JPS6220253A - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPS6220253A JPS6220253A JP60158369A JP15836985A JPS6220253A JP S6220253 A JPS6220253 A JP S6220253A JP 60158369 A JP60158369 A JP 60158369A JP 15836985 A JP15836985 A JP 15836985A JP S6220253 A JPS6220253 A JP S6220253A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- secondary battery
- polydiphenylamine
- positive electrode
- electrode
- 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
- H01M4/36—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
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高いエネルギー密度と高い充放電効率を有す
る改良された二次電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improved secondary battery having high energy density and high charge/discharge efficiency.
（従来の技術とその問題点〕
近年、ポリアセチレン、ポリフェニレン等の高分子材料
を電極活物質として用いることにより、高いエネルギー
密度を有する二次電池を製造し得ることが、例えば特開
昭５６−１３６４６９号公報により知られている。しか
し、このような二次電池は、たとえばリチウムを負極と
し、上述の材料を正極として有機電解液を用いて構成し
た場合充放電効率は最高でも９０％程度しか得ることが
できない。また、ポリアセチレン等の材料は空気中で不
安定であり、劣化もし易い等の問題があった。(Prior art and its problems) In recent years, it has been discovered that secondary batteries with high energy density can be manufactured by using polymeric materials such as polyacetylene and polyphenylene as electrode active materials, for example in Japanese Patent Application Laid-Open No. 56-136469. However, when such a secondary battery is constructed using, for example, lithium as a negative electrode and an organic electrolyte as the above-mentioned material as a positive electrode, the charging/discharging efficiency can only be about 90% at best. In addition, materials such as polyacetylene are unstable in the air and easily deteriorate.
本発明者等は、かかる点に鑑みて鋭意研究を行った結果
、高いエネルギー密度を有し、かつ、充放電効率が９５
％以上であり、しかも劣化し難い特性を有する二次電池
を開発した。The present inventors conducted intensive research in view of the above points, and as a result, the present inventors found that the present invention has a high energy density and a charge/discharge efficiency of 95%.
We have developed a secondary battery that has properties that are more than % and are resistant to deterioration.
（問題点を解決するための手段）
本発明は、電極活物質がジフェニルアミンの重合体であ
ることを特徴とする二次電池である。(Means for Solving the Problems) The present invention is a secondary battery characterized in that the electrode active material is a diphenylamine polymer.
本発明においてジフェニルアミンを重合して得た材料（
以下ポリジフェニルアミンと記す）どしては、ジフェニ
ルアミンを適当な方法で重合したものであり、結合の位
置は問わない。重合方法として好ましいのは、いわゆる
電解重合法である。In the present invention, the material obtained by polymerizing diphenylamine (
Polydiphenylamine (hereinafter referred to as polydiphenylamine) is obtained by polymerizing diphenylamine by an appropriate method, and the bonding position does not matter. A preferred polymerization method is the so-called electrolytic polymerization method.
本発明における二次電池の構成は、非水系の場合には正
極にポリジフェニルアミンを用い、負極にリチウムある
いはその合金、グラファイト、多孔質カーボン、二硫化
チタン、二硫化モリブデンのうちの何れか一つを用いる
。有機電解液としては、過塩素酸リチウム、ホウフッ化
リチウム、六フッ化リン酸リチウム等をプロピレンカー
ボネート。In the case of a non-aqueous secondary battery, the configuration of the secondary battery in the present invention is to use polydiphenylamine for the positive electrode, and use one of lithium or its alloy, graphite, porous carbon, titanium disulfide, and molybdenum disulfide for the negative electrode. Use. Organic electrolytes include lithium perchlorate, lithium fluoroborate, lithium hexafluorophosphate, etc. with propylene carbonate.
ジメトキシエタン、テトラヒドロフラン等に溶解せしめ
たものを用いるのが好ましい。水系の場合には正極にポ
リジフェニルアミンを用い、負極に亜鉛、鉛、酸化鉛の
うち何れか一つを、電解液としては塩化亜鉛と塩化アン
モニウムの水溶液または硫酸を用いるのが好ましい。It is preferable to use one dissolved in dimethoxyethane, tetrahydrofuran, or the like. In the case of an aqueous system, it is preferable to use polydiphenylamine for the positive electrode, one of zinc, lead, or lead oxide for the negative electrode, and use an aqueous solution of zinc chloride and ammonium chloride or sulfuric acid as the electrolyte.
本発明に係る二次電池によれば、ポリジフェニルアミン
を電極活物質としているので、高いエネルギー密度を有
し、かつ、充放電効率が９５％以上であり、しかも劣化
し難い特性を有するものである。According to the secondary battery according to the present invention, since polydiphenylamine is used as an electrode active material, it has a high energy density, a charge/discharge efficiency of 95% or more, and has characteristics that do not easily deteriorate. .
以下、本発明の実施例について説明する。Examples of the present invention will be described below.
１Ｍの濃度の過塩素酸水溶液中にＯ，ＩＭの濃度でジフ
ェニルアミンを溶解し、電析液とした。Diphenylamine was dissolved in a perchloric acid aqueous solution with a concentration of 1M at a concentration of O and IM to prepare an electrodeposition solution.
これに１ ｃｔａ Ｘ １ ｃｐｓの大きさの白金板を
アノードとして設置し、１ｍＡの定電流で電解を行った
。A platinum plate with a size of 1 cta x 1 cps was installed as an anode on this, and electrolysis was performed with a constant current of 1 mA.
３０分接電解を停止し、該白金板をとり出した。The electrolysis was stopped for 30 minutes, and the platinum plate was taken out.
白金板表面はフィルム状のポリジフェニルアミンで被覆
されていた。これを水洗いした後、空気中で乾燥させた
く以下この白金板をポリジフェニルアミン電極と称する
）。このポリジフェニルアミン電極を一方の極とし、も
う一方の電極としてニッケルのエキスバンドメタルに埋
め込んだリチウム板を用い、両極間に短絡防止用のポリ
プロピレン不織布からなるセパレータを介してこれらを
、過塩素酸リチウムを１Ｍの濃度で含むプロピレンカー
ボネート溶液で満したがラスセル内に設置した。以上の
ようにしてリチウム／ポリジフェニルアミン二次電池を
製作した。The surface of the platinum plate was coated with a film of polydiphenylamine. After washing with water, this platinum plate was dried in air (hereinafter this platinum plate will be referred to as a polydiphenylamine electrode). This polydiphenylamine electrode was used as one electrode, and a lithium plate embedded in expanded nickel metal was used as the other electrode. The tube was filled with a propylene carbonate solution containing 1M of water and placed in a glass cell. A lithium/polydiphenylamine secondary battery was manufactured as described above.
この二次電池の未充電状態での回路電圧は約３．５Ｖで
、ポリジフェニルアミン電極が正極であった。The circuit voltage of this secondary battery in an uncharged state was about 3.5 V, and the polydiphenylamine electrode was the positive electrode.
次いで、この二次電池を２．５Ｖ〜４．３ｖの電圧範囲
で、１ｍＡ／ｃｍの定電流密度で充放電させた。この範
囲で約０．１２Ａｈ／ｇの容量が得られた。放電時の平
均電圧は、約３．５ｖでありこれによりエネルギー密度
は約２５０Ｗｈ／／ｒｙとなった。また、１００回の充
放電サイクルにおいて充放電効率は、常に９５％以上で
あった。なお図はこの二次電池の充放電特性を示してい
る。Next, this secondary battery was charged and discharged in a voltage range of 2.5 V to 4.3 V at a constant current density of 1 mA/cm. A capacity of about 0.12 Ah/g was obtained in this range. The average voltage during discharge was about 3.5 V, resulting in an energy density of about 250 Wh/ry. Further, the charge/discharge efficiency was always 95% or more in 100 charge/discharge cycles. The figure shows the charging and discharging characteristics of this secondary battery.
次に、本発明の比較例について説明する。Next, a comparative example of the present invention will be explained.
白州法にて合成した１ ｔ：ｍ Ｘ １ ｃｍの大きさ
で厚さ０．１ｍのシス型ポリアセチレンフィルムと、１
ｃｌｌ×１ｃＩＩｌの大きさの白金板集電体とで電極を
構成し、その他の点は実施例と同様にしてリチウム／ポ
リアセチレン二次電池を製作した。A cis-type polyacetylene film with a size of 1 t:m x 1 cm and a thickness of 0.1 m synthesized by the Hakushu method, and 1
A lithium/polyacetylene secondary battery was manufactured in the same manner as in the example except that the electrode was constituted by a platinum plate current collector having a size of cll x 1 cll.
未充電時の回路電圧は、約２．５■であり、ポリアセチ
レン極側が正極であった。次いで、これを２．５Ｖ〜３
．９Ｖの電圧範囲で、１ＴｒＬＡ／ｃｄの定電流密度で
充放電させたところ、約０．１３Ａｈ／９の容量が得ら
れ、エネルギー密度は、約２８０Ｗｈ／Ｋｇであった。The circuit voltage when uncharged was about 2.5 µ, and the polyacetylene electrode side was the positive electrode. Next, apply this voltage to 2.5V to 3
．． When the battery was charged and discharged at a constant current density of 1 TrLA/cd in a voltage range of 9 V, a capacity of about 0.13 Ah/9 was obtained, and the energy density was about 280 Wh/Kg.
初期の充放電効率は、約７０％であり、２０サイクル後
はポリアセチレン電極の劣化が著しく、充放電効率は、
４０％以下に低下していた。The initial charging and discharging efficiency was about 70%, and after 20 cycles, the polyacetylene electrode deteriorated significantly, and the charging and discharging efficiency decreased.
It had dropped to below 40%.
図は、電池電圧と時間との関係を示す特性図である。 出願人代理人 弁理士 鈴江武彦 ６一 The figure is a characteristic diagram showing the relationship between battery voltage and time. Applicant's agent: Patent attorney Takehiko Suzue 61
Claims (1)
徴とする二次電池。A secondary battery characterized in that the electrode active material is a diphenylamine polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60158369A JPS6220253A (en) | 1985-07-19 | 1985-07-19 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60158369A JPS6220253A (en) | 1985-07-19 | 1985-07-19 | Secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6220253A true JPS6220253A (en) | 1987-01-28 |
Family
ID=15670186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60158369A Pending JPS6220253A (en) | 1985-07-19 | 1985-07-19 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6220253A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61206170A (en) * | 1985-03-09 | 1986-09-12 | Maruzen Sekiyu Kagaku Kk | Secondary battery and its electrode |
-
1985
- 1985-07-19 JP JP60158369A patent/JPS6220253A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61206170A (en) * | 1985-03-09 | 1986-09-12 | Maruzen Sekiyu Kagaku Kk | Secondary battery and its electrode |
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