JPH1032147A - Electrolytic capacitor - Google Patents
Electrolytic capacitorInfo
- Publication number
- JPH1032147A JPH1032147A JP20100696A JP20100696A JPH1032147A JP H1032147 A JPH1032147 A JP H1032147A JP 20100696 A JP20100696 A JP 20100696A JP 20100696 A JP20100696 A JP 20100696A JP H1032147 A JPH1032147 A JP H1032147A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic capacitor
- weight
- driving electrolyte
- foil
- salt
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は基材表面に蒸着被膜
を形成してなる電極材を使用した電解コンデンサに関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic capacitor using an electrode material having a vapor-deposited film formed on a substrate surface.
【０００２】[0002]
【従来の技術】アルミニウムなどの弁作用金属の箔をセ
パレ−タと共に巻回してコンデンサ素子とした電解コン
デンサは、一般にコンデンサ素子に駆動用電解液を含浸
し、これをアルミニウムなどの金属ケ−スや合成樹脂製
のケ−スに収納し密閉した構造を有する。2. Description of the Related Art An electrolytic capacitor which is formed by winding a foil of a valve metal such as aluminum together with a separator to form a capacitor element is generally impregnated with a driving electrolytic solution in a capacitor element, which is then placed in a metal case such as aluminum. It is housed in a synthetic resin case and hermetically closed.
【０００３】電解コンデンサの静電容量を高めるため
に、電極材料の基材であるアルミニウム箔の表面積をエ
ッチングにより拡大することが行われているが、エッチ
ングが過度になるとアルミニウム箔表面の溶解が同時に
進行し却って拡面率の増大を妨げる。そこで基材である
アルミニウム箔の表面を粗面化した後に、この基材表面
に蒸着法により蒸着被膜を形成した電極材料を陰極とし
て使用することが知られている（特開昭６１−１８０４
２０号公報、特開昭６１−２１４４２０号公報、特開昭
６２−５８６０９号公報、特開昭６２−１５８１３号公
報、特開昭６４−３３９１８号公報、特開昭６３−１０
０７１１号公報および特開平１−３０４７２０号公
報）。[0003] In order to increase the capacitance of an electrolytic capacitor, the surface area of an aluminum foil, which is a base material of an electrode material, has been enlarged by etching. It progresses and hinders an increase in the area coverage. Therefore, it is known that after roughening the surface of an aluminum foil as a substrate, an electrode material having a vapor-deposited film formed on the surface of the substrate by a vapor deposition method is used as a cathode (Japanese Patent Laid-Open No. 61-1804).
No. 20, JP-A-61-214420, JP-A-62-58609, JP-A-62-15813, JP-A-64-33918, JP-A-63-10
0711 and JP-A-1-304720).
【０００４】また、蒸着方法について、蒸着角度をつけ
たり、基材を冷却しつつ蒸着することによりチタンを柱
状に形成させる方法なども知られている（特開昭５６−
２９６６９号公報、特開昭６４−３３９１５号公報およ
び特開昭６４−３３９１８号公報）。[0004] Further, as a vapor deposition method, there is also known a method in which titanium is formed in a columnar shape by forming a vapor deposition angle or performing vapor deposition while cooling a base material (Japanese Patent Application Laid-Open No. 56-1981).
29669, JP-A-64-33915 and JP-A-64-33918).
【０００５】これらの電解コンデンサの駆動用電解液と
しては、エチレングリコ−ルなどを溶媒とし、これに溶
質および水を添加してなる水系の駆動用電解液が一般に
使用されているAs a driving electrolyte for these electrolytic capacitors, an aqueous driving electrolyte obtained by adding a solute and water to ethylene glycol or the like as a solvent is generally used.
【０００６】一方、基材表面を粗面化すると基材の強
度、伸度を著しく損なうので基材の厚さを薄くできな
い。そこで実質的に平滑なアルミニウム基材に、柱状に
チタンを形成させたチタン被膜を有する箔を陰極とし、
アルミニウム陽極箔をセパレ−タを介して巻回してコン
デンサ素子とした電解コンデンサが知られ、ここでは駆
動用電解液として低水分の極性有機溶媒に第四級アルキ
ルアンモニウム塩を溶解した非水系の駆動用電解液が使
用されている（特開平４−３０５１０号公報）。On the other hand, if the surface of the substrate is roughened, the strength and elongation of the substrate are significantly impaired, so that the thickness of the substrate cannot be reduced. Therefore, a foil having a titanium coating in which titanium was formed in a columnar shape on a substantially smooth aluminum base material was used as a cathode,
There is known an electrolytic capacitor in which an aluminum anode foil is wound through a separator to provide a capacitor element. In this case, a non-aqueous drive in which a quaternary alkylammonium salt is dissolved in a low-moisture polar organic solvent as a drive electrolyte is known. Electrolyte is used (JP-A-4-30510).
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、蒸着被
膜を有した陰極箔を用いた電解コンデンサにおいて、水
系の駆動用電解液を用いた電解コンデンサでは、静電容
量の経時変化が大きいという欠点がある。また高温貯蔵
下での静電容量変化率は駆動用電解液として低水分の極
性有機溶媒に第四級アルキルアンモニウム塩を溶解した
駆動用電解液を用いることにより、ある程度改善される
がまだ満足すべきものではなかった。However, in an electrolytic capacitor using a cathode foil having a vapor-deposited film, an electrolytic capacitor using an aqueous driving electrolyte has a drawback that the capacitance changes greatly with time. . The rate of change in capacitance under high-temperature storage can be improved to some extent by using a driving electrolyte in which a quaternary alkylammonium salt is dissolved in a low-moisture polar organic solvent as the driving electrolyte. It was not a kimono.
【０００８】本発明は、蒸着被膜を有した陰極箔を用い
た電解コンデンサにおいて、静電容量の経時変化が少な
い電解コンデンサを提供することを目的としている。[0008] An object of the present invention is to provide an electrolytic capacitor using a cathode foil having a vapor-deposited film and having little change in capacitance with time.
【０００９】[0009]
【課題を解決するための手段】上述の目的を達成するた
めに、本発明の電解コンデンサでは、実質的に平滑なア
ルミニウム箔基材にチタン被膜が形成された陰極箔と、
アルミニウム陽極箔とをセパレ−タを介して巻回したコ
ンデンサ素子に、極性有機溶媒に、溶質として有機酸の
第三級アルキルアミン塩を溶解してなる、水分が０．１
〜８重量％の駆動用電解液を含浸して構成してなる。In order to achieve the above-mentioned object, in the electrolytic capacitor of the present invention, a cathode foil comprising a substantially smooth aluminum foil base material and a titanium film formed thereon is provided.
A tertiary alkylamine salt of an organic acid is dissolved as a solute in a polar organic solvent in a capacitor element in which an aluminum anode foil is wound through a separator.
-8% by weight of a driving electrolyte is impregnated.
【００１０】本発明において用いられる溶質である有機
酸の第三級アルキルアミン塩の有機酸としては、ｏ−フ
タル酸、マレイン酸、シトラコン酸が好ましく、また第
三級アルキルアミン塩としては、トリエチルアミン塩、
ジメチルエチルアミン塩が挙げられる。本発明における
有機酸の第三級アルキルアミン塩の具体例としては、例
えばｏ−フタル酸トリエチルアミン、ｏ−フタル酸ジメ
チルエチルアミン、マレイン酸トリエチルアミン、マレ
イン酸ジメチルエチルアミン、シトラコン酸トリエチル
アミン、シトラコン酸ジメチルエチルアミンが挙げられ
る。The organic acid of the tertiary alkylamine salt of an organic acid which is a solute used in the present invention is preferably o-phthalic acid, maleic acid or citraconic acid, and the tertiary alkylamine salt is triethylamine. salt,
Dimethylethylamine salt is exemplified. Specific examples of the tertiary alkylamine salt of an organic acid in the present invention include, for example, triethylamine o-phthalate, dimethylethylamine o-phthalate, triethylamine maleate, dimethylethylamine maleate, triethylamine citraconic acid, dimethylethylamine citraconic acid. No.
【００１１】本発明で用いられる第三級アルキルアミン
塩の駆動用電解液組成中における含有量（濃度）は、適
宜選ぶことができるが、飽和溶液の状態のときに比抵抗
が最も小さい点を考慮すると１〜５０重量％が適当であ
り、なかでも良好な高温安定性を得るためには５〜４０
重量％が好適である。The content (concentration) of the tertiary alkylamine salt used in the present invention in the composition of the driving electrolyte can be appropriately selected. In consideration of the above, 1 to 50% by weight is appropriate.
% By weight is preferred.
【００１２】本発明で用いる極性有機溶媒としては、γ
−ブチロラクトン、アセトニトリルが好ましい。The polar organic solvent used in the present invention includes γ
-Butyrolactone, acetonitrile is preferred.
【００１３】また駆動用電解液組成中の水分は０．１〜
８重量％、好ましくは０．１〜５重量％であるのが好適
である。水分が８重量％を超えると静電容量の経時変化
が大きくなる。The water content in the composition of the driving electrolyte is 0.1 to
Suitably it is 8% by weight, preferably 0.1-5% by weight. If the water content exceeds 8% by weight, the change with time of the capacitance becomes large.
【００１４】本発明で用いられるコンデンサ素子の陰極
箔としては５〜４０μｍの厚さの実質的に平滑なアルミ
ニウム箔が基材として使用されるが、特に７〜３０μｍ
の厚さのものが好適に使用される。アルミニウム基材へ
のチタンの被膜形成方法としては、抵抗加熱蒸着法、ス
パッタリング法、イオンプレ−ティング法、ＣＶＤ法な
どを例示することができる。また真空中または酸素ガ
ス、水素ガス、不活性ガスなどの雰囲気中で０．０５〜
０．３μｍの柱状物の集合体からなるように形成するの
が好ましい。As the cathode foil of the capacitor element used in the present invention, a substantially smooth aluminum foil having a thickness of 5 to 40 .mu.m is used as a base material.
Is preferably used. Examples of a method for forming a titanium film on an aluminum substrate include a resistance heating evaporation method, a sputtering method, an ion plating method, and a CVD method. In addition, in a vacuum or in an atmosphere of oxygen gas, hydrogen gas, inert gas, etc.
It is preferable to form it so as to be composed of an aggregate of 0.3 μm pillars.
【００１５】[0015]
【００１６】＜実施例１＞ 陰極箔の厚さ ： ２０μｍ チタン被膜の厚さ： ０．２μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ７８重量％ 溶質：ｏ−フタル酸トリエチルアミン ２０重量％ 水分 ２重量％Example 1 Thickness of cathode foil: 20 μm Thickness of titanium film: 0.2 μm Composition of driving electrolyte Solvent: 78% by weight of γ-butyrolactone Solute: 20% by weight of triethylamine o-phthalate Water 2 weight%
【００１７】＜実施例２＞ 陰極箔の厚さ ： １２μｍ チタン被膜の厚さ： ０．１μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ８４重量％ 溶質：シチラコン酸トリエチルアミン １５重量％ 水分 １重量％Example 2 Thickness of cathode foil: 12 μm Thickness of titanium film: 0.1 μm Composition of driving electrolyte Solvent: 84% by weight of γ-butyrolactone Solute: 15% by weight of triethylamine citraconic acid 1% by weight of water
【００１８】＜実施例３＞ 陰極箔の厚さ ： １２μｍ チタン被膜の厚さ： ０．１μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ７９重量％ 溶質：ｏ−フタル酸ジメチルエチルアミン ２０重量％ 水分 １重量％Example 3 Thickness of cathode foil: 12 μm Thickness of titanium coating: 0.1 μm Composition of driving electrolyte Solvent: 79% by weight of γ-butyrolactone Solute: 20% by weight of dimethylethylamine o-phthalate Moisture 1% by weight
【００１９】＜実施例４＞ 陰極箔の厚さ ： １２μｍ チタン被膜の厚さ： ０．１μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ８９重量％ 溶質：マレイン酸トリエチルアミン １０重量％ 水分 １重量％Example 4 Thickness of cathode foil: 12 μm Thickness of titanium coating: 0.1 μm Composition of driving electrolyte Solvent: 89% by weight of γ-butyrolactone Solute: Triethylamine maleate 10% by weight Water 1% by weight
【００２０】＜比較例１＞ 陰極箔の厚さ ： ２０μｍ チタン被膜の厚さ： ０．２μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ７４重量％ 溶質：ｏ−フタル酸テトラエチルアミン ２５重量％ 水分 １重量％Comparative Example 1 Thickness of cathode foil: 20 μm Thickness of titanium coating: 0.2 μm Composition of driving electrolyte Solvent: 74% by weight of γ-butyrolactone Solute: 25% by weight of tetraethylamine o-phthalate Moisture 1% by weight
【００２１】＜比較例２＞ 陰極箔の厚さ ： １２μｍ チタン被膜の厚さ： ０．１μｍ 駆動用電解液の組成 溶媒：エチレングリコ−ル ８０重量％ 溶質：アジピン酸アンモニウム １０重量％ 水分 １０重量％<Comparative Example 2> Thickness of cathode foil: 12 μm Thickness of titanium film: 0.1 μm Composition of driving electrolyte Solvent: 80% by weight ethylene glycol Solute: 10% by weight ammonium adipate Water 10% by weight %
【００２２】＜比較例３＞ 陰極箔の厚さ ： １２μｍ チタン被膜の厚さ： ０．１μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ６５重量％ 溶質：ｏ−フタル酸テトラエチルアンモニウム塩 ２５重量％ 水分 １０重量％Comparative Example 3 Cathode foil thickness: 12 μm Titanium coating thickness: 0.1 μm Composition of driving electrolyte Solvent: γ-butyrolactone 65% by weight Solute: o-phthalic acid tetraethylammonium salt 25% by weight Water 10% by weight
【００２３】なお上記各陰極箔は平滑なアルミニウム基
材からなり、その表面に蒸着角度を付けて、柱状にチタ
ンの蒸着被膜が形成されている。これら各陰極箔に、陽
極酸化被膜が形成された厚さ９０μｍの陽極箔とともに
セパレ−タを介して巻回してコンデンサ素子をそれぞれ
製作した。これに上記各駆動用電解液を含浸させて、定
格２５Ｖ、３３００μＦの電解コンデンサを製作した。Each of the above-mentioned cathode foils is made of a smooth aluminum base material, and a titanium vapor deposition coating is formed in a column shape on the surface thereof at a vapor deposition angle. A capacitor element was manufactured by winding each of these cathode foils together with a 90 μm thick anode foil having an anodic oxide film formed thereon through a separator. This was impregnated with each of the above-mentioned driving electrolytes to produce an electrolytic capacitor rated at 25 V and 3300 μF.
【００２４】これら実施例１〜４および比較例１〜３の
各電解コンデンサの静電容量を常温下で測った後、１０
５℃で５００時間無負荷状態で貯蔵した後での静電容量
を測って、その変化率（％）を測定した。その結果を表
１に示す。After measuring the capacitance of each of the electrolytic capacitors of Examples 1-4 and Comparative Examples 1-3 at room temperature, 10
The capacitance after storage at 5 ° C. for 500 hours under no load was measured, and the rate of change (%) was measured. Table 1 shows the results.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１から第三級アルキルアミン塩を溶質と
する水分が少ない実施例１〜４の電解コンデンサは、第
四級アンモニウム塩と水分の少ない組合せ、あるいはア
ンモニウム塩および第四級アンモニウム塩と水分の多い
組合せの比較例１〜３の電解コンデンサに比較して静電
容量変化率が小さいことがわかる。As can be seen from Table 1, the electrolytic capacitors of Examples 1 to 4 containing a tertiary alkylamine salt as a solute and having a low water content are a combination of a quaternary ammonium salt and a low water content, or a combination of an ammonium salt and a quaternary ammonium salt. It can be seen that the rate of change in capacitance is smaller than that of the electrolytic capacitors of Comparative Examples 1 to 3 in which the combination is high in moisture.
【００２７】[0027]
【発明の効果】本発明では、蒸着被膜を有した陰極箔を
用いた電解コンデンサにおいて、静電容量の経時変化が
少ない電解コンデンサを得ることができる。According to the present invention, in an electrolytic capacitor using a cathode foil having a vapor-deposited film, it is possible to obtain an electrolytic capacitor having a small change in capacitance with time.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年９月３日[Submission date] September 3, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２０】＜比較例１＞ 陰極箔の厚さ ： ２０μｍ チタン被膜の厚さ： ０．２μｍ 駆動用電解液の組成 溶媒：γ−ブチロラクトン ７４重量％ 溶質：ｏ−フタル酸テトラエチルアンモニウム塩 ２５重量％ 水分 １重量％Comparative Example 1 Thickness of cathode foil: 20 μm Thickness of titanium film: 0.2 μm Composition of driving electrolyte Solvent: 74% by weight of γ-butyrolactone Solute: 25% by weight of tetraethylammonium o-phthalate Water 1% by weight
Claims (6)
ン被膜が形成された陰極箔と、アルミニウム陽極箔とを
セパレ−タを介して巻回したコンデンサ素子に、極性有
機溶媒に、溶質として有機酸の第三級アルキルアミン塩
を溶解してなる、水分が０．１〜８重量％の駆動用電解
液を含浸して構成してなる電解コンデンサ。1. A capacitor element in which a cathode foil in which a titanium film is formed on a substantially smooth aluminum foil base material and an aluminum anode foil are wound through a separator, in a polar organic solvent, as a solute. An electrolytic capacitor comprising a tertiary alkylamine salt of an organic acid dissolved therein and impregnated with a driving electrolyte having a water content of 0.1 to 8% by weight.
が７〜３０μｍであり、チタン被膜が０．０５〜０．３
μｍの柱状物の集合体からなる請求項１に記載の電解コ
ンデンサ。2. A substantially smooth aluminum foil substrate having a thickness of 7 to 30 μm and a titanium coating of 0.05 to 0.3 μm.
The electrolytic capacitor according to claim 1, comprising an aggregate of μm columns.
アミン塩を溶解してなる、水分が０．１〜５重量％の駆
動用電解液を使用した請求項１または２に記載の電解コ
ンデンサ。3. A driving electrolyte according to claim 1, wherein a tertiary alkylamine salt of an organic acid is dissolved in a polar organic solvent, and the driving electrolyte has a water content of 0.1 to 5% by weight. Electrolytic capacitor.
アセトニトリルの少なくとも一種を用いた請求項１、２
または３に記載の電解コンデンサ。4. A γ-butyrolactone as a polar organic solvent,
3. The method according to claim 1, wherein at least one of acetonitrile is used.
Or the electrolytic capacitor according to 3.
フタル酸、マレイン酸、シトラコン酸のうちの少なくと
も一種の第三級アルキルアミン塩である請求項１〜４の
何れか一つに記載の電解コンデンサ。5. The method of claim 1, wherein the tertiary alkylamine salt of the organic acid is o-
The electrolytic capacitor according to any one of claims 1 to 4, wherein the electrolytic capacitor is at least one tertiary alkylamine salt of phthalic acid, maleic acid, and citraconic acid.
ン塩またはジメチルエチルアミン塩である請求項５に記
載の電解コンデンサ。6. The electrolytic capacitor according to claim 5, wherein the tertiary alkylamine salt is a triethylamine salt or a dimethylethylamine salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20100696A JPH1032147A (en) | 1996-07-12 | 1996-07-12 | Electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20100696A JPH1032147A (en) | 1996-07-12 | 1996-07-12 | Electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1032147A true JPH1032147A (en) | 1998-02-03 |
Family
ID=16433939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20100696A Pending JPH1032147A (en) | 1996-07-12 | 1996-07-12 | Electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1032147A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004040605A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| CN100466122C (en) * | 2002-10-31 | 2009-03-04 | 三菱化学株式会社 | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| US9256203B2 (en) | 2010-10-22 | 2016-02-09 | Samsung Electronics Co., Ltd. | Surface light source device for recording/reproducing holograms |
-
1996
- 1996-07-12 JP JP20100696A patent/JPH1032147A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004040605A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| US7227738B2 (en) | 2002-10-31 | 2007-06-05 | Mitsubishi Chemical Corporation | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| US7295424B2 (en) | 2002-10-31 | 2007-11-13 | Mitsubishi Chemical Corporation | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| US7397651B2 (en) | 2002-10-31 | 2008-07-08 | Mitsubishi Chemical Corporation | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| CN100466122C (en) * | 2002-10-31 | 2009-03-04 | 三菱化学株式会社 | Electrolyte for electrolytic capacitor, electrolytic capacitor and process for producing tetrafluoroaluminate salt of organic onium |
| US9256203B2 (en) | 2010-10-22 | 2016-02-09 | Samsung Electronics Co., Ltd. | Surface light source device for recording/reproducing holograms |
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