JPS618855A - Cell and its manufacture - Google Patents
Cell and its manufactureInfo
- Publication number
- JPS618855A JPS618855A JP59128844A JP12884484A JPS618855A JP S618855 A JPS618855 A JP S618855A JP 59128844 A JP59128844 A JP 59128844A JP 12884484 A JP12884484 A JP 12884484A JP S618855 A JPS618855 A JP S618855A
- Authority
- JP
- Japan
- Prior art keywords
- organic conductive
- conductive film
- charge carrier
- film
- battery
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
〔発明の分野〕
本発明は、有機導電性フィルムを用いた充電可能な電池
において異なる導電性フィルムを積層した薄形の固体電
池およびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a thin solid-state battery in which different conductive films are laminated in a rechargeable battery using an organic conductive film, and a method for manufacturing the same.
従来のこの種の導電性高分子を用いた電池として、ポリ
アセチレンを用いたもの（Ｊ、Ｃ；Ｓ、Ｃｈｅ’ｍ、。As a conventional battery using this type of conductive polymer, one using polyacetylene (J, C; S, Che'm, 2003).
５９４．１９７９．Ｊ、Ｃ，Ｓ、Ｃｈｍ、Ｃｏｍｍｕｎ
、、 ３１７．１９８１） 、ポリチイフェンを用いた
もの（Ｊ、Ｊ、八ｐｐ１．Ｐｈｙｓ、２２． Ｌ５６７
（１９８３） ）などが開発されている。このよう
な導電性高分子を用いた電池は、従来の鉛電池に比較し
てエネルギ密度および最大出力密度が大きいばかりでな
く、軽量であるなどの多くの優れた特性を示すことが分
かった。594.1979. J, C, S, Chm, Commun
,, 317.1981), using polythiphene (J, J, 8pp1. Phys, 22. L567
(1983)) have been developed. It has been found that batteries using such conductive polymers not only have higher energy density and maximum output density than conventional lead batteries, but also exhibit many excellent properties such as being lightweight.
このように優れた特性を示すにもかかわらず、前述の電
池は電解液を用いた湿式の電池であるため完全に封止し
た構造にしなければならない、あるいは電「犠により金
属電極が腐食しやすいなどという欠点があり、このため
使用上および製造上程々の難点があった。Despite these excellent characteristics, the aforementioned batteries are wet-type batteries that use an electrolyte, so they must have a completely sealed structure, or the metal electrodes are susceptible to corrosion due to electric shock. These drawbacks caused some difficulties in use and manufacturing.
本発明は上述の欠点に鑑みなされたもので、ことなる導
電性フィルムの積層による電荷キャリアの保持性の差を
利用することにより、保守の簡便な薄膜状固体電池を提
供することおよび前述の薄膜状固体電池を容易に製造す
る方法を提供することを目的とするものである。The present invention has been made in view of the above-mentioned drawbacks, and it is an object of the present invention to provide a thin-film solid state battery that is easy to maintain by utilizing the difference in charge carrier retention due to the lamination of different conductive films, and to provide a thin-film solid-state battery that is easy to maintain. The object of the present invention is to provide a method for easily manufacturing solid-state batteries.
るものである。It is something that
したがって、本発明による電池によれば、電極−間に有
機導電性フィルムを挟持した充電可能な電池において、
前記有機導電性フィルムは異なる電荷キャリア濃度の複
数の有機導電性フィルムを積層２し、電荷キャリアの濃
度勾配を形成した積層体であることを特徴とするもので
ある。Therefore, according to the battery according to the present invention, in a rechargeable battery in which an organic conductive film is sandwiched between the electrodes,
The organic conductive film is characterized in that it is a laminate in which a plurality of organic conductive films having different charge carrier concentrations are laminated to form a charge carrier concentration gradient.
また本発明による電池の製造方法によれば、有機導電性
フィルム上に、電解酸化により複素環系高分子有機導電
性フィルムを積層し、逆電圧を印加して電荷キャリア濃
度勾配を形成したことを特徴とするものである。Further, according to the method for manufacturing a battery according to the present invention, a heterocyclic polymeric organic conductive film is laminated on an organic conductive film by electrolytic oxidation, and a charge carrier concentration gradient is formed by applying a reverse voltage. This is a characteristic feature.
