JP2600175B2 - Rechargeable battery - Google Patents

Rechargeable battery

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Publication number
JP2600175B2
JP2600175B2 JP62160532A JP16053287A JP2600175B2 JP 2600175 B2 JP2600175 B2 JP 2600175B2 JP 62160532 A JP62160532 A JP 62160532A JP 16053287 A JP16053287 A JP 16053287A JP 2600175 B2 JP2600175 B2 JP 2600175B2
Authority
JP
Japan
Prior art keywords
positive electrode
secondary battery
electrode
negative electrode
polymer material
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 - Fee Related
Application number
JP62160532A
Other languages
Japanese (ja)
Other versions
JPS646383A (en
Inventor
章夫 安田
透 永井
隆幸 山平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sony Corp
Original Assignee
Sony Corp
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Filing date
Publication date
Application filed by Sony Corp filed Critical Sony Corp
Priority to JP62160532A priority Critical patent/JP2600175B2/en
Publication of JPS646383A publication Critical patent/JPS646383A/en
Application granted granted Critical
Publication of JP2600175B2 publication Critical patent/JP2600175B2/en
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Classifications

    • 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

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は二次電池に関し、特に電極に高分子材料を用
い、長寿命化、大容量化、薄型化が可能な二次電池に関
する。Description: TECHNICAL FIELD The present invention relates to a secondary battery, and more particularly to a secondary battery that uses a polymer material for an electrode and can have a long life, a large capacity, and a small thickness.

〔発明の概要〕[Summary of the Invention]

本発明は、二次電池の中でも特に電極が高分子材料に
より形成されているいわゆるポリマーバッテリーにおい
て、正極材料に予めアニオン性官能基を導入し、充放電
に伴ってカチオンを上記正極と負極との間で放出（脱ド
ープ）あるいは吸蔵（ドープ）せしめることにより、長
寿命化、大容量化、薄型化を可能とするものである。The present invention is a secondary battery, in particular, in a so-called polymer battery in which an electrode is formed of a polymer material, an anionic functional group is introduced in advance to a positive electrode material, and a cation is formed between the positive electrode and the negative electrode with charge and discharge. By releasing (de-doping) or occluding (doping) between them, it is possible to extend the life, increase the capacity, and reduce the thickness.

〔従来の技術〕[Conventional technology]

従来、二次電池と言えば、自動車用の鉛蓄電池、VTR
のタイマーやICメモリーのバックアップ電源等に使用さ
れるニッケル・カドミウム電池等が主流である。これら
の二次電池は、pHが酸性側あるいはアルカリ性側に大き
く偏った水溶液系電解質を使用しており、高い導電率が
得られることが特徴である。しかし、高温下での保存
性、電極の腐食性、電位窓の大きさ等に問題点を残して
いる。Conventionally speaking, secondary batteries are lead-acid batteries for automobiles and VTRs.
The mainstream is nickel-cadmium batteries used for timers and backup power supplies for IC memories. These secondary batteries use an aqueous electrolyte whose pH is largely biased toward the acidic side or the alkaline side, and are characterized by high electrical conductivity. However, there remain problems such as the storability at high temperatures, the corrosiveness of the electrodes, and the size of the potential window.

一方、比重が軽く、標準電極電位の低いリチウムある
いはリチウム合金を負極活物質として使用する二次電池
が数十年来検討されている。これは非水溶媒を電解質溶
液として使用するものであり、上述の水溶液系電解質を
使用した二次電池における問題点は解消されているが、
充放電時にリチウムの樹枝状結晶が負極表面に析出する
ことにより、電池の効率、寿命が著しく低下するという
問題が残されている。さらに、リチウムは常温で水と容
易に反応するため、生産に際してはドライルーム等の設
備投資も必要となり、二次電池のコストが高くなる原因
となっていた。On the other hand, secondary batteries using lithium or lithium alloy having a low specific gravity and a low standard electrode potential as a negative electrode active material have been studied for decades. Although this uses a non-aqueous solvent as an electrolyte solution, the problem in the secondary battery using the above-described aqueous electrolyte has been solved,
A problem remains that the efficiency and life of the battery are significantly reduced due to precipitation of lithium dendrites on the surface of the negative electrode during charge and discharge. Further, since lithium easily reacts with water at room temperature, capital investment in a dry room or the like is required for production, which has been a cause of an increase in the cost of the secondary battery.

かかる背景から、電極に高分子材料を使用したいわゆ
るポリマーバッテリーが提案されている。このポリマー
バッテリーには、たとえばポリアセチレンやポリアニリ
ンのような導電性の高分子材料が電極材料として使用さ
れている。From such a background, a so-called polymer battery using a polymer material for an electrode has been proposed. In this polymer battery, a conductive polymer material such as polyacetylene or polyaniline is used as an electrode material.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

ところで、従来のポリマーバッテリーにおいては、よ
り一層の薄型化を図るために正極および負極の両方を共
に高分子材料で形成しようとすると、その充放電容量は
電解質溶液中に溶存するカチオンの濃度で決まり、大容
量化に限界が生じるという問題があった。By the way, in the conventional polymer battery, if both the positive electrode and the negative electrode are made of a polymer material in order to further reduce the thickness, the charge / discharge capacity is determined by the concentration of the cation dissolved in the electrolyte solution. However, there is a problem that the capacity is limited.

そこで本発明は、上述の従来の実情に鑑みて提案され
たものであって、大容量化と薄型化を併せて達成するこ
とのできる二次電池を提供することを目的とするもので
ある。Accordingly, the present invention has been proposed in view of the above-described conventional circumstances, and has an object to provide a secondary battery that can achieve both a large capacity and a low thickness.

〔問題点を解決するための手段〕[Means for solving the problem]

本発明者らは、ポリマーバッテリーの充放電容量を増
大させるためには、少なくとも一方の電極に予めアニオ
ン性の官能基を導入することにより、カチオンを両極間
で可逆的に移動させることが有効であることを見出し、
本発明に至ったものである。In order to increase the charge / discharge capacity of the polymer battery, it is effective to reversibly move cations between the two electrodes by introducing an anionic functional group into at least one electrode in advance. Finding something,
This has led to the present invention.

すなわち、本発明に係る二次電池は、ポリスチレンス
ルホネートが共重合された導電性高分子材料からなり、
カチオンが放電時にドープされ、充電時に脱ドープされ
る正極と、カチオンが充電時にドープされ、放電時に脱
ドープされる高分子材料からなる負極と、電解質層とを
有してなることを特徴とするものである。That is, the secondary battery according to the present invention is made of a conductive polymer material obtained by copolymerizing polystyrene sulfonate,
It is characterized by comprising a positive electrode which is doped with cations during discharging and is undoped during charging, a negative electrode made of a polymer material which is doped with cations during charging and undoped during discharging, and an electrolyte layer. Things.

（作用） 本発明にかかる二次電池においては、正極の高分子材
料に予め重合時にアニオン性官能基が導入されている。
この官能基に由来する負電荷は正極材料中に固定された
ものであり、従来の二次電池における負電荷のように自
由に移動できる性質のものではない。この点が、従来の
二次電池とは異なった独特の充放電機構を実現してい
る。(Operation) In the secondary battery according to the present invention, an anionic functional group is previously introduced into the polymer material of the positive electrode during polymerization.
The negative charge derived from this functional group is fixed in the positive electrode material and does not have such a property that it can move freely like the negative charge in a conventional secondary battery. This realizes a unique charging / discharging mechanism different from the conventional secondary battery.

まず放電時には、負極に吸蔵（ドープ）されていたカ
チオンが該負極から放出（脱ドープ）され、該負極は電
子過剰の状態となる。この過剰の電子は、負荷を有する
外部の接続手段を通じて正極に流入し、該正極の負電荷
を増加させる。すると、上記正極は電気的中性を維持す
るために、先に負極から放出されたカチオンを吸蔵す
る。First, at the time of discharging, the cations occluded (doped) in the negative electrode are released (de-doped) from the negative electrode, and the negative electrode is in an excess electron state. The excess electrons flow into the positive electrode through external connection means having a load, and increase the negative charge of the positive electrode. Then, the positive electrode occludes cations previously released from the negative electrode in order to maintain electrical neutrality.

ここで、本発明にかかる二次電池が従来の二次電池と
大きく異なる点は、正極の材料中にカチオンが吸蔵され
る点である。すなわち、正極に蓄積された負電荷は高分
子材料のアニオン性官能基に由来するものであって、自
由に移動できるものではないので、この電荷を中和する
ためには、カチオンが正極材料の内部にまで浸透する必
要がある。Here, the secondary battery according to the present invention is significantly different from a conventional secondary battery in that cations are occluded in the material of the positive electrode. That is, the negative charge accumulated in the positive electrode is derived from the anionic functional group of the polymer material and cannot be freely moved. It needs to penetrate inside.

逆に充電時には、外部電源により正極から強制的に電
子が奪われるので、正極材料中の負電荷が減少する。そ
こで、電気的中性を維持するために吸蔵されていたカチ
オンが放出される。奪われた電子は外部回路を介して負
極に流入し、該負極は電子過剰の状態となる。そこで、
先に正極から放出されたカチオンを吸蔵して電気的中性
を維持する。Conversely, at the time of charging, electrons are forcibly removed from the positive electrode by the external power supply, so that negative charges in the positive electrode material are reduced. Then, cations that have been occluded to maintain electrical neutrality are released. The deprived electrons flow into the negative electrode via an external circuit, and the negative electrode becomes in a state of excess electrons. Therefore,
The cations previously released from the positive electrode are occluded to maintain electrical neutrality.

この機構も、本発明にかかる二次電池の特徴をなす点
である。従来の二次電池では、正極の負電荷が減少する
と、該正極の表面に電解液中に存在する対イオン（アニ
オン）が引き付けられて電子を供与していた。しかし、
本発明にかかる二次電池においては、正極材料中に固定
されている負電荷が減少するので、電気的中性を維持す
るためにはカチオンを放出するという手段をとる。しか
も、電解液中の対イオン（アニオン）は、もともと正極
材料中に存在するアニオン性官能基の反発に合って吸蔵
されることがない。This mechanism is also a feature of the secondary battery according to the present invention. In a conventional secondary battery, when the negative charge of the positive electrode decreases, a counter ion (anion) present in the electrolytic solution is attracted to the surface of the positive electrode to provide an electron. But,
In the secondary battery according to the present invention, since the negative charge fixed in the positive electrode material is reduced, a means of releasing cations is used to maintain electrical neutrality. In addition, the counter ion (anion) in the electrolyte is not occluded due to the repulsion of the anionic functional group originally present in the positive electrode material.

結局、本発明にかかる二次電池においては、充電時に
も放電時にも吸蔵・放出されるイオンはカチオンのみで
あり、これが両電極間で可逆的に繰返されるので、予め
電解質中に溶存するカチオンの濃度に電池の容量が制御
されることがない。After all, in the secondary battery according to the present invention, only ions that are absorbed and released during charging and discharging are cations only, and this is reversibly repeated between the two electrodes. The concentration does not control the capacity of the battery.

〔実施例〕〔Example〕

以下、本発明の好適な実施例について説明する。 Hereinafter, preferred embodiments of the present invention will be described.

本実施例の二次電池は、予めアニオン性官能基を導入
した高分子材料よりなる正極、導電性高分子材料よりな
る負極、および電解質層とから構成されるものである。The secondary battery according to the present embodiment includes a positive electrode made of a polymer material in which an anionic functional group is introduced in advance, a negative electrode made of a conductive polymer material, and an electrolyte layer.

上記負極を構成する高分子材料としては、導電性を有
する高分子材料がいずれも使用でき、たとえばポリチオ
フェン、ポリアセチレン、ポリパラフェニレン、ポリピ
ロール等が使用可能である。As the polymer material constituting the negative electrode, any polymer material having conductivity can be used, and for example, polythiophene, polyacetylene, polyparaphenylene, polypyrrole and the like can be used.

また、正極を構成する高分子材料は、前述の負極材料
と同様に導電性を有することが必要であるばかりでな
く、アニオン性官能基が導入されることが必要である。
したがって、前述の負極を構成する高分子材料にアニオ
ン性官能性（たとえばスルホン酸基）を共重合等の手法
により導入した高分子材料が使用される。具体的には、
ポリピロール（PPy）とポリスチレンスルホネート（PS
S）の共重合体（以下、PPy−PSSと称する。）等が挙げ
られる。Further, the polymer material constituting the positive electrode needs to have not only conductivity as in the case of the above-described negative electrode material, but also need to introduce an anionic functional group.
Therefore, a polymer material in which an anionic functionality (for example, a sulfonic acid group) is introduced into the above-described polymer material constituting the negative electrode by a method such as copolymerization is used. In particular,
Polypyrrole (PPy) and polystyrene sulfonate (PS
S) (hereinafter referred to as PPy-PSS).

