JPH0122711B2 - - Google Patents
Info
- Publication number
- JPH0122711B2 JPH0122711B2 JP54106858A JP10685879A JPH0122711B2 JP H0122711 B2 JPH0122711 B2 JP H0122711B2 JP 54106858 A JP54106858 A JP 54106858A JP 10685879 A JP10685879 A JP 10685879A JP H0122711 B2 JPH0122711 B2 JP H0122711B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- iron
- battery
- plaque
- weight
- 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
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000011149 active material Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- -1 chromium and sulfur Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Description
本発明はアルカリ蓄電池、特にニツケルカドミ
ウム電池の製法に関するもので、高性能で安価な
ニツケルカドミウム電池を提供することを目的と
する。
従来ニツケルカドミウム電池の製造法として
は、大別して焼結式、ペースト式、ポケツト式の
３方式に分かれる。焼結式の場合、活物質の保持
及び集電体の役目をなす導電芯体（以下プラーク
と云う）はニツケルの薄板又はニツケルメツキを
施こした鉄の薄板等にカルボニルニツケル粉を焼
結し、多孔度80〜85％前後のプラークを作成し、
当該プラークに活物質を含浸させて極板を作り、
電池を製造する。又ペースト式極板の場合は、プ
ラークとしてエクスパンデツトメタル、平担な穿
孔鋼板、導電物質からなる織られたスクリーン又
はメツシユ等に活物質を塗布し、極板を作り、電
池を製造する。ポケツト式極板の場合はニツケル
穿孔ポケツト部に活物質を充填し、極板を作り、
電池を製造する。
以上従来公知のこれらの３方式は、それぞれ一
長一短があるが、３方式に共通の最大の欠点はプ
ラークとしてニツケル材料を多量に使用するため
コスト高になる事である。このコスト高のためニ
ツケルカドミウム電池は高性能であるにも拘ら
ず、蓄電池需要の主力を占める鉛電池等に比較
し、使用される用途が限定され、市場の拡大が制
限されてきた。
本発明はこの点に鑑み、従来ニツケルカドミウ
ム電池の製造法を根本的に改良し、新規で安価な
高性能ニツケルカドミウム電池を提供することに
依り、ニツケルカドミウム電池の用途を拡大せん
とするものである。そのため本発明者は、ニツケ
ルカドミウム蓄電池の極板の活物質の保持、導電
性及び機械的強度のすぐれた低コスト型の鉄プラ
ークについて検討した。
ニツケルカドミウム蓄電池のプラークとして鉄
材質を使用することは、ニツケルと比較し価格の
点で数分の１から10数分の１と有利であるので、
従来種々研究されてきたが、○イ鉄材質に依る繊維
径の細い長繊維で品質精度の良い均一な繊維径の
鉄繊維が適正な価格で大量に製造出来なかつたこ
と、○ロ鉄繊維は非常に錆び易く、製造工程中に錆
びが発生し、工程管理が非常に困難であつたこと
等、の主たる理由に依り末だ実用化に致つていな
かつた。
本発明は前記の問題を解決し、低価格で高性能
なプラークを用いたニツケルカドミウム電池を提
供するものであり、以下その１実施例について詳
述する。
化学成分組成として鉄99.0重量％、ニツケル
0.5重量％、マンガン0.25重量％、炭素0.25重量％
よりなる鉄鋼から切削に依り繊維長さ0.5〜50mm、
繊維径４〜30μφの鉄繊維を切り出す。この鉄繊
維は切削加工特有の形状をしており、厚み約4μ、
巾５〜30μの偏平なもので、繊維長さは使用する
鉄素材によつて変化するが、繊維径の50倍以上の
長さがあれば、充分強度大なる焼結体を得ること
が出来る。この鉄繊維をH2雰囲気中で900℃の温
度で30分間焼結し、多孔度95％の鉄焼結体を作成
する。次いで当該鉄焼結体を電気メツキに依り約
5μのニツケルメツキを行い（ニツケルメツキ処
理後の導電芯体の多孔度は91％）、その後化学含
浸法、ペースト法、電析法等に依り、活物質とし
てNi（OH）2，Cd（OH）2，CdO，Cd等を充填す
る。
このようにして得た極板を使用してニツケルカ
ドミウム蓄電池を作成し、常温５時間率で７時間
の充電と１時間率相当の定抵抗で１時間の放電を
行い、サイクル寿命試験を実施した。そして50∞
毎に10時間率で15時間充電し、５時間率で1.0V
迄放電した時の容量をチエツクした。第１図に各
電池の初期容量、第２図に寿命サイクルテストの
結果を示す。図中は本実施例で得た極板、は
従来のカーボニルニツケル焼結式極板を用いた電
池の特性を示す。第１図から初期容量は本発明に
依る極板を用いた電池が他の従来方式の極板を用
いた電池よりも、放電容量に於て約30〜40％程上
昇している事が分る。放電容量は電極活物質量、
利用率、電池内部構造、電池寸法、電池構造等に
よつて異なるが、中でも電極に充填される活物質
量が最も大きな要因である。
この点本発明に依る鉄プラークに依る場合、プ
ラークの多孔度が90〜95％（ニツケルメツキ処理
後の導電芯体の多孔度は86〜91％）という高多孔
度が達成されるため従来のニツケル焼結式プラー
クの多孔度約80％に比べ約６％増加しているの
で、プラークの細孔空間はその分多く存在する。
従つてその分だけ活物質量を多く充填出来るよう
になつた。又第２図から長期の寿命サイクルに渡
つての容量維持率は、本発明に依る電池も、従来
の電池もほゞ同じであることから、この初期の容
量差を電池の寿命期間を通じて維持する事も判明
した。
この２つの実験事実により、本発明の電池は従
来のニツケルカドミウム電池の容量を約30〜40％
増加させ、かつプラーク材質を高価なニツケルか
ら安価な鉄に置換えた事に依り、経済的にも非常
に利点を有する。
以上のように本発明に依る鉄繊維をプラークと
する極板を用いた電池が、低価格で高性能を達成
出来た第１の理由は、切削鉄繊維の素材を鉄
99.74〜88.80重量％、ニツケル0.20〜10.00重量
％、マンガン0.01〜1.00重量％、炭素0.01〜0.50
重量％に規制する事に依り、切削加工し易い硬度
に調整し得たため、鉄の被削性が向上し、そのた
め高速機械加工性が良くなり、長さ１mmから10mm
以上、繊維径４〜30μφと云う細くて長い鉄繊維
が品質良く、安価に大量に加工、生産出来るよう
になつたことである。従来はこのように繊維径の
均一な細い鉄の繊維を切削に依り生産する事は困
難であつたため、引き伸し方法等に依つて作成さ
れており、能率が悪かつた。尚、各成分組成の範
囲は第１表〜第４表の範囲内である。
The present invention relates to a method for manufacturing an alkaline storage battery, particularly a nickel-cadmium battery, and an object of the present invention is to provide a high-performance, inexpensive nickel-cadmium battery. Conventional methods for manufacturing nickel-cadmium batteries can be roughly divided into three methods: sintering method, paste method, and pocket method. In the case of the sintering type, the conductive core (hereinafter referred to as the plaque) that holds the active material and acts as a current collector is made by sintering carbonyl nickel powder on a thin nickel plate or a thin plate of iron plated with nickel. Create a plaque with a porosity of around 80-85%,
The plaque is impregnated with an active material to make an electrode plate,
Manufacture batteries. In the case of a paste-type electrode plate, the active material is applied to an expanded metal plate, a flat perforated steel plate, a woven screen or mesh made of a conductive material, etc. as a plaque, the electrode plate is made, and a battery is manufactured. In the case of a pocket-type electrode plate, the perforated nickel pocket is filled with active material, the electrode plate is made,
Manufacture batteries. These three conventionally known methods each have their own merits and demerits, but the biggest drawback common to all three methods is that they use a large amount of nickel material as the plaque, resulting in high costs. Due to this high cost, despite the high performance of nickel cadmium batteries, the applications in which they can be used have been limited and the expansion of the market has been restricted compared to lead batteries, etc., which account for the main demand for storage batteries. In view of this point, the present invention aims to expand the uses of nickel cadmium batteries by fundamentally improving the conventional manufacturing method of nickel cadmium batteries and providing a new, inexpensive, high-performance nickel cadmium battery. be. Therefore, the present inventor investigated a low-cost iron plaque that has excellent retention of the active material of the electrode plate of a nickel-cadmium storage battery, excellent conductivity, and mechanical strength. Using iron material as the plaque for nickel cadmium storage batteries is advantageous in terms of price, ranging from a fraction to a tenth of that of nickel.
Although various studies have been conducted in the past, it has been found that (a) Iron fibers with long fibers with a narrow fiber diameter and a uniform fiber diameter of good quality cannot be produced in large quantities at a reasonable price due to the iron material, and (b) Iron fibers are It has never been put into practical use due to the following main reasons: it rusts very easily, rust occurs during the manufacturing process, and process control is extremely difficult. The present invention solves the above problems and provides a low-cost, high-performance nickel cadmium battery using a plaque.One embodiment of the present invention will be described in detail below. Chemical composition: 99.0% iron by weight, nickel
0.5% by weight, 0.25% by weight of manganese, 0.25% by weight of carbon
Fiber length 0.5-50mm, depending on cutting from steel made of
Cut out iron fibers with a fiber diameter of 4 to 30μφ. This iron fiber has a shape unique to cutting processing, and has a thickness of approximately 4 μm.
It is a flat material with a width of 5 to 30μ, and the fiber length varies depending on the iron material used, but if the length is at least 50 times the fiber diameter, a sufficiently strong sintered body can be obtained. . This iron fiber is sintered at a temperature of 900°C for 30 minutes in an H2 atmosphere to create an iron sintered body with a porosity of 95%. Next, the iron sintered body is electroplated.
Nickel plating with a thickness of 5μ is performed (the porosity of the conductive core after nickel plating is 91%), and then Ni(OH) 2 and Cd(OH) 2 are added as active materials by chemical impregnation, paste, electrodeposition, etc. , CdO, Cd, etc. A nickel cadmium storage battery was created using the electrode plates thus obtained, and a cycle life test was conducted by charging for 7 hours at a 5-hour rate at room temperature and discharging for 1 hour at a constant resistance equivalent to a 1-hour rate. . and 50∞
Charge at 10 hour rate for 15 hours every time, 1.0V at 5 hour rate
I checked the capacity when it was fully discharged. Figure 1 shows the initial capacity of each battery, and Figure 2 shows the results of the life cycle test. In the figure, the electrode plate obtained in this example shows the characteristics of a battery using a conventional carbonyl nickel sintered electrode plate. From Figure 1, it can be seen that the initial capacity of the battery using the electrode plate according to the present invention is approximately 30 to 40% higher in discharge capacity than the battery using other conventional electrode plates. Ru. Discharge capacity is determined by the amount of electrode active material,
Although it varies depending on the utilization rate, battery internal structure, battery dimensions, battery structure, etc., the most important factor is the amount of active material filled in the electrode. In this regard, when using the iron plaque according to the present invention, the porosity of the plaque is as high as 90 to 95% (the porosity of the conductive core after nickel plating is 86 to 91%). The porosity of the sintered plaque is approximately 6% higher than the approximately 80% porosity of the sintered plaque, so the pore space of the plaque is correspondingly larger.
Therefore, it became possible to fill the active material in a correspondingly larger amount. Furthermore, as shown in Fig. 2, the capacity retention rate over a long-term life cycle is almost the same for both the battery according to the present invention and the conventional battery, so this initial capacity difference is maintained throughout the life of the battery. The matter has also become clear. Based on these two experimental facts, the battery of the present invention has a capacity of about 30 to 40% of the conventional nickel cadmium battery.
By increasing the number of plaques and replacing the expensive nickel with inexpensive iron as the plaque material, there are great economic advantages. As mentioned above, the first reason why the battery using the electrode plate with iron fiber plaque according to the present invention was able to achieve high performance at a low price is that the cut iron fiber material is made of iron.
99.74-88.80% by weight, Nickel 0.20-10.00% by weight, Manganese 0.01-1.00% by weight, Carbon 0.01-0.50
By regulating the weight percentage, we were able to adjust the hardness to a level that is easy to cut, improving the machinability of iron and improving high-speed machinability, making it possible to reduce the length from 1 mm to 10 mm.
As described above, it has become possible to process and produce thin and long iron fibers with a fiber diameter of 4 to 30 μφ with good quality and in large quantities at low cost. In the past, it was difficult to produce thin iron fibers with uniform fiber diameters by cutting, so they were produced by drawing methods, which were inefficient. In addition, the range of each component composition is within the range of Tables 1 to 4.
【表】【table】
【表】【table】
【表】【table】
【表】
第２の理由は高多孔度90〜95％と云う鉄の焼結
体の表面から内部に渡つて均一にニツケルメツキ
を施す事は非常に困難な技術であるが、鉄素材に
本発明の如くニツケルを0.20〜10.00重量％含ま
せておくと電気メツキに依るニツケルメツキの際
に、効果を発揮し、焼純処理を行わなくてもニツ
ケルメツキが表面から内部に渡つて均一にメツキ
が出来る事が分つた。このため工程中に於ける鉄
焼結体の発錆がなくなり、電池製造工程の合理化
が可能となり、コストダウンに寄与した。但し電
池の起電反応に対して悪影響を及ぼすクロム、イ
オウ等の金属はたとえ鉄材質として優れた特性を
有していてもプラーク合金として使用することは
望ましくない。
以上の如く本発明は、従来実用化が困難とされ
ていた鉄プラークを用いたニツケルカドミウム電
池を経済的に実用化した点は工業的価値よりみて
きわめて効果が大きい。又この本発明の極板はニ
ツケル―鉄電池、ニツケル―亜鉛電池等のアルカ
リ電池に広く適用出来るものである。[Table] The second reason is that it is a very difficult technique to apply nickel plating uniformly from the surface to the inside of a sintered iron body with a high porosity of 90 to 95%. If 0.20 to 10.00% by weight of nickel is included as shown in the figure, it will be effective during nickel plating using electric plating, and the nickel plating can be uniformly plated from the surface to the inside without sintering. I understood. This eliminates rusting of the iron sintered body during the process, making it possible to rationalize the battery manufacturing process and contributing to cost reduction. However, metals such as chromium and sulfur, which have an adverse effect on the electromotive reaction of the battery, are not desirable to be used as a plaque alloy even if they have excellent properties as iron materials. As described above, the present invention is extremely effective in terms of industrial value in that it has economically put into practical use a nickel cadmium battery using an iron plaque, which had been considered difficult to put into practical use. Further, the electrode plate of the present invention can be widely applied to alkaline batteries such as nickel-iron batteries and nickel-zinc batteries.
第１図は本発明に依る極板及び従来方式の極板
を用いた電池の初期容量特性図第２図はその各電
池の充放電サイクルに伴う容量推移の比較特性図
である。
…本発明による電池、…従来電池。
FIG. 1 is an initial capacity characteristic diagram of a battery using the electrode plate according to the present invention and a conventional type electrode plate. FIG. 2 is a comparative characteristic diagram of the capacity change of each battery as the batteries are charged and discharged. ...battery according to the present invention, ...conventional battery.
Claims (1)
ニツケル0.20〜10.00重量％、マンガン0.01〜1.00
重量％、炭素0.01〜0.50重量％よりなる鉄鋼材料
を切削して繊維状削鋼を形成し、当該削鋼繊維を
焼結してなる導電芯体を用いることを特徴とする
蓄電池極板。1 Chemical composition: Iron 99.74-88.50% by weight,
Nickel 0.20-10.00% by weight, manganese 0.01-1.00
A storage battery electrode plate characterized by using a conductive core formed by cutting a steel material consisting of 0.01 to 0.50% by weight of carbon to form fibrous cut steel, and sintering the cut steel fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10685879A JPS5630266A (en) | 1979-08-21 | 1979-08-21 | Alkali storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10685879A JPS5630266A (en) | 1979-08-21 | 1979-08-21 | Alkali storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5630266A JPS5630266A (en) | 1981-03-26 |
| JPH0122711B2 true JPH0122711B2 (en) | 1989-04-27 |
Family
ID=14444271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10685879A Granted JPS5630266A (en) | 1979-08-21 | 1979-08-21 | Alkali storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5630266A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413608U (en) * | 1990-05-21 | 1992-02-04 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60240654A (en) * | 1984-05-07 | 1985-11-29 | 大和製罐株式会社 | Plastic cap mechanism with pill-proof function |
| JPS60177040U (en) * | 1984-05-07 | 1985-11-25 | 株式会社柴崎製作所 | Cap with small hole for cleaning bottle mouth |
| JPS61198562A (en) * | 1985-02-27 | 1986-09-02 | Hitachi Maxell Ltd | Electrode for alkaline secondary battery |
| JPS61208756A (en) * | 1985-03-12 | 1986-09-17 | Hitachi Maxell Ltd | Electrode for alkaline secondary battery |
| JPS62122957A (en) * | 1985-11-20 | 1987-06-04 | 日本クラウンコルク株式会社 | Cap having unjust use preventive function |
| JPH0417483Y2 (en) * | 1986-03-17 | 1992-04-20 | ||
| JPH0737254B2 (en) * | 1991-08-28 | 1995-04-26 | 株式会社柴崎製作所 | Bottle mouth cleaning method |
| JP2673078B2 (en) * | 1992-05-27 | 1997-11-05 | 東芝電池株式会社 | Paste type electrode for alkaline secondary battery |
| JPH0743000Y2 (en) * | 1992-07-08 | 1995-10-04 | 石塚硝子株式会社 | Bottle neck for pill fur proof cap |
| JP3386634B2 (en) * | 1995-07-31 | 2003-03-17 | 松下電器産業株式会社 | Alkaline storage battery |
-
1979
- 1979-08-21 JP JP10685879A patent/JPS5630266A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0413608U (en) * | 1990-05-21 | 1992-02-04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630266A (en) | 1981-03-26 |
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