JP2999813B2 - Rechargeable battery - Google Patents
Rechargeable batteryInfo
- Publication number
- JP2999813B2 JP2999813B2 JP2255720A JP25572090A JP2999813B2 JP 2999813 B2 JP2999813 B2 JP 2999813B2 JP 2255720 A JP2255720 A JP 2255720A JP 25572090 A JP25572090 A JP 25572090A JP 2999813 B2 JP2999813 B2 JP 2999813B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- battery
- electrode
- present
- positive 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.)
- Expired - Fee Related
Links
- 229920001940 conductive polymer Polymers 0.000 claims description 20
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 5
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 3
- -1 polyparaphenylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は、導電性ポリマーを用いた二次電池に関す
る。The present invention relates to a secondary battery using a conductive polymer.
（ロ） 従来の技術 近年、導電性ポリマーを利用した導電材料が提案され
ている。この導電性ポリマーは、各種アニオンやカチオ
ンなどをドーパントとしたドーピング並びにアンドーピ
ング処理が可能であり、ドーピング処理により導電性を
飛躍的に上昇させることが可能である。また、アニオン
がドーピングされる導電性ポリマーを正極材料として、
カチオンがドーピングされる導電性ポリマーを負極材料
として各々使用すると共に、上記ドーパントを含有する
溶液を電解液として用い、ドーピング及びアンドーピン
グを電気化学的に可逆的に行なうことにより充放電可能
な電池が構成される。(B) Conventional technology In recent years, conductive materials using conductive polymers have been proposed. This conductive polymer can be subjected to doping and undoping treatment using various anions and cations as dopants, and the conductivity can be drastically increased by the doping treatment. Further, a conductive polymer doped with an anion as a positive electrode material,
A chargeable / dischargeable battery is obtained by using a conductive polymer doped with a cation as a negative electrode material, using a solution containing the dopant as an electrolyte, and performing reversible electrochemical doping and undoping. Be composed.
このような導電性ポリマーとしては、従来よりポリア
セチレン、ポリパラフェニレン、ポリチエニレン、ポリ
ピロール、ポリアニリン、ポリパラフェニレンビニレン
などのような共役二重結合を有する重合体が知られてい
る。As such conductive polymers, polymers having a conjugated double bond such as polyacetylene, polyparaphenylene, polythienylene, polypyrrole, polyaniline, and polyparaphenylenevinylene have been known.
これらは粉末状、フィルム状で得られるが、このよう
にして得られたものは分子量分布がブロードであり、電
極材料として使用した場合、その電極容量が低くなって
しまう。These can be obtained in the form of a powder or a film, but those obtained in this way have a broad molecular weight distribution, and when used as an electrode material, the electrode capacity is reduced.
（ハ） 発明が解決しようとする課題 そして特に、電解重合法により得た導電性ポリマーは
比較的有機溶媒に溶解しやすいが、これは低分子量のも
のが多いためであり、電極材料として使用した場合、そ
の特性が十分ではないという問題点があった。(C) Problems to be Solved by the Invention In particular, the conductive polymer obtained by the electrolytic polymerization method is relatively easy to dissolve in an organic solvent, but this is because many of them have low molecular weights and are used as electrode materials. In such a case, there is a problem that the characteristics are not sufficient.
そこで本発明は前記問題点に鑑みて成されたものであ
って、導電性ポリマーを用いた場合に、電極特性が優秀
であり、高容量まで充電可能な電極を備えた二次電池を
提供するものである。Therefore, the present invention has been made in view of the above problems, and provides a secondary battery including an electrode that has excellent electrode characteristics and can be charged up to a high capacity when a conductive polymer is used. Things.
（ニ） 課題を解決するための手段 本発明の二次電池は、２−ピロリンからなる電解液溶
媒中で重合した導電性ポリマーを、電極材料とするもの
である。また、この導電性ポリマーが、正極に使用され
たことを特徴とする。(D) Means for Solving the Problems The secondary battery of the present invention uses, as an electrode material, a conductive polymer polymerized in an electrolyte solvent composed of 2-pyrroline. Further, the conductive polymer is used for a positive electrode.