また本発明による電池の製造方法によれば、有機導電性
フィルム上にピンフォール高分子コーティング膜を形成
し、その高分子コーティング股上にさらに、電解酸化に
より複素環系高分子有機導電性フィルムを積層し、逆電
圧を印加して電荷キャリア濃度勾配を形成したことを特
徴とする特許本発明によれば、従来の有機導電性フィル
ムを用いた電池と異なった動作原理を有する、すなわ”
＋′？．Ｃ７，．［＝ｆｔ｛’ｔ：７ ４ ７Ｌ／”（
１）ｆｉｆｉｊｊ ’ｒ ＋ ’Ｊ Ｔｏ”６８
〜力の差を利用した薄形、軽量、フレキシブルな電
ψ池を提供可能であり、前記電池を容易
に製造可能であるという利点がある。In addition, according to the method for manufacturing a battery according to the present invention, a pinfall polymer coating film is formed on an organic conductive film, and a heterocyclic polymer organic conductive film is further laminated on the polymer coating by electrolytic oxidation. According to the patent, which is characterized in that a charge carrier concentration gradient is formed by applying a reverse voltage, the invention has an operating principle different from that of conventional batteries using organic conductive films.
+′? ．． C7,. [=ft{'t:7 4 7L/''(
1) fifijj 'r + 'J To”68
- It is possible to provide a thin, lightweight, and flexible battery that utilizes the difference in force, and there are advantages in that the battery can be easily manufactured.
本発明をさらに詳しく説明する。 The present invention will be explained in more detail.
本発明による電池は、電極間に有機導電性フィルムを挟
持した電池であって、前記有機導電性フィルムは異なる
電荷キャリア濃度の有機導電性フィルムを積層した積層
体である。The battery according to the present invention is a battery in which an organic conductive film is sandwiched between electrodes, and the organic conductive film is a laminate in which organic conductive films having different charge carrier concentrations are laminated.
本発明において用いられる有機導電性フィルムは導電性
があれば、基本的に限定されるものではない。たとえば
、ポリピロール、ｎ−メチルポリピロールなどのピロー
ル系高分子、ポリチオフェンなどのチオフェン系高分子
、ポリフランなどのフラン系高分子、ポリアズレンなど
のアズレン系高分子、ポリインドールなどのインドール
系高分子、ポリセレノフェンなどのセレフェン系高分子
あるいはこれらの共重合体などの複素環系有機導電性フ
ィルムあるいはポリパラフェニレンスルフィド、ポリフ
ェニレン、ポリアセチレンなどの共役系高分子有機導電
性フィルムなどを用いることができる。The organic conductive film used in the present invention is not fundamentally limited as long as it has conductivity. For example, pyrrole polymers such as polypyrrole and n-methylpolypyrrole, thiophene polymers such as polythiophene, furan polymers such as polyfuran, azulene polymers such as polyazulene, indole polymers such as polyindole, and polyseleno polymers. A heterocyclic organic conductive film such as a selephene polymer such as phene or a copolymer thereof, or a conjugated polymer organic conductive film such as polyparaphenylene sulfide, polyphenylene, polyacetylene, etc. can be used.
このような有機導電性フィルム上に積層される異なる電
荷キャリア濃度を有する有機導電性フィルムは電解酸化
により形成された複素環系有機導電性フィルムである。The organic conductive film having different charge carrier concentrations that is laminated on such an organic conductive film is a heterocyclic organic conductive film formed by electrolytic oxidation.
