JPH0575835B2 - - Google Patents
Info
- Publication number
- JPH0575835B2 JPH0575835B2 JP60084590A JP8459085A JPH0575835B2 JP H0575835 B2 JPH0575835 B2 JP H0575835B2 JP 60084590 A JP60084590 A JP 60084590A JP 8459085 A JP8459085 A JP 8459085A JP H0575835 B2 JPH0575835 B2 JP H0575835B2
- Authority
- JP
- Japan
- Prior art keywords
- exchange resin
- diaphragm
- ion exchange
- film
- thickness
- 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 - Lifetime
Links
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Separators (AREA)
Description
【発明の詳細な説明】
「発明の目的」
本発明は電解隔膜の創案に係り、ハロゲン−亜
鉛電池やアルカリ電池などにおける電解隔膜とし
て電気抵抗を低くすると共にクーロン効率を高め
しかもその液中などにおける寸法安定性に優れ、
又乾燥条件下においても機械的強度の優れた製品
を提供しようとするものである。Detailed Description of the Invention "Object of the Invention" The present invention relates to the creation of an electrolytic diaphragm that can be used as an electrolytic diaphragm in halogen-zinc batteries, alkaline batteries, etc. to lower electrical resistance, increase Coulombic efficiency, and to Excellent dimensional stability,
It is also an attempt to provide a product with excellent mechanical strength even under dry conditions.
産業上の利用分野
ハロゲン−亜鉛電池やアルカリ電池などにおけ
る電解隔膜。Industrial applications Electrolytic diaphragms in halogen-zinc batteries, alkaline batteries, etc.
従来の技術
ハロゲン−亜鉛電池やアルカリ電池などのおけ
るセパレータとしてはイオン交換樹脂を製膜した
ものが従来から知られ、既に実用化されている。
又セロフアン等の微孔製天然高分子フイルムやプ
ラスチツクフイルムにアクリル酸やメタクリル酸
をグラフト重合させた膜なども知られている。BACKGROUND ART As a separator for halogen-zinc batteries, alkaline batteries, etc., ion exchange resin films have been known and have already been put into practical use.
Also known are microporous natural polymer films such as cellophane, and films in which acrylic acid or methacrylic acid is graft-polymerized onto plastic films.
更に特開昭56−63770においてはイオン交換樹
脂を多孔質膜に添着一体化したものが発表されて
おり、又特開昭52−114710においてはポリテトラ
フルオロエチレン混抄紙の製造法が発表され、該
製造法による混抄紙として特にシリカのような親
水性固体微粒子を含有させた場合は、内部まで均
一な親水性を有していて水により湿潤するので電
解隔膜として使用され得ることが発表されてい
る。 Furthermore, in JP-A-56-63770, a product in which an ion-exchange resin is integrated with a porous membrane was announced, and in JP-A-52-114710, a method for manufacturing polytetrafluoroethylene mixed paper was announced. It has been announced that the mixed paper made by this manufacturing method, especially when it contains hydrophilic solid fine particles such as silica, has uniform hydrophilicity to the inside and can be wetted by water, so it can be used as an electrolytic diaphragm. There is.
発明が解決しようとする課題
然し上記したような従来のものにおいては夫々
になお問題点を有している。即ちイオン交換樹脂
を製膜したものにおいては酸化剤などに侵されな
い有利性があるが、薄膜状となし或いは交換容量
を上げたりすると強度や液中などにおける寸法安
定性にお劣ることとなるものであつて、乾燥状態
では機械的強度が激減してクラツクを発生し易い
ことになり、水を含むような条件下では極端に膨
脹し、特にこれらの不利は電気抵抗を低くそ、ク
ーロン効果を高めるべく薄層化した場合において
顕著であつて、何れにしても作業性に劣る。Problems to be Solved by the Invention However, each of the above-mentioned conventional devices still has problems. In other words, films made of ion-exchange resins have the advantage of not being attacked by oxidizing agents, but if they are made into thin films or their exchange capacity is increased, their strength and dimensional stability in liquids will deteriorate. In a dry state, the mechanical strength is drastically reduced and cracks are likely to occur, and in conditions containing water, it expands extremely.These disadvantages, in particular, lower electrical resistance and reduce the Coulomb effect. This is noticeable when the layer is made thinner to increase the thickness, and in any case, the workability is poor.
微孔性天然高分子フイルムによるものでは陽極
合剤に用いる二酸化マンガン等の酸化剤によつて
酸化され、劣化が著しい。プラスチツクフイルム
にアクリル酸などをグラフト重合させたものにお
いては電気抵抗は小さいが陽極活物質の対極への
拡散が起こり、電池寿命が短くなる。特にハロゲ
ン−亜鉛電池用隔膜の場合においてはハロゲンの
自己放電が多くなつてクローン効果が低下した
り、ハロゲン化亜鉛に溶解した状態で使用するた
め腐食性が強い。 Those made of microporous natural polymer films are oxidized by oxidizing agents such as manganese dioxide used in the anode mixture, resulting in significant deterioration. Plastic films made by graft polymerizing acrylic acid or the like have low electrical resistance, but diffusion of the anode active material to the counter electrode occurs, shortening the battery life. In particular, in the case of diaphragms for halogen-zinc batteries, self-discharge of halogen increases and the Crohn's effect deteriorates, and since the diaphragm is used dissolved in zinc halide, it is highly corrosive.
「発明の構成」
問題点を解決するための手段
延伸処理により多数の微小結節部の間に無数の
微細繊維を形成した気孔率35％以上のポリテトラ
フルオロエチレンフイルムにパーフロロ系イオン
交換樹脂を均一状態に含浸一体化し、厚さ20〜
50μｍとして成形したことを特徴とする電解隔
膜。"Structure of the Invention" Means for Solving the Problems A perfluorinated ion exchange resin is uniformly applied to a polytetrafluoroethylene film with a porosity of 35% or more, in which numerous fine fibers are formed between numerous micronodules through a stretching process. Impregnated into one piece, thickness 20 ~
An electrolytic diaphragm characterized by being molded to a thickness of 50 μm.
作 用
延伸処理により多数の微小結節部の間に無数の
微細繊維を形成したポリテトラフルオロエチレン
フイルムを用いることにより乾燥条件などにおけ
る機械的強度および液中などにおける寸法安定性
を得しめ、安定した電解隔膜を得しめる。Function: By using a polytetrafluoroethylene film in which countless fine fibers are formed between many micronodules through a stretching process, mechanical strength under dry conditions and dimensional stability in liquids are achieved, resulting in a stable film. Obtain an electrolytic diaphragm.
前記ポリテトラフルオロエチレンフイルムの気
孔率が少なくとも35％以上であることによりパー
フロロ系イオン交換樹脂が適切に該フイルムの組
織内に進入一体化せしめられたものとなる。 When the porosity of the polytetrafluoroethylene film is at least 35%, the perfluorinated ion exchange resin can be appropriately integrated into the structure of the film.
前記した多孔質ポリテトラフルオロエチレンフ
イルムにパーフロロ系イオン交換樹脂を進入一体
化した隔膜の厚さを20〜50μｍとすることによ
り、電解隔膜としての作用を確保し、しかも電気
抵抗を低くすると共にクーロン効率を高く維持す
る。 The thickness of the diaphragm, which is made by incorporating perfluorinated ion exchange resin into the porous polytetrafluoroethylene film described above, is 20 to 50 μm to ensure its function as an electrolytic diaphragm, lower the electrical resistance, and reduce the coulomb resistance. Keep efficiency high.
なお含浸、混合するイオン交換樹脂の量を調整
し、ポリテトラフルオロエチレン膜の比重を調整
することにより活物質の拡散量を制御する。 Note that the amount of diffusion of the active material is controlled by adjusting the amount of ion exchange resin to be impregnated and mixed and by adjusting the specific gravity of the polytetrafluoroethylene membrane.
実施例
上記したような本発明によるものの具体的な実
施態様を添付図面に示すものについて説明する
と、本発明によるものは気孔率35％以上、特に40
％以上のポリテトラフルオロエチレン（以下
PTFEという）樹脂フイルムにパーフロロ系イオ
ン交換樹脂を均一状態に含浸一体化する。Examples Specific embodiments of the present invention as described above are shown in the accompanying drawings.The present invention has a porosity of 35% or more, particularly 40%
% or more of polytetrafluoroethylene (less than or equal to
Perfluorinated ion exchange resin is uniformly impregnated into a resin film (called PTFE).
前記したPTFEフイルムとパーフロロ系イオン
交換樹脂との均一な接着一体化をなす具体的な方
法としては以下のような手法の何れによつてもよ
い。 As a specific method for uniformly adhering and integrating the above-mentioned PTFE film and perfluorinated ion exchange resin, any of the following methods may be used.
延伸処理して得られた多孔質PTFEフイルム
にパーフロロ系イオン交換樹脂液を充分に含浸
させて緻密な隔膜とする。 The porous PTFE film obtained by stretching is sufficiently impregnated with a perfluorinated ion exchange resin liquid to form a dense diaphragm.
上記において、パーフロロ系イオン交換樹
脂液を不充分な状態に含浸させてなお多孔質性
を有する隔膜とする。 In the above, the membrane is impregnated with a perfluorinated ion exchange resin liquid in an insufficient state to obtain a porous membrane.
上記又はの隔膜にさらにパーフロロ系イ
オン交換樹脂を積層一体化する。 A perfluorinated ion exchange resin is further laminated and integrated with the above-mentioned or diaphragm.
何れに場合においてもPTFEに対するパーフロ
ロ系イオン交換樹脂との割合は一般的に重量比で
３〜90％であり、特に10〜30％とすることが好ま
しい。また隔膜の厚さについては20〜50μｍであ
る。 In either case, the ratio of perfluorinated ion exchange resin to PTFE is generally 3 to 90% by weight, preferably 10 to 30%. Moreover, the thickness of the diaphragm is 20 to 50 μm.
上記のようにして得られた隔膜をハロゲン−亜
鉛電池用セパレータとして用いた場合においては
PTFE膜を基材として形成されたものであるから
薄くても機械的強度や寸法安定性に優れたものと
なり、又パーフロロ系であるため電解質による劣
化を受けることがないものであつて、電解抵抗が
低く、しかもクローン効率の優れたものとして得
られる。又電池寿命も従来の微孔性天然高分子フ
イルムによるものに比べて飛躍的に高めることが
でき、その性能を著しく改善できる。 When the diaphragm obtained as described above is used as a separator for halogen-zinc batteries,
Because it is formed using a PTFE membrane as a base material, it has excellent mechanical strength and dimensional stability even if it is thin, and since it is a perfluoro-based membrane, it does not deteriorate due to electrolytes, so it has low electrolytic resistance. It can be obtained with low cloning efficiency and excellent cloning efficiency. Furthermore, the battery life can be dramatically increased compared to conventional microporous natural polymer films, and its performance can be significantly improved.
このことはアルカリ電池用セパレータとする場
合においても同様であつて、上記のように薄層で
電気抵抗を小さくすることができることから陽極
活物質の対極への拡散防止能に優れたものとなり
好ましい製品が得られる。 This also applies to separators for alkaline batteries; as mentioned above, since the electrical resistance can be reduced with a thin layer, the product has an excellent ability to prevent diffusion of the anode active material to the counter electrode, making it a desirable product. is obtained.
本発明によるものの具体的な製造例について説
明すると以下の如くである。 A specific manufacturing example of the product according to the present invention will be described below.
延伸処理によつて多数の微小結節部の間に無数
の微細繊維をくもの巣状に形成し、厚さ25μｍと
された気孔率80％の多孔質PTFE膜材に対しパー
フロロ系イオン交換樹脂液を含浸させて厚さが
25μｍの緻密な組織を有するハロゲン−亜鉛電池
用の隔膜を得た。 A perfluorinated ion exchange resin liquid is applied to a porous PTFE membrane material with a porosity of 80% and a thickness of 25 μm, in which countless fine fibers are formed in a spider web shape between numerous micro nodules through a stretching process. Impregnated with
A diaphragm for a halogen-zinc battery having a dense structure of 25 μm was obtained.
即ち、上記のようにして得られた電解隔膜につ
いてその特性を試験測定した結果は、電気抵抗が
0.13Ω・cm2（35％KOH 1KH2交流にて測定）で
あり、更に35％KOH液に対し2000時間に亘つて
浸漬しても殆ど膨潤その他の変化をすることのな
い優質な製品であることが確認された。 In other words, the results of testing and measuring the properties of the electrolytic diaphragm obtained as described above indicate that the electrical resistance is
0.13Ω・cm 2 (measured at 35% KOH 1KH 2 AC), and is an excellent product that shows almost no swelling or other changes even after being immersed in 35% KOH solution for 2000 hours. This was confirmed.
「発明の効果」
以上説明したような本発明によるときは、この
種電解隔膜の機械的強度を改善して充分に薄膜化
した製品を得しめ、又寸法安定性などのおいても
卓越した特性を示すと共に上記のような薄膜化に
伴い電気抵抗が低く、又クーロン効率の如きに優
れた隔膜を提供し得るものであるから工業的にそ
の効率の大きい発明である。"Effects of the Invention" According to the present invention as explained above, it is possible to improve the mechanical strength of this type of electrolytic diaphragm, to obtain a product with a sufficiently thin film, and to have excellent properties such as dimensional stability. It is an invention that is industrially highly efficient because it can provide a diaphragm that exhibits the above-mentioned properties, has low electrical resistance due to thinning, and has excellent Coulombic efficiency.
Claims (1)
の微細繊維を形成した気孔率35％以上のポリテト
ラフルオロエチレンフイルムにパーフロロ系イオ
ン交換樹脂を均一状態に含浸一体化し、厚さ20〜
50μｍとして成形したことを特徴とする電解隔
膜。1 A polytetrafluoroethylene film with a porosity of 35% or more, which has formed countless fine fibers between many micronodules through a stretching process, is uniformly impregnated with a perfluoro ion exchange resin to form a film with a thickness of 20~
An electrolytic diaphragm characterized by being molded to a thickness of 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60084590A JPS61246394A (en) | 1985-04-22 | 1985-04-22 | Diaphragm for electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60084590A JPS61246394A (en) | 1985-04-22 | 1985-04-22 | Diaphragm for electrolysis |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62240627A Division JPH0610277B2 (en) | 1987-09-28 | 1987-09-28 | Membrane material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61246394A JPS61246394A (en) | 1986-11-01 |
| JPH0575835B2 true JPH0575835B2 (en) | 1993-10-21 |
Family
ID=13834889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60084590A Granted JPS61246394A (en) | 1985-04-22 | 1985-04-22 | Diaphragm for electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61246394A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005028522A1 (en) | 2003-09-10 | 2005-03-31 | Asahi Kasei Chemicals Corporation | Stabilized fluoropolymer and method for producing same |
| JP2005327500A (en) * | 2004-05-12 | 2005-11-24 | Toyota Motor Corp | Method for producing solid polymer electrolyte, solid polymer electrolyte membrane, and fuel cell |
| EP1674508A1 (en) | 2004-12-22 | 2006-06-28 | Asahi Glass Company, Limited | Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells |
| US7125626B2 (en) | 1994-12-07 | 2006-10-24 | Japan Gore-Tex, Inc. | Ion exchange assembly for an electrochemical cell |
| WO2007089017A1 (en) | 2006-02-03 | 2007-08-09 | Daikin Industries, Ltd. | Method for producing -so3h group-containing fluoropolymer and -so3h group-containing fluoropolymer |
| WO2008072673A1 (en) | 2006-12-14 | 2008-06-19 | Asahi Glass Company, Limited | Solid polymer electrolyte membrane for polymer electrolyte fuel cell and membrane electrode assembly |
| DE112007000960T5 (en) | 2006-04-19 | 2009-04-02 | Toyota Jidosha Kabushiki Kaisha, Toyota-shi | A porous material for an electrolyte membrane of a fuel cell, a method of manufacturing the same, an electrolyte membrane for a solid polymer fuel cell, a membrane-electrode assembly (MEA), and a fuel cell |
| WO2010101195A1 (en) | 2009-03-04 | 2010-09-10 | 旭化成イーマテリアルズ株式会社 | Fluorine-containing polymer electrolyte membrane |
| WO2011156937A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof |
| WO2011156938A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof |
| WO2011156933A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Composite having ion exchange function and preparation method and use thereof |
| US9570773B2 (en) | 2010-10-07 | 2017-02-14 | Asahi Kasei E-Materials Corporation | Fluorine-based polymer electrolyte membrane |
| WO2018155598A1 (en) | 2017-02-23 | 2018-08-30 | 旭化成株式会社 | Composition, composite film and membrane electrode assembly |
| US10340544B2 (en) | 2013-12-19 | 2019-07-02 | Treofan Germany Gmbh & Co. Kg | Ion-exchange membrane made of a biaxially stretched β-porous film |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774290B2 (en) * | 1990-05-18 | 1995-08-09 | ジャパンゴアテックス株式会社 | Hydrophilic porous fluororesin material |
| CN100573989C (en) | 2004-03-04 | 2009-12-23 | 松下电器产业株式会社 | Composite electrolyte membrane, catalyst layer-membrane complex, membrane-electrode complex, and polymer electrolyte fuel cell |
| CN103066306A (en) * | 2012-12-22 | 2013-04-24 | 大连理工大学 | A kind of ion exchange membrane for zinc-bromine flow battery and its preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6022120B2 (en) * | 1976-03-23 | 1985-05-31 | ダイキン工業株式会社 | Manufacturing method for polytetrafluoroethylene mixed paper |
| JPS5663770A (en) * | 1979-10-26 | 1981-05-30 | Asahi Glass Co Ltd | Alkaline battery |
-
1985
- 1985-04-22 JP JP60084590A patent/JPS61246394A/en active Granted
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7125626B2 (en) | 1994-12-07 | 2006-10-24 | Japan Gore-Tex, Inc. | Ion exchange assembly for an electrochemical cell |
| WO2005028522A1 (en) | 2003-09-10 | 2005-03-31 | Asahi Kasei Chemicals Corporation | Stabilized fluoropolymer and method for producing same |
| JP2005327500A (en) * | 2004-05-12 | 2005-11-24 | Toyota Motor Corp | Method for producing solid polymer electrolyte, solid polymer electrolyte membrane, and fuel cell |
| EP1674508A1 (en) | 2004-12-22 | 2006-06-28 | Asahi Glass Company, Limited | Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells |
| EP2474562A2 (en) | 2006-02-03 | 2012-07-11 | Daikin Industries, Ltd. | Method for producing -SO3H group-containing fluoropolymer and -SO3H group-containing fluoropolymer |
| WO2007089017A1 (en) | 2006-02-03 | 2007-08-09 | Daikin Industries, Ltd. | Method for producing -so3h group-containing fluoropolymer and -so3h group-containing fluoropolymer |
| DE112007000960T5 (en) | 2006-04-19 | 2009-04-02 | Toyota Jidosha Kabushiki Kaisha, Toyota-shi | A porous material for an electrolyte membrane of a fuel cell, a method of manufacturing the same, an electrolyte membrane for a solid polymer fuel cell, a membrane-electrode assembly (MEA), and a fuel cell |
| WO2008072673A1 (en) | 2006-12-14 | 2008-06-19 | Asahi Glass Company, Limited | Solid polymer electrolyte membrane for polymer electrolyte fuel cell and membrane electrode assembly |
| EP2722921A1 (en) | 2009-03-04 | 2014-04-23 | Asahi Kasei E-materials Corporation | Fluoropolymer electrolyte membrane |
| WO2010101195A1 (en) | 2009-03-04 | 2010-09-10 | 旭化成イーマテリアルズ株式会社 | Fluorine-containing polymer electrolyte membrane |
| WO2011156938A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof |
| WO2011156933A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Composite having ion exchange function and preparation method and use thereof |
| WO2011156937A1 (en) | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Fluorine containing ionomer composite with ion exchange function, preparation method and use thereof |
| US9570773B2 (en) | 2010-10-07 | 2017-02-14 | Asahi Kasei E-Materials Corporation | Fluorine-based polymer electrolyte membrane |
| US10340544B2 (en) | 2013-12-19 | 2019-07-02 | Treofan Germany Gmbh & Co. Kg | Ion-exchange membrane made of a biaxially stretched β-porous film |
| WO2018155598A1 (en) | 2017-02-23 | 2018-08-30 | 旭化成株式会社 | Composition, composite film and membrane electrode assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246394A (en) | 1986-11-01 |
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