JPS5918579A - Electrochemical battery - Google Patents
Electrochemical batteryInfo
- Publication number
- JPS5918579A JPS5918579A JP57128231A JP12823182A JPS5918579A JP S5918579 A JPS5918579 A JP S5918579A JP 57128231 A JP57128231 A JP 57128231A JP 12823182 A JP12823182 A JP 12823182A JP S5918579 A JPS5918579 A JP S5918579A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- battery
- electrochemical battery
- reducing atmosphere
- voltage
- 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
Abstract
Description
【発明の詳細な説明】
本発明は電解質を溶解した溶液に電極を浸漬し、当該電
極へのドーピングおよび/またはアンド−ピングにより
起電力を生じる電池の電極の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a battery electrode in which an electromotive force is generated by doping and/or undoping the electrode by immersing the electrode in a solution containing an electrolyte.
近年、エネルギー問題が重視されるにしたがい、軽量、
尚エネルギー密度の電池が要望されており、その一つと
して、比重が小さく、大きな比表面積を有する炭素成型
品やポリアセチレンのよウナ有機物を電極として用い、
これを電N貴溶液に浸した後、外部から電圧を印加して
両極をそれぞれn型、p型にドープし、しかる後に放電
することにより発生する起電力を利用した電池が提唱さ
れている。In recent years, as energy issues have become more important, lightweight,
In addition, there is a demand for batteries with high energy density, and one such method is to use carbon molded products or organic materials such as polyacetylene as electrodes, which have a low specific gravity and a large specific surface area.
A battery has been proposed that utilizes the electromotive force generated by immersing this in an electro-N noble solution, applying an external voltage to dope both poles into n-type and p-type, and then discharging.
ドーピングおよび/またはアンド−ピングを受ける電極
としては、種々の物質が考えられるが、炭素成型品は人
手も容易であり、化学的に安定で、種々の形状を取り得
ること、電気伝導性が大きいことなどの利点が太きい。Various materials can be used as electrodes to be doped and/or undoped, but carbon molded products are easy to handle, are chemically stable, can take various shapes, and have high electrical conductivity. There are many advantages such as:
さらに特願昭56−134.690号に示されるように
比表面積が100〜2500m2zlのように大きな比
表面積を有する活性炭素繊維成型品は大量のドーピング
が可能となり高エネルヤーの出力が可能である。Furthermore, as shown in Japanese Patent Application No. 56-134.690, activated carbon fiber molded products having a large specific surface area, such as 100 to 2,500 m2zl, can be doped in large quantities and can output high energy.
しかし、活性炭素成型品を電極とするドープおよび/ま
たはアンドープ型電池は自己放電が大きく、経時的に電
圧が低下するという欠点がある。However, doped and/or undoped batteries using activated carbon molded products as electrodes have the disadvantage that self-discharge is large and the voltage decreases over time.
本発明者はかかる欠点を解決すべく檀々検討を行なった
結果、電極として還元性雰囲気下、一定の温度で加熱処
理した炭素成型品を用いれば、ドープおよび/またはア
ンドーゾ屋電池における自己放電を減少せしめることが
できることを児出し、本発明を完成した。The inventors of the present invention have conducted extensive studies to solve these drawbacks, and have found that if a carbon molded product heat-treated at a constant temperature in a reducing atmosphere is used as an electrode, self-discharge in doped and/or andostatic batteries can be reduced. The present invention has been completed by discovering that it is possible to reduce the
すなわち、本発明は、電解質を溶解した有機溶媒溶液に
炭素成型品電極を浸漬してなり、当該電極へのドーピン
グおよび/またはアンド−ピングにより起電力を生じる
電池において、炭素成型品電極が還元性雰囲気下、40
0〜1000℃で加熱処理したものであることを特徴と
する電気化学電池を提供するものである。That is, the present invention provides a battery in which a carbon molded electrode is immersed in an organic solvent solution in which an electrolyte is dissolved, and an electromotive force is generated by doping and/or undoping of the electrode, in which the carbon molded electrode is reducible. Under atmosphere, 40
The present invention provides an electrochemical cell characterized by being heat-treated at 0 to 1000°C.
本発明で用いる炭素成型品電極(以下「電極」という)
は、還元性雰囲気下、400〜1000°Cで加熱処理
される。還元性雰囲気上加熱処理するのは、電極を侵す
ことなく、電極表面に存在する吸着分子、官能基等を還
元、除去するためであり、そのための方法としては、加
熱炉に水素・−酸化炭素等のガスを通じる方法が用い得
るがこれに限られるものではない、また加熱法としては
電気炉の様な一般の炭素材に使用しうる炉を用いること
かできる。Carbon molded electrode used in the present invention (hereinafter referred to as "electrode")
is heat treated at 400 to 1000°C in a reducing atmosphere. The purpose of heat treatment in a reducing atmosphere is to reduce and remove adsorbed molecules, functional groups, etc. present on the electrode surface without damaging the electrode. A method using a gas such as, but not limited to, can be used, and as a heating method, a furnace that can be used for general carbon materials, such as an electric furnace, can be used.
