JP2006134635A

JP2006134635A - Zinc air battery and apparatus using it

Info

Publication number: JP2006134635A
Application number: JP2004320388A
Authority: JP
Inventors: Machi Ohashi; 真智大橋; Yuichi Kikuma; 祐一菊間; Hitoshi Koda; 仁甲田
Original assignee: Toshiba Battery Co Ltd
Current assignee: FDK Twicell Co Ltd
Priority date: 2004-11-04
Filing date: 2004-11-04
Publication date: 2006-05-25

Abstract

<P>PROBLEM TO BE SOLVED: To provide a zinc air battery preventing standing deterioration and applicable to many-kind and wide range apparatuses. <P>SOLUTION: In the zinc air battery using oxygen in a positive electrode and zinc in a negative electrode and having an air hole for taking in oxygen on the bottom of a positive case, since deterioration caused by the outside air is prevented by shutting the outside air off the air hole by arranging a cup-shaped end part on the bottom of the positive case, a standing deterioration ratio can be decreased compared with a usual standing zinc air battery, and widening of the application of the zinc air battery is made possible. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、空気電池の未使用時に外気と電池を遮断し、使用環境の温度・湿度に起因する劣化を防止する空気電池とそれを用いた機器に関する。 The present invention relates to an air battery that shuts off outside air and the battery when the air battery is not in use and prevents deterioration due to temperature and humidity of the use environment, and a device using the air battery.

空気電池は単位体積当たりの容量が大きいことから、補聴器用やペイジャー用として使用されてきている。空気電池を高出力化する要望が高まり、正極側への酸素供給量を向上させることにより、重負荷でも放電可能な電池が開発されるようになってきている。 Air batteries have been used for hearing aids and pagers because of their large capacity per unit volume. There is a growing demand for higher output of air batteries, and by increasing the amount of oxygen supplied to the positive electrode, batteries that can be discharged even under heavy loads have been developed.

しかしながら、正極に大気中の酸素を取り入れるための空気孔を設けると、外気の温度・湿度と電池内の電解液の蒸気圧との関係によって、相対的に外気の湿度が高くなれば電解液は水分吸収により容量が増えて漏液し短寿命を引き起こす恐れがあり、逆に湿度が低くなれば電解液容量が減少して短寿命を引き起こす恐れがある。 However, if the positive hole is provided with an air hole for taking in oxygen in the atmosphere, the electrolyte solution will be better if the humidity of the outside air is relatively high due to the relationship between the temperature and humidity of the outside air and the vapor pressure of the electrolyte in the battery. There is a possibility that the capacity increases due to moisture absorption and the liquid leaks to cause a short life, and conversely, if the humidity is low, the electrolyte capacity may decrease and a short life may be caused.

これらの現象は一般的に放置劣化と呼ばれ、これを評価する尺度として放置劣化率が用いられる。放置劣化率は、一定の温度・湿度において、空気孔を塞いでいるシールテープや電池を密閉する袋を除いてから、直後に放電した場合に得られる持続時間を１００％として、同一の温度・湿度において一定期間放置した後に放電した場合に得られる持続時間が何％となるかで評価した値である。 These phenomena are generally called neglected deterioration, and the neglected deterioration rate is used as a scale for evaluating this phenomenon. The neglected deterioration rate is the same temperature / humidity at a constant temperature / humidity, with the duration obtained when discharging immediately after removing the sealing tape or airtight bag sealing the air hole as 100%. It is a value evaluated by what percentage the duration obtained when discharged after being left standing for a certain period of time in humidity.

従来の空気電池は、電池が使用される対象機器とその使用環境を予測して電池設計しており、必要とする出力から電池内への酸素の供給量を設計し、予想される使用環境から電解液の量、濃度、負極活物質との配合について設計することが一般的であった。したがって、機器に対する汎用性は乏しかった。 Conventional air batteries are designed by predicting the target equipment in which the battery will be used and the environment in which the battery is used, and designing the oxygen supply amount from the required output to the battery. It has been common to design the amount and concentration of the electrolytic solution and the blending with the negative electrode active material. Therefore, the versatility for equipment was poor.

また、特許文献１に開示しているように、機器の電源スイッチの開閉と連動して、空気電池の空気孔を開閉する方法が提案されているが、開閉手段を付加する分、収納ケースが大きくなってしまうという欠点があった。また開閉手段によっては密閉性が十分ではなく、空気電池の劣化防止効果も十分でない場合があった。
特公平５−２１３１３号公報 Further, as disclosed in Patent Document 1, a method for opening and closing the air hole of the air battery in conjunction with opening and closing of the power switch of the device has been proposed. There was a drawback of becoming larger. Further, depending on the opening / closing means, the sealing performance is not sufficient, and the effect of preventing the deterioration of the air battery may not be sufficient.
Japanese Patent Publication No. 5-21313

一方、電池を利用する側でも、長期に使用しない場合は言うに及ばず、毎日使用する場合でも夜間使用しないときは機器容器から電池を取り出してシールテープを貼ったり、袋に入れるなどして空気孔を密閉し、劣化を抑えることが一般的で電池の管理が非常に煩わしいという欠点があった。 On the other hand, on the battery side, it goes without saying that it will not be used for a long period of time, and even if it is used every day or when it is not used at night, take out the battery from the equipment container and put a sticker tape, put it in a bag, etc. It is common to seal the hole and suppress deterioration, and there is a drawback that battery management is very troublesome.

本発明は上記情況に対処するためになされたもので、その課題は空気電池におけるこのような設計上の制約条件や使用者側の煩わしさを、電池を使用する機器側、もしくは電池をセットする電池ホルダーなどの電池周辺部の設計によって回避し、空気電池の放置劣化をできるだけ防いで、より多種広範囲の機器で空気電池を使用可能とするもので、他種電池に比較して格段に大きい電池容量の体積効率を有効に活用できる空気電池の劣化防止手段を提供することである。 The present invention has been made in order to cope with the above-mentioned situation, and the problem is to set such a design constraint condition and annoyance of the user side of the air battery on the side of the device using the battery or the battery. This is avoided by the design of the battery periphery such as battery holder, and the air battery can be prevented from neglected deterioration as much as possible, so that the air battery can be used in a wider variety of devices. The battery is much larger than other types of batteries. An object of the present invention is to provide a means for preventing deterioration of an air battery that can effectively utilize the volumetric efficiency of capacity.

上記課題を解決するために、本発明は、酸素を正極、亜鉛を負極とし、該酸素を取り入れる空気孔を正極ケースの底面に持つ空気亜鉛電池において、前記空気孔の周辺をカップ形状体を用いて、その端部を正極ケース底面に配置して外気と空気孔を遮断することによって、外気の影響による劣化を防止するものである。 In order to solve the above-mentioned problems, the present invention uses a cup-shaped body around the air hole in an air zinc battery having oxygen as a positive electrode, zinc as a negative electrode, and an air hole for taking in the oxygen in the bottom surface of the positive electrode case. In addition, by disposing the end portion on the bottom surface of the positive electrode case and blocking the outside air and the air hole, deterioration due to the influence of outside air is prevented.

空気孔を塞ぐ方法としては、板状平面で空気孔を塞ぐか、あるいは柔軟性のある物質を用いて空気孔を塞ぐかが考えられるが、従来から使用されるシールテープは柔軟性に加えて粘着性もある物質を用いて空気孔を塞いでおり、この状態で販売されていることからも劣化を防止する方法としては極めて有効である。 As a method of closing the air hole, it is conceivable to block the air hole with a plate-like plane, or to close the air hole with a flexible material, but the sealing tape conventionally used is not only flexible. The air hole is blocked using a substance having adhesiveness, and since it is sold in this state, it is extremely effective as a method for preventing deterioration.

しかし、粘着性があるため使用時に空気孔を開けるために相応の剥離力が必要となり、現状の使用者側の煩わしさを軽減させるためには有効とは言えない。また、板状物質を用いても電池正極ケース側の形状は完全な平面とは言えず、さらに放電中に電池は若干の変形を起こすので、空気孔を十分に密閉することは非常に難しい。 However, since it has adhesiveness, a corresponding peeling force is required to open an air hole at the time of use, and it cannot be said to be effective in reducing the current user's troublesomeness. Further, even if a plate-like substance is used, the shape of the battery positive electrode case side cannot be said to be a perfect plane, and the battery is slightly deformed during discharge, so that it is very difficult to sufficiently seal the air holes.

さらに、この板状物質に柔軟性を持たせた場合は、柔軟性が小さければ十分に密閉させることはできず、大きければ使用時、空気孔を開けた時に、空気孔の周辺部に空気の拡散層を確保するために、板状物質を空気孔から大きく離す必要がある。このような構造は、使用機器の電池周辺部の構造としては大きすぎるので、実用的でなく更なる改良が必要である。 Furthermore, when this plate-like substance is made flexible, if the flexibility is small, it cannot be sealed sufficiently. In order to secure the diffusion layer, the plate-like substance needs to be largely separated from the air holes. Such a structure is too large as the structure of the battery peripheral part of the equipment used, and is not practical and requires further improvement.

このため、空気孔の周辺部を本発明のカップ形状体で覆うようにすると、空気孔の周辺部に空気の拡散層を確保し、かつ構造も小さくすることができる。ここで、本発明におけるカップ形状体とは、端部を電池に密着させる構造をいい、その形状は任意である。すなわち、お椀型でもよいし、コの字型でもよい。またリングと平面の組み合わせでもよいし、枡型でもよい。端部が電池に接していれば、密閉は可能となることから、例えばカップ状の端部を内側に折り返し、キャップやパッキングに接触させた場合においても空気孔を密閉することができる。 For this reason, when the peripheral part of the air hole is covered with the cup-shaped body of the present invention, an air diffusion layer can be secured in the peripheral part of the air hole and the structure can be reduced. Here, the cup-shaped body in the present invention refers to a structure in which the end is in close contact with the battery, and the shape thereof is arbitrary. That is, it may be bowl-shaped or U-shaped. Moreover, the combination of a ring and a plane may be sufficient, and a saddle type may be sufficient. If the end portion is in contact with the battery, sealing can be performed. Therefore, for example, even when the cup-shaped end portion is folded inward and brought into contact with a cap or packing, the air hole can be sealed.

また、本発明においては、ＰＲ２３３０タイプの空気亜鉛電池を２０℃−６０％ＲＨにおいて１００Ωで放電して得られた持続時間を１００％として、同じく３ヶ月間２０℃−６０％ＲＨにおいてシールテープを剥離した状態で放置した後に１００Ωで放電した時に得られる持続時間により劣化率を評価した。 In the present invention, the PR2330 type zinc-air battery is discharged at 100Ω at 20 ° C.-60% RH for 100%, and the sealing tape is applied at 20 ° C.-60% RH for 3 months. The deterioration rate was evaluated based on the duration obtained when discharged at 100Ω after being left in the peeled state.

さらに本発明は主に電池使用機器側の電池周辺部の設計について、特に放置劣化の防止の対策としてなされており、電池使用時において酸素を電池内へ供給する方法については、端部を電池から離しても、カップ形状体の一部に開閉式の空気導入部が設置されるように構成してもよい。 Furthermore, the present invention is mainly designed for the battery peripheral design on the battery-using device side, particularly as a measure to prevent neglected deterioration. For the method of supplying oxygen into the battery when the battery is used, the end is connected from the battery. Even if it separates, you may comprise so that an opening-and-closing type air introduction part may be installed in a part of cup-shaped body.

このような放置劣化防止手段は空気電池を使用する機器だけでなく、これを機器に装着することを目的とした電池ホルダーや、空気電池を貯蔵するための電池ケースにも適用することができる。 Such neglected deterioration preventing means can be applied not only to a device using an air battery, but also to a battery holder for mounting the device on a device and a battery case for storing an air battery.

本発明の空気亜鉛電池によると、通常の単なる放置に比較して放置劣化率を小さくすることができるという効果を奏する。 According to the air zinc battery of the present invention, there is an effect that the leaving deterioration rate can be reduced as compared with ordinary mere leaving.

以下、本発明の実施の形態を、図を参照して説明する。
図１は本発明が適用される空気亜鉛電池の断面図である。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a sectional view of a zinc-air battery to which the present invention is applied.

図１に示すように、本空気亜鉛電池は、正極に大気中の酸素を取り込むための空気孔２を設けた正極ケース１と、負極に集電と封口を兼ねる負極ケース１１とをガスケット１２を介して嵌合することで密閉構造とされている。負極ケース１１の内部に、亜鉛粉と電解液（水酸化カリウム水溶液）からなるゲル負極１０が収納されている。 As shown in FIG. 1, the present zinc-air battery has a positive electrode case 1 provided with an air hole 2 for taking in atmospheric oxygen in the positive electrode, and a negative electrode case 11 serving both as a current collector and a seal for the negative electrode. It is set as the sealing structure by fitting via. A gel negative electrode 10 made of zinc powder and an electrolytic solution (potassium hydroxide aqueous solution) is housed inside the negative electrode case 11.

この電池のゲル負極１０は、電解液として３０質量％の水酸化カリウム水溶液、亜鉛粉として１％の水銀と５００ｐｐｍの鉛を合金として含みかつ粒度が１００〜３００μｍの汞化亜鉛粉を用い、この電解液と亜鉛粉の重量比を亜鉛粉１ｋｇに対して電解液２５０ｇとした。これらの材料とゲル化剤としてのポリアクリル酸とを混合してゲル状とし、ゲル負極とした。 The gel negative electrode 10 of this battery uses 30% by mass potassium hydroxide aqueous solution as an electrolyte, 1% mercury and 500 ppm lead as an alloy as a zinc powder, and zinc halide powder having a particle size of 100 to 300 μm. The weight ratio of the electrolytic solution to zinc powder was 250 g of electrolytic solution with respect to 1 kg of zinc powder. These materials and polyacrylic acid as a gelling agent were mixed to obtain a gel negative electrode.

一方、正極側は、底面に０．５ｍｍの空気孔２を６個有する正極ケース１と、その内部に載置された撥水膜（ＰＴＦＥ膜）４、酸素還元電極およびセパレータ７からなっている。この酸素還元電極は、活性炭、マンガン酸化物、導電材、ＰＴＦＥ粉からなる正極触媒粉をシート状に成形した正極触媒層６をニッケルメッキされたステンレスネット製の正極集電体５に圧着充填することにより一体化されたものである。更に、撥水膜４とは別の撥水層（ＰＴＦＥ膜）が圧着されている。 On the other hand, the positive electrode side is composed of a positive electrode case 1 having six air holes 2 of 0.5 mm on the bottom surface, a water-repellent film (PTFE film) 4 placed therein, an oxygen reduction electrode, and a separator 7. . In this oxygen reduction electrode, a positive electrode catalyst layer 6 in which a positive electrode catalyst powder made of activated carbon, manganese oxide, a conductive material, and PTFE powder is formed into a sheet shape is press-fitted into a nickel-plated stainless steel positive electrode current collector 5. Is integrated. Further, a water repellent layer (PTFE film) separate from the water repellent film 4 is bonded.

拡散紙３は空気孔２を覆うように正極ケース１の内側に載置されており、正極ケース１は拡散紙３の径に合わせて、底面で絞り込んでいる。このため、正極ケース１は電池底面で段差を持ち、電池の最外径は２３ｍｍであるが、拡散紙３付近の正極ケース１の段部外径は２０ｍｍであり、段部厚さは０．１ｍｍである。 The diffusion paper 3 is placed inside the positive electrode case 1 so as to cover the air holes 2, and the positive electrode case 1 is narrowed down at the bottom according to the diameter of the diffusion paper 3. For this reason, the positive electrode case 1 has a step at the bottom of the battery, and the outermost diameter of the battery is 23 mm. However, the outer diameter of the step portion of the positive electrode case 1 near the diffusion paper 3 is 20 mm and the step portion thickness is 0. 1 mm.

図２は本発明の劣化防止具の断面図である。この劣化防止具は電池の空気孔２に対応する位置にそれぞれシリコンゴム製のカップ形状体２０を円形の塩ビ板２１に貼り付け配置したものである。 FIG. 2 is a cross-sectional view of the deterioration preventing device of the present invention. This deterioration prevention tool is obtained by attaching a cup-shaped body 20 made of silicon rubber to a circular PVC plate 21 at a position corresponding to the air hole 2 of the battery.

図３は本発明の他の劣化防止具の断面図である。この劣化防止具はシリコンゴムの１つのカップ形状体２０ａを円形の塩ビ板２１に貼り付けている。 FIG. 3 is a cross-sectional view of another deterioration preventing device of the present invention. In this deterioration prevention tool, one cup-shaped body 20 a made of silicon rubber is attached to a circular PVC plate 21.

図４は図２の劣化防止具を電池の正極ケース外底面に配置した状態を示す。すなわち劣化防止具のカップ形状体２０を電池の正極ケース１の底部に設けた空気孔２に一致するように配設して外気と遮断した状態を示しており、図５は、図３の劣化防止具のカップ形状体２０ａを電池の正極ケース１の底部に設けた空気孔２を塞ぐように貼り付けた状態を示したものである。１つのカップ形状体２０ａで空気孔２を塞ぐので、容易に電池内と外気とを遮断することができる。 FIG. 4 shows a state in which the deterioration prevention tool of FIG. 2 is arranged on the bottom surface of the positive electrode case of the battery. That is, the cup-shaped body 20 of the deterioration preventing device is disposed so as to coincide with the air hole 2 provided at the bottom of the positive electrode case 1 of the battery, and is shown in a state where it is blocked from the outside air. FIG. The state which affixed the cup-shaped body 20a of a prevention tool so that the air hole 2 provided in the bottom part of the positive electrode case 1 of a battery might be plugged up is shown. Since the air hole 2 is closed by the single cup-shaped body 20a, the inside of the battery and the outside air can be easily blocked.

以下、実施例、従来例および比較例について具体的に説明する。
（従来例１）
空気亜鉛電池（ＰＲ２３３０）１０個を２０℃−６０％ＲＨに３ヶ月間放置し、その後１００Ωで放電して、放置前の持続時間を１００％としてその劣化率を計算した。電池は正極ケースの空気孔が下になるように平地に設置して放置した。平地の材質は塩化ビニルを用いた。
（従来例２）
従来例１において電池の空気孔を上にして、放置した以外は従来例１と同様にした。 Examples, conventional examples, and comparative examples will be specifically described below.
(Conventional example 1)
Ten air zinc batteries (PR2330) were left at 20 ° C.-60% RH for 3 months, then discharged at 100Ω, and the deterioration rate was calculated with the duration before being left as 100%. The battery was left on the flat ground with the air hole of the positive electrode case facing down. The material of the flat ground was vinyl chloride.
(Conventional example 2)
Conventional Example 1 was the same as Conventional Example 1 except that the air hole of the battery was turned up and left standing.

（比較例１）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り１００ｇを載せ、従来例１と同様に放置した。 (Comparative Example 1)
Place the air hole of the zinc-air battery (PR2330) on top, place a plate made of vinyl chloride with a diameter of 25 mm and a thickness of 0.5 mm on it, place a 100 g iron weight on it, and leave it as in Conventional Example 1 did.

（比較例２）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り５０ｇを載せ、従来例１と同様に放置した。 (Comparative Example 2)
Place the air hole of the zinc-air battery (PR2330) on top, place a plate made of vinyl chloride with a diameter of 25 mm and a thickness of 0.5 mm on it, place a 50 g weight of iron on it, and leave it in the same way as in Conventional Example 1 did.

（比較例３）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、従来例１と同様に放置した。 (Comparative Example 3)
The air hole of the air zinc battery (PR2330) was placed on top, and a plate made of vinyl chloride having a diameter of 25 mm and a thickness of 0.5 mm was placed on the air hole.

（比較例４）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その上にφ２５、厚さ０．５ｍｍのシリコンゴム製の板を置き、従来例１と同様に放置した。 (Comparative Example 4)
A silicon rubber plate having a diameter of 25 mm and a thickness of 0.5 mm was placed on the air hole of the zinc-air battery (PR2330), and the plate was left as in Conventional Example 1.

（実施例１）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その空気孔個々の周辺に厚さ０．５ｍｍ、外径φ１．０、内径φ０．７のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り１００ｇを載せ、従来例１と同様に放置した。 Example 1
With the air holes of the air zinc battery (PR2330) facing upward, a silicon rubber ring having a thickness of 0.5 mm, an outer diameter of φ1.0, and an inner diameter of φ0.7 is placed around each of the air holes. A vinyl chloride plate having a thickness of 0.5 mm was placed, an iron weight 100 g was placed thereon, and the plate was left in the same manner as in Conventional Example 1.

（実施例２）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その空気孔個々の周辺に厚さ０．５ｍｍ、外径φ１．０、内径φ０．７のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り５０ｇを載せ、従来例１と同様に放置した。 (Example 2)
With the air holes of the air zinc battery (PR2330) facing upward, a silicon rubber ring having a thickness of 0.5 mm, an outer diameter of φ1.0, and an inner diameter of φ0.7 is placed around each of the air holes. A vinyl chloride plate having a thickness of 0.5 mm was placed, and an iron weight of 50 g was placed thereon, and the plate was left in the same manner as in Conventional Example 1.

（実施例３）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、その空気孔個々の周辺に厚さ０．５ｍｍ、外径φ１．０、内径φ０．７のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、従来例１と同様に放置した。 (Example 3)
With the air holes of the air zinc battery (PR2330) facing upward, a silicon rubber ring having a thickness of 0.5 mm, an outer diameter of φ1.0, and an inner diameter of φ0.7 is placed around each of the air holes. A plate made of vinyl chloride having a thickness of 0.5 mm was placed and left in the same manner as in Conventional Example 1.

（実施例４）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、正極ケースの上に、全ての空気孔を囲む様に厚さ０．５ｍｍ、外径φ２０、内径φ１６のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り１００ｇを載せ、従来例１と同様に放置した。 Example 4
Place a silicon rubber ring with a thickness of 0.5mm, an outer diameter of φ20, and an inner diameter of φ16 on the positive electrode case so that all the air holes are surrounded, with the air hole of the zinc-air battery (PR2330) facing upward. A vinyl chloride plate having a diameter of 25 mm and a thickness of 0.5 mm was placed on the plate, and an iron weight 100 g was placed on the plate and left as in Conventional Example 1.

（実施例５）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、正極ケースの上に、全ての空気孔を囲む様に厚さ１ｍｍ、外径φ２０、内径φ１６のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り１００ｇを載せ、従来例１と同様に放置した。 (Example 5)
A silicon rubber ring having a thickness of 1 mm, an outer diameter of φ20, and an inner diameter of φ16 is placed on the positive electrode case so as to surround all the air holes, with the air hole of the zinc-air battery (PR2330) facing up, and on that, a φ25 Then, a vinyl chloride plate having a thickness of 0.5 mm was placed, and an iron weight 100 g was placed thereon and left as in the conventional example 1.

（実施例６）
空気亜鉛電池（ＰＲ２３３０）の空気孔を上にして、正極ケースの上に、全ての空気孔を囲む様に厚さ１ｍｍ、外径φ２５、内径φ２２のシリコンゴム製リングを置き、その上にφ２５、厚さ０．５ｍｍの塩化ビニル製の板を置き、その上に鉄製の重り１００ｇを載せ、従来例１と同様に放置した。 (Example 6)
A silicon rubber ring having a thickness of 1 mm, an outer diameter of φ25, and an inner diameter of φ22 is placed on the positive electrode case so as to surround all the air holes, with the air hole of the zinc-air battery (PR2330) facing up, and φ25 on it. Then, a vinyl chloride plate having a thickness of 0.5 mm was placed, and an iron weight 100 g was placed thereon and left as in the conventional example 1.

以上の試験結果を表１にまとめて示した。なお、放置空気亜鉛電池（ＰＲ２３３０）の１００Ω放電の持続時間はｎ＝１０の平均で８１時間であった。劣化率(Ｙ)は放置の結果得られた持続時間を(Ｘ)として(Ｙ)＝(８１−(Ｘ))÷８１×１００：％で計算した。

The above test results are summarized in Table 1. The duration of 100Ω discharge of the left-air zinc battery (PR2330) was 81 hours on the average of n = 10. The deterioration rate (Y) was calculated as (Y) = (81− (X)) ÷ 81 × 100:%, where (X) was the duration obtained as a result of the standing.

表１の試験結果から、実施例１〜６は従来例１〜２、比較例１〜４に比較して、劣化率が明らかに改善されている。実施例の中では実施例３が比較的劣化が大きいことから、本発明のカップ形状体に加えてこれを正極ケースに向けて加圧し、より密着させることにより、密閉性が向上して、より確実に劣化率を低下させることができることも示唆されている。 From the test results in Table 1, the deterioration rates of Examples 1 to 6 are clearly improved as compared with Conventional Examples 1 and 2 and Comparative Examples 1 to 4. Among the examples, since Example 3 is relatively largely deteriorated, in addition to the cup-shaped body of the present invention, this is pressurized toward the positive electrode case, and more closely adhered, thereby improving the sealing performance, and more It has also been suggested that the deterioration rate can be reliably reduced.

また、比較例の中では、比較例４の劣化が小さいが、実施例の電池に比較した場合には十分な改善がなされていない。電池の正極ケースの底面の形状は完全な平面ではなく、形状の歪みによる影響で、実施例の電池に比較して密閉性が劣ると考えられる。２つの従来例を比較した場合には、空気孔を上にして放置した場合が最も劣化が大きく、下にした場合は比較例１〜３と同等の劣化率であった。これも密閉性の違いによると考えられる。 Further, among the comparative examples, the deterioration of the comparative example 4 is small, but sufficient improvement is not made when compared with the battery of the example. The shape of the bottom surface of the positive electrode case of the battery is not a perfect plane, and is considered to be inferior in sealing performance compared to the battery of the example due to the influence of the distortion of the shape. When the two conventional examples were compared, the deterioration was greatest when the air holes were left facing up, and the deterioration rate was the same as in Comparative Examples 1 to 3 when the air holes were lowered. This is also considered to be due to the difference in sealing properties.

本発明に係る空気亜鉛電池の断面図。Sectional drawing of the air zinc battery which concerns on this invention. 本発明で用いた個々の空気孔を塞ぐ劣化防止具の側面図。The side view of the deterioration prevention tool which plugs up each air hole used by the present invention. 本発明で用いた全ての空気孔を塞ぐ他の劣化防止具の側面図。The side view of the other deterioration prevention tool which plugs up all the air holes used by this invention. 図２の劣化防止具で空気亜鉛電池の空気孔を塞いだ状態を示す底面図。The bottom view which shows the state which closed the air hole of the air zinc battery with the deterioration prevention tool of FIG. 図３の劣化防止具で空気亜鉛電池の空気孔を塞いだ状態を示す底面図。The bottom view which shows the state which plugged up the air hole of the air zinc battery with the deterioration prevention tool of FIG.

符号の説明Explanation of symbols

１…正極ケース、２…空気孔、３…拡散紙、４…第１の撥水層、５…集電体、６…正極触媒層、７…セパレータ、８…第２の撥水層、１０…ゲル負極、１１…負極ケース、１２…ガスケット、１３…シールテープ、２０，２０ａ…カップ形状体、２１…塩ビ板。

DESCRIPTION OF SYMBOLS 1 ... Positive electrode case, 2 ... Air hole, 3 ... Diffusion paper, 4 ... 1st water repellent layer, 5 ... Current collector, 6 ... Positive electrode catalyst layer, 7 ... Separator, 8 ... 2nd water repellent layer, 10 DESCRIPTION OF SYMBOLS ... Gel negative electrode, 11 ... Negative electrode case, 12 ... Gasket, 13 ... Seal tape, 20, 20a ... Cup-shaped body, 21 ... PVC board.

Claims

酸素を正極、亜鉛を負極とし、該酸素を取り入れる空気孔を正極ケースの底面に持つ空気亜鉛電池において、カップ形状体の端部を前記正極ケース底面に配置することによって外気と前記空気孔を遮断して外気の影響による劣化を防止することを特徴とした空気亜鉛電池。 In a zinc-air battery that uses oxygen as the positive electrode and zinc as the negative electrode and has air holes for taking in the oxygen in the bottom surface of the positive electrode case, the outside air and the air holes are blocked by placing the end of the cup-shaped body on the bottom surface of the positive electrode case. A zinc-air battery characterized by preventing deterioration due to the influence of outside air.

前記カップ形状体の断面が湾曲型またはコの字型であることを特徴とする請求項１記載の空気亜鉛電池。 The zinc-air battery according to claim 1, wherein the cup-shaped body has a curved or U-shaped cross section.

前記カップ形状体の正極ケースの底面に接する端部もしくはその全部がシリコンゴム製であることを特徴とする請求項１記載の空気亜鉛電池。 2. The zinc-air battery according to claim 1, wherein an end portion of the cup-shaped body contacting the bottom surface of the positive electrode case or the entirety thereof is made of silicon rubber.

カップ形状体が帯状の突出部と平面部とから構成されていることを特徴とする請求項１記載の空気亜鉛電池。 2. The zinc-air battery according to claim 1, wherein the cup-shaped body is composed of a belt-like projecting portion and a flat portion.

カップ形状体がリング状のゴムと任意の板状物とから構成されていることを特徴とする請求項１記載の空気亜鉛電池。 2. The zinc-air battery according to claim 1, wherein the cup-shaped body is composed of a ring-shaped rubber and an arbitrary plate-like material.

２つ以上の空気孔を１つのカップ形状体を用いて外気と遮断させることを特徴とする請求項１記載の空気亜鉛電池。 2. The zinc-air battery according to claim 1, wherein two or more air holes are blocked from outside air by using one cup-shaped body.

カップ形状物を加圧することにより、その端部を正極ケースに密着させることを特徴とする請求項１記載の空気亜鉛電池。 2. The zinc-air battery according to claim 1, wherein the cup-shaped object is pressed to bring its end into close contact with the positive electrode case.

請求項１記載の空気亜鉛電池を電源として内臓する機器において、該カップ形状体の一部を開けるかまたは離して酸素を電池に供給させることを特徴とする機器。

2. A device comprising the zinc-air battery as a power source according to claim 1, wherein a part of the cup-shaped body is opened or separated to supply oxygen to the battery.