JP2531589B2 - Solid electrolytic capacitor - Google Patents
Solid electrolytic capacitorInfo
- Publication number
- JP2531589B2 JP2531589B2 JP8830488A JP8830488A JP2531589B2 JP 2531589 B2 JP2531589 B2 JP 2531589B2 JP 8830488 A JP8830488 A JP 8830488A JP 8830488 A JP8830488 A JP 8830488A JP 2531589 B2 JP2531589 B2 JP 2531589B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- conductive polymer
- film
- electrolytic capacitor
- solid electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003990 capacitor Substances 0.000 title claims description 29
- 239000007787 solid Substances 0.000 title claims description 16
- 239000011888 foil Substances 0.000 claims description 33
- 229920001940 conductive polymer Polymers 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 13
- 239000000123 paper Substances 0.000 description 32
- 229920000128 polypyrrole Polymers 0.000 description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- -1 sulfonate anion Chemical class 0.000 description 5
- 240000000907 Musa textilis Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000002655 kraft paper Substances 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
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003115 supporting 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
- 238000003466 welding Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000414 polyfuran Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000004804 winding Methods 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
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 ［発明の目的］ （産業上の利用分野） 本発明は、導電性高分子膜を固体電解質とした固体電
解コンデンサに関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a solid electrolytic capacitor using a conductive polymer film as a solid electrolyte.
（従来の技術） 固体電解コンデンサは、通常アルミニウム，タンタル
などの皮膜形成性金属表面に誘電体である酸化皮膜を形
成し、該酸化皮膜上に二酸化マンガン,TCNQ錯体などの
固体電解質層及び導電体層を順次積層形成して構成され
ている。(Prior Art) A solid electrolytic capacitor usually has an oxide film that is a dielectric formed on the surface of a film-forming metal such as aluminum or tantalum, and a solid electrolyte layer such as manganese dioxide or a TCNQ complex and a conductor are formed on the oxide film. It is configured by sequentially stacking layers.
一般に大容量小形化のため、渦巻状に巻回した構造を
採用しているが、従来の電解液形コンデンサ同様に陰極
箔が不可欠のため小形化には限度があった。また、二酸
化マンガンを固体電解質として用いたコンデンサは、製
造工程上誘電体酸化皮膜を損傷しやすいなどの欠点をも
ち、一方、TCNQ錯体を用いたコンデンサは、熱安定性に
乏しいなどの欠点がある。In general, a spirally wound structure is used for large-capacity miniaturization, but there is a limit to miniaturization because a cathode foil is indispensable like the conventional electrolytic capacitor. Further, a capacitor using manganese dioxide as a solid electrolyte has a defect that the dielectric oxide film is easily damaged in the manufacturing process, while a capacitor using a TCNQ complex has a defect that thermal stability is poor. .
誘電体酸化皮膜上にピロールなどの複素環式化合物の
重合体を電解重合により形成し固体電解質としたコンデ
ンサが提案されているが、誘電体酸化皮膜は絶縁体であ
るので、その表面に電解重合膜を形成することは非常に
困難であり、均一な皮膜を形成することができなかっ
た。とりわけ陽極箔単体で巻回した構造の素子において
は、渦巻状に密に積層した箔の間に均一な電解重合膜を
形成することは不可能である。また、陽極酸化皮膜上に
酸化剤を用いて化学重合した導電性高分子膜（Ｉ）を形
成し、セパレータ紙及び陰極箔と共に巻回して素子を形
成後、電解重合により導電性高分子膜（II）を形成した
構造の固体電解コンデンサが提案されているが、絶縁体
であるセパレータ紙の影響で導電性高分子膜の生成が不
均一となり、コンデンサの静電容量の減少やバラツキ，
損失角の正接（tanδ）が大きいなどの改良すべき点が
残されていた。A capacitor has been proposed which uses a polymer of a heterocyclic compound such as pyrrole on the dielectric oxide film by electrolytic polymerization to form a solid electrolyte.However, since the dielectric oxide film is an insulator, it is electrolytically polymerized on its surface. It was very difficult to form a film, and it was not possible to form a uniform film. In particular, in an element having a structure in which the anode foil alone is wound, it is impossible to form a uniform electrolytically polymerized film between foils densely laminated in a spiral shape. In addition, a conductive polymer film (I) that is chemically polymerized using an oxidizing agent is formed on the anodized film, and the conductive polymer film (I) is wound with separator paper and a cathode foil to form an element, and then the conductive polymer film (I) is formed by electrolytic polymerization ( II) has been proposed as a solid electrolytic capacitor with a structure, but due to the effect of the separator paper, which is an insulator, the conductive polymer film becomes non-uniform, resulting in a decrease or variation in the capacitance of the capacitor.
There were some points left to be improved, such as a large loss tangent (tan δ).
（発明が解決しようとする課題） 本発明の目的とするところは、導電性高分子膜を固体
電解質とした構造からなり、小形小容積化を可能とする
とともに、均一な導電性高分子膜を形成せしめ、優れた
コンデンサ特性をもつ固体電解コンデンサを提供するこ
とができる。(Problems to be Solved by the Invention) An object of the present invention is to provide a uniform conductive polymer film while having a structure in which a conductive polymer film is used as a solid electrolyte, which enables a small size and a small volume. It is possible to form a solid electrolytic capacitor having excellent capacitor characteristics.
［発明の構成］ （課題を解決するための手段） 本発明者らは、鋭意研究の結果、上記目的を達成し得
る固体電解コンデンサを発生するに至った。[Structure of the Invention] (Means for Solving the Problems) As a result of earnest research, the present inventors have developed a solid electrolytic capacitor that can achieve the above object.
すなわち、表面に誘電体酸化皮膜を形成した陽極箔及
び化学重合による導電性高分子膜（Ｉ）ならびに電解重
合による導電性高分子膜（II）を電解質とするものから
なり、多孔性紙の表面にあらかじめ化学重合により導電
性高分子膜（Ｉ）を形成して多孔性導電化紙となし、陽
極箔と巻回して素子を構成し、次いで電解重合により導
電性高分子膜（II）を形成し、該導電化紙を陰極とした
固体電解コンデンサである。That is, it is composed of an anode foil having a dielectric oxide film formed on its surface, a conductive polymer film (I) formed by chemical polymerization, and a conductive polymer film (II) formed by electrolytic polymerization as electrolytes. To form a conductive polymer film (I) by chemical polymerization in advance to form a porous conductive paper, and wind it with an anode foil to form an element, and then form a conductive polymer film (II) by electrolytic polymerization. The solid electrolytic capacitor uses the electroconductive paper as a cathode.
以下、本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail.
皮膜形成性金属としては、アルミニウム，タンタル，
ニオブなどが用いられ、必要に応じ表面を電気化学的に
エッチングし粗面化する。更に、りん酸アンモニウムや
ほう酸アンモニウムなどの水溶液中で電解酸化を行い、
表面に誘電体酸化皮膜を形成せしめ、陽極箔を得る。こ
の陽極箔を所定の寸法に切断し、その一部にかしめ付
け，超音波溶接などの方法により陽極引出し用のリード
線を接続する。Film forming metals include aluminum, tantalum,
Niobium or the like is used, and the surface is electrochemically etched and roughened if necessary. Furthermore, electrolytic oxidation is performed in an aqueous solution of ammonium phosphate or ammonium borate,
A dielectric oxide film is formed on the surface to obtain an anode foil. This anode foil is cut into a predetermined size, and a part of it is caulked, and a lead wire for drawing out the anode is connected by a method such as ultrasonic welding.
次いで、酸化皮膜上に導電性高分子モノマーを少なく
とも0.01mol/含む溶液を均一に分散させた後、酸化剤
0.001〜2mol/含む溶液と接触させるか、又は逆に酸化
剤を均一に分散した後、導電性高分子モノマー溶液と接
触させる方法により、化学重合した導電性高分子膜
（Ｉ）を形成し表面を導電化する。Then, after uniformly dispersing a solution containing at least 0.01 mol / mol of the conductive polymer monomer on the oxide film, the oxidizer was added.
A chemically polymerized conductive polymer film (I) is formed on the surface by a method of contacting with a solution containing 0.001 to 2 mol / or, on the contrary, uniformly dispersing an oxidizing agent and then contacting with a conductive polymer monomer solution. Is made conductive.
次いで、見掛密度が0.3〜0.6g/cm3の範囲にある多孔
性のクラフト紙，マニラ麻紙又はこれらの混抄紙あるい
はこれらと合成繊維との混抄紙を導電性高分子モノマー
を少なくとも0.01mol/含む溶液中に浸漬した後、酸化
剤を0.001mol/〜2mol/含む溶液と接触させるか、又
は逆に酸化剤を均一に分散した後、導電性高分子モノマ
ー溶液と接触させる方法により化学重合した導電性高分
子膜（Ｉ）を形成し、多孔性紙の表面を導電化する。導
電性高分子としては、ポリピロール，ポリアニリン，ポ
リチオフェン，ポリフランを用い、特に好ましくはポリ
ピロールを用いる。Next, porous kraft paper having an apparent density in the range of 0.3 to 0.6 g / cm 3 , manila hemp paper, or a mixed paper of these or a mixed paper of these and synthetic fibers is mixed with at least 0.01 mol / cm of a conductive polymer monomer. After soaking in the solution containing the oxidant, it is contacted with the solution containing 0.001mol / ~ 2mol / oxidizer, or after the oxidant is uniformly dispersed, chemically polymerized by a method of contacting with a conductive polymer monomer solution A conductive polymer film (I) is formed to make the surface of the porous paper conductive. As the conductive polymer, polypyrrole, polyaniline, polythiophene, or polyfuran is used, and polypyrrole is particularly preferably used.
このようにして得られた多孔性導電化紙を誘電体酸化
皮膜を有する陽極箔と共に渦巻状に巻回し素子を作製す
る。その後、陰イオンがベンゼンスルホン酸，アルキル
ベンゼンスルホン酸などのスルホン酸アニオン，過塩素
酸アニオン，また陽イオンがリチウム，カリウムなどの
アルカリ金属カチオン，テトラアルキルアンモニウムな
どの４級アンモニウムカチオンからなる支持電解質0.01
〜2mol/及び導電性高分子モノマー0.01〜5mol/を含
む電解液中で、前記多孔性導電化紙を陽極とし外部に配
設した陰極との間に直流定電流電解を行い、表面を導電
化した陽極箔と多孔性導電化紙の間に均一に電解重合導
電性高分子膜（II）を形成せしめる。The porous electroconductive paper thus obtained is spirally wound with an anode foil having a dielectric oxide film to produce an element. Then, a supporting electrolyte in which the anion is a sulfonate anion such as benzenesulfonic acid or alkylbenzenesulfonic acid, a perchlorate anion, and the cation is an alkali metal cation such as lithium or potassium, or a quaternary ammonium cation such as tetraalkylammonium 0.01
〜2mol / and conductive polymer monomer 0.01〜5mol / in the electrolytic solution, conduct DC constant current electrolysis between the porous conductive paper as an anode and a cathode arranged outside to make the surface conductive. The electropolymerized conductive polymer film (II) is uniformly formed between the anode foil and the porous conductive paper.
（作用） 以上述べたごとく構成されるコンデンサ素子では、多
孔性導電化紙は陰極として作用し、樹脂モールド又はケ
ースに密封するなどして本発明の固体電解コンデンサを
与える。(Operation) In the capacitor element configured as described above, the porous conductive paper acts as a cathode and is sealed in a resin mold or a case to provide the solid electrolytic capacitor of the present invention.
（実施例） 実施例１ 誘電体酸化皮膜を形成させた厚さ40μm,幅3mmの高純
度アルミニウム箔に超音波溶接により陽極リードを取付
け陽極箔を得た。該陽極箔を2mol/ピロール／エタノ
ール溶液に５分間浸漬した後、更に0.5mol/過硫酸ア
ンモニウム水溶液に浸漬して化学重合によりポリピロー
ル膜を形成した。(Example) Example 1 An anode lead was obtained by attaching an anode lead to a high-purity aluminum foil having a thickness of 40 µm and a width of 3 mm formed with a dielectric oxide film by ultrasonic welding. The anode foil was dipped in a 2 mol / pyrrole / ethanol solution for 5 minutes and then dipped in a 0.5 mol / ammonium persulfate aqueous solution to form a polypyrrole film by chemical polymerization.
次いで、厚さ35μm,見掛密度0.35g/cm3のマニラ麻紙
を2mol/ピロール／エタノール溶液に５分間浸漬した
後、更に0.5mol/過硫酸アンモニウム水溶液に５分間
浸漬して化学重合によりポリピロール膜をマニラ麻繊維
の表面に形成し多孔性の導電化紙を得た。この導電化紙
と前記陽極箔とを渦巻状に巻回して素子を作製後、再化
成により誘電体酸化皮膜の修復を行った。更に、この素
子をピロールモノマー1mol/及び支持電解質としてパ
ラトルエンスルホン酸ナトリウム1mol/を含むアセト
ニトリル溶液中に浸漬し、化学重合したポリピロールを
有する導電化紙を陽極とし、外部に配設した陰極との間
に直流定電流を通電し（1mA/cm2,35min），導電化紙と
表面を導電化した陽極箔上の誘電体酸化皮膜との間に電
解重合によるポリピロール膜を形成せしめた。Then, Manila hemp paper with a thickness of 35 μm and an apparent density of 0.35 g / cm 3 was dipped in a 2 mol / pyrrole / ethanol solution for 5 minutes and then further dipped in a 0.5 mol / ammonium persulfate aqueous solution for 5 minutes to form a polypyrrole film by chemical polymerization. A porous conductive paper formed on the surface of Manila hemp fiber was obtained. The electroconductive paper and the anode foil were spirally wound to produce an element, and the dielectric oxide film was restored by re-chemical conversion. Further, this element was immersed in an acetonitrile solution containing pyrrole monomer 1 mol / and sodium paratoluenesulfonate 1 mol / as a supporting electrolyte, and the electrically conductive paper having the chemically polymerized polypyrrole was used as the anode, and the cathode arranged outside. A DC constant current was applied between them (1 mA / cm 2 , 35 min) to form a polypyrrole film by electrolytic polymerization between the electroconductive paper and the dielectric oxide film on the anode foil whose surface was electroconductive.
しかる後、導電化紙の端面に陰極リードを接続しケー
スに密封して定格電圧33V,公称静電容量15μＦの固体電
解コンデンサを完成した。このコンデンサは、陽極箔，
セパレータ紙及び陰極箔を用いた従来のコンデンサに比
べ約2/3の容積となり、また均一なポリピロール膜が形
成されるため、静電容量やtanδのバラツキを小さくす
ることができる。Then, a cathode lead was connected to the end surface of the conductive paper and sealed in a case to complete a solid electrolytic capacitor having a rated voltage of 33 V and a nominal electrostatic capacity of 15 μF. This capacitor has an anode foil,
The volume is about 2/3 that of a conventional capacitor using separator paper and cathode foil, and a uniform polypyrrole film is formed, so that variations in capacitance and tan δ can be reduced.
実施例２ 実施例１の紙を厚さ40μm,見掛密度0.6g/cm3のクラフ
ト紙に変更した以外は、実施例１と同様にして行った。Example 2 The procedure of Example 1 was repeated except that the paper of Example 1 was changed to kraft paper having a thickness of 40 μm and an apparent density of 0.6 g / cm 3 .
実施例３ 実施例１の紙を厚さ50μm,見掛密度0.30g/cm3のマニ
ラ麻紙とポリプロピレン繊維の混抄紙に変更した以外
は、実施例１と同様にして行った。Example 3 The procedure of Example 1 was repeated except that the paper of Example 1 was changed to a mixed hemp paper having a thickness of 50 μm and an apparent density of 0.30 g / cm 3 and polypropylene fiber.
実施例４ 実施例１において、化学重合により表面を導電化しな
い陽極箔に変更した以外は、実施例１と同様にして行っ
た。Example 4 Example 4 was repeated except that the surface of the anode foil was changed to a non-conductive one by chemical polymerization.
参考例１ 実施例１の紙を厚さ20μm,見掛密度0.75g/cm3のクラ
フト紙に変更した以外は、実施例１と同様にして行っ
た。Reference Example 1 Example 1 was repeated except that the paper of Example 1 was changed to kraft paper having a thickness of 20 μm and an apparent density of 0.75 g / cm 3 .
参考例２ 実施例１において、厚さ35μm,見掛密度0.35g/cm3の
マニラ麻紙に化学重合によるポリピロール膜を形成せず
に、陽極箔と渦巻状に巻回して素子を構成し、実施例１
に準じて電解重合を行ったが、ポリピロールは均一に生
成せず、固体電解コンデンサを作製することはできなか
った。Reference Example 2 In Example 1, a device was formed by spirally winding the anode foil with the anode foil without forming a polypyrrole film by chemical polymerization on a Manila hemp paper having a thickness of 35 μm and an apparent density of 0.35 g / cm 3. Example 1
However, polypyrrole was not uniformly produced and a solid electrolytic capacitor could not be produced.
参考例３ 誘電体酸化皮膜を形成させた厚さ40μm,幅3mmの高純
度アルミニウム箔にかしめ付けにより陽極リードを取付
け50mmに切断して陽極箔を得た。該陽極箔を2mol/ピロ
ール／エタノール溶液に５分間浸漬した後、更に0.5mol
/過硫酸アンモニウム水溶液に５分間浸漬して、化学
重合によりポリピロール膜を形成した。Reference Example 3 An anode foil was obtained by attaching an anode lead by caulking to a high-purity aluminum foil having a thickness of 40 μm and a width of 3 mm on which a dielectric oxide film was formed and cutting it to 50 mm. After immersing the anode foil in a 2 mol / pyrrole / ethanol solution for 5 minutes, 0.5 mol
/ A polypyrrole film was formed by chemical polymerization by immersing in an aqueous solution of ammonium persulfate for 5 minutes.
次いで、この陽極箔を厚さ35μm,見掛密度0.35g/cm3
のマニラ麻紙をセパレータとし陰極箔と重ねて渦巻状に
巻回して素子を作製後、化学重合したポリピロールを陽
極として電解重合を行い、他は実施例１の方法に準じて
コンデンサを作製した。このコンデンサはセパレータ紙
及び陰極箔を有するので、その容積は従来のコンデンサ
と同等である。Next, this anode foil was applied with a thickness of 35 μm and an apparent density of 0.35 g / cm 3
After the manila paper of No. 1 was used as a separator and was laminated with a cathode foil and wound in a spiral shape to prepare an element, electrolytic polymerization was carried out using chemically polymerized polypyrrole as an anode, and otherwise a capacitor was prepared according to the method of Example 1. Since this capacitor has separator paper and cathode foil, its volume is comparable to conventional capacitors.
本発明の実施例のデータを参考例と共に第１表に示
す。The data of the examples of the present invention are shown in Table 1 together with the reference examples.
なお、第１表中の容積比は、陽極箔，セパレータ紙及
び陰極箔で構成される従来のコンデンサ（参考例３）の
大きさを100として算出した各完成品の容積である。The volume ratio in Table 1 is the volume of each finished product calculated with the size of the conventional capacitor (reference example 3) composed of the anode foil, the separator paper and the cathode foil as 100.
［発明の効果］ 導電性高分子膜を固体電解質とした固体電解コンデン
サからなり、誘電体酸化皮膜及び該誘電体酸化皮膜上に
化学重合による導電性高分子膜を形成した陽極箔と、多
孔性紙に化学重合による導電性高分子膜及び電解重合に
よる導電性高分子膜を形成した多孔性導電化紙と巻回さ
れている固体電解コンデンサは、陽極箔と陰極箔とセパ
レータ紙と巻回されている固体電解コンデンサに比べ、
静電容量やtanδのバラツキを小さく、容積も大幅に小
さくすることが可能となった。 [Advantages of the Invention] A solid electrolytic capacitor having a conductive polymer film as a solid electrolyte, a dielectric oxide film, an anode foil having a conductive polymer film formed by chemical polymerization on the dielectric oxide film, and a porous film. A solid electrolytic capacitor is wound with a porous conductive paper that has a conductive polymer film formed by chemical polymerization and a conductive polymer film formed by electrolytic polymerization on paper, and is wound with an anode foil, a cathode foil, and separator paper. In comparison with solid electrolytic capacitors
It has become possible to reduce variations in capacitance and tan δ, and to significantly reduce the volume.
第１図は本発明の一実施例に係る素子構造の概略説明
図、第２図は実施例４における素子構造の概略説明図で
ある。 １……陽極アルミニウム箔 ２……誘電体酸化皮膜 ３……化学重合による導電性高分子膜（Ｉ） ４……多孔性導電化紙［多孔性紙＋導電性高分子膜
（Ｉ）］ ５……電解重合による導電性高分子膜（II）FIG. 1 is a schematic explanatory diagram of an element structure according to one embodiment of the present invention, and FIG. 2 is a schematic explanatory diagram of an element structure in Example 4. 1 ... Anode aluminum foil 2 ... Dielectric oxide film 3 ... Conductive polymer film (I) by chemical polymerization 4 ... Porous conductive paper [porous paper + conductive polymer film (I)] 5 ...... Conductive polymer film by electrolytic polymerization (II)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊佐 功 群馬県渋川市半田2470番地 日本カーリ ット株式会社中央研究所内 (72)発明者 山本 秀雄 群馬県渋川市半田2470番地 日本カーリ ット株式会社中央研究所内 (72)発明者 福田 実 群馬県渋川市半田2470番地 日本カーリ ット株式会社中央研究所内 審査官 大澤 孝次 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Isao Isa 2470 Handa, Shibukawa City, Gunma Prefecture Japan Carlit Co., Ltd. Central Research Institute (72) Hideo Yamamoto 2470 Handa, Shibukawa City, Gunma Prefecture Japan Carlit Co., Ltd. Central Research Laboratory (72) Inventor Minoru Fukuda 2470 Handa, Shibukawa City, Gunma Japan Carlit Co., Ltd. Central Research Laboratory Examiner Koji Osawa
Claims (3)
膜上に化学重合による導電性高分子膜を形成した陽極箔
と、多孔性紙に化学重合による導電性高分子膜及び電解
重合による導電性高分子膜を形成した多孔性導電化紙と
が巻回されている固体電解コンデンサ。1. An anode foil having a dielectric oxide film formed on its surface and a conductive polymer film formed by chemical polymerization on the dielectric oxide film, and a conductive polymer film formed by chemical polymerization on porous paper and electrolytic polymerization. A solid electrolytic capacitor wound with a porous conductive paper on which a conductive polymer film is formed.
使用した請求項（１）記載の固体電解コンデンサ。2. The solid electrolytic capacitor according to claim 1, wherein an anode foil having a dielectric oxide film formed on its surface is used.
求項（１）又は請求項（２）記載の固体電解コンデン
サ。3. The solid electrolytic capacitor as claimed in claim 1, wherein the porous paper has a density of 0.3 to 0.6 g / cm 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8830488A JP2531589B2 (en) | 1988-04-12 | 1988-04-12 | Solid electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8830488A JP2531589B2 (en) | 1988-04-12 | 1988-04-12 | Solid electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01260809A JPH01260809A (en) | 1989-10-18 |
| JP2531589B2 true JP2531589B2 (en) | 1996-09-04 |
Family
ID=13939189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8830488A Expired - Lifetime JP2531589B2 (en) | 1988-04-12 | 1988-04-12 | Solid electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2531589B2 (en) |
-
1988
- 1988-04-12 JP JP8830488A patent/JP2531589B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01260809A (en) | 1989-10-18 |
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