JP2003151647A - Air battery - Google Patents
Air batteryInfo
- Publication number
- JP2003151647A JP2003151647A JP2002245118A JP2002245118A JP2003151647A JP 2003151647 A JP2003151647 A JP 2003151647A JP 2002245118 A JP2002245118 A JP 2002245118A JP 2002245118 A JP2002245118 A JP 2002245118A JP 2003151647 A JP2003151647 A JP 2003151647A
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- Japan
- Prior art keywords
- air
- negative electrode
- positive electrode
- electrode
- area
- 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.)
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Classifications
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- Y02E60/128—
Landscapes
- Hybrid Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、空気電池の特性改
善に関するものである。TECHNICAL FIELD The present invention relates to improvement of characteristics of an air battery.
【０００２】[0002]
【従来の技術】金属類を負極とし、空気中の酸素を正極
とする空気電池は、正極作用物質を電池内に詰め込む必
要がないために、同じ大きさの電池であれば負極作用物
質をより多く詰め込むことが可能で、アルカリマンガン
電池や酸化銀電池に比較して大容量が得られるという特
徴があり、需要が拡大してきている。最近では、デジタ
ル開路を用いた携帯機器の発達により、さらに高容量化
・高出力化が求められ、それとともに過放電漏液・貯蔵
漏液の防止に対する信頼性の要求が高まっている。2. Description of the Related Art In an air battery in which metals are used as a negative electrode and oxygen in the air is used as a positive electrode, it is not necessary to pack the positive electrode active substance in the battery. Demand is expanding because it can be packed in large quantities and has a feature that a large capacity can be obtained compared to alkaline manganese batteries and silver oxide batteries. Recently, due to the development of mobile devices using digital circuit, higher capacity and higher output have been demanded, and along with this, there has been an increasing demand for reliability in preventing over-discharge leakage and storage leakage.
【０００３】次に一般的な空気電池の構造について説明
する。図１はボタンタイプの空気電池の断面図である。
正極ケース２の底面には酸素を取り入れる空気孔１があ
り、正極ケース２の内面上段に、拡散紙３、撥水膜４、
正極触媒層５及びセパレータ６が収納されている。正極
触媒層５は活性炭、マンガン酸化物、導電材、ＰＴＦＥ
（ポリテトラフルオロエチレン）粉からなる正極触媒粉
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７に圧着充填して一体化したものであり、この正極触
媒層５に撥水膜４が圧着されている。さらに、正極触媒
シートと圧着された撥水膜４とは別の撥水膜８が、セパ
レータと反対面に配置されている。Next, the structure of a general air battery will be described. FIG. 1 is a sectional view of a button type air battery.
An air hole 1 for taking in oxygen is provided on the bottom surface of the positive electrode case 2, and a diffusion paper 3, a water repellent film 4,
The positive electrode catalyst layer 5 and the separator 6 are housed. The positive electrode catalyst layer 5 is made of activated carbon, manganese oxide, conductive material, PTFE
A positive electrode catalyst powder made of (polytetrafluoroethylene) powder is pressure-filled and integrated with a nickel-plated stainless steel positive electrode current collector 7, and a water-repellent film 4 is pressure-bonded to the positive electrode catalyst layer 5. Has been done. Further, a water-repellent film 8 different from the water-repellent film 4 that is pressure-bonded to the positive electrode catalyst sheet is arranged on the surface opposite to the separator.
【０００４】セパレータの上部には、絶縁ガスケット９
を介して、ニッケル−ステンレス−銅の三層クラッド材
を成形加工した負極ケース１０が配されており、通常は
絶縁ガスケットと負極ケースとの間には、電解液の漏液
防止のために、ポリアミド樹脂等のシール剤が塗布され
ている。さらに負極ケース内部にはゲル状の負極作用物
質１１が充填され、セパレータに接している。An insulating gasket 9 is provided on the top of the separator.
Via, the negative electrode case 10 formed by processing a nickel-stainless steel-copper three-layer clad material is arranged. Normally, between the insulating gasket and the negative electrode case, in order to prevent leakage of the electrolytic solution, A sealant such as polyamide resin is applied. Further, a gelled negative electrode active material 11 is filled in the negative electrode case and is in contact with the separator.
【０００５】充填されるゲル状負極は、作用物質である
亜鉛、アルカリ電解液、ゲル化剤からなる。電解液は主
にアルカリ電解液が用いられ、水酸化カリウム、水酸化
ナトリウムなどの電解質が使われる。ここでは、水酸化
カリウムの電導度が高いこと、また安価であることか
ら、水酸化カリウムを使用した。ただし、水酸化ナトリ
ウム単体や水酸化カリウムとの混合系で用いてもよい。The gelled negative electrode to be filled comprises zinc as an active substance, an alkaline electrolyte and a gelling agent. As the electrolyte, an alkaline electrolyte is mainly used, and an electrolyte such as potassium hydroxide or sodium hydroxide is used. Here, potassium hydroxide was used because it has a high electric conductivity and is inexpensive. However, it may be used in a mixed system of sodium hydroxide alone or potassium hydroxide.
【０００６】このような空気電池の構造上の特徴から、
高出力化を実現するためには、正極作用物質である酸素
を正極触媒層である空気極へ速やかに供給することが必
要である。この供給速度を向上させる方法として、正極
ケースの空気孔径の拡大、空気孔の個数の増加、および
撥水膜のガーレ値の小さいものなどを用いる方法等があ
る。また、空気極として空気透過性のよいものを用いる
方法等も考えられる。From the structural characteristics of such an air battery,
In order to achieve high output, it is necessary to quickly supply oxygen, which is a positive electrode acting substance, to the air electrode, which is a positive electrode catalyst layer. As a method for improving the supply speed, there are methods such as expanding the air hole diameter of the positive electrode case, increasing the number of air holes, and using a water repellent film having a small Gurley value. Further, a method of using an air electrode having good air permeability may be considered.
【０００７】なお、上記の撥水膜とは、正極触媒層に圧
着した膜のことであり、この撥水性により電池内の電解
液の漏出を防止するとともに、微細孔を通して正極触媒
層へ空気中の酸素を供給する作用をしている。この撥水
膜は、ガーレの大きいものを使用すると過放電漏液を防
止することができるが、その場合は酸素を正極触媒層に
十分取り込めなくなるので、十分な電流値が取り出せな
いというデメリットが生ずる。つまり、空気孔の面積と
撥水膜のガーレ値を検討して、十分な電流値が得られる
ように、酸素供給量をコントロールする必要がある。The above-mentioned water-repellent film is a film that is pressure-bonded to the positive electrode catalyst layer. This water repellency prevents the electrolyte solution from leaking out of the battery and also allows the positive electrode catalyst layer to pass through the fine pores in the air. It acts to supply oxygen. If this water-repellent film has a large Gurley, it is possible to prevent over-discharge leakage, but in that case oxygen cannot be taken in sufficiently into the positive electrode catalyst layer, so there is the disadvantage that a sufficient current value cannot be taken out. . That is, it is necessary to study the area of the air holes and the Gurley value of the water-repellent film to control the oxygen supply amount so that a sufficient current value can be obtained.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、高出力
化のために空気極への酸素供給速度を高めると、次のよ
うな問題が発生する。すなわち、電解液中の水分の逸
散、空気中の炭酸ガスの吸収による電解液の劣化、外部
環境の影響による放電特性の劣化などが長期放電状態に
おいて発生する。これは、特に電流値で空気極の単位面
積当たり０．１Ａ／ｃｍ2以上を取り出す場合、もしく
は０．１８Ａ／ｃｍ2以上を取り出す場合に顕著にな
る。However, if the oxygen supply rate to the air electrode is increased to increase the output, the following problems will occur. That is, dissipation of water in the electrolytic solution, deterioration of the electrolytic solution due to absorption of carbon dioxide gas in the air, deterioration of discharge characteristics due to the influence of the external environment, and the like occur in a long-term discharge state. This is remarkable when taking out the case of taking out per unit area 0.1 A / cm 2 or more of the air electrode, or 0.18 / cm 2 or more particularly at a current value.
【０００９】また、酸素供給を高めるために撥水膜のガ
ーレ値を低くするという試みもなされたが、撥水膜のガ
ーレ値の極端に小さいサンプルを使用したときに、次の
ような問題が生じた。すなわち、撥水膜のガーレ値を小
さくする（透過時間の速いものとする）と、撥水膜は空
隙率が高くなるので、正極触媒層との圧着が弱くなり、
空気極を所定の径に打ち抜く工程で撥水膜剥離などの不
良品が発生した。また、圧着の弱い空気極を用いて電池
試作をしたときに、過放電漏液が発生した。Attempts have also been made to lower the Gurley value of the water-repellent film in order to increase the oxygen supply, but the following problems occur when using a sample having an extremely small Gurley value of the water-repellent film. occured. That is, when the Gurley value of the water-repellent film is made small (the permeation time is fast), the water-repellent film has a high porosity, so that the pressure bonding with the positive electrode catalyst layer becomes weak,
In the process of punching out the air electrode to a predetermined diameter, defective products such as water-repellent film peeling occurred. Also, when a battery was prototyped using an air electrode with weak pressure bonding, over-discharge leakage occurred.
【００１０】また、空気極そのものの空気透過時間を速
くすることによっても酸素の供給を増やすことができ
る。しかし、空気極の空気透過時間の非常に速いサンプ
ルを使用したときに次のような問題が発生した。空気極
の空気透過時間を速くするために、空気極の正極触媒層
と撥水膜層との圧着を、各層が押し潰れない程度にする
と、圧着力が不足するので、空気極の打ち抜き工程で撥
水膜層の剥がれが発生する。その結果、過放電漏液が発
生した。Further, the supply of oxygen can be increased by increasing the air permeation time of the air electrode itself. However, the following problems occurred when a sample having a very fast air permeation time of the cathode was used. In order to speed up the air permeation time of the air electrode, if the pressure bonding of the positive electrode catalyst layer and the water repellent film layer of the air electrode is prevented from being crushed by each layer, the pressure bonding force will be insufficient. Peeling of the water-repellent film layer occurs. As a result, over-discharge leakage occurred.
【００１１】さらに、空気孔の径を大きくして酸素供給
を高めるという試みもなされたが、空気孔を単純に大き
くした場合には、酸素以外の外気成分による影響が大き
くなり、乾燥状態では放電の短寿命が高い確率で発生し
た。また空気孔の径を大きくした結果、外部との接触で
空気孔から拡散紙にキズが付いた。最悪の場合は、撥水
膜、空気極にキズが発生して、使用時に漏液が発生する
ことが考えられる。これに対して空気孔の面積を単純に
小さくした場合には、重負荷特性が得られないという問
題がある。Attempts have also been made to increase the oxygen supply by increasing the diameter of the air holes. However, when the air holes are simply made large, the effect of outside air components other than oxygen becomes large, and discharge occurs in a dry state. Has a high probability of having a short life. As a result of increasing the diameter of the air holes, the diffusion paper was scratched from the air holes due to contact with the outside. In the worst case, it is conceivable that the water repellent film and the air electrode may be scratched, resulting in liquid leakage during use. On the other hand, when the area of the air holes is simply reduced, there is a problem that heavy load characteristics cannot be obtained.
【００１２】そこで、重負荷特性を維持し、過放電漏液
を防止し、かつ長期放電での短寿命を防止するために
は、正極ケースの空気孔、撥水膜、電解液である水酸化
カリウム濃度、水酸化カリウム水溶液と負極作用物質と
の重量比、放電後の負極ゲルの充填率（負極ケースと絶
縁ガスケットと空気極によって形成された空隙体積に対
する放電後の負極ゲルの体積比率）等を総合的に再度見
直す必要がある。Therefore, in order to maintain the heavy load characteristics, prevent over-discharge leakage, and prevent short life due to long-term discharge, air holes in the positive electrode case, a water-repellent film, and a hydroxide that is an electrolyte solution. Potassium concentration, weight ratio of potassium hydroxide aqueous solution and negative electrode active substance, filling rate of negative electrode gel after discharge (volume ratio of negative electrode gel after discharge to void volume formed by negative electrode case, insulating gasket and air electrode), etc. Needs to be comprehensively reviewed again.
【００１３】本発明は、このような問題に対処してなさ
れたもので、重負荷放電特性が向上し、乾燥環境での電
解液の蒸発耐性に優れ、過放電漏液特性も維持し、かつ
長期放電での短寿命発生もない、信頼性の高い空気電池
を提供することを目的とする。The present invention has been made to solve the above problems, and has improved heavy-load discharge characteristics, excellent resistance to evaporation of an electrolytic solution in a dry environment, and maintains over-discharge leakage characteristics. It is an object of the present invention to provide a highly reliable air battery that does not have a short life due to long-term discharge.
【００１４】[0014]
【課題を解決するための手段】本発明者らは上記問題を
解決するために、正極ケースの空気孔、撥水膜のガーレ
値、空気極の空気透過性、電解液である水酸化カリウム
の濃度および水酸化カリウム水溶液と負極作用物質との
重量比等について、それぞれを相互に関連させながら、
詳細に検討した。その結果、以下に示す発明をなすに至
った。In order to solve the above-mentioned problems, the present inventors have found out that the air holes of the positive electrode case, the Gurley value of the water-repellent film, the air permeability of the air electrode, and the potassium hydroxide which is the electrolytic solution. Regarding the concentration and the weight ratio of the potassium hydroxide aqueous solution and the negative electrode active substance, etc.
I examined it in detail. As a result, the invention described below has been achieved.
【００１５】すなわち、請求項１に記載する発明は、底
面に多数の空気孔を有する正極ケース内に、撥水膜層、
正極触媒層および集電体層を有する空気極が収納され、
負極ケース内に電解液を保有する負極作用物質が収納さ
れている空気電池において、空気孔の総面積と正極ケー
ス底面の面積との比率（空気孔の総面積／正極ケース底
面の面積）が０．３〜３．３％の範囲であり、撥水膜の
ガーレ値が２００〜５００秒であり、かつ電解液である
水酸化カリウム濃度が２５〜４３％であることを特徴と
する。That is, according to the first aspect of the invention, a water repellent film layer is provided in a positive electrode case having a large number of air holes on the bottom surface.
An air electrode having a positive electrode catalyst layer and a current collector layer is housed,
In an air battery in which a negative electrode active substance containing an electrolytic solution is contained in a negative electrode case, the ratio of the total area of air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the bottom surface of the positive electrode case) is 0. The water-repellent film has a Gurley value of 200 to 500 seconds and a concentration of potassium hydroxide as an electrolytic solution of 25 to 43%.
【００１６】また、請求項２に記載する発明は、上記空
気電池において、空気孔の総面積と正極ケース底面の面
積との比率（空気孔の総面積／正極ケース底面の面積）
が３．３〜３０％の範囲であり、撥水膜のガーレ値が１
０００〜５０００秒であり、かつ電解液である水酸化カ
リウム濃度が３５〜４０％であることを特徴とする。Further, in the air battery of the present invention as defined in claim 2, the ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (total area of the air holes / area of the bottom surface of the positive electrode case).
Is 3.3 to 30%, and the Gurley value of the water-repellent film is 1.
000 to 5000 seconds, and the concentration of potassium hydroxide, which is an electrolytic solution, is 35 to 40%.
【００１７】まず、空気電池の重負荷放電特性の向上に
ついては、正極触媒層への目標とする電流値を得るため
の酸素供給が問題であることから、空気孔と撥水膜のガ
ーレ値とについて種々の組み合わせ例を作成して調べ
た。First, regarding the improvement of the heavy load discharge characteristic of the air battery, since the oxygen supply for obtaining the target current value to the positive electrode catalyst layer is a problem, the Gurley value of the air holes and the water repellent film are different from each other. About various combination examples were created and investigated.
【００１８】表１に正極ケースの空気孔径および空気孔
個数を組み合わせた仕様を示す。空気孔は直径０．４〜
４．０mmの範囲、空気孔の数は６〜３６個の範囲であ
る。なお、空気孔の位置は後記するように、ケース中心
から放射状に配置すると、酸素供給が効率的に行える。Table 1 shows a combination of the air hole diameter and the number of air holes of the positive electrode case. Air holes have a diameter of 0.4 ~
The range is 4.0 mm, and the number of air holes is 6 to 36. As will be described later, if the air holes are arranged radially from the center of the case, oxygen can be efficiently supplied.
【００１９】また、撥水膜のガーレ値は１５０秒、２７
０秒、１５００秒、６０００秒を設定して検討した。な
お、ガーレ値とは１平方インチ当たり、１００ｍｌの空
気が透過するのに要する時間を、秒の単位で表した値で
ある。つまり、ガーレ値が小さいほど、透過しやすくな
る。The Gurley value of the water-repellent film is 150 seconds, 27
The examination was conducted by setting 0 seconds, 1500 seconds and 6000 seconds. The Gurley value is a value representing the time required for permeation of 100 ml of air per square inch in units of seconds. That is, the smaller the Gurley value, the easier the light is transmitted.
【００２０】さらに、電解液について、種々の水酸化カ
リウム濃度および負極作用物質に対する重量比について
検討した。また、負極作用物質の充填率についても検討
した。これらの条件を綜合して検討した結果、上記の本
発明に達した。Further, with respect to the electrolytic solution, various potassium hydroxide concentrations and weight ratios with respect to the negative electrode acting substance were examined. Further, the filling rate of the negative electrode acting substance was also examined. As a result of comprehensively examining these conditions, the present invention has been achieved.
【００２１】さらに本発明者らは空気の透過性につい
て、上記のように撥水膜のガーレ値で規定するのではな
く、空気極の透過時間によって規定することによって、
上記目的に添った最適値を検討した結果、以下の発明を
なすに至った。Further, the present inventors define the air permeability by the air electrode permeation time rather than by the Gurley value of the water repellent film as described above.
As a result of studying the optimum value for the above purpose, the following inventions have been achieved.
【００２２】すなわち請求項５に記載する発明は、底面
に多数の空気孔を有する正極ケース内に、撥水膜層、正
極触媒層および集電体層を有する空気極が収納され、負
極ケース内に電解液を保有する負極作用物質が収納さ
れ、かつ空気極単位面積当たりの取り出し可能電流密度
の最低値が０．１Ａ／ｃｍ2である空気電池において、
空気孔の総面積と正極ケース底面の面積との比率（空気
孔の総面積／正極ケース底面の面積×１００）が０．１
７〜２．５％の範囲であり、空気極の空気透過時間が１
５〜３５秒であり、かつ電解液である水酸化カリウム濃
度が２９〜３７％であることを特徴とする。That is, in the invention described in claim 5, an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, In an air battery in which the negative electrode active substance holding the electrolytic solution is stored in and the minimum value of the retrievable current density per unit area of the air electrode is 0.1 A / cm 2 ,
The ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the bottom surface of the positive electrode case × 100) is 0.1.
It is in the range of 7 to 2.5%, and the air permeation time of the air electrode is 1
It is 5 to 35 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 29 to 37%.
【００２３】また、請求項６に記載する発明は、上記空
気電池において、空気孔の総面積と正極ケース底面の面
積との比率（空気孔の総面積／正極ケース底面の面積×
１００）が４．４〜１７．７％の範囲であり、空気極の
空気透過時間が５０〜７０秒であり、かつ電解液である
水酸化カリウム濃度が３１〜３９％であることを特徴と
する。In the air battery of the present invention, the ratio of the total area of air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the bottom surface of the positive electrode case ×
100) is in the range of 4.4 to 17.7%, the air permeation time of the air electrode is 50 to 70 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 31 to 39%. To do.
【００２４】さらに、空気極単位面積当たりの取り出し
可能電流密度の最低値が０．１８Ａ／ｃｍ2である上記
と同様のタイプの空気電池について検討し、以下の発明
をなすに至った。Further, an air battery of the same type as described above, in which the minimum value of the current density that can be taken out per unit area of the air electrode is 0.18 A / cm 2 , was studied, and the following invention was made.
【００２５】すなわち請求項９に記載する発明は、底面
に多数の空気孔を有する正極ケース内に、撥水膜層、正
極触媒層および集電体層を有する空気極が収納され、負
極ケース内に電解液を保有する負極作用物質が収納さ
れ、かつ空気極単位面積当たりの取り出し可能電流密度
の最低値が０．１８Ａ／ｃｍ2である空気電池におい
て、空気孔の総面積と正極ケース底面の面積との比率
（空気孔の総面積／正極ケース底面の面積×１００）が
０．５９〜８．４３％の範囲であり、空気極の空気透過
時間が１５〜３５秒であり、かつ電解液である水酸化カ
リウム濃度が２７〜３１％であることを特徴とする。That is, in the invention described in claim 9, an air electrode having a water repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and the negative electrode case is provided. In the air battery in which the negative electrode active substance holding the electrolytic solution is stored, and the minimum value of the current density that can be taken out per unit area of the air electrode is 0.18 A / cm 2 , the total area of the air holes and the bottom surface of the positive electrode case The ratio to the area (total area of air holes / area of bottom surface of positive electrode case × 100) is in the range of 0.59 to 8.43%, air permeation time of the air electrode is 15 to 35 seconds, and the electrolyte solution is And the potassium hydroxide concentration is 27 to 31%.
【００２６】また、請求項１０に記載する発明は、上記
空気電池において、空気孔の総面積と正極ケース底面の
面積との比率（空気孔の総面積／正極ケース底面の面積
×１００）が０．０２６〜０．５９％の範囲であり、空
気極の空気透過時間が５０〜７０秒であり、かつ電解液
である水酸化カリウム濃度が２７〜３３％であることを
特徴とする。According to a tenth aspect of the present invention, in the above air battery, the ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the bottom surface of the positive electrode case × 100) is 0. The range is 0.026 to 0.59%, the air permeation time of the air electrode is 50 to 70 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 27 to 33%.
【００２７】なお、空気極の空気透過時間は次のように
測定して得られたものである。まず、空気極を所定の大
きさに打ち抜く。この空気極を折り曲がらないようにホ
ルダーに充填し、ポンプで減圧状態（２．６６ｋＰａ）
に保つ。この減圧状態から圧力が９．３１ｋＰａに回復
するまでの空気の侵入時間を測定し、これを空気極の空
気透過時間とした。本明細書に記載した空気透過時間は
すべてこの測定による値である。The air permeation time of the air electrode was obtained by the following measurement. First, the air electrode is punched into a predetermined size. This air electrode is packed in a holder so that it will not bend, and the pump is depressurized (2.66 kPa).
Keep on. The invasion time of air from the reduced pressure state until the pressure recovered to 9.31 kPa was measured, and this was taken as the air permeation time of the air electrode. All air permeation times described herein are from this measurement.
【００２８】これらの発明についても、請求項１および
請求項２の発明の場合と同様に、空気孔と空気極の空気
透過時間とについて種々の組み合わせ例を作成して、重
負荷放電特性の向上について検討した。Also in these inventions, as in the case of the inventions of claim 1 and claim 2, various combinations of air holes and air permeation time of the air electrode are prepared to improve the heavy load discharge characteristics. Was examined.
【００２９】詳細は発明の実施の形態の項において説明
するが、空気孔は直径０．４〜４．０mmの範囲、空気孔
の数は６個とし、空気極は空気透過時間が１０，２５，
６０，９０秒のものを用いた。なお、空気孔の位置は後
記するように、ケース中心から放射状に配置すると、酸
素供給が効率的に行える。The details will be described in the embodiment of the invention. The air holes have a diameter of 0.4 to 4.0 mm, the number of air holes is 6, and the air permeation time of the air electrode is 10, 25. ，
The one used for 60 and 90 seconds was used. As will be described later, if the air holes are arranged radially from the center of the case, oxygen can be efficiently supplied.
【００３０】以上の２要素、すなわち正極ケースの空気
孔仕様と空気極の空気透過時間を組み合わせることによ
って、空気極単位面積当たりの取り出し可能な電流密度
が０．１Ａ／ｃｍ２以上の空気電池ができる。By combining the above two elements, that is, the air hole specifications of the positive electrode case and the air permeation time of the air electrode, an air battery with a retrievable current density of 0.1 A / cm 2 or more per unit area of the air electrode is obtained. it can.
【００３１】また、上記において空気孔の直径０．０６
〜２．０mm、空気孔の数を５または１０個とし、空気極
の空気透過時間を上記と同じにすることによって、空気
極単位面積当たりの取り出し可能な電流密度が０．１８
Ａ／ｃｍ2以上の空気電池ができる。さらに、電解液で
ある水酸化カリウム濃度について検討した。これらの条
件を綜合して検討した結果、上記の本発明に達した。In the above, the diameter of the air hole is 0.06.
~ 2.0 mm, the number of air holes is 5 or 10, and the air permeation time of the air electrode is the same as above, so that the extractable current density per unit area of the air electrode is 0.18.
An air battery of A / cm 2 or more is formed. Furthermore, the concentration of potassium hydroxide as an electrolytic solution was examined. As a result of comprehensively examining these conditions, the present invention has been achieved.
【００３２】[0032]
【発明の実施の形態】請求項１および２に記載する発明
の実施の態様を、前記した図１に示すボタン型空気電池
ＰＲ２３３０によって説明する。正極ケース２の底面に
は酸素を取り入れる空気孔１があり、正極ケース２の内
面上段に、拡散紙３、撥水膜４、正極触媒層５及びセパ
レータ６が収納されている。正極触媒層５は活性炭、マ
ンガン酸化物、導電材、ＰＴＦＥ（ポリテトラフルオロ
エチレン）粉からなる正極触媒粉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７に圧着充填して一
体化したものであり、さらに、正極触媒シートと圧着す
る撥水膜４とは別の撥水膜８がセパレータと反対面に圧
着されている。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the invention described in claims 1 and 2 will be described with reference to the button type air battery PR2330 shown in FIG. An air hole 1 for taking in oxygen is provided on the bottom surface of the positive electrode case 2, and a diffusion paper 3, a water repellent film 4, a positive electrode catalyst layer 5 and a separator 6 are housed in the upper part of the inner surface of the positive electrode case 2. The positive electrode catalyst layer 5 is obtained by pressing and filling a positive electrode catalyst powder made of activated carbon, manganese oxide, a conductive material, and PTFE (polytetrafluoroethylene) powder into a nickel-plated positive electrode current collector 7 made of a stainless steel net to be integrated. Further, a water-repellent film 8 different from the water-repellent film 4 pressure-bonded to the positive electrode catalyst sheet is pressure-bonded to the surface opposite to the separator.
【００３３】セパレータの上部には、絶縁ガスケット９
を介して、ニッケル−ステンレス−銅の三層クラッド材
を成形加工した負極ケース１０が配されており、通常は
絶縁ガスケットと負極ケースとの間には、水酸化カリウ
ム電解液の漏液防止のために、ポリアミド樹脂等のシー
ル剤が塗布されている。さらに負極ケース内部にはゲル
状の負極作用物質１１が充填され、セパレータに接して
いる。An insulating gasket 9 is provided on the top of the separator.
The nickel-stainless-copper three-layer clad material is molded and processed, and the negative electrode case 10 is disposed between the insulating gasket and the negative electrode case to prevent leakage of the potassium hydroxide electrolytic solution. Therefore, a sealing agent such as polyamide resin is applied. Further, a gelled negative electrode active material 11 is filled in the negative electrode case and is in contact with the separator.
【００３４】ここで好ましく用いられる負極活物質は、
安価な亜鉛が用いられるが、こればかりでなく他の金属
も使用できる。なお、正極として使用する空気極はφ２
２．８０mmに打ち抜いた。The negative electrode active material preferably used here is
Inexpensive zinc is used, but other metals can be used as well. The air electrode used as the positive electrode is φ2.
I punched it out to 2.80 mm.
【００３５】また、図２は空気孔の位置を示す説明図で
ある。ここで空気孔の位置について述べると、空気孔は
正極ケースの中心から放射状の位置に配置すると、空気
の拡散が効率的に行われ、放電特性が向上する。また空
気孔同士の位置は、空気の拡散がオーバーラップしない
ようにして、同円周上に配置することがよい。すなわ
ち、空気孔の位置が偏らないように、正極ケースの底面
になるべく均等に配置するようにするとよい。FIG. 2 is an explanatory view showing the positions of the air holes. Here, the position of the air holes will be described. When the air holes are arranged radially from the center of the positive electrode case, the air is efficiently diffused and the discharge characteristics are improved. Further, the positions of the air holes are preferably arranged on the same circumference so that the diffusion of air does not overlap. That is, it is preferable to arrange the air holes as evenly as possible on the bottom surface of the positive electrode case so that the positions of the air holes are not biased.
【００３６】図２に示すように、好ましい空気孔配置と
して示した下図では、空気孔は同円周上に均等に配置さ
れており、好ましくない空気孔配置として示した上図で
は、空気孔は偏って配置されている。また、最外周の空
気孔は、ガスケット底面と接触する箇所には設けない方
がよい。空気孔の位置が絶縁ガスケット底部とオーバー
ラップしてしまうと、耐漏液特性に悪影響を与えるから
である。As shown in FIG. 2, in the lower drawing shown as a preferable air hole arrangement, the air holes are evenly arranged on the same circumference, and in the upper drawing shown as an unfavorable air hole arrangement, the air holes are It is arranged unevenly. Further, it is preferable that the outermost air hole is not provided at a portion that comes into contact with the bottom surface of the gasket. This is because if the positions of the air holes overlap with the bottom of the insulating gasket, the liquid leakage resistance is adversely affected.
【００３７】（実施例１）正極ケースの空気孔を、直径
０．４mm、個数６個とし、撥水膜としてガーレ値２７０
秒のものを使用し、図１に示す空気電池を作成した。(Example 1) The air holes of the positive electrode case were 0.4 mm in diameter, and the number of air holes was 6, and the water-repellent film had a Gurley value of 270.
The air battery shown in FIG. 1 was prepared by using the second one.
【００３８】（実施例２〜９）正極ケースの空気孔の直
径および個数、撥水膜ガーレ値を表１に示す通りとし、
それ以外は実施例１と同様にして図１の空気電池を作成
した。(Examples 2 to 9) The diameter and number of air holes of the positive electrode case and the Gurley value of the water repellent film are as shown in Table 1,
The air battery of FIG. 1 was produced in the same manner as in Example 1 except for the above.
【００３９】（比較例１，２，３，４）正極ケースの空
気孔の直径および個数、撥水膜ガーレ値を表１に示す通
りとし、それ以外は実施例１と同様にして図１の空気電
池を作成した。(Comparative Examples 1, 2, 3, 4) The diameter and number of the air holes of the positive electrode case and the Gurley value of the water-repellent film are as shown in Table 1, and the other conditions are the same as in Example 1 and shown in FIG. Created an air battery.
【００４０】（従来例１）表１に示すように、正極ケー
スの空気孔を、直径０．４mm、個数６個とし、撥水膜と
してガーレ値１５００秒のものを使用し、図１に示す空
気電池を作成した。これは従来の空気電池の仕様であ
る。(Conventional Example 1) As shown in Table 1, the positive electrode case has air holes having a diameter of 0.4 mm and a number of six, and a water-repellent film having a Gurley value of 1500 seconds is used as shown in FIG. Created an air battery. This is the specification of a conventional air battery.
【００４１】[0041]
【表１】 [Table 1]
【００４２】上記の各実施例、比較例および従来例の電
池について、限界電流値の測定、常温での１００ｍＡ定
電流放電時間、乾燥条件での１００ｍＡ定電流放電時間
および漏液発生率を試験した。With respect to the batteries of the above Examples, Comparative Examples and Conventional Examples, the limiting current value was measured, 100 mA constant current discharge time at room temperature, 100 mA constant current discharge time under dry condition and leakage rate were tested. .
【００４３】限界電流値はＩＶ曲線から求めた。ＩＶ曲
線は、電池に連続的に電流を流し続ける測定方法で、空
気電池の限界電流値が決定できる。図３に典型的な空気
電池の限界電流値のカーブを示す。このカーブは、２領
域からなり、正極活物質である酸素の足りている状態Ａ
と酸素が不足している状態Ｂとからなる。このＡおよび
Ｂカーブの接線を結んだ交点を、限界電流値として決定
する。この値は、酸素の拡散が間に合っている反応状態
である。また、限界電流値を、空気極の面積で割った値
を電流密度とした。限界電流値の試験数は、５個で行っ
た。The limiting current value was obtained from the IV curve. The IV curve is a measurement method in which current is continuously supplied to the battery, and the limiting current value of the air battery can be determined. FIG. 3 shows a curve of a limiting current value of a typical air battery. This curve is composed of two regions and is in a state where oxygen, which is the positive electrode active material, is sufficient.
And state B lacking oxygen. The intersection point connecting the tangents of the A and B curves is determined as the limiting current value. This value is the reaction state in which the diffusion of oxygen is in time. A value obtained by dividing the limiting current value by the area of the air electrode was defined as the current density. The number of tests for the limiting current value was five.
【００４４】重負荷特性を評価するために、１００ｍＡ
定電流放電を行った。常温（２０℃−６０％ＲＨ）で
の、１００ｍＡ定電流放電の放電時間は２０個の電池の
平均値である。乾燥条件（３０℃−Ｄｒｙ）での１００
ｍＡ定電流放電の放電時間は２０個の電池の平均値であ
る。表２に評価結果を示す。さらに、過放電漏液試験は
２５℃−８５％ＲＨ雰囲気下で、３００Ωの負荷にて放
電終了後（放電は２７０ｈｒで終了）、さらに１００ｈ
ｒ負荷を掛けた時の漏液発生率を調査した。試験数は２
０個行った。To evaluate the heavy load characteristics, 100 mA
A constant current discharge was performed. The discharge time of 100 mA constant current discharge at room temperature (20 ° C.-60% RH) is an average value of 20 batteries. 100 under dry conditions (30 ° C-Dry)
The discharge time of mA constant current discharge is an average value of 20 batteries. Table 2 shows the evaluation results. Further, the over-discharge leakage test was conducted at 25 ° C.-85% RH atmosphere, after the discharge was completed at a load of 300Ω (the discharge was completed at 270 hr), and further 100 h.
The liquid leakage occurrence rate when r load was applied was investigated. The number of tests is 2
I went zero.
【００４５】[0045]
【表２】 [Table 2]
【００４６】実施例１，２，３、比較例３の結果から、
空気孔の面積を大きくすることで、酸素供給が容易にな
り限界電流値も、空気孔の面積に比例して増加する。し
かし、比較例３では空気孔の面積が大きい上に、撥水膜
のガーレ値が２７０秒を使用したため、電池内部から水
酸化カリウム電解液中の水分の蒸発が起こり、長期放電
で短寿命が起こりやすくなった。実施例１と従来例１の
ように、空気孔の面積が同じ場合では、撥水膜のガーレ
値が小さい方が重負荷特性に効果があることも分かっ
た。From the results of Examples 1, 2, 3 and Comparative Example 3,
Increasing the area of the air holes facilitates oxygen supply and increases the limiting current value in proportion to the area of the air holes. However, in Comparative Example 3, since the area of the air holes was large and the Gurley value of the water-repellent film was 270 seconds, the evaporation of water in the potassium hydroxide electrolyte solution from the inside of the battery caused a short life due to long-term discharge. It became easy to happen. It was also found that when the area of the air holes is the same as in Example 1 and Conventional Example 1, the smaller the Gurley value of the water-repellent film is, the more effective the heavy load characteristics are.
【００４７】また、撥水膜のガーレ値が大きい１５００
秒でも、実施例４，５，６と比較例１のように、面積比
率が３．０％以上の仕様でも、目的とする限界電流値が
得られることが分かった。しかし、比較例１では、面積
比率が大きすぎるため、成形強度が低下し、組立時に正
極ケース底部に凹みが発生した。また、比較例２では撥
水膜のガーレが１５０秒であるので、撥水膜の剥がれに
よる過放電漏液が発生した。また、比較例４では、撥水
膜のガーレ値が大きすぎ、目的とする電流値は得られな
かった。Further, the water-repellent film has a large Gurley value of 1,500.
Even in seconds, it was found that the target limiting current value could be obtained even with the specifications in which the area ratio was 3.0% or more, as in Examples 4, 5 and 6 and Comparative Example 1. However, in Comparative Example 1, since the area ratio was too large, the molding strength was lowered, and a dent was generated at the bottom of the positive electrode case during assembly. Further, in Comparative Example 2, since the Gurley of the water-repellent film was 150 seconds, the over-discharge leakage liquid was generated due to the peeling of the water-repellent film. In Comparative Example 4, the Gurley value of the water-repellent film was too large, and the target current value could not be obtained.
【００４８】空気孔の面積が同じ実施例７，８，９を比
較したとき、常温での放電時間で差はないが、乾燥条件
での放電時間は、空気孔の径が大きい方がより低下する
ことがわかった。When Examples 7, 8 and 9 having the same air hole area were compared, there was no difference in the discharge time at room temperature, but the discharge time under dry conditions was smaller when the air hole diameter was larger. I found out that
【００４９】このことから、空気孔の面積を同じにする
場合は、空気孔の径を小さくして、孔数を多くする方が
よいことがわかった。また、安易に空気孔の径を大きく
すると、先端の尖ったもので空気孔を通して拡散紙にキ
ズ、最悪の場合は空気極までダメージを与え、安全性の
面からも悪影響が起こると考えられる。以上の結果か
ら、本発明の条件である空気孔の面積比率と撥水膜のガ
ーレ値が決定された。From this fact, it was found that it is better to reduce the diameter of the air holes and increase the number of the holes when the areas of the air holes are the same. Further, if the diameter of the air hole is easily increased, it is thought that a sharp tip will scratch the diffusion paper through the air hole, and in the worst case, damage the air electrode, which will adversely affect safety. From the above results, the area ratio of air holes and the Gurley value of the water-repellent film, which are the conditions of the present invention, were determined.
【００５０】ただ、上記したように、特定の空気孔の面
積比率と撥水膜のガーレ値の組み合わせによって重負荷
特性には顕著な向上が見られたが、空気供給を向上させ
たことにより、過放電漏液、過放電後の電池膨れ、軽負
荷１ｋΩ放電における短寿命発生などの問題が生じた。
そこで表２で決定した正極ケースと撥水膜との仕様組み
合わせの範囲で、改めて負極仕様を検討し直す必要が生
じた。なお、上記の各例の電池では、負極仕様に関して
は、従来と同様に水酸化カリウム濃度が４３％、負極作
用物質と水酸化カリウム水溶液との重量比（以下、単に
「重量比」）２００／５０、放電後の負極ゲル体積の負
極ケース空隙体積に対する比率（充填率）９６％で、作
成されている。However, as described above, the heavy load characteristic was remarkably improved by the combination of the specific area ratio of the air holes and the Gurley value of the water-repellent film, but by improving the air supply, Problems such as over-discharge leakage, swelling of the battery after over-discharging, and occurrence of short life in light load 1 kΩ discharge occurred.
Therefore, it became necessary to reexamine the negative electrode specifications within the range of the combination of specifications of the positive electrode case and the water repellent film determined in Table 2. In the battery of each of the above examples, regarding the negative electrode specification, the potassium hydroxide concentration was 43% as in the conventional case, and the weight ratio of the negative electrode active substance and the potassium hydroxide aqueous solution (hereinafter, simply “weight ratio”) was 200 / 50, the ratio (filling ratio) of the negative electrode gel volume after discharge to the negative electrode case void volume was 96%.
【００５１】空気電池は空気孔を有するため、電池内部
から水酸化カリウム水溶液中の水分の蒸発、大気中から
の二酸化炭素・水蒸気の吸収による水酸化カリウム濃度
の低下があり、これらを抑止する必要がある。まず、１
ｋΩ（１．３ｍＡに相当）での長期室温放電の不具合に
ついて検討した。Since the air battery has air holes, evaporation of water in the aqueous potassium hydroxide solution from the inside of the battery and absorption of carbon dioxide and water vapor from the atmosphere reduce the concentration of potassium hydroxide, which must be suppressed. There is. First, 1
The problem of long-term room temperature discharge with kΩ (corresponding to 1.3 mA) was examined.
【００５２】対策として、水酸化カリウム濃度を低下さ
せて、水蒸気または二酸化炭素の吸収をさけるか、重量
比における電解液量の割合を高くすることで水分の蒸発
を抑える等が考えられる。As a countermeasure, it is conceivable to reduce the concentration of potassium hydroxide to prevent the absorption of water vapor or carbon dioxide, or to increase the ratio of the amount of the electrolytic solution in the weight ratio to suppress the evaporation of water.
【００５３】まず、水酸化カリウム濃度を変更させて検
討した。すなわち、空気孔の面積比率３．３％以下（実
施例２，８，９）と、空気孔の面積比率３．３％以上
（実施例４，５，６）とについて、水酸化カリウム濃度
２１，２５，２９，３２，３５，３７，４０，４３，４
５，４８％の１０種の濃度を設定し、重量比を２００／
５０、充填率を９６％にして試験を行った。水酸化カリ
ウム濃度別の試験結果を、表３に過放電漏液試験、表４
に１ｋΩの放電時間を示す。First, the potassium hydroxide concentration was changed and examined. That is, for the area ratio of air holes of 3.3% or less (Examples 2, 8, and 9) and the area ratio of air holes of 3.3% or more (Examples 4, 5, and 6), the potassium hydroxide concentration was 21%. , 25, 29, 32, 35, 37, 40, 43, 4
The concentration of 10 kinds of 5,48% is set, and the weight ratio is 200 /
The test was conducted at 50 and a filling rate of 96%. The test results for each concentration of potassium hydroxide are shown in Table 3, an over-discharge leakage test, and Table 4.
Shows the discharge time of 1 kΩ.
【００５４】[0054]
【表３】 [Table 3]
【００５５】[0055]
【表４】 [Table 4]
【００５６】過放電漏液ゼロを維持するには、（実施例
２，８，９）ではＫＯＨ４７％以下、（実施例４，５，
６）ではＫＯＨ４３％以下とする必要がある。また、表
４の放電時間の結果から、（実施例２，８，９）、（実
施例４，５，６）ともに、ＫＯＨ３２％以下では１ｋΩ
放電時間の低下が見られたので（目標値は４５０時間以
上）、ＫＯＨ３５％以上にするとよいことが分かった。In order to maintain zero over-discharge leakage, (Examples 2, 8 and 9), KOH of 47% or less, (Examples 4, 5, and 9)
In 6), KOH needs to be 43% or less. Further, from the results of the discharge time in Table 4, in both (Examples 2, 8, 9) and (Examples 4, 5, 6), 1 kΩ was obtained when KOH was 32% or less.
Since a decrease in discharge time was observed (target value is 450 hours or more), it was found that KOH should be 35% or more.
【００５７】以上のことから、水酸化カリウム濃度が高
いと過放電漏液が発生しやすく、逆に水酸化カリウム濃
度が低すぎると、大気中の水分を吸収するため、電池特
性（１ｋΩ放電特性）を劣化させることが分かった。空
気孔の面積比率３．３％以下では２５％〜４３％ＫＯ
Ｈ、空気孔の面積比率３．３％以上ではＫＯＨ３５％〜
４０％の領域がよいとされる。From the above, when the potassium hydroxide concentration is high, over-discharge leakage is likely to occur, and when the potassium hydroxide concentration is too low, on the other hand, water in the atmosphere is absorbed, so that battery characteristics (1 kΩ discharge characteristics ) Has been found to deteriorate. If the area ratio of air holes is 3.3% or less, 25% to 43% KO
If the area ratio of H and air holes is 3.3% or more, KOH 35% ~
40% area is considered good.
【００５８】次に、負極作用物質と電解液の重量比につ
いて検討した。現在の生産において、負極重量比は、亜
鉛２００ｇに対して電解液５０ｇを使用している。この
仕様では、負極ゲルが硬く、充填ノズルの詰まりなども
生産工程で問題があった。Next, the weight ratio of the negative electrode acting substance and the electrolytic solution was examined. In the current production, the negative electrode weight ratio uses 200 g of zinc and 50 g of electrolyte solution. With this specification, the negative electrode gel was hard and there was a problem in the production process such as clogging of the filling nozzle.
【００５９】そこで、先に最適化した水酸化カリウム濃
度の範囲で、亜鉛重量を２００ｇに対して水酸化カリウ
ム重量を５０ｇ，５５ｇ，６０ｇ，７０ｇ，８０ｇ，９
０ｇ，１００ｇで調整した。表５に１ｋΩ放電時間の結
果を示す。現行（５０ｇ）よりも水酸化カリウム重量を
増やすことで、大気中の炭酸ガス・水分からの影響は抑
えられた。Therefore, in the previously optimized potassium hydroxide concentration range, the weight of potassium hydroxide is 50 g, 55 g, 60 g, 70 g, 80 g and 9 relative to the weight of zinc of 200 g.
It was adjusted with 0 g and 100 g. Table 5 shows the results of 1 kΩ discharge time. By increasing the weight of potassium hydroxide compared to the current level (50 g), the effect of carbon dioxide and water in the atmosphere was suppressed.
【００６０】[0060]
【表５】 [Table 5]
【００６１】また、上記の水酸化カリウム重量の各試作
品で、作業工程の問題について調べた。表６に作業工程
についての結果を示す。水酸化カリウム量５５ｇ以下で
は、ゲルの流れ性が悪く、所定のゲル重量を排出するこ
とが難しかった。また、水酸化カリウム量を８０ｇ以上
とした場合は、負極ケースにゲルを充填する工程で、ゲ
ルが絶縁ガスケットの脇に垂れて、嵌合クリンプ時にゲ
ルずれを起こして嵌合不良を多発した。ここでは、空気
孔の面積比率に限らず、亜鉛２００ｇに対して、電解液
６０〜８０ｇが最適であった。Further, with respect to each of the prototypes having the weight of potassium hydroxide, the problem of the working process was examined. Table 6 shows the results of the work steps. When the amount of potassium hydroxide was 55 g or less, the flowability of the gel was poor and it was difficult to discharge a predetermined gel weight. Further, when the amount of potassium hydroxide was 80 g or more, in the step of filling the negative electrode case with gel, the gel drooped to the side of the insulating gasket, causing gel shift during fitting crimp, resulting in frequent fitting failures. Here, not only the area ratio of the air holes, but 60 to 80 g of the electrolytic solution was optimum for 200 g of zinc.
【００６２】[0062]
【表６】 [Table 6]
【００６３】以上のことから、水酸化カリウム濃度や、
亜鉛／水酸化カリウム水溶液の重量比の範囲が特定化さ
れ、この範囲で軽負荷１ｋΩ放電での放電容量が得られ
た。しかしながら、電池特性は確保できたが、放電終了
時（電池交換時）に電池ホルダーから電池が抜けない問
題、すなわち電池膨れの問題が起きた。これは、従来例
に比べて、実施例の空気孔面積が大きいため、水蒸気を
吸収しやすくなり、放電使用後の電池の総高が０．４mm
以上になるからである。そこで、新たに負極の充填率を
再検討した。これを、水酸化カリウム濃度３９％、重量
比２００／６０で行った。From the above, the potassium hydroxide concentration and
The range of the weight ratio of the zinc / potassium hydroxide aqueous solution was specified, and the discharge capacity at a light load of 1 kΩ discharge was obtained in this range. However, although the battery characteristics could be secured, there was a problem that the battery could not be removed from the battery holder at the end of discharging (when the battery was replaced), that is, a problem of battery swelling. This is because the air hole area of the example is larger than that of the conventional example, so that water vapor is easily absorbed, and the total height of the battery after discharge is 0.4 mm.
This is because it is above. Therefore, the filling rate of the negative electrode was newly reviewed. This was performed at a potassium hydroxide concentration of 39% and a weight ratio of 200/60.
【００６４】充填率は、負極ケース、絶縁ガスケット、
空気極によって形成される空隙体積に対して、放電後の
ゲル体積の比率である。まず、充填率を低くすると、キ
ャップと負極活物質の接触が悪くなることが予想され、
電池の内部抵抗の確認を行った。充填率８０％，８４
％，８８％，９２％，９６％について試作した。The filling rate is as follows: negative electrode case, insulating gasket,
It is the ratio of the gel volume after discharge to the void volume formed by the air electrode. First, if the filling rate is lowered, it is expected that the contact between the cap and the negative electrode active material will deteriorate,
The internal resistance of the battery was confirmed. Filling rate 80%, 84
%, 88%, 92%, and 96% were prototyped.
【００６５】表７に内部抵抗の測定結果を示す。充填率
が８０％では負極ケースと負極ゲルの接触がわずかなが
ら悪く、電池作成後１日後の初期特性で、内部抵抗のバ
ラツキが大きいことが分かった。内部抵抗の不良率を抑
えるために、充填率は８４％以上がよいと考える。Table 7 shows the measurement results of the internal resistance. It was found that when the filling rate was 80%, the contact between the negative electrode case and the negative electrode gel was slightly poor, and the variation in the internal resistance was large in the initial characteristics one day after the production of the battery. In order to suppress the defective rate of the internal resistance, it is considered that the filling rate should be 84% or more.
【００６６】[0066]
【表７】 [Table 7]
【００６７】表８に過放電試験の結果を示す。どの充填
率とも過放電漏液はなかったが、充填率が９６％では過
放電試験後の電池総高が０．６mm増加したため、ホルダ
ーから取り出せなかった。内部抵抗の不良率、電池膨れ
を抑えるには、充填率は、８０％〜９２％が最適な領域
であることが分かった。ＪＩＳ規格では、過放電試験後
の総高変化は、＋０．２mm以下と定められている。Table 8 shows the results of the over-discharge test. There was no over-discharge leakage at any filling rate, but at a filling rate of 96%, the total height of the battery after the over-discharge test increased by 0.6 mm, so it could not be taken out from the holder. It was found that the optimum filling rate is 80% to 92% in order to suppress the defective rate of the internal resistance and the battery swelling. According to the JIS standard, the total height change after the over-discharge test is set to +0.2 mm or less.
【００６８】[0068]
【表８】 [Table 8]
【００６９】以上説明したように、空気孔の径と個数
（空気孔の総面積）と正極ケース底部の面積との比率、
撥水膜のガーレ値を組み合わせることで、重負荷特性の
向上させた空気電池が製造できる。また空気供給が向上
した結果、電池内部からの電解液の蒸発、大気中から炭
酸ガス、水の吸収による影響が大きいので、水酸化カリ
ウム濃度、負極作用物質と電解液との重量比、負極ゲル
の充填率などの負極ゲル組成を検討し直すことで、漏液
特性を維持し、軽負荷放電の短寿命、電池膨れなど使用
時に不具合のない、重負荷特性に優れた空気電池が得ら
れた。As described above, the ratio of the diameter and number of air holes (total area of air holes) to the area of the bottom of the positive electrode case,
By combining the Gurley values of the water repellent film, an air battery with improved heavy load characteristics can be manufactured. In addition, as a result of improved air supply, evaporation of the electrolyte from the inside of the battery and absorption of carbon dioxide and water from the atmosphere have a large effect, so the concentration of potassium hydroxide, the weight ratio of the negative electrode active substance to the electrolyte, and the negative electrode gel. By reconsidering the negative electrode gel composition such as the filling rate of the air battery, an air battery that maintains the liquid leakage characteristics, has a short life of light load discharge, has no problems during use such as battery swelling, and has excellent heavy load characteristics was obtained. .
【００７０】なお、本実施例では、空気の孔をすべて同
じにして試作を行った。しかし、空気孔の径がそれぞれ
異なる径を用いても、請求項範囲であるならば、効果は
得られる。また空気孔の形も、円状だけではなく、空気
孔の形は金型・加工できる範囲でどのような形でもよ
い。In this example, a prototype was made with all the air holes being the same. However, even if the diameters of the air holes are different from each other, the effect can be obtained within the scope of the claims. Further, the shape of the air hole is not limited to a circular shape, and the shape of the air hole may be any shape as long as it can be molded and processed.
【００７１】次に、請求項５および６に記載した発明の
実施の態様を説明する。実施対象とした電池は前記した
図１に示すボタン型空気電池ＰＲ２３３０である。正極
として使用する空気極は、直径２２．８０mmの円形に打
ち抜いた。空気孔の位置は図２に示す配置が好ましい。Next, embodiments of the invention described in claims 5 and 6 will be described. The battery to be implemented is the button type air battery PR2330 shown in FIG. 1 described above. The air electrode used as the positive electrode was punched into a circle having a diameter of 22.80 mm. The position of the air holes is preferably the arrangement shown in FIG.
【００７２】（実施例１０）正極ケースの空気孔を、直
径０．４mm、個数６個とし、空気極は空気透過時間２５
秒のものを使用し、図１に示す空気電池を作成した。正
極ケース底面積は４２４．３４mm２である。(Example 10) The air holes of the positive electrode case were 0.4 mm in diameter, and the number of air holes was 6, and the air electrode had an air permeation time of 25.
The air battery shown in FIG. 1 was prepared by using the second one. The positive electrode case bottom area is 424.34 mm 2 .
【００７３】（実施例１１〜１６）正極ケースの空気孔
の直径および個数、空気極の空気透過時間を表９に示す
通りとし、それ以外は実施例１０と同様にして図１の空
気電池を作成した。(Examples 11 to 16) The diameter and number of air holes in the positive electrode case and the air permeation time of the air electrode are as shown in Table 9, and otherwise the same as in Example 10 except that the air battery of FIG. Created.
【００７４】（比較例５，６，７）正極ケースの空気孔
の直径および個数、空気極の空気透過時間を表９に示す
通りとし、それ以外は実施例１０と同様にして図１の空
気電池を作成した。(Comparative Examples 5, 6 and 7) The diameter and number of air holes in the positive electrode case and the air permeation time of the air electrode are as shown in Table 9, and otherwise the same as in Example 10 except that the air of FIG. I made a battery.
【００７５】（従来例２）表９に示すように、正極ケー
スの空気孔を、直径０．４mm、個数６個とし、空気極の
空気透過時間を６０秒とし、図１に示す空気電池を作成
した。これは従来の空気電池の仕様である。(Conventional Example 2) As shown in Table 9, the air holes of the positive electrode case were 0.4 mm in diameter, the number was 6, and the air permeation time of the air electrode was 60 seconds. Created. This is the specification of a conventional air battery.
【００７６】[0076]
【表９】 [Table 9]
【００７７】上記の各実施例、比較例および従来例の電
池について、限界電流値の測定、常温常湿（２０℃−相
対湿度６０％）での５０ｍＡ定電流放電時間、乾燥条件
（２０℃−相対湿度３０％）での５０ｍＡ定電流放電時
間および漏液発生率を試験した。With respect to the batteries of the above Examples, Comparative Examples and Conventional Examples, the limiting current value was measured, the constant current discharge time was 50 mA at room temperature and normal humidity (20 ° C.-60% relative humidity), and the drying conditions (20 ° C.- A constant current discharge time of 50 mA and a leakage generation rate at a relative humidity of 30%) were tested.
【００７８】限界電流値は前記実施例１〜９の場合と同
様にＩＶ曲線から求めた。限界電流値を、空気極の面積
で割った値を電流密度とした。限界電流値の試験数は、
５個で行った。The limiting current value was obtained from the IV curve in the same manner as in Examples 1 to 9 above. The value obtained by dividing the limiting current value by the area of the air electrode was defined as the current density. The number of tests of limiting current value is
I went with five.
【００７９】重負荷特性を評価するために、５０ｍＡ定
電流放電を行った。室温（２０℃−６０％ＲＨ）での５
０ｍＡ定電流放電の放電時間は、２０個の電池の平均値
である。乾燥条件（２０℃−３０％ＲＨ）での５０ｍＡ
定電流放電の放電時間は２０個の電池の平均値である。In order to evaluate the heavy load characteristics, constant current discharge of 50 mA was performed. 5 at room temperature (20 ° C-60% RH)
The discharge time of 0 mA constant current discharge is an average value of 20 batteries. 50mA under dry condition (20 ℃ -30% RH)
The discharge time of constant current discharge is an average value of 20 batteries.
【００８０】さらに、過放電漏液試験は２５℃−８５％
ＲＨ雰囲気下で、３００Ωの負荷を掛け続け、３６０時
間後の漏液発生率を調査した。試験数は２０個行った。
これらの評価結果を表１０に示す。Further, the over discharge leakage test is 25 ° C.-85%
Under the RH atmosphere, the load of 300Ω was continuously applied and the leakage occurrence rate after 360 hours was examined. The number of tests was 20.
Table 10 shows the evaluation results.
【００８１】[0081]
【表１０】 [Table 10]
【００８２】実施例１０，１１，１２、比較例５の結果
から、空気孔の面積を大きくすることで、酸素供給が容
易になり限界電流値も、空気孔の面積に比例して増加す
る。しかし、比較例５では空気孔の面積が大きい上に、
空気極の空気透過時間２５秒を使用したため、電池内部
から水酸化カリウム電解液中の水分の蒸発が起こり、乾
燥条件で短寿命が起こりやすくなった。From the results of Examples 10, 11, and 12 and Comparative Example 5, increasing the area of the air holes facilitates oxygen supply and increases the limiting current value in proportion to the area of the air holes. However, in Comparative Example 5, in addition to the large area of the air holes,
Since the air permeation time of the air electrode was 25 seconds, the water content in the potassium hydroxide electrolytic solution was evaporated from the inside of the battery, and the short life easily occurred under the drying conditions.
【００８３】また、空気極の透過時間が６０秒というよ
うに多少透過性が悪くても、実施例１４，１５，１６の
ように、面積比率を４．４％以上とすることによって、
目的とする限界電流値が得られることが分かった。Even if the permeation time of the air electrode is a little poor such as 60 seconds, by setting the area ratio to 4.4% or more as in Examples 14, 15 and 16,
It was found that the target limiting current value was obtained.
【００８４】また、比較例６のように空気極の空気透過
時間が１０秒では、空気極打ち抜き工程で撥水膜の剥が
れが発生し、過放電漏液が発生した。また、比較例７で
は、空気極の空気透過時間が９０秒であり、空気の供給
が不足するため、目的とする電流値が得られなかった。Further, as in Comparative Example 6, when the air permeation time of the air electrode was 10 seconds, the water-repellent film was peeled off in the air electrode punching step, and over-discharge leakage occurred. Further, in Comparative Example 7, the air permeation time of the air electrode was 90 seconds, and the supply of air was insufficient, so the target current value could not be obtained.
【００８５】このように、表１０に示す結果から、正極
ケースの空気孔の径と個数で計算される空気孔の面積比
率（空気孔の総面積／正極ケース底面の面積×１００）
と、空気極の空気透過時間とのそれぞれの最適範囲が決
定された。Thus, from the results shown in Table 10, the area ratio of air holes calculated by the diameter and the number of air holes in the positive electrode case (total area of air holes / area of the positive electrode case bottom surface × 100).
And the optimum range of the air permeation time of the cathode was determined.
【００８６】ただし、空気極の空気透過時間は触媒層と
撥水膜層とをローラ方式で圧着するときの圧着具合によ
って決まるので、個々の空気極の空気透過にはばらつき
が生じる。ここで用いた２５秒、６０秒はそれぞれ１２
個で測定してσ＝±３．３、σ＝±５の値をもち、３σ
を考慮すると２５秒は１５〜３５秒、６０秒は５０〜７
０秒の範囲であると推定される。次に、上記実施例１０
〜１６の電池において、空気極の空気透過時間だけを変
えて限界電流値を測定した結果を表１１に示す。However, since the air permeation time of the air electrode is determined by the pressure-bonding condition when the catalyst layer and the water-repellent film layer are pressure-bonded by the roller method, the air permeation of each air electrode varies. The 25 seconds and 60 seconds used here are 12
Measured individually, and have values of σ = ± 3.3 and σ = ± 5, 3σ
Considering that, 25 seconds is 15-35 seconds, 60 seconds is 50-7
Estimated to be in the 0 second range. Next, the above-mentioned Example 10
Table 11 shows the results of measuring the limiting current values of the batteries Nos. 16 to 16 while changing only the air permeation time of the air electrode.
【００８７】[0087]
【表１１】 [Table 11]
【００８８】まず、空気透過時間を１０秒とした場合
は、どの例においても空気極打ち抜き工程において圧着
撥水膜のハガレが生じた。この空気極を用いた試作品で
は過放電漏液が発生した。また、空気透過時間を９０秒
とした場合は、空気供給が不足するため５０ｍＡ放電が
できなかった。First, when the air permeation time was set to 10 seconds, peeling of the pressure-bonded water-repellent film occurred in the air electrode punching process in all examples. Over-discharge leakage occurred in the prototype using this air electrode. Further, when the air permeation time was set to 90 seconds, 50 mA discharge could not be performed because the air supply was insufficient.
【００８９】これら以外の空気透過時間の場合には、実
施例１０，１１，１２において空気極透過時間５０秒以
上の範囲で、空気供給が不足して目的とする電流値が取
り出せなかった。したがつて実施例１０，１１，１２で
は１５〜３５秒の空気透過時間の空気極が適当である。
また、実施例１３，１４，１６では５０秒より低い範囲
でも電池特性を満足するが、正極ケースの空気孔が大き
い上、空気の透過時間が３５秒では、必要以上の空気が
供給されるため、外気の水分や炭酸ガスの影響により、
軽負荷放電での放電時間が低下することがわかった。し
たがって、実施例１３，１４，１６では５０〜７０秒の
空気透過時間の空気極が適当であることがわかった。In the case of air permeation times other than these, in Examples 10, 11 and 12, within the range of air electrode permeation time of 50 seconds or more, the air supply was insufficient and the target current value could not be taken out. Therefore, in Examples 10, 11, and 12, an air electrode having an air permeation time of 15 to 35 seconds is suitable.
Further, in Examples 13, 14 and 16, the battery characteristics are satisfied even in a range lower than 50 seconds, but since the air holes of the positive electrode case are large and the air permeation time is 35 seconds, more air than necessary is supplied. , Due to the influence of moisture and carbon dioxide in the outside air,
It was found that the discharge time was reduced in light load discharge. Therefore, in Examples 13, 14, and 16, it was found that an air electrode having an air permeation time of 50 to 70 seconds is suitable.
【００９０】このように、空気孔と空気極の空気透過時
間とを組み合わせることによって、重負荷特性を向上さ
せることができたが、一方、空気供給を向上させたこと
により、過放電漏液、過放電後の電池膨れ、軽負荷１ｋ
Ω放電における短寿命発生などの問題が生じた。Thus, the heavy load characteristics could be improved by combining the air holes and the air permeation time of the air electrode. On the other hand, by improving the air supply, the over discharge leakage, Battery swells after over discharge, light load 1k
Problems such as the occurrence of short life in Ω discharge occurred.
【００９１】これは、上記の各例の電池では、負極仕様
に関しては、従来と同様に水酸化カリウム濃度が４３
％、負極作用物質と水酸化カリウム水溶液との重量比
（以下、単に「重量比」）が２００／５０、放電後の負
極ゲル体積の負極ケース空隙体積に対する比率（充填
率）が９６％で、作成されているためである。そこで表
１０で決定した正極ケースと撥水膜との仕様組み合わせ
の範囲で、改めて負極仕様を検討し直す必要が生じた。In the batteries of the above-mentioned respective examples, regarding the negative electrode specification, the potassium hydroxide concentration was 43% as in the conventional case.
%, The weight ratio of the negative electrode active substance to the aqueous potassium hydroxide solution (hereinafter simply referred to as “weight ratio”) is 200/50, and the ratio of the negative electrode gel volume after discharge to the negative electrode case void volume (filling rate) is 96%. This is because it has been created. Therefore, it was necessary to reexamine the negative electrode specifications within the range of the specification combinations of the positive electrode case and the water repellent film determined in Table 10.
【００９２】空気電池は空気孔を有するため、電池内部
から水酸化カリウム水溶液中の水分の蒸発、大気中から
の二酸化炭素・水の吸収による水酸化カリウム濃度の低
下があり、これらを抑止する必要がある。まず、上記表
９の仕様において、１ｋΩのような長期室温放電の不具
合について検討した。Since the air battery has air holes, evaporation of water in the aqueous potassium hydroxide solution from the inside of the battery and reduction of potassium hydroxide concentration due to absorption of carbon dioxide and water from the atmosphere must be suppressed. There is. First, in the specifications of Table 9 above, a problem of long-term room temperature discharge such as 1 kΩ was examined.
【００９３】その対策として、水酸化カリウム濃度を低
下させて、二酸化炭素との反応をさけるか、重量比にお
ける電解量の割合を高くすることで水分の蒸発を抑える
ことにした。As a countermeasure against this, the concentration of potassium hydroxide was reduced to avoid the reaction with carbon dioxide, or the ratio of the amount of electrolysis in the weight ratio was increased to suppress the evaporation of water.
【００９４】まず水酸化カリウム濃度別に電池を試作し
て検討した。すなわち、空気孔の面積比率２．５％より
低いもの（実施例１０，１１，１２，１３）と、空気孔
の面積比率４．４％以上（実施例１４，１５，１６）と
について、水酸化カリウム濃度を２９，３１，３３，３
５，３７，３９，４１％に調製し、重量比を２００／５
０、充填率を９６％と従来例と同様にして試験を行っ
た。水酸化カリウム濃度別の試作結果について、表１２
に過放電漏液試験の結果（数値は漏液発生％）を、表１
３に１ｋΩの放電時間（ｈｒ）をそれぞれ示す。First, batteries were experimentally produced and examined for each potassium hydroxide concentration. That is, water having an air hole area ratio of less than 2.5% (Examples 10, 11, 12, 13) and air hole area ratio of 4.4% or more (Examples 14, 15, 16) are used. Adjust the potassium oxide concentration to 29, 31, 33, 3
5,37,39,41% and the weight ratio is 200/5
The test was conducted in the same manner as in the conventional example with 0 and a filling rate of 96%. Table 12 shows the results of trial production by potassium hydroxide concentration.
Table 1 shows the results of the over-discharge leakage test
3 shows the discharge time (hr) of 1 kΩ.
【００９５】[0095]
【表１２】 [Table 12]
【００９６】[0096]
【表１３】 [Table 13]
【００９７】過放電漏液ゼロを維持するには、（実施例
１０，１１，１２）ではＫＯＨ３７％以下、（実施例１
３，１４，１５）ではＫＯＨ３９％以下とする必要があ
る。また、表１３の１ｋΩ放電時間の結果から、（実施
例１０，１１，１２）、（実施例１３，１４，１５）と
もに、ＫＯＨ３１％より少ないと放電時間の低下が見ら
れた。これらの結果から、（実施例１０，１１，１２）
ではＫＯＨ３１〜３７％、（実施例１３，１４，１５）
ではＫＯＨ３１〜３９％が適当であることがわかった。In order to maintain zero over-discharge leakage, in (Examples 10, 11 and 12), KOH of 37% or less, (Example 1)
3, 14, 15), KOH needs to be 39% or less. Further, from the results of the 1 kΩ discharge time in Table 13, in all of (Examples 10, 11, 12) and (Examples 13, 14, 15), when the KOH was less than 31%, the discharge time was decreased. From these results (Examples 10, 11, 12)
Then KOH31-37%, (Examples 13, 14, 15)
Then, it was found that KOH31 to 39% is suitable.
【００９８】すなわち、ＫＯＨ濃度が高いと、過放電漏
液を起こしやすく、逆にＫＯＨ濃度が低すぎると大気中
の水蒸気吸収の影響を大きく受けて放電特性を劣化させ
る。そこで、これらの結果から、空気孔の面積比率が
２．５％以下の場合はＫＯＨ濃度範囲は３１〜３７％、
空気孔の面積比率が４．４％以上の場合はＫＯＨ濃度範
囲は３１〜３９％、がよいことがわかった。That is, when the KOH concentration is high, over-discharge leakage is likely to occur, while when the KOH concentration is too low, it is greatly affected by absorption of water vapor in the atmosphere and deteriorates discharge characteristics. Therefore, from these results, when the area ratio of the air holes is 2.5% or less, the KOH concentration range is 31 to 37%,
It was found that the KOH concentration range of 31 to 39% is preferable when the area ratio of the air holes is 4.4% or more.
【００９９】次に、負極作用物質と電解液の重量比につ
いて検討した。現在の生産において、負極重量比は、亜
鉛２００ｇに対して電解液（水酸化カリウム水溶液）５
０ｇを使用している。この仕様では、負極ゲルが硬く、
充填ノズルの詰まりなど生産工程で問題があった。Next, the weight ratio of the negative electrode acting substance and the electrolytic solution was examined. In the current production, the weight ratio of the negative electrode is 200 g of zinc and 5 parts of electrolyte (potassium hydroxide aqueous solution).
0g is used. With this specification, the negative electrode gel is hard,
There was a problem in the production process such as clogging of the filling nozzle.
【０１００】そこで、先に最適とした水酸化カリウム濃
度（３５％ＫＯＨ）で、亜鉛重量を２００ｇに対して水
酸化カリウム水溶液の重量を５０ｇ，６０ｇ，７０ｇ，
８０ｇ，９０ｇ，１００ｇとして調製した。表１４に１
ｋΩ放電時間の結果を示す。現行（５０ｇ）よりも水酸
化カリウム水溶液重量を増やすことで、大気中の炭酸ガ
ス・水分からの影響は軽減される。また、電解液が多い
ほど亜鉛の利用率が高くなり、長い放電時間が得られる
ことがわかった。Therefore, with the optimum potassium hydroxide concentration (35% KOH), the weight of the aqueous solution of potassium hydroxide is 50 g, 60 g, 70 g, while the weight of zinc is 200 g.
It was prepared as 80 g, 90 g and 100 g. 1 in Table 14
The result of kΩ discharge time is shown. By increasing the weight of the aqueous potassium hydroxide solution compared to the current amount (50 g), the influence of carbon dioxide gas and moisture in the atmosphere can be reduced. It was also found that the more the electrolyte solution is, the higher the zinc utilization rate and the longer the discharge time can be obtained.
【０１０１】[0101]
【表１４】 [Table 14]
【０１０２】また、上記の水酸化カリウム重量の各試作
品で、作業工程の問題について調べた。表１５に作業工
程についての結果を示す。水酸化カリウム量５０ｇ以下
では、ゲルの流れ性が悪く、ノズル詰まりのため所定の
ゲル重量を排出することが難しかった。また、水酸化カ
リウム量を９０ｇ以上とした場合は、負極ケースにゲル
を充填する工程で、ゲルが絶縁ガスケットの脇に垂れ
て、嵌合クリンプ時にゲルずれを起こして嵌合不良を多
発した。Further, with respect to each of the prototypes having the above-mentioned potassium hydroxide weight, the problem of the working process was examined. Table 15 shows the results of the work steps. When the amount of potassium hydroxide was 50 g or less, the flowability of gel was poor, and it was difficult to discharge a predetermined gel weight due to nozzle clogging. Further, when the amount of potassium hydroxide was 90 g or more, in the step of filling the negative electrode case with gel, the gel drooped to the side of the insulating gasket, causing gel shift during the fitting crimp, resulting in frequent fitting failures.
【０１０３】以上により、空気孔の面積比率に関係な
く、亜鉛２００ｇに対して、電解液６０〜８０ｇが最適
であった。つまり、亜鉛／水酸化カリウム水溶液の重量
比が２．５〜３．３のときに、軽負荷の１ｋΩ放電でも
目標の放電時間が得られることがわかった。From the above, regardless of the area ratio of the air holes, 60 to 80 g of the electrolytic solution was optimum for 200 g of zinc. That is, it was found that when the weight ratio of the zinc / potassium hydroxide aqueous solution was 2.5 to 3.3, the target discharge time could be obtained even with a light load of 1 kΩ discharge.
【０１０４】[0104]
【表１５】 [Table 15]
【０１０５】しかしながら、電池特性は確保できたが、
使用後電池ホルダーから電池が抜けない問題、すなわち
電池膨れの問題が起きた。これは、従来例に比べて、空
気供給が向上したため、外部から水分を吸収しやすくな
り、放電使用後の電池の総高が０．４mm以上になるから
である。そこで、新たに負極の充填率を再検討した。こ
れを、水酸化カリウム濃度３５％、亜鉛／電解液重量比
＝２００／６０で行った。However, although the battery characteristics could be secured,
There was a problem that the battery could not be removed from the battery holder after use, that is, a problem of battery swelling. This is because the air supply is improved compared to the conventional example, so that it becomes easier to absorb moisture from the outside, and the total height of the battery after discharge use is 0.4 mm or more. Therefore, the filling rate of the negative electrode was newly reviewed. This was performed at a potassium hydroxide concentration of 35% and a zinc / electrolyte weight ratio = 200/60.
【０１０６】負極充填率は、負極ケース、絶縁ガスケッ
ト、空気極によって形成される空隙体積に対して、負極
１００％放電したと仮定した時の放電後の理論ゲル体積
（すなわち、反応物の体積、水溶液の体積、その他の反
応に寄与しない添加物の体積の総和）の比率である。充
填率７８％，８２％，８６％，９０％，９４％および９
６％について試作した。これらの試作品について内部抵
抗と過放電後の電池総高の変化とを調べた。The filling rate of the negative electrode is the theoretical gel volume after discharge (that is, the volume of the reactant, based on the assumption that 100% of the negative electrode is discharged with respect to the void volume formed by the negative electrode case, the insulating gasket and the air electrode). It is the ratio of the volume of the aqueous solution and the total volume of other additives that do not contribute to the reaction. Filling rate 78%, 82%, 86%, 90%, 94% and 9
A trial production was made for 6%. For these prototypes, the internal resistance and the change in the total cell height after overdischarge were examined.
【０１０７】表１６に内部抵抗の測定結果を示す。充填
率が７８％では負極ケースと負極ゲルの接触がわずかな
がら悪く、電池作成１日後の初期特性で、内部抵抗のバ
ラツキが大きいことが分かった。内部抵抗の不良率を抑
えるために、充填率は８２％以上がよいと考えられる。Table 16 shows the measurement results of the internal resistance. It was found that when the filling rate was 78%, the contact between the negative electrode case and the negative electrode gel was slightly poor, and the initial resistance one day after the production of the battery showed a large variation in the internal resistance. In order to suppress the defective rate of the internal resistance, the filling rate is considered to be 82% or more.
【０１０８】[0108]
【表１６】 [Table 16]
【０１０９】表１７に過放電後の電池総高の変化を示
す。充填率が９８％では過放電試験後の電池総高が最大
値で０．４mm増加したため、ホルダーから取り出せなか
った。充填率が９４％より低い場合はＪＩＳ規格の０．
２mmをほぼ超えないことがわかった。そこで充填率上限
を９４％にすることによって電池膨れを抑えることにし
た。つまり、内部抵抗の不良率および電池膨れを抑える
には、充填率は８２％〜９４％が最適な領域であること
が分かった。Table 17 shows the change in the total cell height after overdischarge. When the filling rate was 98%, the total height of the battery after the over-discharge test increased by 0.4 mm at the maximum value, so that it could not be taken out from the holder. When the filling rate is lower than 94%, the JIS standard of 0.
It turns out that it does not exceed 2 mm. Therefore, the upper limit of the filling rate is set to 94% to suppress the battery swelling. That is, it has been found that the filling rate is optimally in the range of 82% to 94% for suppressing the defective rate of the internal resistance and the battery swelling.
【０１１０】[0110]
【表１７】 [Table 17]
【０１１１】以上説明したように、空気孔の径と個数
（空気孔の総面積）と正極ケース底部の面積との比率、
空気極の透過時間を組み合わせることで、重負荷特性の
向上させた空気電池が製造できる。また空気供給が向上
した結果、電池内部からの電解液の蒸発、大気中から炭
酸ガス、水分の吸収による影響が大きいので、負極仕
様、すなわち水酸化カリウム濃度、負極作用物質と電解
液との重量比、負極ゲルの充填率を検討し直すことで、
漏液特性を維持し、軽負荷放電の短寿命、電池膨れなど
使用時に不具合のない、重負荷特性に優れた空気電池が
得られた。As described above, the ratio of the diameter and number of air holes (total area of air holes) to the area of the bottom of the positive electrode case,
An air battery with improved heavy load characteristics can be manufactured by combining the permeation time of the air electrode. As a result of improved air supply, the evaporation of the electrolyte from the inside of the battery and the absorption of carbon dioxide and water from the atmosphere have a large effect, so the negative electrode specifications, that is, potassium hydroxide concentration, the weight of the negative electrode active substance and the electrolytic solution, are large. By reconsidering the ratio and the filling rate of the negative electrode gel,
An air battery that maintains the liquid leakage characteristics, has a short life under light load discharge, has no problems during use such as battery swelling, and has excellent heavy load characteristics was obtained.
【０１１２】なお、本実施例では、空気の孔をすべて同
じにして試作を行った。しかし、空気孔の径がそれぞれ
異なる径を用いても、請求項範囲であるならば、効果は
得られる。また空気孔の形も、円状だけではなく、空気
孔の形は金型・加工できる範囲でどのような形でもよ
い。In this example, a prototype was made with all the air holes being the same. However, even if the diameters of the air holes are different from each other, the effect can be obtained within the scope of the claims. Further, the shape of the air hole is not limited to a circular shape, and the shape of the air hole may be any shape as long as it can be molded and processed.
【０１１３】また、今回空気極製造の際の正極触媒層と
撥水膜層との圧着工程を、アンカー効果によるローラ方
式で行ったが、圧着工程としては正極触媒層と撥水膜層
とを圧着できてかつ空気極の透過時間をコントロールで
きる方式であればいかなるものでもよく、例えば液体含
浸方式（アルコール含浸方式）などが使用できる。Further, the pressure-bonding step of the positive electrode catalyst layer and the water-repellent film layer at the time of manufacturing the air electrode this time was performed by the roller method by the anchor effect. The pressure-bonding step involves the positive electrode catalyst layer and the water-repellent film layer. Any method can be used as long as it can be pressure-bonded and the permeation time of the air electrode can be controlled. For example, a liquid impregnation method (alcohol impregnation method) can be used.
【０１１４】次に請求項９および請求項１０に記載した
発明の実施の形態を説明する。実施対象とした電池はＰ
Ｒ４４タイプで、前記した図１に示すボタン型空気電池
ＰＲ２３３０と同じ断面構造を有している。正極として
使用する空気極は直径１１．２０mmの円形に打ち抜い
た。空気孔の位置は図２に示すような放射状配置が好ま
しい。Next, an embodiment of the invention described in claims 9 and 10 will be described. The target battery is P
The R44 type has the same sectional structure as the button type air battery PR2330 shown in FIG. The air electrode used as the positive electrode was punched into a circle having a diameter of 11.20 mm. The positions of the air holes are preferably a radial arrangement as shown in FIG.
【０１１５】（実施例１７）正極ケースの空気孔を、直
径０．４mm、個数５個とし、空気極は空気透過時間２５
秒のものを使用し、図１に示す空気電池を作成した。正
極ケース底面積は１０４．７２mm２である。(Embodiment 17) The air holes of the positive electrode case were 0.4 mm in diameter and the number of the air holes was 5, and the air electrode had an air permeation time of 25.
The air battery shown in FIG. 1 was prepared by using the second one. The positive electrode case bottom area is 104.72 mm 2 .
【０１１６】（実施例１８〜２４）正極ケースの空気孔
の直径および個数、空気極の空気透過時間を表１８に示
す通りとし、それ以外は実施例１７と同様にして図１の
空気電池を作成した。(Examples 18 to 24) The diameter and number of the air holes in the positive electrode case and the air permeation time of the air electrode are as shown in Table 18, and otherwise the same as in Example 17 except that the air battery of FIG. Created.
【０１１７】（比較例８，９，１０）正極ケースの空気
孔の直径および個数、空気極の空気透過時間を表１８に
示す通りとし、それ以外は実施例１７と同様にして図１
の空気電池を作成した。(Comparative Examples 8, 9 and 10) The diameter and number of air holes in the positive electrode case and the air permeation time of the air electrode are shown in Table 18.
I made an air battery.
【０１１８】（従来例３）表１８に示すように、正極ケ
ースの空気孔を、直径０．５mm、個数５個とし、空気極
の空気透過時間を６０秒として、図１に示す空気電池を
作成した。これは従来の空気電池の仕様である。(Conventional Example 3) As shown in Table 18, the air holes of the positive electrode case were 0.5 mm in diameter, the number of the air holes was 5, and the air permeation time of the air electrode was 60 seconds. Created. This is the specification of a conventional air battery.
【０１１９】[0119]
【表１８】 [Table 18]
【０１２０】上記の各実施例、比較例および従来例の電
池について、限界電流値の測定、常温常湿（２０℃−相
対湿度６０％）での２０ｍＡ定電流放電時間、乾燥条件
（２０℃−相対湿度３０％）での２０ｍＡ定電流放電時
間および漏液発生率を試験した。With respect to the batteries of the above Examples, Comparative Examples and Conventional Example, the limiting current value was measured, the constant current discharge time was 20 mA at room temperature and normal humidity (20 ° C.-60% relative humidity), and the drying condition (20 ° C.- The 20 mA constant current discharge time and the liquid leakage generation rate at a relative humidity of 30%) were tested.
【０１２１】限界電流値は前記実施例１０〜１７の場合
と同様にＩＶ曲線から求めた。限界電流値を、空気極の
面積で割った値を電流密度とした。限界電流値の試験数
は、５個で行った。The limiting current value was obtained from the IV curve as in the case of Examples 10 to 17 above. The value obtained by dividing the limiting current value by the area of the air electrode was defined as the current density. The number of tests for the limiting current value was five.
【０１２２】重負荷特性を評価するために、２０ｍＡ定
電流放電を行った。室温（２０℃−６０％ＲＨ）での２
０ｍＡ定電流放電の放電時間は、２０個の電池の平均値
である。乾燥条件（２０℃−３０％ＲＨ）での２０ｍＡ
定電流放電の放電時間は２０個の電池の平均値である。
表１８に評価結果を示す。さらに、過放電漏液試験は２
５℃−８５％ＲＨ雰囲気下で、２５０Ωの負荷を掛け続
け、２１６時間後の漏液発生率を調査した。試験数は２
０個行った。In order to evaluate the heavy load characteristics, 20 mA constant current discharge was performed. 2 at room temperature (20 ° C-60% RH)
The discharge time of 0 mA constant current discharge is an average value of 20 batteries. 20mA under dry condition (20 ℃ -30% RH)
The discharge time of constant current discharge is an average value of 20 batteries.
Table 18 shows the evaluation results. Furthermore, the over discharge leak test is 2
Under a 5 ° C.-85% RH atmosphere, a load of 250Ω was continuously applied, and the leakage occurrence rate after 216 hours was investigated. The number of tests is 2
I went zero.
【０１２３】[0123]
【表１９】 [Table 19]
【０１２４】実施例１７，１８，１９、２０および比較
例１０の結果から、空気孔の面積を大きくすることで、
酸素供給が容易になり限界電流値も、空気孔の面積に比
例して増加する。しかし、比較例１０では空気孔の面積
が大きい上に、空気極の空気透過時間２５秒を使用した
ため、電池内部から水酸化カリウム電解液中の水分の蒸
発が起こり、乾燥条件で短寿命が起こりやすくなった。From the results of Examples 17, 18, 19, 20 and Comparative Example 10, by increasing the area of the air holes,
Oxygen supply becomes easier and the limiting current value also increases in proportion to the area of the air holes. However, in Comparative Example 10, since the area of the air holes was large and the air permeation time of the air electrode was 25 seconds, the water content in the potassium hydroxide electrolyte was evaporated from the inside of the battery, resulting in a short life under dry conditions. It's easier.
【０１２５】実施例１８と従来例３のように、空気孔の
面積が同じ場合では空気極の透過時間が小さい方が重負
荷特性に効果があることがわかった。また、実施例２
１，２２，２３，２４のように、空気孔面積比率が０．
５９％以下で、空気透過時間６０秒でも、目的とする限
界電流値が得られることがわかった。これは、小さな孔
をたくさん設けることで、空気孔から空気極への拡散の
効率が良くなったためと考えられる。As in Example 18 and Conventional Example 3, it was found that the shorter the permeation time of the air electrode is, the more effective the heavy load characteristics are when the areas of the air holes are the same. Example 2
1, 22, 23, and 24, the air hole area ratio is 0.
It was found that at 59% or less, the target limiting current value was obtained even when the air permeation time was 60 seconds. This is considered to be because the efficiency of diffusion from the air holes to the air electrode was improved by providing many small holes.
【０１２６】また、比較例８のように空気極の空気透過
時間が１０秒では、空気極打ち抜き工程で撥水膜の剥が
れが発生し、過放電漏液が発生した。また、比較例９で
は、空気極の空気透過時間が９０秒であり、空気の供給
が不足するため、目的とする電流値が得られなかった。Further, as in Comparative Example 8, when the air permeation time of the air electrode was 10 seconds, the water-repellent film was peeled off in the air electrode punching step, and over-discharge leakage occurred. Further, in Comparative Example 9, the air permeation time of the air electrode was 90 seconds, and the supply of air was insufficient, so the target current value could not be obtained.
【０１２７】このように、表１９に示す結果から、正極
ケースの空気孔の径と個数で計算される空気孔の面積比
率（空気孔の総面積／正極ケース底面の面積×１００）
と、空気極の空気透過時間とのそれぞれの最適範囲が決
定された。Thus, from the results shown in Table 19, the area ratio of the air holes calculated by the diameter and the number of the air holes of the positive electrode case (total area of air holes / area of the positive electrode case bottom surface × 100).
And the optimum range of the air permeation time of the cathode was determined.
【０１２８】ただし、空気極の空気透過時間は触媒層と
撥水膜層とをローラ方式で圧着するときの圧着具合によ
って決まるので、個々の空気極の空気透過にはばらつき
が生じる。ここで用いた２５秒、６０秒はそれぞれ１２
個で測定してσ＝±３．３、σ＝±５の値をもち、３σ
を考慮すると２５秒は１５〜３５秒、６０秒は５０〜７
０秒の範囲であると推定される。次に、上記実施例１７
〜２２の電池において、空気極の空気透過時間だけを変
えて限界電流値を測定した結果を表２０に示す。However, since the air permeation time of the air electrode is determined by the pressure bonding condition when the catalyst layer and the water repellent film layer are pressure bonded by the roller method, the air permeation of each air electrode varies. The 25 seconds and 60 seconds used here are 12
Measured individually, and have values of σ = ± 3.3 and σ = ± 5, 3σ
Considering that, 25 seconds is 15-35 seconds, 60 seconds is 50-7
Estimated to be in the 0 second range. Next, in Example 17 above.
Table 20 shows the results of measuring the limiting current values of the batteries Nos. 22 to 22 by changing only the air permeation time of the air electrode.
【０１２９】[0129]
【表２０】 [Table 20]
【０１３０】まず、空気透過時間を１０秒とした場合
は、どの例においても空気極打ち抜き工程において圧着
撥水膜のハガレが生じた。この空気極を用いた試作品で
は過放電漏液が発生した。また、空気透過時間を９０秒
とした場合は、空気供給が不足するため２０ｍＡ放電が
できなかった。First, when the air permeation time was 10 seconds, peeling of the pressure-bonded water-repellent film occurred in the air electrode punching process in all examples. Over-discharge leakage occurred in the prototype using this air electrode. Further, when the air permeation time was set to 90 seconds, 20 mA discharge could not be performed due to insufficient air supply.
【０１３１】これら以外の空気透過時間の場合には、実
施例１７，１８，１９において空気極透過時間５０秒以
上の範囲で、空気供給が不足して目的とする電流値が取
り出せなかった。したがつてこれらの実施例では１５〜
３５秒の空気透過時間の空気極が適当である。また、実
施例２０，２１，２２では１５〜３５秒で漏液発生する
ため、空気極の透過時間は５０〜７０秒が適当である。In the case of air permeation times other than these, in Examples 17, 18, and 19, within the range of the air electrode permeation time of 50 seconds or more, the air supply was insufficient and the target current value could not be taken out. Therefore, in these examples,
A cathode with an air permeation time of 35 seconds is suitable. Further, in Examples 20, 21, and 22, liquid leakage occurs in 15 to 35 seconds, and thus the permeation time of the air electrode is preferably 50 to 70 seconds.
【０１３２】このように、空気孔と空気極の空気透過時
間とを組み合わせることによって、重負荷特性を向上さ
せることができたが、一方、空気供給を向上させたこと
により、過放電漏液、過放電後の電池膨れ、軽負荷６２
０Ω放電における短寿命発生などの問題が生じた。これ
は水酸化カリウム濃度を３５％、負極作用物質と水酸化
カリウム水溶液との重量比を２００／５０、充填率を９
８％、と従来基準で電池を試作したためである。本発明
の正極ケースの空気孔面積比率と空気極の空気透過時間
との組み合わせに合わせて、上記の負極仕様を検討し直
す必要がある。Thus, the heavy load characteristics could be improved by combining the air holes and the air permeation time of the air electrode. On the other hand, by improving the air supply, the over discharge leakage, Battery swells after over-discharging, light load 62
Problems such as the occurrence of a short life in 0Ω discharge occurred. This is because the potassium hydroxide concentration is 35%, the weight ratio of the negative electrode active substance and the potassium hydroxide aqueous solution is 200/50, and the filling rate is 9%.
This is because the battery was prototyped based on the conventional standard of 8%. It is necessary to reexamine the above negative electrode specifications in accordance with the combination of the air hole area ratio of the positive electrode case of the present invention and the air permeation time of the air electrode.
【０１３３】まず、前記表１８の仕様で、６２０Ωのよ
うな長期室内放電で不具合が見られた。その対策とし
て、水酸化カリウム濃度を低下させて二酸化炭素との反
応を軽減するか、前記重量比を電解液量リッチにするこ
とで、水分の蒸発を抑えることにした。First, in the specifications shown in Table 18, a defect was found in long-term indoor discharge such as 620Ω. As a countermeasure, the evaporation of water is suppressed by reducing the concentration of potassium hydroxide to reduce the reaction with carbon dioxide or by making the weight ratio rich in the amount of the electrolytic solution.
【０１３４】まず水酸化カリウムの濃度別例で試作し
た。代表例として、空気孔の面積比率０．５９％以上
（実施例１７，１８，１９）と０．５９％以下（実施例
２１，２２，２３）とについて、水酸化カリウム濃度を
２５，２７，２９，３１，３３，３５％に調整し、前記
重量比は２００／５０、充填率は９８％（いずれも従来
例と同じ）で試作した。First, trial production was carried out by changing the concentration of potassium hydroxide. As a typical example, with respect to the area ratio of air holes of 0.59% or more (Examples 17, 18, 19) and 0.59% or less (Examples 21, 22, 23), the potassium hydroxide concentration was 25, 27 ,. It was adjusted to 29, 31, 33, 35%, the weight ratio was 200/50, and the filling rate was 98% (all are the same as the conventional example).
【０１３５】これらについて過放電漏液試験および６２
０Ωの放電試験を行った。過放電漏液試験は各１０個に
ついて、２５℃−８５％ＲＨで２５０Ω−２１６時間放
電して漏液個数を調べた。結果を表２１に示す。また、
６２０Ωの放電試験は２０℃−６０％ＲＨの条件下、個
数１０個について行った。結果を表２２に示す。For these, the over-discharge leakage test and 62
A discharge test of 0Ω was conducted. In the over discharge leakage test, 10 pieces each were discharged at 25 ° C.-85% RH for 250Ω-216 hours, and the number of leakage pieces was examined. The results are shown in Table 21. Also,
The discharge test of 620 Ω was conducted on 10 pieces under the condition of 20 ° C.-60% RH. The results are shown in Table 22.
【０１３６】[0136]
【表２１】 [Table 21]
【０１３７】[0137]
【表２２】 [Table 22]
【０１３８】これらの試験結果から、実施例１７〜１９
の場合はＫＯＨ３１％以下、実施例２１〜２３ではＫＯ
Ｈ３３％以下とする必要がある。また、表２２の結果か
ら、いずれの実施例においてもＫＯＨ２５％以下では放
電時間の低下が見られたので、ＫＯＨ２７％以上にする
必要がある。つまり、ＫＯＨの濃度が高いと過放電漏液
に不利な傾向があり、逆にＫＯＨの濃度が低すぎると放
電特性を劣化させる。これは大気中の水分吸収によるＫ
ＯＨと独活の低下に起因する。From these test results, Examples 17 to 19
In the case of No. 31% or less of KOH, in Examples 21 to 23, KO
It must be H33% or less. In addition, from the results of Table 22, in any of the examples, a decrease in discharge time was observed when KOH was 25% or less, so KOH needs to be 27% or more. That is, if the concentration of KOH is high, there is a tendency of being disadvantageous to the over-discharge leakage, and conversely, if the concentration of KOH is too low, the discharge characteristics are deteriorated. This is due to absorption of water in the atmosphere
This is due to a decrease in OH and independence.
【０１３９】以上の結果、空気孔の面積比率０．５９％
以上ではＫＯＨ濃度は２７〜３１％、空気孔の面積比率
０．５９％以下ではＫＯＨ濃度は２７〜３３％の範囲が
よいことがわかった。As a result, the area ratio of air holes is 0.59%.
From the above, it was found that the KOH concentration is preferably 27 to 31%, and the KOH concentration is preferably 27 to 33% when the air hole area ratio is 0.59% or less.
【０１４０】次に、負極作用物質と電解液との重量比に
ついて検討した。従来は亜鉛２００ｇに対して水酸化カ
リウム水溶液５０ｇを使用しているが、この重量比では
負極ゲルが硬くなり、充填ノズルの詰まりが発生し、生
産工程で従来から問題があった。Next, the weight ratio of the negative electrode acting substance and the electrolytic solution was examined. Conventionally, 50 g of an aqueous potassium hydroxide solution is used for 200 g of zinc, but at this weight ratio, the negative electrode gel becomes hard and the filling nozzle is clogged, which has been a problem in the production process.
【０１４１】そこで、上記において最適としたＫＯＨ濃
度範囲の２９％で、亜鉛重量２００ｇに対して水酸化カ
リウム水溶液の量を５０ｇ，６０ｇ，７０ｇ，８０ｇ，
９０ｇ，１００ｇとして試験を行った。表２３に２０℃
−６０％ＲＨの条件下での６２０Ω放電における放電持
続時間を示す。Therefore, in the above optimum KOH concentration range of 29%, the amount of the potassium hydroxide aqueous solution is 50 g, 60 g, 70 g, 80 g
The test was conducted using 90 g and 100 g. 20 ° C in Table 23
4 shows the discharge duration in 620Ω discharge under the condition of −60% RH.
【０１４２】[0142]
【表２３】 [Table 23]
【０１４３】上記表に示すように、水酸化カリウム重量
を現行の５０ｇよりも増やすことで、放電持続時間を長
くすることができ、亜鉛の利用率を高めることができ
た。これは水酸化カリウム水溶液重量を増やすことで大
気中の炭酸ガスや水分の影響を低減したためである。次
に同じ仕様において、負極ゲル充填試験を行った。表２
４にその結果を示す。As shown in the above table, by increasing the weight of potassium hydroxide over the current value of 50 g, the discharge duration could be lengthened and the zinc utilization rate could be increased. This is because the influence of carbon dioxide gas and water in the atmosphere was reduced by increasing the weight of the potassium hydroxide aqueous solution. Next, a negative electrode gel filling test was conducted under the same specifications. Table 2
The result is shown in FIG.
【０１４４】[0144]
【表２４】 [Table 24]
【０１４５】水酸化カリウム重量が５０ｇ以下ではゲル
の流れ性が悪く、ノズル詰まりが増えて所定のゲル重量
を排出することが難しかった。また、９０ｇを超すとゲ
ル充填工程中にゲルが絶縁ガスケットの脇に垂れて嵌合
クリンプ時にゲルずれを起こし、嵌合不良を多発した。When the weight of potassium hydroxide was 50 g or less, the flowability of the gel was poor, the nozzle clogging increased, and it was difficult to discharge the predetermined gel weight. Further, when the amount exceeds 90 g, the gel droops to the side of the insulating gasket during the gel filling process, causing a gel shift at the time of crimping the fitting, resulting in frequent fitting failures.
【０１４６】以上の結果から、亜鉛２００ｇに対して水
酸化カリウム水溶液の重量は６０〜８０ｇが適当である
ことがわかった。つまり亜鉛／水酸化カリウム水溶液の
重量比は２．５〜３．３となる。この範囲で軽負荷６２
０Ω放電でも目的の放電時間がえられた。From the above results, it was found that an appropriate weight of the aqueous potassium hydroxide solution is 60 to 80 g per 200 g of zinc. That is, the weight ratio of the zinc / potassium hydroxide aqueous solution is 2.5 to 3.3. Light load 62 in this range
The target discharge time was obtained even with 0Ω discharge.
【０１４７】次に電池膨れの問題について検討した。上
記電池の場合、従来例に比べて空気供給が向上して外部
からの水分吸収が増加し、放電後の電池総高が０．２mm
以上となり、使用後電池ホルダーからの取り外しができ
なくなった。そこで負極充填率について次のように試験
を行った。Next, the problem of battery swelling was examined. In the case of the above battery, compared with the conventional example, the air supply is improved and the absorption of moisture from the outside is increased, and the total battery height after discharge is 0.2 mm.
Now that the battery holder cannot be removed from the battery holder after use. Therefore, the negative electrode filling rate was tested as follows.
【０１４８】負極充填率の説明は先に示したが、今回は
前記の取り出し可能電流密度の最低値が０．１Ａ／ｃｍ
2の電池の場合と同様に、充填率７８％，８２％，８６
％，９０％，９４％および９８％について試作した。こ
れらの試作品について内部抵抗と過放電後の電池総高の
変化とを調べた。なお、水酸化カリウム濃度２９％、亜
鉛／電解液重量比＝２００／６０で行った。これらの試
作品について内部抵抗と過放電後の電池総高の変化とを
調べた。The description of the negative electrode filling rate has been given above, but this time, the minimum value of the current density that can be taken out is 0.1 A / cm.
Similar to the case of the battery No. 2 , the filling rate is 78%, 82%, 86
%, 90%, 94% and 98% were made as prototypes. For these prototypes, the internal resistance and the change in the total cell height after overdischarge were examined. The potassium hydroxide concentration was 29%, and the weight ratio of zinc / electrolyte was 200/60. For these prototypes, the internal resistance and the change in the total cell height after overdischarge were examined.
【０１４９】表２５に内部抵抗の測定結果を示す。充填
率が７８％では負極ケースと負極ゲルの接触がわずかな
がら悪く、電池作成１日後の初期特性で、内部抵抗のバ
ラツキが大きいことが分かった。内部抵抗の不良率を抑
えるために、充填率は８２％以上がよいと考えられる。Table 25 shows the measurement results of the internal resistance. It was found that when the filling rate was 78%, the contact between the negative electrode case and the negative electrode gel was slightly poor, and the initial resistance one day after the production of the battery showed a large variation in the internal resistance. In order to suppress the defective rate of the internal resistance, the filling rate is considered to be 82% or more.
【０１５０】[0150]
【表２５】 [Table 25]
【０１５１】また、表２６に過放電後の電池総高の変化
を示す。充填率が９８％では過放電試験後の電池総高が
最大値で０．３mm増加したため、ホルダーから取り出せ
なかった。充填率が９８％より低い場合はＪＩＳ規格の
０．２mmをほぼ超えないことがわかった。そこで充填率
上限を９４％にすることによって電池膨れを抑えること
にした。つまり、内部抵抗の不良率および電池膨れを抑
えるには、充填率は８２％〜９４％が最適な領域である
ことが分かった。Table 26 shows changes in the total cell height after overdischarge. When the filling rate was 98%, the total height of the battery after the over-discharge test increased by 0.3 mm at the maximum value, so that it could not be taken out from the holder. It was found that when the filling rate was lower than 98%, it did not exceed the JIS standard of 0.2 mm. Therefore, the upper limit of the filling rate is set to 94% to suppress the battery swelling. That is, it has been found that the filling rate is optimally in the range of 82% to 94% for suppressing the defective rate of the internal resistance and the battery swelling.
【０１５２】[0152]
【表２６】 [Table 26]
【０１５３】以上説明したように、空気孔の径と個数
（空気孔の総面積）と正極ケース底部の面積との比率、
空気極の透過時間を組み合わせることで、重負荷特性の
向上させた空気電池が製造できる。また空気供給が向上
した結果、電池内部からの電解液の蒸発、大気中から炭
酸ガス、水分の吸収による影響が大きいので、負極仕
様、すなわち水酸化カリウム濃度、負極作用物質と電解
液との重量比、負極ゲルの充填率を検討し直すことで、
漏液特性を維持し、軽負荷放電の短寿命、電池膨れなど
使用時に不具合のない、重負荷特性に優れた空気電池が
得られた。As described above, the ratio of the diameter and number of air holes (total area of air holes) to the area of the bottom of the positive electrode case,
An air battery with improved heavy load characteristics can be manufactured by combining the permeation time of the air electrode. As a result of improved air supply, the evaporation of the electrolyte from the inside of the battery and the absorption of carbon dioxide and water from the atmosphere have a large effect, so the negative electrode specifications, that is, potassium hydroxide concentration, the weight of the negative electrode active substance and the electrolytic solution, are large. By reconsidering the ratio and the filling rate of the negative electrode gel,
An air battery that maintains the liquid leakage characteristics, has a short life under light load discharge, has no problems during use such as battery swelling, and has excellent heavy load characteristics was obtained.
【０１５４】なお、本実施例では、空気の孔をすべて同
じにして試作を行った。しかし、空気孔の径がそれぞれ
異なる径を用いても、請求項範囲であるならば、効果は
得られる。また空気孔の形も、円状だけではなく、空気
孔の形は金型・加工できる範囲でどのような形でもよ
い。In this example, a prototype was made with all the air holes being the same. However, even if the diameters of the air holes are different from each other, the effect can be obtained within the scope of the claims. Further, the shape of the air hole is not limited to a circular shape, and the shape of the air hole may be any shape as long as it can be molded and processed.
【０１５５】また、今回空気極製造の際の正極触媒層と
撥水膜層との圧着工程を、アンカー効果によるローラ方
式で行ったが、圧着工程としては正極触媒層と撥水膜層
とを圧着できてかつ空気極の透過時間をコントロールで
きる方式であればいかなるものでもよく、例えば液体含
浸方式（アルコール含浸方式）などが使用できる。Further, the pressure-bonding step of the positive electrode catalyst layer and the water-repellent film layer at the time of manufacturing the air electrode this time was carried out by the roller system by the anchor effect. Any method can be used as long as it can be pressure-bonded and the permeation time of the air electrode can be controlled. For example, a liquid impregnation method (alcohol impregnation method) can be used.
【０１５６】[0156]
【発明の効果】本発明によれば、重負荷放電特性を維持
し、長期放電中の劣化、及び過放電時の漏液を防止し、
従来に比べて、信頼性の高い空気電池を提供することが
できる。According to the present invention, heavy load discharge characteristics are maintained, deterioration during long-term discharge, and liquid leakage during overdischarge are prevented,
It is possible to provide a highly reliable air battery as compared with the related art.
【図１】本発明の空気電池の一実施例を示す断面図。FIG. 1 is a sectional view showing an embodiment of an air battery of the present invention.
【図２】空気孔の配列を説明する図。FIG. 2 is a diagram illustrating an arrangement of air holes.
【図３】限界電流値測定曲線を示す図。FIG. 3 is a diagram showing a limiting current value measurement curve.
１…空気孔、２…正極ケース、３…拡散紙、４…５と圧
着する撥水膜、５…正極触媒層、６…セパレータ、７…
正極集電体、８…撥水膜、９…絶縁ガスケット、１０…
負極ケース、１１…負極作用物質。DESCRIPTION OF SYMBOLS 1 ... Air hole, 2 ... Positive electrode case, 3 ... Diffusion paper, 4 ... 5 Water-repellent film press-bonded, 5 ... Positive electrode catalyst layer, 6 ... Separator, 7 ...
Positive electrode current collector, 8 ... Water repellent film, 9 ... Insulation gasket, 10 ...
Negative electrode case, 11 ... Negative electrode acting substance.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H032 AA02 AS03 CC02 CC04 CC06 CC16 HH00 HH01 HH02 HH04 HH08 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 5H032 AA02 AS03 CC02 CC04 CC06 CC16 HH00 HH01 HH02 HH04 HH08
Claims (12)
内に、撥水膜層、正極触媒層および集電体層を有する空
気極が収納され、負極ケース内に電解液を保有する負極
作用物質が収納されている空気電池において、空気孔の
総面積と正極ケース底面の面積との比率（空気孔の総面
積／正極ケース底面の面積）が０．３〜３．３％の範囲
であり、撥水膜のガーレ値が２００〜５００秒であり、
かつ電解液である水酸化カリウム濃度が２５〜４３％で
あることを特徴とする空気電池。1. A negative electrode function in which an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is held in the negative electrode case. In an air battery containing a substance, the ratio of the total area of air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the bottom surface of the positive electrode case) is in the range of 0.3 to 3.3%. , The Gurley value of the water-repellent film is 200 to 500 seconds,
An air battery characterized in that the concentration of potassium hydroxide, which is an electrolytic solution, is 25 to 43%.
内に、撥水膜層、正極触媒層および集電体層を有する空
気極が収納され、負極ケース内に電解液を保有する負極
作用物質が収納されている空気電池において、空気孔の
総面積と正極ケース底面の面積との比率（空気孔の総面
積／正極ケース底面の面積）が３．３〜３０％の範囲で
あり、撥水膜のガーレ値が１０００〜５０００秒であ
り、かつ電解液である水酸化カリウム濃度が３５〜４０
％であることを特徴とする空気電池。2. A negative electrode function in which an air electrode having a water repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is held in the negative electrode case. In an air battery containing a substance, the ratio of the total area of air holes to the area of the bottom surface of the positive electrode case (total area of air holes / area of the positive electrode case bottom surface) is in the range of 3.3 to 30%, The Gurley value of the water film is 1000 to 5000 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 35 to 40.
% Air battery.
重量比（負極作用物質／水酸化カリウム水溶液）が、
２．５〜３．３である請求項１および２のいずれかに記
載の空気電池。3. The weight ratio of the negative electrode acting substance and the potassium hydroxide aqueous solution (negative electrode acting substance / potassium hydroxide aqueous solution) is
The air battery according to any one of claims 1 and 2, which has a size of 2.5 to 3.3.
気極で形成される空隙体積に対する放電後の負極ゲルの
体積の比率（放電後の負極ゲルの体積／上記空隙体積）
が、８４〜９２％である請求項１および２のいずれかに
記載の空気電池。4. The ratio of the volume of the negative electrode gel after discharging to the volume of voids formed by the negative electrode case, the insulating gasket, and the air electrode (volume of negative electrode gel after discharging / the above void volume).
Is 84 to 92%, The air battery according to any one of claims 1 and 2.
内に、撥水膜層、正極触媒層および集電体層を有する空
気極が収納され、負極ケース内に電解液を保有する負極
作用物質が収納され、かつ空気極単位面積当たりの取り
出し可能電流密度の最低値が０．１Ａ／ｃｍ2である空
気電池において、空気孔の総面積と正極ケース底面の面
積との比率（空気孔の総面積／正極ケース底面の面積×
１００）が０．１７〜２．５％の範囲であり、空気極の
空気透過時間が１５〜３５秒であり、かつ電解液である
水酸化カリウム濃度が２９〜３７％であることを特徴と
する空気電池。5. A negative electrode function in which an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is held in the negative electrode case. The ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (in the air holes of an air battery in which the substance is stored and the minimum value of the retrievable current density per unit area of the air electrode is 0.1 A / cm 2 ) Total area / Area of positive electrode case bottom x
100) is in the range of 0.17 to 2.5%, the air permeation time of the air electrode is 15 to 35 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 29 to 37%. Air battery to do.
内に、撥水膜層、正極触媒層および集電体層を有する空
気極が収納され、負極ケース内に電解液を保有する負極
作用物質が収納され、かつ空気極単位面積当たりの取り
出し可能電流密度の最低値が０．１Ａ／ｃｍ2である空
気電池において、空気孔の総面積と正極ケース底面の面
積との比率（空気孔の総面積／正極ケース底面の面積×
１００）が４．４〜１７．７％の範囲であり、空気極の
空気透過時間が５０〜７０秒であり、かつ電解液である
水酸化カリウム濃度が３１〜３９％であることを特徴と
する空気電池。6. A negative electrode function in which an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is held in the negative electrode case. The ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (in the air holes of an air battery in which the substance is stored and the minimum value of the retrievable current density per unit area of the air electrode is 0.1 A / cm 2 ) Total area / Area of positive electrode case bottom x
100) is in the range of 4.4 to 17.7%, the air permeation time of the air electrode is 50 to 70 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 31 to 39%. Air battery to do.
重量比（負極作用物質／水酸化カリウム水溶液）が、
２．５〜３．３である請求項５および６のいずれかに記
載の空気電池。7. The weight ratio of the negative electrode acting substance and the potassium hydroxide aqueous solution (negative electrode acting substance / potassium hydroxide aqueous solution) is
The air battery according to any one of claims 5 and 6, which has a size of 2.5 to 3.3.
気極で形成される空隙体積に対する放電後の負極ゲルの
体積の比率（放電後の負極ゲルの体積／上記空隙体積）
が、８２〜９４％である請求項５および６のいずれかに
記載の空気電池。8. The ratio of the volume of the negative electrode gel after discharge to the void volume formed by the negative electrode case, the insulating gasket, and the air electrode (volume of the negative electrode gel after discharge / the above-mentioned void volume).
Is 82-94%, The air battery in any one of Claim 5 and 6.
内に、撥水膜層、正極触媒層および集電体層を有する空
気極が収納され、負極ケース内に電解液を保有する負極
作用物質が収納され、かつ空気極単位面積当たりの取り
出し可能電流密度の最低値が０．１８Ａ／ｃｍ2である
空気電池において、空気孔の総面積と正極ケース底面の
面積との比率（空気孔の総面積／正極ケース底面の面積
×１００）が０．５９〜８．４３％の範囲であり、空気
極の空気透過時間が１５〜３５秒であり、かつ電解液で
ある水酸化カリウム濃度が２７〜３１％であることを特
徴とする空気電池。9. A negative electrode function in which an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is retained in the negative electrode case. The ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (in the air holes) of the air battery in which the substance is stored and the minimum value of the current density that can be taken out per unit area of the air electrode is 0.18 A / cm 2 . The total area / the area of the bottom surface of the positive electrode case × 100) is in the range of 0.59 to 8.43%, the air permeation time of the air electrode is 15 to 35 seconds, and the concentration of potassium hydroxide as the electrolytic solution is 27. An air battery characterized by being ~ 31%.
ス内に、撥水膜層、正極触媒層および集電体層を有する
空気極が収納され、負極ケース内に電解液を保有する負
極作用物質が収納され、かつ空気極単位面積当たりの取
り出し可能電流密度の最低値が０．１８Ａ／ｃｍ2であ
る空気電池において、空気孔の総面積と正極ケース底面
の面積との比率（空気孔の総面積／正極ケース底面の面
積×１００）が０．０２６〜０．５９％の範囲であり、
空気極の空気透過時間が５０〜７０秒であり、かつ電解
液である水酸化カリウム濃度が２７〜３３％であること
を特徴とする空気電池。10. A negative electrode function in which an air electrode having a water-repellent film layer, a positive electrode catalyst layer and a current collector layer is housed in a positive electrode case having a large number of air holes on the bottom surface, and an electrolytic solution is held in the negative electrode case. The ratio of the total area of the air holes to the area of the bottom surface of the positive electrode case (in the air holes) of the air battery in which the substance is stored and the minimum value of the current density that can be taken out per unit area of the air electrode is 0.18 A / cm 2 . Total area / area of bottom surface of positive electrode case × 100) is in the range of 0.026 to 0.59%,
An air battery, wherein the air permeation time of the air electrode is 50 to 70 seconds, and the concentration of potassium hydroxide as an electrolytic solution is 27 to 33%.
の重量比（負極作用物質／水酸化カリウム水溶液）が、
２．５〜３．３である請求項９および１０のいずれかに
記載の空気電池。11. The weight ratio of the negative electrode active substance and the potassium hydroxide aqueous solution (negative electrode active substance / potassium hydroxide aqueous solution) is
The air battery according to any one of claims 9 and 10, which has a size of 2.5 to 3.3.
空気極で形成される空隙体積に対する放電後の負極ゲル
の体積の比率（放電後の負極ゲルの体積／上記空隙体
積）が、８２〜９４％である請求項５および６のいずれ
かに記載の空気電池。12. The ratio of the volume of the negative electrode gel after discharging to the volume of voids formed by the negative electrode case, the insulating gasket and the air electrode (volume of negative electrode gel after discharging / the above void volume) is 82 to 94%. The air battery according to any one of claims 5 and 6.
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|---|---|---|---|
| JP2002245118A JP4253723B2 (en) | 2001-08-27 | 2002-08-26 | Air battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001255790 | 2001-08-27 | ||
| JP2001-255790 | 2001-08-27 | ||
| JP2002245118A JP4253723B2 (en) | 2001-08-27 | 2002-08-26 | Air battery |
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| Publication Number | Publication Date |
|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018049687A (en) * | 2016-09-20 | 2018-03-29 | マクセルホールディングス株式会社 | Sheet-like air battery |
| WO2022208993A1 (en) * | 2021-03-30 | 2022-10-06 | 日本碍子株式会社 | Air electrode/separator assembly and metal-air secondary battery |
-
2002
- 2002-08-26 JP JP2002245118A patent/JP4253723B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018049687A (en) * | 2016-09-20 | 2018-03-29 | マクセルホールディングス株式会社 | Sheet-like air battery |
| WO2022208993A1 (en) * | 2021-03-30 | 2022-10-06 | 日本碍子株式会社 | Air electrode/separator assembly and metal-air secondary battery |
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| Publication number | Publication date |
|---|---|
| JP4253723B2 (en) | 2009-04-15 |
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