このような複素環系有機導電性フィルムは、たとえば上
述のポリピロール、ｎ−メチルポリピロールなどのピロ
ール系高分子、ポリチオフェンなどのチオフェン系高分
子、ポリフランなどのフラン系高分子、ポリアズレンな
どのアズレン系高分子、ポリインドールなどのインドー
ル系高分子、ポリセレノフェン般どのセレフエン系高分
子あるいはこれらの共重合体などを用いることができる
。Such heterocyclic organic conductive films include, for example, pyrrole polymers such as the above-mentioned polypyrrole and n-methylpolypyrrole, thiophene polymers such as polythiophene, furan polymers such as polyfuran, and azulene polymers such as polyazulene. Molecules, indole polymers such as polyindole, serephene polymers such as polyselenophene, or copolymers thereof can be used.
本発明は前記有機導電性フィルムを少なくとも第１層次
いで第２層と二種類積層するものであるが、この第１層
としては前記有機導電性フィルム中に含有されるイオン
（ドーパント）を脱離しやすいフィルムを用い、第２層
として前記第１層と比較してドーパントを脱離しにくい
フィルムを順次積層する。In the present invention, two types of organic conductive films are laminated, including at least a first layer and a second layer, and the first layer is formed by desorbing ions (dopants) contained in the organic conductive film. Using a film that is easy to release, a film that is less likely to release the dopant than the first layer is sequentially laminated as the second layer.
このような第１眉および第２層間にピンホール高分子コ
ーティング膜によるセパレークを形成してもよい。この
ようなセパレークはビンフォールのある絶縁材料であれ
ばいかなるものでもよい。A separate lake may be formed between the first layer and the second layer using a pinhole polymer coating film. Such a separator may be made of any insulating material that has a binder.
たとえば環化ゴムレジストなどを用いることができる。For example, a cyclized rubber resist can be used.
次ぎに本発明による電池の製造方法について説明する。Next, a method for manufacturing a battery according to the present invention will be explained.
本発明による電池の製造方法によれば、まず基板上に有
機導電性フィルムを形成する。According to the method for manufacturing a battery according to the present invention, an organic conductive film is first formed on a substrate.
このような有機導電性フィルムの形成方法は基本的に限
定されるものではなく、たとえばモノマーを含む電解液
中で電解酸化により基板上に形成してもよいし、有機高
分子粉末を基板上に加熱、加圧してフィルムとしてもよ
い。また蒸着などに−よって形成することができる。The method of forming such an organic conductive film is basically not limited; for example, it may be formed on a substrate by electrolytic oxidation in an electrolytic solution containing monomers, or it may be formed on a substrate by applying organic polymer powder to the substrate. It may be made into a film by heating and pressurizing. Alternatively, it can be formed by vapor deposition or the like.
たとえば、上述の電解酸化法により有機導電性フィルム
を形成する場合、まず基板上に電解酸化ｌ
により二種類の複素環系高分子半導体フィルムを積
層するものであるが、このような電解酸化は、重合すべ
きモノマーを含む電解液中において、電解を行い前記基
板上に複素理系高分子半導体フィルムを形成せしめるも
のである。For example, when forming an organic conductive film by the electrolytic oxidation method described above, first electrolytic oxidation lactic acid is applied on the substrate.
In this electrolytic oxidation method, electrolysis is carried out in an electrolytic solution containing monomers to be polymerized, and a complex polymer semiconductor film is laminated on the substrate. It causes the formation of
このような電解液としては、形成される前記高分子半導
体フィルムにドーパントを取り込むようなものであれば
いかなるものでもよい。たとえば、テトラ−ｎ−ブチル
アンモニウム・ヘキサフルオロポレート（ｎＢｕ ａ
Ｎ −ＢＦ４） 、テトラ−ｎ−ブチルアンモニウム
・過塩素酸硼素（ｎ−ＢｕｋＮ −ＢＣ１０４）、テ
１−ラーｎ−ブチルアンモニウム・六フッ化砒素（ｎ−
１）ｕ４Ｎ −Ｆ ｓ Ａｓ） 、テトラ−ｎ−ブチ
ルアンモニウム・過塩素酸炭素（ｎ−Ｂｕ４Ｎ−ＣＣ１
０４）などの有機電解質あるいはＡｇＢＦ４、ＡｇＣ１
０，１などの無機電解質などの一種以上を用いることが
できる。Any electrolytic solution may be used as long as it can incorporate the dopant into the polymer semiconductor film to be formed. For example, tetra-n-butylammonium hexafluoroporate (nBu a
N-BF4), tetra-n-butylammonium boron perchlorate (n-BukN-BC104), tetra-n-butylammonium boron perchlorate (n-BukN-BF4), tetra-n-butylammonium boron perchlorate (n-
1) u4N-F s As), tetra-n-butylammonium carbon perchlorate (n-Bu4N-CC1
Organic electrolytes such as 04) or AgBF4, AgC1
One or more types of inorganic electrolytes such as 0, 1, etc. can be used.
