JPH0724215B2 - Dry cell - Google Patents
Dry cellInfo
- Publication number
- JPH0724215B2 JPH0724215B2 JP60062071A JP6207185A JPH0724215B2 JP H0724215 B2 JPH0724215 B2 JP H0724215B2 JP 60062071 A JP60062071 A JP 60062071A JP 6207185 A JP6207185 A JP 6207185A JP H0724215 B2 JPH0724215 B2 JP H0724215B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- battery
- indium
- positive electrode
- electrolytic solution
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/04—Cells with aqueous electrolyte
- H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
- H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 《発明の技術分野》 この発明は、負極亜鉛缶の内部にセパレータを介して正
極合剤を充填した乾電池の改良に関し、特に、電池成分
による環境汚染の対策技術に関する。Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to improvement of a dry battery in which a positive electrode mixture is filled inside a negative electrode zinc can via a separator, and more particularly to a technique for preventing environmental pollution due to battery components.
《発明の背景》 周知のように、電池に含まれている水銀が環境汚染源に
なるとして、その対策が社会問題にもなっている。水銀
電池には多量の水銀が含まれているので特に問題視さ
れ、使用済のものは回収するという対策が取られてい
る。<< Background of the Invention >> As is well known, it is known that mercury contained in a battery is a source of environmental pollution, and its countermeasures are becoming a social problem. Since a mercury battery contains a large amount of mercury, it is regarded as a particular problem, and measures are taken to collect used batteries.
また、マンガン乾電池にも微量ながら水銀が含まれてお
り、これら乾電池の消費量が非常に多いことから、これ
も無視できないとされている。In addition, manganese dry batteries also contain a small amount of mercury, and since the consumption of these dry batteries is very large, it is said that this cannot be ignored.
この種の乾電池では、負極亜鉛缶の腐蝕抑制剤として水
銀が使用されている。この水銀はセパレータに含まれて
電池内に組込まれる。セパレータはデンプン質と水溶性
糊材とからなる糊料をセパレータ基紙に塗布したもの
で、正極合剤はこのセパレータで被覆されて負極亜鉛缶
内に充填される。セパレータに塗布されている上記糊料
中に１重量％程度の水銀が添加されている。このセパレ
ータが亜鉛缶の内面に密着すると、亜鉛缶表面がアマル
ガム化され、腐蝕を有効に抑制することができる。In this type of dry battery, mercury is used as a corrosion inhibitor for the negative electrode zinc can. This mercury is contained in the separator and incorporated into the battery. The separator is a separator base paper coated with a starch material and a water-soluble paste material, and the positive electrode mixture is covered with this separator and filled in a negative electrode zinc can. About 1% by weight of mercury is added to the paste applied to the separator. When this separator adheres to the inner surface of the zinc can, the surface of the zinc can becomes an amalgam and corrosion can be effectively suppressed.
ところで、水銀による環境汚染の問題は、使用後の乾電
池の処理についてだけでなく、乾電池の生産段階でも当
然発生する。従来の乾電池の製造には、水銀を含んだ糊
料調整の際に生ずる洗浄廃液の処理や、糊料塗布後の紙
材をセパレータとして裁断する際の端切れや不良品の処
理についても慎重な配慮が必要であった。By the way, the problem of environmental pollution due to mercury naturally occurs not only in the treatment of dry batteries after use but also in the production stage of dry batteries. In the manufacture of conventional dry batteries, careful consideration should be given to the treatment of cleaning waste liquid that occurs when adjusting the paste containing mercury and the processing of scraps and defective products when cutting the paper material after the paste is applied as a separator. Was needed.
《発明の目的》 この発明の目的は、水銀を使用せずに亜鉛缶の腐蝕を有
効に抑制し、電池性能を低下させずに環境汚染の問題を
解消することのできる乾電池を提供することにある。<Object of the Invention> An object of the present invention is to provide a dry battery capable of effectively suppressing corrosion of a zinc can without using mercury and solving a problem of environmental pollution without lowering battery performance. is there.
《発明の構成》 上記の問題点を解決するために、この発明においては、
二酸化マンガンと導電剤に電解液を加えて混合，成形し
て正極合剤を作るが、この時の電解液に亜鉛缶の腐蝕抑
制剤として塩化インジウム又は硫酸インジウムを添加し
たことを特徴とする。<< Structure of the Invention >> In order to solve the above problems, in the present invention,
An electrolytic solution is added to manganese dioxide and a conductive agent and mixed and molded to form a positive electrode mixture. The electrolytic solution at this time is characterized by adding indium chloride or indium sulfate as a corrosion inhibitor for a zinc can.
《実施例》 まず、この発明が適用されるマンガン乾電池の一般的な
構造について図に従って説明する。<< Example >> First, a general structure of a manganese dry battery to which the present invention is applied will be described with reference to the drawings.
有底円筒形の負極亜鉛缶12の内面に電解液を含んだセパ
レータ10が密着配置され、その内部に正極合剤14が充填
されている。正極合剤14の中心には集電体である炭素棒
16が挿入されている。負極亜鉛缶12の上端開口部は封口
ガスケット18で密閉され、炭素棒16はこの封口ガスケッ
ト18の中心孔を貫通している。負極亜鉛缶12の底面には
負極端子板20が当てがわれ、また炭素棒16の突出端には
正極端子板22が被せられる。そして、亜鉛缶12の外周面
が絶縁チューブ24で被覆されるとともに、その外側に外
装缶26が装着される。A separator 10 containing an electrolytic solution is closely arranged on the inner surface of a bottomed cylindrical negative electrode zinc can 12, and a positive electrode mixture 14 is filled therein. A carbon rod, which is a current collector, is located in the center of the positive electrode mixture 14.
16 is inserted. The upper end opening of the negative electrode zinc can 12 is sealed with a sealing gasket 18, and the carbon rod 16 penetrates the center hole of the sealing gasket 18. A negative electrode terminal plate 20 is applied to the bottom surface of the negative electrode zinc can 12, and a protruding end of the carbon rod 16 is covered with a positive electrode terminal plate 22. Then, the outer peripheral surface of the zinc can 12 is covered with the insulating tube 24, and the outer can 26 is mounted on the outer side thereof.
正極合剤14は、活物質としての二酸化マンガンと導電剤
としてのアセチレンブラックや黒鉛粉末に電解液を加え
て混合し、炭素棒16の周囲に密着して円筒形をなすよう
に加圧成形されたものである。このように成形された正
極合剤14の外周囲をセパレータ10で包み、負極亜鉛缶12
内に装填している。セパレータ10はクラフト紙に糊料を
塗布したものである。The positive electrode mixture 14 is prepared by adding manganese dioxide as an active material and acetylene black or graphite powder as a conductive agent to an electrolytic solution and mixing them, and press-molded so as to be in close contact with the periphery of the carbon rod 16 to form a cylindrical shape. It is a thing. The outer periphery of the positive electrode mixture 14 thus formed is wrapped with the separator 10, and the negative electrode zinc can 12
It is loaded inside. The separator 10 is a kraft paper coated with a paste.
正極合剤14に加える電解液は、例えば塩化亜鉛系乾電池
の場合、水100部に対して塩化亜鉛20〜70部、塩化アン
モニウム０〜10部の組成のものを用いる。特にこの発明
の乾電池においては、正極合剤14に含まれる電解液中
に、負極亜鉛缶12の腐蝕抑制剤として塩化インジウム
（InCl3）を0.01〜0.5重量％の範囲で添加している。For example, in the case of a zinc chloride-based dry battery, the electrolytic solution added to the positive electrode mixture 14 has a composition of 20 to 70 parts of zinc chloride and 0 to 10 parts of ammonium chloride to 100 parts of water. In particular, in the dry battery of the present invention, indium chloride (InCl 3 ) as a corrosion inhibitor for the negative electrode zinc can 12 is added to the electrolytic solution contained in the positive electrode mixture 14 in the range of 0.01 to 0.5% by weight.
電解液に含まれて正極合剤14に塩化インジウムの形態で
混合されたインジウムは、電池組立後にはセパレータ10
を通して負極亜鉛缶12の内面側へ浸透し、亜鉛缶12の表
面に速やかに置換され、水銀と同様な作用をし、亜鉛缶
12の腐蝕を効果的に抑制する。特に電池の間欠放電の休
止時において、放電中に破壊された亜鉛缶12の表面のイ
ンジウム置換層が、正極合剤14側から新たに供給される
インジウムにより速やかに修復される。これにより高価
なインジウムを無駄にすることなく有効に活用でき、長
期に亘って負極亜鉛缶12の腐蝕抑制効果が得られる。Indium mixed in the positive electrode mixture 14 in the form of indium chloride contained in the electrolytic solution was used as a separator 10 after the battery was assembled.
Through the inner surface of the negative electrode zinc can 12 and is quickly replaced by the surface of the zinc can 12, which has the same function as mercury.
12 effectively suppresses corrosion. In particular, when the intermittent discharge of the battery is stopped, the indium substitution layer on the surface of the zinc can 12 destroyed during the discharge is promptly restored by the indium newly supplied from the positive electrode mixture 14 side. As a result, expensive indium can be effectively used without wasting, and the effect of suppressing corrosion of the negative electrode zinc can 12 can be obtained for a long period of time.
この発明の効果は、次の３種類の単一型塩化亜鉛系乾電
池の比較試験によって確認できた。The effects of the present invention were confirmed by the following three types of comparative tests of single type zinc chloride type dry batteries.
電池Ａ……セパレータ層および正極合剤層に水銀もイン
ジウムも含まないもの。Battery A: A separator layer and a positive electrode mixture layer containing neither mercury nor indium.
電池Ｂ……セパレータに塗布する糊材に１重量％の水銀
を添加したもの（従来の一般的な乾電池）。Battery B ... 1% by weight mercury added to the paste material applied to the separator (conventional general dry battery).
電池Ｃ……正極合剤に加える電解液に0.1重量％のInCl3
を添加した本発明の実施例。Battery C: 0.1% by weight of InCl 3 in the electrolyte added to the positive electrode mixture
Example of the present invention with the addition of.
上記各電池A,B,Cを45℃の温度下で３ケ月保存した後の
負極亜鉛缶の減量を測定した。亜鉛缶の初期重量は18g
であったが、腐蝕抑制対策を施していない電池Ａは0.27
gの減量、電池Ｂは0.14gの減量、電池Ｃは0.17gの減量
が認められた（各10個の平均値）。Each of the batteries A, B, and C was stored at a temperature of 45 ° C. for 3 months, and the weight loss of the negative electrode zinc can was measured. Initial weight of zinc can is 18g
However, the battery A that does not have corrosion suppression measures is 0.27
A weight loss of 0.1 g was observed for battery B, and a weight loss of 0.17 g was observed for battery C (average value of 10 samples each).
つまり、この発明に係る電池Ｃでは、水銀を含んだ従来
の電池Ｂとほぼ同程度の亜鉛腐蝕抑制効果が認められ
た。That is, in the battery C according to the present invention, the effect of suppressing zinc corrosion which is almost the same as that of the conventional battery B containing mercury was recognized.
また、次の表に示す放電性能の試験結果からも本発明の
効果は明らかである。Further, the effect of the present invention is clear from the results of the discharge performance test shown in the following table.
上記の試験Ｉは、２Ω負荷で１回30分の放電を一日２回
行ない、終止電圧0.9Vになるまでの累計放電時間であ
る。また試験IIは、10Ω負荷で１回４時間の放電を一日
１回行ない、終止電圧1Vになるまでの累計放電時間であ
る。なお試験結果は各10個についての平均値である。 The above test I is a total discharge time until a final voltage of 0.9 V is obtained by discharging once for 30 minutes with a 2Ω load twice a day. Test II is a total discharge time until a final voltage of 1 V is reached by discharging once for 4 hours with a load of 10Ω once a day. The test results are average values for 10 samples each.
亜鉛腐蝕抑制策を施していない電池Ａでは、保存に伴っ
て亜鉛缶が腐蝕し、その結果放電時間の減少が顕著にな
っている。本発明に係る電池Ｃでは、水銀を含んだ従来
の電池Ｂと殆ど同じ放電性能が得られる。これはインジ
ウムが水銀と同様な亜鉛の腐蝕抑制効果を示すからであ
る。In the battery A that is not subjected to the zinc corrosion suppression measure, the zinc can is corroded with storage, and as a result, the discharge time is significantly reduced. In the battery C according to the present invention, almost the same discharge performance as that of the conventional battery B containing mercury can be obtained. This is because indium exhibits the same corrosion inhibition effect of zinc as mercury.
上述した本発明の効果は、正極合剤に加える電解液に対
して0.01重量％以上のインジウム塩を添加することで顕
著になり、添加量が0.5重量％を越えても効果増には殆
どつながらず、むしろインジウム添加によるコスト増が
問題になる。また添加するインジウム塩としては、塩化
インジウム（InCl3）に限定されず、硫酸インジウム（I
n2(SO4)3）などでも同様な効果が得られる。The effect of the present invention described above becomes remarkable by adding 0.01% by weight or more of the indium salt to the electrolytic solution added to the positive electrode mixture, and even if the addition amount exceeds 0.5% by weight, the effect is almost increased. Instead, the increase in cost due to the addition of indium becomes a problem. The indium salt to be added is not limited to indium chloride (InCl 3 ), but indium sulfate (ICl 3
Similar effects can be obtained with n 2 (SO 4 ) 3 ).
《発明の効果》 以上詳細に説明したように、この発明によれば、種々の
面で慎重な取扱を必要としていた水銀を使用せずに、塩
化亜鉛系マンガン乾電池などにおける亜鉛缶の腐蝕を効
果的に抑制することができ、高い放電性能を維持するこ
とができる。<Effects of the Invention> As described in detail above, according to the present invention, corrosion of a zinc can in a zinc chloride-based manganese dry battery or the like is effective without using mercury, which requires careful handling in various aspects. Can be suppressed, and high discharge performance can be maintained.
図は本発明の対象となる乾電池の構造例を示す断面図で
ある。 10……セパレータ、12……負極亜鉛缶 14……正極合剤FIG. 1 is a cross-sectional view showing an example of the structure of a dry battery that is the subject of the present invention. 10 …… Separator, 12 …… Negative electrode zinc can 14 …… Positive electrode mixture
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭48−77332（ＪＰ，Ａ) 特公 昭52−536（ＪＰ，Ｂ２) 特公 昭51−32363（ＪＰ，Ｂ２) 特公 昭51−36450（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 48-77332 (JP, A) JP 52-536 (JP, B2) JP 51-32363 (JP, B2) JP 51- 36450 (JP, B2)
Claims (2)
ータが密着配置され、その内部に二酸化マンガンと導電
剤に電解液を加えて混合、成形した正極合剤が充填され
た乾電池であって、上記正極合剤に含まれる電解液中に
塩化インジウム又は硫酸インジウムが添加されているこ
とを特徴とする乾電池。1. A dry battery in which a separator containing an electrolytic solution is closely arranged on the inner surface of a negative electrode zinc can, and a positive electrode mixture formed by mixing and molding manganese dioxide and a conductive agent with the electrolytic solution is filled therein. A dry battery, wherein indium chloride or indium sulfate is added to the electrolytic solution contained in the positive electrode mixture.
上記電解液中に0.01〜0.5重量％の範囲で含まれている
ことを特徴とする特許請求の範囲第１項記載の乾電池。2. The dry battery according to claim 1, wherein the indium chloride or indium sulfate is contained in the electrolytic solution in a range of 0.01 to 0.5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60062071A JPH0724215B2 (en) | 1985-03-28 | 1985-03-28 | Dry cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60062071A JPH0724215B2 (en) | 1985-03-28 | 1985-03-28 | Dry cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61224265A JPS61224265A (en) | 1986-10-04 |
| JPH0724215B2 true JPH0724215B2 (en) | 1995-03-15 |
Family
ID=13189485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60062071A Expired - Fee Related JPH0724215B2 (en) | 1985-03-28 | 1985-03-28 | Dry cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0724215B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2975773B2 (en) * | 1992-06-30 | 1999-11-10 | 富士電気化学株式会社 | Manufacturing method of manganese dry battery separator |
| CN1087507C (en) * | 1994-04-27 | 2002-07-10 | 富士电气化学株式会社 | Battery anode zinc can, manufacturing method thereof, and manganese dry battery using the zinc can |
| WO2012000195A1 (en) * | 2010-06-30 | 2012-01-05 | China Dragon Group Manufacturing Limited | Battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52536A (en) * | 1975-06-20 | 1977-01-05 | Masakazu Inaoka | Training golf club with an electric measuring sensor disposed within i ts head |
| JPS5242211A (en) * | 1975-10-01 | 1977-04-01 | Mitsubishi Electric Corp | Frequency controller for synchronous machine |
| JPS5334616A (en) * | 1976-09-14 | 1978-03-31 | Fujikura Ltd | Rapid annealing apparatus for wire material |
| JPS5960860A (en) * | 1982-09-29 | 1984-04-06 | Mitsui Mining & Smelting Co Ltd | Manganese dry cell |
-
1985
- 1985-03-28 JP JP60062071A patent/JPH0724215B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61224265A (en) | 1986-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4994333A (en) | Galvanic primary cell | |
| JP3215448B2 (en) | Zinc alkaline battery | |
| JPH0724215B2 (en) | Dry cell | |
| CN1115734C (en) | Manganese dry cell | |
| US3040114A (en) | Primary battery cell | |
| JP3087536B2 (en) | Manganese dry cell | |
| JP2737233B2 (en) | Zinc alkaline battery | |
| JP3512826B2 (en) | Button type alkaline battery | |
| JPH0317181B2 (en) | ||
| JP2780949B2 (en) | Manganese dry cell | |
| JP2563108B2 (en) | Alkaline battery | |
| JP2563107B2 (en) | Alkaline battery | |
| JPH0453073B2 (en) | ||
| JPH06223829A (en) | Zinc alkaline battery | |
| JP2992781B2 (en) | Manganese dry cell | |
| JPH06231757A (en) | Zinc alkaline battery | |
| JPH0136669B2 (en) | ||
| JP2563106B2 (en) | Alkaline battery | |
| JP3094589B2 (en) | Manganese dry battery manufacturing method | |
| JPH0453074B2 (en) | ||
| JPH0748376B2 (en) | Alkaline battery | |
| JPH0317182B2 (en) | ||
| JPS6134228B2 (en) | ||
| JPH08213031A (en) | Alkaline button battery | |
| JPS60236456A (en) | Zinc anode of alkaline battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |