JPS59111249A - Small size alkaline battery - Google Patents
Small size alkaline batteryInfo
- Publication number
- JPS59111249A JPS59111249A JP57220696A JP22069682A JPS59111249A JP S59111249 A JPS59111249 A JP S59111249A JP 57220696 A JP57220696 A JP 57220696A JP 22069682 A JP22069682 A JP 22069682A JP S59111249 A JPS59111249 A JP S59111249A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- nickel layer
- internal surface
- circuit voltage
- stainless steel
- 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.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 210000004051 gastric juice Anatomy 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 229910001430 chromium ion Inorganic materials 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000002496 gastric effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000167880 Hirundinidae Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide 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
- H01M4/66—Selection of materials
- H01M4/669—Steels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/545—Terminals formed by the casing of the cells
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【発明の詳細な説明】
缶の耐腐食性を高めて幼児などがあや才って飲み込んだ
場合でも胃g!による電池破壊を防止できるようにする
とともに、電気性能の向上をはかることを目的とする。[Detailed Description of the Invention] The corrosion resistance of the can has been improved so that even if an infant or other child swallows it prematurely, it will not cause stomach g! The purpose is to prevent battery damage caused by battery damage and to improve electrical performance.
最近、ゲーム機、ゲームウォッチなどの子供向は電池応
用機器の普及に伴ない、幼児があやまって電池を飲み込
むという事故が多発している。Recently, as battery-powered devices such as game consoles and game watches for children have become popular, there have been many accidents in which young children accidentally swallow batteries.
そのため、本発明者らは正極缶にクロム含有量が23係
(重量幅、以下同様)以上の高クロムステンレス鋼を用
いることによって、正極缶の耐腐食性を高め、あやまっ
て飲み込んだ場合でも排泄までの間に胃液による破壊を
受けるおそれがない小型アルカIJ z池を提供し、そ
れについて別途特許出願をした。Therefore, the present inventors increased the corrosion resistance of the positive electrode can by using high chromium stainless steel with a chromium content of 23 or higher (weight range, the same applies hereinafter) for the positive electrode can, and even if it is accidentally swallowed, it will be excreted. In the meantime, we have provided a small Alka IJz pond that is not susceptible to destruction by gastric juices, and have filed a separate patent application for it.
ところか、上記のような高クロムステンレス鋼を正極缶
に用いた場合、高クロムステンレス鋼がアルカ’J 1
!解液中で正極活物質により容易に電解酸化され、6価
クロムイオン(Cr6+)カ溶出シ、この溶出した6価
クロムイオンが負極側へ移行して負極活物質の表面に皮
膜を生成して負祿活5物質を不働態化させ、閉路電圧の
低下など電気性能を低下させると^う問題がある。However, when high chromium stainless steel like the one mentioned above is used for the positive electrode can, the high chromium stainless steel
! It is easily electrolytically oxidized by the positive electrode active material in the solution, and hexavalent chromium ions (Cr6+) are eluted.The eluted hexavalent chromium ions migrate to the negative electrode side and form a film on the surface of the negative electrode active material. There is a problem in that it makes the five negative active substances passivated and reduces electrical performance such as a drop in closed circuit voltage.
本発明はそのような事情に鑑みてなされたものであり、
クロム含有量が23係以上の高クロムステンレス鋼から
なる正極缶の内面にニッケル層を設けることによって、
正極缶からの6価クロムイオンの溶出を防止し、6価ク
ロムイオンに基づく電気特性の低下を防止したものであ
る。The present invention was made in view of such circumstances,
By providing a nickel layer on the inner surface of the positive electrode can made of high chromium stainless steel with a chromium content of 23 or more,
This prevents the elution of hexavalent chromium ions from the positive electrode can and prevents the electrical characteristics from deteriorating due to hexavalent chromium ions.
本発明において、正極缶に用いるクロム含有量が23%
以上の高クロムステンレス鋼としては、例えげSUS
447 J 1、SUS 329 J 1、SUS 3
29 J 2.5US310Sなどがあげられる。In the present invention, the chromium content used in the positive electrode can is 23%.
Examples of the above high chromium stainless steel include SUS.
447 J 1, SUS 329 J 1, SUS 3
29 J 2.5US310S etc.
また、本発明において小型アルカリ電池とはアルカリ水
溶液を電解液とするボタン形電池、コイン形ないしは扁
平形電池および単4、単5より小さい筒形電池、さらに
はボタン形電池やコイン形ないしけ扁平形電池を積重し
た小型の集合電池をいう。Furthermore, in the present invention, small alkaline batteries include button-shaped batteries, coin-shaped or flat batteries, and cylindrical batteries smaller than AAA or AAA, as well as button-shaped batteries and coin-shaped or flat batteries. A small battery that is made up of stacked batteries.
そして、内面へのニッケル層の形成はメッキによっても
よいし、またクランド板の合せ材として形成したもので
あってもよく、ニッケル層の厚さとしては3μm以上が
好捷しい。The nickel layer may be formed on the inner surface by plating, or may be formed as a mating material for the gland plate, and the thickness of the nickel layer is preferably 3 μm or more.
つぎに実施例をあげて本発明を説明する。Next, the present invention will be explained with reference to Examples.
実施例
厚さ0.25ffの高クロムステンレス鋼5us447
J1にニッケルの片面メッキを施し、ニッケル層が缶内
面側になるようにして製缶した。この缶内面側にニッケ
ル層を設けた正極缶を用いて第1図に示すような構成の
LR43形電池を組み立てた。ニッケル帳の厚さは約3
μmであった。なお第1図において、(1)は正極缶、
(2)は正極合剤、(3)は環状台座、(4)はセパレ
ータ、(5)は負極剤、(6)はオーステナイト系ステ
ンレス鋼5US804を母材とし外面側にニッケル、内
面側に銅を合せ材とした銅−ステンレス鋼−ニッケルク
ラツド叛よりなる負極端子飯で、(7)はナイロン製の
環状ガスケットであり、正極缶(1)の内面側には第2
図に示すようにニッケル層(8)が形成されている。そ
して、この電池には酸化亜鉛を溶解させた35%水酸化
カリウム水溶液よりなるアルカリ電解液か注入されてお
り、正極合剤(2)は二酸化マンガン、りん状黒鉛およ
びポリアクリル酸ナトリクムの混合物510叩をit/
□□□2の圧力で加圧成形した!盲径10.9mm、厚
さ1.8πMの成形体よりなり、負極剤(5) fd氷
化率9係の汞化亜鉛1109J:ljナリ、セパレータ
(4)はセロハンとビニロン−レーヨン混抄紙を積重し
たものである。Example High chromium stainless steel 5us447 with thickness 0.25ff
One side of J1 was plated with nickel, and the can was made so that the nickel layer was on the inner surface of the can. Using this positive electrode can with a nickel layer provided on the inner surface of the can, an LR43 battery having the configuration shown in FIG. 1 was assembled. The thickness of the nickel book is approximately 3
It was μm. In Fig. 1, (1) is a positive electrode can,
(2) is a positive electrode mixture, (3) is an annular pedestal, (4) is a separator, (5) is a negative electrode material, and (6) is austenitic stainless steel 5US804 as a base material, with nickel on the outside and copper on the inside. (7) is a nylon annular gasket, and a second
As shown in the figure, a nickel layer (8) is formed. An alkaline electrolyte consisting of a 35% potassium hydroxide aqueous solution in which zinc oxide is dissolved is injected into this battery, and the positive electrode mixture (2) is a mixture of manganese dioxide, phosphorous graphite, and sodium polyacrylate. Hit it/
Pressure molded with □□□2 pressure! The negative electrode agent (5) is made of zinc chloride 1109J with a fd freezing rate of 9: lj, and the separator (4) is made of cellophane and vinylon-rayon mixed paper. It's an accumulation of things.
対照例
高クロムステンレス鋼SUS 447 J 1 ’&ニ
ッケルメッキすることなくそのまま製缶したほかは実施
例と同様にしてLR43形電池を組み立てた。Control Example: An LR43 type battery was assembled in the same manner as in the example except that the can was manufactured using high chromium stainless steel SUS 447 J 1' and without nickel plating.
上記のようにして得られた電池の貯蔵試験結果を第1表
に示す。Table 1 shows the storage test results of the batteries obtained as described above.
第 1 表
(注)閉路電圧は100Ωで5秒間放電後に測定したも
のである。Table 1 (Note) The closed circuit voltage was measured after discharging for 5 seconds at 100Ω.
第1表に示すように、正極缶の内面にニッケル層を設け
た実施例の電池は開路電圧や閉路電圧が安定してめるの
に対し、ニッケル層を設けなかった対照例の電池では貯
蔵により開路電圧や閉路電圧が低下している。特に閉路
電圧の低下が著しい。As shown in Table 1, the battery of the example with a nickel layer on the inner surface of the positive electrode can has stable open-circuit voltage and closed-circuit voltage, while the battery of the control example without a nickel layer has a stable As a result, the open circuit voltage and closed circuit voltage are decreasing. In particular, the decrease in closed circuit voltage is significant.
これは正極活物質と5US447J1中のクロムとが反
応し電解液中に6価のクロムイオンが溶出したためであ
ると考えられる。This is considered to be because the positive electrode active material and the chromium in 5US447J1 reacted and hexavalent chromium ions were eluted into the electrolyte.
つぎに上記実施例の電池と従来電池(厚さ0.25朋の
鉄板から製缶しニッケルメッキを施した正極缶を用いた
LR43形電池)を人工胃液(16中にNaC1を2j
1110%HC1を24 ml含む水溶Q)中に37°
Cで24時間浸漬し電池破壊の有無を人工胃液中のカリ
ウムイオンの検出により調べた。ソ(7)結果を第2表
に示す。なお電池破壊の有無を確認するために、カリウ
ムイオンの検出による方法を採用したのは、腐食により
正極缶にピンホールなどが発生した場合、電池から電解
液が人工胃液中に流出するからである。Next, the battery of the above example and a conventional battery (an LR43 type battery using a positive electrode can made from an iron plate with a thickness of 0.25 mm and plated with nickel) were mixed with artificial gastric fluid (2j of NaCl in 16 mm).
37° in aqueous solution Q) containing 24 ml of 1110% HCl.
The battery was immersed in C for 24 hours, and the presence or absence of battery destruction was examined by detecting potassium ions in the artificial gastric fluid. (7) The results are shown in Table 2. The reason why we adopted a method of detecting potassium ions to confirm whether the battery was damaged or not is because if a pinhole or the like occurs in the positive electrode can due to corrosion, the electrolyte will leak from the battery into the artificial gastric fluid. .
第 2 表
第2表に示されるように、従来電池では人工胃液中に2
4時間浸漬することにより電池破壊を生じたが、本発明
の電池は24時間はもとより200時間経過後もまった
く破壊を生じなかった。Table 2 As shown in Table 2, conventional batteries contain 2
Although the battery was destroyed after being immersed for 4 hours, the battery of the present invention was not destroyed at all not only after 24 hours but also after 200 hours.
【図面の簡単な説明】
第1図は本発明の小型アルカリ電池の一実施例を示す部
分断面図であり、第2図(寸第1図のA部拡大図である
。
(1)・・・正極缶、 (8)・・・ニッケル層特許呂
願人 日立マクセル株式会社
代理人弁理士 三 輪 鐵 雄ン詳−:二山、F巳ン′
:ユ
ip鉢1土
11図
72図[Brief Description of the Drawings] Fig. 1 is a partial sectional view showing one embodiment of a small alkaline battery of the present invention, and Fig. 2 is an enlarged view of section A in Fig. 1. (1)...・Positive electrode can, (8)...Nickel layer patent applicant: Hitachi Maxell Co., Ltd. Representative Patent Attorney: Tetsuo Miwa Details: Niyama, Fumi'
: Yuip pot 1 soil 11 figure 72 figure
Claims (1)
レス鋼を正極缶に用い、該LIE極缶の内面にニッケル
層を設けたことを特徴とする小型アルカリ電池。1. A small alkaline battery characterized in that a high chromium stainless steel with a chromium content of 23% by weight or more is used for the positive electrode can, and a nickel layer is provided on the inner surface of the LIE electrode can.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57220696A JPS59111249A (en) | 1982-12-15 | 1982-12-15 | Small size alkaline battery |
DE8383112530T DE3373595D1 (en) | 1982-12-15 | 1983-12-13 | Alkaline cell |
EP83112530A EP0118614B1 (en) | 1982-12-15 | 1983-12-13 | Alkaline cell |
US07/537,118 US5069989A (en) | 1982-12-15 | 1990-06-13 | Alkaline cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57220696A JPS59111249A (en) | 1982-12-15 | 1982-12-15 | Small size alkaline battery |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59111249A true JPS59111249A (en) | 1984-06-27 |
Family
ID=16755054
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57220696A Pending JPS59111249A (en) | 1982-12-15 | 1982-12-15 | Small size alkaline battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59111249A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001097034A1 (en) * | 2000-06-14 | 2001-12-20 | Seiko Epson Corporation | Automatic evaluation method and automatic evaluation system and storage medium storing automatic evaluation program |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5496742A (en) * | 1978-01-17 | 1979-07-31 | Seiko Instr & Electronics | Alkaline cell |
JPS5630249A (en) * | 1979-08-21 | 1981-03-26 | Matsushita Electric Ind Co Ltd | Terminal treatment of flat type cell |
-
1982
- 1982-12-15 JP JP57220696A patent/JPS59111249A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5496742A (en) * | 1978-01-17 | 1979-07-31 | Seiko Instr & Electronics | Alkaline cell |
JPS5630249A (en) * | 1979-08-21 | 1981-03-26 | Matsushita Electric Ind Co Ltd | Terminal treatment of flat type cell |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001097034A1 (en) * | 2000-06-14 | 2001-12-20 | Seiko Epson Corporation | Automatic evaluation method and automatic evaluation system and storage medium storing automatic evaluation program |
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