JP2522862B2 - Sodium-sulfur battery - Google Patents
Sodium-sulfur batteryInfo
- Publication number
- JP2522862B2 JP2522862B2 JP3029576A JP2957691A JP2522862B2 JP 2522862 B2 JP2522862 B2 JP 2522862B2 JP 3029576 A JP3029576 A JP 3029576A JP 2957691 A JP2957691 A JP 2957691A JP 2522862 B2 JP2522862 B2 JP 2522862B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- storage container
- sulfur battery
- discharge passage
- solid electrolyte
- 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.)
- Expired - Fee Related
Links
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
Landscapes
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電池の作動中において
必要以上に高温にさらされたり短絡等の事故により大電
流が流れて単電池自体が発熱した場合に、負極活物質で
ある金属ナトリウムが流出することを止めて事故の拡大
化を防止することができる安全性に優れたナトリウム−
硫黄電池に関するものである。BACKGROUND OF THE INVENTION The present invention relates to metallic sodium which is a negative electrode active material when a single cell itself generates heat due to a large current flowing due to an accident such as exposure to an excessively high temperature or a short circuit during operation of the battery. Which is excellent in safety that can prevent the spread of accidents and prevent the spread of accidents
It relates to a sulfur battery.
【０００２】[0002]
【従来の技術】ナトリウム−硫黄電池は陽極活物質とし
て溶融硫黄または多硫化ナトリウムを、また、陰極活物
質として金属ナトリウムを用い、大型の収納容器内に多
数個配列して据置型高温電池装置とし、３００〜３５０
℃の高温度で運転されるものである。この種ナトリウム
−硫黄電池として本出願人は先に、陽極室と陰極室とを
区画する有底袋管状の固体電解質管内に金属ナトリウム
を収容する金属製のナトリウム貯蔵容器を設けたものを
発明し、特願昭６３−２６４９９２号、同６３−２６４
９９３号等として出願している。2. Description of the Related Art A sodium-sulfur battery uses molten sulfur or sodium polysulfide as an anode active material and metallic sodium as a cathode active material, and a large number of them are arranged in a large container to form a stationary high temperature battery device. , 300-350
It is operated at a high temperature of ℃. As this kind of sodium-sulfur battery, the present applicant previously invented one in which a metallic sodium storage container for containing metallic sodium was provided in a bottomed bag-shaped solid electrolyte tube that defines an anode chamber and a cathode chamber. Japanese Patent Application Nos. 63-264992 and 63-264.
We have applied for it as No. 993.
【０００３】ところが、前述のナトリウム−硫黄電池に
おいては高温電池装置の作動中に特定の単電池が必要以
上に高温にさらされたり短絡等の事故により大電流が流
れるとジュール熱によって単電池自体が発熱し、この結
果、固体電解質管が破壊されて活物質が直接化学反応し
異常加熱して単電池を破壊したうえ、この単電池を含む
高温電池装置全体あるいは周辺の高温電池装置をも巻き
込んだ大規模な破損事故等を発生させるおそれがあっ
た。However, in the above-mentioned sodium-sulfur battery, when a specific unit cell is exposed to an excessively high temperature during operation of the high temperature battery unit or a large current flows due to an accident such as a short circuit, the unit cell itself is generated by Joule heat. As a result, heat is generated and the solid electrolyte tube is destroyed, the active material directly chemically reacts and abnormally heats to destroy the single battery, and the high temperature battery device including this single battery or the surrounding high temperature battery device is also involved. There was a risk of causing a large-scale damage accident.
【０００４】[0004]
【発明が解決しようとする課題】本発明はこのような従
来の問題点を解決して、いずれかのナトリウム−硫黄単
電池が短絡事故等により異常に発熱した場合にも、初期
段階において事故の発生した単電池における金属ナトリ
ウムの流出を停止させて固体電解質管の破壊を防止し、
事故の拡大化を防止することにより大規模な事故の発生
を未然に防ぐことができる安全性に優れたナトリウム−
硫黄電池を提供することを目的として完成されたもので
ある。SUMMARY OF THE INVENTION The present invention solves the conventional problems described above, and even if any of the sodium-sulfur unit cells abnormally generates heat due to a short circuit accident or the like, an accident occurs in the initial stage. Prevent the destruction of the solid electrolyte tube by stopping the outflow of metallic sodium in the generated single cell,
Highly safe sodium that can prevent the occurrence of large-scale accidents by preventing the spread of accidents.
