JPH02292809A - Solid electrolytic capacitor - Google Patents
Solid electrolytic capacitorInfo
- Publication number
- JPH02292809A JPH02292809A JP11442789A JP11442789A JPH02292809A JP H02292809 A JPH02292809 A JP H02292809A JP 11442789 A JP11442789 A JP 11442789A JP 11442789 A JP11442789 A JP 11442789A JP H02292809 A JPH02292809 A JP H02292809A
- Authority
- JP
- Japan
- Prior art keywords
- complex salt
- electrolyte
- methylindole
- electrolytic capacitor
- solid electrolytic
- 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
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 239000007787 solid Substances 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 21
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000012047 saturated solution Substances 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- -1 radical salt Chemical class 0.000 description 3
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- BJMUOUXGBFNLSN-UHFFFAOYSA-N 1,2-dimethylindole Chemical compound C1=CC=C2N(C)C(C)=CC2=C1 BJMUOUXGBFNLSN-UHFFFAOYSA-N 0.000 description 1
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、良好な皮膜修復性を有する７．７．８．８−
テトラシアノキノジメタンからなるイオンラジカル塩を
固体電解質とする固体電解コンデンサに関するものであ
る．
［従来の技術］
７．７．８．８−テトラシアノキノジメタン（以下、Ｔ
ＣＮＱと略す）からなるイオンラジカル塩を固体電解質
とする固体電解コンデンサとして、例えばキノリンある
いはイソキノリンをカチオンとし、ＴＣＮＱをアニ才ン
とするＴ Ｃ Ｎ Ｑ ＩＩ塩（特開昭５８−１９１４
１４号）を加熱融解し、冷却固化したものを固体電解質
したものが良く知られている．なお、これらＴ Ｃ Ｎ
Ｑ 錯塩のカチオンにおいて、そのＮ位は炭素数２〜
１８までの中で選ばれたアルキル基で置換されている。[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a 7.7.8.8-
This article concerns a solid electrolytic capacitor whose solid electrolyte is an ionic radical salt consisting of tetracyanoquinodimethane. [Prior art] 7.7.8.8-tetracyanoquinodimethane (hereinafter referred to as T
As a solid electrolytic capacitor using an ionic radical salt consisting of CNQ (abbreviated as CNQ) as a solid electrolyte, for example, TCNQ II salt (JP-A-58-1914
No. 14) is heated and melted, cooled and solidified to form a solid electrolyte. In addition, these T C N
Q In the cation of the complex salt, the N position has 2 to 2 carbon atoms.
Substituted with an alkyl group selected from up to 18.
Ｔ Ｃ Ｎ Ｑｌ塩を加熱融解し、冷却固化するという
方法は、エッチングを施されたアルミニウム箔あるいは
タンタル焼結体にＴ Ｃ Ｎ Ｑ’！塩を融解状態で含
浸することができるので、好ましいものである．しかし
、その反面Ｔ Ｃ Ｎ Ｑ ｍ塩の融解温度が高温度で
あったり、または融解時間が長時間であると、有機半導
体であるＴ Ｃ Ｎ Ｑ 錨塩が分解し、絶縁体に変質
してしまうものである．［発明の目的］
一方、本発明は比抵抗値が小さい値を有し，熱的にも安
定である新規有機半導体（新規化合物）としてのＮ一置
換−１−メチルインドールＴＣＮＱ錯塩を固体電解質と
したものである．これにより高性能で信頼性の高い固体
電解コンデンサを提供するものである．
［発明の概要］
本発明に係る固体電解コンデンサの基本的な構成は、陽
極酸化（化成）により表面に陽極酸化皮膜を有する弁作
用金属（例えば、アルミニウム、タンタル，チタンおよ
びこれらの合金）を第１の電極とし、第２の電極（対極
）との間に直接あるいはセバレータを介在させてＴＣＮ
ＱＩ塩からなる固体電解質を有するものである．ＴＣＮ
Ｑ錯塩としては上述したようにＮ一置換−１−メチルイ
ンドールＴＣＮＱ錯塩である．ここで、Ｎ一置換−１−
メチルインドールＴＣＮＱ錯塩の構造式を示すと次のよ
うになる．
Ｎ一置換−１−メチルインドールＴＣＮＱ錯塩の構造式
式［１］中、ｍは１モルの錯塩に含まれる中性７．７，
８．８−テトラシアノキノジメタンのモル故に対応する
正の数（０．５〜１．５）を意味する．ＲはＣ．〜Ｃａ
のアルキル基を示す．次に、Ｎ−メチル−１−メチルイ
ンドールＴＣＮＱ錨塩の合成方法について述べる。０．
００７６モルの１−メチルインドールと０．０１１４モ
ルのヨウ化メチルをフラスコ内で約４０〜４５［℃］に
ウォーターバスで熱して撹拌すると，４級化反応が起こ
る．この溶液を冷却して得られるヨウ化一Ｎ−メチル−
１−メチルインドールの０．００３７モルをアセトニト
リルに沸騰状態で溶解し．０．００５６モルのＴＣＮＱ
錯塩を溶解した沸騰状態のアセトニトリル溶液と混合す
る。The method of heating and melting T C N Ql salt and cooling and solidifying it is a method of applying T C N Q'! to an etched aluminum foil or tantalum sintered body. This is preferable because the salt can be impregnated in a molten state. However, on the other hand, if the melting temperature of the T C N Q m salt is high or the melting time is long, the T C N Q anchor salt, which is an organic semiconductor, decomposes and transforms into an insulator. It's something to put away. [Object of the invention] On the other hand, the present invention uses N-substituted-1-methylindole TCNQ complex salt as a new organic semiconductor (new compound) having a small resistivity value and thermal stability as a solid electrolyte. This is what I did. This provides a solid electrolytic capacitor with high performance and reliability. [Summary of the Invention] The basic structure of the solid electrolytic capacitor according to the present invention is that a valve metal (for example, aluminum, tantalum, titanium, or an alloy thereof) having an anodized film on its surface is formed by anodizing (chemical conversion). TCN is used as one electrode and directly or with a separator interposed between it and the second electrode (counter electrode).
It has a solid electrolyte made of QI salt. TCN
As mentioned above, the Q complex salt is N-monosubstituted-1-methylindole TCNQ complex salt. Here, N-substitution -1-
The structural formula of methylindole TCNQ complex salt is as follows. In the structural formula [1] of the N-monosubstituted-1-methylindole TCNQ complex salt, m is the neutral 7.7 contained in 1 mol of the complex salt,
8.8-It means a positive number (0.5 to 1.5) corresponding to the mole of tetracyanoquinodimethane. R is C. ~Ca
Indicates the alkyl group of Next, a method for synthesizing N-methyl-1-methylindole TCNQ anchor salt will be described. 0.
When 0.076 mol of 1-methylindole and 0.0114 mol of methyl iodide are heated in a flask to about 40-45 [°C] in a water bath and stirred, a quaternization reaction occurs. 1N-methyl iodide obtained by cooling this solution
0.0037 mol of 1-methylindole was dissolved in acetonitrile at boiling temperature. 0.0056 mol TCNQ
Mix with a boiling acetonitrile solution in which the complex salt is dissolved.
その後、約ｌｏ時間、５℃で放置することにより、Ｎ−
メチル−１−メチルインドールＴＣＮＱ錯塩の針状結晶
が得られる。この結晶を少量のアセトニトリルで洗浄し
、さらにメタノールで洗液が着色しなくなるまで洗浄し
た後、エーテルで洗浄し、乾燥し、固体電解コンデンサ
に適用する．このＮ−メチル−１−メチルインドールＴ
ＣＮＱ錯塩の比抵抗値は６．７０［Ω・ｃｍ］であった
．
この合成工程において、ヨウ化メチルに代えて、ヨウ化
エチル、ヨウ化プロビル、ヨウ化ブチル・・・を使用す
れば、それぞれＮ一エチル−１−メチルインドールＴＣ
ＮＱ錯塩、Ｎ − ｎ−プロビルーｌ−メチルインドー
ルＴＣＮＱ鐵塩、Ｎ一ｎ−ブチルー１−メチルインドー
ルＴ Ｃ Ｎ Ｑｔ！塩・を得る．
［実施例］
次に、上述のようにして得たＮ一置換−１−メチルイン
ドールＴＣＮＱ錯塩を電解コンデンサに適用した実施例
について述べる．
（実施例１）
Ｎ−メチル−１−メチルインドールＴＣＮＱＩ塩をアセ
トニトリル中に溶解し、飽和溶液とする．次に、この溶
液中にコンデンサ素子を浸漬し、その後５０〜６０［”
Ｃ］で真空乾燥を行い、溶媒のアセトニトリルを飛散さ
せた．この操作な３回繰返し行なった。コンデンサ素子
は電極として表面を約ｌＯ倍にエッチングしたアルミニ
ウム箔を用い、さらに表面を化成処理した酸化皮膜を形
成したものである．電解質の含浸後にコロイグルカーボ
ンを塗布し、その後に銀ペーストを塗布し、リード線を
ハンダ付けし、外装することにより定格容量１．０［μ
Ｆ］の陽極に対して容量１．０［μＦｌ．損失３．９［
％］の固体電解コンデンサを得た．
上述のようにして得た本発明に係る固体電解コンデンサ
（定格２５ ［Ｖ］ − １．０ ［μＦ］ ）（７
）寿命特性比較を第１表に示す．第１表中，静電容量値
および損失角の正接は周波数が１２０［Ｈｚ ］での値
である．漏れ電流は、定格電圧（２５ ［Ｖ］ ）印加
１分後に測定した値である．引続き、本発明の他の実施
例について述べる９（実施例２）
Ｎ−メチル−１−メチルインドールＴＣＮＱ錯塩とラク
トン系化合物、例えばγ−プチロラクトンの化合物４０
［ｍｇ］を直径５．０ ［ｍｍ］のアルミニウムケース
に充填し、Ｌ５０［’Ｃ］まで約１０秒で加熱し、溶解
した．その中にアルミニウム箔からなる陽極箔と陰極箔
をセパレー夕を介して巻回した巻取コンデンサ素子を浸
漬し、浸漬後約１２秒で冷却した．なお、電解質の含浸
に先立ち、コンデンサ素子は１５０［”Ｃ］の温度まで
上昇させておいた．これにより、定格容Ｎ１．０［μＦ
］の陽極に対して容量１．０［μＦ］、損失３． １
［％］の固体電解コンデンサを得た。After that, N-
Needle-shaped crystals of methyl-1-methylindole TCNQ complex salt are obtained. The crystals are washed with a small amount of acetonitrile, then with methanol until the washing solution is no longer colored, then washed with ether, dried, and applied to solid electrolytic capacitors. This N-methyl-1-methylindole T
The specific resistance value of the CNQ complex salt was 6.70 [Ωcm]. In this synthesis step, if ethyl iodide, proyl iodide, butyl iodide, etc. are used in place of methyl iodide, each N-ethyl-1-methylindole TC
NQ complex salt, N-n-probyl-l-methylindole TCNQ iron salt, N-n-butyl-l-methylindole T C N Qt! Obtain salt. [Example] Next, an example will be described in which the N-substituted-1-methylindole TCNQ complex salt obtained as described above was applied to an electrolytic capacitor. (Example 1) Dissolve N-methyl-1-methylindole TCNQI salt in acetonitrile to make a saturated solution. Next, the capacitor element is immersed in this solution, and then
C] to scatter the solvent acetonitrile. This operation was repeated three times. The capacitor element uses an aluminum foil whose surface is etched approximately 10 times as much as the electrode, and an oxide film is formed on the surface by chemical conversion treatment. After impregnating with electrolyte, apply coroiglu carbon, then apply silver paste, solder the lead wires, and package it to achieve a rated capacity of 1.0 [μ
F] with a capacity of 1.0 [μFl. Loss 3.9 [
%] solid electrolytic capacitor was obtained. Solid electrolytic capacitor (rated 25 [V] - 1.0 [μF]) (7
) Comparison of life characteristics is shown in Table 1. In Table 1, the capacitance value and the tangent of the loss angle are the values at a frequency of 120 [Hz]. Leakage current is the value measured 1 minute after applying the rated voltage (25 [V]). Next, other examples of the present invention will be described 9 (Example 2) Compound 40 of N-methyl-1-methylindole TCNQ complex salt and a lactone compound, such as γ-butyrolactone
[mg] was filled into an aluminum case with a diameter of 5.0 [mm], and heated to L50 ['C] in about 10 seconds to melt it. A wound capacitor element, in which an anode foil and a cathode foil made of aluminum foil were wound with a separator in between, was immersed in the solution, and cooled approximately 12 seconds after immersion. Furthermore, prior to impregnation with the electrolyte, the temperature of the capacitor element was raised to 150 ["C]. As a result, the rated capacity N1.0 [μF
] Capacity 1.0 [μF] and loss 3. 1
[%] solid electrolytic capacitor was obtained.
［効果］
以上にて述べた本発明に係るＮ一置換−１−メチルイン
ドールＴ Ｃ Ｎ Ｑ 錯塩は、熱安定性が高く、また
比抵抗値も小さい値の有機半導体を提供できるものであ
る，さらに、このＮ−置換−１−メチルインドールＴ
Ｃ Ｎ Ｑ ８Ｂ塩を固体電解コンテンサの電解質とし
て用いた場合，第１表から分かるように寿命特性が優れ
た固体電解コンデンサを提供できるものである．[Effect] The N-monosubstituted-1-methylindole T C N Q complex salt according to the present invention described above can provide an organic semiconductor with high thermal stability and a small specific resistance value. Furthermore, this N-substituted-1-methylindole T
When C N Q 8B salt is used as the electrolyte of a solid electrolytic capacitor, it is possible to provide a solid electrolytic capacitor with excellent life characteristics, as shown in Table 1.
Claims (1)
７，７，８，８−テトラシアノキノジメタン錯塩を用い
たことを特徴とする固体電解コンデンサ。(1) N-substituted-1-methylindole as an electrolyte
A solid electrolytic capacitor characterized by using a 7,7,8,8-tetracyanoquinodimethane complex salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11442789A JPH02292809A (en) | 1989-05-08 | 1989-05-08 | Solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11442789A JPH02292809A (en) | 1989-05-08 | 1989-05-08 | Solid electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02292809A true JPH02292809A (en) | 1990-12-04 |
Family
ID=14637446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11442789A Pending JPH02292809A (en) | 1989-05-08 | 1989-05-08 | Solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02292809A (en) |
-
1989
- 1989-05-08 JP JP11442789A patent/JPH02292809A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02292809A (en) | Solid electrolytic capacitor | |
| JPH02294009A (en) | Solid electrolytic capacitor | |
| JPH0553051B2 (en) | ||
| JPH02260410A (en) | Solid electrolytic capacitor | |
| JPH02224316A (en) | Manufacture of solid electrolytic capacitor | |
| JPH02235323A (en) | Solid electrolytic capacitor | |
| JPH01255209A (en) | Solid electrolytic capacitor | |
| JPH02235322A (en) | Solid electrolytic capacitor | |
| JPH02237010A (en) | Solid electrolytic capacitor | |
| JPH02235325A (en) | Solid electrolytic capacitor | |
| JPS63198313A (en) | Solid electrolytic capacitor | |
| JPH02235324A (en) | Solid electrolytic capacitor | |
| JPH02234409A (en) | Solid electrolytic capacitor | |
| JPH02291106A (en) | Solid electrolytic capacitor | |
| JPH01255208A (en) | Solid electrolytic capacitor | |
| JPH02239609A (en) | Solid electrolytic capacitor | |
| JPH02294010A (en) | Solid electrolytic capacitor | |
| JPH02260409A (en) | Solid electrolytic capacitor | |
| JPH02237009A (en) | Solid electrolytic capacitor | |
| JPH02241014A (en) | Solid electrolytic capacitor | |
| JPS63132417A (en) | Solid electrolytic capacitor | |
| JPS63239912A (en) | Solid electrolytic capacitor | |
| JPS63215034A (en) | Solid electrolytic capacitor | |
| JP3221889B2 (en) | Method for manufacturing solid electrolytic capacitor | |
| JPH02256219A (en) | Solid state electrolytic capacitor |