JP2003068577A - Solid electrolytic capacitor and manufacturing method therefor - Google Patents
Solid electrolytic capacitor and manufacturing method thereforInfo
- Publication number
- JP2003068577A JP2003068577A JP2001255117A JP2001255117A JP2003068577A JP 2003068577 A JP2003068577 A JP 2003068577A JP 2001255117 A JP2001255117 A JP 2001255117A JP 2001255117 A JP2001255117 A JP 2001255117A JP 2003068577 A JP2003068577 A JP 2003068577A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic capacitor
- solid electrolytic
- conductive polymer
- polymer layer
- capacitor element
- 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.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 81
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 229920001940 conductive polymer Polymers 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 15
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical group 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 150000003577 thiophenes Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract description 9
- -1 Ions sulfate Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 11
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は固体電解コンデン
サおよびその製造方法に関するもので、特に固体電解質
として導電性高分子を用いた固体電解コンデンサおよび
その製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolytic capacitor and a manufacturing method thereof, and more particularly to a solid electrolytic capacitor using a conductive polymer as a solid electrolyte and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】電解コンデンサは、アルミニウム等から
なる陽極箔と陰極箔をセパレータを介して巻回してなる
コンデンサ素子に、電解液を含浸または固体電解質を保
持してなるいわゆる巻回型の電解コンデンサや、タンタ
ル微粉末を焼結してなるコンデンサ素子の表面に固体電
解質層を形成してなる焼結型の電解コンデンサが知られ
ている。2. Description of the Related Art An electrolytic capacitor is a so-called wound type electrolytic capacitor in which an electrolytic solution is impregnated or a solid electrolyte is held in a capacitor element formed by winding an anode foil and a cathode foil made of aluminum or the like through a separator. There is also known a sintered electrolytic capacitor in which a solid electrolyte layer is formed on the surface of a capacitor element obtained by sintering fine powder of tantalum.
【０００３】このような電解コンデンサに用いられる固
体電解質としては、近年、低ＥＳＲ化を目的として導電
性高分子が着目され、導電性高分子を固体電解質として
用いる固体電解コンデンサが実用化されている。一般
に、これら導電性高分子としては、ポリチオフェン、ポ
リピロール又はポリアニリン等があり、中でもポリチオ
フェンは、ポリピロール又はポリアニリンと比較して、
導電率が高く熱安定性が特に優れていることから近年注
目されており、ポリチオフェンを固体電解質として用い
た固体電解コンデンサとして特開平２−１５６１１号公
報等に開示されているものがある。As a solid electrolyte used in such an electrolytic capacitor, a conductive polymer has recently attracted attention for the purpose of lowering ESR, and a solid electrolytic capacitor using a conductive polymer as a solid electrolyte has been put into practical use. . Generally, these conductive polymers include polythiophene, polypyrrole, polyaniline, etc. Among them, polythiophene is compared to polypyrrole or polyaniline,
Since it has a high electrical conductivity and is particularly excellent in thermal stability, it has been attracting attention in recent years, and there is a solid electrolytic capacitor using polythiophene as a solid electrolyte, which is disclosed in JP-A-2-15611.
【０００４】しかして、ポリチオフェンは、化学酸化重
合及び電解重合によって製作できるが、電解重合手段を
講じた場合、一個に数点の重合用電極を取り付けること
が必要であることと、導電性高分子が電極上にフィルム
状に形成されるため大量に製造することに困難性が伴う
問題を抱えているのに対して、化学酸化重合手段の場合
は、そのような問題はなく、電解重合と比較して大量の
導電性高分子層を容易に得ることができることは当業者
の中では良く知られている。Polythiophene can be produced by chemical oxidative polymerization and electrolytic polymerization. However, when electrolytic polymerization means is adopted, it is necessary to attach several polymerization electrodes to one, and the conductive polymer. Since it is formed as a film on the electrode, it has a problem that it is difficult to manufacture in large quantities, whereas in the case of the chemical oxidative polymerization means, there is no such problem, and it is compared with electrolytic polymerization. It is well known to those skilled in the art that a large amount of conductive polymer layers can be easily obtained.
【０００５】化学酸化重合を行う場合の酸化剤として
は、アルカリ金属、アンモニウム等の過硫酸塩、若しく
は、Ｆｅ3+、Ｃｕ3+、Ｃｒ6+、Ｃｅ4+、Ｒｕ3+およびＭ
ｎ7+等の遷移金属の塩が用いられるが、安全な溶媒とし
て水が使用される場合、過硫酸アンモニウムを酸化剤と
して用いることが多い。As the oxidizer for the chemical oxidative polymerization, alkali metal, persulfate such as ammonium, or Fe 3+ , Cu 3+ , Cr 6+ , Ce 4+ , Ru 3+ and M are used.
Salts of transition metals such as n 7+ are used, but when water is used as a safe solvent, ammonium persulfate is often used as an oxidant.
【０００６】また、焼結素体をコンデンサ素子として用
いる場合には、素体表面が平滑なため付着力が低く、形
成した導電性高分子層が剥離するおそれがある。このた
めには導電性高分子が面状よりも粒子状に成長する酸化
剤が好適であり、このような酸化剤としては過硫酸塩の
水溶液からなる酸化剤が知られている。When a sintered element is used as a capacitor element, the surface of the element is smooth, so that the adhesion is low and the formed conductive polymer layer may peel off. For this purpose, an oxidizing agent that allows the conductive polymer to grow in a particle shape rather than a planar shape is suitable, and as such an oxidizing agent, an oxidizing agent composed of an aqueous solution of persulfate is known.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、酸化剤
として過硫酸塩を用いた場合には、導電性高分子層内に
ドーパントとして硫酸イオンが取り込まれ、電導度を向
上させるために好適であるが、導電性高分子層内の硫酸
イオンは吸湿して硫酸となる、あるいは導電性高分子を
脱水、又は酸化劣化させるという性質を有するために、
導電性高分子層内の硫酸イオンが過剰となると、固体電
解コンデンサの信頼性を低下させるという問題がある。However, when a persulfate is used as the oxidizing agent, sulfate ions are incorporated as a dopant in the conductive polymer layer, which is suitable for improving the conductivity. The sulfate ion in the conductive polymer layer absorbs moisture to form sulfuric acid, or has a property of dehydrating or oxidatively degrading the conductive polymer.
If the sulfate ion in the conductive polymer layer becomes excessive, there is a problem that the reliability of the solid electrolytic capacitor is lowered.
【０００８】[0008]
【課題を解決するための手段】本発明は、上記従来技術
の課題を解決すべく検討した結果、完成するに至ったも
のである。すなわち、陽極となる弁作用金属基体の表面
に誘電体酸化皮膜を形成してなるコンデンサ素子に重合
性モノマーと酸化剤を含浸し、前記誘電体酸化皮膜の表
面に導電性高分子層を形成してなる固体電解コンデンサ
において、前記導電性高分子層内に硫酸イオンを０．５
〜２重量％含有させたことを特徴とする。The present invention has been completed as a result of studies to solve the above-mentioned problems of the prior art. That is, a capacitor element formed by forming a dielectric oxide film on the surface of a valve action metal substrate serving as an anode is impregnated with a polymerizable monomer and an oxidizing agent, and a conductive polymer layer is formed on the surface of the dielectric oxide film. The solid electrolytic capacitor having
.About.2% by weight.
【０００９】導電性高分子層に含まれる硫酸イオンを
０．５〜２重量％の範囲とすることで、ドーパントとし
ての機能を充分に発揮して高電導度を維持することがで
きるとともに、硫酸イオンを過剰に含まないために導電
性高分子の化学変化を抑制し、信頼性の高い固体電解コ
ンデンサを提供できるものであるWhen the sulfate ion contained in the conductive polymer layer is in the range of 0.5 to 2% by weight, the function as a dopant can be sufficiently exhibited, and high conductivity can be maintained. Since it does not contain excess ions, it suppresses chemical changes in the conductive polymer and can provide a highly reliable solid electrolytic capacitor.
【００１０】また、本願発明は、陽極となる弁作用金属
基体の表面に誘電体酸化皮膜を形成したコンデンサ素子
に重合性モノマーと酸化剤を含浸し、前記誘電体酸化皮
膜の表面に導電性高分子層を形成してなる固体電解コン
デンサの製造方法において、前記コンデンサ素子内に導
電性高分子層を形成した後、前記コンデンサ素子を流水
洗浄または電解洗浄を行い、前記硫酸イオン量を０．５
〜２重量％の範囲に制御することを特徴とする。Further, according to the present invention, a capacitor element in which a dielectric oxide film is formed on the surface of a valve action metal substrate serving as an anode is impregnated with a polymerizable monomer and an oxidizer, and the surface of the dielectric oxide film has high conductivity. In the method for producing a solid electrolytic capacitor having a molecular layer, a conductive polymer layer is formed in the capacitor element, and then the capacitor element is washed with running water or electrolytically to reduce the amount of sulfate ion to 0.5.
It is characterized in that it is controlled in the range of 2 wt%.
【００１１】本発明は、前記導電性高分子層の硫酸イオ
ンの含有量を、前記コンデンサ素子内に導電性高分子層
を形成した後、前記コンデンサ素子を流水洗浄または電
解洗浄の手段によって前記硫酸イオン量を容易に制御す
ることができる。According to the present invention, the content of sulfate ion in the conductive polymer layer is adjusted to the sulfuric acid by means of washing with running water or electrolytic cleaning of the capacitor element after forming the conductive polymer layer in the capacitor element. The amount of ions can be easily controlled.
【００１２】前記重合性モノマーがチオフェン又はその
誘導体からなるモノマーであり、前記酸化剤が過硫酸イ
オンを含む塩を酸化剤とすると好適である。It is preferable that the polymerizable monomer is a monomer composed of thiophene or a derivative thereof, and the oxidizing agent is a salt containing a persulfate ion.
【００１３】チオフェンの誘導体としては次に掲げる構
造のものを例示できる。チオフェン又はその誘導体は、
ポリピロール又はポリアニリンと比較して、導電率が高
いとともに熱安定性が特に優れているため、低ＥＳＲで
耐熱特性に優れた固体電解コンデンサを得ることができ
る。また、弁作用金属の微粉末を焼結させた焼結体をコ
ンデンサ素子として用いる固体電解コンデンサにおいて
は、導電性高分子が面状よりも粒子状に成長する酸化剤
が好ましく、このような酸化剤としては過硫酸イオンを
含む塩が好適である。Examples of the thiophene derivative include those having the following structures. Thiophene or its derivative is
As compared with polypyrrole or polyaniline, the solid electrolytic capacitor has a high electric conductivity and particularly excellent thermal stability, and thus a solid electrolytic capacitor having low ESR and excellent heat resistance can be obtained. Further, in a solid electrolytic capacitor using a sintered body obtained by sintering a fine powder of a valve metal as a capacitor element, an oxidizer in which a conductive polymer grows in a particle shape rather than a planar shape is preferable. A salt containing a persulfate ion is preferable as the agent.
【００１４】過硫酸イオンを含む塩を酸化剤として用い
るには、過硫酸イオンを含む塩と硫酸を水に溶解した水
溶液を用いると好ましい。溶媒として水を用いると、引
火のおそれがなく、また、有機溶媒を用いた場合のよう
な安全衛生上の問題もなく、取り扱いやすいという利点
がある。硫酸を加える理由としては、モノマーの酸化重
合にはプロトンが必要であるが、酸を添加することによ
りプロトン供給源となり、酸化重合を促進することがで
きる。また、過硫酸イオンを酸化剤として用いた場合、
過硫酸は分解し硫酸を生成することがあるが、酸化剤水
溶液に添加する酸を硫酸とすると、同種の酸であるた
め、反応系が複雑になることがなく、好適である。In order to use the salt containing persulfate ion as the oxidizing agent, it is preferable to use an aqueous solution in which the salt containing persulfate ion and sulfuric acid are dissolved in water. When water is used as the solvent, there is an advantage that there is no risk of ignition, there is no safety and health problem as in the case of using an organic solvent, and the handling is easy. As a reason for adding sulfuric acid, a proton is necessary for the oxidative polymerization of the monomer, but the addition of an acid serves as a proton supply source and can accelerate the oxidative polymerization. When persulfate ion is used as an oxidant,
Persulfuric acid may be decomposed to generate sulfuric acid, but it is preferable to use sulfuric acid as the acid to be added to the aqueous oxidant solution, because it is the same kind of acid and the reaction system does not become complicated.
【００１５】[0015]
【化１】
ＸはＯまたはＳ
ＸがＯのとき、Ａはアルキレン、又はポリオキシアルキ
レン
Ｘの少なくとも一方がＳのとき、Ａはアルキレン、ポリ
オキシアルキレン、置換アルキレン、置換ポリオキシア
ルキレン：ここで、置換基はアルキル基、アルケニル
基、アルコキシ基[Chemical 1] X is O or S When X is O, A is alkylene, or polyoxyalkylene When at least one of X is S, A is alkylene, polyoxyalkylene, substituted alkylene, substituted polyoxyalkylene: where the substituent is Alkyl group, alkenyl group, alkoxy group
【００１６】チオフェンの誘導体の中でも、３，４−エ
チレンジオキシチオフェンを用いると好適である。Among the derivatives of thiophene, it is preferable to use 3,4-ethylenedioxythiophene.
【００１７】３，４−エチレンジオキシチオフェンは、
酸化剤と接触することで、緩やかな重合反応によってポ
リ−（３，４−エチレンジオキシチオフェン）を生成す
るため、３，４−エチレンジオキシチオフェンのモノマ
ー溶液を微細な構造を有するコンデンサ素子の内部にま
で浸透した状態で重合させることができる。この結果、
コンデンサ素子の内部にまで導電性高分子層を形成する
ことができるようになり、固体電解コンデンサの静電容
量の増大を図ることができる。3,4-ethylenedioxythiophene is
Upon contact with an oxidant, poly- (3,4-ethylenedioxythiophene) is generated by a gradual polymerization reaction, so that a monomer solution of 3,4-ethylenedioxythiophene is used in a capacitor element having a fine structure. It is possible to polymerize while penetrating to the inside. As a result,
The conductive polymer layer can be formed even inside the capacitor element, and the capacitance of the solid electrolytic capacitor can be increased.
【００１８】[0018]
【発明の実施の形態】次にこの発明の実施の形態につい
てより詳細に説明する。図１は固体電解コンデンサの内
部構造を示す断面図である。１はコンデンサ素子であ
り、タンタル微粉末を所定形状に成型するとともに、タ
ンタル線等の陽極導出線を埋設して、さらに焼結してタ
ンタル焼結体を得、さらにリン酸水溶液等に浸漬し、所
定電圧を印加してタンタル微粉末の表面に誘電体となる
陽極酸化皮膜を形成したものである。なお、焼結体はタ
ンタルに限らず、アルミニウム、ニオブ、チタン等の弁
作用金属を用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in more detail. FIG. 1 is a sectional view showing the internal structure of a solid electrolytic capacitor. Reference numeral 1 is a capacitor element, which is formed by molding fine tantalum powder into a predetermined shape, embedding an anode lead wire such as tantalum wire, and further sintering to obtain a tantalum sintered body, which is further dipped in a phosphoric acid aqueous solution or the like. A predetermined voltage is applied to form an anodized film as a dielectric on the surface of the tantalum fine powder. The sintered body is not limited to tantalum, and valve metal such as aluminum, niobium, or titanium can be used.
【００１９】２は陽極酸化皮膜の上に形成された導電性
高分子層である。導電性高分子層は、３，４−エチレン
ジオキシチオフェンを所定溶媒で希釈したモノマー溶液
にコンデンサ素子を浸漬し、さらに硫酸イオンを含む酸
化剤溶液に浸漬する工程を繰り返すことにより、３，４
−エチレンジオキシチオフェンを酸化重合して形成す
る。Reference numeral 2 is a conductive polymer layer formed on the anodized film. The conductive polymer layer is prepared by repeating the steps of immersing the capacitor element in a monomer solution prepared by diluting 3,4-ethylenedioxythiophene with a predetermined solvent, and further immersing the capacitor element in an oxidizing agent solution containing sulfate ions.
-Formed by oxidative polymerization of ethylenedioxythiophene.
【００２０】導電性高分子層が形成されたコンデンサ素
子は、アンモニア水あるいは炭酸アンモニウム希薄水溶
液に浸漬し、逆電を印加することで電解洗浄し、導電性
高分子中に含まれる硫酸イオンを除去することができ
る。その後、コンデンサ素子を乾燥する。アンモニア水
あるいは炭酸アンモニウム水溶液はこの乾燥工程で、溶
媒・溶質ともに揮発するため、水洗等をすることなく不
純物を除去することができる。The capacitor element on which the conductive polymer layer is formed is immersed in aqueous ammonia or a dilute aqueous solution of ammonium carbonate and electrolytically cleaned by applying a reverse voltage to remove sulfate ions contained in the conductive polymer. can do. Then, the capacitor element is dried. Ammonia water or ammonium carbonate aqueous solution volatilizes both the solvent and the solute in this drying step, so that impurities can be removed without washing with water.
【００２１】３は導電性高分子層２の上に形成されたカ
ーボン層であり、４は、カーボン層の上に形成された銀
ペースト層である。Reference numeral 3 is a carbon layer formed on the conductive polymer layer 2, and 4 is a silver paste layer formed on the carbon layer.
【００２２】５は陽極リード線であり、コンデンサ素子
の陽極導出線と溶接され、外部と電気的に連絡する。６
は陰極リード線であり、銀ペースト層によって接続さ
れ、外部と電気的に連絡する。Reference numeral 5 denotes an anode lead wire, which is welded to the anode lead wire of the capacitor element and electrically connected to the outside. 6
Is a cathode lead wire, which is connected by a silver paste layer and is in electrical communication with the outside.
【００２３】そして、陽極リード線および陰極リード線
は表面実装が可能となるよう後述する外装樹脂に端面に
沿って折り曲げられる。Then, the anode lead wire and the cathode lead wire are bent along the end faces of the exterior resin, which will be described later, so that they can be surface-mounted.
【００２４】７は外装樹脂であり、コンデンサ素子を陽
極リード線及び陰極リード線の一部を除き、トランスフ
ァーモールドによって樹脂被覆することによって形成さ
れる。Reference numeral 7 denotes an exterior resin, which is formed by coating the capacitor element with transfer molding except for a part of the anode lead wire and the cathode lead wire.
【００２５】[0025]
【実施例】次に具体的な実施例について比較例と対比し
て詳細に説明する。
（参考例１）陽極として大きさが３．９×３．３×１．
６ｍｍ3のタンタル焼結体を用い、陽極線としてタンタ
ル線を用いた重量が約１００ｍｇの陽極体を０．０５重
量％燐酸水溶液中で９０℃、４０Ｖで１８０分陽極酸化
し、脱イオン水の流水により洗浄して、乾燥を行いコン
デンサ素子とした。なお、この状態をコンデンサと見立
て化成液中の静電容量を測定した結果１０４μＦであっ
た。EXAMPLES Next, specific examples will be described in detail in comparison with comparative examples. (Reference Example 1) The size of the anode was 3.9 × 3.3 × 1.
Using a 6 mm 3 tantalum sintered body and using a tantalum wire as an anode wire, an anode body having a weight of about 100 mg was anodized in a 0.05 wt% phosphoric acid aqueous solution at 90 ° C. and 40 V for 180 minutes, and deionized water was used. It was washed with running water and dried to obtain a capacitor element. The state was regarded as a capacitor and the electrostatic capacity in the chemical conversion liquid was measured and the result was 104 μF.
【００２６】次に、このコンデンサ素子をブチルアルコ
ール５０ｇと３，４−エチレンジオキシチオフェン５０
ｇとを混ぜ合わせてなるモノマー溶液に３０秒間浸漬
し、次に過硫酸イオンを含む酸化剤として過硫酸アンモ
ニウム４０ｇと硫酸４ｇを１００ｇの純水に溶解させて
得た酸化剤溶液に９０分間浸漬し、化学酸化重合を行
い、コンデンサ素子を構成する陽極酸化皮膜上に導電性
高分子層を形成し、脱イオン水の流水２５０ｍｌ／分に
よる流水洗浄、並びに３Ｖの逆電印加の電解洗浄とを５
分から６０分間行った後、１０５℃で５分間乾燥した。
次いで、前記コンデンサ素子を０．４％の燐酸水溶液中
で６０℃、２０Ｖで３０分再化成し、脱イオン水の流水
により洗浄して乾爆を行った。その後前記高分子層が所
望の厚さになるまで、モノマー溶液への浸漬−乾燥まで
の重合回数を５回繰り返した。Next, 50 g of butyl alcohol and 50 g of 3,4-ethylenedioxythiophene were added to this capacitor element.
g for 30 seconds, then 40 g of ammonium persulfate as an oxidizing agent containing persulfate ion and 4 g of sulfuric acid in 100 g of pure water for 90 minutes. , Conducting chemical oxidative polymerization to form a conductive polymer layer on the anodic oxide film constituting the capacitor element, and washing with running water of 250 ml / min of deionized water and electrolytic cleaning by applying a reverse voltage of 3V.
After 60 minutes from the minute, it was dried at 105 ° C. for 5 minutes.
Then, the capacitor element was re-formed in a 0.4% phosphoric acid aqueous solution at 60 ° C. and 20 V for 30 minutes, washed with running deionized water, and dried and bombed. Thereafter, the number of times of polymerization from dipping in a monomer solution to drying was repeated 5 times until the polymer layer had a desired thickness.
【００２７】このコンデンサ素子３０個の導電性高分子
層の形成前後の重量から導電性高分子量を求めておき、
前記重合終了後、当該コンデンサ素子を純水中加熱して
硫酸を抽出し、イオンクロマトで定量し、導電性高分子
層中の硫酸イオン含有量を求めた（図２）。The amount of the conductive polymer is obtained from the weights of the 30 conductive polymer layers before and after the formation of the conductive polymer layer.
After the completion of the polymerization, the capacitor element was heated in pure water to extract sulfuric acid, which was quantified by ion chromatography to determine the sulfate ion content in the conductive polymer layer (Fig. 2).
【００２８】次に、この洗浄を施したコンデンサ素子の
導電性高分子層の上に、カーボン層、このカーボン層の
上に陰極となる銀塗料層を形成し、この銀塗料層の上に
陰極引出端子を、前記陽極体から引出した陽極線に陽極
引出端子をそれぞれ取付け、トランスファーモールドに
より樹脂外装を行い、前記陰極引出端子及び陽極引出端
子を所定の位置に折曲げてチップ型固体電解コンデンサ
を完成した。当該コンデンサは、初期特性を測定され、
１５０℃の環境で定格電圧を印加する信頼性試験で評価
された。Next, a carbon layer is formed on the conductive polymer layer of the washed capacitor element, and a silver paint layer serving as a cathode is formed on the carbon layer, and the cathode is formed on the silver paint layer. Attach the lead-out terminal to the anode wire drawn out from the anode body, and coat the anode lead-out terminal with resin by transfer molding, and bend the cathode lead-out terminal and the anode lead-out terminal to predetermined positions to form a chip-type solid electrolytic capacitor. completed. The capacitor has its initial characteristics measured,
It was evaluated in a reliability test of applying a rated voltage in an environment of 150 ° C.
【００２９】洗浄を実施した製品のＥＳＲは洗浄時間の
増加に従って増加するが洗浄時間と残留硫酸量の関係
（図３）からＥＳＲが増加し始める硫酸イオン含有率は
０．５重量％であることが判明した。The ESR of the product subjected to cleaning increases with an increase in the cleaning time, but from the relationship between the cleaning time and the amount of residual sulfuric acid (FIG. 3), the ESR starts to increase and the sulfate ion content is 0.5% by weight. There was found.
【００３０】一方、１５０℃の信頼性試験において、洗
浄を実施した製品のＥＳＲは洗浄時間の増加に従って変
化が少なくなるが、洗浄時間と残量硫酸量の関係（図
４）から、ＥＳＲが変化し始める硫酸イオン含有率は２
重量％以上であることが判明した。On the other hand, in the reliability test at 150 ° C., the ESR of the product subjected to cleaning changes little as the cleaning time increases, but the ESR changes from the relationship between the cleaning time and the residual sulfuric acid amount (FIG. 4). Sulfate ion content rate to start is 2
It was found to be more than weight%.
【００３１】（実施例１）参考例１と同様な手段で、コ
ンデンサ素子を構成する陽極酸化皮膜上に導電性高分子
層を形成し、４５℃の脱イオン水の流水２５０ｍｌ／分
による流水洗浄を３０分行い、前記コンデンサ素子を同
様な手段で再化成、洗浄、乾燥を行った。高分子層が所
望の厚さになるまで、モノマー溶液への浸漬一乾燥まで
の重合回数を５回繰り返した。(Example 1) A conductive polymer layer was formed on the anodic oxide film constituting the capacitor element by the same means as in Reference Example 1, and deionized water at 45 ° C was washed with running water at 250 ml / min. Was carried out for 30 minutes, and the capacitor element was re-formed, washed and dried by the same means. The number of times of polymerization from dipping in the monomer solution to drying was repeated 5 times until the polymer layer had a desired thickness.
【００３２】このコンデンサ素子の一部で導電性高分子
層の重量を求め、該導電性高分子層に含有する硫酸イオ
ンの量を求めたところ１．４重量％であった。The weight of the conductive polymer layer in a part of this capacitor element was determined, and the amount of sulfate ion contained in the conductive polymer layer was determined to be 1.4% by weight.
【００３３】次に、この導電性高分子層の上に、カーボ
ン層、このカーボン層の上に陰極となる銀塗料層を形成
し、この銀塗料層の上に陰極引出端子を、前記陽極体か
ら引出した陽極線に陽極引出端子をそれぞれ取付け、ト
ランスファーモールドにより樹脂外装を行い、前記陰極
引出端子及び陽極引出端子を所定の位置に折曲げてチッ
プ状の固体電解コンデンサを完成した。当該コンデンサ
は、初期特性を測定され、１５０℃の信頼性試験で評価
された。Next, a carbon layer is formed on the conductive polymer layer, a silver paint layer serving as a cathode is formed on the carbon layer, and a cathode lead terminal is formed on the silver paint layer. Anode lead terminals were attached to the anode wires drawn from, and resin coating was performed by transfer molding, and the cathode lead terminal and the anode lead terminal were bent at predetermined positions to complete a chip-shaped solid electrolytic capacitor. The capacitor was measured for initial characteristics and evaluated in a reliability test at 150 ° C.
【００３４】（比較例１）脱イオン水の温度が常温であ
り洗浄時間が５分であることを除き、参考例１と同様な
手段で固体電解コンデンサを完成した。この場合の該導
電性高分子層に含まれる硫酸イオンは２．９重量％であ
った。同じく当該コンデンサは初期特性を測定され、１
５０℃の信頼性試験で評価された。Comparative Example 1 A solid electrolytic capacitor was completed in the same manner as in Reference Example 1 except that the temperature of deionized water was room temperature and the cleaning time was 5 minutes. In this case, the sulfate ion contained in the conductive polymer layer was 2.9% by weight. Similarly, the capacitor was measured for initial characteristics and
It was evaluated in a reliability test at 50 ° C.
【００３５】（比較例２）脱イオン水中の３Ｖ電解洗浄
であり洗浄時間が６０分であることを除き、実施例１と
同様な手段で固体電解コンデンサを完成した。この場合
の該導電性高分子層に含まれる硫酸イオンは０．４重量
％であった。同じく当該コンデンサは初期特性を測定さ
れ、１５０℃の信頼性試験で評価された。(Comparative Example 2) A solid electrolytic capacitor was completed in the same manner as in Example 1 except that the cleaning was 3V electrolytic cleaning in deionized water and the cleaning time was 60 minutes. In this case, the sulfate ion contained in the conductive polymer layer was 0.4% by weight. Similarly, the capacitor was measured for initial characteristics and evaluated in a reliability test at 150 ° C.
【００３６】（実施例２）洗浄方法が常温脱イオン水中
３Ｖの電解洗浄であり洗浄時間が１５分であることを除
き、参考例と同様な手段で、固体電解コンデンサを完成
した。この場合の該導電性高分子層に含まれる硫酸イオ
ンは０．７重量％であった。同じく当該コンデンサは初
期特性を測定され、１５０℃の信頼性試験で評価され
た。(Example 2) A solid electrolytic capacitor was completed in the same manner as in the reference example, except that the cleaning method was electrolytic cleaning with 3 V of room temperature deionized water and the cleaning time was 15 minutes. In this case, the sulfate ion contained in the conductive polymer layer was 0.7% by weight. Similarly, the capacitor was measured for initial characteristics and evaluated in a reliability test at 150 ° C.
【００３７】実施例１及び２、比較例１及び２の信頼性
試験前後の特性を表１に示す。Table 1 shows the characteristics of Examples 1 and 2 and Comparative Examples 1 and 2 before and after the reliability test.
【００３８】[0038]
【表１】 [Table 1]
【００３９】表１から明らかなように、実施例１，２の
ものは、いずれもＥＳＲ特性に優れ信頼性の高い固体電
解コンデンサを得ることができるのに対し、硫酸含有率
が２．０重量％を超える比較例１は初期のＥＳＲ特性は
問題ないものの、信頼性試験後のＥＳＲの上昇が大き
く、寿命特性が劣ることが判る。また、硫酸含有率が
０．５重量％未満の比較例２では、初期のＥＳＲが、実
施例１，２と比較して大きなものとなっているととも
に、信頼性試験後のＥＳＲも大きな値となり、実用上好
ましくないものであることが分かる。As is clear from Table 1, in each of Examples 1 and 2, a solid electrolytic capacitor having excellent ESR characteristics and high reliability can be obtained, while the sulfuric acid content is 2.0% by weight. Although the initial ESR characteristics of Comparative Example 1 in which the content exceeds 0.1% are satisfactory, it is understood that the ESR after the reliability test largely increases and the life characteristics are inferior. In Comparative Example 2 in which the sulfuric acid content is less than 0.5% by weight, the initial ESR is larger than those in Examples 1 and 2, and the ESR after the reliability test is also a large value. It turns out that it is not preferable in practical use.
【００４０】この差は実施例の場合、コンデンサ素子に
形成される導電性高分子層が、流水洗浄あるいは電解洗
浄で硫酸イオンの含有量が適正化され、よって特性良好
で信頼性も良好な固体電解コンデンサが得られるが、比
較例の場合は、硫酸イオンの含有量が適正でないため
に、特性良好であっても信頼性に問題があるか、信頼性
と特性に問題あるなど、両方の要求を満たすものでない
ことがわかる。In the case of the embodiment, the difference is that the conductive polymer layer formed on the capacitor element has a sulfate ion content optimized by washing with running water or electrolytic washing, and thus has good characteristics and good reliability. Although an electrolytic capacitor can be obtained, in the case of the comparative example, since the sulfate ion content is not appropriate, there is a problem in reliability even if the characteristics are good, or there is a problem in both reliability and characteristics. It turns out that it doesn't satisfy.
【００４１】[0041]
【発明の効果】陽極となる弁作用金属基体の表面に誘電
体酸化皮膜を形成してなるコンデンサ素子に重合性モノ
マーと酸化剤を含浸し、前記誘電体酸化皮膜の表面に導
電性高分子層を形成してなる固体電解コンデンサにおい
て、前記導電性高分子層内に硫酸イオンを０．５〜２重
量％含有させたことで、特性と信頼性の両方を満足でき
る良好な固体電解コンデンサを得ることができる。EFFECTS OF THE INVENTION A capacitor element having a valve metal substrate serving as an anode and a dielectric oxide film formed on the surface thereof is impregnated with a polymerizable monomer and an oxidizing agent, and a conductive polymer layer is formed on the surface of the dielectric oxide film. In the solid electrolytic capacitor formed by forming 0.5 to 2% by weight of sulfate ion in the conductive polymer layer, a good solid electrolytic capacitor satisfying both characteristics and reliability is obtained. be able to.
【図１】本発明の固体電解コンデンサの基本構造を示す
断面図である。FIG. 1 is a sectional view showing a basic structure of a solid electrolytic capacitor of the present invention.
【図２】参考例１の洗浄時間による導電性高分子層中の
硫酸イオンの変化を表すグラフである。FIG. 2 is a graph showing changes in sulfate ion in a conductive polymer layer according to cleaning time in Reference Example 1.
【図３】参考例１の含有硫酸イオンと特性および信頼性
を示すグラフである。FIG. 3 is a graph showing sulfate ions contained in Reference Example 1, characteristics and reliability.
１ コンデンサ素子 ２ 導電性高分子層 ３ カーボン層 ４ 銀ペースト層 ５ 陽極リード線 ６ 陰極リード線 ７ 外装樹脂 1 Capacitor element 2 Conductive polymer layer 3 carbon layer 4 Silver paste layer 5 Anode lead wire 6 Cathode lead wire 7 Exterior resin
Claims (7)
体酸化皮膜を形成してなるコンデンサ素子に重合性モノ
マーと酸化剤を含浸し、前記誘電体酸化皮膜の表面に導
電性高分子層を形成してなる固体電解コンデンサにおい
て、 前記導電性高分子層内に硫酸イオンを０．５〜２重量％
含有させたことを特徴とする固体電解コンデンサ。1. A capacitor element formed by forming a dielectric oxide film on the surface of a valve action metal base serving as an anode is impregnated with a polymerizable monomer and an oxidizing agent, and a conductive polymer layer is formed on the surface of the dielectric oxide film. In the solid electrolytic capacitor, the sulfate ion is contained in the conductive polymer layer in an amount of 0.5 to 2% by weight.
A solid electrolytic capacitor characterized by being contained.
の誘導体からなるモノマーであり、前記酸化剤が過硫酸
イオンを含む塩を酸化剤とすることを特徴とする固体電
解コンデンサ。2. The solid electrolytic capacitor, wherein the polymerizable monomer is a monomer made of thiophene or a derivative thereof, and the oxidizing agent is a salt containing a persulfate ion.
レンジオキシチオフェンであることを特徴とする請求項
１又は２のいずれかに記載の固体電解コンデンサ。3. The solid electrolytic capacitor according to claim 1, wherein the derivative of thiophene is 3,4-ethylenedioxythiophene.
体酸化皮膜を形成したコンデンサ素子に重合性モノマー
と酸化剤を含浸し、前記誘電体酸化皮膜の表面に導電性
高分子層を形成してなる固体電解コンデンサの製造方法
において、 前記コンデンサ素子内に導電性高分子層を形成した後、
前記コンデンサ素子の流水洗浄または電解洗浄を行い、
導電性高分子層内の前記硫酸イオン量を０．５〜２重量
％の範囲に制御することを特徴とする固体電解コンデン
サの製造方法。4. A capacitor element in which a dielectric oxide film is formed on the surface of a valve action metal substrate serving as an anode is impregnated with a polymerizable monomer and an oxidizing agent, and a conductive polymer layer is formed on the surface of the dielectric oxide film. In the method for producing a solid electrolytic capacitor comprising, after forming a conductive polymer layer in the capacitor element,
Perform running water cleaning or electrolytic cleaning of the capacitor element,
A method for producing a solid electrolytic capacitor, characterized in that the amount of sulfate ions in the conductive polymer layer is controlled within a range of 0.5 to 2% by weight.
の誘導体からなるモノマーであり、前記酸化剤が過硫酸
イオンを含む塩を酸化剤とすることを特徴とする請求項
４に記載の固体電解コンデンサの製造方法。5. The solid electrolytic capacitor according to claim 4, wherein the polymerizable monomer is thiophene or a derivative thereof, and the oxidizing agent is a salt containing a persulfate ion. Production method.
レンジオキシチオフェンであることを特徴とする請求項
４又は５のいずれかに記載の固体電解コンデンサの製造
方法。6. The method for producing a solid electrolytic capacitor according to claim 4, wherein the derivative of thiophene is 3,4-ethylenedioxythiophene.
した水溶液を用いたことを特徴とする請求項４ないし６
のいずれかに記載の固体電解コンデンサの製造方法。7. An aqueous solution of sulfuric acid and persulfate dissolved in water is used as an oxidizing agent.
5. A method for manufacturing a solid electrolytic capacitor as described in any one of 1.
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|---|---|---|---|
| JP2001255117A JP5116130B2 (en) | 2001-08-24 | 2001-08-24 | Solid electrolytic capacitor and manufacturing method thereof |
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| JP5116130B2 JP5116130B2 (en) | 2013-01-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021193212A1 (en) * | 2020-03-25 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Capacitor element and electrolytic capacitor |
| JP2023095573A (en) * | 2021-12-24 | 2023-07-06 | パナソニックＩｐマネジメント株式会社 | Method for manufacturing electrolytic capacitor and method for evaluating conductive polymer layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11251192A (en) * | 1998-03-03 | 1999-09-17 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacture |
| JP2000012394A (en) * | 1997-11-28 | 2000-01-14 | Showa Denko Kk | Solid electrolytic capacitor and manufacture of the same |
-
2001
- 2001-08-24 JP JP2001255117A patent/JP5116130B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000012394A (en) * | 1997-11-28 | 2000-01-14 | Showa Denko Kk | Solid electrolytic capacitor and manufacture of the same |
| JPH11251192A (en) * | 1998-03-03 | 1999-09-17 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacture |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021193212A1 (en) * | 2020-03-25 | 2021-09-30 | パナソニックＩｐマネジメント株式会社 | Capacitor element and electrolytic capacitor |
| JP2023095573A (en) * | 2021-12-24 | 2023-07-06 | パナソニックＩｐマネジメント株式会社 | Method for manufacturing electrolytic capacitor and method for evaluating conductive polymer layer |
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| JP5116130B2 (en) | 2013-01-09 |
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