JPS59141168A - Manufacturing method of gas diffusion type air pole - Google Patents
Manufacturing method of gas diffusion type air poleInfo
- Publication number
- JPS59141168A JPS59141168A JP58015622A JP1562283A JPS59141168A JP S59141168 A JPS59141168 A JP S59141168A JP 58015622 A JP58015622 A JP 58015622A JP 1562283 A JP1562283 A JP 1562283A JP S59141168 A JPS59141168 A JP S59141168A
- Authority
- JP
- Japan
- Prior art keywords
- gas diffusion
- sheet
- type air
- resin film
- air pole
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (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、空気（酸素）燃料電池、ボタン型空気電池な
どに用いられるガス拡散型空気極に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a gas diffusion type air electrode used in air (oxygen) fuel cells, button type air cells, and the like.
従来例の構成とその問題点
従来、空気電池の空気極は、次の如く作られているのが
一般的である。まず、活性炭や貴金属、マンガン酸化物
などをフッ素樹脂ディスパージョンで十分混練しペース
ト状となし、これを金属スクリーンにシート状に塗着し
て乾燥した後多孔性のフッ素樹脂膜を密着させていた。Conventional Structure and Problems Conventionally, the air electrode of an air battery has generally been made as follows. First, activated carbon, precious metals, manganese oxide, etc. were thoroughly kneaded with a fluororesin dispersion to form a paste, which was then applied to a metal screen in the form of a sheet, dried, and then covered with a porous fluororesin membrane. .
ここで触媒シート中にフッ素樹脂を混入するのは、空気
中の酸素を正極活物質として利用するため、酸素を触媒
中に拡散し易いように撥水性を保持させる目的からであ
る。まだ、多孔性フン素樹脂膜を密着させるのは、触媒
シート中を通過したアルカリ電解液が触媒シート表面に
たまっだシ、電池外へ漏出するのを防止するためである
。The reason why the fluororesin is mixed into the catalyst sheet is to maintain water repellency so that oxygen can easily diffuse into the catalyst since oxygen in the air is used as a positive electrode active material. The reason why the porous fluororesin membrane is placed in close contact with the catalyst sheet is to prevent the alkaline electrolyte that has passed through the catalyst sheet from accumulating on the surface of the catalyst sheet and leaking out of the battery.
この観点からすると、従来の触媒シートと多孔性フッ素
樹脂膜との界面は必ずしも密着力及び撥水力が強くない
ため、長期保存中にフッ素樹脂膜が触媒シートより部分
的にはがれ、触媒シートを通過した電解液がその剥離部
分にたまり、酸素の拡散を妨害して電池の放電特性を劣
下させる原因となっていた。From this point of view, the interface between the conventional catalyst sheet and porous fluororesin membrane does not necessarily have strong adhesion and water repellency, so during long-term storage, the fluororesin membrane may partially peel off from the catalyst sheet and pass through the catalyst sheet. The electrolytic solution accumulated in the peeled part interfered with the diffusion of oxygen, causing a deterioration in the discharge characteristics of the battery.
発明の目的
本発明は、従来例の問題点を解決したものであシ、ガス
拡飯型空気極を構成する触媒シートと多孔性フッ素樹脂
膜との密着強度を高めてガス拡散型空気極の信頼性（寿
命）を向上させ、空気電池の長期保存性を確保すること
を目的としたものである。 −
発明の構成
本発明は上記目的を達成するため、フッ素樹脂を含む触
媒シートの多孔性フン素樹脂膜が加圧密着される片面に
、あらかじめポリ４フツ化エチレン（ｐＴＦＥ、）の水
性ディスパージョンを塗着乾燥させ、多孔性フッ素樹脂
膜を加圧密着させる前又は後で１００〜４００ ’Ｃの
温度で加熱処理すること番特徴としたものである。こう
することにより、ＰＴＦＥの水性ディスパージョンよシ
得た柔かい繊維状のフッ素樹脂により触媒シートと多孔
性フッ素樹脂膜との密着強度を強くすることができると
ともに、触媒シートと多孔性フッ素樹脂膜ｆの境界面の
撥水性を大とすることができる。したがって、電解液が
万一触媒シートを浸透しても、この境界面に漏出するこ
とはなく、ガス拡散空気極の寿命を大巾に伸ばすことが
できる。Purpose of the Invention The present invention solves the problems of the prior art, and improves the adhesion strength between the catalyst sheet and the porous fluororesin membrane that constitute the gas diffusion type air electrode. The purpose is to improve reliability (life) and ensure long-term storage of air batteries. - Structure of the Invention In order to achieve the above-mentioned object, the present invention provides an aqueous dispersion of polytetrafluoroethylene (pTFE) on one side of a catalyst sheet containing a fluororesin to which a porous fluororesin membrane is adhered under pressure. The main feature of this method is that it is applied and dried, and that it is heat-treated at a temperature of 100 to 400'C before or after the porous fluororesin membrane is pressed and adhered. By doing this, the adhesion strength between the catalyst sheet and the porous fluororesin membrane can be strengthened by the soft fibrous fluororesin obtained from the aqueous dispersion of PTFE, and the adhesive strength between the catalyst sheet and the porous fluororesin membrane can be strengthened. The water repellency of the interface can be increased. Therefore, even if the electrolytic solution should permeate the catalyst sheet, it will not leak to this interface, and the life of the gas diffusion air electrode can be greatly extended.
以下、本発明の詳細は実施例によって説明する。Hereinafter, the details of the present invention will be explained with reference to Examples.
実施例の説明
二酸化マンガンと活性炭とカーボンブランクとを重量比
で２０：５０．：１０の割合で配合し、これにさらにフ
ッ素樹脂の水性デイスノく−ジョンを固形分にして２０
重量部を加え約３０分間混練し、ペースト状トシてニッ
ケルスクリーンにシート状に塗着し厚さ０．５酷の触媒
シート１−１を得だ。Description of Examples Manganese dioxide, activated carbon and carbon blank in a weight ratio of 20:50. : 10%, and further added fluororesin aqueous discontinuum to a solid content of 20%.
Parts by weight were added, kneaded for about 30 minutes, and applied to a paste in the form of a sheet on a nickel screen to obtain a catalyst sheet 1-1 with a thickness of 0.5 mm.
この触媒シート１−１の片面にＰＴＦＥの水性ディスパ
ージョン１−２をそれぞれを塗着し、その塗着量が０
、０．５ 、１．９ 、３．０ 、５．０ 、１０．１
６”ｆ ／ ｃ７Ｊとなるようにして乾燥した。さらに
、これらと未処理のものと１００’Ｃ，２００”Ｃ，３
００”Ｃ，４００’Ｃ，５００’Ｃにて加熱処理をした
ものについて用惹し、それぞれｌ（率さ０．１ｍｔｎ、
気孔率４０％の多孔性フン素樹脂膜１−３を片面に加圧
密着させた。このそれぞれを直径１１．０’ｌｌｌ＃Ｉ
に打ち抜き、空気極１とした・
この空気極１の断面図を第１図に示す。Each of the PTFE aqueous dispersions 1-2 was applied to one side of the catalyst sheet 1-1, and the applied amount was 0.
, 0.5 , 1.9 , 3.0 , 5.0 , 10.1
It was dried at 6"f/c7J.Furthermore, these, the untreated one, 100'C, 200"C, 3
The samples heat-treated at 00'C, 400'C, and 500'C were used, respectively.
A porous fluororesin membrane 1-3 having a porosity of 40% was adhered to one side under pressure. Each of these has a diameter of 11.0'lll#I
A cross-sectional view of this air electrode 1 is shown in FIG. 1.
またこの空気極１を、空気孔２を底部に有した正極ケー
ス３内に空気拡散紙４を下に敷いた状態で配置し、セパ
レータ５、亜鉛負極６と組み合わせて直径１１．６−１
高さ５．４朋の第２図に示すボタン型空気電池を構成し
た。Further, this air electrode 1 is placed in a positive electrode case 3 having air holes 2 at the bottom with air diffusion paper 4 laid underneath, and is combined with a separator 5 and a zinc negative electrode 6 to form a cathode case 3 with a diameter of 11.6-1.
A button-type air cell shown in FIG. 2 with a height of 5.4 mm was constructed.
図中７は負極端子を兼ねた封目板、８は絶縁ガスケット
、９は空気孔２を閉塞するシール紙である。In the figure, 7 is a sealing plate that also serves as a negative electrode terminal, 8 is an insulating gasket, and 9 is a sealing paper that closes the air hole 2.
