JP3458438B2 - Na / S battery - Google Patents
Na / S batteryInfo
- Publication number
- JP3458438B2 JP3458438B2 JP02011694A JP2011694A JP3458438B2 JP 3458438 B2 JP3458438 B2 JP 3458438B2 JP 02011694 A JP02011694 A JP 02011694A JP 2011694 A JP2011694 A JP 2011694A JP 3458438 B2 JP3458438 B2 JP 3458438B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- active material
- electrode active
- negative electrode
- positive electrode
- 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、Ｎａ／Ｓ電池に係り、
特に夜間電力貯蔵用や電気自動車用電池等大電力貯蔵用
に好適なＮａ／Ｓ電池に関する。The present invention relates to relates to a Na / S cell,
Especially for nighttime electricity storage and large electricity storage such as batteries for electric vehicles
For a suitable Na / S battery.
【０００２】[0002]
【従来の技術】Ｎａ／Ｓ電池では、電気絶縁シール部が
破損すると、電気活物質ならびにカバーガスが電池外に
放出したり、大気が電池容器に流入して固体電解質管が
破損する可能性がある。固体電解質が破損した場合、負
極活物質と正極活物質との直接反応が生じ、直接反応の
反応熱により電池が破損に至った場合、他の健全な電池
へ破損が拡大したり、モジュールの運転継続が困難にな
るという問題が生じる可能性がある。2. Description of the Related Art In a Na / S battery , if the electrically insulating seal portion is damaged, the electrically active material and the cover gas may be released to the outside of the battery, or the atmosphere may flow into the battery container to damage the solid electrolyte tube. is there. When the solid electrolyte is damaged, a direct reaction between the negative electrode active material and the positive electrode active material occurs, and when the battery is damaged by the reaction heat of the direct reaction, the damage spreads to other healthy batteries or the module operation The problem of difficulty in continuation may arise.
【０００３】従来技術としては、固体電解質管に破損が
生じた場合の負極活物質および正極活物質の直接反応を
抑制するために、負極電池容器内部および、電池容器外
部に反応抑制剤を配置したり（特開平６−６８９０５号
公報参照）、電池活物質の漏出を防止するために、電気
絶縁シート部と正極電池容器との間隙に耐熱材料を塗布
し熱処理して固化させる方法（特開平２−１６５５７４
号公報参照）が知られている。In the prior art, in order to suppress the direct reaction of the negative electrode active material and the positive electrode active material when the solid electrolyte tube is damaged, a reaction inhibitor is placed inside the negative electrode battery container and outside the battery container. or (Hei 6 - see JP 68905), in order to prevent leakage of the battery active material, a method (JP-a-2 to the gap solidify the heat-resistant material coated was heat-treated in the electrical insulating sheet portion and the positive electrode battery container 165574
(See Japanese Patent Publication).
【０００４】[0004]
【発明が解決しようとする課題】電気絶縁シール部は、
セラミックスと正極電池容器，負極電池容器をそれぞれ
熱圧接によりシールしている。電気絶縁シール部が破損
すると、電池活物質ならびにカバーガスが電池外に放出
したり、大気が電池容器内に流入し、負極活物質が燃焼
して、固体電解質管が破損し、電池が破損する可能性が
ある。電気絶縁シール部に関しては、電気絶縁シール部
の強度向上対策はあるが、電気絶縁シール部破損時のリ
ーク防止対策は十分なものではない。The electrical insulating seal portion is
The ceramics, the positive electrode battery container, and the negative electrode battery container are sealed by thermocompression bonding. If the electrical insulation seal part is damaged, the battery active material and the cover gas are released to the outside of the battery, the atmosphere flows into the battery container, the negative electrode active material is burned, the solid electrolyte tube is damaged, and the battery is damaged. there is a possibility. Regarding the electrical insulation seal part, there are measures for improving the strength of the electrical insulation seal part, but leak prevention measures when the electrical insulation seal part is damaged are not sufficient.
【０００５】また、モジュール内の電池が破損した場
合、健全な電池があるにもかかわらず、モジュールの運
転を停止しなければならないという問題が生じる可能性
がある。In addition, when the battery inside the module is damaged, there is a possibility that the operation of the module must be stopped even though there is a healthy battery.
【０００６】本発明は、電気絶縁シール部破損時のシー
ル方法、そのシール方法を有することを特徴としたＮａ
／Ｓ電池、およびモジュール内の電池が破損した場合
に、モジュールの運転を維持する電池システムを提供す
ることにある。The present invention is characterized by having a sealing method when the electrically insulating seal portion is damaged, and a sealing method therefor.
It is to provide a battery system that maintains the operation of the module when the / S battery and the battery in the module are damaged.
【０００７】[0007]
【課題を解決するための手段】上記問題点を解決する
に、電池活物質と反応し安定な反応生成物を生じるシー
ルリーク防止剤，電池の正極電池容器と負極電池容器と
を短絡する手段は以下のとおりである。In order to solve the above problems, a seal leak preventive agent that reacts with a battery active material to generate a stable reaction product, and means for short-circuiting the positive electrode battery container and the negative electrode battery container of the battery are provided. It is as follows.
【０００８】電気絶縁シール部が破損した場合、シール
リーク防止剤と電池活物質とが反応して安定な反応生成
物を生じ、電気絶縁シール部の破損部を閉塞し、かつ電
池の運転を継続できるＮａ／Ｓ電池に用いるシールリー
ク防止剤は、例えばメタバナジン酸ナトリウム(ＮａＶ
Ｏ3)やシリカ(ＳｉＯ2)と炭酸カルシウム(ＣａＣ
Ｏ3）、炭酸鉄（ＦｅＣＯ3 ）などとを混合したものが
ある。シールリーク防止剤は、電池運転温度（３１０
℃）で高抵抗であり、Ｎａと反応して安定な反応生成物
であるバナジン酸ナトリウム（Ｎａ3ＶＯ4），珪酸ナト
リウム（Ｎａ2ＳｉＯ3）などを生じ、Ｓと反応して安定
な反応生成物である硫化カルシウム(ＣａＳ)，硫化鉄
(ＦｅＳ)などを生じる。これらの安定な反応生成物は、
電池運転温度（３１０℃）で固体であり、かつ高抵抗物
質であり、電気絶縁シール部の破損部を閉塞し、かつ電
池の運転を継続することができる。When the electrically insulating seal portion is damaged, the seal leak preventive agent and the battery active material react to generate a stable reaction product, the damaged portion of the electrically insulating seal portion is closed, and the battery operation is continued. A seal leak preventive agent used in a Na / S battery that can be used is, for example, sodium metavanadate (NaV
O 3 ) or silica (SiO 2 ) and calcium carbonate (CaC
There is a mixture of O 3 ), iron carbonate (FeCO 3 ), and the like. The seal leak preventive agent is used at the battery operating temperature (310
It has a high resistance at ℃) and reacts with Na to generate stable reaction products such as sodium vanadate (Na 3 VO 4 ), sodium silicate (Na 2 SiO 3 ), etc., and reacts with S to give a stable reaction. Product calcium sulfide (CaS), iron sulfide
(FeS) is generated. These stable reaction products are
It is a solid and a high resistance material at the battery operating temperature (310 ° C.), can block the damaged part of the electrical insulation seal part, and can continue the battery operation.
【０００９】[0009]
【作用】本発明のシールリーク防止剤は、請求項１、又
は２の発明では電池活物質と反応して安定な反応生成物
を生じ、安定な反応生成物により電気絶縁シール部の破
損部を閉塞するものである。また、請求項３の発明では
電池活物質と反応して安定な反応生成物を生じ、安定な
反応生成物により電気絶縁シール部の破損部を閉塞し、
かつ正極電池容器と負極電池容器とを短絡するものであ
る。In the invention of claim 1 or 2, the seal leak preventer of the present invention reacts with the battery active material to produce a stable reaction product, and the stable reaction product causes damage to the electrically insulating seal portion. It will block. Further, in the invention of claim 3 , a stable reaction product is produced by reacting with the battery active material, and the stable reaction product closes the damaged portion of the electric insulation seal portion,
Moreover, the positive electrode battery container and the negative electrode battery container are short-circuited.
【００１０】次式（１）に反応式の代表例を示す。A typical example of the reaction formula is shown in the following formula (1).
【００１１】
２Ｎａ＋Ｓ＋ＮａＶＯ3＋ＣａＣＯ3→Ｎａ3ＶＯ4＋ＣａＳ …（１）
第２の実施例として、電気絶縁シール部が破損した場
合、シールリーク防止剤と電池活物質とが反応して安定
な反応生成物を生じ、電気絶縁シール部の破損部を閉塞
し、かつ正極電池容器と負極電池容器とを短絡するＮａ
／Ｓ電池のシール方法について述べる。シールリーク防
止剤は、電池運転温度で高抵抗である物質、例えば金属
塩化物（塩化銀（ＡｇＣｌ），塩化鉛（ＰｂＣｌ2 ）な
ど），金属ヨウ化物（ヨウ化リチウム（ＬｉＩ），ヨウ
化鉛（ＰｂＩ2 ）など），金属臭化物（臭化銀（ＡｇＢ
ｒ），臭化鉛（ＰｂＢｒ2 ）など），金属フッ化物（フ
ッ化カリウム（ＫＦ）など）などを用いると、Ｎａと反
応して安定な反応生成物であるナトリウム塩（塩化ナト
リウム（ＮａＣｌ），ヨウ化ナトリウム（ＮａＩ），臭
化ナトリウム（ＮａＢｒ），フッ化ナトリウム（Ｎａ
Ｆ）など）と、金属間化合物（Ｎａ−Ｐｂ，Ｎａ−Ａ
ｇ，Ｎａ−Ｌｉ，Ｎａ−Ｋなど）とを生じる。ナトリウ
ム塩は、電池運転温度で固体であり、電気絶縁シール部
の破損部を閉塞することができ、金属間化合物は低抵抗
であり、正極電池容器と負極電池容器とを短絡できる。2Na + S + NaVO 3 + CaCO 3 → Na 3 VO 4 + CaS (1) As a second embodiment, when the electrically insulating seal part is damaged, the seal leak preventive agent reacts with the battery active material to generate a stable reaction. Na that creates a substance, closes the damaged portion of the electrically insulating seal portion, and short-circuits the positive electrode battery container and the negative electrode battery container.
A method of sealing the / S battery will be described. The seal leak preventive agent is a substance having high resistance at a battery operating temperature, for example, metal chloride (silver chloride (AgCl), lead chloride (PbCl 2 ), etc.), metal iodide (lithium iodide (LiI), lead iodide). (PbI 2 ), metal bromide (silver bromide (AgB
r), lead bromide (PbBr 2 etc.), and metal fluorides (potassium fluoride (KF) etc.) are used, sodium salt (sodium chloride (NaCl)) which is a stable reaction product by reacting with Na. , Sodium iodide (NaI), sodium bromide (NaBr), sodium fluoride (Na
F)) and intermetallic compounds (Na-Pb, Na-A).
g, Na-Li, Na-K, etc.). The sodium salt is solid at the battery operating temperature, can block the damaged portion of the electrical insulating seal portion, the intermetallic compound has low resistance, and can short-circuit the positive electrode battery container and the negative electrode battery container.
【００１２】[0012]
【実施例】以下、本発明の一実施例を説明する。EXAMPLE An example of the present invention will be described below.
【００１３】（実施例１）図１は、Ｎａ／Ｓ電池の縦断
面図である。図２に電気絶縁シール部６の拡大図を示
す。正極電池容器１の内側に固体電解質管５があり、正
極電池容器１と固体電解質管５との間に正極活物質４で
ある硫黄（Ｓ）と、Ｓと負極活物質（Ｎａ）３との化合
物である多硫化ナトリウムとが、補助導電材(グラファ
イトフェルト)８と一緒に充填してある。固体電解質管
５の内側に負極活物質（Ｎａ）３が充填してある。電気
絶縁物であるセラミックス７と正極電池容器１，負極電
池容器２，固体電解質管５はそれぞれ熱圧接により接合
され、電気絶縁シール部６を形成している。電気絶縁シ
ール部６の外側に第１の実施例で説明したシールリーク
防止剤９（例えばメタバナジン酸ナトリウムと炭酸カル
シウムの混合物など）を配置している。電気絶縁シール
部６に破損部が生じ、電池活物質ならびにカバーガス１
８が電気絶縁シール部６を経て電池容器外部に漏洩した
場合、シールリーク防止剤９が電池活物質と反応して、
安定な反応生成物（例えばバナジン酸ナトリウム，硫化
カルシウム）を生じ、電気絶縁シール部６の破損部を閉
塞し、電池の運転を継続することができる。(Embodiment 1) FIG. 1 is a longitudinal sectional view of a Na / S battery. FIG. 2 shows an enlarged view of the electrically insulating seal portion 6. There is a solid electrolyte tube 5 inside the positive electrode battery container 1, and between the positive electrode battery container 1 and the solid electrolyte tube 5, sulfur (S) which is the positive electrode active material 4, S and negative electrode active material (Na) 3 A compound, sodium polysulfide, is filled together with an auxiliary conductive material (graphite felt) 8. A negative electrode active material (Na) 3 is filled inside the solid electrolyte tube 5. The ceramics 7, which is an electrical insulator, and the positive electrode battery container 1, the negative electrode battery container 2, and the solid electrolyte tube 5 are joined by thermocompression bonding to form an electrical insulating seal portion 6. The seal leak preventive agent 9 (for example, a mixture of sodium metavanadate and calcium carbonate) described in the first embodiment is arranged outside the electrically insulating seal portion 6. A breakage occurs in the electrically insulating seal portion 6, and the battery active material and the cover gas 1
When 8 leaks to the outside of the battery container through the electrically insulating seal portion 6, the seal leak preventive agent 9 reacts with the battery active material,
A stable reaction product (for example, sodium vanadate, calcium sulfide) is generated, the damaged portion of the electrical insulation seal portion 6 is closed, and the battery operation can be continued.
【００１４】（実施例２）図３は、電気絶縁シール部６
の外側に、電池運転温度で固体であるシールリーク防止
剤１０（例えば、塩化鉛，塩化銀，ヨウ化鉛など）の配
置図である。電気絶縁シール部６に破損部が生じ、Ｎａ
ならびにカバーガス１８が電気絶縁シール部６を経て電
池容器外部に漏洩した場合、シールリーク防止剤１０が
Ｎａと反応して、安定な反応生成物であるナトリウム塩
（例えば、塩化ナトリウム，ヨウ化ナトリウムなど）と
金属間化合物（Ｎａ−Ｐｂ，Ｎａ−Ａｇなど）を生じ、
電気絶縁シール部１０の破損部を閉塞し、金属間化合物
により正極電池容器１と負極電池容器２とを短絡するこ
とができる。また、Ｓが電気絶縁シール部６を経て電池
容器外部に漏洩した場合、シールリーク防止剤１０がＳ
と反応して、安定な反応生成物（硫化鉛（ＰｂＳ），硫
化銀（Ａｇ2Ｓ ）など）を生じ、電気絶縁シール部６の
破損部を閉塞し、かつ電池の運転を継続することができ
る。(Embodiment 2) FIG. 3 shows an electrically insulating seal portion 6.
FIG. 3 is a layout view of a seal leak preventive agent 10 (for example, lead chloride, silver chloride, lead iodide, etc.) which is solid at the battery operating temperature on the outside of FIG. A breakage occurs in the electrical insulation seal 6 and Na
In addition, when the cover gas 18 leaks to the outside of the battery container through the electrically insulating seal portion 6, the seal leak preventive agent 10 reacts with Na to form a stable reaction product such as sodium salt (for example, sodium chloride or sodium iodide). Etc.) and intermetallic compounds (Na-Pb, Na-Ag, etc.),
The damaged portion of the electrically insulating seal portion 10 can be closed, and the positive electrode battery container 1 and the negative electrode battery container 2 can be short-circuited by the intermetallic compound. When S leaks to the outside of the battery container through the electrically insulating seal portion 6, the seal leak preventive agent 10 is S
Reacts with a stable reaction product (lead sulfide (PbS), silver sulfide (Ag 2 S), etc.) to block the damaged portion of the electrical insulating seal portion 6 and to continue the operation of the battery. it can.
【００１５】（実施例３）
図４には、第１の実施例のシールリーク防止剤９または
第２の実施例のシールリーク防止剤１０と、第１の実施
例のシールリーク防止剤９よりも粒径の大きな粒体４０
とを混合して、シールリーク防止剤４１を構成してい
る。粒体４０は、正極活物質または負極活物質に耐食性
を有する物質、例えば酸化アルミニウム（Ａｌ2Ｏ3），
シリコン（Ｓｉ）などを用いる。電気絶縁シール部６に
破損部が生じ電池活物質がシールリーク防止剤に漏出し
た場合、第１の実施例のシールリーク防止剤９または第
２の実施例のシールリーク防止剤１０と電池活物質とが
反応し、安定な反応性生物を生じる。この時、粒体４０
が核となり、反応性生物の固化が促進され、効果的に電
気絶縁シール部の破損部を閉塞できる。また、固化した
反応性生物中の粒体４０により、電気絶縁シール部の破
損部の閉塞部の強度が増す。[0015] (Embodiment 3) FIG. 4, a seal leakage inhibitor 10 of the first embodiment of the seal leakage inhibitor 9 or the second embodiment, the sealing leakage inhibitor 9 of the first embodiment Also large particles 40
And are mixed to form the seal leak preventive agent 41. The granules 40 are made of a material having corrosion resistance to the positive electrode active material or the negative electrode active material, such as aluminum oxide (Al 2 O 3 ),
Silicon (Si) or the like is used. In the case where a breakage occurs in the electrically insulating seal portion 6 and the battery active material leaks to the seal leak preventive agent, the seal leak preventive agent 9 or the seal leak preventive agent of the first embodiment is used.
The seal leak preventive agent 10 of Example 2 and the battery active material react with each other to generate a stable reaction product. At this time, granules 40
Serves as a nucleus to promote solidification of reactive organisms and effectively block the damaged portion of the electrically insulating seal portion. In addition, the solidified particles 40 in the reactive organism increase the strength of the closed portion of the damaged portion of the electrically insulating seal portion.
【００１６】（実施例４）図５は、電気絶縁シール部６
の外側に、電池運転温度で液体であるシールリーク防止
剤１１（例えば、塩化亜鉛（ＺｎＣｌ2 ）など）の配置
図である。電気絶縁シール部６に破損部が生じると、液
体であるシールリーク防止剤１１が電気絶縁シール部６
の破損部に進入していく。電気絶縁シール部６の破損部
においてＮａと接触した場合、安定な反応生成物である
ナトリウム塩（塩化ナトリウムなど）と金属間化合物
（Ｎａ−Ｚｎなど）を生じ、電気絶縁シール部の破損部
を閉塞し、電池の運転を継続することができる。また、
金属間化合物が電気絶縁シール部６の外側に成長してい
くと、正極電池容器１と負極電池容器２とを短絡するこ
とができる。電気絶縁シール部６の破損部においてＳと
接触した場合、シールリーク防止剤がＳと反応して、安
定な反応生成物（硫化亜鉛（ＺｎＳ）など）を生じ、電
気絶縁シール部の破損部６を閉塞し、かつ電池の運転を
継続することができる。(Embodiment 4) FIG. 5 shows an electrically insulating seal portion 6.
FIG. 4 is a layout view of a seal leak preventive agent 11 (for example, zinc chloride (ZnCl 2 ), etc.) that is a liquid at a battery operating temperature, on the outer side of FIG. When the electrically insulating seal portion 6 is damaged, the seal leak preventive agent 11 which is a liquid is discharged from the electrically insulating seal portion 6.
Enter the damaged part. When the damaged portion of the electrical insulating seal portion 6 comes into contact with Na, a stable reaction product such as sodium salt (sodium chloride) and an intermetallic compound (Na—Zn etc.) are generated, and the damaged portion of the electrical insulating seal portion is damaged. The battery can be closed and the operation of the battery can be continued. Also,
As the intermetallic compound grows outside the electrically insulating seal portion 6, the positive electrode battery container 1 and the negative electrode battery container 2 can be short-circuited. When the damaged portion of the electrically insulating seal portion 6 comes into contact with S, the seal leak preventer reacts with S to generate a stable reaction product (zinc sulfide (ZnS), etc.), and the damaged portion 6 of the electrically insulating seal portion 6 Can be closed and the operation of the battery can be continued.
【００１７】（実施例５）図６は、カバーガス１９を外
気に比べて負圧にしてあることが特徴である。カバーガ
ス１９を外気に比べて負圧にしてあることで、電気絶縁
シール部６に破損部が生じた場合、電池容器内部と外気
との圧力差により、液体であるシールリーク防止剤１１
を電気絶縁シール部６の破損部に誘導することができ
る。(Embodiment 5) FIG. 6 is characterized in that the cover gas 19 has a negative pressure as compared with the outside air. Since the cover gas 19 has a negative pressure as compared with the outside air, when a breakage occurs in the electrically insulating seal portion 6, the seal leak preventive agent 11 which is liquid due to the pressure difference between the inside of the battery container and the outside air.
Can be guided to the damaged portion of the electrically insulating seal portion 6.
【００１８】（実施例６）図７は、電気絶縁シール部の
上方の間隙にバネ機構を利用した短絡機構である。一方
の電池容器（例えば正極電池容器１）にバネ３０の一端
を固定し他方の電池容器(負極電池容器２)とバネ３０と
の間に電気抵抗の大きな物質３１を配置している。電池
の温度が上昇し、電気抵抗の大きな物質３１の融点に達
すると、電気抵抗の大きな物質３１が溶融し、バネ３０
の復元力により正極電池容器１と負極電池容器２とが短
絡される。電気抵抗の大きな物質３１の例として、Ｎａ
Ｃｌ（融点８０１℃）やヨウ化カリウム（ＫＩ）(融点
６８０℃）やＰｂＣｌ2（融点５０１℃）などがある。(Embodiment 6) FIG. 7 shows a short-circuit mechanism using a spring mechanism in the gap above the electrically insulating seal portion. One end of a spring 30 is fixed to one battery container (for example, positive electrode battery container 1), and a substance 31 having a large electric resistance is arranged between the other battery container (negative electrode battery container 2) and the spring 30. When the temperature of the battery rises and reaches the melting point of the substance 31 having a large electric resistance, the substance 31 having a large electric resistance melts and the spring 30
The positive electrode battery container 1 and the negative electrode battery container 2 are short-circuited by the restoring force of. As an example of the substance 31 having a large electric resistance, Na
There are Cl (melting point 801 ° C.), potassium iodide (KI) (melting point 680 ° C.), PbCl 2 (melting point 501 ° C.) and the like.
【００１９】（実施例７）図８は、高温（例えば４００
℃以上）で動作する一方向性形状記憶合金３２の使用例
である。一方の電池容器（例えば正極電池容器１）に、
一方向性形状記憶合金３２の一端を固定し、他方の電池
容器（負極電池容器２）と一方向性形状記憶合金３２と
の間に空間を保持しておく。電池の温度が上昇し、一方
向性形状記憶合金３２の変形温度に達すると、図９のご
とく一方向性形状記憶合金３２が変形し、正極電池容器
１と負極電池容器２とが短絡される。(Embodiment 7) FIG. 8 shows a high temperature (for example, 400
This is an example of use of the unidirectional shape memory alloy 32 that operates at (° C or higher). In one battery container (for example, positive electrode battery container 1),
One end of the unidirectional shape memory alloy 32 is fixed, and a space is held between the other battery container (negative electrode battery container 2) and the unidirectional shape memory alloy 32. When the temperature of the battery rises and reaches the deformation temperature of the unidirectional shape memory alloy 32, the unidirectional shape memory alloy 32 is deformed as shown in FIG. 9, and the positive electrode battery container 1 and the negative electrode battery container 2 are short-circuited. .
【００２０】（実施例８）図１０は、一方の電池容器
（例えば正極電池容器１）に、高温（約５００℃）で動
作する二方向性形状記憶合金３３、例えばチタン−パラ
ジウム(Ｔｉ−Ｐｄ)系の形状記憶合金の一端を固定し、
他方の電池容器（負極電池容器２）と二方向性形状記憶
合金３３との間に空間を保持する場合の実施例である。
電池の温度が上昇し、二方向性形状記憶合金３３の変形
温度に達すると、図１１のごとく二方向性形状記憶合金
３３が変形し、正極電池容器１と負極電池容器２とが短
絡できる。(Embodiment 8) FIG. 10 shows a bidirectional shape memory alloy 33, such as titanium-palladium (Ti-Pd), which operates at high temperature (about 500 ° C.) in one battery container (for example, positive electrode battery container 1). ) Fix one end of the shape memory alloy of the system,
In this example, a space is maintained between the other battery container (negative electrode battery container 2) and the bidirectional shape memory alloy 33.
When the temperature of the battery rises and reaches the deformation temperature of the bidirectional shape memory alloy 33, the bidirectional shape memory alloy 33 is deformed as shown in FIG. 11, and the positive electrode battery container 1 and the negative electrode battery container 2 can be short-circuited.
【００２１】（実施例９）図１２は、二方向性形状記憶
合金のストッパー３４を配置したものである。二方向性
形状記憶合金の変形温度に達すると、図１３のごとく二
方向性形状記憶合金が変形し、正極電池容器と負極電池
容器と短絡できる。(Embodiment 9) FIG. 12 shows an arrangement of stoppers 34 of bidirectional shape memory alloy. When the deformation temperature of the bidirectional shape memory alloy is reached, the bidirectional shape memory alloy is deformed as shown in FIG. 13, and the positive electrode battery container and the negative electrode battery container can be short-circuited.
【００２２】（実施例１０）図１４は、電気抵抗の小さ
な物質３５（例えばステンレス鋼）を保持するストッパ
ー３６を、正極電池容器１と負極電池容器２に設け、電
気抵抗の小さな物質３５とストッパー３６との間に、電
気抵抗の大きな物質３７を配置する。電池温度が、電気
抵抗の大きな物質３７の融点に達すると、電気抵抗の大
きな物質３７が融解し、電気抵抗の小さな物質３５とス
トッパー３６とが接触し、正極電池容器１と負極電池容
器２とを短絡できる。(Embodiment 10) FIG. 14 shows that a stopper 36 for holding a substance 35 having a small electric resistance (for example, stainless steel) is provided in the positive electrode battery container 1 and the negative electrode battery container 2, and the substance 35 having a small electric resistance and the stopper are provided. A substance 37 having a large electric resistance is placed between the substance 36 and the electrode 36. When the battery temperature reaches the melting point of the substance 37 having a large electric resistance, the substance 37 having a large electric resistance melts, the substance 35 having a small electric resistance contacts the stopper 36, and the positive electrode battery container 1 and the negative electrode battery container 2 are connected. Can be short circuited.
【００２３】（実施例１１）図１５は、シールリーク防
止剤９とバネ機構とを組み合わせたものである。シール
リーク防止剤９によって、電気絶縁シール部６に破損部
が生じた場合、電気絶縁シール部６の破損部を閉塞でき
る。また、バネ３０によって、電池温度の異常な上昇に
より正極電池容器１と負極電池容器２とを短絡できる。(Embodiment 11) FIG. 15 shows a combination of a seal leak preventive agent 9 and a spring mechanism. The seal leak preventive agent 9 can block the damaged portion of the electric insulating seal portion 6 when the damaged portion occurs in the electric insulating seal portion 6. Further, the spring 30 can short-circuit the positive electrode battery container 1 and the negative electrode battery container 2 due to an abnormal increase in battery temperature.
【００２４】（実施例１２）図１６は、シールリーク防
止剤９と一方向性形状記憶合金３２とを組み合わせたも
のである。シールリーク防止剤９によって、電気絶縁シ
ール部６に破損部が生じた場合、電気絶縁シール部６の
破損部を閉塞できる。また、一方向性形状記憶合金３２
によって、電池温度の異常な上昇により正極電池容器１
と負極電池容器２とを短絡できる。(Embodiment 12) FIG. 16 shows a combination of the seal leak preventive agent 9 and the unidirectional shape memory alloy 32. The seal leak preventive agent 9 can block the damaged portion of the electric insulating seal portion 6 when the damaged portion occurs in the electric insulating seal portion 6. In addition, the unidirectional shape memory alloy 32
Due to an abnormal rise in battery temperature, the positive electrode battery container 1
And the negative electrode battery container 2 can be short-circuited.
【００２５】（実施例１３）図１７は、シールリーク防
止剤９と二方向性形状記憶合金３３とを組み合わせたも
のである。シールリーク防止剤９によって、電気絶縁シ
ール部６に破損部が生じた場合、電気絶縁シール部６の
破損部を閉塞できる。また、二方向性形状記憶合金３３
によって、電池温度の異常な上昇により正極電池容器１
と負極電池容器２とを短絡できる。(Embodiment 13) FIG. 17 shows a combination of the seal leak preventive agent 9 and the bidirectional shape memory alloy 33. The seal leak preventive agent 9 can block the damaged portion of the electric insulating seal portion 6 when the damaged portion occurs in the electric insulating seal portion 6. In addition, the bidirectional shape memory alloy 33
Due to an abnormal rise in battery temperature, the positive electrode battery container 1
And the negative electrode battery container 2 can be short-circuited.
【００２６】（実施例１４）図１８は、実施例９にシー
ルリーク防止剤９を組み合わせたものである。シールリ
ーク防止剤９によって、電気絶縁シール部６に破損部が
生じた場合、電気絶縁シール部６の破損部を閉塞でき
る。また、電気抵抗の大きな物質３７の融点に達する
と、電気抵抗の大きな物質３７が融解し、電気抵抗の小
さな物質３５とストッパー３６とが接触し、正極電池容
器１と負極電池容器２とを短絡できる。(Embodiment 14) FIG. 18 shows a combination of Embodiment 9 with a seal leak preventive agent 9. The seal leak preventive agent 9 can block the damaged portion of the electric insulating seal portion 6 when the damaged portion occurs in the electric insulating seal portion 6. When the melting point of the substance 37 having a large electric resistance is reached, the substance 37 having a large electric resistance is melted, the substance 35 having a small electric resistance contacts the stopper 36, and the positive electrode battery container 1 and the negative electrode battery container 2 are short-circuited. it can.
【００２７】（実施例１５）図１９は、電気絶縁シール
部の破損または電池の異常温度により作動する短絡機構
を有している。電池モジュール１７は、単電池１６を直
列に接続して構成したＮａ／Ｓ電池システムである。電
池２２は、電気絶縁シール部の破損または電池温度が異
常に上昇し、短絡機構が作動した電池である。電気絶縁
シール部の破損または電池温度が異常に上昇しても短絡
機構が作動し、モジュール内の他の電池システムは運転
を継続できる。(Embodiment 15) FIG. 19 has a short circuit mechanism which operates due to breakage of the electrically insulating seal portion or abnormal temperature of the battery. The battery module 17 is a Na / S battery system configured by connecting the unit cells 16 in series. The battery 22 is a battery in which the short circuit mechanism is activated due to damage to the electrically insulating seal portion or abnormal increase in battery temperature. Even if the electric insulation seal part is damaged or the battery temperature rises abnormally, the short-circuit mechanism operates and the other battery systems in the module can continue to operate.
【００２８】[0028]
【発明の効果】本発明によれば、Ｎａ／Ｓ電池の電気絶
縁シール部が破損部が生じても、電池内の電池活物質な
らびにカバーガスの電池外への流出または外気の電池内
への流入を防止し、電池の安全性を高めることができ
る。また、Ｎａ／Ｓ電池の電気絶縁シール部が破損部が
生じたり、電池の温度が異常に上昇した場合、電池内の
電池活物質ならびにカバーガスの電池外への流出または
外気の電池内への流入を防止し、電池ならびにモジュー
ルの運転を継続できる。According to the present invention, even if the electrically insulating seal portion of the Na / S battery is damaged, the battery active material in the battery and the cover gas flow out of the battery or the outside air flows into the battery. Inflow can be prevented and battery safety can be improved. In addition, when the electrically insulating seal part of the Na / S battery is damaged or the temperature of the battery rises abnormally, the battery active material in the battery and the cover gas flow out of the battery or the outside air enters the battery. Inflow can be prevented and operation of batteries and modules can be continued.
【図１】本発明の一実施例を示すＮａ／Ｓ電池の縦断面
図。FIG. 1 is a vertical sectional view of a Na / S battery showing an embodiment of the present invention.
【図２】本発明の一実施例を示す電気絶縁シール部付近
の拡大図。FIG. 2 is an enlarged view of the vicinity of an electrically insulating seal portion showing an embodiment of the present invention.
【図３】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 3 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図４】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 4 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図５】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 5 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図６】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 6 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図７】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 7 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery according to another embodiment of the present invention.
【図８】本発明の他の実施例を示すＮａ／Ｓ電池の電気
絶縁シール部付近の縦断面図。FIG. 8 is a vertical cross-sectional view of the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図９】本発明の他の実施例である、一方向性形状記憶
合金の変形後を示すＮａ／Ｓ電池の電気絶縁シール部付
近の縦断面図。FIG. 9 is a vertical cross-sectional view of the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention after deformation of a unidirectional shape memory alloy.
【図１０】本発明の他の実施例を示すＮａ／Ｓ電池の電
気絶縁シール部付近の縦断面図。FIG. 10 is a vertical cross-sectional view of the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図１１】本発明の他の実施例を示すＮａ／Ｓ電池の二
方向性形状記憶合金の変形後を示す、電気絶縁シール部
付近の縦断面図。FIG. 11 is a vertical cross-sectional view of the vicinity of an electrically insulating seal portion, showing a modified Na / S battery bidirectional shape memory alloy according to another embodiment of the present invention.
【図１２】本発明の他の実施例を示すＮａ／Ｓ電池の電
気絶縁シール部付近の縦断面図。FIG. 12 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery showing another embodiment of the present invention.
【図１３】本発明の他の実施例である、二方向性形状記
憶合金の変形後を示す、Ｎａ／Ｓ電池の電気絶縁シール
部付近の縦断面図。FIG. 13 is a vertical cross-sectional view of the vicinity of an electrically insulating seal portion of a Na / S battery, which shows another embodiment of the present invention after deformation of a bidirectional shape memory alloy.
【図１４】本発明の他の実施例を示す、Ｎａ／Ｓ電池の
電気絶縁シール部付近の縦断面図。FIG. 14 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery, showing another embodiment of the present invention.
【図１５】本発明の他の実施例を示す、Ｎａ／Ｓ電池の
電気絶縁シール部付近の縦断面図。FIG. 15 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery, showing another embodiment of the present invention.
【図１６】本発明の他の実施例を示す、Ｎａ／Ｓ電池の
電気絶縁シール部付近の縦断面図。FIG. 16 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery, showing another embodiment of the present invention.
【図１７】本発明の他の実施例を示す、Ｎａ／Ｓ電池の
電気絶縁シール部付近の縦断面図。FIG. 17 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery, showing another embodiment of the present invention.
【図１８】本発明の他の実施例を示す、Ｎａ／Ｓ電池の
電気絶縁シール部付近の縦断面図。FIG. 18 is a vertical cross-sectional view showing the vicinity of an electrically insulating seal portion of a Na / S battery, showing another embodiment of the present invention.
【図１９】本発明の他の実施例を示す、Ｎａ／Ｓ電池シ
ステム。FIG. 19 is a Na / S battery system showing another embodiment of the present invention.
１…正極電池容器、２…負極電池容器、３…負極活物質
（Ｎａ）、４…正極活物質、５…固体電解質管、６…電
気絶縁シール部、７…セラミックス、８…補助導電材
（グラファイトフェルト）、９…シールリーク防止剤、
１４…シールリーク防止板、１５…固定溝、１６…単電
池、１７…電池モジュール、１８…カバーガス、２０…
熱膨張の逃げのための空間、２１…シールリーク防止板
押さえ、２２…電気絶縁シール部が破損した電池、３０
…バネ、３１…電気抵抗の大きな物質、３２…一方向性
形状記憶合金、３３…二方向性形状記憶合金、３４…ス
トッパー、３５…電気抵抗の小さな物質、４０…粒体。DESCRIPTION OF SYMBOLS 1 ... Positive electrode battery container, 2 ... Negative electrode battery container, 3 ... Negative electrode active material (Na), 4 ... Positive electrode active material, 5 ... Solid electrolyte tube, 6 ... Electrical insulation sealing part, 7 ... Ceramics, 8 ... Auxiliary conductive material ( Graphite felt), 9 ... Seal leak preventive agent,
14 ... Seal leak prevention plate, 15 ... Fixing groove, 16 ... Single cell, 17 ... Battery module, 18 ... Cover gas, 20 ...
Space for escape of thermal expansion, 21 ... Seal leak prevention plate retainer, 22 ... Battery with electrically insulating seal part damaged, 30
... Spring, 31 ... Substance with high electric resistance, 32 ... Unidirectional shape memory alloy, 33 ... Bidirectional shape memory alloy, 34 ... Stopper, 35 ... Substance with low electric resistance, 40 ... Granules.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 床井 博見 茨城県日立市大みか町七丁目２番１号 株式会社 日立製作所 エネルギー研究 所内 (72)発明者 宇佐美 三郎 神奈川県横浜市戸塚区吉田町292番地 株式会社 日立製作所 試作開発センタ 内 (72)発明者 佐藤 善美 茨城県土浦市神立町502番地 株式会社 日立製作所 機械研究所内 (56)参考文献 特開 平２−165574（ＪＰ，Ａ) 特開 平４−292868（ＪＰ，Ａ) 特開 平４−298970（ＪＰ，Ａ) 特開 平４−298971（ＪＰ，Ａ) 特開 昭61−54166（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/39 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiromi Tokoi, 7-2-1, Omika-cho, Hitachi-shi, Ibaraki, Hitachi, Ltd. Inside the Energy Research Laboratory, Hitachi, Ltd. (72) Saburo Usami, 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Address: Hitachi Ltd., Prototype Development Center (72) Inventor: Yoshimi Sato, 502, Jinmachi, Tsuchiura City, Ibaraki Prefecture, Hitachi Ltd., Mechanical Research Laboratory (56) Reference JP-A-2-165574 (JP, A) JP Patent 4-292868 (JP, A) JP 4-298970 (JP, A) JP 4-298971 (JP, A) JP 61-54166 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 10/39
Claims (7)
活物質，硫黄（Ｓ）を必須成分とする正極活物質、前記
負極活物質と正極活物質間に介在し、Ｎａイオウが通過
可能な固体電解質を主たる構成要素とするＮａ／Ｓ電池
であって、正極及び負極間の電気絶縁材からなる電気絶
縁シール部を経て、電池内の電池活物質ならびにカバー
ガスの電池外への流出または外気の電池内への流入を防
止する手段に、負極活物質または正極活物質と反応し、
安定な反応生成物を生じる物質を用いることを特徴とし
たＮａ／Ｓ電池。1. A negative electrode active material containing sodium (Na) as an essential component, a positive electrode active material containing sulfur (S) as an essential component, and an intercalation between the negative electrode active material and the positive electrode active material to allow passage of Na sulfur. A Na / S battery having a solid electrolyte as a main constituent element, which flows out of a battery active material in the battery and a cover gas to the outside of the battery or outside air through an electrically insulating seal part made of an electrically insulating material between a positive electrode and a negative electrode. To react with the negative electrode active material or the positive electrode active material,
A Na / S battery characterized by using a substance that produces a stable reaction product.
活物質，硫黄（Ｓ）を必須成分とする正極活物質、前記
負極活物質と正極活物質間に介在し、Ｎａイオウが通過
可能な固体電解質を主たる構成要素とするＮａ／Ｓ電池
であって、正極及び負極間の電気絶縁材からなる電気絶
縁シール部を経て、電池内の電池活物質ならびにカバー
ガスの電池外への流出または外気の電池内への流入を防
止し、かつ電池の運転を継続できる手段に、負極活物質
または正極活物質と反応し、安定な反応生成物を生じる
物質を用いることを特徴としたＮａ／Ｓ電池。2. A negative electrode active material containing sodium (Na) as an essential component, a positive electrode active material containing sulfur (S) as an essential component, and a negative electrode active material interposing between the negative electrode active material and the positive electrode active material to allow passage of Na sulfur. A Na / S battery having a solid electrolyte as a main constituent element, which flows out of a battery active material in the battery and a cover gas to the outside of the battery or outside air through an electrically insulating seal part made of an electrically insulating material between a positive electrode and a negative electrode. Na / S battery characterized by using a substance which reacts with a negative electrode active material or a positive electrode active material and produces a stable reaction product, as a means for preventing the inflow into the battery and continuing the operation of the battery .
活物質，硫黄（Ｓ）を必須成分とする正極活物質、前記
負極活物質と正極活物質間に介在し、Ｎａイオウが通過
可能な固体電解質を主たる構成要素とするＮａ／Ｓ電池
であって、正極及び負極間の電気絶縁材からなる電気絶
縁シール部を経て、電池内の電池活物質ならびにカバー
ガスの電池外への流出または外気の電池内への流入を防
止し、かつ電池の正極と負極を短絡する手段に、負極活
物質または正極活物質と反応し、安定な反応生成物を生
じる物質を用いることを特徴としたＮａ／Ｓ電池。3. A negative electrode active material containing sodium (Na) as an essential component, a positive electrode active material containing sulfur (S) as an essential component, and a negative electrode active material interposed between the negative electrode active material and the positive electrode active material so that Na sulfur can pass through. A Na / S battery having a solid electrolyte as a main constituent element, which flows out of a battery active material in the battery and a cover gas to the outside of the battery or outside air through an electrically insulating seal part made of an electrically insulating material between a positive electrode and a negative electrode. To prevent the inflow of the battery into the battery and to short-circuit the battery's positive and negative electrodes.
Reacts with the substance or the positive electrode active material to produce a stable reaction product.
A Na / S battery characterized by using a substance that melts .
し、安定な反応生成物を生じる物質として、メタバナジ
ン酸ナトリウム（ＮａＶＯ3）やシリカ（ＳｉＯ2）と炭
酸カルシウム（ＣａＣＯ3），炭酸鉄（ＦｅＣＯ3）とを
混合したものを用いることを特徴とした請求項１，２又
は３記載のＮａ／Ｓ電池。4. As a substance which reacts with the negative electrode active material or the positive electrode active material to produce a stable reaction product, sodium metavanadate (NaVO 3 ) or silica (SiO 2 ) and calcium carbonate (CaCO 3 ) or iron carbonate. The Na / S battery according to claim 1, wherein a mixture of (FeCO 3 ) is used.
し、安定な反応生成物を生じる物質として、金属塩化物
または金属ヨウ化物または金属臭化物または金属フッ化
物を用いることを特徴とした請求項１，２又は３記載の
Ｎａ／Ｓ電池。5. A reacts with the negative electrode active material or cathode active material, a stable reaction product as a substance causing claim which is characterized by using a metal salt compound or a metal iodide or metal bromide or metal fluoride The Na / S battery according to 1, 2, or 3.
し、安定な反応生成物を生じる物質として、固体または
液体または固体と液体を用いることを特徴とした請求項
１，２又は３記載のＮａ／Ｓ電池。6. A solid or a liquid or a solid and a liquid are used as a substance which reacts with the negative electrode active material or the positive electrode active material to produce a stable reaction product. Na / S battery.
活物質、硫黄（Ｓ）を必須成分とする正極活物質、前記
負極活物質と正極活物質間に介在し、Ｎａイオウが通過
可能な固体電解質を主たる構成要素とするＮａ／Ｓ電池
であって、正極及び負極間の電気絶縁材からなる電気絶
縁シール部を経て、電池内の電池活物質ならびにカバー
ガスの電池外への流出または外気の電池内への流入を防
止し、かつ電池の正極と負極とを短絡する手段に、負極
活物質または正極活物質と反応し、安定な反応生成物を
生じる物質を用い、他の電池システムを正常に維持でき
ることを特徴としたＮａ／Ｓ電池システム。7. A negative electrode active material containing sodium (Na) as an essential component, a positive electrode active material containing sulfur (S) as an essential component, and being interposed between the negative electrode active material and the positive electrode active material, Na sulfur can pass through. A Na / S battery having a solid electrolyte as a main component, which flows out of a battery active material in the battery and a cover gas to the outside of the battery or outside air through an electrically insulating seal part made of an electrically insulating material between a positive electrode and a negative electrode. In order to prevent the inflow into the battery and to short-circuit the positive electrode and the negative electrode of the battery, a substance that reacts with the negative electrode active material or the positive electrode active material to produce a stable reaction product is used, and other battery systems can be used. A Na / S battery system that can be maintained normally.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02011694A JP3458438B2 (en) | 1994-02-17 | 1994-02-17 | Na / S battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02011694A JP3458438B2 (en) | 1994-02-17 | 1994-02-17 | Na / S battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07230822A JPH07230822A (en) | 1995-08-29 |
| JP3458438B2 true JP3458438B2 (en) | 2003-10-20 |
Family
ID=12018160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02011694A Expired - Fee Related JP3458438B2 (en) | 1994-02-17 | 1994-02-17 | Na / S battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3458438B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5712928B2 (en) | 2010-04-06 | 2015-05-07 | 住友電気工業株式会社 | Separator manufacturing method, molten salt battery manufacturing method, separator, and molten salt battery |
| KR20130083837A (en) * | 2010-05-24 | 2013-07-23 | 스미토모덴키고교가부시키가이샤 | Molten salt battery |
| EP2860788A1 (en) * | 2013-10-14 | 2015-04-15 | Siemens Aktiengesellschaft | Electrochemical energy storage device with conducting section for overload protection |
-
1994
- 1994-02-17 JP JP02011694A patent/JP3458438B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07230822A (en) | 1995-08-29 |
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