JPS6180757A - Air button battery - Google Patents
Air button batteryInfo
- Publication number
- JPS6180757A JPS6180757A JP59203432A JP20343284A JPS6180757A JP S6180757 A JPS6180757 A JP S6180757A JP 59203432 A JP59203432 A JP 59203432A JP 20343284 A JP20343284 A JP 20343284A JP S6180757 A JPS6180757 A JP S6180757A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- air
- film
- button battery
- ptfe
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、正極に空気触媒物質とフッ素樹脂フイルムを
便用した空気ボタン電池に１関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an air button battery that conveniently uses an air catalyst material and a fluororesin film as a positive electrode.
従来列の構成とその問題点
従来空気ボタン電池は、金属正極ケース内底部に挿入さ
れたフッ素樹脂フィルムの上に、別のフッ素樹脂フィル
ムと一体になった正極触媒層を２枚のフッ素樹脂フィル
ム面が相対する形で載置し、さらにその上にセパレータ
を載置後、正極触媒層の周縁部を電池の封口締付けによ
る負極ケースを押圧するための圧力によって固定してい
た。Conventional row configuration and its problems Conventional air button batteries have two fluororesin films that are integrated with another fluororesin film to form a positive electrode catalyst layer on top of a fluororesin film inserted into the inner bottom of the metal positive electrode case. After placing the cells so that their surfaces faced each other and placing a separator thereon, the peripheral edge of the positive electrode catalyst layer was fixed by applying pressure to press the negative electrode case by tightening the battery seal.
しかし、この方法による空気ボタン電池は、フッ素樹脂
フィルムと一体になった正極触媒層が、フッ素樹脂膜か
ら分離させてしまうことがある。また空気ボタン電池の
保存又は放電中にその密着不充分の箇所に強アルカリの
電解液が侵入してくる欠点を有していた。However, in the air button battery manufactured by this method, the positive electrode catalyst layer integrated with the fluororesin film may be separated from the fluororesin membrane. Furthermore, during storage or discharge of the air button battery, a strong alkaline electrolyte may penetrate into areas where the adhesion is insufficient.
正極部材側への電解液の侵入は、正極触媒物質の活性を
劣化させたり、正極ケース底部に開孔した空気孔からの
電解液の漏出につながったりするため好ましくない。Intrusion of the electrolytic solution into the positive electrode member side is undesirable because it deteriorates the activity of the positive electrode catalyst material or leads to leakage of the electrolytic solution from the air holes formed in the bottom of the positive electrode case.
この問題を解決するために考えられた正極部材間の密着
力を強くするための一つの方法として、活性炭を主体と
する触媒物質の片面にポリ４７ソ化エチレンのディスパ
ージョンを塗布し、フッ素樹脂膜と圧着する方法がある
。この方法は、従来よりもより液密に触媒物質とフッ素
樹脂膜とは密着するが、必ずしも充分ではない。To solve this problem, one method to strengthen the adhesion between the positive electrode members is to apply a dispersion of poly(47)isoethylene to one side of the catalyst material, which is mainly made of activated carbon, and to There is a method of crimping it with the membrane. Although this method allows the catalyst material and the fluororesin membrane to adhere more liquid-tightly than conventional methods, it is not always sufficient.
それは、ポリ４７ソ化エチレン等のフッ素樹脂は、極性
官能基を持っていないため、充分な密着ができないから
である。This is because fluororesins such as poly(47-isoethylene) do not have a polar functional group, and therefore cannot achieve sufficient adhesion.
発明の目的
本発明は、正極部材として使用するフッ素樹脂フィルム
の表面を、プラズマで照射処理することにより、フッ素
樹脂フィルムの表面に極性官能基を形成し、各正極部材
間の密着性を良好にしたものである。そして電池組立て
時、放電中又は保存において、電解液が正極部材の間に
侵入することによる電池の劣化や、空気孔からの漏液を
防止することを目的とする。Purpose of the Invention The present invention aims to form a polar functional group on the surface of a fluororesin film used as a positive electrode member by irradiating the surface of the fluororesin film with plasma, thereby improving the adhesion between each positive electrode member. This is what I did. The purpose of this invention is to prevent battery deterioration due to electrolyte entering between the positive electrode members and leakage from air holes during battery assembly, discharge, or storage.
発明の構成
上記の目的を達成するために、空気ボタン電池の正極部
材として使用するフッ素樹脂フイルムの少なくとも一方
の表面をプラズマ照射処理し、処理面と触媒物質との密
着を良好にしたことを特徴とする。Structure of the Invention In order to achieve the above object, at least one surface of a fluororesin film used as a positive electrode member of an air button battery is subjected to plasma irradiation treatment to improve the adhesion between the treated surface and the catalyst substance. shall be.
実施例の説明
図は本発明の実施例における空気ボタン電池の部分断面
図を示す。図中、１は正極ケースであり、その底面には
空気供給孔２を設けた凹部を有している。３は凹部の内
径とほぼ等しい外径で厚さ０．４ｍｂ以下の多孔性空気
拡散紙である。この拡散紙３の上には正極ケース１の内
径と同径に打ち抜かれた空孔率２ｏ〜６０係、厚さ０．
ＩＭのフッ素樹脂フイルムからなる撥水膜４・を載置す
る。The explanatory diagram of the embodiment shows a partial cross-sectional view of an air button battery in an embodiment of the present invention. In the figure, 1 is a positive electrode case, and the bottom surface thereof has a recessed portion in which an air supply hole 2 is provided. 3 is a porous air diffusion paper having an outer diameter approximately equal to the inner diameter of the recess and a thickness of 0.4 mb or less. On this diffusion paper 3, a punch is punched out to have the same diameter as the inner diameter of the positive electrode case 1, with a porosity of 2o to 60 and a thickness of 0.
A water-repellent film 4 made of IM fluororesin film is placed.
撥水膜４は、変位温度３２７℃以下で製造されたポリ４
フツ化エチレン（ＰＴＦＥ）フィルムからなる。The water-repellent film 4 is made of poly 4 manufactured at a displacement temperature of 327°C or lower.
Made of fluorinated ethylene (PTFE) film.
５は空気極であり、活性炭を主成分とする触媒物質６ａ
を塗着した６ｏメツシユで厚さ０．３ Ｍのニッケルス
クリーンｅｂと、厚さｏ、ｔｓ〜ｏ、１賜テ空孔率２０
〜３０係のＰＴＦＥフィルム７とがら構成されている。5 is an air electrode, and a catalyst material 6a whose main component is activated carbon
A nickel screen with a thickness of 0.3M is coated with a 6o mesh, and a porosity of 20
It is composed of a PTFE film 7 of ~30 parts.
空気極６は活性炭を主成分とし、これをアセチレンプラ
ックの導電性助材と共に、ＰＴＦＥの水性ディスパージ
ョンで充分練合し、ニノヶルスクリー７６ｂに厚さ０．
３〜０．４Ｍで充填し、１００℃以上で乾燥する。The air electrode 6 has activated carbon as its main component, which is sufficiently kneaded with an aqueous dispersion of PTFE together with a conductive additive such as acetylene plaque, and is coated on a Ninogal screen 76b with a thickness of 0.5 mm.
Fill with 3-0.4M and dry at 100°C or higher.
次に変異温度３２７℃以下で製造されたＰＴＨＥフィル
ムγの片面をプラズマ照射処理する。Next, one side of the PTHE film γ produced at a variation temperature of 327° C. or less is subjected to plasma irradiation treatment.
プラズマ照射処理は、ＰＴＦＥフィルムの表面を無機ガ
スのプラズマがたたいて改質するものであり、本発明で
は酸素ガスを使用した。In the plasma irradiation treatment, the surface of the PTFE film is modified by hitting the surface with inorganic gas plasma, and oxygen gas was used in the present invention.
このように処理したＰＴＦＥフィルムアの処理面と、ニ
ッケルスクリーン６ｂに充填した触媒物質６ａとを接さ
せ、２本のロールの間を通過させてブレスすることによ
って圧着し、空気極５を完成させることができる。The treated surface of the PTFE film treated in this way is brought into contact with the catalyst substance 6a filled in the nickel screen 6b, and the air electrode 5 is completed by passing between two rolls and pressing to bond them. be able to.
この空気極５は正極ケース１の内径と同径で打ち抜かれ
、ＰＴＦＥフィルム７面を下側にして、正極ケース１に
挿入する。This air electrode 5 is punched out to have the same diameter as the inside diameter of the positive electrode case 1, and is inserted into the positive electrode case 1 with the PTFE film 7 facing downward.