またこの電解液中に添加されるモノマーは、前述のよう
な複素環系高分子材料を形成するモノマーであればいか
なるものでもよい。Further, the monomer added to this electrolytic solution may be any monomer as long as it forms the above-mentioned heterocyclic polymer material.
このように少なくとも二種の有機導電性フィル
１ムを積層したのち、逆電圧を印加し、脱ド
ープを行う。このような高分子半導体フィルムに電荷キ
ャリアの濃度勾配を形成させるためには、前記有機導電
性フィルム中にフィルムの厚さ方向にイオン分布を形成
することが必要であるが、本発明によればこのイオン分
布は、逆電圧を印加して脱ドープを行い形成させる。こ
のように脱ドープを行うことにより有機導電性フィルム
の電荷キャリア濃度が異なることになり電荷キャリア濃
度勾配が形成される。In this way, at least two types of organic conductive films
After one layer is stacked, a reverse voltage is applied to perform dedoping. In order to form a concentration gradient of charge carriers in such a polymer semiconductor film, it is necessary to form an ion distribution in the thickness direction of the organic conductive film. This ion distribution is formed by dedoping by applying a reverse voltage. By performing dedoping in this manner, the charge carrier concentration of the organic conductive film differs, and a charge carrier concentration gradient is formed.
この逆電圧は好ましくはＩＯＶ以下であるのがよい。Ｉ
ＯＶを超えると、脱イオンが激しくなり、有機導電性フ
ィルム自体に損傷を生じる虞があるからである。This reverse voltage is preferably less than or equal to IOV. I
This is because if it exceeds OV, deionization becomes intense and there is a risk of damage to the organic conductive film itself.
本発明による第２の製造方法にあっては、第１層の有機
導電性フィルムを形成したのち、ビンフォール高分子コ
ーティング膜によるセパレークを形成し、このセパレー
タ上に上述のように説明した方法によって有機導電性フ
ィルムをさらに積層する。In the second manufacturing method according to the present invention, after forming the first layer of organic conductive film, a separator lake of Vinfall polymer coating film is formed, and the above-described method is applied on the separator. An organic conductive film is further laminated.
このようなセパレータとしては、たとえば環化ゴムレジ
ストを第１層上に塗布し、光硬化させて形成したもので
あってよい。Such a separator may be formed, for example, by applying a cyclized rubber resist onto the first layer and photocuring it.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
実施例１
厚さ１００μｍ 、３ ｃｍＸ５ ｃｍのニッケル板を
陽極とし、対極として白金板を用いてグローブボックス
中で電解重合を行った。Example 1 Electrolytic polymerization was carried out in a glove box using a 100 μm thick, 3 cm x 5 cm nickel plate as an anode and a platinum plate as a counter electrode.
電解液はアセトニトリル ８０ｍ１、チオフェノン３．
６ｍｌ、テトラ−ｎ−ブチルアンモニウム・ヘキサフル
オロポレート（ｎＢｕ ４ Ｎ −ＢＦ４） ４．
５ｇをビーカー中で混合して作製した。このなかに電極
を差込み、４．Ｉ Ｖ 、１００ ｍＡの電流を１０分
間電解重合を行い、ニッケル板上に黒色チオフェノン膜
ヲ作製した。これをアセトニトリルで洗浄し、ついでピ
ロール電解液（アセトニトリル８０ ｍｌ、ビロール
３．４ｇ、テトラ−ｎ−ブチルアンモニウム・ヘキサフ
ルオロポレート（ｎＢｕ ４Ｎ −ＢＦ４） ４．５
ｇ）中で１．５ｖ、１００μ八で５０分間電電解層重合
を行った。この積層体をアセトニトリルで洗浄後、膜上
部に白金極板を密着させ、アセトニトリル溶媒中に入れ
、積層基板のニッケル板を陰極、白金板を陽極として、
１．３ Ｖ 、１０分間逆電圧を印加して脱ドープを行
った。この結果、ポリチオフェン膜層部分のみが主に脱
ドープされた。The electrolyte is acetonitrile 80ml, thiophenone 3.