It was completed for the purpose of providing a sulfur battery.
【０００５】[0005]
【課題を解決するための手段】上記の課題を解決するた
めになされた本発明のナトリウム−硫黄電池は、陽極室
と陰極室とを区画する有底袋管状の固体電解質管内に金
属製のナトリウム貯蔵容器を設けたナトリウム−硫黄電
池において、前記ナトリウム貯蔵容器の排出通路に事故
発生時の昇温によりナトリウム貯蔵容器自身の熱膨張に
より熱変形して前記の排出通路を閉鎖する通路閉鎖機構
を設けたことを特徴とするものであり、また陽極室と陰
極室とを区画する有底袋管状の固体電解質管内に金属製
のナトリウム貯蔵容器を設けたナトリウム−硫黄電池に
おいて、前記ナトリウム貯蔵容器に収納した溶融金属ナ
トリウムを固体電解質管の内表面へ供給する排出通路、
および該排出通路を閉鎖するための通路閉鎖機構を設
け、該通路閉鎖機構は事故発 生時の昇温による前記ナト
リウム貯蔵容器自身の熱膨張により排出通路を閉鎖する
ものであることを特徴とするものである。The sodium-sulfur battery of the present invention, which has been made to solve the above-mentioned problems, has a bottomed bag-shaped solid electrolyte tube for partitioning an anode chamber and a cathode chamber and is made of metallic sodium. In a sodium-sulfur battery provided with a storage container, thermal expansion of the sodium storage container itself occurs due to a temperature rise in the discharge passage of the sodium storage container when an accident occurs.
Is intended, characterized in that a passage closing mechanism for closing the discharge passage of more thermal deformation, also the anode chamber and the negative
Made of metal inside the solid electrolyte tube in the shape of a bottomed bag that separates the polar chamber
Sodium-sulfur battery with a sodium storage container
The molten metal container stored in the sodium storage container.
A discharge passage for supplying thorium to the inner surface of the solid electrolyte tube,
And a passage closing mechanism for closing the discharge passage.
Only, the passage closing mechanism the diisocyanato by heating at the time of the accident onset raw
The discharge passage is closed due to the thermal expansion of the lithium storage container itself.
It is characterized by being a thing .
【０００６】[0006]
【実施例】以下に本発明を図示の実施例について詳細に
説明する。図中、１はナトリウム−硫黄電池の容器本
体、２は陽極室３と陰極室４とを区画するセラミックス
製有底袋状の固体電解質管であり、前記陽極室３内には
活物質としての溶融硫黄または多硫化ナトリウムが収容
され、一方、陰極室４内には金属製のナトリウム貯蔵容
器５により活物質としての金属ナトリウムが収容されて
いる。また、前記容器本体１の上部には金属製の蓋体６
が被装されているとともに、陽極室３と陰極室４との間
には電気的絶縁を図るようセラミックス製の絶縁リング
７が装着されている。The present invention will be described in detail below with reference to the illustrated embodiments. In the drawing, 1 is a container body of a sodium-sulfur battery, 2 is a bottomed bag-shaped solid electrolyte tube made of ceramics that divides the anode chamber 3 and the cathode chamber 4, and the inside of the anode chamber 3 serves as an active material. Molten sulfur or sodium polysulfide is stored, while metallic sodium storage container 5 stores metallic sodium as an active material in cathode chamber 4. Further, a metal lid 6 is provided on the upper part of the container body 1.
And an insulating ring 7 made of ceramics is mounted between the anode chamber 3 and the cathode chamber 4 for electrical insulation.
【０００７】ナトリウム貯蔵容器５は金属ナトリウムに
対する耐蝕性に優れたアルミニウム、銅、ニッケル、ス
テンレスあるいはそれらの合金からなるとともに、融点
が５００℃以上でかつ４００℃前後における熱膨張率が
比較的大きい金属よりなるものとし、また、上部には収
納した金属ナトリウムを少量ずつ加圧流出させるための
加圧室８が設けられているとともに、流出した金属ナト
リウムを固体電解質管２の内表面へ供給するための排出
通路９および該排出通路９を閉鎖するための通路閉鎖機
構が設けられている。The sodium storage container 5 is made of aluminum, copper, nickel, stainless steel or an alloy thereof having excellent corrosion resistance against metallic sodium, and has a melting point of 500 ° C. or more and a relatively large thermal expansion coefficient around 400 ° C. In addition, a pressurizing chamber 8 for pressurizing and discharging the stored metallic sodium little by little is provided at the upper part, and the supplied metallic sodium is supplied to the inner surface of the solid electrolyte tube 2. The discharge passage 9 and the passage closing mechanism for closing the discharge passage 9 are provided.
【０００８】通路閉鎖機構としては、図１に示す第１の
実施例のように、サイホン式吸い上げ管を兼ねた排出通
路９の上端にある金属ナトリウムの吐出口１０に、蓋体
６に突設した閉塞部１１を臨ませたものとして、事故発
生により大電流が流れて温度が異常昇温した場合にナト
リウム貯蔵容器５自身の熱膨張により前記排出通路９の
吐出口１０が閉塞部１１で密封されるよう構成したもの
とする外、図２に示される第２の実施例のように、ナト
リウム貯蔵容器５の底部に設けた吐出口１０がナトリウ
ム貯蔵容器５自身の熱膨張により固体電解質管２に突設
した閉塞部１１により閉鎖されるようにしたものであっ
てもよいし、また、図３に示す第３の実施例のように、
ナトリウム貯蔵容器５を二重構造としたうえで外側のナ
トリウム貯蔵容器5aの上端部に蓋体６から垂設された閉
塞部１１を臨ませて、両者の間に形成されたスリット状
の吐出口１０が外側のナトリウム貯蔵容器5aの熱膨張に
応じて閉鎖されるようにしたものであってもよい。As the passage closing mechanism, as in the first embodiment shown in FIG. 1, the metallic sodium discharge port 10 at the upper end of the discharge passage 9 which also serves as a siphon suction pipe is provided with a projection on the lid 6. The discharge port 10 of the discharge passage 9 is hermetically sealed by the thermal expansion of the sodium storage container 5 itself when a large current flows due to the occurrence of an accident and the temperature rises abnormally. In addition to the above configuration, as in the second embodiment shown in FIG. 2, the discharge port 10 provided at the bottom of the sodium storage container 5 has a solid electrolyte tube 2 due to thermal expansion of the sodium storage container 5 itself. It may be configured so as to be closed by a closing portion 11 projecting from the above, or as in the third embodiment shown in FIG.
The sodium storage container 5 has a double structure, and the closed portion 11 vertically extending from the lid 6 faces the upper end of the outer sodium storage container 5a, and a slit-shaped discharge port formed between the two. 10 may be closed according to the thermal expansion of the outer sodium storage container 5a.
【０００９】[0009]
【作用】このように構成されたものにおいては、通常運
転時には加圧室８内のガス体の加圧力によってナトリウ
ム貯蔵容器５より金属ナトリウムが吐出口１０および排
出通路９を経て適量ずつ固体電解質管２の内表面に供給
され充放電が適正に行なわれることとなる。そして、万
が一短絡等の事故が発生して大電流が流れ電池内部の温
度が通常運転時よりも高くなった場合には、通路閉鎖機
構の作動によりナトリウム貯蔵容器５からの金属ナトリ
ウムの流出を停止させてそれ以上の電流の流れを遮断し
ジュール熱による発熱を抑制して、事故の拡大化を防止
するものである。With the above-described structure, during normal operation, the metallic sodium from the sodium storage container 5 is passed through the discharge port 10 and the discharge passage 9 by the pressurizing force of the gas in the pressurizing chamber 8, and the solid sodium electrolyte tube It is supplied to the inner surface of 2 and charging / discharging is properly performed. If an accident such as a short circuit occurs and a large current flows and the temperature inside the battery becomes higher than that during normal operation, the passage closing mechanism is actuated to stop the outflow of metallic sodium from the sodium storage container 5. Then, the flow of current beyond that is cut off to suppress heat generation due to Joule heat and prevent the spread of the accident.
【００１０】すなわち、図１〜図３に示されるように事
故発生時のジュール熱による昇温によりナトリウム貯蔵
容器５自身が熱膨張して吐出孔１０が閉塞部１１により
密閉され、この結果、排出通路９が閉鎖されて以後の金
属ナトリウムの流出が確実に停止されて発熱が抑制さ
れ、固体電解質管２の破壊が防止されるとともに陽極活
物質である硫黄との直接化学反応を防止して単電池の破
壊を防止して事故の拡大化を防止し、安全性を確保する
のである。That is, as shown in FIGS. 1 to 3, the sodium storage container 5 itself is thermally expanded by the temperature rise due to Joule heat at the time of occurrence, and the discharge hole 10 is sealed by the closing portion 11. As a result, the discharge passage 9 is closed and the subsequent outflow of metallic sodium is reliably stopped, heat generation is suppressed, destruction of the solid electrolyte tube 2 is prevented, and direct chemical reaction with sulfur, which is the anode active material, is prevented. the to prevent to destruction of the cell preventing prevent the spread of the accident, ensuring the safety
Of .
【００１１】このようにしていずれかの単電池が何らか
の理由で異常昇温した場合であっても、初期段階におい
て金属ナトリウムの流出を確実に停止させると同時にナ
トリウム貯蔵容器５内に金属ナトリウムを完全に封じ込
めることにより、それ以上の発熱を抑制して単電池の破
壊を未然に防ぎ、他の正常なナトリウム−硫黄単電池へ
の事故の拡大化を防止して優れた安全性を発揮すること
となる。なお、万が一初期段階における昇温で固体電解
質管２が破壊した場合であっても、金属ナトリウムを封
じ込めてあるので硫黄との直接化学反応も最小限に留め
られることとなり、昇温を抑制することにより単電池の
破壊を防止して事故の拡大化を防止し、安全性を確保す
ることとなる。In this way, even if the temperature of any one of the cells is abnormally raised for some reason, the outflow of the metallic sodium is surely stopped at the initial stage, and at the same time, the metallic sodium is completely stored in the sodium storage container 5. By encapsulating it in the battery, it is possible to suppress further heat generation and prevent the destruction of the cell, prevent the spread of accidents to other normal sodium-sulfur cells, and exert excellent safety. Become. Even if the solid electrolyte tube 2 is destroyed by the temperature rise in the initial stage, since the sodium metal is contained, the direct chemical reaction with sulfur can be minimized and the temperature rise can be suppressed. By doing so, it is possible to prevent the destruction of the unit cells, prevent the accident from spreading, and ensure safety.
【００１２】[0012]
【発明の効果】本発明は以上の説明からも明らかなよう
に、いずれかのナトリウム−硫黄単電池が事故等により
異常昇温した場合にも、初期段階において事故の発生し
た単電池における金属ナトリウムの流出を停止させて固
体電解質管の破壊を防止し、単電池の破壊を防いで事故
の拡大化を防止することにより大規模な事故の発生を未
然に防ぐことができるものである。よって、本発明は従
来の問題点を一掃したナトリウム−硫黄電池として、産
業の発展に寄与するところは極めて大である。As is apparent from the above description, the present invention makes it possible to detect metallic sodium in a cell in which an accident occurs in the initial stage even when any of the sodium-sulfur cells has an abnormal temperature rise due to an accident or the like. It is possible to prevent the occurrence of a large-scale accident by stopping the outflow of the solid electrolyte tube to prevent the solid electrolyte tube from being destroyed, and from preventing the destruction of the unit cell to prevent the accident from spreading. Therefore, the present invention, as a sodium-sulfur battery that eliminates the conventional problems, has an extremely large contribution to industrial development.
【００１４】[0014]
【図１】本発明の第１の実施例を示す縦断正面図であ
る。FIG. 1 is a vertical sectional front view showing a first embodiment of the present invention.
【図２】本発明の第２の実施例を示す縦断正面図であ
る。FIG. 2 is a vertical sectional front view showing a second embodiment of the present invention.
【図３】本発明の第３の実施例を示す縦断正面図であ
る。FIG. 3 is a vertical sectional front view showing a third embodiment of the present invention.
２ 固体電解質管 ３ 陽極室 ４ 陰極室 ５ ナトリウム貯蔵容器 ９ 排出通路 2 Solid electrolyte tube 3 Anode chamber 4 Cathode chamber 5 Sodium storage container 9 Discharge passage
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭54−143825（ＪＰ，Ａ) 特開 昭59−23475（ＪＰ，Ａ) 特開 昭62−10880（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 54-143825 (JP, A) JP 59-23475 (JP, A) JP 62-10880 (JP, A)
Claims (3)
の固体電解質管内に金属製のナトリウム貯蔵容器を設け
たナトリウム−硫黄電池において、前記ナトリウム貯蔵
容器の排出通路に事故発生時の昇温によりナトリウム貯
蔵容器自身の熱膨張により熱変形して前記の排出通路を
閉鎖する通路閉鎖機構を設けたことを特徴とするナトリ
ウム−硫黄電池。1. A sodium-sulfur battery in which a metallic sodium storage container is provided in a bottomed bag-shaped solid electrolyte tube for partitioning an anode chamber and a cathode chamber, and a sodium-sulfur battery is provided in the discharge passage of the sodium storage container when an accident occurs. Sodium storage due to temperature rise
A sodium-sulfur battery characterized in that a passage closing mechanism is provided for closing the discharge passage by thermally deforming due to thermal expansion of the storage container itself .
の固体電解質管内に金属製のナトリウム貯蔵容器を設け
たナトリウム−硫黄電池において、前記ナトリウム貯蔵
容器に収納した溶融金属ナトリウムを固体電解質管の内
表面へ供給する排出通路、および該排出通路を閉鎖する
ための通路閉鎖機構を設け、該通路閉鎖機構は事故発生
時の昇温による前記ナトリウム貯蔵容器自身の熱膨張に
より排出通路を閉鎖するものであることを特徴とするナ
トリウム−硫黄電池。 2. A sodium in the solid electrolyte tube of a bottomed bag tubular partitioning the anode compartment and a cathode compartment provided with a metal sodium storage container - the sulfur battery, said sodium storage
The molten sodium metal contained in the container is placed inside the solid electrolyte tube.
A discharge passage for supplying to a surface and closing the discharge passage
A passage closing mechanism is provided to prevent the occurrence of an accident.
Due to the thermal expansion of the sodium storage container itself due to the temperature rise during
A feature that the discharge passage is closed more
Thorium-sulfur battery.
とを特徴とする請求項２に記載のナトリウム−硫黄電
池。3. The sodium-sulfur battery according to claim 2, wherein the sodium storage container has a double structure .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029576A JP2522862B2 (en) | 1991-01-29 | 1991-01-29 | Sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3029576A JP2522862B2 (en) | 1991-01-29 | 1991-01-29 | Sodium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04253168A JPH04253168A (en) | 1992-09-08 |
| JP2522862B2 true JP2522862B2 (en) | 1996-08-07 |
Family
ID=12279933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3029576A Expired - Fee Related JP2522862B2 (en) | 1991-01-29 | 1991-01-29 | Sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2522862B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2819027C2 (en) * | 1978-04-29 | 1982-09-23 | Brown, Boveri & Cie Ag, 6800 Mannheim | Electrochemical storage cell |
| DE3225861A1 (en) * | 1982-07-10 | 1984-01-12 | Brown, Boveri & Cie Ag, 6800 Mannheim | ELECTROCHEMICAL STORAGE CELL |
-
1991
- 1991-01-29 JP JP3029576A patent/JP2522862B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04253168A (en) | 1992-09-08 |
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