なお、上記両極を構成する高分子材料は通常はフィル
ム状に成形して使用されるが、必ずしもフィルム状であ
る必要はなく、高分子材料の粉末にバインダーを配合し
て得られる成形体であっても良い。The polymer material constituting the above two electrodes is usually used after being formed into a film, but it is not necessarily required to be in the form of a film, but a formed body obtained by blending a binder with a powder of the polymer material. May be.

本実施例の二次電池においては、これら正極および負
極の間でカチオンを吸蔵・放出することにより充放電が
繰返されるが、上記両極間で吸蔵・放出されるカチオン
としては、リチウムイオン、ナトリウムイオン、カリウ
ムイオン、アンモニウムイオン、第四アンモニウムイオ
ン等が挙げられる。これらのカチオンは、予め上記正極
あるいは負極にドープするか、電解質層から供給する
か、あるいはこれらの手段の組合わせにより与えられ
る。In the secondary battery of this embodiment, charge and discharge are repeated by inserting and extracting cations between the positive electrode and the negative electrode. The cations that are inserted and released between the two electrodes include lithium ions and sodium ions. , Potassium ions, ammonium ions, and quaternary ammonium ions. These cations are previously doped into the positive electrode or the negative electrode, supplied from the electrolyte layer, or provided by a combination of these means.

一方、上記電解質層は、上記正極・負極間におけるカ
チオンの吸蔵・放出の媒体となるものであり、通常は電
解質を非水溶媒に溶解したものが用いられる。この電解
質としては、LiClO4,LiCl,LiBr,LiBF4,LiPF6,CH3SO3Li,
CF3SO3Li,NaClO4,NaBF4,NaPF6,NaB（C6H5）4,あるいは
塩素酸、四フッ化ホウ素、塩素、臭素等の第四アンモニ
ウム塩、すなわちテトラメチルアンモニウム塩、テトラ
エチルアンモニウム塩、テトラブチルアンモニウム塩等
が使用される。なおこの場合、電解質のカチオンと正極
・負極間において吸蔵・放出されるカチオンとは同種で
あることが好ましい。On the other hand, the electrolyte layer serves as a medium for occluding and releasing cations between the positive electrode and the negative electrode, and is usually formed by dissolving an electrolyte in a non-aqueous solvent. Examples of the electrolyte include LiClO 4 , LiCl, LiBr, LiBF 4 , LiPF 6 , CH 3 SO 3 Li,
Quaternary ammonium salts such as CF 3 SO 3 Li, NaClO 4 , NaBF 4 , NaPF 6 , NaB (C 6 H 5 ) 4 or chloric acid, boron tetrafluoride, chlorine, bromine, etc., ie, tetramethylammonium salt, tetraethyl Ammonium salts, tetrabutylammonium salts and the like are used. In this case, it is preferable that the cation of the electrolyte and the cation occluded and released between the positive electrode and the negative electrode are of the same type.

また、上述のようなカチオンを溶解させるための電解
質溶液として使用される非水溶媒には、たとえば炭酸プ
ロピレン、炭酸エチレン、炭酸ビニレン等の環状炭酸エ
ステル系溶媒、γ−ブチロラクトン、２−メチル−γ−
ブチロラクトン等の環状エステル系溶媒、テトラヒドロ
フラン、ジメトキシエタン、ジエチルエーテル等のエー
テル系溶媒、スルホラン、メチルスルホラン等の含硫黄
系溶媒、アセトニトリル、プロピオニトリル、ベンゾニ
トリル等のニトリル系溶媒等が使用できる。あるいは、
上記電解質層は、いわゆる固体電解質により構成されて
も良い。Examples of the non-aqueous solvent used as an electrolyte solution for dissolving the cations described above include cyclic carbonate solvents such as propylene carbonate, ethylene carbonate, and vinylene carbonate, γ-butyrolactone, and 2-methyl-γ. −
Cyclic ester solvents such as butyrolactone, ether solvents such as tetrahydrofuran, dimethoxyethane, and diethyl ether; sulfur-containing solvents such as sulfolane and methylsulfolane; and nitrile solvents such as acetonitrile, propionitrile, and benzonitrile can be used. Or,
The electrolyte layer may be composed of a so-called solid electrolyte.

本発明者らは、以下に挙げる手法により実際に二次電
池を作成した。The present inventors have actually produced a secondary battery by the following method.

作成した二次電池は、PPy−PSSを正極材料とし、ポリ
チオフェン（以下、PTと称する。）を負極材料とし、吸
蔵・放出されるカチオンとしてリチウム・イオンを使用
するものである。The prepared secondary battery uses PPy-PSS as a positive electrode material, polythiophene (hereinafter, referred to as PT) as a negative electrode material, and uses lithium ions as cations to be absorbed and released.

まず、正極材料となるPPy−PSSの製法について説明す
る。First, a method for producing PPy-PSS as a positive electrode material will be described.

すなわち、1gのPSS（平均分子量７×104）を50mlの水
に溶解し、この水溶液にピロールを0.2Mの濃度となるよ
うに添加した。この溶液に銀−塩化銀電極を挿入し、プ
ラチナ基板を使用して1Vの定電界で電解重合を行い、薄
いフィルム状に成形した。That is, 1 g of PSS (average molecular weight 7 × 10 4 ) was dissolved in 50 ml of water, and pyrrole was added to this aqueous solution to a concentration of 0.2M. A silver-silver chloride electrode was inserted into this solution, and electropolymerization was performed at a constant electric field of 1 V using a platinum substrate to form a thin film.

上述のようにして得られたPPy−PSSに金属リチウム、
リチウム−ナフタレン錯体、リチウム−ベンゾフェノン
錯体等を反応させるか、あるいはリチウム・イオンを含
有する電解液中において電気化学的還元反応を行うこと
により、該PPy−PSSにリチウム・イオンをドープさせ
た。ドープされたリチウム・イオンは、PPy−PSS中のス
ルホン酸基の負電荷により安定に吸蔵された。Metallic lithium is added to the PPy-PSS obtained as described above,
The PPy-PSS was doped with lithium ions by reacting a lithium-naphthalene complex, a lithium-benzophenone complex, or the like, or by performing an electrochemical reduction reaction in an electrolyte solution containing lithium ions. The doped lithium ion was stably occluded by the negative charge of the sulfonic acid group in PPy-PSS.

なお本実施例では、上述のように正極側に予めリチウ
ム・イオンをドープしたが、これは負極側であっても構
わない。In this embodiment, as described above, the positive electrode side is doped with lithium ions in advance, but this may be on the negative electrode side.

次に、リチウム電極を参照電極として、正極である上
記PPy−PSSのサイクリックボルタンメトリーを行うと、
充電時（脱ドープ時）のピーク電位は3.1V、放電時（ド
ープ時）のピーク電位は2.8Vであることがわかった。Next, using the lithium electrode as a reference electrode and performing cyclic voltammetry of the positive electrode, PPy-PSS,
It was found that the peak potential during charging (dope) was 3.1 V and the peak potential during discharge (dope) was 2.8 V.

同様にリチウム電極を参照電極として、薄いフィルム
状に成形された負極であるPTのサイクリックボルタンメ
トリーを行うと、充電時（ドープ時）のピーク電位は0.
8V、放電時（脱ドープ時）のピーク電位は1.0Vであるこ
とがわかった。Similarly, using a lithium electrode as a reference electrode and performing cyclic voltammetry of the PT, which is a negative electrode formed into a thin film, the peak potential at the time of charging (dope) is 0.
It was found that the peak potential was 8 V and the peak potential at the time of discharge (dope) was 1.0 V.

次に、LiClO4を1M濃度に溶解した炭酸プロピレンに、
上述の正極と負極とを浸漬し、両極間を適当な接続手段
により接続した。Next, in propylene carbonate in which LiClO 4 was dissolved at a concentration of 1 M,
The above-described positive electrode and negative electrode were immersed, and the two electrodes were connected by an appropriate connecting means.

このようにして構成される二次電池の素反応および全
反応は、次式のように表される。The elementary reaction and the total reaction of the secondary battery configured as described above are represented by the following equations.

充電時 正 極:PPy−PSS-−Li+→PPy−PSS＋Li+＋e- 負 極:PT＋Li+＋e-→PT−Li 全反応:PPY−PSS-−Li+＋PT→PPy−PSS＋PT−Li 放電時 正 極:PPy−PSS＋Li+＋e-→PPy−PSS-−Li+ 負 極:PT−Li→PT＋Li+＋e- 全反応:PPy−PSS＋PT−Li→PPy−PSS-−Li+＋PT 上述の二次電池の開回路電圧は、およそ1.8Vであっ
た。During charging Positive: PPy−PSS − −Li + → PPy−PSS + Li + + e − Negative: PT + Li + + e − → PT−Li Total reaction: PPY−PSS − −Li + + PT → PPy−PSS + PT−Li Positive during discharging electrode: PPy-PSS + Li + + e - → PPy-PSS - -Li + anode: PT-Li → PT + Li + + e - total reaction: PPy-PSS + PT-Li → PPy-PSS - -Li + + PT of the above secondary battery The open circuit voltage was approximately 1.8V.

〔発明の効果〕〔The invention's effect〕

以上の説明からも明らかなように、上述のような構成
を有する二次電池においては、同種のカチオンが両極に
おいて可逆的にドープあるいは脱ドープされるため、充
放電容量が電解質溶液中に存在するカチオンの濃度に制
限されないという長所がある。しかも、両極は高分子材
料で製造されているために、量産性に優れ、電解質溶液
中における腐食や劣化等の問題がなく、薄型化も容易で
ある。As is clear from the above description, in the secondary battery having the above-described configuration, since the same kind of cation is reversibly doped or undoped in both electrodes, the charge / discharge capacity exists in the electrolyte solution. It has the advantage of not being restricted by the concentration of cations. In addition, since both electrodes are made of a polymer material, they are excellent in mass productivity, have no problems such as corrosion and deterioration in an electrolyte solution, and can be easily made thin.

したがって、大容量で極めて安定した特性を有する二
次電池を経済的に提供することが可能となる。Therefore, it is possible to economically provide a secondary battery having a large capacity and extremely stable characteristics.

フロントページの続き (56)参考文献 特開 昭63−178442（ＪＰ，Ａ) 特開 昭63−133451（ＪＰ，Ａ) 特開 昭63−55861（ＪＰ，Ａ) 特開 昭63−135453（ＪＰ，Ａ)Continuation of the front page (56) References JP-A-63-178442 (JP, A) JP-A-63-133451 (JP, A) JP-A-63-55861 (JP, A) JP-A-63-135453 (JP) , A)

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】ポリスチレンスルホネートが共重合された
導電性高分子材料からなり、カチオンが放電時にドープ
され、充電時に脱ドープされる正極と、 カチオンが充電時にドープされ、放電時に脱ドープされ
る高分子材料からなる負極と、電解質層とを有してなる
二次電池。1. A positive electrode comprising a conductive polymer material in which polystyrene sulfonate is copolymerized, wherein a cation is doped during discharge and undoped during charging, and a positive electrode which is doped with cation during charging and undoped during discharging. A secondary battery having a negative electrode made of a molecular material and an electrolyte layer.
JP62160532A 1987-06-27 1987-06-27 Rechargeable battery Expired - Fee Related JP2600175B2 (en)

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JP62160532A JP2600175B2 (en) 1987-06-27 1987-06-27 Rechargeable battery

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JPS646383A JPS646383A (en) 1989-01-10
JP2600175B2 true JP2600175B2 (en) 1997-04-16

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Application Number Title Priority Date Filing Date
JP62160532A Expired - Fee Related JP2600175B2 (en) 1987-06-27 1987-06-27 Rechargeable battery

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Country Link
JP (1) JP2600175B2 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61199780A (en) * 1985-03-01 1986-09-04 Junji Morinaga Separation of hydrated alcohol containing garlic extract from shochu containing garlic
JPS61279666A (en) * 1985-06-04 1986-12-10 Citizen Watch Co Ltd Formation of metallic film for ornaments
JPS628912A (en) * 1985-07-05 1987-01-16 Shinko Electric Co Ltd Parts sorting and feeding device

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