JP2017027992A - Solid electrolytic capacitor and manufacturing method therefor - Google Patents
Solid electrolytic capacitor and manufacturing method therefor Download PDFInfo
- Publication number
- JP2017027992A JP2017027992A JP2015142412A JP2015142412A JP2017027992A JP 2017027992 A JP2017027992 A JP 2017027992A JP 2015142412 A JP2015142412 A JP 2015142412A JP 2015142412 A JP2015142412 A JP 2015142412A JP 2017027992 A JP2017027992 A JP 2017027992A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolytic
- electrolytic capacitor
- conductive polymer
- capacitor element
- oxide film
- 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 94
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 36
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 23
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 23
- -1 polyoxypropylene glyceryl ether Polymers 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000008859 change Effects 0.000 abstract description 10
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract 1
- 229960002796 polystyrene sulfonate Drugs 0.000 abstract 1
- 239000011970 polystyrene sulfonate Substances 0.000 abstract 1
- 229920001940 conductive polymer Polymers 0.000 description 51
- 239000010410 layer Substances 0.000 description 47
- 239000011888 foil Substances 0.000 description 30
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229920000767 polyaniline Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 229920000123 polythiophene Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000004815 dispersion polymer Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- RGHNJXZEOKUKBD-NRXMZTRTSA-N (2r,3r,4r,5s)-2,3,4,5,6-pentahydroxyhexanoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-NRXMZTRTSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- YXCDZXGJZDGMEP-UHFFFAOYSA-N 4-hydroxy-3,3-bis(hydroxymethyl)butan-2-one Chemical compound CC(=O)C(CO)(CO)CO YXCDZXGJZDGMEP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008439 repair process Effects 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
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、固体電解コンデンサおよびその製造方法に関する。 The present invention relates to a solid electrolytic capacitor and a method for manufacturing the same.
固体電解コンデンサとして、表面に誘電体酸化皮膜が形成された陽極箔と、陰極箔とをセパレータを介して巻回したコンデンサ素子の陽極箔上に、導電性高分子層を形成したものや、誘電体酸化皮膜を形成した陽極箔に導電性高分子層を形成した後、積層したコンデンサ素子や、弁作用金属の粉体を焼結後、誘電体酸化皮膜を形成したコンデンサ素子に導電性高分子層を形成したものが知られている。 As a solid electrolytic capacitor, a conductive polymer layer is formed on an anode foil of a capacitor element in which an anode foil having a dielectric oxide film formed on a surface and a cathode foil are wound through a separator, After forming a conductive polymer layer on the anode foil on which the body oxide film is formed, the conductive polymer is applied to the capacitor element on which the laminated capacitor element and the valve action metal powder are sintered, and then the capacitor element on which the dielectric oxide film is formed. What formed the layer is known.
固体電解コンデンサは一般的に、アルミニウム、タンタル、ニオブ等の弁作用金属からなり、表面にエッチングピットや微細孔が形成された陽極体（陽極箔または焼結体）を備えており、陽極体の表面に誘電体酸化皮膜を形成し、この誘電体酸化皮膜上に導電性高分子層を形成させて、電極を引き出して構成される。この導電性高分子層は、電解コンデンサにおける真の陰極としての役割を担っており、電解コンデンサの電気特性に大きな影響を及ぼす。 A solid electrolytic capacitor is generally made of a valve metal such as aluminum, tantalum, or niobium, and includes an anode body (anode foil or sintered body) having etching pits and fine holes formed on the surface. A dielectric oxide film is formed on the surface, a conductive polymer layer is formed on the dielectric oxide film, and electrodes are drawn out. This conductive polymer layer plays a role as a true cathode in the electrolytic capacitor, and greatly affects the electrical characteristics of the electrolytic capacitor.
導電性高分子層とは、電子導電性である固体の電解質を含む層であって、ポリチオフェンの誘導体であるポリエチレンジオキシチオフェン（ＰＥＤＯＴ）、ポリチオフェン、ポリアニリン、ポリピロールなどの導電性高分子を固体電解質として用いることが知られている（特許文献１）。 A conductive polymer layer is a layer containing a solid electrolyte that is electronically conductive, and a conductive polymer such as polyethylenedioxythiophene (PEDOT), polythiophene, polyaniline, or polypyrrole, which is a derivative of polythiophene, is a solid electrolyte. It is known to use as (patent document 1).
このような導電性高分子層を形成する方法として、予め酸化剤とモノマーとの混合液を調製し、この混合液にコンデンサ素子を浸漬して含浸する方法や、酸化剤とモノマーとを別々に順次コンデンサ素子に含浸する方法がある。例えば、特許文献２記載の固体電解コンデンサは、重合性モノマーと酸化剤とを混合した混合液にコンデンサ素子を浸漬し、コンデンサ素子内で導電性ポリマーの重合反応を発生させている。そして、固体電解質層を形成した後に、このコンデンサ素子を所定のイオン伝導性物質に浸漬して、コンデンサ素子内の空隙部にイオン伝導性物質を充填することによって、高温リフロー下における耐電圧特性の劣化を防止している。
上記の方法はいずれも、コンデンサ素子上で重合反応を進行させながら導電性高分子層を形成するものであるが、これらの方法には、重合の進行に伴う溶液粘度の変化や、酸化剤とモノマーとの混合が不十分になることなど工程管理上の困難があることも知られていた。
As a method for forming such a conductive polymer layer, a mixed solution of an oxidizing agent and a monomer is prepared in advance, and a capacitor element is immersed in the mixed solution and impregnated, or the oxidizing agent and the monomer are separately provided. There is a method of sequentially impregnating capacitor elements. For example, in the solid electrolytic capacitor described in
Each of the above methods forms a conductive polymer layer while a polymerization reaction proceeds on a capacitor element. These methods include changes in solution viscosity accompanying the progress of polymerization, It has also been known that there are difficulties in process control such as insufficient mixing with monomers.
一方、予め重合反応させた導電性高分子を含む分散液を、コンデンサ素子に含浸および乾燥し、塗膜とすることで導電性高分子層を形成する方法も知られている。この方法は、誘電体酸化皮膜上で重合反応を行う必要がないため、工程の制御が比較的容易であり量産性の面で有利であるという特徴がある（特許文献３）。 On the other hand, a method of forming a conductive polymer layer by impregnating and drying a dispersion liquid containing a conductive polymer that has been polymerized in advance to form a coating film is also known. Since this method does not require a polymerization reaction on the dielectric oxide film, the process is relatively easy to control and is advantageous in terms of mass productivity (Patent Document 3).
特許文献３の発明は、導電性高分子であるポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との水分散体である商品名Ｂａｙｔｒｏｎ−Ｐ（ＢＡＹＴＲＯＮは登録商標、ドイツ・スタルク社製）を導電性高分子層の形成に用いており、導電性高分子層における導電性の向上（等価直列抵抗（ＥＳＲ）増加の回避）と電気的特性の長期信頼性の向上を目的としている。特許文献３の発明では、まず陽極酸化皮膜が形成され、その表面にプリコート層（ポリスチレンスルホン酸を塗布・乾燥した層）及び内部導電性高分子層（化学酸化重合によって形成される、比較的分子量の小さい導電性高分子の膜）が形成された陽極体を準備する。次いで、ＰＥＤＯＴおよびＰＳＳを含む水分散液に、ナフタレンスルホン酸類、高分子量ＰＳＳ、ホウ酸、マンニトールやグリコール類及び水を含む溶液を混合し、それにより高分子重合溶液を作製する。そして、この重合溶液を前記の陽極体に塗布又は含浸し、乾燥することによって導電性高分子層を設けることを特徴とする。
The invention of
ところで、固体電解コンデンサの用途が拡大するにつれて、より厳しい環境下でも問題なく使用できるコンデンサが求められている。
そこで、高温・高湿度下における電気特性の変化を小さくするために、コンデンサ素子をポリエチレングリコール（沸点：約２５０℃）等の高沸点溶媒を含浸させることが提案されている。しかしながら、高沸点溶媒としてポリエチレングリコールのみを含浸させた場合、８５℃−８５％ＲＨ等の高湿度雰囲気においては良好な特性を呈すが、近年要求されている１２５℃以上の高温度雰囲気下及び温度サイクル試験の厳しい条件下においては、酸化劣化による特性変化が大きくなるという課題があった。
By the way, as the use of solid electrolytic capacitors expands, there is a demand for capacitors that can be used without problems even in harsher environments.
Accordingly, it has been proposed to impregnate the capacitor element with a high boiling point solvent such as polyethylene glycol (boiling point: about 250 ° C.) in order to reduce the change in electrical characteristics under high temperature and high humidity. However, when impregnated only with polyethylene glycol as a high boiling point solvent, it exhibits good characteristics in a high humidity atmosphere such as 85 ° C.-85% RH, but in a high temperature atmosphere of 125 ° C. or higher and a temperature required recently. Under severe conditions of the cycle test, there has been a problem that the characteristic change due to oxidative degradation becomes large.
本発明は、このような従来技術における問題点を解決し、１２５℃以上の高温度雰囲気下でも静電容量の変化が少なく、低いＥＳＲが維持され、温度サイクル特性に優れた固体電解コンデンサを提供することを課題とする。 The present invention solves such problems in the prior art, and provides a solid electrolytic capacitor excellent in temperature cycle characteristics with little change in capacitance even under a high temperature atmosphere of 125 ° C. or higher, low ESR maintained. The task is to do.
上記の課題を解決可能な本発明の固体電解コンデンサは、誘電体酸化皮膜が形成されたコンデンサ素子に、少なくとも１回、ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸を基本組成とする分散溶液を含浸および乾燥させることによって誘電体酸化皮膜の表面に電解質が形成された固体電解コンデンサにおいて、前記コンデンサ素子内に、
ポリエチレングリコールと、
（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物（但し、Ｒは炭素数１〜４のアルキル基を示し、ｎは整数を示す）と
が含まれることを特徴とし、この際、ｎは１〜５０が好ましい。
The solid electrolytic capacitor of the present invention capable of solving the above problems is impregnated with a dispersion solution having a basic composition of polyethylenedioxythiophene / polystyrenesulfonic acid at least once on a capacitor element on which a dielectric oxide film is formed and dried. In the solid electrolytic capacitor in which the electrolyte is formed on the surface of the dielectric oxide film, in the capacitor element,
Polyethylene glycol,
(—CH 2 —CH (R) —O—) is a compound having a chemical structure of n (where R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer). In this case, n is preferably 1 to 50.
また、本発明は、上記の特徴を有した固体電解コンデンサにおいて、前記の（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物が、ポリオキシプロピレングリセリルエーテル、ポリオキシプロピレンまたはその誘導体（ポリオキシプロピレントリメチロールプロパンエーテル、ポリオキシプロピレンソルビトールエーテル）であることを特徴とするものである。 Further, the present invention provides the solid electrolytic capacitor having the above characteristics, wherein the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n is polyoxypropylene glyceryl ether, polyoxypropylene Or a derivative thereof (polyoxypropylene trimethylolpropane ether, polyoxypropylene sorbitol ether).
さらに、本発明は、上記の特徴を有した固体電解コンデンサにおいて、前記の（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物が、ポリエチレングリコール重量の０．５〜５倍の重量で含有されていることを特徴とするものでもある。 Further, according to the present invention, in the solid electrolytic capacitor having the above characteristics, the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n is 0.5 to 5 in weight of polyethylene glycol. It is also characterized by being contained in double weight.
また、本発明は、上記の特徴を有した固体電解コンデンサにおいて、前記の（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物の数平均分子量が、４００〜４０００であることを特徴とするものでもある。 In the solid electrolytic capacitor having the above characteristics according to the present invention, the number average molecular weight of the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n is 400 to 4000. It is also a feature.
また、本発明は、上記の特徴を有した固体電解コンデンサを製造するための方法でもあり、当該製造方法は、
誘電体酸化皮膜が形成されたコンデンサ素子を、ＰＥＤＯＴ／ＰＳＳを基本組成とする分散溶液に含浸および乾燥させる工程と、ポリエチレングリコールと、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物（但し、Ｒは炭素数１〜４のアルキル基を示し、ｎは整数を示す）
を含む混合溶液に含浸させる工程
を含むことを特徴とする。
The present invention is also a method for manufacturing a solid electrolytic capacitor having the above characteristics,
Impregnating and drying a capacitor element on which a dielectric oxide film is formed in a dispersion solution having a basic composition of PEDOT / PSS, chemistry of polyethylene glycol, and (—CH 2 —CH (R) —O—) n Compound containing structure (wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer)
A step of impregnating a mixed solution containing
本発明の固体電解コンデンサにおいては、誘電体酸化皮膜が形成された陽極箔と、陰極箔とをセパレータを介して巻回したコンデンサ素子に、ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸（ＰＥＤＯＴ／ＰＳＳ）を基本組成とする分散溶液を少なくとも１回含浸および乾燥させることによって導電性高分子層が形成されており、ＰＥＤＯＴ／ＰＳＳからなる層で構成された導電性高分子層により、導電性の高い固体電解コンデンサが得られる。 In the solid electrolytic capacitor of the present invention, polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) is applied to a capacitor element in which an anode foil on which a dielectric oxide film is formed and a cathode foil are wound through a separator. The conductive polymer layer is formed by impregnating and drying the dispersion solution having the basic composition at least once, and the conductive polymer layer composed of the layer made of PEDOT / PSS is used to perform solid electrolysis with high conductivity. A capacitor is obtained.
なお、本発明では、上記の導電性高分子層が水分の影響により膨潤するのを抑制し、固体電解コンデンサの耐湿性を向上させるために、予め誘電体酸化皮膜上にポリチオフェン、ポリピロール、ポリアニリン又はその誘導体を含む溶液を含浸および乾燥させることによって第一の導電性高分子層を形成しておくことが好ましく、この上に第二の導電性高分子層としてＰＥＤＯＴ／ＰＳＳ層が形成される。
また、本発明の固体電解コンデンサにおけるセパレータとしては、加水分解性を有さないセパレータ、例えば、ポリアクリロニトリル、アラミドを主体とするセパレータであることが好ましく、このようなセパレータを用いることで、特に高温領域において、より耐久性に優れた固体電解コンデンサを得ることができる。
In the present invention, in order to suppress the swelling of the conductive polymer layer due to the influence of moisture and improve the moisture resistance of the solid electrolytic capacitor, polythiophene, polypyrrole, polyaniline or It is preferable to form a first conductive polymer layer by impregnating and drying a solution containing the derivative, and a PEDOT / PSS layer is formed thereon as the second conductive polymer layer.
Further, as the separator in the solid electrolytic capacitor of the present invention, a separator having no hydrolyzability, for example, a separator mainly composed of polyacrylonitrile or aramid is preferable. In the region, a solid electrolytic capacitor having higher durability can be obtained.
本発明の固体電解コンデンサにあっては、コンデンサ素子内に、ポリエチレングリコールと、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物（但し、Ｒは炭素数１〜４のアルキル基を示す）を含む混合溶液が含浸されており、本発明において好ましい（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物としては、Ｒがメチル基で、このオキシプロピレン繰り返し構造がグリセリンのＯＨ基に結合したポリオキシプロピレングリセリルエーテルや、化学構造式がＨＯ（−ＣＨ２−ＣＨ（ＣＨ３）−Ｏ−）ｎＨで表されるポリオキシプロピレン等が挙げられる。なお、本発明では、前記の（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物が、ポリエチレングリコール重量の０.５〜５倍の重量で混合されていることがより好ましい。 In the solid electrolytic capacitor of the present invention, a polyethylene glycol and a compound containing a chemical structure of (—CH 2 —CH (R) —O—) n (where R is 1 to 4 carbon atoms) in the capacitor element. A compound containing a chemical structure of (—CH 2 —CH (R) —O—) n which is preferable in the present invention, R is a methyl group, Examples include polyoxypropylene glyceryl ether in which the oxypropylene repeating structure is bonded to the OH group of glycerin, and polyoxypropylene in which the chemical structural formula is represented by HO (—CH 2 —CH (CH 3 ) —O—) n H. It is done. In the present invention, the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n is preferably mixed in a weight of 0.5 to 5 times the weight of polyethylene glycol. preferable.
次に、上記の本発明の固体電解コンデンサを製造するための本発明の製法について説明する。本発明の製造方法における最初の工程では、誘電体酸化皮膜が形成された陽極箔と、陰極箔とをセパレータを介して巻回したコンデンサ素子に、導電性高分子が溶解された溶液を含浸及び乾燥させて、誘電体酸化皮膜上に第一の導電性高分子層を形成させる。この際、導電性高分子が溶解された溶液としては、ポリチオフェン、ポリピロール、ポリアニリン又はその誘導体のいずれかが溶解された溶液であることが好ましく、固体電解コンデンサのセパレータは、加水分解性を有さないセパレータであることが好ましい。
本発明では、導電性高分子が溶解された溶液として上記のものを用いることで、汎用的な方法で陽極箔表面に導電性高分子層を一層形成することが可能である。また、導電性高分子の溶液を用いることによって、陽極酸化皮膜上で重合反応を行う場合よりも均一に導電性高分子層を形成することが可能であり、また、コンデンサ素子内に未反応モノマーや酸化剤等の不要物質が残存することがないため、固体電解コンデンサの耐湿性を向上させると共に電気特性を改善することが可能である。
Next, the production method of the present invention for producing the solid electrolytic capacitor of the present invention will be described. In the first step in the production method of the present invention, a capacitor element obtained by winding an anode foil with a dielectric oxide film and a cathode foil wound through a separator is impregnated with a solution in which a conductive polymer is dissolved. A first conductive polymer layer is formed on the dielectric oxide film by drying. At this time, the solution in which the conductive polymer is dissolved is preferably a solution in which any of polythiophene, polypyrrole, polyaniline or a derivative thereof is dissolved, and the separator of the solid electrolytic capacitor has hydrolyzability. It is preferable that there is no separator.
In the present invention, by using the above-mentioned solution in which the conductive polymer is dissolved, it is possible to form a single layer of the conductive polymer layer on the anode foil surface by a general method. Also, by using a conductive polymer solution, it is possible to form a conductive polymer layer more uniformly than when a polymerization reaction is carried out on the anodized film, and unreacted monomers in the capacitor element. Since unnecessary substances such as oxidants and oxidants do not remain, it is possible to improve the moisture resistance of the solid electrolytic capacitor and improve the electrical characteristics.
そして、本発明の製造方法における次の工程では、ポリエチレンジオキシチオフェンとポリスチレンスルホン酸とを含む分散液を、コンデンサ素子に含浸及び乾燥させることで、第一の導電性高分子層上に第二の導電性高分子層（ＰＥＤＯＴ／ＰＳＳ層）を形成させる。このようなポリエチレンジオキシチオフェンとポリスチレンスルホン酸との分散液を使用した場合には、コンデンサ素子内に酸化剤やモノマー成分が残存することが少なくなり、特に高温度下における誘電体皮膜の劣化が抑えられ、これにより、低温領域における静電容量の変化が小さく、また、高温度下においてもコンデンサの特性変化が少ない固体電解コンデンサを得ることができる。 In the next step of the production method of the present invention, the capacitor element is impregnated and dried with a dispersion liquid containing polyethylenedioxythiophene and polystyrenesulfonic acid, so that the second conductive material is formed on the first conductive polymer layer. The conductive polymer layer (PEDOT / PSS layer) is formed. When such a dispersion of polyethylene dioxythiophene and polystyrene sulfonic acid is used, the oxidizer and monomer components are less likely to remain in the capacitor element, and deterioration of the dielectric film particularly at high temperatures. Thus, it is possible to obtain a solid electrolytic capacitor in which the capacitance change in the low temperature region is small and the capacitor characteristic change is small even at a high temperature.
本発明の製造方法における最終工程では、ポリエチレングリコールと、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物とを含む混合溶液を減圧下で一定時間、コンデンサ素子に含浸させる。ポリエチレングリコールを単体で含浸させた場合には、高温度雰囲気下、温度サイクル試験時に自動酸化劣化により短時間で特性が悪化するが、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物と混合することによって熱酸化劣化の反応性が抑制され、耐高温度特性及び温度サイクル特性が改善する。 In the final step in the production method of the present invention, a capacitor element is impregnated with a mixed solution containing polyethylene glycol and a compound containing a chemical structure of (—CH 2 —CH (R) —O—) n for a certain period of time under reduced pressure. Let When polyethylene glycol is impregnated alone, the properties deteriorate in a short time due to auto-oxidation degradation during a temperature cycle test in a high temperature atmosphere, but the chemistry of (—CH 2 —CH (R) —O—) n By mixing with a compound containing a structure, the reactivity of thermal oxidative degradation is suppressed, and the high temperature resistance and temperature cycle characteristics are improved.
本発明によれば、１２５℃以上の高温度雰囲気下でも静電容量の変化が少なく、低いＥＳＲが維持され、温度サイクル特性に優れた固体電解コンデンサが得られる。 According to the present invention, it is possible to obtain a solid electrolytic capacitor that has little change in capacitance even under a high temperature atmosphere of 125 ° C. or higher, maintains low ESR, and has excellent temperature cycle characteristics.
図１はコンデンサ素子の概要を示す分解斜視図である。コンデンサ素子４内には、陽極箔１と陰極箔３がセパレータ２を介して巻回されて収納されており、陽極箔に接続された陽極リード線５及び陰極箔に接続された陰極リード線６が引き出されている。
FIG. 1 is an exploded perspective view showing an outline of a capacitor element. In the capacitor element 4, an
本発明の固体電解コンデンサの陽極箔は、所定の幅の平板状の弁作用金属の表面をエッチング処理で粗面化した後に化成酸化処理を行って、表面上に誘電体酸化皮膜が形成されたものを用いる。弁金属作用としては、アルミニウム、タンタル、ニオブ、チタンから選択される少なくとも一つを含む金属が好ましく、中でもアルミニウムが好ましい。 The anode foil of the solid electrolytic capacitor of the present invention was formed by subjecting the surface of a plate-like valve action metal having a predetermined width to a rough surface by etching treatment, followed by chemical oxidation treatment to form a dielectric oxide film on the surface. Use things. As the valve metal action, a metal containing at least one selected from aluminum, tantalum, niobium, and titanium is preferable, and aluminum is particularly preferable.
エッチング処理および化成酸化処理は公知の方法で行うことが可能であり、購入品を用いることもできる。例えば、化成酸化処理に用いる化成液は、カルボン酸基を有する有機酸塩類、リン酸等の無機酸塩類の溶質を有機溶媒又は無機溶媒に溶解した化成液が使用できる。 Etching treatment and chemical oxidation treatment can be performed by known methods, and purchased products can also be used. For example, the chemical conversion liquid used for the chemical conversion treatment may be a chemical conversion liquid in which a solute of an organic acid salt having a carboxylic acid group or an inorganic acid salt such as phosphoric acid is dissolved in an organic solvent or an inorganic solvent.
陽極箔は前述のとおりセパレータ及び陰極箔とともに巻回されるが、巻回後に、陽極箔の切り口や外部引き出し電極の取り付け時に欠損した誘電体酸化皮膜を修復するために、修復化成を行う。修復化成のための化成液としては、カルボン酸基を有する有機酸塩類、リン酸等の無機酸塩類の溶質を有機溶媒又は無機溶媒に溶解した化成液が使用できる。 As described above, the anode foil is wound together with the separator and the cathode foil, and after the winding, restoration conversion is performed in order to repair the dielectric oxide film that is lost when the cut end of the anode foil or the external lead electrode is attached. As a chemical conversion liquid for restoration chemical conversion, a chemical conversion liquid in which a solute of an organic acid salt having a carboxylic acid group or an inorganic acid salt such as phosphoric acid is dissolved in an organic solvent or an inorganic solvent can be used.
そして次に、誘電体酸化皮膜上に第一の導電性高分子層を形成する。第一の導電性高分子層は、溶液タイプの導電性高分子溶液を含浸・乾燥することによって形成されることが好ましい。第一の導電性高分子層は、ポリチオフェン、ポリピロール、ポリアニリンまたはその誘導体を主体とする溶液を用いて形成されること、つまり、ポリチオフェン、ポリピロール、ポリアニリン又はその誘導体を主体とする導電性高分子層であることが好ましい。溶液における導電性高分子の濃度は０．１〜２．０ｗｔ％が好ましく、溶媒としてはアルコールやエーテル類、芳香族系を問わず、導電性高分子を溶解し且つ、２５０℃未満の乾燥温度にて蒸散可能な溶媒を用いることができる。乾燥条件は、溶媒を除去可能かつコンデンサ素子に悪影響を及ぼさない限り制限されないが、例えば１００〜２５０℃で３０〜１２０分、乾燥させることができる。第一の導電性高分子層を形成するための溶液として、特に好ましくは、０．５〜１．５ｗｔ％のポリアニリン／エタノール溶液を用い、１５０℃で３０分乾燥させることにより形成できる。ポリアニリンのドーパントには、例えば、スルホコハク酸エステルを用いることができる。 Next, a first conductive polymer layer is formed on the dielectric oxide film. The first conductive polymer layer is preferably formed by impregnating and drying a solution type conductive polymer solution. The first conductive polymer layer is formed using a solution mainly composed of polythiophene, polypyrrole, polyaniline or a derivative thereof, that is, a conductive polymer layer mainly composed of polythiophene, polypyrrole, polyaniline or a derivative thereof. It is preferable that The concentration of the conductive polymer in the solution is preferably 0.1 to 2.0% by weight, and the solvent dissolves the conductive polymer regardless of alcohol, ethers or aromatic solvent, and the drying temperature is less than 250 ° C. A solvent capable of being evaporated at a temperature can be used. The drying conditions are not limited as long as the solvent can be removed and the capacitor element is not adversely affected. For example, the drying can be performed at 100 to 250 ° C. for 30 to 120 minutes. Particularly preferably, the solution for forming the first conductive polymer layer can be formed by using a polyaniline / ethanol solution of 0.5 to 1.5 wt% and drying at 150 ° C. for 30 minutes. As the polyaniline dopant, for example, a sulfosuccinate can be used.
このようにして形成された第一の導電性高分子層の上には、第二の導電性高分子層が形成される。第二の導電性高分子層は、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）とを含むポリマー分散液に、コンデンサ素子を浸漬・含浸させた後、乾燥によって水分を除去することによって形成されることが好ましい。ＰＥＤＯＴ／ＰＳＳ分散液としては、溶媒として水を使用したものが好ましく、分散液中のＰＥＤＯＴ／ＰＳＳの濃度を０．５〜３．０ｗｔ％として作製したものを用いてもよい。第二の導電性高分子層を形成する際、含浸を常圧下で行ってもよいが、減圧下で行うことも好ましい。また、含浸及び乾燥は、２回以上繰り返して行うことができる。乾燥条件は、溶媒を除去可能かつコンデンサ素子に悪影響を及ぼさない限り制限されないが、例えば８５〜１５０℃で３０〜１２０分、乾燥させることができる。特に好ましくは、１．０ｗｔ％のＰＥＤＯＴ／ＰＳＳを含むポリマー分散体溶液を用いて、１０ｋＰａの減圧下で１５分間浸漬・含浸させ、１００℃で６０分乾燥を行う工程を３回繰り返すことによって、第二の導電性高分子層を形成することができる。 A second conductive polymer layer is formed on the first conductive polymer layer thus formed. The second conductive polymer layer is formed by immersing and impregnating the capacitor element in a polymer dispersion containing polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS), and then removing moisture by drying. Preferably it is formed. As the PEDOT / PSS dispersion, those using water as the solvent are preferable, and those prepared with the concentration of PEDOT / PSS in the dispersion being 0.5 to 3.0 wt% may be used. When forming the second conductive polymer layer, the impregnation may be performed under normal pressure, but it is also preferable to perform it under reduced pressure. The impregnation and drying can be repeated twice or more. The drying conditions are not limited as long as the solvent can be removed and the capacitor element is not adversely affected. For example, drying can be performed at 85 to 150 ° C. for 30 to 120 minutes. Particularly preferably, by repeating the step of immersing and impregnating for 15 minutes under a reduced pressure of 10 kPa using a polymer dispersion solution containing 1.0 wt% PEDOT / PSS and drying at 100 ° C. for 60 minutes, A second conductive polymer layer can be formed.
そして、上記の工程により導電性高分子層を形成させたコンデンサ素子を、ポリエチレングリコールと、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物とを含む混合溶液を減圧下（例えば１０ｋＰａ）で一定時間（例えば３０分間）、コンデンサ素子に含浸させ、その後、このコンデンサ素子を金属ケースに収納し、金属ケースの開口部をカーリングし、１５０℃程度の温度条件にてコンデンサに定格電圧を印加してエージング処理を施すことにより、本発明の固体電解コンデンサが得られる。 Then, the capacitor element in which the conductive polymer layer is formed by the above process is reduced in pressure with respect to a mixed solution containing polyethylene glycol and a compound containing a chemical structure of (—CH 2 —CH (R) —O—) n. The capacitor element is impregnated for a certain period of time (for example, 30 minutes) at a lower temperature (for example, 10 kPa), and then the capacitor element is housed in a metal case, the opening of the metal case is curled, and the capacitor is heated at about 150 ° C. The solid electrolytic capacitor of the present invention can be obtained by applying an aging treatment by applying a rated voltage to the capacitor.
以下に、実施例によって本発明をより具体的に説明するが、本発明は下記の実施例に制限されない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples.
［実施例１］
所定の幅に切断された陽極箔及び陰極箔に外部引き出し電極用のタブ端子を接続した。陽極箔は、弁金属としてアルミニウム箔を用い、弁金属の表面にエッチング処理及び化成処理を施すことによって、誘電体酸化皮膜が形成されたものを用いた。
前記の陽極箔及び、表面に酸化チタンが形成された陰極箔を、ポリアクリロニトリルを主体としたセパレータを介して巻回し、巻回素子を完成した。
続いて、陽極箔の切り口や外部引き出し電極取り付け時に欠損した誘電体酸化皮膜の修復、いわゆる化成処理を行った。アジピン酸アンモニウムを水溶媒に溶解させた０．５〜３ｗｔ％の化成液を用いて、誘電体酸化皮膜の化成電圧値に近似した電圧を印加し、化成処理を行った。
[Example 1]
A tab terminal for an external lead electrode was connected to the anode foil and the cathode foil cut to a predetermined width. As the anode foil, an aluminum foil was used as a valve metal, and the surface of the valve metal was subjected to an etching treatment and a chemical conversion treatment to form a dielectric oxide film.
The anode foil and the cathode foil having titanium oxide formed on the surface were wound through a separator mainly composed of polyacrylonitrile, thereby completing a wound element.
Subsequently, a so-called chemical conversion treatment was performed to repair the dielectric oxide film that was missing when the anode foil was cut or the external lead electrode was attached. Using a 0.5 to 3 wt% chemical conversion solution in which ammonium adipate was dissolved in an aqueous solvent, a voltage approximate to the chemical conversion voltage value of the dielectric oxide film was applied to perform chemical conversion treatment.
次に、固体電解コンデンサの陰極層である導電性高分子層の形成を行った。
まず、巻回素子に１．０ｗｔ％ポリアニリン／エタノール溶液を含浸し、１５０℃で３０分乾燥させることで第一の導電性高分子層を形成させた。
その後、１．０ｗｔ％のＰＥＤＯＴ／ＰＳＳを含むポリマー分散体溶液を１０ｋＰａの減圧下で１５分間浸漬・含浸させ、１００℃で６０分加熱することによって水分を除去した。この含浸及び乾燥を３回繰り返して、第二の導電性高分子層を形成させた。
さらに、ポリエチレングリコール（三洋化成工業社製のＰＥＧ−６００、水酸基価から求めた数平均分子量：６００）とポリオキシプロピレングリセリルエーテル（三洋化成工業社製のサンニックスＧＰ−４００、水酸基価から求めた数平均分子量：４００）を４０：６０の重量比率で混合し、この混合溶液に上記巻回素子を１０ｋＰａ減圧下で３０分含浸させた。
Next, a conductive polymer layer that is a cathode layer of the solid electrolytic capacitor was formed.
First, the wound element was impregnated with a 1.0 wt% polyaniline / ethanol solution and dried at 150 ° C. for 30 minutes to form a first conductive polymer layer.
Thereafter, a polymer dispersion solution containing 1.0 wt% PEDOT / PSS was immersed and impregnated under a reduced pressure of 10 kPa for 15 minutes, and the water was removed by heating at 100 ° C. for 60 minutes. This impregnation and drying were repeated three times to form a second conductive polymer layer.
Further, polyethylene glycol (PEG-600 manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight determined from hydroxyl value: 600) and polyoxypropylene glyceryl ether (Sanix GP-400 manufactured by Sanyo Chemical Industries, Ltd., determined from hydroxyl values) Number average molecular weight: 400) was mixed at a weight ratio of 40:60, and this mixed solution was impregnated with the above wound element under a reduced pressure of 10 kPa for 30 minutes.
上記方法で導電性高分子層が形成されたコンデンサ素子を金属ケースに収納し、金属ケースの開口部をカーリングした。続いて、１５０℃程度の温度条件にてコンデンサに定格電圧を印加してエージング処理を施し、固体電解コンデンサを完成した。 The capacitor element on which the conductive polymer layer was formed by the above method was housed in a metal case, and the opening of the metal case was curled. Subsequently, an aging treatment was performed by applying a rated voltage to the capacitor under a temperature condition of about 150 ° C. to complete a solid electrolytic capacitor.
［実施例２］
コンデンサ素子に含浸させる後処理溶液として、ＰＥＧ−６００とＧＰ−４００を３０：７０の重量比率で混合した溶液を使用する以外は、実施例１と同様に固体電解コンデンサを作製した。
[Example 2]
A solid electrolytic capacitor was produced in the same manner as in Example 1 except that a solution obtained by mixing PEG-600 and GP-400 at a weight ratio of 30:70 was used as a post-treatment solution to be impregnated into the capacitor element.
［実施例３］
コンデンサ素子に含浸させる後処理溶液として、ＰＥＧ−６００とＧＰ−４００を７０：３０の重量比率で混合した溶液を使用する以外は、実施例１と同様に固体電解コンデンサを作製した。
[Example 3]
A solid electrolytic capacitor was produced in the same manner as in Example 1 except that a solution obtained by mixing PEG-600 and GP-400 at a weight ratio of 70:30 was used as a post-treatment solution to be impregnated into the capacitor element.
［実施例４］
コンデンサ素子に含浸させる後処理溶液として、ＰＥＧ−６００とＧＰ−４００と純水を３０：２０：５０の重量比率で混合した溶液を使用する以外は、実施例１と同様に固体電解コンデンサを作製した。
[Example 4]
A solid electrolytic capacitor is produced in the same manner as in Example 1 except that a solution obtained by mixing PEG-600, GP-400, and pure water at a weight ratio of 30:20:50 is used as a post-treatment solution to be impregnated into the capacitor element. did.
［従来例］
コンデンサ素子に含浸させる後処理溶液として、ＰＥＧ−６００の５０％水溶液を使用する以外は、実施例１と同様に固体電解コンデンサを作製した。
[Conventional example]
A solid electrolytic capacitor was produced in the same manner as in Example 1 except that a 50% aqueous solution of PEG-600 was used as a post-treatment solution to be impregnated into the capacitor element.
［実施例および従来例の固体電解コンデンサの評価］
実施例および従来例の固体電解コンデンサについて下記の評価方法にて評価を行った。
検討製品：φ８×１０Ｌ ３５ＷＶ−１５０μＦ
１．温度サイクル試験
試験条件：−５５℃／＋１２５℃ 各３０ｍｉｎを１サイクルとし、１，０００サイクル実施後の静電容量（Ｃａｐ）、ｔａｎδ及び等価直列抵抗（ＥＳＲ）を測定し、試験前と値からの変化率を計算した。その結果を以下の表１に示す。
２．信頼性試験
試験条件：試験雰囲気：１４５℃
印加電圧・経過時間：３５Ｖ印加、２，０００時間
１４５℃、３５Ｖ印加、２，０００時間後の静電容量（Ｃａｐ）、ｔａｎδ、等価直列抵抗（ＥＳＲ）を測定し、試験前の値から変化率を計算した。その結果を以下の表２に示す。
[Evaluation of Solid Electrolytic Capacitors of Examples and Conventional Examples]
The solid electrolytic capacitors of Examples and Conventional Examples were evaluated by the following evaluation methods.
Products to be examined: φ8 × 10L 35WV-150μF
1. Temperature cycle test Test conditions: −55 ° C./+125° C. Each 30 min is one cycle, and the capacitance (Cap), tan δ and equivalent series resistance (ESR) after 1,000 cycles are measured. The rate of change was calculated. The results are shown in Table 1 below.
2. Reliability test Test condition: Test atmosphere: 145 ° C
Applied voltage / elapsed time: 35 V applied, 2,000 hours 145 ° C., 35 V applied, 2,000 hours later, the capacitance (Cap), tan δ, and equivalent series resistance (ESR) were measured and changed from the values before the test. The rate was calculated. The results are shown in Table 2 below.
実施例１〜４及び従来例において使用したポリマー溶液
従来例：ＰＥＧ−６００ ５０％ａｑの後処理溶液
実施例１：ＰＥＧ−６００ ４０％、ＧＰ−４００ ６０％を混合した後処理溶液
実施例２：ＰＥＧ−６００ ３０％、ＧＰ−４００ ７０％を混合した後処理溶液
実施例３：ＰＥＧ−６００ ７０％、ＧＰ−４００ ３０％を混合した後処理溶液
実施例４：ＰＥＧ−６００ ３０％、ＧＰ−４００ ２０％、純水５０％を混合した後処理溶液
Polymer solutions used in Examples 1 to 4 and the conventional example Conventional example: PEG-600 50% aq after-treatment solution Example 1: PEG-600 40% and GP-400 60% mixed after-treatment solution Example 2 : PEG-600 30%, GP-400 70% after-treatment solution Example 3: PEG-600 70%, GP-400 30% after-treatment solution Example 4: PEG-600 30%, GP -400 20% post-treatment solution mixed with pure water 50%
上表１および表２の実験結果に示されるとおり、上記の温度サイクル試験および高温度信頼試験における静電容量（Ｃａｐ）、ｔａｎδ、等価直列抵抗（ＥＳＲ）の変化率は、実施例１〜４の方が、従来例よりも小さく、安定している。また、表２には、高温度信頼性試験において、実施例１〜４の静電容量（Ｃａｐ）、ｔａｎδ、等価直列抵抗（ＥＳＲ）の変化率が、従来例よりも小さく、高温領域（１４５℃）においても安定性に優れていることが示されており、特に、ＧＰ−４００の重量がＰＥＧ−６００の重量の０．５倍を超える場合（実施例１，２，４）に、より良好な高温度安定性が得られることがわかった。なお、ＧＰ−４００の重量をＰＥＧ−６００の重量の５倍以下とすることで耐電圧特性が向上するので、高温度安定性と耐電圧特性とを両立させる観点から、ＧＰ−４００の重量はＰＥＧ−６００の重量の０．５〜５倍とすることがより好ましい。また、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの数平均分子量は４００〜４０００の化合物を使用すると、コンデンサ素子への含浸性を向上させることができる。 As shown in the experimental results of Table 1 and Table 2 above, the rate of change in capacitance (Cap), tan δ, and equivalent series resistance (ESR) in the above-described temperature cycle test and high-temperature reliability test are shown in Examples 1-4. Is smaller and more stable than the conventional example. Table 2 also shows that in the high temperature reliability test, the rate of change in capacitance (Cap), tan δ, and equivalent series resistance (ESR) in Examples 1 to 4 is smaller than that in the conventional example, and the high temperature region (145 (° C.), it is also shown that the stability is excellent, particularly when the weight of GP-400 exceeds 0.5 times the weight of PEG-600 (Examples 1, 2, 4). It has been found that good high temperature stability can be obtained. In addition, since the withstand voltage characteristics are improved by making the weight of GP-400 5 times or less than the weight of PEG-600, from the viewpoint of achieving both high temperature stability and withstand voltage characteristics, the weight of GP-400 is More preferably, it is 0.5 to 5 times the weight of PEG-600. Further, when a compound having a number average molecular weight of (—CH 2 —CH (R) —O—) n of 400 to 4000 is used, the impregnation property to the capacitor element can be improved.
そして、本発明は、上記実施例において、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物として、ポリオキシプロピレングリセリルエーテルを用いたが、他に、ポリオキシプロピレン、ポリオキシプロピレントリメチロールプロパンエーテル、ポリオキシプロピレンソルビトールエーテルを用いても同様の効果が得られる。 In the above embodiment, the present invention uses polyoxypropylene glyceryl ether as the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n . The same effect can be obtained by using polyoxypropylene trimethylolpropane ether or polyoxypropylene sorbitol ether.
さらに、本発明は、上記実施例において、導電性高分子層形成後、巻回素子を、ポリエチレングリコールとポリオキシプロピレングリセリルエーテルの混合溶液に含浸させたが、誘電体酸化皮膜形成後、巻回素子を、ＰＥＤＯＴ／ＰＳＳを含むポリマー分散体溶液にポリエチレングリコールとポリオキシプロピレングリセリルエーテルなど（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物とを混合させた溶液に含浸させても同様の効果が得られる。 Furthermore, the present invention provides a winding element impregnated with a mixed solution of polyethylene glycol and polyoxypropylene glyceryl ether after the formation of the conductive polymer layer in the above embodiment. The element is impregnated with a solution obtained by mixing a polymer dispersion solution containing PEDOT / PSS with a compound containing a chemical structure of (—CH 2 —CH (R) —O—) n such as polyethylene glycol and polyoxypropylene glyceryl ether. Even if it makes it, the same effect is acquired.
また、本発明では、（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物として、Ｒがメチル基のものを用いたが、他にエチル基、プロピル基、ブチル基のものを用いても同様の効果が得られる。そして、Ｒが炭素数１〜４のアルキル基の場合、化合物の合成が比較的容易であることから、Ｒは炭素数１〜４のアルキル基が好ましい。 In the present invention, as the compound containing the chemical structure of (—CH 2 —CH (R) —O—) n , those in which R is a methyl group are used, but in addition, an ethyl group, a propyl group, a butyl group The same effect can be obtained even if one is used. And when R is a C1-C4 alkyl group, since the synthesis | combination of a compound is comparatively easy, R is a C1-C4 alkyl group.
なお、上記実施例では、コンデンサ素子を誘電体酸化皮膜が形成された陽極箔と陰極箔とをセパレータを介して巻回して形成したが、誘電体酸化皮膜が形成された陽極箔を積層したコンデンサ素子や、弁作用金属の粉体を焼結後、誘電体酸化皮膜を形成したコンデンサ素子を使用してもよい。 In the above embodiment, the capacitor element is formed by winding the anode foil and the cathode foil on which the dielectric oxide film is formed through the separator, but the capacitor is formed by stacking the anode foil on which the dielectric oxide film is formed. A capacitor element in which a dielectric oxide film is formed after sintering the element or valve action metal powder may be used.
１ 陽極箔
２ セパレータ
３ 陰極箔
４ コンデンサ素子
５ 陽極リード線
６ 陰極リード線
1
Claims (5)
ポリエチレングリコールと、
（−ＣＨ２−ＣＨ（Ｒ）−Ｏ−）ｎの化学構造を含む化合物（但し、Ｒは炭素数１〜４のアルキル基を示し、ｎは整数を示す）と
が含まれることを特徴とする固体電解コンデンサ。 In a solid electrolytic capacitor in which an electrolyte is formed on the surface of a dielectric oxide film by impregnating and drying a dispersion solution having a basic composition of polyethylenedioxythiophene / polystyrenesulfonic acid on a capacitor element on which the dielectric oxide film is formed In the capacitor element,
Polyethylene glycol,
(—CH 2 —CH (R) —O—) and a compound having a chemical structure of n (where R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer), Solid electrolytic capacitor.
を含む混合溶液に含浸させる工程
を含むことを特徴とする、固体電解コンデンサの製造方法。 Impregnating and drying the capacitor element on which the dielectric oxide film is formed in a dispersion solution having a basic composition of polyethylenedioxythiophene / polystyrenesulfonic acid, polyethylene glycol, (—CH 2 —CH (R) —O) -) Compound having a chemical structure of n (wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer)
A method for producing a solid electrolytic capacitor comprising a step of impregnating a mixed solution containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015142412A JP6537105B2 (en) | 2015-07-16 | 2015-07-16 | Solid electrolytic capacitor and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015142412A JP6537105B2 (en) | 2015-07-16 | 2015-07-16 | Solid electrolytic capacitor and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017027992A true JP2017027992A (en) | 2017-02-02 |
| JP6537105B2 JP6537105B2 (en) | 2019-07-03 |
Family
ID=57949907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015142412A Active JP6537105B2 (en) | 2015-07-16 | 2015-07-16 | Solid electrolytic capacitor and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6537105B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110491674A (en) * | 2019-08-07 | 2019-11-22 | 上海永铭电子股份有限公司 | A kind of solid-liquid mixing alminium electrolytic condenser and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007531233A (en) * | 2004-04-01 | 2007-11-01 | ディーピーアイ ソリューションズ インコーポレイテッド | Composition for coating organic electrode and method for producing highly transparent organic electrode using the same |
| WO2011099261A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Electrolytic capacitor |
| JP2011157535A (en) * | 2010-01-29 | 2011-08-18 | Nihon Sentan Kagaku Kk | Method of production of electroconductive composition |
| JP2013539227A (en) * | 2010-10-01 | 2013-10-17 | ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー | Method for improving electrical parameters in capacitors containing PEDOT / PSS as solid electrolyte with polyalkylene glycol |
| JP2015515746A (en) * | 2012-03-12 | 2015-05-28 | ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー | Addition of polymer to thiophene monomer in in situ polymerization |
-
2015
- 2015-07-16 JP JP2015142412A patent/JP6537105B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007531233A (en) * | 2004-04-01 | 2007-11-01 | ディーピーアイ ソリューションズ インコーポレイテッド | Composition for coating organic electrode and method for producing highly transparent organic electrode using the same |
| JP2011157535A (en) * | 2010-01-29 | 2011-08-18 | Nihon Sentan Kagaku Kk | Method of production of electroconductive composition |
| WO2011099261A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Electrolytic capacitor |
| JP2013539227A (en) * | 2010-10-01 | 2013-10-17 | ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー | Method for improving electrical parameters in capacitors containing PEDOT / PSS as solid electrolyte with polyalkylene glycol |
| JP2015515746A (en) * | 2012-03-12 | 2015-05-28 | ヘレウス プレシャス メタルズ ゲーエムベーハー ウント コンパニー カーゲー | Addition of polymer to thiophene monomer in in situ polymerization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110491674A (en) * | 2019-08-07 | 2019-11-22 | 上海永铭电子股份有限公司 | A kind of solid-liquid mixing alminium electrolytic condenser and preparation method thereof |
| CN110491674B (en) * | 2019-08-07 | 2024-02-13 | 上海永铭电子股份有限公司 | Solid-liquid mixed aluminum electrolytic capacitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6537105B2 (en) | 2019-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6384896B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
| JP4916416B2 (en) | Electrolytic capacitor manufacturing method and electrolytic capacitor | |
| JP6358646B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
| JP5388811B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
| JP2012186452A (en) | Method for improving electrical parameters in capacitors containing pedot/pss as solid electrolyte by polyglycerol | |
| JP6669461B2 (en) | Electrolytic capacitor and method of manufacturing the same | |
| JP4975237B2 (en) | Method for producing conductive composition and solid electrolytic capacitor using the same | |
| JP2012244077A (en) | Method for manufacturing solid electrolytic capacitor | |
| JP2012246427A (en) | Conductive polymer, conductive polymer aqueous solution, conductive polymer film, solid electrolytic capacitor and method for producing the same | |
| WO2004075220A1 (en) | Solid electrolytic capacitor and method for manufacturing same | |
| JP6154461B2 (en) | Oxidant solution for producing conductive polymer, solid electrolytic capacitor using the same, and method for producing solid electrolytic capacitor | |
| JP6433024B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
| JP6652835B2 (en) | Solid electrolytic capacitor and method of manufacturing the same | |
| JP2017027992A (en) | Solid electrolytic capacitor and manufacturing method therefor | |
| JP5557638B2 (en) | Oxidant solution for producing conductive polymer and method for producing solid electrolytic capacitor using the same | |
| JP5327842B2 (en) | Oxidizing agent for producing conductive polymer, solid electrolytic capacitor using the same, and method for producing the same | |
| JP2008288342A (en) | Method of forming electrolyte for electrolytic capacitor | |
| JP2004265941A (en) | Solid state electrolytic capacitor and its manufacturing method | |
| JP6395202B2 (en) | Solid electrolytic capacitor and manufacturing method thereof | |
| JP2008060556A (en) | Solid-state electrolytic capacitor, and its manufacturing process | |
| JP2010177498A (en) | Wound type solid electrolyte capacitor | |
| JP4668140B2 (en) | Manufacturing method of solid electrolytic capacitor | |
| JP4442285B2 (en) | Manufacturing method of solid electrolytic capacitor | |
| JP2004288958A (en) | Manufacturing method of solid electrolytic capacitor | |
| JP5116130B2 (en) | Solid electrolytic capacitor and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181022 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181214 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190529 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190530 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6537105 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |