JPH08162100A - Flat alkaline battery - Google Patents
Flat alkaline batteryInfo
- Publication number
- JPH08162100A JPH08162100A JP6297191A JP29719194A JPH08162100A JP H08162100 A JPH08162100 A JP H08162100A JP 6297191 A JP6297191 A JP 6297191A JP 29719194 A JP29719194 A JP 29719194A JP H08162100 A JPH08162100 A JP H08162100A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- electrode mixture
- silver
- battery
- nickelite
- 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.)
- Granted
Links
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、偏平形アルカリ電池に
関し、とくに正極合剤の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat alkaline battery, and more particularly to improvement of a positive electrode mixture.
【０００２】[0002]
【従来の技術】一般に、ボタン形、コイン形等と称され
ている偏平形アルカリ電池は、電子腕時計や電子卓上計
算機等の小型電子機器に使用され、これら電子機器の普
及に伴い、近年、ますます需要が高まる方向にある。そ
して、これら電子機器では、低消費電流化、高性能化が
進められており、上記偏平形アルカリ電池に対しても、
これに対応すべく長寿命化、大電流化が求められてい
る。2. Description of the Related Art Flat type alkaline batteries, which are generally called button type, coin type, etc., are used in small electronic devices such as electronic wrist watches and electronic desk calculators. The demand is increasing. And in these electronic devices, low current consumption and high performance are being advanced, and even for the flat alkaline battery,
In order to cope with this, long life and large current are required.
【０００３】このような状況から、偏平形アルカリ電池
では、各種種類の活物質の使用が検討され、正極の活物
質としては、コスト及び特性の両面から酸化銀と安価な
二酸化マンガンの混合物が用いられることが増えてい
る。Under such circumstances, the use of various kinds of active materials in flat alkaline batteries has been studied, and a mixture of silver oxide and inexpensive manganese dioxide is used as the positive electrode active material in terms of cost and characteristics. Is being increased.
【０００４】[0004]
【発明が解決しようとする課題】ところで、偏平形アル
カリ電池を製造するには、負極端子を兼ねる負極缶と、
これよりも一回り大きさの大きい正極端子を兼ねる正極
缶を用意する。このうち正極缶には正極活物質、導電材
及び結着材よりなる正極合剤を充填し、この上からセパ
レータを敷設する。負極缶には負極活物質と結着材より
なる負極合剤およびアルカリ電解液を充填する。そし
て、負極缶の開口部を、正極缶の開口部へ向けて、ガス
ケットを介してはめ込み、正極缶の開口縁部をかしめる
ことで上記偏平形電池は製造される。By the way, in order to manufacture a flat alkaline battery, a negative electrode can which also serves as a negative electrode terminal,
A positive electrode can that is also slightly larger than this and doubles as a positive electrode terminal is prepared. Of these, the positive electrode can is filled with a positive electrode mixture composed of a positive electrode active material, a conductive material and a binder, and a separator is laid on the positive electrode mixture. The negative electrode can is filled with a negative electrode mixture composed of a negative electrode active material and a binder and an alkaline electrolyte. Then, the flat battery is manufactured by fitting the opening of the negative electrode can toward the opening of the positive electrode via a gasket and caulking the opening edge of the positive can.
【０００５】しかしながら、上記酸化銀と二酸化マンガ
ンを正極活物質とする正極合剤は、二酸化マンガンが比
較的柔らかい材質であることから、酸化銀のみを活物質
として用いる正極合剤に比べて柔らかい。このため、図
２に示すように、正極缶２２の開口縁部をかしめるに際
して、正極合剤２６のガスケット２４で押される部分が
沈み込み、その沈み込んだ分が負極合剤側に盛り上がっ
て電池内圧を上昇させたり、負極カップ２３、ガスケッ
ト２４、正極合剤２６間の圧縮が低下し、電解液の漏れ
が発生するといった不都合が生じている。However, the positive electrode mixture containing silver oxide and manganese dioxide as the positive electrode active material is softer than the positive electrode mixture using only silver oxide as the active material because manganese dioxide is a relatively soft material. Therefore, as shown in FIG. 2, when the opening edge portion of the positive electrode can 22 is caulked, the portion of the positive electrode mixture 26 pressed by the gasket 24 sinks, and the amount of the sinking rises toward the negative electrode mixture side. There are inconveniences such as an increase in the battery internal pressure and a decrease in compression between the negative electrode cup 23, the gasket 24, and the positive electrode mixture 26, causing leakage of the electrolytic solution.
【０００６】そこで、本発明はこのような従来の実情に
鑑みて提案されたものであり、電池のかしめ工程によっ
て、正極合剤が沈み込むことがなく、正極合剤の沈み込
みによる電池内圧の上昇、電解液の漏液が防止される偏
平形アルカリ電池を提供することを目的とする。Therefore, the present invention has been proposed in view of such a conventional situation, and the positive electrode mixture does not sink due to the caulking process of the battery, and the internal pressure of the battery due to the sinking of the positive electrode mixture is reduced. It is an object of the present invention to provide a flat alkaline battery in which rising and leakage of electrolyte are prevented.
【０００７】[0007]
【課題を解決するための手段】上述の目的を達成するた
めに、本発明の偏平形アルカリ電池は、正極合剤が、酸
化銀と２０〜５０重量％の二酸化マンガン及び５〜２０
重量％の銀・ニッケライトよりなる正極活物質混合物
と、結着材とを加圧成形したものであることを特徴とす
るものである。In order to achieve the above object, in the flat alkaline battery of the present invention, the positive electrode mixture contains silver oxide, 20 to 50% by weight of manganese dioxide and 5 to 20%.
The present invention is characterized in that a positive electrode active material mixture made of silver / nickelite in weight% and a binder are pressure-molded.
【０００８】また、正極合剤に、結着剤としてフッ素系
樹脂が０．３〜５重量％なる割合で混合されていること
を特徴とするものである。Further, the present invention is characterized in that the positive electrode mixture is mixed with a fluororesin as a binder in a proportion of 0.3 to 5% by weight.
【０００９】本発明は、一般にコイン形、ボタン形と称
される偏平形アルカリ電池に適用されるものである。偏
平形の電池では、負極合剤が充填された負極カップの開
口部を、正極合剤およびセパレータが収容された正極缶
の開口部へ向けて、ガスケットを介してはめ込み、正極
缶の開口縁部をかしめることで組み立てられる。The present invention is applied to flat alkaline batteries generally called coin type and button type. In a flat battery, fit the opening of the negative electrode cup filled with the negative electrode mixture toward the opening of the positive electrode can containing the positive electrode mixture and the separator through the gasket, and open the edge of the positive electrode can. It can be assembled by caulking.
【００１０】この正極缶の開口縁部がかしめられるに際
しては、正極合剤のガスケットで押される部分に大きな
圧力がかかる。このとき、正極合剤が柔らかい材質であ
る場合には、そのガスケットと接触する部分が沈み込
み、その分が負極合剤側に盛り上がって電池内圧を上昇
させたり、負極缶、ガスケット、正極合剤との間の圧縮
が低下し、電解液の漏液が発生する。When the opening edge of the positive electrode can is caulked, a large pressure is applied to the portion of the positive electrode mixture that is pressed by the gasket. At this time, if the positive electrode mixture is made of a soft material, the part that comes into contact with the gasket sinks, and that portion rises to the negative electrode mixture side to raise the battery internal pressure, or the negative electrode can, the gasket, the positive electrode mixture. The compression between and decreases, and electrolyte leakage occurs.
【００１１】本発明では、このような電池のかしめ工程
によって生じる正極合剤の沈み込みを防止するために、
正極合剤として、酸化銀と２０〜５０重量％の二酸化マ
ンガン及び５〜２０重量％の銀・ニッケライトよりなる
正極活物質混合物と、結着材とを加圧成形したものを用
いる。In the present invention, in order to prevent the positive electrode mixture from sinking due to such a caulking process of the battery,
As the positive electrode mixture, a positive electrode active material mixture composed of silver oxide, 20 to 50% by weight of manganese dioxide, and 5 to 20% by weight of silver-nickelite, and a binder are pressure-molded.
【００１２】これら成分よりなる正極合剤は、銀・ニッ
ケライト（ＡｇＮｉＯ2）が混合されていることによ
り、硬度が高くなっている。このため、電池のかしめ工
程によって、ガスケットで押される部分のしずみ込む量
が小さく抑えられる。したがって、正極合剤の沈み込み
によって生じる電池内圧の上昇や電解液の漏液が防止さ
れることになる。The positive electrode mixture composed of these components has a high hardness due to the mixture of silver nickelite (AgNiO 2 ). Therefore, the amount of squeezing of the portion pressed by the gasket is suppressed to be small by the crimping process of the battery. Therefore, it is possible to prevent the internal pressure of the battery from rising and the electrolyte from leaking due to the sinking of the positive electrode mixture.
【００１３】また、この他、銀・ニッケライトを正極合
剤に混合すると以下のような副次的効果も得られる。In addition to the above, the following secondary effects can be obtained by mixing silver / nickelite with the positive electrode mixture.
【００１４】すなわち、酸化銀、二酸化マンガンのみを
正極活物質として用いる場合には、これら自身が絶縁物
に近いため、正極合剤にさらにグラファイトやカーボン
等の導電剤を加えるのが通常である。しかし、このグラ
ファイトやカーボンは、かさ密度が低いために正極合剤
のかなりの体積を占有し、その分、電池容量が小さくな
ってしまう。That is, when only silver oxide or manganese dioxide is used as the positive electrode active material, it is usual that a conductive agent such as graphite or carbon is further added to the positive electrode mixture because they are close to insulators. However, since graphite and carbon have a low bulk density, they occupy a considerable volume of the positive electrode mixture, and the battery capacity becomes smaller accordingly.
【００１５】これに対して、銀・ニッケライトは、電気
容量の大きい活物質であるとともにそれ自身良好な導電
性を有する。したがって、この銀・ニッケライトを混合
すれば他の導電剤を加える必要がなく、導電剤によって
活物質充填量が小さくなるのが抑えられ、大きな電池容
量が得られることになる。On the other hand, silver-nickelite is an active material having a large electric capacity and has good conductivity by itself. Therefore, if this silver / nickelite is mixed, it is not necessary to add another conductive agent, and it is possible to prevent the conductive material from filling the active material in a small amount, thereby obtaining a large battery capacity.
【００１６】なお、この銀・ニッケライトの混合率は、
５〜２０重量％が適当である。銀・ニッケライトの量
が、この混合率よりも少ない場合には銀・ニッケライト
の上述のような効果が十分に得られない。逆に、銀・ニ
ッケライトの量が、この混合率を越える場合には、正極
合剤の硬度が高くなり過ぎ、圧縮成形に際してパンチに
変形を来す虞れがある。The mixing ratio of silver and nickelite is
5-20% by weight is suitable. When the amount of silver / nickelite is less than this mixing ratio, the above-described effects of silver / nickelite cannot be sufficiently obtained. On the other hand, when the amount of silver / nickelite exceeds this mixing ratio, the hardness of the positive electrode mixture becomes too high, which may cause deformation of the punch during compression molding.
【００１７】また、正極合剤に混合する結着剤として
は、フッ素系樹脂が適している。Fluorine-based resin is suitable as the binder mixed with the positive electrode mixture.
【００１８】フッ素系樹脂を用いると、正極合剤に靱性
が付与され、外部応力による縁欠け等の生じ難い、ハン
ドリング性の良好な正極合剤が得られる。また、フッ素
系樹脂が混合された正極合剤は、圧縮成形に際してパン
チ等へ付着し難く、質量ばらつきが抑えられる。したが
って、電池の生産性が向上することになる。When a fluorine-based resin is used, toughness is imparted to the positive electrode mixture, and it is possible to obtain a positive electrode mixture having good handleability, which is unlikely to cause edge chipping due to external stress. In addition, the positive electrode mixture mixed with the fluororesin is unlikely to adhere to the punch or the like during compression molding, and the variation in mass is suppressed. Therefore, the productivity of the battery is improved.
【００１９】このフッ素系樹脂の混合率は０．３〜５重
量％が適当である。樹脂の混合量が、この範囲よりも少
ない場合には上述の効果が十分に得られず、多い場合に
は正極合剤の導電性が低くなり、電流特性が劣化する。A suitable mixing ratio of this fluorine-based resin is 0.3 to 5% by weight. If the amount of the resin mixed is less than this range, the above-mentioned effects cannot be sufficiently obtained, and if the amount is larger than the above range, the conductivity of the positive electrode mixture becomes low and the current characteristics deteriorate.
【００２０】以上のように本発明では、正極合剤とし
て、銀・ニッケライトを含有するものを用いるが、負極
や電解液としては偏平形のアルカリ電池で通常用いられ
ているものがいずれも使用可能である。As described above, in the present invention, as the positive electrode mixture, the one containing silver / nickelite is used, but as the negative electrode and the electrolytic solution, any of those usually used in flat alkaline batteries is used. It is possible.
【００２１】[0021]
【作用】偏平形アルカリ電池において、正極合剤とし
て、酸化銀と２０〜５０重量％の二酸化マンガン及び５
〜２０重量％の銀・ニッケライトよりなる正極活物質混
合物と、結着材とを加圧成形したものを用いると、この
正極合剤は銀・ニッケライトが混合されていることによ
り硬度が高くなっているので、電池のかしめ工程によっ
て生じる沈み込みが抑えられ、正極合剤の沈み込みによ
って生じる電池内圧の上昇や電解液の漏液が防止される
また、この銀・ニッケライトは、電気容量の大きい活物
質であるとともにそれ自身良好な導電性を有する。この
ため、この銀・ニッケライトを混合すれば正極合剤にグ
ラファイト等のかさ密度の低い導電剤を加える必要がな
く、その分、活物質充填量が確保され、大きな電池容量
が得られる。In a flat alkaline battery, as a positive electrode mixture, silver oxide, 20 to 50% by weight of manganese dioxide and 5
When a positive electrode active material mixture consisting of ˜20 wt% silver / nickelite and a binder is pressure-molded, this positive electrode mixture has a high hardness due to the mixture of silver / nickelite. As a result, the submergence caused by the caulking process of the battery is suppressed, and the rise of the internal pressure of the battery and the leakage of the electrolyte caused by the subsidence of the positive electrode mixture are prevented. It has a large conductivity and has good conductivity by itself. Therefore, if this silver / nickelite is mixed, it is not necessary to add a conductive agent having a low bulk density such as graphite to the positive electrode mixture, and the amount of the active material filled can be secured accordingly, and a large battery capacity can be obtained.
【００２２】なお、このような正極合剤の結着材として
は、フッ素系樹脂が適当である。Fluorine-based resin is suitable as a binder for such a positive electrode mixture.
【００２３】フッ素系樹脂を用いると、正極合剤に靱性
が付与され、外部応力による縁欠け等の生じ難い、ハン
ドリング性の良好な正極合剤が得られる。また、フッ素
系樹脂が混合された正極合剤は、圧縮成形に際してパン
チ等へ付着し難く、質量ばらつきも抑えられる。When a fluorine-based resin is used, toughness is imparted to the positive electrode mixture, and a positive electrode mixture having good handleability, in which edge cracking due to external stress does not easily occur, can be obtained. Further, the positive electrode mixture mixed with the fluororesin is unlikely to adhere to the punch or the like during compression molding, and the variation in mass can be suppressed.
【００２４】[0024]
【実施例】本発明の好適な実施例について実験結果に基
づいて説明する。EXAMPLES Preferred examples of the present invention will be described based on experimental results.
【００２５】実施例１ 図１に、本実施例で作製したＳＲ６２６ＳＷ型（外径
６．８ｍｍ、高さ２．６ｍｍ）の偏平形電池を示す。本
実施例ではこのような偏平形電池を作製するために、ま
ず正極合剤６を次のようにして作製した。 Example 1 FIG. 1 shows an SR626SW type flat battery (having an outer diameter of 6.8 mm and a height of 2.6 mm) manufactured in this example. In this example, in order to manufacture such a flat battery, first, the positive electrode mixture 6 was manufactured as follows.
【００２６】銀・ニッケライトを得るために、２ｍｏｌ
／ｌなる濃度の次亜塩素酸ソーダ水溶液２００ｃｃに、
１０ｍｏｌ／ｌなる濃度の水酸化カリウム水溶液５００
ｃｃ、２ｍｏｌ／ｌなる濃度の硫酸ニッケル水溶液１０
０ｃｃを添加し、よく混合した。そして、生じた黒色沈
澱物（オキシ水酸化ニッケル：γ−ＮｉＯＯＨ）を、純
水でよく洗浄してろ過し、６０℃の恒温槽にて２０時間
乾燥した。乾燥後、乾燥物を粉砕し、そのうち１００メ
ッシュパスの粉末を１０ｇ秤量した。この１０ｇのオキ
シ水酸化ニッケル（ＮｉＯＯＨ）を、５ｍｏｌ／ｌなる
濃度の水酸化カリウム水溶液３００ｃｃ中に投入してよ
く攪はんし、さらに１ｍｏｌ／ｌなる濃度の硝酸銀水溶
液１００ｃｃを加え、温度６０℃で１６時間攪はんを続
けた。そして、その沈澱物をろ過、水洗、乾燥すること
で銀・ニッケライト（ＡｇＮｉＯ2）を生成した。To obtain silver / nickelite, 2 mol
200 cc of sodium hypochlorite aqueous solution having a concentration of
500 mol of potassium hydroxide aqueous solution having a concentration of 10 mol / l
cc 2 mol / l concentration of nickel sulfate aqueous solution 10
0 cc was added and mixed well. Then, the resulting black precipitate (nickel oxyhydroxide: γ-NiOOH) was thoroughly washed with pure water, filtered, and dried in a constant temperature bath at 60 ° C. for 20 hours. After drying, the dried product was crushed, and 10 g of 100-mesh pass powder was weighed. This 10 g of nickel oxyhydroxide (NiOOH) was put into 300 cc of a potassium hydroxide aqueous solution having a concentration of 5 mol / l and well stirred, and 100 cc of a silver nitrate aqueous solution having a concentration of 1 mol / l was added, and the temperature was 60 ° C. The stirring was continued for 16 hours. Then, the precipitate was filtered, washed with water, and dried to produce silver nickelite (AgNiO 2 ).
【００２７】このようにして合成された銀・ニッケライ
ト（ＡｇＮｉＯ2）５重量％、酸化銀（Ａｇ2Ｏ）６４．
５重量％、二酸化マンガン（ＭｎＯ2）３０重量％と、
結着材となるポリテトラフルオロエチレン（ＰＴＦＥ：
フッ素系樹脂）０．５重量％とを混合し、ペレット状に
圧縮成形することで正極合剤６を作製した。5% by weight of silver nickelite (AgNiO 2 ) and silver oxide (Ag 2 O) 64.
5% by weight, manganese dioxide (MnO 2 ) 30% by weight,
Polytetrafluoroethylene (PTFE: Binder)
Fluorine-based resin) was mixed with 0.5% by weight, and the mixture was compression-molded into pellets to prepare a positive electrode mixture 6.
【００２８】一方、負極合剤１は、水銀でアマルガム化
した亜鉛粉末に、アルカリ電解液とゲル化剤を混合し、
ペレット状に成形することで作製した。On the other hand, the negative electrode mixture 1 was prepared by mixing a zinc powder amalgamated with mercury with an alkaline electrolyte and a gelling agent,
It was produced by molding into pellets.
【００２９】そして、このようにして作製された正極合
剤６をニッケルメッキが施されたステンレススチール製
の正極缶２に収容し、その上からセパレータ５を敷設し
た。一方、負極合剤１を銅、ステンレススチール及びニ
ッケルの３層クラッド板よりなる負極カップ３に収容し
た。そして、負極カップ３の開口部を、正極缶２の開口
部に向けて、ガスケット４を介してはめ込み、正極缶２
の開口縁部をかしめることで上記偏平形電池を作製し
た。Then, the positive electrode mixture 6 thus prepared was housed in a nickel-plated stainless steel positive electrode can 2, and a separator 5 was laid on the positive electrode can 2. On the other hand, the negative electrode mixture 1 was contained in a negative electrode cup 3 made of a three-layer clad plate of copper, stainless steel and nickel. Then, the opening of the negative electrode cup 3 is fitted into the opening of the positive electrode can 2 via the gasket 4, and the positive electrode can 2 is inserted.
The flat-shaped battery was manufactured by caulking the opening edge portion of.
【００３０】なお、セパレータ５は、ポリエチレンフィ
ルムとセロファン及び不織布よりなるものであり、ガス
ケット４は、ナイロン製である。The separator 5 is made of polyethylene film, cellophane, and non-woven fabric, and the gasket 4 is made of nylon.
【００３１】比較例１ 正極合剤として、酸化銀６０重量％、二酸化マンガン３
０重量％と、導電剤となるグラファイト８重量％、結着
剤となるフッ素樹脂２重量％を混合し、ペレット状に圧
縮成形することで得られたものを用いること以外は実施
例１と同様にして偏平形電池を作製した。 Comparative Example 1 As a positive electrode mixture, silver oxide 60% by weight, manganese dioxide 3
Same as Example 1 except that 0% by weight, 8% by weight of graphite as a conductive agent, and 2% by weight of fluororesin as a binder were mixed and compression-molded into pellets. Then, a flat battery was manufactured.
【００３２】以上のようにして作製された偏平形電池に
ついて耐漏液特性を調べた。The liquid leakage resistance of the flat battery thus manufactured was examined.
【００３３】耐漏液特性は、同様にして作製された各電
池５０個を、温度４５℃、湿度９３％の条件下で、８０
日間、１００日間、１２０日間及び１４０日間保存し、
保存後、漏液が発生している電池の個数を測定すること
で調べた。なお、漏液の発生状況の観察は、倍率１０倍
での顕微鏡観察によって行った。その結果を表１に示
す。The liquid leakage resistance was 50 when each of the 50 batteries produced in the same manner was tested under the conditions of a temperature of 45 ° C. and a humidity of 93%.
Stored for 100 days, 120 days and 140 days,
After storage, it was examined by measuring the number of batteries in which liquid leakage had occurred. It should be noted that the occurrence of liquid leakage was observed under a microscope at a magnification of 10 times. Table 1 shows the results.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１に示すように、正極合剤に銀・ニッケ
ライトが混合されている実施例１の電池は、１４０日保
存後においても一つの電池にも漏液が発生していない。
これに対して、正極合剤に銀・ニッケライトを混合して
いない比較例１の電池は、１２０日保存後で既に３個の
電池に漏液が発生し、１４０日保存後には１０個の電池
に漏液が発生してしまう。As shown in Table 1, in the battery of Example 1 in which silver / nickelite was mixed in the positive electrode mixture, no leakage occurred in one battery even after storage for 140 days.
On the other hand, in the battery of Comparative Example 1 in which the positive electrode mixture was not mixed with silver / nickelite, three batteries leaked after 120 days of storage and 10 batteries after 140 days of storage. Battery leaks.
【００３６】このことから、正極合剤に銀・ニッケライ
トを混合することは、電池のかしめ工程による正極合剤
の沈み込みを抑え、電池の耐漏液特性を改善する上で有
効であることがわかった。Therefore, it is effective to mix silver / nickelite in the positive electrode mixture in order to prevent the positive electrode mixture from sinking due to the caulking process of the battery and to improve the leakage resistance of the battery. all right.
【００３７】次に、作製された電池について放電容量を
測定した。Next, the discharge capacity of the manufactured battery was measured.
【００３８】なお、放電容量の測定は、負荷抵抗３０ｋ
Ωで、終止電圧０．９Ｖまで連続放電することで行っ
た。測定電池個数は５個である。その結果を表２に示
す。The discharge capacity is measured with a load resistance of 30 k.
It was performed by continuously discharging to a final voltage of 0.9 V with Ω. The number of measurement batteries is 5. The results are shown in Table 2.
【００３９】[0039]
【表２】 [Table 2]
【００４０】表２に示すように、実施例１の電池の放電
容量が２９．１ｍＡｈであるのに対して、比較例１の電
池の放電容量は２４．４ｍＡｈと小さい値になってい
る。As shown in Table 2, the discharge capacity of the battery of Example 1 was 29.1 mAh, whereas the discharge capacity of the battery of Comparative Example 1 was a small value of 24.4 mAh.
【００４１】このように比較例１の電池で放電容量が小
さくなるのは、比較例１の電池では、銀・ニッケライト
を混合しない代わりに、かさ密度の小さいグラファイト
が導電剤として混合されており、そのため活物質充填率
が小さくなるからである。As described above, the discharge capacity of the battery of Comparative Example 1 becomes smaller because the battery of Comparative Example 1 does not contain silver / nickelite but contains graphite having a low bulk density as a conductive agent. Therefore, the active material filling rate is reduced.
【００４２】このことから、正極合剤に銀・ニッケライ
トを混合することは、電池のかしめ工程による正極合剤
の沈み込みを抑えるとともに、電池容量を確保する上で
も有利であることがわかった。From the above, it was found that mixing silver / nickelite in the positive electrode mixture is advantageous not only for preventing the positive electrode mixture from sinking due to the caulking process of the battery but also for ensuring the battery capacity. .
【００４３】銀・ニッケライトの混合率の検討 銀・ニッケライトの最適混合率を調べるために、銀・ニ
ッケライトの混合率を各種変化させた正極合剤を作製
し、圧縮成形性を調べた。また。正極缶に収容する正極
合剤をこのように作製した正極合剤に置き換えて実施例
１と同じタイプの偏平形電池を作製し、電流特性、耐漏
液特性を調べた。 Examination of Mixing Ratio of Silver / Nickelite In order to investigate the optimum mixing ratio of silver / nickelite, a positive electrode mixture having various mixing ratios of silver / nickelite was prepared and its compression moldability was examined. . Also. The positive electrode mixture housed in the positive electrode can was replaced with the positive electrode mixture prepared in this way to prepare a flat battery of the same type as in Example 1, and the current characteristics and the leakage resistance characteristics were examined.
【００４４】圧縮成形性は、正極混合物を所定の容積に
圧縮するのに要した圧力を測定することで調べた。The compression moldability was examined by measuring the pressure required to compress the positive electrode mixture to a predetermined volume.
【００４５】電流特性は、温度−１０℃下、０％，４０
％，８０％の放電深度で、負荷抵抗２ｋΩで５秒間放電
を行い、その際の最低電圧（閉路電圧）を測定すること
によって評価した。測定電池数は２０個である。The current characteristic is 0%, 40% at a temperature of -10 ° C.
% And 80% of the depth of discharge, discharge was carried out for 5 seconds with a load resistance of 2 kΩ, and the lowest voltage (closed circuit voltage) at that time was measured for evaluation. The number of measurement batteries is 20.
【００４６】また、耐漏液特性の評価は上述と同様の条
件で行った。The evaluation of the liquid leakage resistance property was conducted under the same conditions as described above.
【００４７】電流特性（電池２０個の平均値）、耐漏液
特性、圧縮成形性を表３、表４、表５にそれぞれ示す。The current characteristics (average value of 20 batteries), leakage resistance characteristics and compression moldability are shown in Tables 3, 4 and 5, respectively.
【００４８】[0048]
【表３】 [Table 3]
【００４９】[0049]
【表４】 [Table 4]
【００５０】[0050]
【表５】 [Table 5]
【００５１】まず、電流特性を示す表３を見ると、正極
合剤に銀・ニッケライトを３重量％以上、好ましくは５
重量％以上混合することにより、十分な閉路電圧が得ら
れるようになることがわかる。銀・ニッケライトの混合
率が３重量％未満になると、銀・ニッケライトによる導
電性付与効果が不足し、閉路電圧を十分に高めることが
できない。First, referring to Table 3 showing the current characteristics, 3% by weight or more, preferably 5% by weight of silver / nickelite was added to the positive electrode mixture.
It can be seen that a sufficient closed circuit voltage can be obtained by mixing in an amount of not less than wt%. If the mixing ratio of silver / nickelite is less than 3% by weight, the effect of imparting conductivity by silver / nickelite is insufficient and the closed circuit voltage cannot be sufficiently increased.
【００５２】次に、耐漏液特性を示す表４を見ると、耐
漏液特性は正極合剤に銀・ニッケライトを１重量％以上
混合することにより改善されている。Next, referring to Table 4 showing the liquid leakage resistance property, the liquid leakage resistance property is improved by mixing 1% by weight or more of silver / nickelite in the positive electrode mixture.
【００５３】一方、圧縮成形性を示す表５を見ると、正
極合剤に混合する銀・ニッケライトの混合率があまり大
きくなると、硬度がかなり高くなることから圧縮成形に
大きな圧力が必要となることがわかる。一般に、外径６
ｍｍ程度の電池では、正極合剤の成形は３ｔｏｎ／ｃｍ
2以下の圧力で行われる。なぜなら、それ以上の圧力で
正極合剤を成形しようとすると、成形用のパンチが変形
してしまうからである。正極合剤に銀・ニッケライトを
２０重量％を越えて混合した場合、硬度がそのようなパ
ンチの変形を生じせしめる域に達してしまう。なお、銀
・ニッケライトの混合量増により、成形圧力が高くなる
原因は、酸化銀よりも銀・ニッケライトの方がかさ密度
が低いためである。On the other hand, referring to Table 5 showing the compression moldability, when the mixing ratio of silver / nickelite mixed in the positive electrode mixture becomes too large, the hardness becomes considerably high, and thus a large pressure is required for the compression molding. I understand. Generally, outer diameter 6
For a battery of about mm, molding of the positive electrode mixture is 3 ton / cm
It is performed at a pressure of 2 or less. This is because if the positive electrode mixture is to be formed with a pressure higher than that, the forming punch will be deformed. When silver / nickelite is mixed in the positive electrode mixture in an amount of more than 20% by weight, the hardness reaches a range that causes such punch deformation. The reason why the molding pressure is increased by increasing the mixing amount of silver / nickelite is that the bulk density of silver / nickelite is lower than that of silver oxide.
【００５４】以上のように、電流特性、耐漏液特性を改
善するには銀・ニッケライトの混合率は５重量％以上で
あることが望ましいが、圧縮成形性を考慮すると銀・ニ
ッケライトの混合率は２０重量％以下に抑える必要があ
る。したがって、これら電流特性、耐漏液特性及び圧縮
成形性の両立の観点から、銀・ニッケライトの混合率は
５〜２０重量％とするのが好ましい。As described above, it is desirable that the mixing ratio of silver and nickelite is 5% by weight or more in order to improve the current characteristics and the liquid leakage resistance, but considering the compression moldability, the mixture of silver and nickelite is preferable. The rate must be kept below 20% by weight. Therefore, from the viewpoint of satisfying both the current characteristics, the leakage resistance characteristics and the compression moldability, the mixing ratio of silver and nickelite is preferably 5 to 20% by weight.
【００５５】樹脂の混合率の検討 樹脂の最適混合率を調べるために、ＰＴＦＥの混合率を
各種変化させて正極合剤を作製し、縁欠け発生率、質量
のバラツキを調べた。また、正極缶に収容する正極合剤
をこのように作製した正極合剤に置き換えて実施例１と
同じタイプの偏平形電池を作製し、電流特性を調べた。 Examination of Resin Mixing Ratio In order to examine the optimum resin mixing ratio, various positive electrode mixing agents were prepared by varying the PTFE mixing ratio, and the edge chipping occurrence rate and the variation in mass were examined. In addition, the positive electrode mixture housed in the positive electrode can was replaced with the positive electrode mixture prepared in this way to prepare a flat battery of the same type as in Example 1, and the current characteristics were examined.
【００５６】正極合剤の縁欠け発生率および質量のばら
つきは、正極合剤１００個について調べた。電流特性の
評価は、上述と同様の条件で行った。The occurrence of edge defects and the variation in mass of the positive electrode mixture were examined for 100 positive electrode mixture. The current characteristics were evaluated under the same conditions as above.
【００５７】正極合剤の縁欠け発生率、質量のばらつ
き、電池の電流特性の調査結果を表６、表７、表８にそ
れぞれ示す。Tables 6, 7, and 8 show the results of investigations on the occurrence of edge chipping of the positive electrode mixture, variations in mass, and current characteristics of the battery.
【００５８】[0058]
【表６】 [Table 6]
【００５９】[0059]
【表７】 [Table 7]
【００６０】[0060]
【表８】 [Table 8]
【００６１】まず、正極合剤の縁欠け発生率を示す表６
及び正極合剤の質量バラツキを示す表７を見ると、正極
合剤の縁欠けおよび質量のばらつきを十分に抑えるに
は、ＰＴＦＥを０．３重量％以上の混合率で混合する必
要があることがわかる。First, Table 6 showing the edge chipping occurrence rate of the positive electrode mixture.
Also, referring to Table 7 showing the variation in the mass of the positive electrode mixture, it is necessary to mix PTFE at a mixing ratio of 0.3% by weight or more in order to sufficiently suppress the edge chipping and the variation in the mass of the positive electrode mixture. I understand.
【００６２】一方、電流特性を示す表８を見ると、ＰＴ
ＦＥの混合率が５重量％を越えると、閉路電圧が小さく
なり、電流特性が劣化することがわかる。これは、ＰＴ
ＦＥの割合が増えることで正極合剤の導電性が低下する
とともに、溌水性が高まるからと推察される。On the other hand, looking at Table 8 showing the current characteristics, PT
It can be seen that when the mixing ratio of FE exceeds 5% by weight, the closed circuit voltage becomes small and the current characteristics deteriorate. This is PT
It is presumed that the conductivity of the positive electrode mixture is decreased and the water repellent property is increased by increasing the proportion of FE.
【００６３】したがって、正極合剤の縁欠けおよび質量
のばらつきを防止し且つ電流特性を改善するには、正極
合剤に混合するフッ素系樹脂の混合率は０．３〜５重量
％が適当であることがわかった。Therefore, in order to prevent the edging of the positive electrode mixture and the variation in mass and to improve the current characteristics, the mixing ratio of the fluororesin to be mixed with the positive electrode mixture is suitably 0.3 to 5% by weight. I knew it was.
【００６４】[0064]
【発明の効果】以上の説明からも明らかなように、本発
明の偏平形アルカリ電池では、正極合剤が、酸化銀と２
０〜５０重量％の二酸化マンガン及び５〜２０重量％の
銀・ニッケライトよりなる正極活物質混合物と、結着材
とを加圧成形したものであるので、電池のかしめ工程に
よる正極合剤の沈み込みが抑えられ、正極合剤の沈み込
みによる電池内圧の上昇、電解液の漏液が防止できる。
また、銀・ニッケライトが活物質であるとともに導電剤
としても作用するので、正極合剤に他の導電剤を混合す
る必要がなく、その分大きな電池容量が得られる。As is apparent from the above description, in the flat alkaline battery of the present invention, the positive electrode mixture contains silver oxide and 2
Since a positive electrode active material mixture consisting of 0 to 50% by weight of manganese dioxide and 5 to 20% by weight of silver-nickelite and a binder are pressure-molded, the positive electrode mixture prepared by the caulking process of the battery is Sinking is suppressed, and the rise of the battery internal pressure and the electrolyte leakage due to the sinking of the positive electrode mixture can be prevented.
In addition, since silver / nickelite is an active material and also acts as a conductive agent, it is not necessary to mix another conductive agent with the positive electrode mixture, and accordingly a large battery capacity can be obtained.
【図１】本発明を適用した偏平形アルカリ電池の一構成
を示す断面図である。FIG. 1 is a cross-sectional view showing one configuration of a flat alkaline battery to which the present invention is applied.
【図２】従来の偏平形アルカリ電池において、正極合剤
のガスケットに押される部分が沈み込んでいる様子を示
す断面図である。FIG. 2 is a cross-sectional view showing a state in which a portion of a conventional flat alkaline battery pressed by a gasket of a positive electrode mixture is depressed.
１ 負極合剤 ２ 正極缶 ３ 負極カップ ４ ガスケット ５ セパレータ ６ 正極合剤 1 Negative Electrode Mixture 2 Positive Electrode Can 3 Negative Electrode Cup 4 Gasket 5 Separator 6 Positive Electrode Mixture
Claims (2)
の二酸化マンガン及び５〜２０重量％の銀・ニッケライ
トよりなる正極活物質混合物と、結着材とを加圧成形し
たものであることを特徴とする偏平形アルカリ電池。1. A positive electrode mixture containing silver oxide and 20 to 50% by weight.
A flat alkaline battery, characterized in that the positive electrode active material mixture consisting of manganese dioxide and 5-20% by weight of silver-nickelite and a binder are pressure-molded.
が０．３〜５重量％なる割合で混合されていることを特
徴とする請求項１記載の偏平形アルカリ電池。2. The flat alkaline battery according to claim 1, wherein the positive electrode mixture is mixed with a fluorine-based resin as a binder in a proportion of 0.3 to 5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29719194A JP3505823B2 (en) | 1994-11-30 | 1994-11-30 | Flat alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29719194A JP3505823B2 (en) | 1994-11-30 | 1994-11-30 | Flat alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08162100A true JPH08162100A (en) | 1996-06-21 |
| JP3505823B2 JP3505823B2 (en) | 2004-03-15 |
Family
ID=17843368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29719194A Expired - Fee Related JP3505823B2 (en) | 1994-11-30 | 1994-11-30 | Flat alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3505823B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1187236A2 (en) * | 2000-09-08 | 2002-03-13 | Sony Corporation | Alkaline battery |
| EP1675199A1 (en) * | 2004-12-27 | 2006-06-28 | Dowa Mining Co., Ltd. | Battery positive electrode material |
| JP2008258098A (en) * | 2007-04-09 | 2008-10-23 | Seiko Instruments Inc | Flat alkaline cell |
| WO2020149086A1 (en) * | 2019-01-15 | 2020-07-23 | Fdk株式会社 | Alkaline cell |
| CN113526572A (en) * | 2021-08-20 | 2021-10-22 | 上海蕴邦新材料有限公司 | Silver nickelate material and preparation method thereof |
-
1994
- 1994-11-30 JP JP29719194A patent/JP3505823B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1187236A2 (en) * | 2000-09-08 | 2002-03-13 | Sony Corporation | Alkaline battery |
| US6794082B2 (en) * | 2000-09-08 | 2004-09-21 | Sony Corporation | Alkaline battery |
| EP1187236A3 (en) * | 2000-09-08 | 2005-06-08 | Sony Corporation | Alkaline battery |
| EP1675199A1 (en) * | 2004-12-27 | 2006-06-28 | Dowa Mining Co., Ltd. | Battery positive electrode material |
| AU2005247037B2 (en) * | 2004-12-27 | 2011-01-27 | Dowa Mining Co., Ltd. | Battery positive electrode material |
| JP2008258098A (en) * | 2007-04-09 | 2008-10-23 | Seiko Instruments Inc | Flat alkaline cell |
| WO2020149086A1 (en) * | 2019-01-15 | 2020-07-23 | Fdk株式会社 | Alkaline cell |
| JPWO2020149086A1 (en) * | 2019-01-15 | 2021-11-25 | Fdk株式会社 | Alkaline battery |
| US11888163B2 (en) | 2019-01-15 | 2024-01-30 | Fdk Corporation | Alkaline battery |
| CN113526572A (en) * | 2021-08-20 | 2021-10-22 | 上海蕴邦新材料有限公司 | Silver nickelate material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3505823B2 (en) | 2004-03-15 |
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