6 ml, tetra-n-butylammonium hexafluoroporate (nBu4N-BF4) 4.
5g were mixed in a beaker. Insert the electrode into this, 4. Electrolytic polymerization was performed at IV and a current of 100 mA for 10 minutes to produce a black thiophenone film on a nickel plate. This was washed with acetonitrile, and then pyrrole electrolyte solution (acetonitrile 80 ml, pyrrole
3.4 g, tetra-n-butylammonium hexafluoroporate (nBu 4N -BF4) 4.5
Electrolytic layer polymerization was carried out for 50 minutes at 1.5 V and 100 μm in (g). After cleaning this laminate with acetonitrile, a platinum electrode plate was placed in close contact with the top of the membrane, and placed in an acetonitrile solvent, with the nickel plate of the laminate substrate being used as a cathode and the platinum plate as an anode.
Dedoping was performed by applying a reverse voltage of 1.3 V for 10 minutes. As a result, only the polythiophene film layer portion was mainly dedoped.
アセトニトリルで洗浄後、乾燥し、真空蒸着してポリピ
ロール股上に金の電極を形成した。After washing with acetonitrile, it was dried and vacuum evaporated to form a gold electrode on the polypyrrole crotch.
このような電池にニッケル板側を陽極、金電極側を陰極
としてアセトニトリル中で１．５ Ｖ 、 ３０分間電
圧を印加し、電圧印加状態のまま前記アセトニトリル液
中より引出し、風乾することにより充電を行った。To such a battery, a voltage of 1.5 V was applied for 30 minutes in acetonitrile with the nickel plate side as the anode and the gold electrode side as the cathode, and the battery was pulled out from the acetonitrile solution while the voltage was being applied and was air-dried to charge it. went.
このようにして製造され、充電された電池の断面図（充
電状態）を第１図に示す。A cross-sectional view (charged state) of a battery manufactured and charged in this manner is shown in FIG.
この第１図より明らかなように、この実施例２にける電
池は最外側にニッケル板１を有し、このニッケル板１に
充電により電荷キャリア４の濃度のＣ高くなったポリチ
オフェノンフィルム（有機導電性フィルム）２および電
荷キャリア４の濃度が小さくなったポリピロールフィル
ム３が積層され、さらにこのポリピロールフィルム３上
に金蒸着層５ （電極）が形成された構造を有している
。As is clear from FIG. 1, the battery according to Example 2 has a nickel plate 1 on the outermost side, and this nickel plate 1 is covered with a polythiophenone film ( It has a structure in which an organic conductive film) 2 and a polypyrrole film 3 having a low concentration of charge carriers 4 are laminated, and a gold vapor deposited layer 5 (electrode) is further formed on the polypyrrole film 3.
このように充電した電池はセル電圧２．６シが得られ、
５０μＡ／ｃｕｔの放電電流で放電を行ったところ、理
論エネルギ密度６１Ｗｈ／Ｋｇが得られた。The battery charged in this way has a cell voltage of 2.6,
When discharge was performed with a discharge current of 50 μA/cut, a theoretical energy density of 61 Wh/Kg was obtained.
また、充電操作をドライ状態で２．０■、３時間に亘っ
て行った場合も、前記と同様な特性が得られた。Further, when the charging operation was carried out in a dry state for 2.0 hours and 3 hours, the same characteristics as described above were obtained.
このような本発明による電池は、導電性フィルム中のＢ
Ｆａアニオンが前記導電性フィルムの電荷移動錯体のド
ーパントとして電気伝導度の向上とともに、電荷キャリ
アとしてポリチオフェノンフィルム中に高濃度に、ポリ
ピロール中に低濃度に分散し、不安定なポリチオフェノ
ンフィルムを脱出し、より安定な保持体であるポリピロ
ールフィルム方向に移動しようとする性質を利用したも
のであり、従来の有機導電性フィルムを応用した２次電
池とは動作原理が異なっている。
〜実施例２
実施例１において使用したポリチオフェンの作製工程に
おいてチオフェノンのかわりにフランを用いた。この場
合の電解液はアセトニトリル８０ｍ１、フラン３ｍｌ、
Ｂｕａ Ｎ ・ＢＦ４４．５ ｇ使用し、ポリフラン
導電性フィルム膜を形成した。その後、実施例１と同様
にしてポリピロールフィルム膜およびその後の処理を行
い、セル電圧 ２．９Ｖ、エネルギ密度８０Ｗｈ／Ｋｇ
の電池が得られた。Such a battery according to the present invention has B in the conductive film.
The Fa anion improves the electrical conductivity as a dopant of the charge transfer complex of the conductive film, and is dispersed as a charge carrier at a high concentration in the polythiophenone film and at a low concentration in the polypyrrole, resulting in an unstable polythiophenone film. This utilizes the property of the battery to escape from the organic conductive film and move toward the polypyrrole film, which is a more stable support, and its operating principle is different from that of conventional secondary batteries that utilize organic conductive films.
~Example 2 Furan was used in place of thiophenone in the production process of polythiophene used in Example 1. The electrolyte in this case is 80ml of acetonitrile, 3ml of furan,
A polyfuran conductive film was formed using 44.5 g of Bua N.BF. Thereafter, a polypyrrole film film and subsequent treatments were performed in the same manner as in Example 1, and the cell voltage was 2.9V and the energy density was 80Wh/Kg.
batteries were obtained.
実施例３
厚さ１００μｍ１）×１ｃｍのニッケル板上にポリパラ
フェニレンスルフィド粉末を加熱加圧法により熔融プレ
ス成形し、膜厚５０μｍ程度の積層体を得た。次いでこ
の積層体に真空ライン中で５フン化砒素をドーピングし
、導電性を付与した。Example 3 Polyparaphenylene sulfide powder was melt press-molded on a 100 μm thick 1 cm x 1 cm nickel plate by heating and pressing to obtain a laminate with a film thickness of about 50 μm. Next, this laminate was doped with arsenic pentafluoride in a vacuum line to impart electrical conductivity.
この後、実施例１と同様にポリピロールフィルム膜を積
層し、実施例１と同様に脱ドープを行った後、金電極を
形成し、充電を行った。Thereafter, polypyrrole film membranes were laminated in the same manner as in Example 1, and after dedoping was performed in the same manner as in Example 1, gold electrodes were formed and charging was performed.
これによりセル電圧１．９Ｖ、 ２０Ｗｈ／Ｋｇのエネ
ルギ密度の電池が得られた。As a result, a battery with a cell voltage of 1.9 V and an energy density of 20 Wh/Kg was obtained.
実施例４
実施例１と同様な操作においてニッケル板上にポリチオ
フェンフィルム膜を作製したのち、環化ゴムレジスト（
日本合成ゴム製）をスプレーし、乾燥し、光硬化した。Example 4 After producing a polythiophene film on a nickel plate in the same manner as in Example 1, a cyclized rubber resist (
(manufactured by Japan Synthetic Rubber) was sprayed, dried, and photocured.
実施例１と同様な工程において、ポリピロールを積層重
合させ、電極を形成し、脱ドープを行い、充電した。In the same steps as in Example 1, polypyrrole was laminated and polymerized to form an electrode, dedoped, and charged.
このように製造された電池のセル電圧は２．４ｖであり
、６０Ｗｈ／ＫＨのエネルギ密度であった。The cell voltage of the battery manufactured in this manner was 2.4V, and the energy density was 60Wh/KH.
以上説明したように、本発明によれば異なる導電性フィ
ルムの電荷キャリアの保持能力の差を利用した薄形、軽
量、フレキシブルの固体二次電池を提供でき、かつ電解
重合法あるいは簡便なプレス法を用いることにより前記
電池を容易に製造できる利点がある。As explained above, according to the present invention, it is possible to provide a thin, lightweight, and flexible solid state secondary battery that takes advantage of the difference in charge carrier retention ability of different conductive films, and which can be produced using an electrolytic polymerization method or a simple pressing method. There is an advantage that the battery can be manufactured easily by using the above.
このため移動パーソナル通信機の電源、電幸、時計など
の小型、軽量機器に使用する電源として最適な電源とし
て使用できる利点を生じる。Therefore, it has the advantage that it can be used as an optimal power source for small and lightweight devices such as power sources for mobile personal communication devices, electric appliances, and watches.
第１図は本発明による実施例１における電池の断面図で
ある。
■ ・・・ニッケル板、２ ・・・ポリチオフェンフィ
ルム（有機導電性フィルム）、３ ・・・ポリピロール
フィルム（有機導電性フィルム）、４ ・・・電荷キャ
リア、５ ・・・金電極。FIG. 1 is a sectional view of a battery in Example 1 according to the present invention. ■ Nickel plate, 2 Polythiophene film (organic conductive film), 3 Polypyrrole film (organic conductive film), 4 Charge carrier, 5 Gold electrode.
Claims (4)
な電池において、前記有機導電性フィルムは異なる電荷
キャリア濃度の複数の有機導電性フィルムを積層し、電
荷キャリアの濃度勾配を形成した積層体であることを特
徴とする電池。(1) In a rechargeable battery in which an organic conductive film is sandwiched between electrodes, the organic conductive film is a laminate in which a plurality of organic conductive films having different charge carrier concentrations are laminated to form a charge carrier concentration gradient. A battery characterized by:
系高分子有機導電性フィルムを積層し、逆電圧を印加し
て電荷キャリア濃度勾配を形成したことを特徴とする電
池の製造方法。(2) A method for manufacturing a battery, comprising laminating a heterocyclic polymer organic conductive film on an organic conductive film by electrolytic oxidation, and applying a reverse voltage to form a charge carrier concentration gradient.
ることを特徴とする特許請求の範囲第２項記載の電池の
製造方法。(3) The method for manufacturing a battery according to claim 2, wherein the organic conductive film is produced by electrolytic oxidation.
ティング膜を形成し、その高分子コーティング膜上にさ
らに、電解酸化により複素環系高分子有機導電性フィル
ムを積層し、逆電圧を印加して電荷キャリア濃度勾配を
形成したことを特徴とする電池の製造方法。(4) A pinfall polymer coating film is formed on the organic conductive film, a heterocyclic polymer organic conductive film is further laminated on the polymer coating film by electrolytic oxidation, and a reverse voltage is applied. A method for manufacturing a battery, characterized in that a charge carrier concentration gradient is formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59128844A JPS618855A (en) | 1984-06-22 | 1984-06-22 | Cell and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59128844A JPS618855A (en) | 1984-06-22 | 1984-06-22 | Cell and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS618855A true JPS618855A (en) | 1986-01-16 |
Family
ID=14994779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59128844A Pending JPS618855A (en) | 1984-06-22 | 1984-06-22 | Cell and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS618855A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816359A (en) * | 1986-03-06 | 1989-03-28 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element with at least one polymer electrode |
| WO1991003921A1 (en) * | 1989-08-29 | 1991-03-21 | At&E Corporation | Watchband battery powered system |
-
1984
- 1984-06-22 JP JP59128844A patent/JPS618855A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816359A (en) * | 1986-03-06 | 1989-03-28 | Varta Batterie Aktiengesellschaft | Electrochemical secondary element with at least one polymer electrode |
| WO1991003921A1 (en) * | 1989-08-29 | 1991-03-21 | At&E Corporation | Watchband battery powered system |
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