JPS63257634A - Continuous manufacture of laminated and/or composite body film - Google Patents
Continuous manufacture of laminated and/or composite body filmInfo
- Publication number
- JPS63257634A JPS63257634A JP62092789A JP9278987A JPS63257634A JP S63257634 A JPS63257634 A JP S63257634A JP 62092789 A JP62092789 A JP 62092789A JP 9278987 A JP9278987 A JP 9278987A JP S63257634 A JPS63257634 A JP S63257634A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polymer
- ion
- composite
- monomer
- 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.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920001940 conductive polymer Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- 239000002322 conducting polymer Substances 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 48
- 229920000642 polymer Polymers 0.000 description 33
- 150000002500 ions Chemical class 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 6
- 229920000128 polypyrrole Polymers 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- FDRNXKXKFNHNCA-UHFFFAOYSA-N 4-(4-anilinophenyl)-n-phenylaniline Chemical compound C=1C=C(C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 FDRNXKXKFNHNCA-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
艮嵐分互
本発明は、レドックス性高分子材料とイオン伝導性高分
子材料との積層複合体フィルムの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a laminated composite film of a redox polymeric material and an ion-conductive polymeric material.
丈來１監
白州らによってフィルム状アセチレンの合成が成功して
以来、導電性高分子材料に関する研究が盛んになり、そ
の電極材料、電磁シールド材料等への応用が提案されて
いる。Since the successful synthesis of film-like acetylene by Hakushu and his colleagues, research into conductive polymer materials has become more active, and their application to electrode materials, electromagnetic shielding materials, etc. has been proposed.
導電性高分子材料を用いたデバイスの一つの応用として
１Ｍ、Ｏｇａｗａらは二次電池を試作した例を報告して
おり、正極にポリアニリン、負極にリチウム、電極質と
してプロピレンカーボネート−１，２−ジメチルエタン
−Ｌ ｘ Ｂ Ｆ ４を使用している（電池討論会’
８６）。As one application of devices using conductive polymer materials, 1M and Ogawa et al. reported an example of prototyping a secondary battery using polyaniline as the positive electrode, lithium as the negative electrode, and propylene carbonate-1,2- as the electrode material. Dimethylethane-L x B F4 is used (Battery Discussion Group'
86).
しかしながら、この有機二次電池は電解質として溶液系
を用いるため、濡液性の問題があり、また、容積あたり
のエネルギー密度の改善もなされていない。However, since this organic secondary battery uses a solution system as an electrolyte, there is a problem with wettability, and the energy density per volume has not been improved.
これらを改善すべく、以前より電解質として固体系を使
用する提案がなされ、種々の無機固体電解質に関する報
告がある。これらの中には、かなり高い電気伝導度を有
するものが知られているが、スパッタやＣＶＤなどの製
造工程を必要とし、量産には向いていない。In order to improve these problems, proposals have been made to use solid electrolytes as electrolytes, and there have been reports on various inorganic solid electrolytes. Some of these are known to have fairly high electrical conductivity, but they require manufacturing processes such as sputtering and CVD, and are not suitable for mass production.
以上のような背景の中で、容易に薄膜化でき成形性、加
工性に優れた高分子固体電解質の応用が期待されている
。Ｍ、Ｇａｕｔｈｉｅｒらは、高分子固体電解質の柔軟
性、成形性を利用して、ポリエチレンオキシドを電解質
とし、電極材料にニッケルとリチウムを用いた積層型の
二次電池を試作している（リチウム電池国際学会′８６
゜５月）。この電池は成形性に優れ、２４層積層するこ
とにより１００℃で約１５Ｖの開放電圧が得られており
、高分子電解質を用いたデバイスの応用における今後の
大きな可能性を示唆している。Against this background, there are high expectations for the application of solid polymer electrolytes, which can be easily made into thin films and have excellent moldability and processability. M. Gauthier et al. have utilized the flexibility and moldability of solid polymer electrolytes to prototype a stacked secondary battery using polyethylene oxide as an electrolyte and nickel and lithium as electrode materials (lithium battery). International Academic Conference '86
゜May). This battery has excellent moldability, and by laminating 24 layers, an open circuit voltage of approximately 15V at 100°C was obtained, suggesting great potential in the future application of devices using polymer electrolytes.
しかしながら、デバイスを構成している要素がすべて固
体であることは、同時に解決しなければならない問題も
含んでいる。その１つが、電極と電解質との界面の密着
性の改善である。However, the fact that all the elements constituting the device are solid also includes problems that must be solved at the same time. One of these is the improvement of the adhesion of the interface between the electrode and the electrolyte.
レドックス性材料は、イオン伝導性材料と組合せてデバ
イスに応用する場合が多く、例えば、電池、センサー、
エレクトロクロミック素子などが挙げられる。その際、
両者の界面では電子移動反応が起こるが、固体−液体の
界面に比べ。Redox materials are often applied to devices in combination with ion-conducting materials, such as batteries, sensors,
Examples include electrochromic elements. that time,
Electron transfer reactions occur at the interface between the two, but compared to the solid-liquid interface.
固体と固体との界面では接着性が悪いために反応の効率
が低くなり、デバイスとしての特性が低下する。すなわ
ち、レドックス性高分子とイオン伝導性高分子の界面で
電荷移動が起こる系においては、両者の密着性が良好で
あるか否かが、界面での反応効率を大きく左右するが、
物理的圧着では密着性に限界がある。Due to poor adhesion at the interface between solids, the efficiency of the reaction is low and the properties of the device are degraded. In other words, in systems where charge transfer occurs at the interface between a redox polymer and an ion-conducting polymer, the efficiency of the reaction at the interface is greatly influenced by whether or not the adhesion between the two is good.
Physical pressure bonding has a limit to adhesion.
一方、我々は、電解質フィルム中に、電界重合により電
子伝導性高分子が成長するという事実を見出した。また
、この方法により、ポリエチレンオキシドトリオールと
トルエン−２，４−ジイソシアナートとの反応で得られ
る架橋体にアルカリ金属塩をドープしたものを高分子固
体電解質として用い、これにピロールを取り込ませて電
界重合することにより、ポリピロール／高分子固体電解
質の複合膜を得られることが報告されている（渡辺ら、
Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔｓ＋Ｊａｐａｎ、１
９８６） 。On the other hand, we have discovered that electronically conductive polymers grow in electrolyte films through electropolymerization. In addition, by this method, a crosslinked product obtained by the reaction of polyethylene oxide triol and toluene-2,4-diisocyanate doped with an alkali metal salt was used as a polymer solid electrolyte, and pyrrole was incorporated into this. It has been reported that a composite membrane of polypyrrole/polymer solid electrolyte can be obtained by electropolymerization (Watanabe et al.
Polymer Preprints+Japan, 1
986).
このように、電界重合を応用することにより、レドック
ス性高分子材料とイオン伝導性高分子材料との密着性を
改善した複合積層体を形成することができる。しかし、
電界重合法では、得られる重合体のフィルムの大きさが
、電極の大きさによって制限されるという根本的な欠点
がある。In this way, by applying electric field polymerization, it is possible to form a composite laminate with improved adhesion between the redox polymer material and the ion conductive polymer material. but,
The electric field polymerization method has a fundamental drawback in that the size of the resulting polymer film is limited by the size of the electrode.
一方、電極の大きさに依らずに、ピロールのフィルム状
ポリマーを連続的に製造する方法が特開昭５９−２３８
５９号公報に記載されており、回転ドラムを電解重合用
電極として使用している。On the other hand, a method for continuously producing a film-like polymer of pyrrole without depending on the size of the electrode was disclosed in Japanese Patent Application Laid-Open No. 59-238.
It is described in Japanese Patent No. 59, and a rotating drum is used as an electrode for electrolytic polymerization.
この方法では、電極ドラムを電解をかけながら回転させ
ることにより、ドラム上に成長したポリピロールの剥離
と、新たなポリピロールの重合とを同時に、かつ連続的
に処理でき、結果として任意の面積のポリピロール膜が
連続的に製造できるというものである。In this method, by rotating the electrode drum while applying electrolysis, it is possible to peel off the polypyrrole grown on the drum and polymerize new polypyrrole simultaneously and continuously, resulting in a polypyrrole film of any area. can be produced continuously.
しかしながら、この方法では、他に搬送用の基体等を使
用しないため、重合時にクラスター等が生じて不均質に
なった膜が剥離、搬送過程で亀裂が生じ、扱いにくい。However, since this method does not use any other substrate for transportation, it is difficult to handle because clusters and the like occur during polymerization, resulting in a non-uniform film that peels off and cracks during the transportation process.
さらに重要な問題は、膜状に成長しないポリマーや、膜
状であっても強度に劣るポリマーには適用できないこと
である。A more important problem is that it cannot be applied to polymers that do not grow into a film or to polymers that have poor strength even if they grow into a film.
１浬Ｆ口り剃
本発明は、レドックス性高分子材料とイオン伝導性高分
子材料との密着性に優れた複合積層体を、連続工程で製
造することを目的とする。1. An object of the present invention is to manufacture a composite laminate with excellent adhesion between a redox polymer material and an ion conductive polymer material in a continuous process.
凡匪夙盪處
本発明のイオン伝導性高分子フィルムと電解重合膜との
積層および／または複合体フィルムの連続的製造方法は
、
イオン伝導性高分子フィルムと電解重合膜との積層およ
び／または複合体フィルムの連続的製造方法において、
十分に機械的強度を有するイオン伝導性高分子フィルム
を連続的担体として、少なくとも該担体内部に電解重合
しうるモノマーを含浸せしめる工程；および
この含浸担体に電界を印加する工程とからなることを特
徴とする。The method of laminating an ion-conductive polymer film and an electrolytic polymer film and/or continuously producing a composite film of the present invention includes laminating an ion-conducting polymer film and an electrolytic polymer film and/or a composite film. In a continuous method for producing a composite film, an ion-conductive polymer film having sufficient mechanical strength is used as a continuous carrier, and at least the inside of the carrier is impregnated with a monomer that can be electrolytically polymerized; and the impregnated carrier is subjected to an electric field. The method is characterized by comprising a step of applying .
以下、添付図面に沿って本発明の詳細な説明する。Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
イオン伝導性高分子フィルムとしては、例えば、主鎖ま
たは側鎖に、
−ＣＨ２−ＣＨ，−０−１−ＣＨ−ＣＨ，−０−１の構
造単位を有するポリマーをマトリックスとし、これにキ
ャリアとなる電解質塩を含有せしめたポリマーマトリッ
クス−電解質塩の複合体を用いることができる。As an ion-conducting polymer film, for example, a polymer having structural units of -CH2-CH, -0-1-CH-CH, -0-1 in the main chain or side chain is used as a matrix, and a carrier and a polymer are used as a matrix. A polymer matrix-electrolyte salt composite containing an electrolyte salt can be used.
このポリマーの具体例としては、ポリエチレンオキシド
、ポリプロピレンオキシド、ポリエチレンイミンまたは
これらの架橋体が挙げられ、特に連続的なキアリアフィ
ルム（担体フィルム）として使用するに耐える強度、均
質製を有するポリマーが望ましい。具体的には、強度が
２０００ＰＳＩ以上、好ましくは３５００ＰＳＩ以上の
ポリマーが良い。Specific examples of this polymer include polyethylene oxide, polypropylene oxide, polyethyleneimine, or crosslinked products thereof. In particular, a polymer having strength and homogeneity suitable for use as a continuous chiaria film (carrier film) is desirable. . Specifically, a polymer having a strength of 2000 PSI or more, preferably 3500 PSI or more is good.
キャリアとして用いられる電解質塩の具体例としては、
Ｌ ｉ Ｐ ＦイＮ ａ Ｐ Ｆ、。Specific examples of electrolyte salts used as carriers include:
L i P F i N a P F,.
ＫＰＦＧ、Ｌｉ５ｂＦ、、Ｎａ５ｂＦ、。KPFG, Li5bF,, Na5bF,.
ＫＳｂＦいＬｉＡｓＦ、、ＮａＡｓＦ、。KSbF, LiAsF,, NaAsF,.
ＫＡ ｓ Ｆ、、 Ｌ ｉ ＣＱ Ｏ，、Ｎ ａ ＣＱ
Ｏ，。KA s F,, L i CQ O,, N a CQ
O.
ＫＣｆｌＯ４，Ｎａ Ｉ、Ｋ Ｉ 、 Ｌ ｉ Ａ Ａ
ＣＡ＜−Ｌ ｚ Ｂ Ｆ ４− ＣＦ ａ ＣＯＯＬ
ｘ、ＣＦ −ＣＯＯＮ ａ 、 ＣＦ ａ ＣＯＯＫ
。KCflO4, Na I, K I, L i A A
CA<-L z B F 4- CF a COOL
x, CF-COON a, CF a COOK
.
Ｌｉ５ＣＮ、Ｎａ５ＣＮ、ＫＳＣＮなどが挙げられる。Examples include Li5CN, Na5CN, KSCN, and the like.
これら電解質塩は、電解重合によって形成されるレドッ
クス性高分子のドーパントとしても機能する。These electrolyte salts also function as dopants for redox polymers formed by electrolytic polymerization.
ポリマーマトリックスと電解質塩の複合体は、例えば、
電解質塩を溶解せしめたポリマーが不溶の溶液に、ポリ
マーマトリックスを浸漬して含浸させる方法；ポリマー
前駆体と電解質塩とを溶かした溶液からキャスティング
法によって成膜させる方法などが挙げられる。Complexes of polymer matrix and electrolyte salts can be made by e.g.
Examples include a method in which a polymer matrix is impregnated by dipping into a solution in which an electrolyte salt is dissolved and a polymer is not dissolved; a method in which a film is formed by a casting method from a solution in which a polymer precursor and an electrolyte salt are dissolved; and the like.
本発明では、先ず、連続フィルム状のイオン伝導性高分
子を用意する。これは、イオン伝導性高分子をキャスト
、モールディング、延伸。In the present invention, first, an ion conductive polymer in the form of a continuous film is prepared. This involves casting, molding, and stretching ionically conductive polymers.
ローラー処理等で、所定の厚さに成膜させることにより
得られる。It is obtained by forming a film to a predetermined thickness by roller treatment or the like.
次に、イオン伝導性高分子フィルムに、電解重合により
レドックス性高分子を形成するモノマーを含浸させる。Next, the ion conductive polymer film is impregnated with a monomer that forms a redox polymer by electrolytic polymerization.
モノマーの含浸は、モノマーを液体のままイオン伝導性
高分子に接触させる方法や；モノマーを蒸気にして接触
させる方法により行うことができるが、後者の方が電解
重合膜の膜厚をコントロールしやすく好ましい。Impregnation with the monomer can be carried out by contacting the monomer with the ion conductive polymer while it is in a liquid state, or by contacting the monomer with the monomer in the form of vapor, but the latter method makes it easier to control the thickness of the electropolymerized membrane. preferable.
七ツマ−の具体例としては、ピロール、チオフェン、ア
セチレン、アニリン、トリフェニルアミン、ジフェニル
ベンジジン、ジフェニルアミン、ベンゼン、アズレンや
その誘導体などが用いられる。Specific examples of the hexamer include pyrrole, thiophene, acetylene, aniline, triphenylamine, diphenylbenzidine, diphenylamine, benzene, azulene, and derivatives thereof.
モノマーが含浸されたイオン伝導性高分子フィルムは、
対向電極間に移送され、イオン伝導性フィルムを挾むよ
うにして電界を印加することにより電解重合が起こり、
レドックス性ポリマーがイオン伝導性高分子の内部に成
長し、複合膜が得られる。The ion conductive polymer film impregnated with monomer is
Transferred between opposing electrodes, electrolytic polymerization occurs by applying an electric field while sandwiching the ion conductive film.
A redox polymer grows inside the ion-conducting polymer, resulting in a composite membrane.
第１図は、本発明の実施方法の一例を示す説明図であり
、電極シートｌｌ上にイオン伝導性フィルム１３を形成
した複合シート１５を用意し、これをモノマー含浸帯域
２１から電解重合帯域３１に連続的に補給する。FIG. 1 is an explanatory diagram showing an example of the method of implementing the present invention, in which a composite sheet 15 in which an ion conductive film 13 is formed on an electrode sheet 11 is prepared, and this is transferred from a monomer impregnation zone 21 to an electrolytic polymerization zone 31. Continuously replenish.
電極シート１１としては１例えば、Ｃｕ、Ｚｎ。The electrode sheet 11 may be made of, for example, Cu or Zn.
Ｎｉ等の金属のフィルム；これら金属やＩＴ○等をプラ
スチックフィルム等に蒸着した導体化フィルムなどが挙
げられる。これは、重合後そのまま用いることができ１
例えば電池であれば電極の集電体として用いられる。Films of metals such as Ni; conductive films obtained by vapor-depositing these metals, IT○, etc. on plastic films, etc., and the like. This can be used as is after polymerization.
For example, in the case of a battery, it is used as a current collector for an electrode.
モノマー含浸帯域２１で、モノマー供給器２３によりモ
ノマー２５をイオン伝導性フィルム１３に含゛浸させる
。この含浸は、モノマー２５を液状で滴下してイオン伝
導性フィルム１３に接触させたり、気体状で吹き付けて
接触させることにより行う。In the monomer impregnation zone 21 , the ion conductive film 13 is impregnated with monomer 25 by a monomer feeder 23 . This impregnation is carried out by dropping the monomer 25 in liquid form and bringing it into contact with the ion conductive film 13, or by spraying it in gas form and bringing it into contact.
モノマーが含浸されたイオン伝導性高分子フィルム１３
は、ついで、電解重合帯域３１でｆｆｉ極シート１１と
エンドレスベルト状の対向電極３３との間に挾まれるよ
うにして電界が印加されて電解重合がなされる。エンド
レスベルト状の対向電極３３の材質としては１例えば、
Ｃｕ、Ｚｕ、Ｎｉ等の金属、これら金属やＩＴ○を蒸着
したもの等の導電性を有する素材が用いられる。３５は
支持プレートを示す。Ion conductive polymer film 13 impregnated with monomer
Then, in the electrolytic polymerization zone 31, an electric field is applied so that the FFI electrode sheet 11 is sandwiched between the FFI electrode sheet 11 and an endless belt-shaped counter electrode 33, and electrolytic polymerization is performed. For example, the material of the endless belt-shaped counter electrode 33 is as follows:
A conductive material such as a metal such as Cu, Zu, or Ni, or a material on which these metals or IT◯ is deposited is used. 35 indicates a support plate.
電解重合によりレドックス性高分子が内部に成長したイ
オン伝導性フィルム（複合積層体フィルム４１）は、連
続的にローラ５１に巻取られる。The ion conductive film (composite laminate film 41) in which a redox polymer has grown through electrolytic polymerization is continuously wound around a roller 51.
第１図に示した方法では、電解重合時に必要な対向電極
の一方を、イオン伝導性フィルムの支持体として利用す
るので、イオン伝導性フィルムの薄膜を用いるとき等１
強度に問題がある場合に好適である。In the method shown in Figure 1, one of the counter electrodes required during electrolytic polymerization is used as a support for the ion-conducting film, so when using a thin film of the ion-conducting film, etc.
Suitable when strength is a problem.
第２図は、ローラ状の対向電極３３を用いる他は、第１
図の場合と同様の製造例を示す６図中、３７は支持ロー
ラを示す。In FIG. 2, the first
In Figure 6, which shows a manufacturing example similar to that shown in the figure, 37 indicates a support roller.
第３図は、本発明の他の製造例を示す説明図であり、イ
オン伝導性フィルム１３をモノマー含浸帯域２１から電
解重合帯域３１に連続的に搬送して、ローラ５１により
巻きとる。電極は一対の回転ドラム状の対向電極３３．
３９から構成され、この電極３３．３９間を挾むように
して移動させながら電界を印加することにより、イオン
伝導性高分子フィルム１３中にレドックス性高分子が成
長した複合積層体フィルム４１が得られる。FIG. 3 is an explanatory view showing another manufacturing example of the present invention, in which the ion conductive film 13 is continuously conveyed from the monomer impregnation zone 21 to the electrolytic polymerization zone 31 and wound up by the roller 51. The electrodes are a pair of rotating drum-shaped opposing electrodes 33.
By applying an electric field while moving between the electrodes 33 and 39, a composite laminate film 41 in which a redox polymer has grown in the ion-conductive polymer film 13 can be obtained.
第３図による方法によれば、電極シートを用いることな
くイオン伝導性高分子とレドックス性高分子との複合積
層体が得られ、イオン伝導性高分子フィルムが搬送等の
処理に耐えられる強度をもっている場合に有用である。According to the method shown in FIG. 3, a composite laminate of an ion-conducting polymer and a redox polymer can be obtained without using an electrode sheet, and the ion-conducting polymer film has a strength that can withstand processing such as transportation. This is useful if you have
電極（陽極−陰極）間に電界が印加されると、イオン伝
導性フィルムに含浸されている七ツマ−が重合し、陽極
酸化重合であればイオン伝導性フィルムの陽極側に、陰
極還元重合であればイオン伝導性フィルムの陰極側に、
レドックス性高分子が重合、成長する。第４図は、この
状態を模式的に示す断面図であり、複合積層体フィルム
４１の片側には、レドックス性高分子がイオン伝導性高
分子中に重合、成長したレドックス性高分子層４３が形
成され、一方、他面側にはイオン伝導性高分子がそのま
まの状態で残ったイオン伝導性高分子層４５を形成する
。レドックス性高分子の中には、成膜性が悪く膜状物と
して得ることは困難であり通常は粉状等の形態でしか得
られないものもあるが、本発明の方法によれば、イオン
伝導性高分子フィルム中に成長させることにより、膜状
物として取り扱うことができる。When an electric field is applied between the electrodes (anode-cathode), the 7-mer impregnated in the ion-conductive film polymerizes. If there is, on the cathode side of the ion conductive film,
Redox polymers polymerize and grow. FIG. 4 is a cross-sectional view schematically showing this state. On one side of the composite laminate film 41, there is a redox polymer layer 43 in which a redox polymer is polymerized and grown into an ion conductive polymer. On the other hand, an ion conductive polymer layer 45 in which the ion conductive polymer remains as it is is formed on the other side. Some redox polymers have poor film-forming properties and are difficult to obtain as a film, and are usually obtained only in the form of powder, etc. However, according to the method of the present invention, ion By growing it in a conductive polymer film, it can be handled as a membrane-like material.
レドックス性高分子層４３の膜厚は、電解重合に費やす
総クーロン数および含浸させるモノマー量で調整するこ
とができる。電解重合は、電流密度０．０５〜５ｍＡ／
ｆｆｌで行うことが好ましい。The film thickness of the redox polymer layer 43 can be adjusted by the total number of coulombs spent on electrolytic polymerization and the amount of monomer to be impregnated. Electrolytic polymerization is performed at a current density of 0.05 to 5 mA/
It is preferable to use ffl.
なお、イオン伝導性高分子がゴム状態で、かつ融点を有
する場合、電解重合は融点付近で行うことが望ましい。Note that when the ion conductive polymer is in a rubber state and has a melting point, it is desirable that the electrolytic polymerization be performed near the melting point.
電池での用途を考えると、レドックス性高分子層４３が
電極活物質として働き、イオン伝導性高分子層４５が固
体電解質として作用する。レドックス性高分子層４３と
イオン伝導性高分子層４５とは一体的に構成されること
になるので、両者のコンタクトは極めて良好である。Considering the application in a battery, the redox polymer layer 43 acts as an electrode active material, and the ion-conductive polymer layer 45 acts as a solid electrolyte. Since the redox polymer layer 43 and the ion conductive polymer layer 45 are integrally constructed, the contact between them is extremely good.
見尻立羞米
本発明によれば、イオン伝導性フィルム中に、電解重合
によりレドックス性高分子を形成する七ツマ−を含浸さ
せ、これを連続的に対向電極間に供給して電解重合する
ことにより、レドックス性高分子とイオン伝導性高分子
との密着性に優れた複合積層体を、連続工程で製造する
ことができる。According to the present invention, an ion-conductive film is impregnated with a sulfuric acid that forms a redox polymer by electrolytic polymerization, and this is continuously supplied between opposing electrodes to perform electrolytic polymerization. As a result, a composite laminate with excellent adhesion between the redox polymer and the ion conductive polymer can be manufactured in a continuous process.
さらに本発明によれば、膜状では得られないレドックス
性高分子においても、これを十分な強度を有するイオン
伝導性高分子に積層および／または複合化することで、
膜状複合体として扱うことができる。Furthermore, according to the present invention, even if a redox polymer cannot be obtained in the form of a membrane, it can be layered and/or composited with an ion conductive polymer having sufficient strength.
It can be treated as a membranous complex.
実施例１
三官能性のポリエチレンオキシド（平均分子量３，００
０）に、トリレン−２，４−ジイソシアナートを官能基
比が１；１になるように調整して混合し、さらに、キャ
リアイオンとなるＬｉＣＱＯ，をエチレンオキシドユニ
ットあたり０．０２モルの割合で添加した。この混合液
をＩＴＯ蒸着ポリエチレンフィルム（電極シート１１）
上に流延し、８０℃で７２時間反応させ、ポリエチレン
オキシド架橋体−Ｌ ｉ Ｃｎ Ｏ，複合体層（厚さ５
μｍ）を形成した。Example 1 Trifunctional polyethylene oxide (average molecular weight 3,00
0), tolylene-2,4-diisocyanate was adjusted and mixed so that the functional group ratio was 1:1, and LiCQO, which served as a carrier ion, was mixed at a ratio of 0.02 mol per ethylene oxide unit. Added. This mixed solution is applied to an ITO vapor-deposited polyethylene film (electrode sheet 11).
A polyethylene oxide crosslinked product-LiCnO, composite layer (thickness 5
μm) was formed.
これをローラに巻き取り、第１図に示したように、モノ
マー含浸帯域２１から電解重合帯域３１に搬送した。対
極電極３３としてＮｉフィルム（厚さ０ 、０１ ｎｕ
）を用い、ピロール蒸気を吹き付けて含浸させたフィ
ルムを、電極シート１３と対向電極３３間で１ｍＡ／ａ
＃の定電流を流して３０℃でピロールを電解重合したと
ころ、均一な複合積層体が得られた。This was wound up on a roller and conveyed from the monomer impregnation zone 21 to the electrolytic polymerization zone 31 as shown in FIG. As the counter electrode 33, a Ni film (thickness 0, 01 nu
), a film impregnated with pyrrole vapor was sprayed at 1 mA/a between the electrode sheet 13 and the counter electrode 33.
When pyrrole was electrolytically polymerized at 30° C. by applying a constant current of #, a uniform composite laminate was obtained.
実施例２
実施例１において、ピロールを液体として滴下する以外
は同様に行ったところ、同様に均質な複合積層体が得ら
れた。Example 2 The same procedure as in Example 1 was carried out except that pyrrole was added dropwise as a liquid, and a homogeneous composite laminate was similarly obtained.
ポリピロールの膜厚の制御はピロール蒸気を用いる方が
容易であったが、液体ピロールを用いる方が含浸装置は
簡単となる。It was easier to control the film thickness of polypyrrole using pyrrole vapor, but using liquid pyrrole makes the impregnation device simpler.
実施例３
実施例１と同様にイオン伝導性フィルムをガラス板上に
成膜し、成膜後にガラスより分離した（膜厚０ 、５
ｍ ）。このフィルム１１にピロール蒸気を含浸させ、
第３図に示すように、Ｎｉ電極３３とＮｉｌ！極３９と
の間を通し、２ ｒｐｍで回転ドラム（直径２０１）を
回転させながら、３０℃において０．５ｍＡ／ｄで定電
流重合を行ったところ、均一な複合積層体が得られた。Example 3 An ion conductive film was formed on a glass plate in the same manner as in Example 1, and separated from the glass after film formation (film thickness: 0, 5
m). This film 11 is impregnated with pyrrole vapor,
As shown in FIG. 3, the Ni electrode 33 and Ni! A uniform composite laminate was obtained by constant current polymerization at 0.5 mA/d at 30° C. while rotating a rotating drum (diameter 201) at 2 rpm.
実施例４
電解重合時の雰囲気温度を１５℃とする以外は実施例３
と同様にした。イオン伝導性高分子の融点が３０℃付近
であるため、ポリピロールの成長は反応が進みにくく不
均一であった。Example 4 Example 3 except that the atmospheric temperature during electrolytic polymerization was 15°C.
I did the same thing. Since the melting point of the ion conductive polymer is around 30° C., the reaction of polypyrrole was difficult to proceed and the growth was non-uniform.
実施例５
実施例１においてピロールの代わりにアニリンを用い、
２〜５Ｃ／ａｆの電荷を５ｖの定電圧で流して重合させ
たところ、均一な複合積層体が得られた。Example 5 Using aniline instead of pyrrole in Example 1,
When a charge of 2 to 5 C/af was applied at a constant voltage of 5 V for polymerization, a uniform composite laminate was obtained.
第１図、第２図および第３図は本発明方法による製造例
を示す説明図である。
第４図は、本発明で得られる複合積層体の構成を模式的
に示す断面図である。
１１・・・電極シート
１３・・・イオン伝導性フィルム
１５・・・複合シート
２１・・・モノマー含浸帯域
２３・・・モノマー供給器 ２５・・・モノマー３１・
・・電解重合帯域 ３３ 、３９・・・対向電極３５
・・・支持プレート ３７・・・支持ローラ４１・・
・複合積層体フィルムFIG. 1, FIG. 2, and FIG. 3 are explanatory diagrams showing manufacturing examples according to the method of the present invention. FIG. 4 is a cross-sectional view schematically showing the structure of a composite laminate obtained by the present invention. 11... Electrode sheet 13... Ion conductive film 15... Composite sheet 21... Monomer impregnated zone 23... Monomer supply device 25... Monomer 31...
... Electrolytic polymerization zone 33 , 39 ... Counter electrode 35
...Support plate 37...Support roller 41...
・Composite laminate film
Claims (1)
および／または複合体フィルムの製造方法において、 十分に機械的強度を有するイオン伝導性高 分子フィルムを連続的担体として、少なくとも該担体内
部に電解重合しうるモノマーを含浸せしめる工程； および この含浸担体に電界を印加する工程とから なることを特徴とする伝導性高分子フィルムと電解重合
膜の積層および／または複合体フィルムの連続的製造方
法。[Claims] 1. A method for laminating an ion-conducting polymer film and an electrolytically polymerized membrane and/or manufacturing a composite film, wherein an ion-conducting polymer film having sufficient mechanical strength is used as a continuous carrier. A laminate and/or composite of a conductive polymer film and an electropolymerized membrane, comprising the steps of impregnating at least the inside of the carrier with an electrolytically polymerizable monomer; and applying an electric field to the impregnated carrier. Continuous production method for film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092789A JPH0830279B2 (en) | 1987-04-15 | 1987-04-15 | Continuous manufacturing method of laminated composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092789A JPH0830279B2 (en) | 1987-04-15 | 1987-04-15 | Continuous manufacturing method of laminated composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63257634A true JPS63257634A (en) | 1988-10-25 |
| JPH0830279B2 JPH0830279B2 (en) | 1996-03-27 |
Family
ID=14064187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62092789A Expired - Lifetime JPH0830279B2 (en) | 1987-04-15 | 1987-04-15 | Continuous manufacturing method of laminated composite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830279B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5923859A (en) * | 1982-07-29 | 1984-02-07 | Sumitomo Metal Ind Ltd | Double-plated steel plate |
| JPS60228548A (en) * | 1984-04-27 | 1985-11-13 | Nippon Telegr & Teleph Corp <Ntt> | Continuous production of conductive polymer film and apparatus therefor |
| JPS61243198A (en) * | 1985-04-19 | 1986-10-29 | Hitachi Chem Co Ltd | Production of electrically-conductive plastic composite material |
| JPS62296376A (en) * | 1986-06-16 | 1987-12-23 | Yuasa Battery Co Ltd | Manufacture of polymer solid electrolyte battery |
| JPS63181273A (en) * | 1987-01-23 | 1988-07-26 | Ube Ind Ltd | Manufacture of cell |
-
1987
- 1987-04-15 JP JP62092789A patent/JPH0830279B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5923859A (en) * | 1982-07-29 | 1984-02-07 | Sumitomo Metal Ind Ltd | Double-plated steel plate |
| JPS60228548A (en) * | 1984-04-27 | 1985-11-13 | Nippon Telegr & Teleph Corp <Ntt> | Continuous production of conductive polymer film and apparatus therefor |
| JPS61243198A (en) * | 1985-04-19 | 1986-10-29 | Hitachi Chem Co Ltd | Production of electrically-conductive plastic composite material |
| JPS62296376A (en) * | 1986-06-16 | 1987-12-23 | Yuasa Battery Co Ltd | Manufacture of polymer solid electrolyte battery |
| JPS63181273A (en) * | 1987-01-23 | 1988-07-26 | Ube Ind Ltd | Manufacture of cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0830279B2 (en) | 1996-03-27 |
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