加熱処理温度が高過ぎると、電極が更に炭素化(6)
を起こし、構造が変化し、電池容量の低下を引き起こす
恐れがある。また、温度が低すぎると炭素成型品表面の
吸着分子、官能基等の還元反応を充分に起こすことがで
きず自己放電を充分に抑えることができなくなる。した
がって望ましい処理温度範囲は400〜1000℃であ
る。If the heat treatment temperature is too high, the electrode may undergo further carbonization (6), changing its structure and causing a decrease in battery capacity. On the other hand, if the temperature is too low, the reduction reaction of adsorbed molecules, functional groups, etc. on the surface of the carbon molded product cannot occur sufficiently, making it impossible to sufficiently suppress self-discharge. Therefore, the desirable treatment temperature range is 400 to 1000°C.
また、電極の加熱処理時間は、処理温度により異なるが
1〜10時間程時間子分である。Further, the heating treatment time of the electrode is about 1 to 10 hours, although it varies depending on the treatment temperature.
本発明の電池は、前記の如く処理した電極を、電解質を
溶解した有機溶媒に浸漬することにより製造される。The battery of the present invention is manufactured by immersing the electrode treated as described above in an organic solvent in which an electrolyte is dissolved.
電解質としては、ドープおよび/またはアンドーゾ型電
池において使用される公知の電解質、例えばテトラアル
キルアンモニウム塩、アルカリ金属塩、アルカリ土類金
属塩(これらの対陰イオンとしては、過塩素酸イオン、
6フツ化リンイオン、6フフ化タリウムイオン、6フフ
化ヒ素イオン、6フフ化アンチモンイオン、ハロダンイ
オン、硝酸イオン、硫酸イオン、4酸化レニウムイオン
等が挙げられる)が挙げられる。また、有機溶媒と(4
)
しても一般にこの種の電池に使用される溶媒、例えば、
ジメチルスルホキシド、アセトニトリル、プロビレ/カ
ーボネート、4−ブチロラクトン、ホルムアミド、ジメ
チルホルムアミド、メチルホルムアミド、テトラヒドロ
フラン、1.2−ジメトキシエタン等を用いることがで
きる。As the electrolyte, there may be used known electrolytes used in doped and/or andoso type batteries, such as tetraalkylammonium salts, alkali metal salts, alkaline earth metal salts (counter anions thereof include perchlorate ion,
Examples include phosphorus hexafluoride ion, thallium hexafluoride ion, arsenic hexafluoride ion, antimony hexafluoride ion, halodane ion, nitrate ion, sulfate ion, rhenium tetraoxide ion, etc.). In addition, organic solvent and (4
) Even the solvents commonly used in this type of battery, e.g.
Dimethyl sulfoxide, acetonitrile, propylene/carbonate, 4-butyrolactone, formamide, dimethylformamide, methylformamide, tetrahydrofuran, 1,2-dimethoxyethane, etc. can be used.
次に実施例を挙げ本発明を説明する。Next, the present invention will be explained with reference to Examples.
実施例1
東洋紡績■製油性炭素繊維(KFフェル)F−1600
)を熱電対をセットした石英ガラス管に入れ、管状電気
炉にセットする。石英管に水素ガスを通じながら電気炉
の温度を昇温させ、石英管を500−600℃に5時間
保ち、活性炭素繊維を処理する。この処理された活性炭
素繊維1.5cmx1.5cm(約4 orn9)を、
穴をあけたテフロン板2枚で、白金線と共にはさみ固定
し電極とする。Example 1 Toyobo ■ Oil-based carbon fiber (KF Fell) F-1600
) into a quartz glass tube equipped with a thermocouple, and set it in a tubular electric furnace. The temperature of the electric furnace is raised while hydrogen gas is passed through the quartz tube, and the quartz tube is kept at 500-600° C. for 5 hours to treat the activated carbon fibers. This treated activated carbon fiber 1.5cm x 1.5cm (approximately 4 or9) was
Two Teflon plates with holes are sandwiched together with a platinum wire to form an electrode.
このようにして作った電極2組を0.5モル濃度の過塩
素酸リチウムを含むプロビレ/カーボネート溶液に浸し
、両極を外部電源と接続し、2ポルトの定電圧で電流が
ほとんど流れなくなるまで充電する。しかる後電圧測定
装置により両極間電圧を測定する。電圧測定開始直後に
は急激な電圧の降下がみられるが、その後、約1.6ボ
ルトでほぼ一定となり、測定開始後20時間で1.56
ボルト、50時間で1.5ボルトでありその後の電圧降
下もほとんどみられなかった。The two sets of electrodes made in this way are immersed in a probire/carbonate solution containing 0.5 molar lithium perchlorate, both electrodes are connected to an external power source, and charged at a constant voltage of 2 ports until almost no current flows. do. Thereafter, the voltage between the two electrodes is measured using a voltage measuring device. Immediately after starting the voltage measurement, there is a sudden drop in voltage, but after that it becomes almost constant at about 1.6 volts, and 20 hours after starting the measurement, it drops to 1.56 volts.
The voltage was 1.5 volts in 50 hours, and there was almost no voltage drop after that.
一方、比較例として活性炭素繊維を加熱処理しないこと
以外は全く同様の操作で得た電池は、電圧測定開始後2
0時間で1.6ボルトにまで電圧が低下し、さらに電圧
は下り続けた。On the other hand, as a comparative example, a battery obtained in exactly the same manner except that the activated carbon fibers were not heat-treated was
The voltage dropped to 1.6 volts at 0 hours and continued to drop further.
この二つの電池の電圧の時間変化を示したものが第1図
であり、これから水素ガス中で加熱処理された電極が電
圧降下防止効果を有することがあきらかとなった。Figure 1 shows the temporal change in voltage of these two batteries, and it is clear from this that the electrodes heat-treated in hydrogen gas have the effect of preventing voltage drop.
第1図は、水素気流下で加熱処理した電極を用いた電池
と、処理しない電極を用いた電池について、両極間電圧
の経時変化を示す図面である。FIG. 1 is a diagram showing changes in interelectrode voltage over time for a battery using electrodes heat-treated under a hydrogen stream and a battery using electrodes that were not treated.
Claims (1)
を浸漬してなり、当該電極へのドーピングおよび/また
はアンド−ピングにより起電力を生じる電池において、
炭素成型品電極が還元性雰囲気下、400〜1000℃
で加熱処理したものであることを特徴とする電気化学電
池。1. In a battery in which a carbon molded electrode is immersed in an organic solvent solution in which an electrolyte is dissolved, an electromotive force is generated by doping and/or undoping the electrode.
The carbon molded electrode is heated to 400 to 1000℃ in a reducing atmosphere.
An electrochemical cell characterized by being heat-treated with.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57128231A JPS5918579A (en) | 1982-07-22 | 1982-07-22 | Electrochemical battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57128231A JPS5918579A (en) | 1982-07-22 | 1982-07-22 | Electrochemical battery |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5918579A true JPS5918579A (en) | 1984-01-30 |
Family
ID=14979731
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57128231A Pending JPS5918579A (en) | 1982-07-22 | 1982-07-22 | Electrochemical battery |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5918579A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6290863A (en) * | 1985-05-10 | 1987-04-25 | Asahi Chem Ind Co Ltd | Secondary cell |
EP0690518A1 (en) * | 1994-06-28 | 1996-01-03 | Sharp Kabushiki Kaisha | Non-aqueous secondary battery and negative electrode |
WO2016021443A1 (en) * | 2014-08-05 | 2016-02-11 | Necエナジーデバイス株式会社 | Method for manufacturing negative electrode of lithium-ion cell, and method for manufacturing lithium-ion cell |
-
1982
- 1982-07-22 JP JP57128231A patent/JPS5918579A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6290863A (en) * | 1985-05-10 | 1987-04-25 | Asahi Chem Ind Co Ltd | Secondary cell |
JPH0424831B2 (en) * | 1985-05-10 | 1992-04-28 | Asahi Chemical Ind | |
EP0690518A1 (en) * | 1994-06-28 | 1996-01-03 | Sharp Kabushiki Kaisha | Non-aqueous secondary battery and negative electrode |
US5900335A (en) * | 1994-06-28 | 1999-05-04 | Sharp Kabushiki Kaisha | Non-aqueous secondary battery and negative electrode for non-aqueous secondary battery |
WO2016021443A1 (en) * | 2014-08-05 | 2016-02-11 | Necエナジーデバイス株式会社 | Method for manufacturing negative electrode of lithium-ion cell, and method for manufacturing lithium-ion cell |
JPWO2016021443A1 (en) * | 2014-08-05 | 2017-05-25 | Necエナジーデバイス株式会社 | Method for producing negative electrode of lithium ion battery, and method for producing lithium ion battery |
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