight of 5i02 and 8-1
7 parts by weight of Ag2O3 and 8-17 parts by weight of 8203
and 8 to 15 parts by weight of N a ? For example, 5 g of a powdered glass composition consisting of 0 and 0 is weighed.
次に、接着助剤を含む有機溶剤５ｇに前記粉末状のガラ
ス組成物を加え、アルミナ製乳鉢内で混合し、ガラスペ
ーストを作製する。Next, the powdered glass composition is added to 5 g of an organic solvent containing an adhesive aid and mixed in an alumina mortar to prepare a glass paste.
次に、前記ベースト状のガラス組成物をβ−アルミナ袋
管４及びα−アルミナリング２の接合面に刷毛等で塗布
する。そして、室温で３０分以上乾燥し、窯詰め作業に
耐え得る接着強度にする。Next, the base-like glass composition is applied to the joint surfaces of the β-alumina bag tube 4 and the α-alumina ring 2 with a brush or the like. Then, dry at room temperature for 30 minutes or more to obtain adhesive strength that can withstand kiln filling.
さらに、大気雰囲気中でガラスシール電気炉によりβ−
アルミナ袋管４とα−アルミナリング２の接合部を局所
加熱する。この局所加熱は温度を急速に昇降させるため
である。又、ガラス溶融〜冷却時の結晶析出による接合
強度が低下するのを防止するためでもある。Furthermore, β-
The joint between the alumina bag tube 4 and the α-alumina ring 2 is locally heated. This local heating causes the temperature to rise and fall rapidly. This is also to prevent the bonding strength from decreasing due to crystal precipitation during glass melting and cooling.
第３図は前記電気炉の一実施例の断面を示すものである
。この電気炉は炉床台１１上に立設されるβ−アルミナ
袋管４を挿入する加熱空間を形成した断熱体１２の内周
面近傍にヒーター１３を埋設し、該断熱体１２の上面に
は炉蓋１４を載置している。又、前記β−アルミナ袋管
４は炉床台１１上に係止されたα−アルミナリング２に
嵌合立設されている。FIG. 3 shows a cross section of one embodiment of the electric furnace. In this electric furnace, a heater 13 is buried near the inner circumferential surface of a heat insulating body 12 that forms a heating space into which a β-alumina bag tube 4 is inserted, which is set upright on a hearth stand 11. The furnace lid 14 is placed on the furnace lid 14. Further, the β-alumina bag tube 4 is fitted into an α-alumina ring 2 which is fixed on the hearth stand 11 and stands upright.
上記焼成工程における時間−温度のグラフを第１図に示
す。このグラフにおいて、常温から１０００℃の最高温
度まで加熱して乾燥状態のガラス組成物を溶融する過程
で、３００°Ｃで６０分間と５００℃で１０分間それぞ
れ一定温度に保持するのは、接着助剤の有機物を完全燃
焼させるためである。又、１０００℃の最高温度を１５
分間保持するのはガラス組成物を完全に溶融させるため
である。さらに、冷却過程の５００℃の保持はガラス組
成物を除歪（アニール）処理するためである。FIG. 1 shows a time-temperature graph in the above firing process. In this graph, in the process of melting the dry glass composition by heating from room temperature to the maximum temperature of 1000°C, holding the temperature constant at 300°C for 60 minutes and 500°C for 10 minutes is an adhesion aid. This is to completely burn out the organic matter in the agent. Also, the maximum temperature of 1000℃ is 15
The purpose of holding the glass composition for 1 minute is to completely melt the glass composition. Further, the temperature is maintained at 500° C. during the cooling process to remove strain (anneal) the glass composition.
さらに詳しくは第２図に示すようにβ−アルミナとα−
アルミナの熱膨張率は加熱温度が上昇するに従いほぼ正
比例して増加するが、ガラス組成物の熱膨張率は、５０
０°Ｃにおいてα−アルミナの熱膨張率を上回り、６０
０℃で軟化し、それ以」二となると、熱膨張率は急減す
るという特性を有しているため、本願発明者等は実験に
より前記転移温度の５００°Ｃで１０〜２０分間保持し
て除歪したところ、後述するようにβ−アルミナ袋管と
α−アルミナリングの接合強度が向上したのである。More specifically, as shown in Figure 2, β-alumina and α-
The coefficient of thermal expansion of alumina increases in almost direct proportion as the heating temperature increases, but the coefficient of thermal expansion of a glass composition increases by 50
It exceeds the coefficient of thermal expansion of α-alumina at 0°C, 60
Since it has the characteristic that it softens at 0°C and then rapidly decreases its coefficient of thermal expansion, the inventors of the present application conducted experiments to hold it at the transition temperature of 500°C for 10 to 20 minutes. When the strain was removed, the bonding strength between the β-alumina bag tube and the α-alumina ring was improved, as will be described later.
このようにして、β−アルミナ袋管４とα−ア″ルミナ
リング２はガラス組成物により接合される。In this way, the β-alumina bag tube 4 and the α-alumina ring 2 are joined by the glass composition.
なお、表１は接合ガラスの冷却過程における除歪条件と
接合強度との関係を調べたものであり、従来法のように
ガラスの軟化温度付近での除歪よりも本発明のようにガ
ラスの転移温度付近での除歪条件の方が、機械的接合強
度が高いことが判る。Table 1 examines the relationship between strain removal conditions and bonding strength during the cooling process of bonded glass. It can be seen that the mechanical bonding strength is higher when the strain is removed near the transition temperature.
表１
又、表２はガラスが転位する温度から、軟化溶融するま
での温度域の昇降温速度とガラス接合強度及びガラス中
の結晶の有無の関係を確認したものである。Table 1 Table 2 also confirms the relationship between the temperature increase/decrease rate in the temperature range from the temperature at which the glass undergoes dislocation to the point at which it softens and melts, the glass bonding strength, and the presence or absence of crystals in the glass.
表２
この表２のデータから明らかなように、上記温度域の昇
降温速度が６００℃／ ｈ ｒ以上であると接合強度が
強くなり、かつガラス中の結晶も無くなるごとがわかる
。しかし、あまり昇降温速度を速くしてもそれほど接合
強度は向上せず、１０００℃／ ｈ ｒが望ましいとい
える。Table 2 As is clear from the data in Table 2, it can be seen that when the temperature increase/decrease rate in the above temperature range is 600°C/hr or more, the bonding strength becomes stronger and crystals in the glass disappear. However, even if the temperature increase/decrease rate is increased too much, the bonding strength does not improve much, and 1000° C./hr is desirable.
（発明の効果）
以上詳述したように、請求項１記載のナトリウム−硫黄
電池のβ−アルミナ袋管とα−アルミナリングの接合方
法は、加熱溶融状態から冷却凝固過程において、ガラス
組成物の転移温度とほぼ同温度に一定時間保持するので
、ガラス中に発生する残留応力を減少し、機械的強度を
向上することができ、さらに、耐熱衝撃性、ヘリウムリ
ーク特性及び高温での耐久性を向上することができる効
果がある。(Effects of the Invention) As described in detail above, the method for joining the β-alumina bag tube and the α-alumina ring of the sodium-sulfur battery according to claim 1 is such that the glass composition is Since the temperature is maintained at approximately the same temperature as the transition temperature for a certain period of time, it is possible to reduce the residual stress generated in the glass and improve mechanical strength.It also improves thermal shock resistance, helium leak characteristics, and durability at high temperatures. There are effects that can be improved.
第１図は本発明のβ−アルミナ袋管とα−アルミナリン
グとのガラス接合方法の焼成温度線を示すグラフ、第２
図は各材料の温度と熱膨脂率との関係を示すグラフ、第
３図は焼成用の電気炉を示す中央部縦断面図、第４図は
ナトリウム−硫黄電池の一例を示す中央部縦断面図であ
る。
１・・・陽極容器、２・・・α−アルミナリング、３・
・・陰極容器、４・・・β−アルミナ袋管、５・・・陰
極管、６・・・接着用ガラス。
特
許
出
願
人
中
川
幹
夫
代
理
人Fig. 1 is a graph showing the firing temperature line of the glass bonding method of the β-alumina bag tube and α-alumina ring of the present invention;
The figure is a graph showing the relationship between temperature and coefficient of thermal expansion of each material, Figure 3 is a longitudinal cross-sectional view of the center showing an electric furnace for firing, and Figure 4 is a longitudinal cross-section of the center showing an example of a sodium-sulfur battery. It is a front view. 1...Anode container, 2...α-alumina ring, 3.
...Cathode container, 4...β-alumina bag tube, 5...Cathode tube, 6...Glass for adhesion. Patent applicant Mikio Nakagawa representative
Claims (1)
にガラス組成物を介在させた状態で、前記接合面を加熱
し、常温から最高温度までの加熱溶融過程において所定
温度に一定時間保持し、最高温度から冷却過程において
前記ガラス組成物の転移温度とほぼ同温度に１０〜２０
分間保持し、その後冷却することを特徴とするβ−アル
ミナ袋管とα−アルミナリングとの接合方法。 ２、請求項１記載のβ−アルミナ袋管とα−アルミナリ
ングとの接合方法において、ガラスが転移する温度から
軟化溶融するまでの温度域の昇降温速度を６００℃／ｈ
ｒ以上とするβ−アルミナ袋管とα−アルミナリングと
の接合方法。[Claims] 1. With a glass composition interposed between the joint surface of the β-alumina bag tube and the α-alumina ring, the joint surface is heated, and in a heating melting process from room temperature to the highest temperature. The temperature is maintained at a predetermined temperature for a certain period of time, and from the maximum temperature to approximately the same temperature as the transition temperature of the glass composition during the cooling process, the temperature is reduced to approximately the same temperature as the transition temperature of the glass composition for 10 to 20 minutes.
A method for joining a β-alumina bag tube and an α-alumina ring, the method comprising holding the β-alumina bag tube for a minute and then cooling it. 2. In the method for joining a β-alumina bag tube and an α-alumina ring according to claim 1, the temperature increase/decrease rate in the temperature range from the temperature at which the glass transitions to the point at which it softens and melts is 600°C/h.
A method for joining a β-alumina bag tube and an α-alumina ring to a diameter of r or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63139033A JPH0214885A (en) | 1988-06-06 | 1988-06-06 | Jointing of beta-alumina bag tube and alpha-alumina ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63139033A JPH0214885A (en) | 1988-06-06 | 1988-06-06 | Jointing of beta-alumina bag tube and alpha-alumina ring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0214885A true JPH0214885A (en) | 1990-01-18 |
| JPH052629B2 JPH052629B2 (en) | 1993-01-12 |
Family
ID=15235896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63139033A Granted JPH0214885A (en) | 1988-06-06 | 1988-06-06 | Jointing of beta-alumina bag tube and alpha-alumina ring |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0214885A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426565A (en) * | 1990-05-18 | 1992-01-29 | Ngk Insulators Ltd | Glass joining body and production thereof |
| JPH04187571A (en) * | 1990-11-22 | 1992-07-06 | Ngk Insulators Ltd | Glass joining body and production thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4942711A (en) * | 1972-09-01 | 1974-04-22 | ||
| JPS55140732A (en) * | 1979-04-19 | 1980-11-04 | Chloride Silent Power Ltd | Sealing glass |
-
1988
- 1988-06-06 JP JP63139033A patent/JPH0214885A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4942711A (en) * | 1972-09-01 | 1974-04-22 | ||
| JPS55140732A (en) * | 1979-04-19 | 1980-11-04 | Chloride Silent Power Ltd | Sealing glass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426565A (en) * | 1990-05-18 | 1992-01-29 | Ngk Insulators Ltd | Glass joining body and production thereof |
| JPH04187571A (en) * | 1990-11-22 | 1992-07-06 | Ngk Insulators Ltd | Glass joining body and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH052629B2 (en) | 1993-01-12 |
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