またここで使用する導電性ポリマーとしては、電解重
合可能なものならばその種類を問わないが、具体的に
は、ポリアニリン、ポリピロール、ポリチオフェンなど
の共役二重結合を有する導電性ポリマー等が、特に望ま
しい。The type of the conductive polymer used herein is not particularly limited as long as it can be electrolytically polymerized.Specifically, conductive polymers having a conjugated double bond such as polyaniline, polypyrrole, and polythiophene are particularly preferable. desirable.
（ホ） 作用 上記のような２−ピロリンを含有した電解液溶媒中
で、導電性ポリマーを電解重合して合成することによ
り、導電性ポリマーの低分子量成分が溶解し、高分子量
の成分が残る。導電性ポリマーは分子量が高い程、電池
電極として用いた場合の電極特性が優秀となり、高容量
まで充電可能な電極が得られる。(E) Action In the electrolytic solution solvent containing 2-pyrroline as described above, the conductive polymer is electrolytically polymerized and synthesized, whereby the low molecular weight component of the conductive polymer is dissolved and the high molecular weight component remains. . The higher the molecular weight of the conductive polymer, the more excellent the electrode characteristics when used as a battery electrode, and an electrode that can be charged to a high capacity can be obtained.
（ヘ） 実施例 以下に実施例を挙げ、本発明を具体的に説明する。(F) Examples The present invention will be specifically described below with reference to examples.
［本発明］ アニリンを、ホウフッ化リチウムの２−ピロリン溶液
に溶解したものを電解液とし、陽極としてステンレス
網、一方、陰極としてリチウム金属を用いて、1mA/cm2
の定電流で電解重合を行った。このようにして陽極上に
得られたポリアニリンを乾燥して、ポリアニリン粉米を
得た。このポリアニリンを加圧成形し、正極として使用
した。The present invention] aniline, those dissolved in 2-pyrroline solution of lithium borofluoride as the electrolyte, stainless steel mesh as an anode, whereas, by using the lithium metal as a cathode, 1 mA / cm 2
Was carried out at a constant current of. The polyaniline thus obtained on the anode was dried to obtain polyaniline powdered rice. This polyaniline was molded under pressure and used as a positive electrode.
一方、負極にはリチウム−アルミニウム合金を用い、
電解液としてはホウフッ化リチウム／プロピレンカーボ
ネート溶液を使用して、第１図に示した構造を有する本
発明電池Ａを作製した。On the other hand, a lithium-aluminum alloy is used for the negative electrode,
A battery A of the present invention having the structure shown in FIG. 1 was produced using a lithium borofluoride / propylene carbonate solution as an electrolyte.
ここで、第１図は本発明電池の縦断面図である。第１
図中、１は正極、２は負極であり、これらはセパレータ
３によって隔離されている。また４は正極缶、５は負極
缶であり、その内底面にはそれぞれ正極集電体６及び負
極集電体７が固定されている。そして前記極缶４及び負
極缶５は、絶縁パッキング８によって、絶縁されてい
る。Here, FIG. 1 is a longitudinal sectional view of the battery of the present invention. First
In the figure, 1 is a positive electrode, 2 is a negative electrode, which are separated by a separator 3. Reference numeral 4 denotes a positive electrode can, and 5 denotes a negative electrode can. A positive electrode current collector 6 and a negative electrode current collector 7 are fixed to the inner bottom surface, respectively. The electrode can 4 and the negative electrode can 5 are insulated by an insulating packing 8.
［比較例１］ 比較例として、電解重合の電解液溶媒としてプロピレ
ンカーボネートを用いて重合して得たポリアニリンを正
極材料とした以外は、前記実施例１と同様にして、比較
電池Ｘを組み立てた。Comparative Example 1 As a comparative example, a comparative battery X was assembled in the same manner as in Example 1 except that polyaniline obtained by polymerization using propylene carbonate as an electrolytic solution solvent for electrolytic polymerization was used as a positive electrode material. .
これらの本発明電池Ａ、比較電池Ｘを用いて、電池の
充放電試験を行なった。この時の充電は充電電流1mA
で、3.6Vまで、放電は放電電流1mAで2.5Vまでとした。A battery charge / discharge test was performed using the battery A of the present invention and the comparative battery X. Charging at this time is a charging current of 1 mA
The discharge was set to 2.5 V at a discharge current of 1 mA.
第２図に、これらの電池の充放電特性を示す。いずれ
も電池も充放電効率は100％を示したが、本発明電池Ａ
は6mAh以上充電できるのに対し、比較電池Ｘは4mAh以下
しか充電できない。これは本発明電池Ａに用いた導電性
ポリマーであるポリアニリンが、比較電池Ｘに用いたも
のと比較して、重合度が大きいためと考えられる。FIG. 2 shows the charge / discharge characteristics of these batteries. In each case, the charging / discharging efficiency was 100%.
Can charge 6 mAh or more, while the comparative battery X can charge only 4 mAh or less. This is probably because polyaniline, which is the conductive polymer used in Battery A of the present invention, has a higher degree of polymerization than that used in Comparative Battery X.
（ト） 発明の効果 以上述べた如く、本発明によれば、導電性ポリマーを
用いた二次電池の放電容量の増大が図られるので、その
工業的価値は極めて大きい。(G) Effect of the Invention As described above, according to the present invention, the discharge capacity of a secondary battery using a conductive polymer can be increased, so that its industrial value is extremely large.
第１図は本発明電池の縦断面図、第２図は電池の充放電
特性を示す図である。 １……正極、２……負極、３……セパレータ、４……正
極缶、５……負極缶、６……正極集電体、７……負極集
電体、８……絶縁パッキング、Ａ……本発明電池、Ｘ…
…比較電池。FIG. 1 is a longitudinal sectional view of the battery of the present invention, and FIG. 2 is a diagram showing the charge / discharge characteristics of the battery. DESCRIPTION OF SYMBOLS 1 ... Positive electrode, 2 ... Negative electrode, 3 ... Separator, 4 ... Positive electrode can, 5 ... Negative electrode can, 6 ... Positive electrode current collector, 7 ... Negative electrode current collector, 8 ... Insulating packing, A .... Battery of the present invention, X ...
... Comparative batteries.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−259350（ＪＰ，Ａ) 特開 昭63−2251（ＪＰ，Ａ) 特開 昭61−200669（ＪＰ，Ａ) 特開 昭64−79221（ＪＰ，Ａ) 特開 昭64−41166（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 4/60 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-259350 (JP, A) JP-A-63-2251 (JP, A) JP-A-61-200669 (JP, A) JP-A 64-64 79221 (JP, A) JP-A-64-41166 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01M 10/40 H01M 4/60
Claims (3)
した導電性ポリマーを、電極材料とする二次電池。1. A secondary battery in which a conductive polymer polymerized in an electrolyte solvent comprising 2-pyrroline is used as an electrode material.
ことを特徴とする請求項記載の二次電池。2. The secondary battery according to claim 1, wherein the conductive polymer is used for a positive electrode.
リピロール、ポリチオフェンからなる群から選択された
少なくとも１種であることを特徴とする請求項又は
記載の二次電池。3. The secondary battery according to claim 1, wherein the conductive polymer is at least one selected from the group consisting of polyaniline, polypyrrole, and polythiophene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255720A JP2999813B2 (en) | 1990-09-25 | 1990-09-25 | Rechargeable battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255720A JP2999813B2 (en) | 1990-09-25 | 1990-09-25 | Rechargeable battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04133275A JPH04133275A (en) | 1992-05-07 |
| JP2999813B2 true JP2999813B2 (en) | 2000-01-17 |
Family
ID=17282715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255720A Expired - Fee Related JP2999813B2 (en) | 1990-09-25 | 1990-09-25 | Rechargeable battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2999813B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025262A1 (en) | 2004-08-30 | 2006-03-09 | Shin-Etsu Polymer Co., Ltd. | Conductive composition and conductive crosslinked material, capacitor and method for manufacturing same, antistatic coating composition, antistatic coat, antistatic film, optical filter and optical information recording medium |
| JP4987239B2 (en) * | 2004-08-30 | 2012-07-25 | 信越ポリマー株式会社 | Conductive composition |
-
1990
- 1990-09-25 JP JP2255720A patent/JP2999813B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04133275A (en) | 1992-05-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |