JP2998564B2 - Air battery - Google Patents
Air batteryInfo
- Publication number
- JP2998564B2 JP2998564B2 JP13868294A JP13868294A JP2998564B2 JP 2998564 B2 JP2998564 B2 JP 2998564B2 JP 13868294 A JP13868294 A JP 13868294A JP 13868294 A JP13868294 A JP 13868294A JP 2998564 B2 JP2998564 B2 JP 2998564B2
- Authority
- JP
- Japan
- Prior art keywords
- air
- battery
- film
- uneven portion
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y02E60/128—
Landscapes
- Hybrid Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、空気電池の、とくに酸
素供給と漏液防止のためのＰＴＦＥ膜に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a PTFE membrane for an air battery, particularly for supplying oxygen and preventing liquid leakage.
【０００２】[0002]
【従来の技術】空気電池は、正極活物質として空気中の
酸素を、負極活物質に亜鉛を用いた電池である。図４に
ボタン形空気電池の断面図を示す。図４に示すように、
亜鉛極１を負極ケース２に収納しておりガスケット３を
介して正極ケース４を封口している。セパレータ５は空
気極６と負極亜鉛極１を隔離している。空気極６には多
孔性のポリテトラフルオロエチレン（ＰＴＦＥ）膜７が
接しており、このＰＴＦＥ膜７の下部には空気拡散紙９
がありこの拡散紙９は空気孔８を設けた正極ケース４と
接している。なお、電池使用時までは空気孔８はシール
紙１０でシールされている。2. Description of the Related Art An air battery is a battery using oxygen in the air as a positive electrode active material and zinc as a negative electrode active material. FIG. 4 shows a cross-sectional view of the button type air battery. As shown in FIG.
The zinc electrode 1 is housed in the negative electrode case 2, and the positive electrode case 4 is sealed via the gasket 3. The separator 5 separates the air electrode 6 from the negative electrode zinc electrode 1. A porous polytetrafluoroethylene (PTFE) film 7 is in contact with the air electrode 6, and an air diffusion paper 9 is provided below the PTFE film 7.
The diffusion paper 9 is in contact with the positive electrode case 4 provided with the air holes 8. The air holes 8 are sealed with a seal paper 10 until the battery is used.
【０００３】ここで、多孔性ＰＴＦＥ膜７の役割は、空
気中の酸素の電池内部への供給量をコントロールするこ
とと、電解液の電池外部への漏出を防止することであ
る。Here, the role of the porous PTFE membrane 7 is to control the supply amount of oxygen in the air to the inside of the battery and to prevent the electrolyte from leaking out of the battery.
【０００４】空気拡散紙９の役割は、電池放電時に空気
孔から電池内に取り入れられる酸素を、空気極に均一に
拡散することである。この空気拡散紙は、正極ケースの
底面内側の中央部に設けられた凹部内に載置されてお
り、この拡散紙上にＰＴＦＥ膜や空気極を順次重ね合わ
せて固定していた。The role of the air diffusion paper 9 is to uniformly diffuse oxygen taken into the battery from the air holes at the time of battery discharge to the air electrode. This air diffusion paper was placed in a concave portion provided at the central portion inside the bottom surface of the positive electrode case, and a PTFE film and an air electrode were sequentially superposed and fixed on the diffusion paper.
【０００５】[0005]
【発明が解決しようとする課題】しかし、ボタン形空気
電池では、空気拡散紙は正極ケースの底面内側の凹部に
載置されているだけであるため位置ずれが起こりやすか
った。However, in the button type air battery, since the air diffusion paper is merely placed in the concave portion inside the bottom surface of the positive electrode case, the air gap is easily shifted.
【０００６】空気拡散紙が正極ケースの凹部内からはみ
出た場合は、その上に載置されている撥水膜と正極ケー
スの周縁部との間に空気拡散紙がはさまれることがあっ
た。When the air diffusion paper protrudes from the inside of the concave portion of the positive electrode case, the air diffusion paper is sometimes caught between the water-repellent film placed thereon and the peripheral portion of the positive electrode case. .
