JPS6229065A - Secondary cell - Google Patents
Secondary cellInfo
- Publication number
- JPS6229065A JPS6229065A JP60167615A JP16761585A JPS6229065A JP S6229065 A JPS6229065 A JP S6229065A JP 60167615 A JP60167615 A JP 60167615A JP 16761585 A JP16761585 A JP 16761585A JP S6229065 A JPS6229065 A JP S6229065A
- Authority
- JP
- Japan
- Prior art keywords
- polyaniline
- battery
- positive electrode
- active material
- electrode active
- 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
- 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
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】
〔発明の利用分野〕
本発明は、二次電池、特に正極、負極及び電解質を含み
、正極の電極活物質に導電性ポリマーを用いてなる二次
電池に関するものである。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a secondary battery, and particularly to a secondary battery that includes a positive electrode, a negative electrode, and an electrolyte, and uses a conductive polymer as the electrode active material of the positive electrode. .
導電性ポリマーを電極活物質に使用する電池は高エネル
ギー密度あるいは高出力密度がとれる電池でかつ充電が
可能なものとして注目されている。Batteries using conductive polymers as electrode active materials are attracting attention as batteries that have high energy density or high output density and are rechargeable.
導電性ポリマーの代表的なものは、例えばポリアセチレ
ンであり、電気化学的にＣΩ０４−、 ＰＦ６−。A typical conductive polymer is, for example, polyacetylene, which has an electrochemical resistance of CΩ04-, PF6-.
ＢＦ、−やＡｓＦ、−等の陰イオンが、またＬｉ”や（
Ｃ，Ｈ，） ４Ｎ”などの陽イオンがドーピングされ、
ｐ型及びｎ型導電性ポリアセチレンとなり、この反応を
利用して電池をつくることが報告されている（例えば特
開昭５６−１ｓ６４６９号公報）。その他ポリピロール
（第２５回電池討論会、講演要旨集、（１９８４） ｐ
２５６） 、ポリチオフェン（特開昭５８−２１２０
６７号公報）やポリフェニルキノリン（特表昭５９−５
０００３３号公報）を電極活物質に使う充電可能な二次
電池が提案されている。これらの電池ではいずれも電解
液は非水溶媒系を使用している。Anions such as BF, - and AsF, -, as well as Li'' and (
Doped with cations such as C, H, ) 4N”,
It has been reported that it becomes p-type and n-type conductive polyacetylene, and that batteries can be made using this reaction (for example, JP-A-56-1S6469). Other polypyrroles (25th Battery Symposium, collection of lecture abstracts, (1984) p.
256), polythiophene (JP-A-58-2120
Publication No. 67) and polyphenylquinoline (Special Publication No. 59-5
A rechargeable secondary battery has been proposed that uses a material (No. 00033) as an electrode active material. All of these batteries use non-aqueous solvent electrolytes.
いずれの電池においても未だ二次電池としてのサイクル
寿命は短かく、また自己放電が大きく実用化の域には至
っていない。All of these batteries still have a short cycle life as secondary batteries, and self-discharge is large so that they have not yet reached the level of practical use.
一方、ポリアニリンは前述のポリマーと同様の電気化学
的挙動を示し、電池への応用が可能である。ポリアニリ
ンはアニリンの酸性水溶液で電解酸化反応により合成す
ることができる（例えば、Ｊ、Ｅｌｅｃｔｒｏａｎａｌ
、Ｃｈｅｉ、＋ ＶｏＱ 、ｌ ６１ （１９８４
）ｐ ３９９）。電極上に生成した重合膜は支持塩を含
む酸性水溶液中で可逆的に酸化還元反応を示し、電気化
学的に活性である。乾燥状態でのポリアニリンの電気伝
導度は１０−１５から１０−１８／ｃｍまで変化する（
日本化学会誌、Ｎα１１ （１９８４）ｐ １８０１）
。On the other hand, polyaniline exhibits electrochemical behavior similar to the aforementioned polymers and can be applied to batteries. Polyaniline can be synthesized by electrolytic oxidation reaction in an acidic aqueous solution of aniline (for example, J. Electroanal.
, Chei, + VoQ, l 61 (1984
) p 399). The polymer film formed on the electrode exhibits a reversible redox reaction in an acidic aqueous solution containing a supporting salt, and is electrochemically active. The electrical conductivity of polyaniline in dry state varies from 10-15 to 10-18/cm (
Journal of the Chemical Society of Japan, Nα11 (1984) p 1801)
.
正極に電解酸化反応により合成したポリアニリンを、負
極に亜鉛を、電解液に１ＭＺｎＳＯ４水溶液、または同
水溶液に硫酸を加えてｐＨを低下させたものを用いた電
池は充放電が可能で、充電後の開路電圧は１．２〜１．
６ｖが得られている（電気化学協会第５０回大会、講演
要旨集、 （１９８４）ｐ２２Ｂ）。この電池は電解
液に水溶液を使用しており、亜鉛を負極としているので
、電池電圧が低く、かつ充電時の亜鉛の樹枝状析出があ
り、電極の脱落や電極の短絡が避けられず、二次電池と
しての機能をはたすことが非常に薙かしい。Batteries that use polyaniline synthesized by electrolytic oxidation reaction as the positive electrode, zinc as the negative electrode, and a 1M ZnSO4 aqueous solution as the electrolyte, or a solution whose pH has been lowered by adding sulfuric acid to the same aqueous solution, can be charged and discharged, and the The open circuit voltage is 1.2 to 1.
6v was obtained (Electrochemical Society of Japan 50th Conference, Abstracts of Lectures, (1984) p22B). This battery uses an aqueous solution as the electrolyte and uses zinc as the negative electrode, so the battery voltage is low and dendritic precipitation of zinc occurs during charging, making it inevitable that the electrodes will fall off or short-circuit. It is very difficult to function as a secondary battery.
またアニリンを含む２Ｍ ＨＣＱＯ４水溶液で白金上に
定電位電解してポリアニリンを合成し、これを正極に、
負極にリチウム金属を、電解液に１ｍｏΩ／ＱのＬ ｉ
ＣＱ Ｏ４を溶解した炭酸プロピレン溶液を用いた非水
系のポリアニリン電池は充放電可能であり、充電後の開
路電圧は３．６〜４．ＯＶが得られている（第２３回電
池討論会、講演要旨集、（１９８３） ｐ １９７）。In addition, polyaniline was synthesized by constant potential electrolysis on platinum using a 2M HCQO4 aqueous solution containing aniline, and this was used as a positive electrode.
Lithium metal is used as the negative electrode, and Li of 1 moΩ/Q is used as the electrolyte.
A nonaqueous polyaniline battery using a propylene carbonate solution in which CQ O4 is dissolved can be charged and discharged, and the open circuit voltage after charging is 3.6 to 4. OV has been obtained (23rd Battery Symposium, Collection of Lecture Abstracts, (1983) p. 197).
この電池の電圧は高く、エネルギー密度も従来の電池よ
り高いが、サイクル寿命も短かく、かつ負極にリチウム
金属を使用しているため、充電時のリチウム金属の樹枝
状析出があり、実用的二次電池となる可能性が少ない。Although this battery has a high voltage and a higher energy density than conventional batteries, its cycle life is short, and since lithium metal is used in the negative electrode, dendritic precipitation of lithium metal occurs during charging, making it impractical. There is little possibility that it will become the next battery.
このように、導電性ポリマーを電極活物質に使用する電
池は、高エネルギー密度あるいは高出力密度がとれる二
次電池として注目されているにも拘ねらず、未だ実用的
な二次電池は得られていない。As described above, although batteries that use conductive polymers as electrode active materials are attracting attention as secondary batteries that can achieve high energy density or high output density, practical secondary batteries have not yet been obtained. Not yet.
本発明は、前述の問題点を除去し、導電性ポリマーを正
極の電極活物質として用いる実用的な二次電池を提供可
能とすることを目的とするものである。An object of the present invention is to eliminate the above-mentioned problems and to provide a practical secondary battery that uses a conductive polymer as a positive electrode active material.
本発明は、正極、負極及び電解液を含み、前記正極の電
極活物質に導電性ポリマーを用いてなる二次電池におい
て、前記導電性ポリマーが、そのＸ線光電子スペクトル
から測定される窒素原子の１ｓの結合エネルギー４００
ｅＶの主ピークと４０２ｅＶのピークとの面積強度比が
７５〜７６：２３〜２５であるポリアニリンであること
を特徴とするものである。The present invention provides a secondary battery including a positive electrode, a negative electrode, and an electrolytic solution, in which a conductive polymer is used as an electrode active material of the positive electrode, in which the conductive polymer has nitrogen atoms measured from its X-ray photoelectron spectrum. 1s binding energy 400
The polyaniline is characterized in that the area intensity ratio between the eV main peak and the 402 eV peak is 75-76:23-25.
本発明はポリアニリンの構造の検討結果に基づいてなさ
れたものである。The present invention was made based on the results of studies on the structure of polyaniline.
アニリンの重合体であるポリアニリンの構造は元素分析
等から決められているが、確かなものでない。本発明者
らは、導電性を示すポリアニリンの光電子スペクトルを
測定し、窒素原子の１ｓの結合エネルギーに相当する二
つのピークを観測した。その結合エネルギーは４００．
２ｅＶ と４０２．２ｅＶであり、それらのピークの面
積比（％）は７５〜７６ ： ２３〜２５をとることが
分かった。またこのポリアニリンをアルカリの水溶液で
処理すると窒素原子の１８の結合エネルギーは低エネル
ギー側にシフトし、かつ結合エネルギーにもとづくピー
クも一つになることがわかった。The structure of polyaniline, a polymer of aniline, has been determined through elemental analysis, but it is not certain. The present inventors measured the photoelectron spectrum of polyaniline exhibiting electrical conductivity, and observed two peaks corresponding to the 1s bond energy of nitrogen atoms. Its binding energy is 400.
2 eV and 402.2 eV, and the area ratio (%) of those peaks was found to be 75-76:23-25. It was also found that when this polyaniline was treated with an aqueous alkali solution, the bond energy of nitrogen atom 18 shifted to the lower energy side, and the peaks based on the bond energies became one.
これらのポリアニリンを電極に成形し、これを正極に、
負極にＬｉ−ＡＱ金合金使用する非水系の −電池では
、前者のポリアニリンを使用した場合、正常に電池とし
ての機能を発揮したが、後者のそれは機能しなかった。These polyanilines are molded into electrodes, and this is used as a positive electrode.
A non-aqueous battery using a Li-AQ gold alloy for the negative electrode normally functioned as a battery when polyaniline was used in the former case, but it did not function in the latter case.
電池性能を示すポリアニリンの窒素の結合状態は第３級
アミン及び第４級アンモニウムであり、いずれもポリマ
ーの主鎖に存在するものと思われる。それゆえ、電池性
能を得るためには、ポリアニリンの窒素は第３級アミン
と第４級アンモニウムの形である必要のあることがわか
ったにのポリアニリンの電気伝導度は乾燥状態において
５８／ａｍを示し、後に述べる電解液でアンド−ピング
すると０．１ｓ７０ｍに減少するが、これは電極活物質
に対して低すぎる値ではない。ポリアニリンは電気化学
的に合成したものでも、あるいは酸化剤を使用して化学
的に合成したものでもはぼ上述の結果が得られる。The bonding states of nitrogen in polyaniline that indicate battery performance are tertiary amine and quaternary ammonium, both of which are thought to exist in the main chain of the polymer. Therefore, it was found that the nitrogen in polyaniline needs to be in the form of tertiary amine and quaternary ammonium to obtain battery performance.The electrical conductivity of polyaniline is 58/am in the dry state. When the electrolytic solution shown in FIG. The above-mentioned results can be obtained regardless of whether polyaniline is synthesized electrochemically or chemically using an oxidizing agent.
