JP2001110681A - Solid electrolytic capacitor and method for manufacturing the same - Google Patents
Solid electrolytic capacitor and method for manufacturing the sameInfo
- Publication number
- JP2001110681A JP2001110681A JP28895499A JP28895499A JP2001110681A JP 2001110681 A JP2001110681 A JP 2001110681A JP 28895499 A JP28895499 A JP 28895499A JP 28895499 A JP28895499 A JP 28895499A JP 2001110681 A JP2001110681 A JP 2001110681A
- Authority
- JP
- Japan
- Prior art keywords
- capacitor element
- capacitor
- solid electrolytic
- electrolytic capacitor
- oxidizing agent
- 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 86
- 239000007787 solid Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 239000011888 foil Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 4
- 239000001741 Ammonium adipate Substances 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 235000019293 ammonium adipate Nutrition 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000007784 solid electrolyte 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
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- H01G11/52—Separators
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体電解コンデン
サおよびその製造方法に関し、更に詳しくは、導電性高
分子を電解質とした固体電解コンデンサに関するもので
ある。The present invention relates to a solid electrolytic capacitor and a method of manufacturing the same, and more particularly, to a solid electrolytic capacitor using a conductive polymer as an electrolyte.
【０００２】[0002]
【従来の技術】周知のように、巻回型電解コンデンサ
は、図１に例示されているように、それぞれ電気的な引
出しリード１、２を設けた陽極電極箔３と陰極電極箔４
をセパレータ紙５を介して巻回してコンデンサ素子６を
形成し、実質上陰極となる電解液をセパレータ紙にしみ
込ませ、アルミケースに入れ、ゴム等で封止して作られ
ている。2. Description of the Related Art As is well known, a wound electrolytic capacitor has an anode electrode foil 3 and a cathode electrode foil 4 provided with electrical lead-out leads 1 and 2, respectively, as shown in FIG.
Is wound around a separator paper 5 to form a capacitor element 6, and an electrolytic solution substantially serving as a cathode is impregnated into the separator paper, placed in an aluminum case, and sealed with rubber or the like.
【０００３】ところで、陽極箔は、弁金属の代表である
アルミニウムが使用され、これの箔状のものを電気化学
的手法で粗面化し、陽極酸化の手法で誘電体となる酸化
膜を形成して作られる。一方、陰極箔は、陽極箔と同様
の方法で作られるが、陽極箔以上の実効面積を持つ様粗
面化した状態もしくは陽極酸化を施したものが使用され
る。As the anode foil, aluminum, which is a representative of valve metal, is used. The foil is roughened by an electrochemical method, and an oxide film serving as a dielectric is formed by an anodic oxidation method. Made On the other hand, the cathode foil is made in the same manner as the anode foil, but is used in a roughened state or anodized so as to have an effective area larger than the anode foil.
【０００４】電解液を用いるコンデンサでは、有機溶媒
に無機酸もしくは有機酸、例えばカルボン酸、ジカルボ
ン酸およびこれらのアンモニウム、第一アミン、第三ア
ミン、第四アンモニウム、アルカリ金属および有機アル
カリ物質の塩もしくはそれぞれの組合わせで用いられ
る。また、高周波で低インピーダンスな性能を電解コン
デンサに保持させるために低抵抗な電解液を要求されて
いるが、電解液はイオン伝導のため限界があり、また、
液状であるためと封止の不完全さから電解液が外部に飛
散するため有限寿命部品とされている。In a capacitor using an electrolytic solution, an inorganic or organic acid such as carboxylic acid, dicarboxylic acid and their ammonium, primary amine, tertiary amine, quaternary ammonium, salts of alkali metals and organic alkali substances are used in an organic solvent. Alternatively, each combination is used. In addition, low-resistance electrolytic solutions are required to maintain high-frequency, low-impedance performance in electrolytic capacitors, but electrolytic solutions have limitations due to ionic conduction.
Since the electrolyte is liquefied and the electrolyte is scattered to the outside due to imperfect sealing, the component is considered to have a finite life.
【０００５】[0005]
【発明が解決しようとする課題】そこで、この問題を解
決するために最近、電解質を固体化した固体電解コンデ
ンサが提案されている。In order to solve this problem, a solid electrolytic capacitor having a solid electrolyte has been recently proposed.
【０００６】一例として、固体電解質に二酸化マンガン
を用いた巻回型コンデンサでは、硝酸マンガンから熱処
理で二酸化マンガンを形成するため、高温にさらされた
セパレータ紙が焼失してしまうため、一般のセパレータ
紙からガラスペーパーに変更して用い、コンデンサ化し
ている。このガラスペーパーは、セパレータ紙より厚さ
が厚く、コンデンサに収容する電極面積に制限を受け、
小型化しにくいという欠点がある。As an example, in a wound capacitor using manganese dioxide as a solid electrolyte, manganese dioxide is formed by heat treatment from manganese nitrate, so that the separator paper exposed to high temperatures is burned off. Changed to glass paper and used as a capacitor. This glass paper is thicker than the separator paper and is limited by the electrode area accommodated in the capacitor.
There is a disadvantage that it is difficult to reduce the size.
【０００７】また、７、７、８、８−テトラシアノキノ
ジメタン（ＴＣＮＱ）錯塩を用いたコンデンサでは、Ｔ
ＣＮＱ錯塩の耐熱温度が低く、基板搭載時のプレヒート
で漏れ電流（ＬＣ）が増大するといった欠点を有してい
る。In a capacitor using a 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex salt, T
The CNQ complex has a drawback that the heat-resistant temperature is low and the leakage current (LC) is increased by preheating when the substrate is mounted.
【０００８】更に、ピロールを酸化剤で電解重合して得
られるポリピロールを電解質として用いるコンデンサで
は、前述のように、陽極箔が酸化剤で覆われているた
め、電解重合のためには新たに電極を設ける必要があ
り、巻回型のコンデンサでは作られておらず、また、大
型のコンデンサの製造は困難である。また、化学重合で
電解質を得るには低温で長時間を要することから、小型
のコンデンサのみが製造されている。Further, in a capacitor using polypyrrole obtained by electrolytic polymerization of pyrrole with an oxidizing agent as an electrolyte, the anode foil is covered with the oxidizing agent as described above. And it is not made with a wound-type capacitor, and it is difficult to manufacture a large-sized capacitor. Further, since it takes a long time at low temperature to obtain an electrolyte by chemical polymerization, only a small capacitor is manufactured.
【０００９】バイエル社から出された３、４エチレンジ
オキシチオフェンをパラトルエンスルホン酸第二鉄で化
学重合して得られるポリエチレンジオキシチオフェンを
電解質とするコンデンサが提案されているが（特開平２
−１５６１１号、特開平９−２９３６３９号公報参
照）、これらはモノマーと酸化剤を予め混合した液にコ
ンデンサ素子を含浸している。ところが、この方法では
酸化剤の濃度が高い場合は重合液の粘度が高く、コンデ
ンサ素子の細孔の中まで混合液を送り込むことが難し
く、容量出現率が低く、等価直列抵抗（ＥＳＲ）も高く
なる。また、酸化剤の濃度が低い場合は重合液の粘度が
低くなり、コンデンサ素子の細孔の奥まで混合液が入る
ようになるが、１回の重合では必要な量の電解質を得る
ことができなく、繰り返しの重合が必要となる。また、
得られる電解質も多層になるため、層間での剥離および
接触抵抗の増大という問題が発生し、コンデンサの等価
直列抵抗（ＥＳＲ）は７、７、８、８−テトラシアノキ
ノジメタン（ＴＣＮＱ）錯塩により作成されるコンデン
サの値が得られない。There has been proposed a capacitor using polyethylene dioxythiophene as an electrolyte obtained by chemically polymerizing 3,4 ethylenedioxythiophene produced by Bayer AG with ferric paratoluenesulfonate (Japanese Unexamined Patent Publication No. Hei.
No. 15611 and JP-A-9-293639), in which a capacitor element is impregnated with a liquid obtained by previously mixing a monomer and an oxidizing agent. However, in this method, when the concentration of the oxidizing agent is high, the viscosity of the polymerization solution is high, it is difficult to feed the mixed solution into the pores of the capacitor element, the capacity appearance rate is low, and the equivalent series resistance (ESR) is high. Become. In addition, when the concentration of the oxidizing agent is low, the viscosity of the polymerization liquid becomes low, and the mixed liquid enters into the pores of the capacitor element, but a single polymerization can obtain a necessary amount of electrolyte. And require repeated polymerization. Also,
Since the obtained electrolyte is also multilayered, problems such as separation between layers and increase in contact resistance occur, and the equivalent series resistance (ESR) of the capacitor is 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex salt. Cannot obtain the value of the capacitor created by
【００１０】本発明は、このような従来技術における性
能上および製造上の問題点を解決した固体電解コンデン
サおよびその製造方法を提供することにある。An object of the present invention is to provide a solid electrolytic capacitor and a method of manufacturing the same, which have solved the problems in performance and manufacturing in the prior art.
【００１１】[0011]
【課題を解決するための手段】上記課題を解決するた
め、請求項１に係る発明は、有機高分子モノマーと酸化
剤との混合液をコンデンサ素子に含浸し、減圧により該
コンデンサ素子の細孔中の空気を除去した後、加圧によ
り前記混合液を前記コンデンサ素子の内部に押し込むこ
とによって充填し、加温により前記有機高分子モノマー
と酸化剤を化学重合反応させて生成した導電性高分子を
電解質とした構成を特徴とするものである。In order to solve the above-mentioned problems, the invention according to claim 1 is to impregnate a capacitor element with a mixed solution of an organic polymer monomer and an oxidizing agent, and reduce the pressure of the capacitor element by reducing the pressure. After removing the air therein, the mixture is filled by pressing the mixed solution into the inside of the capacitor element by pressurization, and the conductive polymer produced by chemically polymerizing the organic polymer monomer and the oxidizing agent by heating. Is characterized by having an electrolyte as an electrolyte.
【００１２】請求項２に係る発明は、導電性高分子を電
解質とした固体電解コンデンサの製造方法において、有
機高分子モノマーと酸化剤との混合液をコンデンサ素子
に含浸し、減圧により該コンデンサ素子の細孔中の空気
を除去した後、加圧により前記混合液を前記コンデンサ
素子の内部に押し込むことによって充填し、加温により
前記有機高分子モノマーと酸化剤を化学重合反応させて
導電性高分子を生成することを特徴とするものである。According to a second aspect of the present invention, there is provided a method of manufacturing a solid electrolytic capacitor using a conductive polymer as an electrolyte, wherein a mixed solution of an organic polymer monomer and an oxidizing agent is impregnated in the capacitor element, and the capacitor element is depressurized. After the air in the pores is removed, the mixture is filled by pressing the mixed solution into the inside of the capacitor element under pressure, and the organic polymer monomer and the oxidant are chemically polymerized by heating to increase the conductivity. It is characterized by generating molecules.
【００１３】[0013]
【発明の実施の形態】本発明の実施の形態について説明
すると、本発明に係る固体電解コンデンサおよびその製
造方法は、図１に例示された固体電解コンデンサにおい
て、有機高分子モノマー（ピロール、チオフェン、アニ
リンおよびその誘導体等）と酸化剤（パラトルエンスル
ホン酸第二鉄、ドデシルベンゼンスルホン酸第二鉄等）
を重合反応に最適なモル比にて混合し、当該混合液をコ
ンデンサ素子（タンタル焼結体でもよい）に含浸し、減
圧によりコンデンサ素子の細孔中の空気を抜き、続いて
加圧により細孔の奥深くまで混合液を送り込むことによ
り充填し、加温により有機高分子モノマーと酸化剤を化
学重合反応させて細孔の奥深くまで導電性高分子の電解
質を形成する。これにより、粘度が高く、混合液が細孔
の奥まで入り難い場合でも確実に混合液を細孔内部に送
り込むことが可能となり、容量出現率の高く、等価直列
抵抗（ＥＳＲ）の低い固体電解コンデンサが得られる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described. The solid electrolytic capacitor and the method of manufacturing the same according to the present invention are different from the solid electrolytic capacitor shown in FIG. 1 in that the organic polymer monomer (pyrrole, thiophene, Aniline and its derivatives) and oxidizing agents (ferric paratoluenesulfonate, ferric dodecylbenzenesulfonate)
Is mixed at the optimum molar ratio for the polymerization reaction, the mixed solution is impregnated into a capacitor element (which may be a tantalum sintered body), air in the pores of the capacitor element is evacuated by pressure reduction, and then fineness is applied by pressure. The mixture is filled by feeding the mixture deep into the pores, and the organic polymer monomer and the oxidant are chemically polymerized by heating to form a conductive polymer electrolyte deep into the pores. This makes it possible to reliably feed the mixture into the pores even when the viscosity is high and the mixture is difficult to penetrate into the pores, and the solid electrolytic solution with a high capacity appearance rate and a low equivalent series resistance (ESR) is obtained. A capacitor is obtained.
【００１４】[0014]
【実施例】以下に具体的実施例について説明する。 実施例１ ６．３Ｖ６８０μＦ用（Ф１０×１０．５mm）の巻き上
げ済コンデンサ素子６をアジピン酸アンモン、リン酸系
の化成液で化成し、純水洗浄して高温熱処理し、これを
２回実施した。その後、再び化成、純水洗浄して、１２
５℃で６０分間乾燥した。次いで、コンデンサ素子６
を、３、４エチレンジオキシチオフェンモノマーとパラ
トルエンスルホン酸第二鉄／１−ブタノール（５０ｗｔ
％）を混合した液に到達真空度１０〜２０mmＨｇで５分
間減圧浸漬し、常圧復帰後直ちに４９Paに加圧して５分
間浸漬した。常圧復帰後４０〜８０℃で３〜１２時間化
学重合反応を実施した。よって得られたコンデンサ素子
をアルミケースに挿入し、エポキシ樹脂を入れ、加温硬
化させて封止し、スリーブを嵌着して固体電解コンデン
サを完成させた。EXAMPLES Specific examples will be described below. Example 1 A rolled-up capacitor element 6 for 6.3 V, 680 μF (１10 × 10.5 mm) was formed with an ammonium adipate / phosphoric acid-based chemical solution, washed with pure water, and subjected to a high-temperature heat treatment, and this was performed twice. . After that, it was again formed and washed with pure water.
Dry at 5 ° C. for 60 minutes. Next, the capacitor element 6
Was prepared by adding 3,4 ethylenedioxythiophene monomer and ferric paratoluenesulfonate / 1-butanol (50 wt.
%) Under reduced pressure of 10 to 20 mmHg for 5 minutes, and immediately after returning to normal pressure, pressurized to 49 Pa and immersed for 5 minutes. After returning to normal pressure, a chemical polymerization reaction was carried out at 40 to 80 ° C. for 3 to 12 hours. Thus, the obtained capacitor element was inserted into an aluminum case, filled with epoxy resin, heated and cured, sealed, and fitted with a sleeve to complete a solid electrolytic capacitor.
【００１５】次に、参考例１として ６．３Ｖ６８０μＦ用（Ф１０×１０．５mm）の巻き上
げ済コンデンサ素子６をアジピン酸アンモン、リン酸系
の化成液で化成し、純水洗浄して高温熱処理し、これを
２回実施した。その後、再び化成、純水洗浄して、１２
５℃で６０分間乾燥した。次いで、コンデンサ素子６
を、３、４エチレンジオキシチオフェンモノマーとパラ
トルエンスルホン酸第二鉄／１−ブタノール（５０ｗｔ
％）を混合した液に到達真空度１０〜２０mmＨｇで５分
間減圧浸漬し、常圧復帰後４０〜８０℃で３〜１２時間
化学重合反応を実施した。よって得られたコンデンサ素
子をアルミケースに挿入し、エポキシ樹脂を入れ、加温
硬化させて封止し、スリーブを嵌着して固体電解コンデ
ンサを完成させた。Next, as Reference Example 1, a rolled-up capacitor element 6 for 6.3 V and 680 μF (Ф10 × 10.5 mm) was formed with an ammonium adipate / phosphoric acid-based chemical solution, washed with pure water, and subjected to a high-temperature heat treatment. This was performed twice. After that, it was again formed and washed with pure water.
Dry at 5 ° C. for 60 minutes. Next, the capacitor element 6
Was prepared by adding 3,4 ethylenedioxythiophene monomer and ferric paratoluenesulfonate / 1-butanol (50 wt.
%) Was immersed in a reduced pressure of 10 to 20 mmHg for 5 minutes under reduced pressure, and after returning to normal pressure, a chemical polymerization reaction was carried out at 40 to 80 ° C. for 3 to 12 hours. Thus, the obtained capacitor element was inserted into an aluminum case, filled with epoxy resin, heated and cured, sealed, and fitted with a sleeve to complete a solid electrolytic capacitor.
【００１６】参考例２として 参考例１において、パラトルエンスルホン酸第二鉄／１
−ブタノール濃度が４０ｗｔ％であること以外は参考例
１と同様の手順で固体電解コンデンサを完成させた。Reference Example 2 In Reference Example 1, ferric paratoluenesulfonate / 1
-A solid electrolytic capacitor was completed in the same procedure as in Reference Example 1 except that the butanol concentration was 40 wt%.
【００１７】実施例と参考例１、２の各固体電解コンデ
ンサにつき、その静電容量、誘電損失（ｔａｎδ）、漏
れ電流、等価直列抵抗（ＥＳＲ）の初期特性の平均値の
測定結果を表１に示す。Table 1 shows the measurement results of the average values of the initial values of the capacitance, dielectric loss (tan δ), leakage current, and equivalent series resistance (ESR) of each of the solid electrolytic capacitors of the embodiment and Reference Examples 1 and 2. Shown in
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、本発明に係る実
施例の固体電解コンデンサは、容量出現率、誘電損失
（ｔａｎδ）、等価直列抵抗（ＥＳＲ）特性に優れた固
体電解コンデンサが得られたことが判る。一方、参考例
１のものは、容量出現率が低く、等価直列抵抗（ＥＳ
Ｒ）も劣る。また、参考例２のものは、誘電損失（ｔａ
ｎδ）、等価直列抵抗（ＥＳＲ）が悪く、製品としては
供し得ないことが判る。As is clear from Table 1, the solid electrolytic capacitor of the embodiment according to the present invention has a solid electrolytic capacitor excellent in capacitance appearance ratio, dielectric loss (tan δ), and equivalent series resistance (ESR) characteristics. You can see that. On the other hand, the reference example 1 has a low capacitance appearance rate and an equivalent series resistance (ES
R) is also inferior. In the case of Reference Example 2, the dielectric loss (ta
nδ), the equivalent series resistance (ESR) is poor, and the product cannot be provided.
【００２０】[0020]
【発明の効果】しかして、請求項１の発明によれば、従
来の導電性高分子を電解質に用いた固体電解コンデンサ
に比し、容量出現率、誘電損失（ｔａｎδ）、等価直列
抵抗（ＥＳＲ）等の電気的諸特性が向上し、かつ静電容
量が増大し、その改善効果が顕著である。According to the first aspect of the present invention, the capacitance appearance ratio, dielectric loss (tan δ), and equivalent series resistance (ESR) are higher than those of a conventional solid electrolytic capacitor using a conductive polymer as an electrolyte. ) Are improved, and the capacitance is increased, and the improvement effect is remarkable.
【００２１】また、請求項２の発明によれば、コンデン
サ素子の含浸時に減圧、加圧の工程を数分間行うだけで
あり、重合を繰り返す従来の方法に比し、その工程が短
く、極めて実用的な製造方法である。なお、本発明方法
は、巻回型コンデンサに限定されるものではなく、焼結
体、箔等を素子とするコンデンサにも利用できる。According to the second aspect of the present invention, the steps of decompression and pressurization are only performed for a few minutes during the impregnation of the capacitor element. Production method. The method of the present invention is not limited to a wound capacitor, but can be applied to a capacitor having a sintered body, a foil or the like as an element.
【図１】本発明に係る固体電解コンデンサの一例での斜
視図的説明図である。FIG. 1 is an explanatory perspective view of an example of a solid electrolytic capacitor according to the present invention.
１、２ 引出しリード ３ 陽極電極箔 ４ 陰極電極箔 ５ セパレータ ６ コンデンサ素子 1, 2 Leader lead 3 Anode electrode foil 4 Cathode electrode foil 5 Separator 6 Capacitor element
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年１２月１１日（２０００．１２．
１１）[Submission date] December 11, 2000 (200.12.
11)
【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】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】[0011]
【課題を解決するための手段】上記課題を解決するた
め、請求項１に係る発明は、導電性高分子となるモノマ
ーと酸化剤との混合液をコンデンサ素子に含浸し、減圧
により該コンデンサ素子の細孔中の空気を除去した後、
加圧により前記混合液を前記コンデンサ素子の内部に押
し込むことによって充填し、加温により前記モノマーと
酸化剤を化学重合反応させて生成した導電性高分子を電
解質とした構成を特徴とするものである。According to a first aspect of the present invention, a capacitor element is impregnated with a mixed solution of a monomer to be a conductive polymer and an oxidizing agent, and the capacitor element is depressurized. After removing the air in the pores of
The mixture is filled by pressing the mixed solution into the inside of the capacitor element by applying pressure, and a conductive polymer produced by chemically polymerizing the monomer and the oxidizing agent by heating is used as an electrolyte. is there.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１２】請求項２に係る発明は、導電性高分子を電
解質とした固体電解コンデンサの製造方法において、導
電性高分子となるモノマーと酸化剤との混合液をコンデ
ンサ素子に含浸し、減圧により該コンデンサ素子の細孔
中の空気を除去した後、加圧により前記混合液を前記コ
ンデンサ素子の内部に押し込むことによって充填し、加
温により前記モノマーと酸化剤を化学重合反応させて導
電性高分子を生成することを特徴とするものである。According to a second aspect of the present invention, there is provided a method for manufacturing a solid electrolytic capacitor using a conductive polymer as an electrolyte, wherein a mixed solution of a monomer to be a conductive polymer and an oxidizing agent is impregnated in the capacitor element, After the air in the pores of the capacitor element is removed, the mixture is filled by pressing the mixture into the interior of the capacitor element by pressurization, and the monomer and the oxidant are chemically polymerized by heating to increase the conductivity. It is characterized by generating molecules.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１３】[0013]
【発明の実施の形態】本発明の実施の形態について説明
すると、本発明に係る固体電解コンデンサおよびその製
造方法は、図１に例示された固体電解コンデンサにおい
て、導電性高分子となるモノマー（ピロール、チオフェ
ン、アニリンおよびその誘導体等）と酸化剤（パラトル
エンスルホン酸第二鉄、ドデシルベンゼンスルホン酸第
二鉄等）を重合反応に最適なモル比にて混合し、当該混
合液をコンデンサ素子（タンタル焼結体でもよい）に含
浸し、減圧によりコンデンサ素子の細孔中の空気を抜
き、続いて加圧により細孔の奥深くまで混合液を送り込
むことにより充填し、加温によりモノマーと酸化剤を化
学重合反応させて細孔の奥深くまで導電性高分子の電解
質を形成する。これにより、粘度が高く、混合液が細孔
の奥まで入り難い場合でも確実に混合液を細孔内部に送
り込むことが可能となり、容量出現率の高く、等価直列
抵抗（ＥＳＲ）の低い固体電解コンデンサが得られる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described. The solid electrolytic capacitor and the method of manufacturing the same according to the present invention are different from the solid electrolytic capacitor shown in FIG. , Thiophene, aniline and derivatives thereof) and an oxidizing agent (ferric paratoluenesulfonate, ferric dodecylbenzenesulfonate, etc.) in a molar ratio optimal for the polymerization reaction, and the mixed solution is mixed with a capacitor element ( Tantalum sintered body may be impregnated), air is removed from the pores of the capacitor element by depressurization, and then the mixture is filled by sending the mixture deep into the pores by pressurization. Is subjected to a chemical polymerization reaction to form a conductive polymer electrolyte deep into the pores. This makes it possible to reliably feed the mixture into the pores even when the viscosity is high and the mixture is difficult to penetrate into the pores, and the solid electrolytic solution with a high capacity appearance rate and a low equivalent series resistance (ESR) is obtained. A capacitor is obtained.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】[0014]
【実施例】以下に具体的実施例について説明する。 実施例１ ６．３Ｖ６８０μＦ用（Ф１０×１０．５mm）の巻き上
げ済コンデンサ素子６をアジピン酸アンモニウム、リン
酸系の化成液で化成し、純水洗浄して高温熱処理し、こ
れを２回実施した。その後、再び化成、純水洗浄して、
１２５℃で６０分間乾燥した。次いで、コンデンサ素子
６を、３、４エチレンジオキシチオフェンモノマーとパ
ラトルエンスルホン酸第二鉄／１−ブタノール（５０ｗ
ｔ％）を混合した液に到達真空度１３〜３０ｈＰａで５
分間減圧浸漬し、常圧復帰後直ちに２０００〜３０００
ｈPaに加圧して５分間浸漬した。常圧復帰後４０〜８０
℃で３〜１２時間化学重合反応を実施した。よって得ら
れたコンデンサ素子をアルミケースに挿入し、エポキシ
樹脂を入れ、加温硬化させて封止し、スリーブを嵌着し
て固体電解コンデンサを完成させた。EXAMPLES Specific examples will be described below. Example 1 A rolled-up capacitor element 6 for 6.3 V, 680 μF (１10 × 10.5 mm) was formed with an ammonium adipate / phosphoric acid-based chemical solution, washed with pure water, heat-treated at a high temperature, and carried out twice. . After that, chemical formation, washing with pure water again,
Dry at 125 ° C. for 60 minutes. Next, the capacitor element 6 was replaced with a 3,4 ethylenedioxythiophene monomer and ferric paratoluenesulfonate / 1-butanol (50 w
5% at an ultimate vacuum of 13 to 30 hPa.
Immersion under reduced pressure for 20 minutes, and immediately after returning to normal pressure, 2000 to 3000
It was immersed in a pressurized hPa for 5 minutes. 40-80 after normal pressure return
The chemical polymerization reaction was performed at a temperature of 3 to 12 hours. Thus, the obtained capacitor element was inserted into an aluminum case, filled with epoxy resin, heated and cured, sealed, and fitted with a sleeve to complete a solid electrolytic capacitor.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】次に、参考例１として ６．３Ｖ６８０μＦ用（Ф１０×１０．５mm）の巻き上
げ済コンデンサ素子６をアジピン酸アンモニウム、リン
酸系の化成液で化成し、純水洗浄して高温熱処理し、こ
れを２回実施した。その後、再び化成、純水洗浄して、
１２５℃で６０分間乾燥した。次いで、コンデンサ素子
６を、３、４エチレンジオキシチオフェンモノマーとパ
ラトルエンスルホン酸第二鉄／１−ブタノール（５０ｗ
ｔ％）を混合した液に到達真空度１３〜３０ｈＰａで５
分間減圧浸漬し、常圧復帰後４０〜８０℃で３〜１２時
間化学重合反応を実施した。よって得られたコンデンサ
素子をアルミケースに挿入し、エポキシ樹脂を入れ、加
温硬化させて封止し、スリーブを嵌着して固体電解コン
デンサを完成させた。Next, as Reference Example 1, a rolled-up capacitor element 6 for 6.3 V, 680 μF (Ф10 × 10.5 mm) is formed with an ammonium adipate / phosphoric acid-based chemical solution, washed with pure water, and subjected to a high-temperature heat treatment. This was performed twice. After that, chemical formation, washing with pure water again,
Dry at 125 ° C. for 60 minutes. Next, the capacitor element 6 was replaced with a 3,4 ethylenedioxythiophene monomer and ferric paratoluenesulfonate / 1-butanol (50 w
5% at an ultimate vacuum of 13 to 30 hPa.
After immersion under reduced pressure for a minute, the chemical polymerization reaction was carried out at 40 to 80 ° C. for 3 to 12 hours after returning to normal pressure. Thus, the obtained capacitor element was inserted into an aluminum case, filled with epoxy resin, heated and cured, sealed, and fitted with a sleeve to complete a solid electrolytic capacitor.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】[0018]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉原 和生 長野県須坂市大字小山460番地 富士通メ ディアデバイス株式会社内 Ｆターム(参考） 5G301 CA30 CD01 CD02 CE01 5H014 AA06 BB00 BB01 BB03 BB05 BB08 CC01 EE02 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuo Yoshihara 460 Oyama Oyama, Suzaka City, Nagano Prefecture F-term in Fujitsu Media Devices Co., Ltd. 5G301 CA30 CD01 CD02 CE01 5H014 AA06 BB00 BB01 BB03 BB05 BB08 CC01 EE02
Claims (2)
をコンデンサ素子に含浸し、減圧により該コンデンサ素
子の細孔中の空気を除去した後、加圧により前記混合液
を前記コンデンサ素子の内部に押し込むことによって充
填し、加温により前記有機高分子モノマーと酸化剤を化
学重合反応させて生成した導電性高分子を電解質とした
固体電解コンデンサ。1. A capacitor element is impregnated with a mixture of an organic polymer monomer and an oxidizing agent, air in pores of the capacitor element is removed by depressurization, and then the mixture is applied to the capacitor element by pressurization. A solid electrolytic capacitor which is filled by being pushed into the inside thereof, and is made of a conductive polymer produced by a chemical polymerization reaction of the organic polymer monomer and an oxidant by heating.
ンデンサの製造方法において、 有機高分子モノマーと酸化剤との混合液をコンデンサ素
子に含浸し、減圧により該コンデンサ素子の細孔中の空
気を除去した後、加圧により前記混合液を前記コンデン
サ素子の内部に押し込むことによって充填し、加温によ
り前記有機高分子モノマーと酸化剤を化学重合反応させ
て導電性高分子を生成することを特徴とする固体電解コ
ンデンサの製造方法。2. A method for manufacturing a solid electrolytic capacitor using a conductive polymer as an electrolyte, comprising: impregnating a capacitor element with a mixed solution of an organic polymer monomer and an oxidizing agent; After the removal, the mixed solution is filled by being pressed into the inside of the capacitor element by applying pressure, and the organic polymer monomer and the oxidizing agent are chemically polymerized by heating to produce a conductive polymer. A method for manufacturing a solid electrolytic capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28895499A JP2001110681A (en) | 1999-10-12 | 1999-10-12 | Solid electrolytic capacitor and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28895499A JP2001110681A (en) | 1999-10-12 | 1999-10-12 | Solid electrolytic capacitor and method for manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001110681A true JP2001110681A (en) | 2001-04-20 |
Family
ID=17736962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28895499A Pending JP2001110681A (en) | 1999-10-12 | 1999-10-12 | Solid electrolytic capacitor and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001110681A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109853A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacturing method |
| JPWO2004068517A1 (en) * | 2003-01-31 | 2006-05-25 | 昭和電工株式会社 | Manufacturing method of solid electrolytic capacitor |
| US8696767B2 (en) | 2007-05-21 | 2014-04-15 | Showa Denko K.K. | Dipping method of forming cathode of solid electrolytic capacitor |
| JP2018504785A (en) * | 2015-02-06 | 2018-02-15 | 肇慶緑宝石電子科技股▲フン▼有限公司 | Method for producing high-voltage solid aluminum electrolytic capacitor |
| CN113327772A (en) * | 2016-12-27 | 2021-08-31 | Tdk电子股份有限公司 | Mixed polymer aluminum electrolytic capacitor and method of manufacturing the same |
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| JPH05304055A (en) * | 1992-04-25 | 1993-11-16 | Nichicon Corp | Manufacture of solid-state electrolytic capacitor |
| JPH08213287A (en) * | 1995-02-07 | 1996-08-20 | Matsushita Electric Ind Co Ltd | Impregnating method with electrolyte to capacitor element in aluminum electrolytic capacitor |
| JPH09293639A (en) * | 1996-04-26 | 1997-11-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and manufacture thereof |
| JP2001155966A (en) * | 1999-09-14 | 2001-06-08 | Matsushita Electric Ind Co Ltd | Method of manufacturing capacitor |
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| JPS63314822A (en) * | 1987-06-17 | 1988-12-22 | Nippon Chemicon Corp | Manufacture of solid electrolytic capacitor |
| JPH05304055A (en) * | 1992-04-25 | 1993-11-16 | Nichicon Corp | Manufacture of solid-state electrolytic capacitor |
| JPH08213287A (en) * | 1995-02-07 | 1996-08-20 | Matsushita Electric Ind Co Ltd | Impregnating method with electrolyte to capacitor element in aluminum electrolytic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003109853A (en) * | 2001-09-28 | 2003-04-11 | Nippon Chemicon Corp | Solid electrolytic capacitor and its manufacturing method |
| JPWO2004068517A1 (en) * | 2003-01-31 | 2006-05-25 | 昭和電工株式会社 | Manufacturing method of solid electrolytic capacitor |
| JP4596543B2 (en) * | 2003-01-31 | 2010-12-08 | 昭和電工株式会社 | Manufacturing method of solid electrolytic capacitor |
| US8696767B2 (en) | 2007-05-21 | 2014-04-15 | Showa Denko K.K. | Dipping method of forming cathode of solid electrolytic capacitor |
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| CN113327772A (en) * | 2016-12-27 | 2021-08-31 | Tdk电子股份有限公司 | Mixed polymer aluminum electrolytic capacitor and method of manufacturing the same |
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