JP2919163B2 - Anode container for sodium-sulfur battery - Google Patents
Anode container for sodium-sulfur batteryInfo
- Publication number
- JP2919163B2 JP2919163B2 JP4068849A JP6884992A JP2919163B2 JP 2919163 B2 JP2919163 B2 JP 2919163B2 JP 4068849 A JP4068849 A JP 4068849A JP 6884992 A JP6884992 A JP 6884992A JP 2919163 B2 JP2919163 B2 JP 2919163B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- anode
- coating
- film
- container
- 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 - Lifetime
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
Description
【０００１】[0001]
【産業上の利用分野】この発明は、電力貯蔵用などの二
次電池として利用されるナトリウム−硫黄電池の陽極容
器に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anode container for a sodium-sulfur battery used as a secondary battery for storing electric power.
【０００２】[0002]
【従来の技術】一般に、この種のナトリウム−硫黄電池
では、筒状の陽極容器内において固体電解質管の内側と
外側にそれぞれ陰極室と陽極室が形成され、その陰極室
内には陰極活物質としての金属ナトリウムが収容される
と共に、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、３００〜３５０℃に加熱された状態
で、陰極室のナトリウムと陽極室の硫黄とがイオン化さ
れ、そのイオン化されたナトリウムが固体電解質管を透
過して硫黄と反応し、多硫化ナトリウムが生成されると
共に、放電が行われるようになっている。2. Description of the Related Art Generally, in a sodium-sulfur battery of this type, a cathode chamber and an anode chamber are formed inside and outside a solid electrolyte tube in a cylindrical anode vessel, respectively. And sulfur as an anode active material is accommodated in the anode chamber. Then, while being heated to 300 to 350 ° C., sodium in the cathode chamber and sulfur in the anode chamber are ionized, and the ionized sodium permeates through the solid electrolyte tube and reacts with sulfur to produce sodium polysulfide. At the same time as discharging.
【０００３】この電池の放電時に生成される多硫化ナト
リウムは腐食性が大きいので、アルミニウム又はアルミ
ニウム合金よりなる陽極容器に多硫化ナトリウムが直接
接触すると、陽極容器が損傷を受けて耐久性が低下する
おそれがある。そのため、従来のナトリウム−硫黄電池
の陽極容器では、金属溶射により陽極容器の容器本体の
内周面に、ステライト合金等の耐腐食性材料よりなる皮
膜を全体に亘ってほぼ均一の厚さに形成していた。[0003] Since sodium polysulfide generated during discharge of this battery is highly corrosive, if sodium polysulfide directly contacts an anode container made of aluminum or an aluminum alloy, the anode container is damaged and its durability is reduced. There is a risk. Therefore, in a conventional anode container of a sodium-sulfur battery, a film made of a corrosion-resistant material such as a stellite alloy is formed on the inner peripheral surface of the container body of the anode container by metal spraying to have a substantially uniform thickness throughout. Was.
【０００４】[0004]
【発明が解決しようとする課題】ところが、この従来構
成の陽極容器においては、ステライト合金等よりなる皮
膜の厚さが約１００μｍもあったので、加熱、冷却によ
る膨張、収縮の繰り返しに伴う熱ひずみに起因して、皮
膜に大きな残留応力が発生し、皮膜にクラックが生じや
すいという問題があった。However, in this conventional anode container, the thickness of the coating made of a stellite alloy or the like was about 100 μm, so that the thermal strain caused by repeated expansion and contraction due to heating and cooling was reduced. As a result, there is a problem that a large residual stress is generated in the film and cracks are easily generated in the film.
【０００５】又、この従来構成のように皮膜の厚さが大
きいと、皮膜の形成時に大量の溶射用金属粉末を必要と
して、製作コストが高くなると共に、電池全体の重量も
大きくなり、さらには、電池内部からの熱放散が悪くな
って、安全性が低下するという問題もあった。When the thickness of the coating is large as in the conventional structure, a large amount of metal powder for thermal spraying is required at the time of forming the coating, so that the production cost is increased and the weight of the whole battery is increased. However, there is also a problem that heat dissipation from the inside of the battery is deteriorated and safety is reduced.
【０００６】この発明は、このような従来技術に存在す
る問題点に着目してなされたものであって、その目的と
するところは、皮膜に生じる残留応力を少なくして、皮
膜にクラックが生じるおそれを防止することができ、し
かも、皮膜の形成時に大量の溶射用金属粉末を必要とせ
ず、製作コストを低減することができると共に、電池全
体を軽量化することができ、さらには、電池内部からの
熱放散を良好にして、安全性を向上させることができる
ナトリウム−硫黄電池の陽極容器を提供することにあ
る。The present invention has been made in view of the problems existing in the prior art, and has as its object to reduce the residual stress generated in the film and to cause cracks in the film. In addition, it is possible to reduce the manufacturing cost and to reduce the weight of the battery as a whole. It is an object of the present invention to provide an anode container of a sodium-sulfur battery capable of improving heat dissipation from a fuel cell and improving safety.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めに、第１の発明では、筒状の容器本体の内周面に、金
属溶射により皮膜を形成してなるナトリウム−硫黄電池
の陽極容器において、前記皮膜の厚さの上限を６０μｍ
に設定するとともに、皮膜内の気孔率は５％以下とした
ものである。According to a first aspect of the present invention, there is provided an anode for a sodium-sulfur battery in which a coating is formed on the inner peripheral surface of a cylindrical container body by metal spraying. In the container, the upper limit of the thickness of the coating is 60 μm.
And the porosity in the film is set to 5% or less .
【０００８】又、第２の発明では、前記容器本体の外径
は、５０〜１２０ｍｍに設定され、さらに、第３の発明
では 、 粒径が１０〜６０μｍの金属粉末を金属溶射する
ものである。In the second invention, the outer diameter of the container body is
Is set to 50 to 120 mm, and the third invention
In is <br/> that the particle size is metal spraying metal powder of 10 to 60 [mu] m.
【０００９】[0009]
【作用】この発明の陽極容器では、容器本体の内周面に
形成される皮膜が薄膜となるように、その皮膜の厚さが
上限６０μｍに設定されるとともに、皮膜内の気孔率は
５％以下に設定されている。このため、電池作動時の加
熱、冷却による膨張、収縮の繰り返しに伴う熱ひずみに
起因して、皮膜に大きな残留応力が発生するのを抑制す
ることができ、皮膜にクラックが生じるおそれを防止す
ることができる。又、 皮膜の形成時に大量の溶射用金属
粉末を必要とせず、製作コストを低減することができる
と共に、電池全体を軽量化することができる。さらに
は、電池内部からの熱放散を良好にして、安全性を向上
させることができる。According to the anode container of the present invention, the thickness of the film is set to an upper limit of 60 μm so that the film formed on the inner peripheral surface of the container body becomes a thin film, and the porosity in the film is reduced.
It is set to 5% or less . For this reason, it is possible to suppress the occurrence of a large residual stress in the film due to the thermal strain caused by the repetition of expansion and contraction due to heating and cooling during the operation of the battery, and to prevent the possibility of cracks in the film. be able to. Further, a large amount of metal powder for thermal spraying is not required at the time of forming the coating, so that the manufacturing cost can be reduced and the weight of the whole battery can be reduced. Further, heat dissipation from the inside of the battery can be improved, and safety can be improved.
【００１０】[0010]
【実施例】以下、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、図面に基づいて説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of a sodium-sulfur battery embodying the present invention will be described below with reference to the drawings.
【００１１】図１に示すように、陽極容器１は円筒状の
容器本体２と、その下端部に溶接された円盤状の底蓋３
とにより有底円筒状に形成されている。そして、この陽
極容器１は軽量かつ安価であるアルミニウム又はアルミ
ニウム合金で形成されているが、鉄、ステンレス鋼、ク
ラッド鋼等であってもよい。容器本体２の内周面には皮
膜４が金属溶射により所定厚さで均一に形成されてい
る。なお、前記容器本体２の上部外周には陽極端子５が
取着されている。As shown in FIG. 1, an anode container 1 has a cylindrical container body 2 and a disk-shaped bottom cover 3 welded to its lower end.
This forms a bottomed cylindrical shape. The anode container 1 is formed of aluminum or aluminum alloy which is lightweight and inexpensive, but may be iron, stainless steel, clad steel or the like. A coating 4 is uniformly formed on the inner peripheral surface of the container body 2 with a predetermined thickness by metal spraying. An anode terminal 5 is attached to the outer periphery of the upper part of the container body 2.
【００１２】前記陽極容器１の上端部にはα−アルミナ
よりなる絶縁リング６が固着されている。この絶縁リン
グ６の下部内周面にはβ−アルミナよりなる有底円筒状
の固体電解質管７が上端外周にて接合固定されている。
この固体電解質管７の内側には陰極室８が区画形成さ
れ、外側には陽極室９が区画形成されている。前記陰極
室８内には陰極活物質としてのナトリウム（Ｎａ）が収
容され、陽極室９内には陽極活物質としての硫黄（Ｓ）
が収容されている。前記絶縁リング６上には陰極蓋１０
が取付けられ、その上面には陰極端子１１が突設されて
いる。An insulating ring 6 made of α-alumina is fixed to the upper end of the anode container 1. A cylindrical solid electrolyte tube 7 having a bottom and made of β-alumina is fixedly joined to the lower inner peripheral surface of the insulating ring 6 at the outer periphery at the upper end.
A cathode chamber 8 is defined inside the solid electrolyte tube 7, and an anode chamber 9 is defined outside. The cathode chamber 8 contains sodium (Na) as a cathode active material, and the anode chamber 9 contains sulfur (S) as an anode active material.
Is housed. On the insulating ring 6, a cathode lid 10 is provided.
The cathode terminal 11 protrudes from the upper surface.
【００１３】さて、この実施例においては、図２に示す
ように、前記陽極容器１の容器本体２の外径Ｌ１が５０
〜１２０ｍｍ、長さＬ２が３００〜５００ｍｍ、厚さＴ
が１．０〜２．５ｍｍに設定されている。又、皮膜４の
厚さｔは上限が６０μｍとなるように、２０〜６０μｍ
の範囲に設定され、好ましくは３０〜５０μｍの範囲で
設定されている。In this embodiment, as shown in FIG. 2, the outer diameter L1 of the container body 2 of the anode container 1 is 50
~ 120mm, length L2 is 300 ~ 500mm, thickness T
Is set to 1.0 to 2.5 mm. The thickness t of the coating 4 is 20 to 60 μm so that the upper limit is 60 μm.
, And preferably in the range of 30 to 50 μm.
【００１４】さらに、この皮膜４の材料としては、多硫
化ナトリウムや硫黄に対して耐食性の良好な合金である
ステライト、すなわちコバルト(Co)にクロム(Cr)及びタ
ングステン(W) を添加した合金が使用されている。な
お、この材料としては、ハステロイ、インコロイ、イン
コネル等のニッケル(Ni)基合金や鉄(Fe)基合金を使用し
てもよい。Further, as a material of the film 4, stellite which is an alloy having good corrosion resistance to sodium polysulfide and sulfur, that is, an alloy obtained by adding chromium (Cr) and tungsten (W) to cobalt (Co) is used. in use. As this material, a nickel (Ni) -based alloy such as Hastelloy, Incoloy, or Inconel or an iron (Fe) -based alloy may be used.
【００１５】そして、この皮膜４は金属溶射法により次
のようにして形成される。すなわち、図２に示すよう
に、溶射装置本体１２の下部にパイプ状の溶射ノズル１
３が延出され、その先端部には噴出口１４が開口されて
いる。そして、まず装置本体１２に前記の金属材料が粉
末状態で供給され、溶融状態にしてノズル１３の噴出口
１４から容器本体２の内面に吹き付けられて、皮膜４が
形成される。この場合、皮膜４の厚さｔは、溶射装置本
体１２の上下移動速度を加減したり、噴出口１４からの
金属粉末の噴出量を加減したりすることにより、任意に
調節設定することができる。The coating 4 is formed by a metal spraying method as follows. In other words, as shown in FIG.
3 is extended, and a spout 14 is opened at the tip. Then, first, the metal material is supplied to the apparatus main body 12 in a powdered state, is melted, and is sprayed from the ejection port 14 of the nozzle 13 onto the inner surface of the container main body 2 to form the coating 4. In this case, the thickness t of the coating 4 can be arbitrarily adjusted and set by adjusting the vertical movement speed of the thermal spraying apparatus main body 12 or adjusting the amount of the metal powder ejected from the ejection port 14. .
【００１６】又、前記溶射用金属粉末の粒径は１０〜６
０μｍの範囲がよく、２０〜４０μｍの範囲が最もよ
い。皮膜４内の気孔率は５％以下がよい。さらに、容器
本体２の内面粗度はＲａ（中心線平均粗さ、JIS B 060
1）：２〜１０μｍの範囲がよく、２〜５μｍの範囲が
最もよい。皮膜４の表面粗度はＲａ：４〜１２μｍの範
囲がよく、７μｍ以下が最もよい。The metal powder for thermal spraying has a particle size of 10-6.
The range of 0 μm is good, and the range of 20 to 40 μm is best. The porosity in the coating 4 is preferably 5% or less. Further, the inner surface roughness of the container body 2 is Ra (center line average roughness, JIS B 060
1): The range of 2 to 10 μm is good, and the range of 2 to 5 μm is best. The surface roughness of the film 4 is preferably Ra: 4 to 12 μm, and most preferably 7 μm or less.
【００１７】前記のようにこの実施例の陽極容器１で
は、容器本体２の内周面に形成される皮膜４が薄層とな
るように、その皮膜４の厚さが上限６０μｍ又は２０〜
６０μｍの範囲に設定されている。このため、電池作動
時の加熱、冷却による膨張、収縮の繰り返しに伴う熱ひ
ずみに起因して、皮膜４に大きな残留応力が発生するの
を抑制することができ、皮膜４にクラックが生じるおそ
れを防止することができる。As described above, in the anode container 1 of this embodiment, the thickness of the coating 4 is 60 μm or 20 to 20 μm so that the coating 4 formed on the inner peripheral surface of the container body 2 is a thin layer.
It is set in the range of 60 μm. For this reason, it is possible to suppress the occurrence of a large residual stress in the film 4 due to the thermal strain caused by the repetition of expansion and contraction due to heating and cooling during the operation of the battery. Can be prevented.
【００１８】又、前記のように金属溶射により容器本体
２の内周面に皮膜４を形成する際に、大量の溶射用金属
粉末を必要としないため、製作コストを低減することが
できる。さらに、皮膜４が薄層であるため、電池全体を
軽量化することができると共に、、電池内部からの熱放
散を良好にして、安全性を向上させることもできる。Further, as described above, when forming the coating 4 on the inner peripheral surface of the container body 2 by metal spraying, a large amount of metal powder for spraying is not required, so that the manufacturing cost can be reduced. Furthermore, since the film 4 is a thin layer, the weight of the whole battery can be reduced, and the heat dissipation from the inside of the battery can be improved to improve the safety.
【００１９】因みに、皮膜４の厚さｔを６０μｍ以下に
設定した場合と、６０μｍを越えた値に設定した場合と
について、溶射後の皮膜４の残留応力試験を行ったとこ
ろ、表１に示すような結果を得ることができた。Incidentally, when the thickness t of the coating 4 was set to 60 μm or less and when it was set to a value exceeding 60 μm, the residual stress test of the coating 4 after thermal spraying was performed. We were able to obtain such a result.
【００２０】すなわち、皮膜４の厚さｔを１２０μｍに
設定した従来例品Ａと、８０μｍに設定した従来例品Ｂ
と、６０μｍに設定した第１実施例品Ｃと、４０μｍに
設定した第２実施例品Ｄと、２０μｍに設定した第３実
施例品Ｅとを用意し、これらに微少Ｘ線を照射して、格
子定数の変化から図２に示す円周Ｘ方向と長さＹ方向の
残留応力を求めた。That is, the conventional product A in which the thickness t of the film 4 is set to 120 μm and the conventional product B in which the thickness t is set to 80 μm
, A first embodiment product C set to 60 μm, a second embodiment product D set to 40 μm, and a third embodiment product E set to 20 μm, and these are irradiated with micro X-rays. The residual stress in the circumferential X direction and the length Y direction shown in FIG. 2 was determined from the change in the lattice constant.
【００２１】[0021]
【表１】 [Table 1]
【００２２】又、前記のように異なった厚さの皮膜４を
形成した各陽極容器１について、皮膜４の耐久性試験を
行ったところ、図３のグラフに示すような結果を得るこ
とができた。すなわち、各陽極容器１内に多硫化ナトリ
ウムを入れた状態で、３５０℃まで８時間で昇温し、そ
の温度に２４時間保持し、室温まで８時間かけて降温す
るサイクルを繰り返し行い、降温後にＸ線透過法によっ
てクラックの数を測定した。Further, when a durability test of the coating 4 was performed on each anode container 1 on which the coatings 4 having different thicknesses were formed as described above, the results shown in the graph of FIG. 3 could be obtained. Was. That is, in a state in which sodium polysulfide is put in each anode container 1, a cycle of raising the temperature to 350 ° C. in 8 hours, maintaining the temperature for 24 hours, and lowering the temperature to room temperature in 8 hours is repeated. The number of cracks was measured by the X-ray transmission method.
【００２３】前記の表１に示すように、Ｘ方向の残留応
力が、従来例Ａ，Ｂでは４ Kg/mm2以上あったものが、
実施例Ｃ，Ｄ，Ｅでは１〜２ Kg/mm2 の範囲に抑えるこ
とができ、Ｙ方向の残留応力が、従来例Ａ，Ｂでは６ K
g/mm2 以上あったものが、実施例Ｃ，Ｄ，Ｅでは３〜４
Kg/mm2 の範囲に抑えることができた。又、図３に示す
ように、従来例Ａ，Ｂではサイクルを繰り返すごとにク
ラック数が増大して、特性曲線の角度が大きくなるのに
対し、実施例Ｃ，Ｄ，Ｅではサイクルを繰り返してもク
ラック数がさほど増加せず、特性曲線の角度が小さくな
った。これらのことから、皮膜４の残留応力、さらに皮
膜４のクラックの発生は、皮膜４の厚さについて６０μ
ｍを境に顕著に変化することがわかった。As shown in Table 1 above, the residual stress in the X direction was 4 kg / mm 2 or more in Conventional Examples A and B.
In Examples C, D and E, the residual stress in the Y direction can be suppressed to the range of 1-2 kg / mm 2 , and in the conventional examples A and B, the residual stress is 6 Kg / mm 2.
g / mm 2 or more, but 3 to 4 in Examples C, D and E
Kg / mm 2 range. Further, as shown in FIG. 3, in the conventional examples A and B, the number of cracks increases each time the cycle is repeated, and the angle of the characteristic curve increases, whereas in the examples C, D and E, the cycle is repeated. Also, the number of cracks did not increase so much, and the angle of the characteristic curve became small. From these facts, the residual stress of the coating 4 and the occurrence of cracks in the coating 4 were reduced by 60 μm with respect to the thickness of the coating 4.
It turned out that it changes remarkably at m.
【００２４】この発明は前記実施例の構成に限定される
ものではなく、例えば、皮膜４の厚さを前記所定の範囲
内で下部ほど厚くなるように構成したり、材料や表面粗
さを適宜に変更する等、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。The present invention is not limited to the configuration of the above-described embodiment. For example, the thickness of the coating 4 may be increased toward the lower part within the above-mentioned predetermined range, or the material and the surface roughness may be appropriately adjusted. It is also possible to arbitrarily change and embody the present invention without departing from the spirit of the present invention.
【００２５】[0025]
【発明の効果】以上詳述したようにこの発明によれば、
皮膜に生じる残留応力を少なくして、皮膜にクラックが
生じるおそれを防止することができ、しかも、皮膜の形
成時に大量の溶射用金属粉末を必要とせず、製作コスト
を低減することができると共に、電池全体を軽量化する
ことができ、さらには、電池内部からの熱放散を良好に
して、安全性を向上させることができるという優れた効
果を奏する。As described in detail above, according to the present invention,
By reducing the residual stress generated in the coating, it is possible to prevent the possibility of cracks in the coating, and, furthermore, it is not necessary to use a large amount of metal powder for thermal spraying at the time of forming the coating, thereby reducing the manufacturing cost, It is possible to reduce the weight of the whole battery, and furthermore, it is possible to improve heat dissipation from the inside of the battery, thereby improving safety.
【図１】この発明を具体化したナトリウム−硫黄電池の
一実施例を示す縦断面図である。FIG. 1 is a longitudinal sectional view showing one embodiment of a sodium-sulfur battery embodying the present invention.
【図２】陽極容器に皮膜を形成する状態を示す断面図で
ある。FIG. 2 is a sectional view showing a state in which a film is formed on an anode container.
【図３】加熱、冷却のサイクル数と皮膜内のクラック発
生数との関係を示すグラフである。FIG. 3 is a graph showing the relationship between the number of heating and cooling cycles and the number of cracks generated in a coating.
【符号の説明】 １…陽極容器、２…容器本体、４…皮膜。[Description of Signs] 1 ... Anode container, 2 ... Container body, 4 ... Coating.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 10/39 H01M 2/02 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) H01M 10/39 H01M 2/02
Claims (3)
より皮膜を形成してなるナトリウム−硫黄電池の陽極容
器において、 前記皮膜の厚さの上限を６０μｍに設定するとともに、
皮膜内の気孔率は５％以下としたことを特徴とするナト
リウム−硫黄電池の陽極容器。1. An anode container for a sodium-sulfur battery in which a film is formed on the inner peripheral surface of a cylindrical container body by metal spraying, wherein the upper limit of the thickness of the film is set to 60 μm .
An anode container for a sodium-sulfur battery , wherein the porosity in the film is 5% or less .
ｍに設定されている請求項１記載のナトリウム−硫黄電
池の陽極容器。 2. The outer diameter of the container body is 50 to 120 m.
2. The sodium-sulfur battery according to claim 1, wherein m is set to m.
Pond anode vessel.
射する請求項１又は請求項２記載のナトリウム−硫黄電
池の陽極容器。 3. A metal powder having a particle size of 10 to 60 μm is melted.
3. The sodium-sulfur battery according to claim 1 or 2,
Pond anode vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4068849A JP2919163B2 (en) | 1992-03-26 | 1992-03-26 | Anode container for sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4068849A JP2919163B2 (en) | 1992-03-26 | 1992-03-26 | Anode container for sodium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05275109A JPH05275109A (en) | 1993-10-22 |
| JP2919163B2 true JP2919163B2 (en) | 1999-07-12 |
Family
ID=13385541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4068849A Expired - Lifetime JP2919163B2 (en) | 1992-03-26 | 1992-03-26 | Anode container for sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2919163B2 (en) |
-
1992
- 1992-03-26 JP JP4068849A patent/JP2919163B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05275109A (en) | 1993-10-22 |
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