JPH0793148B2 - Secondary battery - Google Patents
Secondary batteryInfo
- Publication number
- JPH0793148B2 JPH0793148B2 JP58029942A JP2994283A JPH0793148B2 JP H0793148 B2 JPH0793148 B2 JP H0793148B2 JP 58029942 A JP58029942 A JP 58029942A JP 2994283 A JP2994283 A JP 2994283A JP H0793148 B2 JPH0793148 B2 JP H0793148B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- electrode
- battery
- conductive polymer
- secondary 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.)
- Expired - Lifetime
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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 本発明は二次電池に関し、更に詳細には第１の電極とし
て金属電極を用い、第２の電極として炭素繊維上に導電
性高分子化合物を被覆させた電極を用いた、電池の充放
電特性の向上及び電池の電圧保持性の向上を可能にした
二次電池に関する。Description: TECHNICAL FIELD The present invention relates to a secondary battery, and more specifically, a metal electrode is used as a first electrode, and a carbon fiber coated conductive polymer compound is used as a second electrode. The present invention also relates to a secondary battery capable of improving the charge / discharge characteristics of the battery and the voltage holding property of the battery.
近年エネルギー問題が重要視されるに従い新しい型の軽
量で高エネルギー密度の電池の開発が熱望されるように
なつてきている。この要望を満たすための研究として、
ポリアセチレンを電極として用いる報告があり、この方
法によれば電池自体の性能としてはほぼ満足できるもの
であるが、電極であるポリアセチレン自体が不安定であ
るという難点があつた。本発明者らは先にかかる欠点を
解消するものとして、炭素繊維、殊に比表面積の大きい
炭素繊維を電極として用いた電池を開発し、特許出願し
た（特願昭56−134690号）。この発明により、従来公知
のものより軽量で、かつ高エネルギー密度の電池を得る
ことができるが、更に性能のよい電池を得ようとすると
工夫の余地はあり、例えば、二次電池として用いる場合
に充放電特性を向上せしめ、電池の電圧保持性を向上せ
しめると、更に電池の用途を著しく広げることができる
ものと期待することができる。In recent years, as the energy problem has been emphasized, there has been an eager desire to develop a new type of lightweight and high energy density battery. As research to meet this demand,
There is a report that polyacetylene is used as an electrode. According to this method, the performance of the battery itself is almost satisfactory, but there is a drawback in that the electrode polyacetylene itself is unstable. The present inventors have developed a battery using a carbon fiber, particularly a carbon fiber having a large specific surface area, as an electrode and applied for a patent (Japanese Patent Application No. 56-134690) as a solution to the above drawbacks. According to the present invention, it is possible to obtain a battery which is lighter in weight and higher in energy density than a conventionally known one, but there is room for devising to obtain a battery having better performance. For example, when the battery is used as a secondary battery. If the charge / discharge characteristics are improved and the voltage holding property of the battery is improved, it can be expected that the use of the battery can be remarkably expanded.
そこで、本発明者らは、かかる要望を満すべく鋭意研究
を重ねた結果、炭素繊維を導電性高分子で処理した電極
を用いれば充放電特性及び電池の電圧保持特性が良好な
電池を構成しうる電極を得ることができることを見出し
本発明を完成した。Therefore, the inventors of the present invention have conducted extensive studies to satisfy such demands, and as a result, use of an electrode obtained by treating carbon fiber with a conductive polymer constitutes a battery having good charge / discharge characteristics and voltage holding characteristics of the battery. The present inventors have completed the present invention by finding that it is possible to obtain a viable electrode.
すなわち、本発明は電解質を溶解した溶液に電極を浸漬
してなる電池において、第１の電極として金属電極を用
い、第２の電極として導電性高分子で被覆した炭素繊維
電極を用いた二次電池を提供するものである。That is, the present invention relates to a battery obtained by immersing an electrode in a solution in which an electrolyte is dissolved, in which a metal electrode is used as a first electrode and a carbon fiber electrode coated with a conductive polymer is used as a second electrode. A battery is provided.
本発明において、第１の電極として用いられる金属は、
特に限定されないが、アルカリ金属、アルカリ土類金属
及び周期律表第３族の金属等が好ましく、例えば、リチ
ウム、カリウム、ルビジウム、セシウム、バリウム、ス
トロンチウム、カルシウム、ナトリウム、マグネシウム
等を挙げることができ、就中、高い起電力が得られ、電
池の軽量化が可能なリチウムが好ましい。In the present invention, the metal used as the first electrode is
Although not particularly limited, alkali metals, alkaline earth metals, metals of Group 3 of the periodic table and the like are preferable, and examples thereof include lithium, potassium, rubidium, cesium, barium, strontium, calcium, sodium and magnesium. Above all, lithium is preferable because it can obtain a high electromotive force and can reduce the weight of the battery.
本発明に使用される、第２の電極である導電性高分子を
被覆した炭素繊維電極における炭素繊維としては500〜4
000m2/gの比表面積を有するものが好ましい。形状は棒
状、シート状等、特に限定されないが、直径が８〜30μ
ｍの炭素繊維から構成されたシート状のものが好まし
い。シートの構造はフエルト状、紙状、ハニカム状等い
づれであつても良い。本発明にかかる炭素繊維で著しく
効果の高いものは、10〜20Åの直径の無数の細孔を有
し、その比表面積が1000〜4000m2/gとなる炭素繊維（以
下活性炭素繊維という）のシートである。この活性炭素
繊維はフイブリル構造を有し、且つ表面積が極めて大き
いために、電気化学的に大量のドーピングを行うことが
できる。The carbon fiber used in the present invention is 500 to 4 as the carbon fiber in the carbon fiber electrode coated with the conductive polymer which is the second electrode.
Those having a specific surface area of 000 m 2 / g are preferable. The shape is not particularly limited, such as a rod shape or a sheet shape, but the diameter is 8 to 30 μ.
A sheet-shaped material composed of m carbon fibers is preferable. The structure of the sheet may be any of felt, paper, honeycomb, and the like. The carbon fiber according to the present invention, which is remarkably highly effective, has a large number of pores having a diameter of 10 to 20 Å and has a specific surface area of 1000 to 4000 m 2 / g (hereinafter referred to as activated carbon fiber). It is a sheet. Since this activated carbon fiber has a fibril structure and has a very large surface area, a large amount of doping can be performed electrochemically.
また、第２の電極において用いられる導電性高分子とし
ては電気伝導度が1ohm-1cm-1以上で、かつ常温で固体の
有機化合物が好ましい。この導電性高分子は、使用に際
し電解質溶液に溶けてしまわないものを選択する必要が
ある。また、導電性高分子は、高分子化合物がドープさ
れたことにより1ohm-1cm-1以上の電気伝導度を持つに到
つたものであつてもよい。導電性高分子化合物として好
ましいものとしては、例えば、ポリアセチレン、ポリパ
ラフエニレン、ポリピロール、ポリチオフエン等を挙げ
ることができる。The conductive polymer used in the second electrode is preferably an organic compound having an electric conductivity of 1 ohm -1 cm -1 or more and solid at room temperature. It is necessary to select a conductive polymer that does not dissolve in the electrolyte solution during use. Further, the conductive polymer may be one having a conductivity of 1 ohm -1 cm -1 or more due to being doped with a polymer compound. Preferable examples of the conductive polymer compound include polyacetylene, polyparaphenylene, polypyrrole, polythiophene and the like.
導電性高分子で炭素繊維を被覆する方法としては、炭素
繊維に導電性高分子を塗布する方法または炭素繊維上で
導電性高分子の前駆体もしくは単量体を重合する方法等
が挙げられる。炭素繊維に導電性高分子を塗布するに
は、溶融又は溶媒に溶解した導電性高分子を炭素繊維に
塗布すればよい。炭素繊維上で導電性高分子の前駆体も
しくは単量体を重合するには、単量体に触媒を加えたも
のを炭素繊維に塗布するか、またはピロール等の単量体
の溶液に炭素繊維を浸漬して炭素繊維電極上で電解重合
すればよい。炭素繊維を被覆する導電性高分子の重量
は、炭素繊維に対し１〜200重量％、好ましくは10〜100
重量％である。Examples of the method of coating the carbon fiber with the conductive polymer include a method of coating the carbon fiber with the conductive polymer and a method of polymerizing a precursor or monomer of the conductive polymer on the carbon fiber. To apply the conductive polymer to the carbon fiber, the conductive polymer dissolved or dissolved in a solvent may be applied to the carbon fiber. To polymerize the precursor or monomer of the conductive polymer on the carbon fiber, the catalyst is added to the carbon fiber, or the carbon fiber is added to the solution of the monomer such as pyrrole. May be immersed and electrolytically polymerized on the carbon fiber electrode. The weight of the conductive polymer coating the carbon fiber is 1 to 200% by weight with respect to the carbon fiber, preferably 10 to 100
% By weight.
本発明において用いられる電解質としてはテトラアルキ
ルアンモニウム塩（対陰イオンとしては過塩素酸イオ
ン、４フツ化ホウ素イオン、６フツ化リンイオン、６フ
ツ化タリウムイオン、６フツ化ヒ素イオン、６フツ化ア
ンチモンイオン、チオシアンイオン、ハロゲンイオン、
硝酸イオン、硫酸イオン、４酸化レニウムイオン等）、
アルカリ金属塩、アルカリ土類金属塩（いずれも対陰イ
オンは上記列挙したものに同じ）、遷移金属、希土類元
素、貴金属のハロゲン塩、過塩素酸塩、硝酸塩など一般
公知の電解質が挙げられる。The electrolyte used in the present invention includes a tetraalkylammonium salt (as a counter anion, perchlorate ion, boron tetrafluoride ion, hexafluorophosphorus ion, thallium hexafluoride ion, arsenic hexafluoride ion, arsenic hexafluoride ion, antimony hexafluoride ion). Ion, thiocyanate, halogen ion,
Nitrate ion, sulfate ion, rhenium oxide ion, etc.),
Commonly known electrolytes such as alkali metal salts, alkaline earth metal salts (the counter anions are the same as those listed above), transition metals, rare earth elements, noble metal halogen salts, perchlorates and nitrates can be mentioned.
また、本発明において用いられる溶媒としては、ジメチ
ルスルホキシド、アセトニトリル、プロピレンカーボネ
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、一般に電池に用いられ
ている有機溶媒を挙げることができる。As the solvent used in the present invention, dimethylsulfoxide, acetonitrile, propylene carbonate, 4-butyrolactone, formamide, dimethylformamide, methylformamide, tetrahydrofuran, 1,2-dimethoxyethane, etc., organic solvents commonly used in batteries. Can be mentioned.
以下、一実施例を示す図面とともに本発明を説明する。The present invention will be described below with reference to the drawings illustrating one embodiment.
第１図において、１は導電性高分子を被覆した炭素繊維
からなる陽極である。２はセパレーターでガラスフアイ
バーからなるもので、炭素繊維陽極１と金属陰極３の間
に介在せしめてある。４は集電板で白金からなるもの
で、炭素繊維陽極１と金属陰極３のセパレーター２とは
反対側にそれぞれ貼着せしめてある。５は白金よりなる
リード線である。In FIG. 1, reference numeral 1 is an anode made of carbon fiber coated with a conductive polymer. A separator 2 is made of glass fiber and is interposed between the carbon fiber anode 1 and the metal cathode 3. A collector plate 4 made of platinum is attached to the carbon fiber anode 1 and the metal cathode 3 on the opposite sides of the separator 2. 5 is a lead wire made of platinum.
次に、炭素繊維をその約50重量％相当の電解重合ポリピ
ロールで被覆したものを陽極、リチウム金属を陰極、そ
して４フツ化ホウ素リチウムの１モルプロピレンカーボ
ネート溶液を電解液に用い、図１と同様の二次電池（本
発明品）及び本発明品の陽極の変りに炭素繊維をそのま
ま陽極とした二次電池（従来品）について、充電サイク
ル寿命及び起電力の電圧安定性を調べた結果を示す。Next, using carbon fiber coated with about 50% by weight of the electrolytically polymerized polypyrrole as an anode, lithium metal as a cathode, and a 1 mol propylene carbonate solution of lithium tetrafluoroborate as an electrolyte, the same as in FIG. 2 shows the result of examining the charge cycle life and the voltage stability of electromotive force of the secondary battery (invention product) and the secondary battery (conventional product) in which carbon fiber was used as an anode instead of the anode of the invention product. .
（１） 充放電サイクル寿命 0.5mA/cm2の定電流で充放電（充電終止電圧4.0V:放電終
止電圧3.3V）を繰り返し行い、充放電のサイクル数と充
放電効率との関係を調べた。この結果を第２図に示す。
なお充放電効率は次式により求めた。(1) Charge / discharge cycle life Charge / discharge (charge end voltage 4.0V: discharge end voltage 3.3V) was repeatedly performed at a constant current of 0.5mA / cm 2 , and the relationship between the number of charge / discharge cycles and charge / discharge efficiency was investigated. . The results are shown in FIG.
The charging / discharging efficiency was calculated by the following formula.
ただし、式中、放電時間は充電終止電圧から放電終止電
圧に、また充電時間は放電終止電圧から充電終止電圧に
到るまでの所要時間である。 However, in the formula, the discharge time is the time required to reach the discharge end voltage from the discharge end voltage, and the charge time is the time required to reach the charge end voltage from the discharge end voltage.
第２図から、導電性高分子を被覆した炭素繊維陽極を使
用した本発明品は、炭素繊維をそのまま陽極とした従来
品に比べ充放電サイクル寿命が延びていることがわか
る。It can be seen from FIG. 2 that the product of the present invention using the carbon fiber anode coated with the conductive polymer has a longer charge / discharge cycle life than the conventional product using the carbon fiber as an anode.
（２） 電圧安定性 1.0mA/cm2の定電流で3.8Vになるまで充電を行つた後、
開回路電圧の時間変化を調べた。この結果を第３図に示
す。(2) Voltage stability After charging at a constant current of 1.0mA / cm 2 to 3.8V,
The time change of the open circuit voltage was investigated. The results are shown in FIG.
第３図から、本発明品は従来品に比べ電圧安定性に優れ
ていることがわかる。It can be seen from FIG. 3 that the product of the present invention is superior in voltage stability to the conventional product.
【図面の簡単な説明】 第１図は、本発明の二次電池の構成例の断面図を示す。 第２図は、本発明の二次電池と、従来の二次電池につい
て、充放電サイクル数と充放電効率の関係を示す。 第３図は、本発明の二次電池と、従来の二次電池につい
て、電池電圧の経時変化を示す。 １……導電性高分子を被覆した炭素繊維電極 ２……セパレーター ３……金属電極 ４……集電板 ５……リード線BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a sectional view of a constitutional example of a secondary battery of the present invention. FIG. 2 shows the relationship between the number of charge / discharge cycles and the charge / discharge efficiency of the secondary battery of the present invention and the conventional secondary battery. FIG. 3 shows changes in battery voltage over time for the secondary battery of the present invention and the conventional secondary battery. 1 ... Carbon fiber electrode coated with conductive polymer 2 ... Separator 3 ... Metal electrode 4 ... Current collector 5 ... Lead wire
Claims (2)
る電池において、第１の電極として金属電極を用い、第
２の電極として導電性高分子で被覆した炭素繊維電極を
用いたことを特徴とする二次電池。1. A battery obtained by immersing an electrode in a solution in which an electrolyte is dissolved, wherein a metal electrode is used as a first electrode and a carbon fiber electrode coated with a conductive polymer is used as a second electrode. Characteristic secondary battery.
を有する活性炭素繊維である特許請求の範囲第１項記載
の二次電池。2. The secondary battery according to claim 1, wherein the carbon fiber electrode is an activated carbon fiber having a specific surface area of 500 to 4000 m 2 / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58029942A JPH0793148B2 (en) | 1983-02-24 | 1983-02-24 | Secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58029942A JPH0793148B2 (en) | 1983-02-24 | 1983-02-24 | Secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59157974A JPS59157974A (en) | 1984-09-07 |
| JPH0793148B2 true JPH0793148B2 (en) | 1995-10-09 |
Family
ID=12290036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58029942A Expired - Lifetime JPH0793148B2 (en) | 1983-02-24 | 1983-02-24 | Secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0793148B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0630260B2 (en) * | 1985-03-25 | 1994-04-20 | 鐘紡株式会社 | Organic electrolyte battery |
| DE3531019A1 (en) * | 1985-08-30 | 1987-03-05 | Basf Ag | METHOD FOR THE ELECTROCHEMICAL COATING OF CARBON FIBERS |
| JPS6289749A (en) * | 1985-10-15 | 1987-04-24 | Mitsubishi Petrochem Co Ltd | electrode material |
| JP4639410B2 (en) * | 1999-11-05 | 2011-02-23 | ソニー株式会社 | Negative electrode and non-aqueous electrolyte battery |
-
1983
- 1983-02-24 JP JP58029942A patent/JPH0793148B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59157974A (en) | 1984-09-07 |
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