セパレータ８は、厚さ０．０５〜０．１賜の微孔性ポリ
エチレン又はポリプロピレンであり、同様に正極ケース
内径と同径に打ち抜き、正極触媒物質５の上に載置させ
る。The separator 8 is made of microporous polyethylene or polypropylene with a thickness of 0.05 to 0.1 mm, is similarly punched out to have the same diameter as the inside diameter of the positive electrode case, and is placed on the positive electrode catalyst material 5 .
一方負極側はナイロンよりなる封口リング９を嵌着した
負極ケース１０の中に、負極活物質となる亜鉛粉１１と
濃度３０〜４０重量％の水酸化カリウム水溶液を充填し
て構成する。On the other hand, the negative electrode side is constructed by filling a negative electrode case 10 fitted with a sealing ring 9 made of nylon with zinc powder 11 serving as a negative electrode active material and an aqueous potassium hydroxide solution having a concentration of 30 to 40% by weight.
前記正極側封口体と、負極側封口体の両者を嵌合し、正
極ケース１の開口部を内方に折曲し、封口リング９を介
して負極ケース１０と締め付けることによって、空気ボ
タン電池を完成する。By fitting both the positive electrode side sealing body and the negative electrode side sealing body, bending the opening of the positive electrode case 1 inward, and tightening the positive electrode case 10 with the negative electrode case 10 via the sealing ring 9, an air button battery is manufactured. Complete.
空気極５はＰＴＦＥフィルム７の表面をプラズマ照射処
理することにより、触媒物質５との密着は非常に良好と
なり、その効果は太きかつ永）また、別の実施例として
、空気極５を構成するＰＴＦＥフィルム７が変異温度３
２７℃以上で製造された場合は、プラズマ照射処理の効
果は非常に大きく未処理のフィルム７と比べると密着力
は著しく増大する。３２７℃以上で焼結されたＰＴＦＥ
フィルム７はその機械的強度は、未焼結のフィルムと比
べると著しく増大し、空気極５を製造する上で非常に有
効となる。The air electrode 5 has a plasma irradiation treatment on the surface of the PTFE film 7, so that the adhesion with the catalyst substance 5 is very good, and the effect is strong and long-lasting. The PTFE film 7 has a variation temperature of 3.
When manufactured at 27° C. or higher, the effect of the plasma irradiation treatment is very large and the adhesion is significantly increased compared to the untreated film 7. PTFE sintered above 327℃
The mechanical strength of the film 7 is significantly increased compared to that of an unsintered film, and is very effective in manufacturing the air electrode 5.
またプラズマ処理に期用する電磁波は、普通、周波数０
．２〜１０３ＭＨ２のラジオ波と１０３〜１０６ＭＨｚ
のマイクロ波であるが、本発明におけるＰＴＦＥフィル
ムの表面処理は、マイクロ波を使用した方が、密着力が
良好となる。Furthermore, the electromagnetic waves used for plasma processing usually have a frequency of 0.
．． Radio waves from 2 to 103 MHz and 103 to 106 MHz
However, when the surface treatment of the PTFE film in the present invention is performed using microwaves, the adhesion becomes better.
また本発明者らは、空気極５の触媒物質６ａとＰＴＦＥ
フィルム７との密着力をビール強度で測定した。ビール
強度の測定法は、２ｃｍ幅のサンプルで５０ ｒｔｔｖ
ｂ／ｌ；）−の測定である。The present inventors also discovered that the catalyst material 6a of the air electrode 5 and PTFE
The adhesion force with Film 7 was measured using beer strength. The beer strength measurement method is 50 rttv with a 2 cm wide sample.
It is a measurement of b/l;)-.
１・・・従来の空気極（未焼成フィルム使用）１１・・
触媒物質とＰＴＦＥフィルムとをＰＴＦＥ水性ディスパ
ージョンで貼り合わせた空気極１ｉｉ−、Ｊ：［結Ｐ
Ｔ Ｆ Ｅフィルムをプラズマ照射処理後、触媒物質と
貼り合わせたもの
１■・・３２７℃以上で焼結したＰＴＦＥフィルムをプ
ラズマ照射処理後、触媒物質と貼り合わせた空気極
上記の各試料（Ａ−Ｄ）のビール強度の測定値を表−１
に示す。1... Conventional air electrode (using unfired film) 11...
Air electrode 1ii-, J: [bound P
TFE film was laminated with a catalyst material after plasma irradiation treatment 1 ■ Air electrode in which a PTFE film sintered at 327°C or higher was laminated with a catalyst material after plasma irradiation treatment Each of the above samples (A -D) The measured values of beer strength are shown in Table-1.
Shown below.
以下余白
表−１（ｎ＝５ ）
上記に示した結果からもＰＴＦＥフィルムにプラズマ表
面処理後、触媒物質５と圧着することは、その効果が非
常に大きいことが判明した。Margin Table 1 (n=5) The results shown above also show that press-bonding the PTFE film with the catalyst material 5 after plasma surface treatment is very effective.
発明の効果
本発明の正極部材として使用するフッ素樹脂フィルムを
プラズマ照射処理することにより、各正極部材間の密着
は非常に良好となり、電池組立て時又は放電中あるいは
保存において、電解波が各部材間に侵入することに起因
した電池の劣化や、空気孔からの漏液を防止することが
可能とな・た・ １表−２に従来の空気ボ
タン電池Ａと本発明による１１、実施例の空気ボタン電
池Ｂを外径１１．６朋、高さす。Effects of the Invention By subjecting the fluororesin film used as the positive electrode member of the present invention to plasma irradiation treatment, the adhesion between each positive electrode member becomes very good, and electrolytic waves are generated between each member during battery assembly, discharge, or storage. It is possible to prevent deterioration of the battery caused by intrusion into the air and leakage from the air holes. The button battery B has an outer diameter of 11.6 mm and a height.
表−２
６２０，０連続放電時間（終止電圧０．９Ｖ）各放電は
ｎ＝５個の平均持続時間Table-2 620,0 continuous discharge time (ending voltage 0.9V) Each discharge has an average duration of n = 5
図は本発明の空気ボタン電池の要部を示す断面図である
。
１ 正極ケース、２ ・・空気供給孔、３・ ・空気
拡散紙、４− フッ素樹脂撥水膜、５・・空気極、６ａ
・触媒物質、６ｂ・・ −ニッケルスクリーン、７
・・フッ素樹脂フィルム、８− セパレータ、９・・
・封口リング、１０ 負極ケース、１１ ・・負極亜
鉛。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
／ｌThe figure is a sectional view showing the main parts of the air button battery of the present invention. 1 Positive electrode case, 2... Air supply hole, 3... Air diffusion paper, 4- Fluorine resin water repellent membrane, 5... Air electrode, 6a
・Catalytic material, 6b... -Nickel screen, 7
・・Fluororesin film, 8- Separator, 9・・
・Sealing ring, 10 Negative electrode case, 11 ・Negative electrode zinc. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure/l
Claims (3)
なくとも一方の表面はプラズマ照射処理されていて、こ
の処理面が触媒物質と密着している空気ボタン電池。(1) An air button battery in which at least one surface of a fluororesin film used as a positive electrode member is plasma irradiated, and this treated surface is in close contact with a catalyst substance.
変異温度３２７℃以上で焼結されている特許請求の範囲
第１項記載の空気ボタン電池。(2) Fluororesin film subjected to plasma irradiation treatment:
The air button battery according to claim 1, which is sintered at a variation temperature of 327° C. or higher.
＾３〜１０＾６ＭＨｚのマイクロ波である特許請求の範
囲第１項または第２項記載の空気ボタン電池。(3) The electromagnetic waves used for plasma irradiation treatment have a frequency of 10
The air button battery according to claim 1 or 2, which is a microwave of ^3 to 10^6 MHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59203432A JPS6180757A (en) | 1984-09-28 | 1984-09-28 | Air button battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59203432A JPS6180757A (en) | 1984-09-28 | 1984-09-28 | Air button battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6180757A true JPS6180757A (en) | 1986-04-24 |
Family
ID=16473989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59203432A Pending JPS6180757A (en) | 1984-09-28 | 1984-09-28 | Air button battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6180757A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015160884A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2018184614A (en) * | 2018-07-26 | 2018-11-22 | 日東電工株式会社 | Adhesive sheet |
-
1984
- 1984-09-28 JP JP59203432A patent/JPS6180757A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015160884A (en) * | 2014-02-27 | 2015-09-07 | 日東電工株式会社 | adhesive sheet |
| JP2018184614A (en) * | 2018-07-26 | 2018-11-22 | 日東電工株式会社 | Adhesive sheet |
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