【０００７】そして、空気拡散紙のはさまれた部分は圧
縮されて亀裂が発生し、この亀裂から電池内部の電解液
空気孔から電池外部へ漏出することがあった。[0007] The portion between the air diffusion papers is compressed and cracks are generated, and the cracks may leak from the electrolyte air holes inside the battery to the outside of the battery.
【０００８】このため、空気拡散紙を排除することが考
えられており、その１つの方法としてＰＴＦＥ膜を部分
的に圧縮してへこませることで膜に凹凸部を形成し、こ
の凹凸部によって空気拡散を行う方法が考えられる。し
かし、膜を圧縮することで膜の細孔が塞がれることにな
り、結果として膜の透気度がほぼゼロになって酸素が供
給されず電池が放電できないことがあった。[0008] For this reason, it has been considered to eliminate the air diffusion paper. As one of the methods, an uneven portion is formed on the PTFE film by partially compressing and denting the film. A method of performing air diffusion is conceivable. However, when the membrane is compressed, the pores of the membrane are closed, and as a result, the air permeability of the membrane becomes almost zero, so that oxygen is not supplied and the battery cannot be discharged.
【０００９】本発明は、このような課題を解決するもの
であり、空気拡散紙を用いることなく空気極への酸素拡
散を行い、安定した放電性能が得られる空気電池を提供
するものである。The present invention has been made to solve such a problem, and an object of the present invention is to provide an air battery capable of diffusing oxygen to an air electrode without using an air diffusion paper and obtaining stable discharge performance.
【００１０】[0010]
【課題を解決するための手段】この目的を達成するため
に、本発明の空気電池は多孔性ＰＴＦＥ膜に、網状のポ
リオレフィン膜をラミネートするか、あるいは溶解時の
粘度が１万ｃｐ以下のホットメルト樹脂を溶解して部分
的に転写するかによってＰＴＦＥ膜の一面に凹凸部を形
成し、この凹凸部を正極ケース側に配したものである。In order to achieve this object, the air battery of the present invention is provided by laminating a network-like polyolefin membrane on a porous PTFE membrane, or by dissolving a hot polyolefin membrane having a viscosity of 10,000 cp or less upon dissolution. An uneven portion is formed on one surface of the PTFE film depending on whether the melt resin is dissolved and partially transferred, and the uneven portion is arranged on the positive electrode case side.
【００１１】[0011]
【作用】本発明の空気電池では、ＰＴＦＥ膜の一面に凹
凸部を形成してこの凹凸部を正極ケース側に配したもの
であるので、空気拡散紙を用いることなく、電池内での
酸素の拡散を行うことができ、良好な放電性能を発揮す
る空気電池を得ることが可能となる。In the air battery of the present invention, since the uneven portion is formed on one surface of the PTFE film and the uneven portion is arranged on the positive electrode case side, the oxygen in the battery can be reduced without using an air diffusion paper. Diffusion can be performed, and an air cell exhibiting good discharge performance can be obtained.
【００１２】[0012]
【実施例】以下に本発明の実施例を図面を参照しながら
説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１３】図１に本発明のボタン形空気電池の側面断
面図を示す。図１で１１は下面に凹凸部を有するＰＴＦ
Ｅ膜であり、図２に示すように多孔性ＰＴＦＥ膜７の一
面に網状のポリプロピレン膜１２をラミネートして凹凸
部を形成したものである。平均ガーレイ数を３５０００
ｓｅｃとして作製した多孔性ＰＴＦＥ膜にポリプロピレ
ン膜をラミネートしてＰＴＦＥ膜のガーレイ数を３８５
００〜４９５００ｓｅｃの範囲としている。この電池を
本発明の電池Ａとした。ここで、ガーレイ数が大きくな
ると膜の通気度は小さくなる。FIG. 1 is a side sectional view of a button type air battery according to the present invention. In FIG. 1, reference numeral 11 denotes a PTF having an uneven portion on the lower surface.
As shown in FIG. 2, an E film is formed by laminating a network-like polypropylene film 12 on one surface of a porous PTFE film 7 to form an uneven portion. 35,000 average Gurley
The Gurley number of the PTFE membrane was 385 by laminating a polypropylene membrane on the porous PTFE membrane produced in sec.