これらの電池を製造直後と、３０′ｃ″に６力月間保存
後の条件で２０ ”Ｃ下５００Ω負荷により放電を行い
、１００時間後の維持電圧を比較した。その結果を次表
に示した。These batteries were discharged immediately after manufacture and after storage at 30'C'' for 6 months under a 500Ω load at 20''C, and the sustained voltages after 100 hours were compared. The results are shown in the table below.
以下余白
表から明らかなよ−うに、製造直後ではＰＴＦＥの水性
ディスパージョンの塗着量が０〜１０．０ｗＣ７Ｒまで
は維持電圧が変わらず、１５．０■４４ではや５劣化し
ている。また、処理温度が未処理から５００ででは未処
理と５００ ’Ｃが悪く、１００′ｃ〜４ＱＯ′ｃと（
ＶＣ２００〜３００ ’Ｃが良好である。これは、未処
理ではＰＴＦＥの水性ディスパージョンに含まれる界面
活性剤が残存しているため、触媒が濡れ易く、空気の拡
散が明害されただめと思われる。As is clear from the margin table below, immediately after manufacture, the maintenance voltage did not change when the coating amount of the aqueous PTFE dispersion ranged from 0 to 10.0wC7R, and deteriorated by 5 at 15.0wC7R. In addition, when the treatment temperature is from untreated to 500°C, untreated and 500'C are bad, and from 100'c to 4QO'c (
VC200-300'C is good. This is thought to be because the surfactant contained in the aqueous dispersion of PTFE remains when untreated, making the catalyst easy to wet and hindering air diffusion.
また６ｏＯ′Ｃではフッ素樹脂が熱劣化し、やけシ未処
理と同様に触媒が濡れ易くなった。Further, at 6oO'C, the fluororesin was thermally degraded, and the catalyst became easily wetted, similar to the untreated case.
さらに、３０ ’Ｃ６力月保存後においては、処理温度
面で未処理とＳＯＯ℃がさらに劣化しているが、１ｏＯ
′Ｃ：〜４００ ’Ｃでは全般的に安定しており、製造
直後に比べて同等以上である。なかでもＰＴＦＥの水性
ディスパージョン塗着量は０．５〜１ｏ、ｏｆｌｆ／／
ｃｉがよく、とくに２００−３００℃下、１．０〜５．
ｏｌＶｃ肩が最高である。Furthermore, after storage at 30'C, SOO℃ further deteriorated compared to untreated in terms of processing temperature, but 1oO
'C: It is generally stable at ~400'C, and is equivalent or better than immediately after production. Among them, the coating amount of PTFE aqueous dispersion is 0.5 to 1o, oflf//
ci is good, especially at 200-300℃, 1.0-5.
olVc shoulder is the best.
これらのことからＰＴＦＨの水性ディスパージー１７塗
着量が０．５〜１０．０ ｍｙ／ｃｔＡで処理温度が１
００〜４００ ’Ｃであれば、従来のフッ素樹脂を塗布
しないものよシも保存特性にすぐれることが明らかであ
る。これは先述したように、触媒シート表面に塗着した
ＰＴＦＥ樹脂が、触媒シート中のフッ素樹脂及びシート
片面に密着させる多孔性のフッ素樹脂膜とに強化に結合
し、しかも境界面部分の撥ＪＫ性を強めて空気の拡散を
良好にしているためである。From these facts, it is assumed that the coating amount of PTFH aqueous disperge 17 is 0.5 to 10.0 my/ctA and the treatment temperature is 1.
It is clear that at temperatures between 00 and 400'C, the storage properties are superior to those not coated with conventional fluororesin. As mentioned above, this is because the PTFE resin applied to the surface of the catalyst sheet strongly bonds to the fluororesin in the catalyst sheet and the porous fluororesin membrane that adheres to one side of the sheet, and the repellency of the interface area. This is because it strengthens the air and improves air diffusion.
この加熱処理は多孔性フッ素樹脂膜を触媒シートに加圧
密着させた後に行なった場合も、上記とまったく同じよ
うな結果が得られた。Even when this heat treatment was carried out after the porous fluororesin membrane was brought into close contact with the catalyst sheet under pressure, results exactly similar to those described above were obtained.
発明の効果
このように本発明によれば、フッ素樹脂を含む触媒シー
トと多孔性フッ素樹脂膜との密着強度を高めるとともに
、両者の境界面の撥水性を犬として漏液を抑制して空気
の拡散を良好に保つため、ガス拡散型空気極の寿命を向
上させることができる。Effects of the Invention As described above, according to the present invention, the adhesion strength between the catalyst sheet containing a fluororesin and the porous fluororesin membrane is increased, and the water repellency at the interface between the two is improved to suppress leakage and prevent air from flowing out. Since good diffusion is maintained, the life of the gas diffusion type air electrode can be improved.
第１図は本発明の実施例における空気極の断面図、第２
図は同空気極を用いたボタン型空気電池を示す断面図で
ある。
１・・・・・・空気極、１−１・・・・・・触媒シート
、１−２・・・・・・ＰＴＦＥディスパージョン、１−
３・・・・・・多孔性フッ素樹脂膜。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名第１
図
第２図Fig. 1 is a sectional view of the air electrode in the embodiment of the present invention, Fig.
The figure is a sectional view showing a button-type air cell using the same air electrode. 1... Air electrode, 1-1... Catalyst sheet, 1-2... PTFE dispersion, 1-
3... Porous fluororesin membrane. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
Figure 2
Claims (2)
フッ素樹脂膜を加圧密着させたガス拡散型空気極の製造
法であって、前記触媒シートの多孔性フッ素樹脂膜と対
向する面にあらかじめポリ４フツ化エチレンの水性ディ
スパージョンを塗着乾燥させ、前記多孔性フッ素樹脂膜
を加圧密着させる前又は後で１ｏＯ〜４００での温度で
加熱処理するガス拡散型空気極の製造法。(1) A method for manufacturing a gas diffusion type air electrode in which a porous fluororesin membrane is adhered under pressure to one side of a catalyst sheet containing a fluororesin, wherein A method for producing a gas diffusion type air electrode, which comprises applying and drying an aqueous dispersion of polytetrafluoroethylene, and heat-treating the porous fluororesin membrane at a temperature of 1 to 400 degrees Celsius before or after applying pressure and adhering the membrane.
触媒シートへの塗着量が０．６〜１０”ｆｌｃ−である
特許請求の範囲第１項記載のガス拡散型空気極の製造法
。(2) The method for producing a gas diffusion type air electrode according to claim 1, wherein the amount of the aqueous dispersion of polytetrafluoroethylene applied to the catalyst sheet is 0.6 to 10"flc-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58015622A JPS59141168A (en) | 1983-02-01 | 1983-02-01 | Manufacturing method of gas diffusion type air pole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58015622A JPS59141168A (en) | 1983-02-01 | 1983-02-01 | Manufacturing method of gas diffusion type air pole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59141168A true JPS59141168A (en) | 1984-08-13 |
Family
ID=11893803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58015622A Pending JPS59141168A (en) | 1983-02-01 | 1983-02-01 | Manufacturing method of gas diffusion type air pole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59141168A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62268060A (en) * | 1986-05-15 | 1987-11-20 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion type air electrode |
| JP2017076538A (en) * | 2015-10-15 | 2017-04-20 | Fdk株式会社 | Method for manufacturing air electrode of air secondary battery, and air-hydrogen secondary battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723470A (en) * | 1980-07-18 | 1982-02-06 | Sanyo Electric Co Ltd | Manufacture of gas diffusion electrode |
| JPS5792752A (en) * | 1980-12-01 | 1982-06-09 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusing electrode |
| JPS5795079A (en) * | 1980-12-04 | 1982-06-12 | Matsushita Electric Ind Co Ltd | Gas diffusion electrode |
-
1983
- 1983-02-01 JP JP58015622A patent/JPS59141168A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5723470A (en) * | 1980-07-18 | 1982-02-06 | Sanyo Electric Co Ltd | Manufacture of gas diffusion electrode |
| JPS5792752A (en) * | 1980-12-01 | 1982-06-09 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusing electrode |
| JPS5795079A (en) * | 1980-12-04 | 1982-06-12 | Matsushita Electric Ind Co Ltd | Gas diffusion electrode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62268060A (en) * | 1986-05-15 | 1987-11-20 | Matsushita Electric Ind Co Ltd | Manufacture of gas diffusion type air electrode |
| JP2017076538A (en) * | 2015-10-15 | 2017-04-20 | Fdk株式会社 | Method for manufacturing air electrode of air secondary battery, and air-hydrogen secondary battery |
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