JPH0453074B2 - - Google Patents
Info
- Publication number
- JPH0453074B2 JPH0453074B2 JP59199423A JP19942384A JPH0453074B2 JP H0453074 B2 JPH0453074 B2 JP H0453074B2 JP 59199423 A JP59199423 A JP 59199423A JP 19942384 A JP19942384 A JP 19942384A JP H0453074 B2 JPH0453074 B2 JP H0453074B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- separator
- battery
- weight
- mercury
- 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
-
- 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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
- H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
-
- 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)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
≪発明の技術分野≫
この発明は、いわゆるペーパラインド方式の乾
電池に使用されるセパレータに関し、特に、電池
成分による環境汚染の対策技術に関する。
≪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
いう対策が採られている。
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。
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み込まれる。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。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。
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。従来の乾電池用セパ
レータの製造には、水銀を含んだ糊料調製の際に
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。
≪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用セ
パレータを提供することにある。
≪発明の構成≫
上記の問題点を解決するために、この発明は、
セパレータの亜鉛缶に接する面に塗布された糊料
中に、亜鉛缶の腐蝕抑制剤として糊料に対して
0.2〜10重量％のガリウムをガリウム塩の形態で
添加したことを特徴とする。
≪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、図に従つて説明する。
図において、１０がセパレータ、１２が有底円
筒形の負極亜鉛缶、１４が二酸化マンガンを活物
質とする正極合剤である。正極合剤１４はセパレ
ータ１０に包まれて負極亜鉛缶１２に充填され、
その中心に正極炭素棒１６が挿入される。亜鉛缶
１２の開口は封口ガスケツト１８で密閉される。
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
縁チユーブ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。
セパレータ１０は、クラフト紙にデンプン質と
水溶性糊材とからなる糊料を塗布したもので、特
にこの発明に係るセパレータ１０では、その糊料
中にガリウム塩が添加されている。
以下、本発明に係るセパレータの具体例を詳述
する。クラフト紙に塗布する糊料成分は次のとお
りである。水100重量部中に、糊化剤として架橋
コンスターチ50重量部、バインダとしてロカスト
ビン−ガム５％溶液を40重量部とPVA（ポリビニ
ルアルコール）５％溶液を20重量部をそれぞれ加
え、さらに亜鉛腐蝕抑制剤としてガリウム塩
（GaCl3）を２重量部添加し、撹拌混合する。ガ
リウム塩の形態で添加するため、糊料液中に容易
に溶解する。
上記の混合糊料脱泡のため一昼夜放置し、その
後、基材であるクラフト紙の片面に上記糊料を塗
布する。この燃料を乾燥させた後、所定の寸法に
裁断してセパレータが完成する。
電池組立時には、セパレータ１０の糊料塗布面
を負極亜鉛缶１４に密着させる。そうすると、糊
料中に添加したガリウムが亜鉛缶１４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
１４の腐蝕を効果的に抑制する。
この発明の効果は、次の３種類のUM−１型塩
化亜鉛電池の比較試験によつて確認できた。
電池Ａ…セパレータ糊料に水銀もガリウムも含ま
ないもの。
電池Ｂ…セパレータ糊料に１重量％の水銀を添加
したもの。
電池Ｃ…セパレータ糊料に４重量％のGaCl3を添
加した本発明品を用いたもの。
上記各電池Ａ、Ｂ、Ｃを45℃の温度下で３ケ月
間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、電池Ａは0.29g
の減量、電池Ｂは0.15gの減量、電池Ｃは0.18gの
減量が認められた（各10個の平均値）。
つまり、本発明によるセパレータを用いた電池
Ｃでは、水銀を含んだ従来の電池Ｂと同程度の亜
鉛腐蝕抑制効果が認められる。
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。
<<Technical Field of the Invention>> The present invention relates to a separator used in a so-called paper-bound type dry cell battery, and particularly relates to a technique for preventing environmental pollution caused by battery components. <<Background of the Invention>> As is well known, mercury contained in batteries pollutes the environment, and countermeasures have become a social issue. Mercury batteries are considered a particular problem because they contain large amounts of mercury, and measures are being taken to collect used batteries. In addition, manganese dry batteries also contain mercury, albeit in a small amount, and since the consumption of these batteries is extremely large, this cannot be ignored. In this type of dry battery, mercury is used as a corrosion inhibitor for the negative electrode zinc can. This mercury is included in the separator and incorporated into the battery. The separator is a separator base paper coated with a paste made of starch and a water-soluble adhesive, and the positive electrode mixture is covered with this separator and filled into the negative electrode zinc can. 1 in the above glue applied to the separator.
About % by weight of mercury is added. When the separator comes into close contact with the inner surface of the zinc can, the surface of the zinc can is amalgamated, and corrosion can be effectively suppressed. By the way, the problem of environmental pollution due to mercury naturally occurs not only in the treatment of dry cell batteries after use, but also in the production stage of dry cell batteries. In the production of conventional dry battery separators, care must be taken to dispose of cleaning waste liquid generated during the preparation of glue containing mercury, and to dispose of scraps and defective products when paper material is cut into separators after the glue has been applied. special consideration was required. <<Object of the invention>> The object of the invention is to provide a separator for dry batteries that can effectively suppress corrosion of zinc cans without using mercury and solve the problem of environmental pollution without reducing battery performance. There is a particular thing. <<Structure of the invention>> In order to solve the above problems, this invention has the following features:
The paste applied to the surface of the separator that comes into contact with the zinc can is used as a corrosion inhibitor for the zinc can.
It is characterized by the addition of 0.2 to 10% by weight of gallium in the form of gallium salt. <<Example>> First, the general structure of a manganese dry battery to which the present invention is applied will be described with reference to the drawings. In the figure, 10 is a separator, 12 is a bottomed cylindrical negative electrode zinc can, and 14 is a positive electrode mixture containing manganese dioxide as an active material. The positive electrode mixture 14 is wrapped in a separator 10 and filled into a negative electrode zinc can 12.
A positive electrode carbon rod 16 is inserted into the center. The opening of the zinc can 12 is sealed with a sealing gasket 18.
A negative terminal plate 20 is applied to the bottom of the zinc can 12, and a positive terminal plate 22 is applied to the protruding end of the carbon rod 16.
is covered. The outer peripheral surface of the zinc can 12 is covered with an insulating tube 24, and an outer can 26 is attached to the outside thereof. The separator 10 is made by coating kraft paper with a sizing agent made of starch and a water-soluble sizing agent. Particularly, in the separator 10 according to the present invention, gallium salt is added to the sizing agent. Hereinafter, specific examples of the separator according to the present invention will be described in detail. The glue components applied to the kraft paper are as follows. To 100 parts by weight of water, 50 parts by weight of cross-linked cornstarch as a gelatinizing agent, 40 parts by weight of a 5% solution of locustvin gum as a binder, and 20 parts by weight of a 5% solution of PVA (polyvinyl alcohol) were added, and further zinc corrosion inhibition was added. Two parts by weight of gallium salt (GaCl 3 ) as an agent are added and mixed by stirring. Since it is added in the form of gallium salt, it easily dissolves in the thickening solution. The above-mentioned mixed glue was left to stand overnight for defoaming, and then the above-mentioned glue was applied to one side of the kraft paper as a base material. After drying this fuel, it is cut into predetermined dimensions to complete the separator. When assembling the battery, the glue coated surface of the separator 10 is brought into close contact with the negative electrode zinc can 14. Then, the gallium added to the paste is quickly substituted on the surface of the zinc can 14, acts in the same way as mercury, and effectively suppresses corrosion of the zinc can 14. The effects of this invention were confirmed through the following comparative test of three types of UM-1 type zinc chloride batteries. Battery A: Separator paste that does not contain mercury or gallium. Battery B: Separator paste containing 1% by weight of mercury. Battery C: A battery of the present invention in which 4% by weight of GaCl 3 was added to the separator paste. After each of the batteries A, B, and C was stored at a temperature of 45° C. for 3 months, the weight loss of the negative electrode zinc can was measured. The initial weight of the zinc can was 18g, but the weight of battery A was 0.29g.
A weight loss of 0.15g was observed for battery B, and a weight loss of 0.18g was observed for battery C (average value of 10 each). In other words, in Battery C using the separator according to the present invention, the effect of suppressing zinc corrosion to the same extent as in the conventional Battery B containing mercury is observed. Furthermore, the effects of the present invention are clear from the discharge performance test results shown in the following table.
【表】
上記の試験は、2Ω負荷で１回30分の放電を
１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。また試験は、10Ω負荷で１
回４時間の放電を１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。試験結果は各
10個についての平均値である。
亜鉛腐蝕抑制策を施していない電池Ａでは、保
存に伴つて亜鉛缶が腐蝕し、その結果放電時間の
減少が顕著になつている。本発明によるセパレー
タを用いた電池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。
上述した本発明の効果は、糊料に対して0.2重
量％以上のガリウムを添加することで顕著にな
り、添加量が10重量％を越えても効果増には殆ど
つながらず、むしろガリウム添加によるコスト増
が問題になる。また、添加するガリウム塩として
は、GaCl3に限定されず、Ga2（SO4）3あるいは
NH4Ga（SO4）2等でも同様な効果が得られる。
ところで、負極亜鉛缶自体に腐蝕抑制剤として
ガリウムを添加することも考えられるが、亜鉛缶
の腐蝕が問題になるのはその表面であり、本発明
のセパレータによつて亜鉛缶表面に腐蝕抑制膜を
形成する方がガリウムの必要量は少なくてすみ、
コスト的に有利である。
≪発明の効果≫
以上詳細に説明したように、この発明に係る乾
電池乾電池用セパレータによれば、種々の面で慎
重な取扱いを必要としていた水銀を使用せずに、
マンガン乾電池や塩化亜鉛乾電池における亜鉛缶
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。[Table] In the above test, discharge was performed twice a day for 30 minutes at a time with a 2Ω load, and the cumulative discharge time was measured until the final voltage reached 0.9V. Also, the test is 1 with a 10Ω load.
Discharge for 4 hours once a day, with a final voltage of 1V.
This is the cumulative discharge time until . The test results are
This is the average value for 10 pieces. In battery A, in which no measures were taken to inhibit zinc corrosion, the zinc can corroded during storage, and as a result, the discharge time was significantly reduced. The battery C using the separator according to the present invention has almost the same discharge performance as the conventional battery B containing mercury. The above-mentioned effects of the present invention become noticeable when 0.2% by weight or more of gallium is added to the paste, and even if the amount added exceeds 10% by weight, there is almost no increase in the effect; rather, the effect of the addition of gallium increases. Increased costs become a problem. Further, the gallium salt to be added is not limited to GaCl 3 but may be Ga 2 (SO 4 ) 3 or
Similar effects can be obtained with NH 4 Ga (SO 4 ) 2 and the like. By the way, it is possible to add gallium as a corrosion inhibitor to the negative electrode zinc can itself, but the corrosion of the zinc can becomes a problem on its surface, and the separator of the present invention can form a corrosion-inhibiting film on the surface of the zinc can. The amount of gallium required is smaller when forming
It is advantageous in terms of cost. <<Effects of the Invention>> As explained in detail above, the separator for dry cell batteries according to the present invention does not use mercury, which requires careful handling in various aspects.
Corrosion of zinc cans in manganese dry batteries and zinc chloride dry batteries can be effectively suppressed, and high discharge performance can be maintained.
図は本発明の対象となる乾電池の製造例を示す
断面図である。
１０……セパレータ、１２……負極亜鉛缶、１
４……正極合剤。
The figure is a sectional view showing an example of manufacturing a dry battery to which the present invention is applied. 10...Separator, 12...Negative electrode zinc can, 1
4...Positive electrode mixture.
Claims (1)
パレータ基紙に塗布してなるもので、正極合剤を
被覆して負極亜鉛缶の内面に密着する乾電池用セ
パレータであつて、上記亜鉛缶に接する面に塗布
された上記糊料中に、亜鉛缶の腐蝕抑制剤として
糊料に対して0.2〜10重量％のガリウムをガリウ
ム塩の形態で添加したことを特徴とする乾電池用
セパレータ。1. A separator for dry batteries, which is made by coating a separator base paper with a glue consisting of starch and a water-soluble glue, and is coated with a positive electrode mixture and adheres to the inner surface of a negative electrode zinc can, which A separator for a dry battery, characterized in that 0.2 to 10% by weight of gallium in the form of gallium salt is added to the paste as a corrosion inhibitor for the zinc can, which is applied to the surface in contact with the paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59199423A JPS6178052A (en) | 1984-09-26 | 1984-09-26 | Separator for dry cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59199423A JPS6178052A (en) | 1984-09-26 | 1984-09-26 | Separator for dry cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6178052A JPS6178052A (en) | 1986-04-21 |
| JPH0453074B2 true JPH0453074B2 (en) | 1992-08-25 |
Family
ID=16407558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59199423A Granted JPS6178052A (en) | 1984-09-26 | 1984-09-26 | Separator for dry cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6178052A (en) |
-
1984
- 1984-09-26 JP JP59199423A patent/JPS6178052A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6178052A (en) | 1986-04-21 |
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