The range is from 00 to 49500 sec. This battery was designated as Battery A of the present invention. Here, as the Gurley number increases, the air permeability of the membrane decreases.
【００１４】多孔性ＰＴＦＥ膜７周縁部の凹凸部は、電
池封口時の圧力により押しつぶされるため、電池の密封
性は問題なく、電池内部の電解液が多孔性ＰＴＦＥ膜７
と正極ケース４の境界から漏出することはない。Since the irregularities on the peripheral edge of the porous PTFE membrane 7 are crushed by the pressure at the time of closing the battery, there is no problem in the sealing performance of the battery, and the electrolyte inside the battery can be removed by the porous PTFE membrane 7.
Does not leak from the boundary of the positive electrode case 4.
【００１５】また、凹凸部を有するＰＴＦＥ膜１１とし
て、平均ガーレイ数を３５０００ｓｅｃとして作製した
多孔性ＰＴＦＥ膜に溶解時の粘度が１万ｃｐ以下のホッ
トメルト樹脂を溶解して部分的に転写して膜の下面に凹
凸部を形成したものを用い、これを本発明の電池Ｂとし
た。ＰＴＦＥ膜のガーレイ数はホットメルト樹脂を転写
することによって３９０００〜５２０００ｓｅｃの範囲
となった。Further, as a PTFE film 11 having an uneven portion, a hot melt resin having a viscosity of 10,000 cp or less upon melting is melted and partially transferred to a porous PTFE film having an average Gurley number of 35,000 sec. A battery having an uneven portion formed on the lower surface of the film was used as a battery B of the present invention. The Gurley number of the PTFE film was in the range of 39000 to 52000 sec by transferring the hot melt resin.
【００１６】ここでホットメルト樹脂としてエチレンビ
ニルアセテートを用い、図３に示すようにＰＴＦＥ膜７
に溶解したエチレンビニルアセテート１３をロールによ
り転写した。Here, ethylene vinyl acetate was used as the hot melt resin, and as shown in FIG.
The ethylene vinyl acetate 13 dissolved in the above was transferred by a roll.
【００１７】一方、比較例として平均ガーレイ数４５０
００ｓｅｃの多孔性ＰＴＦＥ膜を用いたものを比較の電
池Ｃとした。On the other hand, as a comparative example, the average Gurley number was 450.
A battery using a porous PTFE membrane of 00 sec was used as a comparative battery C.
【００１８】さらに、比較例として平均ガーレイ数３５
０００ｓｅｃの多孔性ＰＴＦＥ膜に、表面に凹凸部を備
えた樹脂板を重ね合わせて圧縮することによって、膜表
面に凹凸部を形成したものを用い、これを比較の電池Ｄ
とした。このＰＴＦＥ膜のガーレイ数は３６５００〜５
１０００ｓｅｃの範囲となった。Further, as a comparative example, the average Gurley number was 35.
A battery having irregularities formed on the surface of the film by overlaying and compressing a resin plate having irregularities on the surface on a porous PTFE film of 2,000 sec.
And The Gurley number of this PTFE membrane is 36,500 to 5,
The range was 1000 sec.
【００１９】電池Ａ，Ｂ，Ｄでは膜の下面に形成した凹
凸部の凹部の深さは０．１０ｍｍとしており、空気拡散
紙は用いなかった。また、電池Ｃは空気拡散紙を用いた
ものと用いないものを作製し、それぞれ電池Ｃ１，Ｃ２
とした。ここで電池は直径２３．１ｍｍ高さ３．０ｍ
ｍ、公称仕様１．４Ｖ８５０ｍＡｈとした。In the batteries A, B and D, the depth of the concave portions of the concave and convex portions formed on the lower surface of the film was 0.10 mm, and no air diffusion paper was used. The batteries C were prepared using air diffusion paper and those not using the air diffusion paper.
And Here, the battery has a diameter of 23.1 mm and a height of 3.0 m.
m, the nominal specification was 1.4V850mAh.
【００２０】これらの電池の放電特性を図５に示す。図
５に示したように、電池Ａ，Ｂでは通常の電池Ｃ１と同
等の放電特性を得ることができた。FIG. 5 shows the discharge characteristics of these batteries. As shown in FIG. 5, the batteries A and B were able to obtain the same discharge characteristics as the normal battery C1.
【００２１】電池Ｃ２では空気拡散紙がないため、酸素
流入不足により、電池の放電電圧が低下した。Since there was no air diffusion paper in the battery C2, the discharge voltage of the battery was lowered due to insufficient oxygen flow.
【００２２】また、電池ＤでもＰＴＦＥ膜を圧縮するこ
とによって膜内の細孔が塞がってしまい、膜の通気状態
が低下して電池の放電電圧が低下した。Also, in the battery D, the pores in the membrane were closed by compressing the PTFE membrane, and the ventilation state of the membrane was lowered, and the discharge voltage of the battery was lowered.
【００２３】なお、本実施例では、ガーレイ数３５００
０ｓｅｃの多孔性ＰＴＦＥ膜に凹凸部を形成したが、ガ
ーレイ数５００〜４００００ｓｅｃの膜に凹凸部を形成
し、ガーレイ数２５０００〜５５０００ｓにした膜を用
いても同様の効果が得られた。In this embodiment, the Gurley number is 3500
Although the uneven portion was formed on the porous PTFE film of 0 sec, the same effect was obtained by using the film having the Gurley number of 25,000 to 55000 s by forming the uneven portion on the film of Gurley number of 500 to 40000 sec.
【００２４】また、本実施例では、ＰＴＦＥ膜にホット
メルト樹脂をロールで転写する方法を用いたが、スクリ
ーン転写（中から樹脂を押し出す方法）でも同様の効果
が得られた。In this embodiment, the method of transferring the hot melt resin to the PTFE film by a roll is used. However, the same effect can be obtained by screen transfer (a method of extruding the resin from the inside).
【００２５】さらに、本実施例では凹凸部の凹部の深さ
を０．１０ｍｍとしたが、０．０３〜０．１８ｍｍの範
囲でも同様の効果が得られた。Further, in the present embodiment, the depth of the concave portion of the concave / convex portion is set to 0.10 mm, but the same effect is obtained in the range of 0.03 to 0.18 mm.
【００２６】[0026]
【発明の効果】以上のように、本発明の空気電池では、
多孔性ＰＴＦＥ膜の一面に凹凸部を付与してこの凹凸部
を空気孔を有する正極ケースに配しており、凹凸部によ
って空気の拡散を行っているので空気拡散紙を電池内に
配する必要はない。As described above, in the air battery of the present invention,
Irregularities are provided on one surface of the porous PTFE film, and the irregularities are arranged in a positive electrode case having air holes. Since the air is diffused by the irregularities, air diffusion paper needs to be arranged in the battery. There is no.
【００２７】したがって、空気拡散紙の位置ずれに起因
する電解液の電池外への漏出を防止することができる。Therefore, it is possible to prevent the electrolyte from leaking out of the battery due to the displacement of the air diffusion paper.
【図１】本発明のボタン形空気電池の側面断面図FIG. 1 is a side sectional view of a button type air battery of the present invention.
【図２】凹凸部を有するＰＴＦＥ膜の側面図FIG. 2 is a side view of a PTFE film having an uneven portion.
【図３】凹凸部を有するＰＴＦＥ膜の作製時の例を示す
図FIG. 3 is a diagram showing an example of manufacturing a PTFE film having an uneven portion.
【図４】従来のボタン形空気電池の側面断面図FIG. 4 is a side sectional view of a conventional button type air battery.
【図５】本発明と比較の電池の放電特性図FIG. 5 is a discharge characteristic diagram of a battery in comparison with the present invention.
１ 亜鉛極 ２ 負極ケース ３ ガスケート ４ 正極ケース ５ セパレータ ６ 空気極 ７ ＰＴＦＥ膜 ８ 空気孔 ９ 空気拡散紙 １０ シール紙 １１ 凹凸部を有するＰＴＦＥ膜 １２ ポリプロレン膜 １３ エチレンビニルアセテート DESCRIPTION OF SYMBOLS 1 Zinc electrode 2 Negative electrode case 3 Gasket 4 Positive electrode case 5 Separator 6 Air electrode 7 PTFE film 8 Air hole 9 Air diffusion paper 10 Seal paper 11 PTFE film having unevenness 12 Polypropylene film 13 Ethylene vinyl acetate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大尾 文夫 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 平５−29025（ＪＰ，Ａ) 特開 昭63−239783（ＪＰ，Ａ) 特開 昭61−273864（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 12/06 - 12/08 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Fumio Oo 1006 Oaza Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP 5-29025 (JP, A) JP Sho 63 -239783 (JP, A) JP-A-61-273864 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 12/06-12/08
Claims (4)
に多孔性のポリテトラフルオロエチレン（ＰＴＦＥ）膜
を配した電池であって、前記多孔性ＰＴＦＥ膜の一面に
網状のポリオレフィン膜をラミネートして凹凸部を形成
するとともに前記凹凸部を正極ケース側に向けて配した
空気電池。1. A battery having a porous polytetrafluoroethylene (PTFE) film disposed between a cathode case having an air hole and an air electrode, wherein a reticulated polyolefin film is provided on one surface of the porous PTFE film. An air battery in which an uneven portion is formed by laminating and the uneven portion is arranged toward the positive electrode case.
に多孔性のポリテトラフルオロエチレン（ＰＴＦＥ）膜
を配した電池であって、前記多孔性ＰＴＦＥ膜の一面に
溶解時の粘度が１万ｃｐ以下のホットメルト樹脂で形成
した凹凸部があり、この凹凸部を正極ケース側に向けて
配した空気電池。2. A battery in which a porous polytetrafluoroethylene (PTFE) film is disposed between a positive electrode case having an air hole and an air electrode, wherein one surface of the porous PTFE film has a viscosity when dissolved. An air battery having an uneven portion formed of a hot melt resin of 10,000 cp or less, and the uneven portion is arranged toward the positive electrode case.
部の深さが０．０３〜０．１８ｍｍである請求項１また
は２記載の空気電池。3. The air battery according to claim 1, wherein the depth of the concave portion of the concave and convex portion formed on the porous PTFE film is 0.03 to 0.18 mm.
孔性ＰＴＦＥ膜に凹凸部を形成することによってＰＴＦ
Ｅ膜のガーレイ数を２５０００〜５５０００ｓｅｃにし
た請求項１または２記載の空気電池。4. A PTF by forming an uneven portion on a porous PTFE film having a Gurley number of 500 to 40000 sec.
3. The air battery according to claim 1, wherein the Gurley number of the E film is 25,000 to 55000 sec.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13868294A JP2998564B2 (en) | 1994-06-21 | 1994-06-21 | Air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13868294A JP2998564B2 (en) | 1994-06-21 | 1994-06-21 | Air battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH087935A JPH087935A (en) | 1996-01-12 |
| JP2998564B2 true JP2998564B2 (en) | 2000-01-11 |
Family
ID=15227649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13868294A Expired - Fee Related JP2998564B2 (en) | 1994-06-21 | 1994-06-21 | Air battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2998564B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8377149B2 (en) | 2006-12-27 | 2013-02-19 | Eveready Battery Company, Inc. | Process for making a catalytic electrode and electrochemical cell using the electrode |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270921B1 (en) * | 2000-01-19 | 2001-08-07 | The Gillette Company | Air recovery battery |
| US9276301B2 (en) | 2012-12-07 | 2016-03-01 | Samsung Electronics Co., Ltd. | Polymeric compound, oxygen permeable membrane, and electrochemical device |
| US9343786B2 (en) | 2012-12-10 | 2016-05-17 | Samsung Electronics Co., Ltd. | Electrochemical device |
-
1994
- 1994-06-21 JP JP13868294A patent/JP2998564B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8377149B2 (en) | 2006-12-27 | 2013-02-19 | Eveready Battery Company, Inc. | Process for making a catalytic electrode and electrochemical cell using the electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH087935A (en) | 1996-01-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |