JPH06208854A - Sodium-sulfur battery and manufacture thereof - Google Patents

Sodium-sulfur battery and manufacture thereof

Info

Publication number
JPH06208854A
JPH06208854A JP5250783A JP25078393A JPH06208854A JP H06208854 A JPH06208854 A JP H06208854A JP 5250783 A JP5250783 A JP 5250783A JP 25078393 A JP25078393 A JP 25078393A JP H06208854 A JPH06208854 A JP H06208854A
Authority
JP
Japan
Prior art keywords
tube
solid electrolyte
sodium
safety
electrolyte tube
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
Application number
JP5250783A
Other languages
Japanese (ja)
Other versions
JP2725982B2 (en
Inventor
Yoshihiko Kurashima
吉彦 蔵島
Hiromochi Tsuji
博以 辻
Akihiro Bito
章博 尾藤
Kenji Morimoto
健司 森本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to JP5250783A priority Critical patent/JP2725982B2/en
Publication of JPH06208854A publication Critical patent/JPH06208854A/en
Application granted granted Critical
Publication of JP2725982B2 publication Critical patent/JP2725982B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Secondary Cells (AREA)

Abstract

PURPOSE:To restrict the direct reaction of sodium and sulfur for convergence in the case where a solid electrolyte tube is broken and the high temperature sodium polysulfide is generated by the direct reaction of sodium and sulfur by sealing a gap between the solid electrolyte tube and a safety tube to stop the supply of sodium. CONSTITUTION:A cathode chamber R1 is formed inside of a cylindrical solid electrolyte tube 4 having a bottom and an anode chamber R2 is formed outside thereof. A cylindrical safety tube 8 having a bottom, which is made of metal material having the corrosion resistance, is arranged inside of the solid electrolyte tube 4 at a position near the tube 4. Sodium N is housed inside of the cathode chamber R1, and sulfur S is housed inside of the anode chamber R2. The solid electrolyte tube 4 and the safety tube 8 are made of the material, of which coefficient of thermal expansion is different from each other, so that a gap (g) between the solid electrolyte tube 4 and the safety tube 8 becomes a predetermined value at the battery operating temperature and that the gap (g) is sealed at an abnormal temperature impossible to use the battery.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】 この発明は、電力貯蔵用等の二
次電池として利用されるナトリウム−硫黄電池及びその
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sodium-sulfur battery used as a secondary battery for power storage and a method for manufacturing the same.

【０００２】[0002]

【従来の技術】 従来のナトリウム−硫黄電池において
は、有底円筒状の固体電解質管の内側と外側に陰極室及
び陽極室が形成され、その陰極室内にはカートリッジが
配設されている。そして、そのカートリッジの内部から
カートリッジと固体電解質管との間の間隙部に陰極活物
質としてのナトリウムが供給され、陽極室内には陽極活
物質としての硫黄が収容されている。そして、２９０〜
３５０℃の動作温度に加熱された状態で、陰極室のナト
リウムがナトリウムイオンとなって固体電解質管を透過
し、陽極室の硫黄と反応して、放電が行われるようにな
っている。2. Description of the Related Art In a conventional sodium-sulfur battery, a cathode chamber and an anode chamber are formed inside and outside a bottomed cylindrical solid electrolyte tube, and a cartridge is arranged in the cathode chamber. Then, sodium as a cathode active material is supplied from the inside of the cartridge to a gap between the cartridge and the solid electrolyte tube, and sulfur as an anode active material is contained in the anode chamber. And 290-
While being heated to the operating temperature of 350 ° C., sodium in the cathode chamber becomes sodium ions, permeates the solid electrolyte tube, reacts with sulfur in the anode chamber, and discharge is performed.

【０００３】この種のナトリウム−硫黄電池において
は、その動作中に固体電解質管が破損した場合、陰極室
のナトリウムと陽極室の硫黄とが直接反応して、発熱を
伴いながら多硫化ナトリウムを生成する。そして、この
多硫化ナトリウムの腐食性と発熱反応による高温とか
ら、金属製の容器が溶けてしまうという危険があった。
また、この反応はナトリウムと硫黄とが存在している限
り、継続して発生するものであった。In this type of sodium-sulfur battery, when the solid electrolyte tube is damaged during its operation, sodium in the cathode chamber directly reacts with sulfur in the anode chamber to generate sodium polysulfide while generating heat. To do. Then, there is a risk that the metal container is melted due to the corrosive nature of the sodium polysulfide and the high temperature due to the exothermic reaction.
Also, this reaction continued to occur as long as sodium and sulfur were present.

【０００４】このような反応を抑制するために、例えば
特開平２−１１２１６８号公報に示すように、カートリ
ッジと固体電解質管との間の間隙部に、耐食性を有する
アルミニウムやステンレス等の金属材料よりなる有底円
筒状の安全管を配設したナトリウム−硫黄電池が、従来
から提案されている。そして、このナトリウム−硫黄電
池では、固体電解質管の内側に滞留するナトリウムの量
を少なくするようにしている。In order to suppress such a reaction, as shown in, for example, Japanese Patent Application Laid-Open No. 2-112168, a metal material such as aluminum or stainless steel having corrosion resistance is used in the gap between the cartridge and the solid electrolyte tube. Conventionally, a sodium-sulfur battery in which a bottomed cylindrical safety tube is arranged has been proposed. Then, in this sodium-sulfur battery, the amount of sodium retained inside the solid electrolyte tube is reduced.

【０００５】[0005]

【発明が解決しようとする課題】 ところが、この従来
構成のナトリウム−硫黄電池においては、固体電解質管
と安全管との間に、常に所定の間隙が形成されるように
なっている。そのため、固体電解質管が破損した場合に
は、ナトリウムの供給が続行されて、ナトリウムと硫黄
との直接反応を抑制することができず、十分な安全性を
確保することができないという問題があった。However, in this conventional sodium-sulfur battery, a predetermined gap is always formed between the solid electrolyte tube and the safety tube. Therefore, when the solid electrolyte tube is broken, the supply of sodium is continued and the direct reaction between sodium and sulfur cannot be suppressed, and there is a problem that sufficient safety cannot be ensured. .

【０００６】また、固体電解質管はベータアルミナなど
のセラミック製であるため、直径などの寸法及び真円度
等にはバラツキが生じ、上記間隙を均一に確保すること
が困難となって、間隙が広くなった場合にはナトリウム
量が増大し安全性を損なうおそれがあるという問題があ
った。Further, since the solid electrolyte tube is made of a ceramic such as beta-alumina, the dimensions such as the diameter and the roundness vary, and it becomes difficult to ensure the above-mentioned gap uniformly, and the gap becomes If it becomes wider, there is a problem that the amount of sodium increases and the safety may be impaired.

【０００７】さらに、上記間隙が上下に均一に形成され
ている場合、固体電解質管が下部又は底部で部分的に破
損されたとき、上部で破損したときと比べて、温度上昇
が大きく、大事故に繋がるおそれがあるという問題があ
った。Further, when the above-mentioned gaps are formed uniformly in the upper and lower parts, when the solid electrolyte tube is partially damaged at the lower part or the bottom part, the temperature rise is large as compared with the case where it is damaged at the upper part, which causes a serious accident. There was a problem that could lead to.

【０００８】この発明は、このような従来の技術に存在
する問題点に着目してなされたものである。その第１の
目的は、固体電解質管が破損した場合、ナトリウムと硫
黄との直接反応を最小に制限することができると共に、
その直接反応による発熱に基づき、固体電解質管と安全
管との間隙を閉塞して、その後のナトリウムの供給を停
止させることができ、ナトリウムと硫黄との直接反応を
速やかに収束抑制することができて、大事故に繋がるお
それを防止することができるナトリウム−硫黄電池を提
供することにある。The present invention has been made by paying attention to the problems existing in such conventional techniques. Its first purpose is to minimize the direct reaction between sodium and sulfur when the solid electrolyte tube is broken, and
Based on the heat generated by the direct reaction, the gap between the solid electrolyte tube and the safety tube can be closed, and the supply of sodium thereafter can be stopped, and the direct reaction between sodium and sulfur can be promptly suppressed. In addition, it is to provide a sodium-sulfur battery that can prevent the risk of a major accident.

【０００９】また、第２の目的は、固体電解質管が破損
しても陰極室のナトリウムが陽極室に浸入することを防
止し、大事故に繋がるおそれを回避することができるナ
トリウム−硫黄電池を提供することにある。A second object of the present invention is to provide a sodium-sulfur battery which can prevent sodium in the cathode chamber from entering the anode chamber even if the solid electrolyte tube is damaged, and can prevent a serious accident. To provide.

【００１０】さらに、第３の目的は、固体電解質管が破
損し、ナトリウムと硫黄との直接反応によって電池内の
温度が上昇した場合に、固体電解質管と安全管との間隙
を下部ほど先に閉塞させてナトリウムの供給を断ち、事
故が継続するおそれを防止できるナトリウム−硫黄電池
を提供することにある。A third object is that, when the solid electrolyte tube is damaged and the temperature in the battery rises due to the direct reaction between sodium and sulfur, the gap between the solid electrolyte tube and the safety tube is moved downward toward the bottom. An object of the present invention is to provide a sodium-sulfur battery that can be blocked to cut off the supply of sodium and prevent the risk of continuing an accident.

【００１１】また、この発明の第４の目的は、固体電解
質管と安全管とを所定間隙をおいた状態に容易に組み付
けることができるナトリウム−硫黄電池の製造方法を提
供することにある。A fourth object of the present invention is to provide a method of manufacturing a sodium-sulfur battery which can easily assemble a solid electrolyte tube and a safety tube with a predetermined gap.

【００１２】さらに、第５の目的は、絶縁リングに陽極
容器と陰極金具を熱圧接合する操作と同時に、固体電解
質管と安全管との間隙を設定でき、ナトリウム−硫黄電
池の製造工程数を減少させることができて、製造コスト
を低減できるナトリウム−硫黄電池の製造方法を提供す
ることにある。Further, a fifth object is that the gap between the solid electrolyte tube and the safety tube can be set at the same time as the operation of thermocompression bonding the anode container and the cathode fitting to the insulating ring, and the number of manufacturing steps of sodium-sulfur battery It is an object of the present invention to provide a method for manufacturing a sodium-sulfur battery, which can be reduced in manufacturing cost.

【００１３】[0013]

【課題を解決するための手段】 上記の第１及び第２の
目的を達成するために、請求項１に記載のナトリウム−
硫黄電池の発明では、有底筒状の固体電解質管の内側と
外側に陰極室及び陽極室を形成し、固体電解質管の内側
に金属材料よりなる有底筒状の安全管を近接配置し、陰
極室内にはナトリウムを収容すると共に、陽極室内には
硫黄を収容してなるナトリウム−硫黄電池において、前
記固体電解質管と安全管との間隙が、電池動作温度では
所定値となり、電池の異常高温度では閉塞するように、
固体電解質管の熱膨張率よりも大きな熱膨張率を有する
安全管を備えたことを特徴とするものである。Means for Solving the Problems In order to achieve the above first and second objects, a sodium salt according to claim 1
In the invention of the sulfur battery, the cathode chamber and the anode chamber are formed inside and outside the bottomed cylindrical solid electrolyte tube, and the bottomed cylindrical safety tube made of a metal material is disposed inside the solid electrolyte tube, In a sodium-sulfur battery in which sodium is contained in the cathode chamber and sulfur is contained in the anode chamber, the gap between the solid electrolyte tube and the safety tube has a predetermined value at the battery operating temperature, and the battery has an abnormally high temperature. To block at temperature,
The present invention is characterized in that a safety tube having a coefficient of thermal expansion larger than that of the solid electrolyte tube is provided.

【００１４】また、上記の第１及び第２の目的を達成す
るために、請求項２に記載の発明では、請求項１に記載
の発明において、電池の充電時及び放電時にわたって、
陽極室の圧力が陰極室の圧力よりも高いことを特徴とす
るものである。Further, in order to achieve the above first and second objects, in the invention described in claim 2, in the invention described in claim 1, during charging and discharging of the battery,
The pressure in the anode chamber is higher than the pressure in the cathode chamber.

【００１５】さらに、上記の第１〜第３の目的を達成す
るために、請求項３に記載の発明では、請求項１に記載
の発明において、電池の動作温度において、固体電解質
管と安全管との間隙が上部より下部の方が小さいことを
特徴とするものである。Further, in order to achieve the above first to third objects, in the invention according to claim 3, in the invention according to claim 1, the solid electrolyte tube and the safety tube are provided at the operating temperature of the battery. It is characterized in that the gap between and is smaller in the lower part than in the upper part.

【００１６】また、第４の目的を達成するために、請求
項４に記載のナトリウム−硫黄電池の製造方法の発明で
は、有底筒状の固体電解質管の内側と外側に陰極室及び
陽極室を形成し、固体電解質管の内側に金属材料よりな
る有底筒状の安全管を近接配置し、陰極室内にはナトリ
ウムを収容すると共に、陽極室内には硫黄を収容してな
るナトリウム−硫黄電池において、前記固体電解質管内
に安全管を挿入した後、安全管の内部から圧力を付与し
て、安全管を固体電解質管の内周面と接触又は一定の間
隙を有するように変形させ、この状態で固体電解質管及
び安全管を電池動作温度よりも高い温度まで加熱した後
に冷却して、固体電解質管と安全管との間隙を、電池動
作温度では所定値となり、電池の異常高温度では閉塞す
るように設定することを特徴とするものである。Further, in order to achieve the fourth object, in the invention of the method for producing a sodium-sulfur battery according to claim 4, the cathode chamber and the anode chamber are provided inside and outside the bottomed cylindrical solid electrolyte tube. A sodium-sulfur battery in which a bottomed cylindrical safety tube made of a metal material is closely arranged inside the solid electrolyte tube, sodium is contained in the cathode chamber, and sulfur is contained in the anode chamber. In the above, after inserting the safety tube into the solid electrolyte tube, pressure is applied from the inside of the safety tube to deform the safety tube into contact with the inner peripheral surface of the solid electrolyte tube or to have a certain gap, The solid electrolyte tube and the safety tube are heated to a temperature higher than the battery operating temperature and then cooled, and the gap between the solid electrolyte tube and the safety tube becomes a predetermined value at the battery operating temperature and is closed at an abnormally high temperature of the battery. To set And it is characterized in and.

【００１７】また、第４の目的を達成するために、請求
項５に記載の発明では、請求項４に記載の発明におい
て、前記安全管の開口端部側の加熱温度を安全管の底部
側の加熱温度より高く設定したことを特徴とするもので
ある。Further, in order to achieve the fourth object, in the invention according to claim 5, in the invention according to claim 4, the heating temperature at the opening end side of the safety pipe is set to the bottom side of the safety pipe. It is characterized by being set higher than the heating temperature of.

【００１８】加えて、第４，第５の目的を達成するため
に、請求項６に記載のナトリウム−硫黄電池の製造方法
の発明では、有底筒状の固体電解質管の開口端部外周に
絶縁リングを接合し、この絶縁リングに陽極金具又は陽
極容器と陰極金具とを熱圧接合し、前記固体電解質管の
内側と外側に陰極室及び陽極室を形成すると共に、固体
電解質管の内側に金属材料よりなる有底筒状の安全管を
近接配置し、前記陰極室内にはナトリウムを収容し、か
つ陽極室内には硫黄を収容してなるナトリウム−硫黄電
池において、前記固体電解質管内に安全管を挿入した
後、安全管の内部から圧力を付与して、安全管を固体電
解質管の内周面と接触又は一定の間隙を有するように変
形させ、この状態で固体電解質管及び安全管を電池動作
温度よりも高い温度まで加熱して、絶縁リングに陽極金
具又は陽極容器と陰極金具を熱圧接合した後、冷却し
て、固体電解質管と安全管との間隙を、電池動作温度で
は所定値となり、電池の異常高温度では閉塞するように
設定することを特徴とするものである。In addition, in order to achieve the fourth and fifth objects, in the invention of the method for manufacturing a sodium-sulfur battery according to claim 6, the outer periphery of the open end of the bottomed cylindrical solid electrolyte tube is provided. An insulating ring is joined, and an anode fitting or an anode container and a cathode fitting are thermocompression-bonded to this insulating ring to form a cathode chamber and an anode chamber inside and outside the solid electrolyte tube, and inside the solid electrolyte tube. In a sodium-sulfur battery in which a bottomed cylindrical safety tube made of a metal material is closely arranged, sodium is stored in the cathode chamber, and sulfur is stored in the anode chamber, a safety pipe is provided in the solid electrolyte tube. After inserting the safety tube, pressure is applied from the inside of the safety tube to deform the safety tube into contact with the inner peripheral surface of the solid electrolyte tube or deform it so that it has a certain gap. Temperature higher than operating temperature After heating by heating, the anode metal fitting or the anode container and the cathode metal fitting are thermocompression bonded to the insulating ring, and then cooled, the gap between the solid electrolyte pipe and the safety pipe becomes a predetermined value at the battery operating temperature, and the battery is abnormally high. It is characterized in that the temperature is set so as to be closed.

【００１９】[0019]

【作用】 上記のように構成されたナトリウム−硫黄電
池においては、固体電解質管と安全管との間隙が、電池
動作温度では所定値となり、電池の異常高温度では閉塞
されるように狭く設定されている。そのため、電池の動
作中に固体電解質管が破損した場合、固体電解質管と安
全管との間隙に滞留するナトリウムの量を少なくして、
ナトリウムと硫黄との直接反応を最小に制限することが
できる。In the sodium-sulfur battery configured as described above, the gap between the solid electrolyte tube and the safety tube is set to a predetermined value at the battery operating temperature and set to be narrow so as to be blocked at an abnormally high temperature of the battery. ing. Therefore, when the solid electrolyte tube is damaged during the operation of the battery, the amount of sodium retained in the gap between the solid electrolyte tube and the safety tube is reduced,
The direct reaction of sodium with sulfur can be minimized.

【００２０】また、このナトリウムと硫黄との直接反応
により高温の多硫化ナトリウムが生成され、その発熱に
基づき安全管が固体電解質管よりも大きな熱膨張率で膨
脹して、固体電解質管と安全管との間隙が閉塞される。
このため、その後のナトリウムの供給が停止されて、ナ
トリウムと硫黄との直接反応を速やかに収束抑制するこ
とができ、大事故に繋がるおそれを防止することができ
る。Further, high-temperature sodium polysulfide is produced by the direct reaction between sodium and sulfur, and the heat generation causes the safety tube to expand at a coefficient of thermal expansion higher than that of the solid electrolyte tube. The gap between and is closed.
Therefore, the subsequent supply of sodium can be stopped, the direct reaction between sodium and sulfur can be quickly suppressed, and the risk of a major accident can be prevented.

【００２１】さらに、電池の充電時及び放電時にわたっ
て、陽極室の圧力が陰極室の圧力よりも高くなるように
設定されている。そのため、陰極室のナトリウムが陽極
室に浸入することが効果的に防止され、固体電解質管が
破損しても大事故に繋がるおそれを回避することができ
る。Further, the pressure in the anode chamber is set to be higher than the pressure in the cathode chamber during charging and discharging of the battery. Therefore, sodium in the cathode chamber is effectively prevented from entering the anode chamber, and it is possible to avoid the possibility of causing a serious accident even if the solid electrolyte tube is damaged.

【００２２】しかも、電池の動作温度において、固体電
解質管と安全管との間隙が上部より下部の方が小さく設
定されている。従って、固体電解質管が破損して、ナト
リウムと硫黄との直接反応により電池内の温度が上昇し
た場合に、固体電解質管と安全管との間隙が下部ほど先
に閉塞される。その結果、ナトリウムの供給が断たれ、
事故が継続するおそれを防止することができる。Moreover, at the operating temperature of the battery, the gap between the solid electrolyte tube and the safety tube is set smaller in the lower portion than in the upper portion. Therefore, when the solid electrolyte tube is damaged and the temperature in the battery rises due to the direct reaction between sodium and sulfur, the gap between the solid electrolyte tube and the safety tube is closed earlier toward the bottom. As a result, the supply of sodium was cut off,
It is possible to prevent the possibility of an accident continuing.

【００２３】また、この発明のナトリウム−硫黄電池の
製造方法においては、固体電解質管内に安全管が挿入さ
れた後、安全管の内部から圧力が付与されて安全管が固
体電解質管の内周面と接触するか、又は固体電解質管と
の間に一定の間隔が形成される。この状態で、固体電解
質管と安全管が電池動作温度よりも高い温度まで加熱さ
れ、その後冷却されることにより固体電解質管と安全管
との間に所定の間隙が容易に形成される。その結果、固
体電解質管と安全管との間隙が電池動作温度では所定値
に保持され、異常温度ではその間隙が閉塞される。Further, in the method for manufacturing a sodium-sulfur battery of the present invention, after the safety tube is inserted into the solid electrolyte tube, pressure is applied from the inside of the safety tube so that the safety tube becomes the inner peripheral surface of the solid electrolyte tube. Or a certain space is formed between the solid electrolyte tube and the solid electrolyte tube. In this state, the solid electrolyte tube and the safety tube are heated to a temperature higher than the battery operating temperature, and then cooled to easily form a predetermined gap between the solid electrolyte tube and the safety tube. As a result, the gap between the solid electrolyte pipe and the safety pipe is maintained at a predetermined value at the battery operating temperature, and the gap is closed at the abnormal temperature.

【００２４】しかも、安全管の開口端部側の加熱温度を
安全管の底部側の加熱温度より高く設定したことから、
冷却後に形成される固体電解質管と安全管との間隙が安
全管の開口端部より底部で小さくなる。従って、異常時
には安全管の底部側の隙間が早く閉塞されて、間隙に存
在するナトリウムがなくなりナトリウムと硫黄の反応が
抑制されて、安全性が向上する。Moreover, since the heating temperature on the opening end side of the safety pipe is set higher than the heating temperature on the bottom side of the safety pipe,
The gap between the solid electrolyte tube formed after cooling and the safety tube is smaller at the bottom than at the open end of the safety tube. Therefore, at the time of abnormality, the gap on the bottom side of the safety pipe is quickly closed, the sodium existing in the gap disappears, the reaction between sodium and sulfur is suppressed, and the safety is improved.

【００２５】加えて、この発明の方法では絶縁リングに
陽極金具又は陽極容器と陰極金具を熱圧接合する操作と
ともに、固体電解質管と安全管との間隙を形成した後、
冷却する。従って、熱圧接合と同時に固体電解質管と安
全管との間隙を形成することができて、製造工程を削減
することができる。In addition, in the method of the present invention, after the anode metal fitting or the anode container and the cathode metal fitting are thermocompression bonded to the insulating ring, and after forming the gap between the solid electrolyte tube and the safety tube,
Cooling. Therefore, the gap between the solid electrolyte tube and the safety tube can be formed at the same time as the thermocompression bonding, and the manufacturing process can be reduced.

【００２６】[0026]

【実施例】 （第１実施例） 以下、請求項１〜３に記載の発明を具体化したナトリウ
ム−硫黄電池の第１実施例を、図１〜図３に基づいて詳
細に説明する。EXAMPLES First Example A first example of a sodium-sulfur battery embodying the invention described in claims 1 to 3 will be described in detail below with reference to FIGS. 1 to 3.

【００２７】図１に示すように、陽極容器１は有底円筒
状に形成されている。アルファアルミナよりなる絶縁リ
ング２は陽極容器１の上端開口部に接合固定され、その
上面には陰極蓋３が接合固定されている。ベータアルミ
ナ等よりなる有底円筒状の固体電解質管４は絶縁リング
２の下端内周に接合固定され、この固体電解質管４の内
側には陰極室Ｒ１が区画形成されると共に、外側には陽
極室Ｒ２が区画形成されている。As shown in FIG. 1, the anode container 1 has a bottomed cylindrical shape. An insulating ring 2 made of alpha-alumina is bonded and fixed to the upper end opening of the anode container 1, and a cathode lid 3 is bonded and fixed to the upper surface thereof. A bottomed cylindrical solid electrolyte tube 4 made of beta-alumina or the like is joined and fixed to the inner periphery of the lower end of the insulating ring 2, a cathode chamber R1 is defined inside the solid electrolyte tube 4, and an anode is formed outside. The chamber R2 is partitioned and formed.

【００２８】カートリッジ５は前記陰極室Ｒ１内に配設
され、このカートリッジ５内には陰極活物質としてのナ
トリウムＮａが収容されている。小孔６はカートリッジ
５の底部に設けられ、この小孔６を通してカートリッジ
５内のナトリウムＮａが、カートリッジ５と固体電解質
管４との間の間隙部に供給される。The cartridge 5 is arranged in the cathode chamber R1, and the cartridge 5 contains sodium Na as a cathode active material. The small hole 6 is provided at the bottom of the cartridge 5, and the sodium Na in the cartridge 5 is supplied to the gap between the cartridge 5 and the solid electrolyte tube 4 through the small hole 6.

【００２９】窒素ガスやアルゴンガス等の不活性ガスＧ
は前記カートリッジ５の上部空間に所定の圧力で封入さ
れ、この不活性ガスＧによりカートリッジ５内のナトリ
ウムＮａが小孔６から流出する方向へ加圧されている。
カーボンマット等よりなる陽極用導電材７は陽極室Ｒ２
内に収容され、この陽極用導電材７には陽極活物質とし
ての硫黄Ｓが含浸されている。Inert gas G such as nitrogen gas or argon gas
Is sealed in the upper space of the cartridge 5 at a predetermined pressure, and the inert gas G pressurizes sodium Na in the cartridge 5 in a direction to flow out from the small hole 6.
Anode conductive material 7 made of carbon mat or the like is used in the anode chamber R2.
The anode conductive material 7 is housed inside and is impregnated with sulfur S as an anode active material.

【００３０】有底円筒状の安全管８は前記カートリッジ
５と固体電解質管４との間の間隙部に配設され、ナトリ
ウムや多硫化ナトリウムに対して耐食性を有するアルミ
ニウム、アルミニウム合金、ステンレス等の金属材料か
ら形成されている。従って、固体電解質管４が破損して
多硫化ナトリウムが上記間隙部に浸入しても安全管８が
浸食されるおそれはない。また、この実施例において
は、固体電解質管４と安全管８との熱膨張率の差によ
り、固体電解質管４と安全管８との間隙ｇが、電池動作
温度（２９０〜３５０℃）では所定値（０．０１〜０．
１ｍｍ）となり、電池の異常高温度では閉塞されるよう
に設定されている。ここで、電池の異常高温度とは、電
池動作温度を越えるような高温度をいい、例えば３７０
℃以上の温度をいう。The bottomed cylindrical safety tube 8 is disposed in the gap between the cartridge 5 and the solid electrolyte tube 4, and is made of aluminum, aluminum alloy, stainless steel or the like having corrosion resistance to sodium or sodium polysulfide. It is made of a metal material. Therefore, even if the solid electrolyte tube 4 is damaged and sodium polysulfide enters the gap, the safety tube 8 is not eroded. Further, in this embodiment, the gap g between the solid electrolyte tube 4 and the safety tube 8 is predetermined at the battery operating temperature (290 to 350 ° C.) due to the difference in the coefficient of thermal expansion between the solid electrolyte tube 4 and the safety tube 8. Value (0.01-0.
1 mm), and is set to be blocked at an abnormally high temperature of the battery. Here, the abnormally high temperature of the battery means a high temperature exceeding the battery operating temperature, for example, 370.
A temperature of ℃ or more.

【００３１】そして、放電時に前記カートリッジ５の小
孔６から供給されるナトリウムＮａが、この安全管８と
カートリッジ５との間の間隙内で上方に移動された後、
安全管８の上端を乗り越えて、安全管８と固体電解質管
４との間の間隙ｇ内で下方に移動され、さらに、固体電
解質管４をナトリウムイオンとなって透過して、陽極室
Ｒ２側へ移動されるようになっている。After the sodium Na supplied from the small hole 6 of the cartridge 5 at the time of discharging is moved upward in the gap between the safety tube 8 and the cartridge 5,
It moves over the upper end of the safety tube 8 and is moved downward in the gap g between the safety tube 8 and the solid electrolyte tube 4, and further permeates the solid electrolyte tube 4 as sodium ions to the anode chamber R2 side. To be moved to.

【００３２】次に、前記のように構成されたこの実施例
のナトリウム−硫黄電池について作用を説明する。さ
て、このナトリウム−硫黄電池の充電完了状態において
は、大半のナトリウムＮａがカートリッジ５内に貯留さ
れている。この状態で放電を開始すると、カートリッジ
５の上部空間に封入された不活性ガスＧの圧力により、
カートリッジ５内のナトリウムＮａが小孔６を通って流
出され、安全管８とカートリッジ５との間の間隙内で上
方に移動される。その後、ナトリウムＮａは安全管８の
上端を乗り越えて、安全管８と固体電解質管４との間の
間隙ｇ内で下方に移動され、さらに、固体電解質管４を
ナトリウムイオンとなって透過して、陽極室Ｒ２側へ移
動される。そして、このナトリウムＮａが陽極室Ｒ２内
の硫黄Ｓと反応して、多硫化ナトリウムが生成される。Next, the operation of the sodium-sulfur battery of this embodiment constructed as described above will be described. Now, in the state where the sodium-sulfur battery is completely charged, most of the sodium Na is stored in the cartridge 5. When the discharge is started in this state, the pressure of the inert gas G sealed in the upper space of the cartridge 5 causes
The sodium Na in the cartridge 5 flows out through the small hole 6 and is moved upward in the gap between the safety pipe 8 and the cartridge 5. After that, sodium Na goes over the upper end of the safety pipe 8 and is moved downward in the gap g between the safety pipe 8 and the solid electrolyte pipe 4, and further passes through the solid electrolyte pipe 4 as sodium ions. , Are moved to the anode chamber R2 side. Then, this sodium Na reacts with the sulfur S in the anode chamber R2 to generate sodium polysulfide.

【００３３】この電池の動作中において、固体電解質管
４が破損した場合には、陰極室Ｒ１のナトリウムＮａと
陽極室Ｒ２の硫黄Ｓとが直接反応して、高温の多硫化ナ
トリウムが発生する。ところが、この実施例において
は、固体電解質管４と安全管８との間隙ｇが、電池動作
温度（２９０〜３５０℃）では所定値（０．０１〜０．
１ｍｍ）となるように設定されているため、固体電解質
管４と安全管８との間隙ｇに滞留するナトリウムＮａの
量が少なくて、ナトリウムＮａと硫黄Ｓとの直接反応を
最小に制限することができる。When the solid electrolyte tube 4 is broken during the operation of this battery, sodium Na in the cathode chamber R1 and sulfur S in the anode chamber R2 directly react with each other to generate high-temperature sodium polysulfide. However, in this embodiment, the gap g between the solid electrolyte tube 4 and the safety tube 8 is a predetermined value (0.01-0.
1 mm), the amount of sodium Na retained in the gap g between the solid electrolyte tube 4 and the safety tube 8 is small, and the direct reaction between sodium Na and sulfur S is limited to the minimum. You can

【００３４】また、この実施例においては、固体電解質
管４と安全管８との間隙ｇが、電池の異常高温度では閉
塞するように設定されている。このため、固体電解質管
４の破損部において、ナトリウムＮａと硫黄Ｓとの直接
反応により高温の多硫化ナトリウムが生成されると、そ
の発熱に基づき安全管８が固体電解質管４よりも大きな
熱膨張率で膨脹して、固体電解質管４と安全管８との間
隙ｇが閉塞される。その上、ベータアルミナにより形成
された固体電解質管４の形状にばらつきがあったとして
も、電池の異常高温時には上記のようにして間隙ｇが閉
塞される。従って、その後のナトリウムＮａの供給が停
止され、ナトリウムＮａと硫黄Ｓとの直接反応を速やか
に収束抑制することができて、大事故に繋がるおそれを
防止することができる。Further, in this embodiment, the gap g between the solid electrolyte tube 4 and the safety tube 8 is set so as to be closed at an abnormally high temperature of the battery. Therefore, when high-temperature sodium polysulfide is generated by the direct reaction between sodium Na and sulfur S in the damaged portion of the solid electrolyte tube 4, the safety tube 8 has a larger thermal expansion than the solid electrolyte tube 4 due to the heat generation thereof. Expands at a rate to close the gap g between the solid electrolyte tube 4 and the safety tube 8. Moreover, even if the solid electrolyte tube 4 formed of beta alumina has a variation in shape, the gap g is blocked as described above when the battery has an abnormally high temperature. Therefore, the supply of sodium Na thereafter is stopped, the direct reaction between sodium Na and sulfur S can be promptly suppressed, and it is possible to prevent a possibility of causing a serious accident.

【００３５】次に、過充電による固体電解質管の破損後
の温度挙動について、その後の経過時間と陽極容器中央
部で測定した温度との関係を図２に示す。なお、図中
（イ）は本実施例に基づく場合、（ロ）は陽極室Ｒ２の
圧力を陰極室Ｒ１の圧力より高くした場合、（ハ）は固
体電解質管４と安全管８との間隙が上部よりも下部の方
が小さい場合を示す。Next, with respect to the temperature behavior after the solid electrolyte tube is broken due to overcharge, the relationship between the elapsed time after that and the temperature measured at the center of the anode container is shown in FIG. In the figure, (a) is based on this embodiment, (b) is a pressure in the anode chamber R2 higher than that in the cathode chamber R1, and (c) is a gap between the solid electrolyte tube 4 and the safety tube 8. Indicates that the lower part is smaller than the upper part.

【００３６】図２に示したように、従来のナトリウム−
硫黄電池では固体電解質管の破損後に温度が急激に上昇
し４２０℃にまで達して低下することがない。それに対
し、（イ）の場合には、固体電解質管の破損後、ナトリ
ウムの供給が断たれることから、３分経過時より温度が
低下する。（ロ）の場合には、陽極室Ｒ２の圧力を陰極
室Ｒ１の圧力より高くしてナトリウムの供給を一層抑制
したことから、固体電解質管の破損後２分経過時より急
激に温度が低下する。そして、（ハ）の場合にも固体電
解質管の破損後３分経過時より温度低下が見られる。As shown in FIG. 2, conventional sodium-
In the sulfur battery, the temperature does not rapidly rise to 420 ° C. and drop after the solid electrolyte tube is broken. On the other hand, in the case of (a), since the supply of sodium is cut off after the solid electrolyte tube is broken, the temperature lowers after 3 minutes. In the case of (b), since the pressure of the anode chamber R2 is made higher than the pressure of the cathode chamber R1 to further suppress the supply of sodium, the temperature drops sharply from the time 2 minutes after the breakage of the solid electrolyte tube. . Also in the case of (C), a temperature drop is observed from the time 3 minutes after the breakage of the solid electrolyte tube.

【００３７】なお、図示されていないが、（ロ）と
（ハ）の組合わせ、すなわち陽極室Ｒ２の圧力を陰極室
Ｒ１の圧力より高くし、かつ間隙を上部よりも下部で小
さくすると、温度低下はさらに顕著となる。また、陽極
室Ｒ２の圧力を陰極室Ｒ１の圧力より高くする場合、陰
極室Ｒ１の通常の圧力に対して３気圧以下の圧力範囲内
で陰極室Ｒ１の圧力より高く設定される。Although not shown, if the combination of (b) and (c), that is, the pressure in the anode chamber R2 is made higher than the pressure in the cathode chamber R1 and the gap is made smaller in the lower portion than in the upper portion, the temperature The decrease is even more pronounced. When the pressure in the anode chamber R2 is made higher than the pressure in the cathode chamber R1, it is set higher than the pressure in the cathode chamber R1 within a pressure range of 3 atm or less with respect to the normal pressure in the cathode chamber R1.

【００３８】次に、固体電解質管４の破損箇所について
の上下位置とその位置での陽極容器１表面の温度を測定
した結果を図３（ａ），（ｂ）に示した。なお、実施例
では固体電解質管４と安全管８との間隙が上部よりも下
部の方が小さい場合を示す。また、各位置における温度
は陽極容器１の表面で測定した値である。また、破損位
置は解体して調査した。Next, FIGS. 3A and 3B show the results of measuring the temperature of the surface of the anode container 1 at the upper and lower positions of the damaged portion of the solid electrolyte tube 4 and at that position. In the example, the gap between the solid electrolyte tube 4 and the safety tube 8 in the lower portion is smaller than that in the upper portion. The temperature at each position is a value measured on the surface of the anode container 1. The damaged position was disassembled and investigated.

【００３９】この図３（ｂ）に示したように、従来例で
は固体電解質管４の中央位置より下部では相当の発熱が
あって温度上昇が大きく、底部では４５０℃に達してい
る。それに比べて、図３（ａ）に示したように、実施例
では固体電解質管４の下部における固体電解質管４と安
全管８との間隙が小さくナトリウムの供給が断たれるこ
とから、その温度上昇が抑制され底部で３９０℃にとど
まっている。 （第２実施例）次に、請求項４に記載の発明を具体化し
たナトリウム−硫黄電池の製造方法の第２実施例を、図
４に基づいて説明する。As shown in FIG. 3 (b), in the conventional example, a considerable amount of heat is generated below the central position of the solid electrolyte tube 4 to cause a large temperature rise, and the temperature reaches 450 ° C. at the bottom. On the other hand, as shown in FIG. 3A, in the embodiment, since the gap between the solid electrolyte tube 4 and the safety tube 8 in the lower part of the solid electrolyte tube 4 is small and the supply of sodium is cut off, the temperature of the solid electrolyte tube 4 decreases. The rise was suppressed and remained at 390 ° C at the bottom. (Second Embodiment) Next, a second embodiment of the method for manufacturing a sodium-sulfur battery embodying the invention described in claim 4 will be described with reference to FIG.

【００４０】さて、この実施例においては、例えば固体
電解質管４として外径が４０．０ｍｍで、肉厚が１．７
ｍｍで、長さが３５０ｍｍのベータアルミナ製のものを
用い、安全管８として外径が３５．６ｍｍで、肉厚が
１．０ｍｍのアルミニウム製のものを用いる。そして、
図４（ａ）に示すように、まず固体電解質管４内に予め
熱処理して焼なました安全管８を挿入する。その後、図
４（ｂ）に示すように、安全管９の内部からチューブ等
を用いて水圧等の圧力を付与して、安全管８を固体電解
質管４の内周面と接触するように変形させる。In this embodiment, for example, the solid electrolyte tube 4 has an outer diameter of 40.0 mm and a wall thickness of 1.7.
The safety tube 8 is made of aluminum and has an outer diameter of 35.6 mm and a wall thickness of 1.0 mm. And
As shown in FIG. 4 (a), first, the safety tube 8 which has been previously heat-treated and annealed is inserted into the solid electrolyte tube 4. Thereafter, as shown in FIG. 4B, pressure such as water pressure is applied from inside the safety pipe 9 using a tube or the like, and the safety pipe 8 is deformed so as to come into contact with the inner peripheral surface of the solid electrolyte pipe 4. Let

【００４１】この状態で、固体電解質管４及び安全管８
を電池動作温度（３５０℃）よりも高い温度（５５０
℃）まで加熱処理した後に冷却する。すると、電池動作
温度と熱処理温度との差に基づく固体電解質管４と安全
管８との熱膨張差によって、図４（ｃ）に示すように、
固体電解質管４と安全管８との間に所定の間隙ｇが形成
され、この間隙ｇが電池動作温度では０．０１〜０．１
ｍｍとなり、異常高温度では閉塞される。In this state, the solid electrolyte tube 4 and the safety tube 8
Above the battery operating temperature (350 ° C) (550
C.) and then cooled. Then, due to the difference in thermal expansion between the solid electrolyte tube 4 and the safety tube 8 based on the difference between the battery operating temperature and the heat treatment temperature, as shown in FIG.
A predetermined gap g is formed between the solid electrolyte tube 4 and the safety tube 8, and this gap g is 0.01 to 0.1 at the battery operating temperature.
mm, which is blocked at an abnormally high temperature.

【００４２】このように製造することにより、金属材料
製の安全管８をセラミック焼結体である固体電解質管４
の内周面に沿わせて、所定の微小間隙ｇを形成した状態
で容易に組付配置することができ、安全性を飛躍的に向
上させることができる。 （第３実施例）次に、請求項６に記載の発明を具体化し
たナトリウム−硫黄電池の製造方法の第３実施例を、図
５（ａ）〜（ｅ）及び図６に基づいて説明する。By manufacturing in this way, the safety tube 8 made of a metal material is replaced with the solid electrolyte tube 4 which is a ceramic sintered body.
It can be easily assembled and arranged along the inner peripheral surface with a predetermined minute gap g formed, and the safety can be dramatically improved. (Third Embodiment) Next, a third embodiment of the method for manufacturing a sodium-sulfur battery embodying the invention described in claim 6 will be described with reference to FIGS. 5 (a) to 5 (e) and FIG. To do.

【００４３】図５（ａ）に示すように、ベータアルミナ
製の固体電解質管４は絶縁リング２の下端内周に接合固
定されている。図５（ｂ）に示すように、アルミニウム
製の安全管８は固体電解質管４内に挿入され、安全管８
と固体電解質管４との間隙ｇ 0 が０．２〜０．４５mmに
設定されている。図５（ｃ）に示すように、ゴム製のチ
ューブ１０は安全管８内に挿入され、そのチューブ１０
内に水Ｗが圧入されて安全管８の内側から６０kg/cm2の
水圧が加えられる。そして、安全管８を固体電解質管４
の内面に沿わせるようにして膨張圧着させる。As shown in FIG. 5 (a), beta-alumina
The solid electrolyte tube 4 made of steel is bonded and fixed to the inner circumference of the lower end of the insulating ring 2.
It is fixed. As shown in FIG. 5 (b), aluminum
The safety tube 8 made of is inserted into the solid electrolyte tube 4,
Gap between the solid electrolyte tube 4 and 0To 0.2 to 0.45 mm
It is set. As shown in Fig. 5 (c),
The tube 10 is inserted into the safety tube 8 and the tube 10
Water W is press-fitted inside and 60kg / cm from inside the safety pipe 8.2of
Water pressure is applied. Then, the safety tube 8 is connected to the solid electrolyte tube 4
Expand and crimp along the inner surface of.

【００４４】この場合、安全管８と固体電解質管４との
間にはわずかな一定間隙ｇ1 、すなわち０．０５〜０．
０７mmの間隙が形成される。その場合、この間隙ｇ1 を
固体電解質管４の内径に対して０．４％以下に設定する
ことにより、後の加熱工程で安全管８を固体電解質管４
に確実に密着させることができる。ただし、固体電解質
管４がセラミックの一種であるベータアルミナにより形
成されており、真円状に形成することが困難であること
から、予め安全管８を固体電解質管４に密着させておく
ことが望ましい。すなわち、固体電解質管４に発生する
直径のばらつき、つまり公差に対応させておく方がその
後に形成される間隙ｇ2 を所定値に保持するために好ま
しい。また、前記水圧は固体電解質管４の強度と安全管
８の材質や厚さなどに応じて適切な値に設定される。そ
して、その後このチューブ１０を安全管８内から抜き出
す。In this case, a slight constant gap g 1 between the safety pipe 8 and the solid electrolyte pipe 4, that is, 0.05 to 0.
A gap of 07 mm is formed. In that case, by setting this gap g 1 to 0.4% or less with respect to the inner diameter of the solid electrolyte tube 4, the safety tube 8 is set in the subsequent heating step.
Can be firmly adhered to. However, since the solid electrolyte tube 4 is formed of beta-alumina, which is a type of ceramic, and it is difficult to form it into a perfect circular shape, it is necessary to attach the safety tube 8 to the solid electrolyte tube 4 in advance. desirable. That is, it is preferable that the diameter of the solid electrolyte tube 4 varies, that is, the tolerance of the solid electrolyte tube 4 is adjusted to keep the gap g 2 formed thereafter at a predetermined value. The water pressure is set to an appropriate value according to the strength of the solid electrolyte tube 4 and the material and thickness of the safety tube 8. Then, thereafter, the tube 10 is pulled out from the safety tube 8.

【００４５】図５（ｄ）に示すように、絶縁リング２の
下面には蝋材１１を介して上端が内側へ折曲形成された
陽極容器１が配置されるとともに、陽極容器１の内側に
加圧治具１２が配置される。絶縁リング２の上面には蝋
材１１を介して陰極金具１３が配置されると同時に、そ
の上に加圧治具１２が配置される。この蝋材１１として
は、アルミニウム−シリカ−マグネシウム系のものやア
ルミニウム−マグネシウム系のものが使用される。そし
て、この状態で装置全体がアルミニウムの酸化を防止す
るため真空下、例えば１×１０-4torrの真空下に置か
れ、５５０℃に加熱されるとともに、両加圧治具１２が
約６kg/mm2の圧力に加圧される。この熱圧接合（ＴＣ
Ｂ）により、絶縁リング２に陽極容器１と陰極金具１３
が接合される。この熱圧接合は通常５００〜６００℃の
温度範囲で行われる。このとき、真空状態に保持する操
作に代えて、窒素などの不活性ガスの雰囲気下で操作し
てもよい。なお、図７に示すように、陽極容器１と絶縁
リング２との間に陽極金具１４が介装される場合には、
熱圧接合により絶縁リング２にこの陽極金具１４が接合
される。As shown in FIG. 5D, an anode container 1 having an upper end bent inwardly via a brazing material 11 is arranged on the lower surface of the insulating ring 2, and inside the anode container 1. The pressure jig 12 is arranged. On the upper surface of the insulating ring 2, a cathode metal fitting 13 is arranged via a brazing material 11, and at the same time, a pressure jig 12 is arranged thereon. As the wax material 11, an aluminum-silica-magnesium-based material or an aluminum-magnesium-based material is used. Then, in this state, the entire apparatus is placed under a vacuum, for example, under a vacuum of 1 × 10 −4 torr, to be heated to 550 ° C., and both pressure jigs 12 are about 6 kg / kg. Pressurized to a pressure of mm 2 . This thermo-compression bonding (TC
According to B), the insulating ring 2 is attached to the anode container 1 and the cathode fitting 13.
Are joined. This thermocompression bonding is usually performed in the temperature range of 500 to 600 ° C. At this time, the operation may be performed in an atmosphere of an inert gas such as nitrogen, instead of the operation of maintaining the vacuum state. In addition, as shown in FIG. 7, when the anode metal fitting 14 is interposed between the anode container 1 and the insulating ring 2,
The anode fitting 14 is joined to the insulating ring 2 by thermocompression joining.

【００４６】その後、電池の動作温度である３３０℃ま
で冷却されると、ナトリウムの移動が許容される０．０
５〜０．０６mmの間隙ｇ2 が形成される。次いで、さら
に冷却されて、常温に戻される。このとき、図５（ｅ）
に示すように、安全管８と固体電解質管４との間に０．
１５〜０．１６mmの間隙ｇ3 が形成される。After that, when the battery is cooled to the operating temperature of 330 ° C., the movement of sodium is allowed to be 0.0.
A gap g 2 of 5 to 0.06 mm is formed. Then, it is further cooled and returned to room temperature. At this time, FIG.
As shown in FIG.
Gap g 3 of 15~0.16mm is formed.

【００４７】この間隙ｇ3 の形成過程を図６によって説
明すると、３０℃では安全管８の外径は固体電解質管４
の内径より寸法がわずかに小さく、一定の間隙ｇ1 が形
成されている。次に、５５０℃までヒータにより加熱す
ると、アルミニウム製の安全管８はベータアルミナ製の
固体電解質管４より熱膨張率が大きいため、固体電解質
管４の内側に位置する安全管８は固体電解質管４に密着
し、初期の間隙ｇ1 はなくなる。The process of forming the gap g 3 will be described with reference to FIG. 6. At 30 ° C., the outer diameter of the safety tube 8 is the solid electrolyte tube 4
The size is slightly smaller than the inner diameter of the and the constant gap g 1 is formed. Next, when heated by a heater to 550 ° C., the safety tube 8 made of aluminum has a higher coefficient of thermal expansion than the solid electrolyte tube 4 made of beta-alumina, so that the safety tube 8 positioned inside the solid electrolyte tube 4 is a solid electrolyte tube. 4, the initial gap g 1 disappears.

【００４８】ちなみに、熱膨張率はアルミニウムが２４
×１０-6／℃、ベータアルミナが７．２×１０-6／℃で
ある。次に、その状態から電池の動作温度である３３０
℃まで冷却すると、安全管８の方が固体電解質管４より
収縮が大きいことから、安全管８と固体電解質管４との
間に一定の間隙ｇ2 が形成される。すなわち、この間隙
ｇ2 は活物質であるナトリウムの移動を許容するもの
で、０．０５〜０．０６mmの範囲である。そして、さら
に冷却して室温に戻すと、その間隙ｇ3 は０．１５〜
０．１６mmとなる。Incidentally, the coefficient of thermal expansion of aluminum is 24
It is x10 -6 / ° C and beta alumina is 7.2 x 10 -6 / ° C. Next, from that state, the operating temperature of the battery is 330
When cooled to 0 ° C., the safety tube 8 contracts more than the solid electrolyte tube 4, so that a constant gap g 2 is formed between the safety tube 8 and the solid electrolyte tube 4. That is, this gap g 2 allows the movement of sodium as the active material, and is in the range of 0.05 to 0.06 mm. Then, when it is further cooled and returned to room temperature, the gap g 3 is 0.15 to
It will be 0.16 mm.

【００４９】このように、この実施例では絶縁リング２
に陽極容器１と陰極金具１３とを熱圧接合する作業を行
うときに、同時に間隙形成を行うことができるため、作
業が容易で、能率が良く、工程を簡略化することができ
る。そして、安全管８と固体電解質管４との間隙ｇ3 が
電池動作温度では所定間隙ｇ2 として保持され、異常高
温度ではその間隙ｇ2 が閉塞され、その部分へのナトリ
ウムの供給が絶たれる。そのため、ナトリウムと硫黄と
の反応が停止され、電池の安全性を確保することができ
る。As described above, the insulating ring 2 is used in this embodiment.
In addition, since the gap can be formed at the same time when the work of hot pressing the anode container 1 and the cathode fitting 13 is performed, the work is easy and efficient, and the process can be simplified. The gap g 3 between the safety pipe 8 and the solid electrolyte pipe 4 is maintained as a predetermined gap g 2 at the battery operating temperature, and the gap g 2 is closed at an abnormally high temperature, so that the supply of sodium to that portion is cut off. . Therefore, the reaction between sodium and sulfur is stopped, and the safety of the battery can be ensured.

【００５０】加えて、固体電解質管４が破損すると、そ
の破損部位で内部短絡が起きてその部分で電流集中によ
りジュール熱が発生する。しかし、この実施例では前述
のようにナトリウムの供給が絶たれることから、破損部
位での異常高温の発生が防止される。 （第４実施例）次に、請求項５に記載の発明を具体化し
た第４実施例について説明する。In addition, when the solid electrolyte tube 4 is damaged, an internal short circuit occurs at the damaged portion, and Joule heat is generated at that portion due to current concentration. However, in this embodiment, since the supply of sodium is cut off as described above, the generation of abnormally high temperature at the damaged portion is prevented. (Fourth Embodiment) Next, a fourth embodiment of the invention as defined in claim 5 will be described.

【００５１】この実施例では、第３実施例とは加熱条件
が異なる。すなわち、安全管８の底部側の温度を開口端
部側の温度より低い４５０℃に設定し、安全管８の上下
方向で温度勾配を設ける。この場合、図６に示すよう
に、加熱後動作温度まで冷却したとき、安全管８の底部
側は温度差が少ないので、その収縮量が少ない。そのた
め、図８に示すように、安全管８の底部側と固体電解質
管４との間隙ｇ4 は、安全管８の開口端部側と固体電解
質管４との間隙ｇ2 に比べて狭くなる。In this embodiment, heating conditions are different from those in the third embodiment. That is, the temperature on the bottom side of the safety pipe 8 is set to 450 ° C. which is lower than the temperature on the opening end side, and a temperature gradient is provided in the vertical direction of the safety pipe 8. In this case, as shown in FIG. 6, when cooled to the operating temperature after heating, the temperature difference on the bottom side of the safety pipe 8 is small, so that the shrinkage amount is small. Therefore, as shown in FIG. 8, the gap g 4 between the bottom side of the safety tube 8 and the solid electrolyte tube 4 is narrower than the gap g 2 between the open end side of the safety tube 8 and the solid electrolyte tube 4. .

【００５２】従って、電池の異常時に温度上昇したと
き、安全管８の底部側の間隙ｇ4 が先に閉塞される。ナ
トリウム−硫黄電池においては、この安全管８の底部側
に破損部分があるときに、温度上昇が大きいことから、
この部分は異常時には危険な領域となる。そのため、こ
の部分にナトリウムが供給されなくなることにより、ナ
トリウムと硫黄の反応の継続が停止され、安全性が向上
する。Therefore, when the temperature rises when the battery is abnormal, the gap g 4 on the bottom side of the safety pipe 8 is closed first. In the sodium-sulfur battery, when there is a damaged portion on the bottom side of the safety pipe 8, the temperature rise is large,
This area becomes a dangerous area in case of abnormality. Therefore, by stopping supply of sodium to this portion, the continuation of the reaction between sodium and sulfur is stopped, and safety is improved.

【００５３】なお、この発明は前記各実施例の構成に限
定されるものではなく、この発明の趣旨から逸脱しない
範囲で、任意に変更して具体化することも可能である。 （ａ）前記安全管８の材料として、アルミニウムやステ
ンレスの外に、アルミニウム合金や超塑性合金、例えば
二相ステンレス鋼や銅を使用すること。 （ｂ）第２実施例において、５５０℃より低い温度で間
隙ｇを０になるように構成すること。 （ｃ）第２実施例で加熱状態において安全管８を変形さ
せること。 （ｄ）第３又は第４実施例において、ゴム製のチューブ
１０内に水以外の液体やエアなどの気体を圧入するこ
と。 （ｅ）第４実施例で、安全管８の開口端部より底部側の
温度を電池の動作温度からＴＣＢに必要な温度の範囲内
で適宜の温度に設定したり、複数の温度に設定したりす
ること。The present invention is not limited to the configuration of each of the above-mentioned embodiments, and may be embodied by being arbitrarily modified within the scope not departing from the spirit of the present invention. (A) As the material of the safety pipe 8, in addition to aluminum or stainless steel, use an aluminum alloy or a superplastic alloy, for example, duplex stainless steel or copper. (B) In the second embodiment, the gap g should be zero at a temperature lower than 550 ° C. (C) Deformation of the safety pipe 8 in the heated state in the second embodiment. (D) In the third or fourth embodiment, a gas other than water or a gas such as air is pressed into the rubber tube 10. (E) In the fourth embodiment, the temperature on the bottom side from the open end of the safety pipe 8 is set to an appropriate temperature within the temperature range required for TCB from the operating temperature of the battery, or set to a plurality of temperatures. To do.

【００５４】[0054]

【発明の効果】 この発明は、以上説明したように構成
されているため、次のような優れた効果を奏する。この
発明のナトリウム−硫黄電池の発明によれば、固体電解
質管が破損した場合、ナトリウムと硫黄との直接反応を
最小に制限することができると共に、その直接反応によ
る発熱に基づき、固体電解質管の寸法、形状にばらつき
があった場合でも固体電解質管と安全管との間隙を閉塞
することができる。そして、その後のナトリウムの供給
を停止させることができ、ナトリウムと硫黄との直接反
応を速やかに収束抑制することができて、大事故に繋が
るおそれを防止することができる。Since the present invention is configured as described above, it has the following excellent effects. According to the invention of the sodium-sulfur battery of the present invention, when the solid electrolyte tube is broken, the direct reaction between sodium and sulfur can be limited to the minimum, and the heat generated by the direct reaction causes the solid electrolyte tube Even if there are variations in size and shape, the gap between the solid electrolyte tube and the safety tube can be closed. Then, the subsequent supply of sodium can be stopped, the direct reaction between sodium and sulfur can be promptly suppressed from converging, and the risk of causing a serious accident can be prevented.

【００５５】さらに、固体電解質管が破損し、ナトリウ
ムと硫黄との直接反応によって電池内の温度が上昇した
場合に、固体電解質管と安全管との間隙を下部ほど先に
閉塞させてナトリウムの供給を断ち、事故が継続するお
それを防止することができる。Furthermore, when the solid electrolyte tube is damaged and the temperature inside the battery rises due to the direct reaction of sodium and sulfur, the gap between the solid electrolyte tube and the safety tube is closed earlier toward the bottom to supply sodium. It is possible to prevent the possibility that the accident will continue by turning off.

【００５６】また、ナトリウム−硫黄電池の製造方法の
発明によれば、固体電解質管と安全管とを、所定間隙を
おいた状態に容易に組み付けることができる。しかも、
固体電解質管と安全管との間により安全性を高めるため
の間隙を形成して容易に組み付けることができる。Further, according to the invention of the method for manufacturing a sodium-sulfur battery, the solid electrolyte tube and the safety tube can be easily assembled with a predetermined gap. Moreover,
A gap for enhancing safety can be formed between the solid electrolyte tube and the safety tube to facilitate the assembly.

【００５７】加えて、絶縁リングに陽極容器と陰極金具
を熱圧接合すると同時に、固体電解質管と安全管との間
隙を設定でき、ナトリウム−硫黄電池の製造工程数を減
少させることができて、製造コストの低減を図ることが
できる。In addition, the anode container and the cathode fitting can be thermocompression bonded to the insulating ring, and at the same time, the gap between the solid electrolyte tube and the safety tube can be set, and the number of manufacturing steps of the sodium-sulfur battery can be reduced. The manufacturing cost can be reduced.

【図面の簡単な説明】[Brief description of drawings]

【図１】 この発明を具体化したナトリウム−硫黄電池
の第１実施例を示す縦断面図である。FIG. 1 is a vertical cross-sectional view showing a first embodiment of a sodium-sulfur battery embodying the present invention.

【図２】 陽極容器の中央部の温度と固体電解質管の破
損後の経過時間との関係を示すグラフである。FIG. 2 is a graph showing the relationship between the temperature at the center of the anode container and the elapsed time after breakage of the solid electrolyte tube.

【図３】 （ａ）は実施例における固体電解質管の上下
位置と温度上昇との関係を示すグラフ、（ｂ）は従来例
における固体電解質管の上下位置と温度上昇との関係を
示すグラフである。FIG. 3A is a graph showing the relationship between the vertical position of the solid electrolyte tube and the temperature rise in the example, and FIG. 3B is a graph showing the relationship between the vertical position of the solid electrolyte tube and the temperature rise in the conventional example. is there.

【図４】 （ａ）〜（ｃ）は、この発明を具体化したナ
トリウム−硫黄電池の製造方法の第２実施例を示す断面
図である。4 (a) to 4 (c) are cross-sectional views showing a second embodiment of the method for manufacturing a sodium-sulfur battery embodying the present invention.

【図５】 （ａ）〜（ｅ）は第３実施例のナトリウム−
硫黄電池の製造工程を示す断面図である。5 (a) to (e) are sodium of a third embodiment;
It is sectional drawing which shows the manufacturing process of a sulfur battery.

【図６】 安全管と固体電解質管の間隙の温度による変
化を示すグラフである。FIG. 6 is a graph showing changes in the gap between the safety tube and the solid electrolyte tube depending on the temperature.

【図７】 この発明の別の態様を示す陽極容器と絶縁リ
ングとの接合構造の部分断面図である。FIG. 7 is a partial cross-sectional view of a joint structure between an anode container and an insulating ring showing another embodiment of the present invention.

【図８】 第４実施例のナトリウム−硫黄電池を示す要
部断面図である。FIG. 8 is a cross-sectional view of essential parts showing a sodium-sulfur battery of a fourth example.

【符号の説明】[Explanation of symbols]

４…固体電解質管、８…安全管、９…凹凸状の溝、Ｒ１
…陰極室、Ｒ２…陽極室、Ｎａ…ナトリウム、Ｓ…硫
黄、ｇ，ｇ0 ，ｇ1 ，ｇ2 ，ｇ3 ，ｇ4 …安全管と固体
電解質管との間隙。4 ... Solid electrolyte tube, 8 ... Safety tube, 9 ... Uneven groove, R1
... cathode chamber, R2 ... anode chamber, Na ... sodium, S ... Sulfur, g, g 0, g 1 , g 2, g 3, g 4 ... gap between the safety tube and the solid electrolyte tube.

フロントページの続き (72)発明者 森本 健司 名古屋市瑞穂区須田町２番56号 日本碍子 株式会社内Front page continuation (72) Inventor Kenji Morimoto 2-56 Sudamachi, Mizuho-ku, Nagoya

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 有底筒状の固体電解質管の内側と外側に
陰極室及び陽極室を形成し、固体電解質管の内側に金属
材料よりなる有底筒状の安全管を近接配置し、陰極室内
にはナトリウムを収容すると共に、陽極室内には硫黄を
収容してなるナトリウム−硫黄電池において、 前記固体電解質管と安全管との間隙が、電池動作温度で
は所定値となり、電池の異常高温度では閉塞するよう
に、固体電解質管の熱膨張率よりも大きな熱膨張率を有
する安全管を備えたことを特徴とするナトリウム−硫黄
電池。1. A cathode chamber and an anode chamber are formed inside and outside a bottomed cylindrical solid electrolyte tube, and a bottomed cylindrical safety tube made of a metal material is disposed inside the solid electrolyte tube in close proximity to the cathode. In a sodium-sulfur battery in which sodium is stored in the chamber and sulfur is stored in the anode chamber, the gap between the solid electrolyte tube and the safety tube becomes a predetermined value at the battery operating temperature, and an abnormally high temperature of the battery. Then, the sodium-sulfur battery is provided with a safety tube having a coefficient of thermal expansion larger than that of the solid electrolyte tube so as to be blocked. 【請求項２】 電池の充電時及び放電時にわたって、陽
極室の圧力が陰極室の圧力よりも高いことを特徴とする
請求項１に記載のナトリウム−硫黄電池。2. The sodium-sulfur battery according to claim 1, wherein the pressure in the anode chamber is higher than the pressure in the cathode chamber during charging and discharging of the battery. 【請求項３】 電池の動作温度において、固体電解質管
と安全管との間隙が上部より下部の方が小さいことを特
徴とする請求項１に記載のナトリウム−硫黄電池。3. The sodium-sulfur battery according to claim 1, wherein the gap between the solid electrolyte tube and the safety tube is smaller in the lower portion than in the upper portion at the operating temperature of the battery. 【請求項４】 有底筒状の固体電解質管の内側と外側に
陰極室及び陽極室を形成し、固体電解質管の内側に金属
材料よりなる有底筒状の安全管を近接配置し、陰極室内
にはナトリウムを収容すると共に、陽極室内には硫黄を
収容してなるナトリウム−硫黄電池において、 前記固体電解質管内に安全管を挿入した後、安全管の内
部から圧力を付与して、安全管を固体電解質管の内周面
と接触又は一定の間隙を有するように変形させ、この状
態で固体電解質管及び安全管を電池動作温度よりも高い
温度まで加熱した後に冷却して、固体電解質管と安全管
との間隙を、電池動作温度では所定値となり、電池の異
常高温度では閉塞するように設定することを特徴とする
ナトリウム−硫黄電池の製造方法。4. A cathode chamber and an anode chamber are formed inside and outside a bottomed cylindrical solid electrolyte tube, and a bottomed cylindrical safety tube made of a metal material is disposed inside the solid electrolyte tube in close proximity to the cathode. In a sodium-sulfur battery in which sodium is contained in the chamber and sulfur is contained in the anode chamber, a safety tube is inserted into the solid electrolyte tube, and then pressure is applied from the inside of the safety tube to form a safety tube. Contact with the inner peripheral surface of the solid electrolyte tube or deformed so as to have a constant gap, and in this state, the solid electrolyte tube and the safety tube are heated to a temperature higher than the battery operating temperature and then cooled, A method for producing a sodium-sulfur battery, wherein a gap between the safety pipe and the safety pipe has a predetermined value at a battery operating temperature and is closed at an abnormally high temperature of the battery. 【請求項５】 前記安全管の開口端部側の加熱温度を安
全管の底部側の加熱温度より高く設定したことを特徴と
する請求項４に記載のナトリウム−硫黄電池の製造方
法。5. The method for producing a sodium-sulfur battery according to claim 4, wherein the heating temperature on the open end side of the safety pipe is set higher than the heating temperature on the bottom side of the safety pipe. 【請求項６】 有底筒状の固体電解質管の開口端部外周
に絶縁リングを接合し、この絶縁リングに陽極金具又は
陽極容器と陰極金具とを熱圧接合し、前記固体電解質管
の内側と外側に陰極室及び陽極室を形成すると共に、固
体電解質管の内側に金属材料よりなる有底筒状の安全管
を近接配置し、前記陰極室内にはナトリウムを収容し、
かつ陽極室内には硫黄を収容してなるナトリウム−硫黄
電池において、 前記固体電解質管内に安全管を挿入した後、安全管の内
部から圧力を付与して、安全管を固体電解質管の内周面
と接触又は一定の間隙を有するように変形させ、この状
態で固体電解質管及び安全管を電池動作温度よりも高い
温度まで加熱して、絶縁リングに陽極金具又は陽極容器
と陰極金具を熱圧接合した後、冷却して、固体電解質管
と安全管との間隙を、電池動作温度では所定値となり、
電池の異常高温度では閉塞するように設定することを特
徴とするナトリウム−硫黄電池の製造方法。6. An inner side of the solid electrolyte tube, wherein an insulating ring is joined to an outer periphery of an open end of a bottomed cylindrical solid electrolyte tube, and an anode metal fitting or an anode container and a cathode metal fitting are thermocompression bonded to the insulating ring. While forming a cathode chamber and an anode chamber on the outside, the bottomed cylindrical safety tube made of a metal material is disposed in proximity to the inside of the solid electrolyte tube, and the cathode chamber contains sodium.
And in a sodium-sulfur battery containing sulfur in the anode chamber, after inserting a safety tube into the solid electrolyte tube, a pressure is applied from the inside of the safety tube to form the safety tube on the inner peripheral surface of the solid electrolyte tube. Contact with or deform it so that it has a certain gap, and in this state heat the solid electrolyte tube and the safety tube to a temperature higher than the battery operating temperature, and heat and pressure bond the anode fitting or the anode container and the cathode fitting to the insulating ring. After cooling, cool the gap between the solid electrolyte tube and the safety tube to the specified value at the battery operating temperature.
A method for manufacturing a sodium-sulfur battery, characterized in that the battery is set so as to be blocked at an abnormally high temperature of the battery.
JP5250783A 1992-11-19 1993-10-06 Sodium-sulfur battery and method of manufacturing the same Expired - Lifetime JP2725982B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5250783A JP2725982B2 (en) 1992-11-19 1993-10-06 Sodium-sulfur battery and method of manufacturing the same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP31064192 1992-11-19
JP4-310641 1992-11-19
JP5250783A JP2725982B2 (en) 1992-11-19 1993-10-06 Sodium-sulfur battery and method of manufacturing the same

Publications (2)

Publication Number Publication Date
JPH06208854A true JPH06208854A (en) 1994-07-26
JP2725982B2 JP2725982B2 (en) 1998-03-11

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013129783A1 (en) * 2012-02-27 2013-09-06 Sk Innovation Co., Ltd. Sodium secondary battery having predetermined gap between safety tube and solid electrolyte tube
KR101353602B1 (en) * 2011-12-28 2014-01-23 주식회사 포스코 sodium sulfur battery
KR101419475B1 (en) * 2012-12-21 2014-07-16 재단법인 포항산업과학연구원 Sodium sulfur rechargeable battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101353602B1 (en) * 2011-12-28 2014-01-23 주식회사 포스코 sodium sulfur battery
WO2013129783A1 (en) * 2012-02-27 2013-09-06 Sk Innovation Co., Ltd. Sodium secondary battery having predetermined gap between safety tube and solid electrolyte tube
KR101419475B1 (en) * 2012-12-21 2014-07-16 재단법인 포항산업과학연구원 Sodium sulfur rechargeable battery

Also Published As

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