電解液は従来リチウム電池で用いられている電解液、す
なわちＬｉＢＦ４．ＬｉＰＦ、、ＬｉＣ＋２０゜ＬｉＡ
ｓＦＩ、などのリチウム塩を炭酸プロピレンとジメトキ
シエタンの混合溶媒に溶解したものが優れた電池性能を
示すが、非プロトン性溶媒であれば作業限定されること
はない。The electrolytic solution is the electrolytic solution conventionally used in lithium batteries, namely LiBF4. LiPF, LiC+20°LiA
A solution of a lithium salt such as sFI in a mixed solvent of propylene carbonate and dimethoxyethane shows excellent battery performance, but there are no limitations on the work as long as it is an aprotic solvent.
一方、負極は電池電圧、エネルギー密度の点からリチウ
ムなどのアルカリ金属やアルカリ土類金属を使用するの
が好ましく、充電時にリチウム金属の樹脂状析出を防ぐ
ため、これら金属とＡＱの合金が使われる。On the other hand, from the viewpoint of battery voltage and energy density, it is preferable to use an alkali metal or alkaline earth metal such as lithium for the negative electrode, and an alloy of these metals and AQ is used to prevent resinous precipitation of lithium metal during charging. .
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）
０．２Ｍのアニリンを含む０．５ＭＨＢＦ４水溶液中で
作用極及び対極に白金を使用し、作用極の電位を銀−塩
化銀参照電極に対し０．８ Ｖに保ち、電解酸化を行い
、作用極上にポリアニリンを合成した。ポリアニリンを
電極からかき取り、水洗を行い、８０℃で真空乾燥を行
い、微粉化した。このポリアニリについてＸ線光電子ス
ペクトロメータ ターで窒素原子の１５の結合エネル
ギーを測定し、波形解析を行った結果、４００．２ｅＶ
と４０２．２ｅＶに基づくピークを観測した。それらの
ピークの面積比（％）は７５ ： ２５であった。(Example 1) Platinum was used as the working electrode and the counter electrode in a 0.5M HBF4 aqueous solution containing 0.2M aniline, and the potential of the working electrode was kept at 0.8 V with respect to the silver-silver chloride reference electrode, and electrolytic oxidation was performed. Polyaniline was synthesized on the working electrode. The polyaniline was scraped off from the electrode, washed with water, vacuum dried at 80° C., and pulverized. The 15 bond energies of nitrogen atoms were measured for this polyaniline using an X-ray photoelectron spectrometer, and as a result of waveform analysis, it was found to be 400.2 eV.
A peak based on 402.2 eV was observed. The area ratio (%) of those peaks was 75:25.
上述のポリアニリンに炭素（アセチレンブラック）を１
０重量パーセント添加して混合し、１６ｍｇを３００
ｋｇ／ｃｍ２の圧力で、直径９ｍｍのペレットに成形し
たものを正極に、３ＭのＬ ｉ Ｂ Ｆ４ を溶解した
炭酸プロピレンとジメトキシエタン（１：１の容量比）
ラミ薄液に、５０Ｌｉ−５０ＡＱ（Ｍ子パーセント）の
合金を負極にし、電極間のセパレータにポリプロピレン
を用いて電池を構成し、この電池のポリアニリンに対す
るＢＦ４−のドーピング率を３０モルパーセント（対ア
ニリンユニット、分子量＝９１）とし、電流密度１ｍＡ
／ｃｍ”で充電し、同じ電流密度で電池電圧が１ｖにな
るまで放電した。このときの電圧の変化を示したのが第
１図で、横軸には充電率Ｃ％）及び放電率（％）が、縦
軸には電池電圧（Ｖ）がとっである。本電池の開路電圧
は３．３５Ｖであった。充電時の電気量と放電時の電気
量の割合であるクーロン効率（％）は９９％以上が得ら
れた。上記の充放電の条件でサイクル試験を行った結果
、７５０サイクルでもクーロン効率は９９％以上であっ
た。Add 1 carbon (acetylene black) to the above polyaniline
Add 0 weight percent and mix, add 16 mg to 300
Propylene carbonate and dimethoxyethane (1:1 volume ratio) in which 3M Li B F4 was dissolved were formed into pellets with a diameter of 9 mm at a pressure of kg/cm2 and used as the positive electrode.
A battery is constructed using a 50Li-50AQ (M%) alloy as a negative electrode and polypropylene as a separator between the electrodes, and the doping rate of BF4- to polyaniline in this battery is 30 mol% (to aniline). Unit, molecular weight = 91), current density 1 mA
/cm" and discharged at the same current density until the battery voltage reached 1 V. Figure 1 shows the change in voltage at this time. The horizontal axis shows the charging rate (C%) and the discharging rate ( %), but the vertical axis shows the battery voltage (V).The open circuit voltage of this battery was 3.35 V.The Coulombic efficiency (%) is the ratio of the amount of electricity during charging to the amount of electricity during discharging. ) was obtained at 99% or more.As a result of a cycle test conducted under the above charge/discharge conditions, the Coulombic efficiency was 99% or more even after 750 cycles.
３７回め充電終了後、電池を開路状態に保ち２１日間放
置し、その後充電と同じ条件で放電し、その電気量から
自己放電率を求めた結果、０．６％／日であった。After the 37th charge, the battery was left open for 21 days, then discharged under the same conditions as charging, and the self-discharge rate was determined from the amount of electricity, which was 0.6%/day.
（実施例２）
０．２Ｍのアニリンを含む０．５ＭＨＢＦ４水溶液に室
温で過硫酸アンモニウム（（ＮＨ４）２８２０７）を０
．１Ｍになるように添加し、室温で攪拌しながら５時間
放置した。沈澱物を水洗し、真空乾燥して微粉末状にし
た。このポリアニリンについてＸ線光電子スペクトロメ
ーターで窒素原子の１ｓの結合エネルギーを測定し、波
形解析を行った結果、４００．２ａＶと４０２．２ ｅ
Ｖに基づくピークをｍ測した。それらのピークの面積
比（％）は７５：２５であった。(Example 2) Ammonium persulfate ((NH4)28207) was added to a 0.5M HBF4 aqueous solution containing 0.2M aniline at room temperature.
．． The mixture was added to a concentration of 1M and left at room temperature for 5 hours with stirring. The precipitate was washed with water and dried under vacuum to form a fine powder. The 1s bond energy of the nitrogen atom was measured for this polyaniline using an X-ray photoelectron spectrometer, and as a result of waveform analysis, it was found to be 400.2 aV and 402.2 e.
The peak based on V was measured. The area ratio (%) of those peaks was 75:25.
このポリアニリンに炭素（アセチレンブラック）を１０
重量パーセント添加して混合し、１６．９ｍｇを３００
ｋｇ／ｃｎ＋２の圧力で直径９ｍｍのペレットに成形
し、これを正極にして実施例１と同様の電池を構成した
。この電池を１ ｍ Ａ ／ ｃｍ” の電流密度で電
池電圧が１ｖになるまで放電し、２．８クーロンの電気
量を得た。Add 10 carbon (acetylene black) to this polyaniline.
Add weight percent and mix, add 16.9 mg to 300 mg
It was molded into a pellet with a diameter of 9 mm under a pressure of kg/cn+2, and this was used as a positive electrode to construct a battery similar to Example 1. This battery was discharged at a current density of 1 mA/cm'' until the battery voltage reached 1 V, yielding an amount of electricity of 2.8 coulombs.
この放電した電池をＢＦ４−のポリアニリンのドーピン
グ率を３０モルパーセント（対アニリンユニット、分子
量：９１）とし、電流密度１ｍＡ／ａｍ２で充電し、同
じ電流密度で電池電圧が１ｖになるまで放電するサイク
ル試験を行った。６３０サイクルでも本電池のクーロン
効率は９９％以上であった。５２回めの充電終了後、電
池を開路状態に保ち３０日間放置したときの自己放電率
は１．１％７日であった。This discharged battery is charged at a current density of 1 mA/am2 with a doping rate of BF4- polyaniline of 30 mole percent (relative to aniline units, molecular weight: 91), and then discharged at the same current density until the battery voltage reaches 1 V. The test was conducted. Even after 630 cycles, the Coulombic efficiency of this battery was 99% or more. After the 52nd charge, the battery was left open for 30 days, and the self-discharge rate was 1.1% for 7 days.
（実施例３）
０．２ Ｍのアニリンを含むＩＭＨａＳ０４水溶液に、
室温で過硫酸アンモニウム（（ＮＨ４）２Ｓ、○７）を
０．１Ｍになるように添加し、攪拌しながら５時間放置
した。沈澱物は実施例２と同様に処理し、微粉末を得た
。このポリアニリンについてＸ線光電子スペクトロメー
ターで窒素原子の１８の結合エネルギーの測定を行った
結果は４００．２ｅＶと４０２．２θＶであった。それ
らのピークの面積比（％）は７６ ： ２３であった。(Example 3) In an IMHaS04 aqueous solution containing 0.2 M aniline,
Ammonium persulfate ((NH4)2S, ○7) was added at room temperature to a concentration of 0.1M, and the mixture was left for 5 hours with stirring. The precipitate was treated in the same manner as in Example 2 to obtain a fine powder. The bond energies of 18 nitrogen atoms of this polyaniline were measured using an X-ray photoelectron spectrometer, and the results were 400.2 eV and 402.2θV. The area ratio (%) of those peaks was 76:23.
このポリアニリンを実施例２と同様に１４ｍｇをペレッ
トにし、同様の電池を構成した。この電池を１ｍＡ／ａ
ｍ２の電流密度で電池電圧が１ｖになるまで放電し、２
．４クーロンの電気量を得た。14 mg of this polyaniline was made into pellets in the same manner as in Example 2, and a similar battery was constructed. This battery is 1mA/a
Discharge at a current density of m2 until the battery voltage reaches 1v,
．． An amount of electricity of 4 coulombs was obtained.
この放電した電池をＢＦ、−のポリアニリンのドーピン
グ率３０モルパーセントとし、実施例２と同様の条件で
充放電サイクル試験を行った６９９％以上のクーロン効
率の得られるサイクル数は５２５回であった。３８回め
の充電終了後、電池を開路状態に保ち３１日間放置した
ときの自己放電率は０．８％／日であった。This discharged battery was subjected to a charge/discharge cycle test under the same conditions as in Example 2, with a doping rate of BF, - polyaniline of 30 mole percent.The number of cycles at which a coulombic efficiency of 699% or more was obtained was 525. . After the 38th charge, the self-discharge rate was 0.8%/day when the battery was left open for 31 days.
（比較例）
実施例１で得られたポリアニリン粉末を２ＭのＫＯＨ溶
液に浸漬し、攪拌して５時間アルカリ処理を行い、水洗
、８０℃で真空乾燥を行い微粉化した。このポリアニリ
ンについてｘｉ光電子スペクトロメーターで窒素原子の
ＩＳの結合エネルギーの測定を行った結果は３９９ｅＶ
で、波形解析をした結果、この結果エネルギーに基づく
ピークは一つであった。(Comparative Example) The polyaniline powder obtained in Example 1 was immersed in a 2M KOH solution, stirred and subjected to alkali treatment for 5 hours, washed with water, and vacuum dried at 80° C. to be pulverized. The IS binding energy of the nitrogen atom was measured using a xi photoelectron spectrometer for this polyaniline, and the result was 399 eV.
As a result of waveform analysis, there was only one peak based on energy.
このポリアニリンにアセチレンブラックを１０重量パー
セント添加して混合し、１２ｍｇを３００ｋｇ／ｃｍ２
の圧力で直径９ｍｍのペレットに成形し、実施例１と同
様の電池を構成した。この電池を１ｍＡ／ｃｍ２の電流
密度で放電したが、はとんど電気量はとれなかった。さ
らに本電池を１ ｍ Ａ ／ ａｍ”の電流密度で充電
したが、電池電圧は充電初期から急激に高くなり、第１
図に示すような充電パターンは得られなかった。10% by weight of acetylene black was added to this polyaniline and mixed, and 12mg was added to 300kg/cm2.
The pellets were molded into pellets with a diameter of 9 mm at a pressure of 1.5 mm to form a battery similar to that of Example 1. This battery was discharged at a current density of 1 mA/cm2, but hardly any electricity could be obtained. Furthermore, this battery was charged at a current density of 1 mA/am'', but the battery voltage rose rapidly from the beginning of charging, and
The charging pattern shown in the figure was not obtained.
以上の実施例及び比較例から明らかなように、ＸＩ！光
電子スペクトルから測定される窒素原子には１ｓの結合
エネルギーが４００．２ ｅＶと４０２．２ ｅＶ
の二つの結合状態があり、かつそれらに基づくピークの
面積比（％）が７５〜７６：２３〜２５にあるポリアニ
リンを電極活物質とする二次電池は、実用的な二次電池
として優れた性能を発揮することができる。As is clear from the above Examples and Comparative Examples, XI! The 1s binding energies of nitrogen atoms measured from the photoelectron spectrum are 400.2 eV and 402.2 eV.
A secondary battery using polyaniline as an electrode active material, which has two bonding states and has a peak area ratio (%) of 75-76:23-25, is excellent as a practical secondary battery. performance.
本発明は、導電性ポリマーを正極の電極活物質として用
いる実用的な二次電池を提供可能とするもので、産業上
の効果の大なるものである。The present invention makes it possible to provide a practical secondary battery using a conductive polymer as a positive electrode active material, and has great industrial effects.
第１図は、本発明の二次電池の一実施例の特性線図であ
る。FIG. 1 is a characteristic diagram of an embodiment of the secondary battery of the present invention.
Claims (1)
質に導電性ポリマーを用いてなる二次電池において、前
記導電性ポリマーが、そのＸ線光電子スペクトルから測
定される窒素原子の１ｓの結合エネルギー４００ｅＶの
主ピークと４０２ｅＶのピークとの面積強度比が７５〜
７６：２３〜２５であるポリアニリンであることを特徴
とする二次電池。1. In a secondary battery including a positive electrode, a negative electrode, and an electrolyte, and using a conductive polymer as the electrode active material of the positive electrode, the conductive polymer has a The area intensity ratio between the main peak with binding energy of 400 eV and the peak with binding energy of 402 eV is 75 ~
76: A secondary battery characterized by being made of polyaniline of 23 to 25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167615A JPS6229065A (en) | 1985-07-31 | 1985-07-31 | Secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60167615A JPS6229065A (en) | 1985-07-31 | 1985-07-31 | Secondary cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6229065A true JPS6229065A (en) | 1987-02-07 |
Family
ID=15853066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60167615A Pending JPS6229065A (en) | 1985-07-31 | 1985-07-31 | Secondary cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6229065A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282068A2 (en) * | 1987-03-13 | 1988-09-14 | Showa Denko Kabushiki Kaisha | Nonaqueous secondary battery |
-
1985
- 1985-07-31 JP JP60167615A patent/JPS6229065A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282068A2 (en) * | 1987-03-13 | 1988-09-14 | Showa Denko Kabushiki Kaisha | Nonaqueous secondary battery |
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