JP2022017716A - Manufacturing method of electrolytic capacitor - Google Patents
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
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- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000005068 transpiration Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
Description
本発明は、電解コンデンサの製造方法、特に導電性高分子ハイブリッドアルミニウム電解コンデンサの製造方法に関する。 The present invention relates to a method for manufacturing an electrolytic capacitor, particularly a method for manufacturing a conductive polymer hybrid aluminum electrolytic capacitor.
従来、電解コンデンサは、アルミニウム、タンタル、ニオブ等の弁作用金属からなる、エッチングピットや微細孔を持つ陽極電極の表面上に誘電体となる酸化皮膜層を形成した後、この酸化皮膜層上に電解質層を形成し、電極を引き出して構成される。
このように形成した電解質層が真の陰極であり、電解コンデンサの電気特性に大きな影響を及ぼすことから、従来から種々の方法により電解質層を形成することが提案されている。
Conventionally, an electrolytic capacitor has formed an oxide film layer as a dielectric on the surface of an anode electrode having etching pits and micropores made of a valve acting metal such as aluminum, tantalum, and niob, and then is placed on the oxide film layer. It is configured by forming an electrolyte layer and pulling out the electrodes.
Since the electrolyte layer thus formed is a true cathode and has a great influence on the electrical characteristics of the electrolytic capacitor, it has been conventionally proposed to form the electrolyte layer by various methods.
中でも、固体電解コンデンサは、高周波領域でインピーダンス特性を改善するために、イオン伝導性である液状の電解質に替えて、電子伝導性である固体の電解質を用いるものである。例えば、かかる固体電解質として７，７，８，８－テトラシアノキノジメタン（ＴＣＮＱ）錯体を用い、このＴＣＮＱ錯体を熱溶融して陽極電極に浸漬、塗布し、固体電解質層を形成したものや、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）等の導電性高分子を固体電解質として用いたものが公知である。 Among them, the solid electrolytic capacitor uses a solid electrolyte having electron conductivity instead of a liquid electrolyte having ion conductivity in order to improve the impedance characteristics in a high frequency region. For example, a 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex is used as the solid electrolyte, and the TCNQ complex is thermally melted, immersed in an anode electrode, and applied to form a solid electrolyte layer. , Polyethylenedioxythiophene (PEDOT) and other conductive polymers are known as solid electrolytes.
ところで、かかる固体電解コンデンサに関しては、その漏れ電流を低くするために、所定の条件下で、当該電解コンデンサの両電極間に所定の電圧を適切な時間だけ印加することによるエージング処理がなされるのが一般的であり、歩留向上のためのエージング処理を含む様々な固体電解コンデンサの製造方法が検討されている。
例えば、下記の特許文献１には、エージング後の常温放置中に漏れ電流（Leakage Current, ＬＣ）が増大する固体電解コンデンサを予め排除するために、エージング工程の後に１００～１５０℃で１～５分放置し、その後に漏れ電流を測定して、その値が規定値以上のものを不良品として排除することを特徴とする固体電解コンデンサの製造方法が開示されている。また、下記の特許文献２には、エージング工程でショートが発生するのを防止するために、化学重合タイプの固体電解コンデンサのエージング前に２００℃未満の熱処理を行う製造方法が開示されている。
By the way, in order to reduce the leakage current of such a solid electrolytic capacitor, an aging process is performed by applying a predetermined voltage between both electrodes of the electrolytic capacitor for an appropriate time under predetermined conditions. Is common, and various methods for manufacturing solid electrolytic capacitors including aging treatment for improving yield are being studied.
For example, in Patent Document 1 below, in order to eliminate in advance a solid electrolytic capacitor whose leakage current (LC) increases during standing at room temperature after aging, 1 to 5 at 100 to 150 ° C. after the aging step. Disclosed is a method for manufacturing a solid electrolytic capacitor, which comprises leaving it for a minute, then measuring a leakage current, and excluding those having a value equal to or higher than a specified value as defective products. Further,
一方、近年では自動車等の分野において、電解質に導電性高分子および電解液を用いたハイブリッド型のコンデンサ（以下「ハイブリッドコンデンサ」という）が使用されている。しかしながら、一般的な電解液（１ｋΩ・ｃｍ未満）を使用したハイブリッドコンデンサの場合、熱処理温度が２００℃未満では、コンデンサを基板の電極とはんだ接続するためのフローまたはリフロー工程の熱によりＬＣ変動が起きやすく、ＬＣ改善効果が小さく、２００℃以上の高温で熱処理するとＬＣ改善効果は大きくなるものの、電解液が導電性高分子と反応し、導電性高分子の脱ドープによる等価直列抵抗（ＥＳＲ）の増大を引き起こすという問題があり、熱処理温度を高くすることが困難であった。 On the other hand, in recent years, in the field of automobiles and the like, a hybrid type capacitor (hereinafter referred to as "hybrid capacitor") using a conductive polymer and an electrolytic solution as an electrolyte has been used. However, in the case of a hybrid capacitor using a general electrolytic solution (less than 1 kΩ · cm), if the heat treatment temperature is less than 200 ° C., LC fluctuation will occur due to the heat of the flow or reflow process for soldering the capacitor to the electrodes of the substrate. It is easy to occur, the LC improvement effect is small, and the LC improvement effect is large when heat-treated at a high temperature of 200 ° C or higher, but the electrolytic solution reacts with the conductive polymer and the equivalent series resistance (ESR) due to dedoping of the conductive polymer. It was difficult to raise the heat treatment temperature due to the problem of causing an increase in the heat treatment.
本発明は、従来技術における上記の問題点を解決し、ＥＳＲの増大を引き起こすことなく、ＬＣの改善が可能な電解コンデンサの製造方法、特に導電性高分子ハイブリッドアルミニウム電解コンデンサの製造方法を提供することを課題とする。
本発明者等は種々検討を行った結果、電解コンデンサのエージング前に製品を封口した状態で高温無負荷処理を実施することによって、ＥＳＲの増大を引き起こさずに、ＬＣ変動の少ない電解コンデンサ、特にハイブリッドアルミニウム電解コンデンサが製造できることを見出して、本発明を完成した。
The present invention provides a method for manufacturing an electrolytic capacitor capable of improving LC without causing an increase in ESR, particularly a method for manufacturing a conductive polymer hybrid aluminum electrolytic capacitor, by solving the above-mentioned problems in the prior art. That is the issue.
As a result of various studies, the present inventors have conducted high-temperature no-load treatment in a state where the product is sealed before aging the electrolytic capacitor, so that the electrolytic capacitor with less LC fluctuation, particularly, without causing an increase in ESR. The present invention was completed by finding that a hybrid aluminum electrolytic capacitor can be manufactured.
上記の問題点を解決可能な本発明の電解コンデンサの製造方法は、外部引出電極用のタブ端子を接続した陽極箔と陰極箔とをセパレータを介して巻回することにより巻回素子を作製し、前記陽極箔の切断された断面および前記タブ端子との取り付け部を化成処理し、導電性高分子層を形成させてコンデンサ素子を作製した後、封口部材を取り付けた当該コンデンサ素子と電解液を有底筒状の金属ケース内に収納し、当該金属ケースの開口部を封止した後、エージング処理を行う電解コンデンサの製造方法において、
前記電解液として、比抵抗が５ｋΩ・ｃｍ以上の電解液を使用すること、および
前記当該金属ケースの開口部を封止した後、エージング処理を行う前に、１５０～２１０℃で１０～３０分間の条件にて熱処理を実施することを特徴とする。
In the method for manufacturing an electrolytic capacitor of the present invention that can solve the above problems, a winding element is manufactured by winding an anode foil and a cathode foil to which a tab terminal for an external extraction electrode is connected via a separator. , The cut cross section of the anode foil and the attachment portion with the tab terminal are chemically treated to form a conductive polymer layer to produce a capacitor element, and then the capacitor element and the electrolytic solution to which the sealing member is attached are applied. In a method for manufacturing an electrolytic capacitor, which is housed in a bottomed tubular metal case and the opening of the metal case is sealed and then aged.
As the electrolytic solution, an electrolytic solution having a specific resistance of 5 kΩ · cm or more is used, and after sealing the opening of the metal case and before performing the aging treatment, the temperature is 150 to 210 ° C. for 10 to 30 minutes. It is characterized in that the heat treatment is carried out under the conditions of.
また、本発明は、上記の特徴を有した電解コンデンサの製造方法において、前記電解液が、溶媒として、ジオール類およびラクトン類からなるグループより選ばれたものを含み、かつ、溶質として、ジカルボン酸、ポリカルボン酸、リン酸、亜リン酸、次亜リン酸およびアミン類からなるグループより選ばれたものを含み、当該溶質の濃度が０．５～１５．０重量％であることを特徴とするものである。 Further, according to the present invention, in the method for producing an electrolytic capacitor having the above-mentioned characteristics, the electrolytic solution contains a solvent selected from the group consisting of diols and lactones, and the solute is a dicarboxylic acid. , Polycarboxylic acid, phosphoric acid, phosphoric acid, hypophosphite and amines selected from the group, characterized in that the concentration of the solute is 0.5 to 15.0% by weight. It is something to do.
溶媒のジオール類としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，５－ペンタンジオールおよびこれらの誘導体等を使用でき、ラクトン類としては、γ－ブチロラクトン、γ－バレロラクトン等を使用できる。 As the solvent diols, ethylene glycol, diethylene glycol, propylene glycol, 1,5-pentanediol and derivatives thereof can be used, and as the lactones, γ-butyrolactone, γ-valerolactone and the like can be used.
溶質のジカルボン酸としては、リンゴ酸、酒石酸、タルトロン酸、リシノール酸等を使用でき、ポリカルボン酸としては、クエン酸、イソクエン酸等を使用でき、アミン類としては、ジエチルアミン、ジプロピルアミン、ジブチルアミン、トリメチルアミン、エチルジメチルアミン、ジエチルメチルアミン、トリエチルアミン等を使用できる。 As the solute dicarboxylic acid, apple acid, tartrate acid, tartronic acid, ricinoleic acid and the like can be used, as the polycarboxylic acid, citric acid, isocitrate and the like can be used, and as the amines, diethylamine, dipropylamine and dipropylamine can be used. Butylamine, trimethylamine, ethyldimethylamine, diethylmethylamine, triethylamine and the like can be used.
また、本発明は、上記の特徴を有した電解コンデンサの製造方法において、前記電解液の比抵抗が５～１００ｋΩ・ｃｍであることを特徴とするものである。 Further, the present invention is characterized in that, in the method for manufacturing an electrolytic capacitor having the above-mentioned characteristics, the specific resistance of the electrolytic solution is 5 to 100 kΩ · cm.
本発明によれば、ＥＳＲの増大を引き起こさずに、ＬＣ変動の少ない電解コンデンサ、特にハイブリッドアルミニウム電解コンデンサが製造できる。 According to the present invention, an electrolytic capacitor having less LC fluctuation, particularly a hybrid aluminum electrolytic capacitor, can be manufactured without causing an increase in ESR.
以下、本発明の製造方法により製造される電解コンデンサ（ハイブリッドコンデンサ）の好ましい実施形態を、図面を参照しつつ説明する。
図１に例示したハイブリッドコンデンサ１は、外装ケース２と、外装ケース２に収容されたコンデンサ素子３と、外装ケース２の開口を封止した封口体４とを備えている。
Hereinafter, a preferred embodiment of the electrolytic capacitor (hybrid capacitor) manufactured by the manufacturing method of the present invention will be described with reference to the drawings.
The hybrid capacitor 1 illustrated in FIG. 1 includes an
コンデンサ素子３は、図２に示すように、陽極箔（陽極）１１と陰極箔（陰極）１２とをセパレータ１３を介して円筒形に巻回して形成され、外周面に貼り付けられたテープ１４により巻止めされている。
As shown in FIG. 2, the
陽極箔１１は、表面に誘導体酸化皮膜が形成されたアルミニウム等の弁作用金属の箔である。誘導体酸化皮膜は、エッチング処理にて表面を粗面化した弁作用金属箔に化成処理を施すことによって形成されている。
The
陰極箔１２もアルミニウム等の弁作用金属箔を用いて形成され、エッチング処理により表面が粗面化されたもの（粗面化箔）が使用される。陰極箔１２として、他にエッチング処理を施さないプレーン箔も使用でき、また、前記粗面化箔もしくはプレーン箔の表面に、チタンやニッケルやその炭化物、窒化物、炭窒化物またはこれらの混合物からなる金属薄膜や、カーボン薄膜を形成したコーティング箔も使用することができる。
The
陽極箔１１および陰極箔１２にはそれぞれ図示しないリードタブが接続されている。陽極箔１１および陰極箔１２は、それぞれリードタブを介して、リード端子２１およびリード端子２２と接続されている。リード端子２１およびリード端子２２は、図１に示すように、封口体４に形成された孔３１および孔３２を通って外部に引き出されている。
図２に示すセパレータ１３は、導電性高分子および電解液を保持している。
Lead tabs (not shown) are connected to the
The
次に、上述の構造を有する電解コンデンサを製造するための本発明の製造方法について説明する。
先ず最初に、所定の幅に切断された陽極箔および陰極箔を準備し、この陽極箔および陰極箔に外部引出電極用のタブ端子を接続し、陽極箔と陰極箔とをセパレータを介して巻回することにより巻回素子を作製する。
この際に使用される陽極箔は、表面上に誘電体酸化皮膜が形成された弁金属からなり、陽極箔に用いられる弁金属としてはアルミニウムやタンタル等が挙げられる。また、陽極箔の表面上の誘電体酸化皮膜は、弁金属の表面にエッチング処理および化成酸化処理を施すことにより形成される。一方、陰極箔は、表面に炭化物粒子またはチタン粒子が保持されたアルミニウム箔または、箔表面をエッチング処理したアルミニウム箔からなるものが一般的であるが、これに限定されるものではない。また、巻回素子を作製する際に使用されるセパレータは、セルロース繊維を含むものを用いることができ、セパレータ表面上には導電性高分子が付着してもよい。
Next, the manufacturing method of the present invention for manufacturing an electrolytic capacitor having the above-mentioned structure will be described.
First, an anode foil and a cathode foil cut to a predetermined width are prepared, a tab terminal for an external extraction electrode is connected to the anode foil and the cathode foil, and the anode foil and the cathode foil are wound via a separator. A winding element is manufactured by turning.
The anode foil used at this time is made of a valve metal having a dielectric oxide film formed on the surface, and examples of the valve metal used for the anode foil include aluminum and tantalum. Further, the dielectric oxide film on the surface of the anode foil is formed by subjecting the surface of the valve metal to an etching treatment and a chemical oxidation oxidation treatment. On the other hand, the cathode foil is generally, but is not limited to, an aluminum foil in which carbide particles or titanium particles are retained on the surface, or an aluminum foil in which the foil surface is etched. Further, as the separator used when manufacturing the winding element, one containing cellulose fibers may be used, and a conductive polymer may be attached on the surface of the separator.
そして、陽極箔の切断された断面およびタブ端子との取り付け部を化成処理する。
このような化成処理を行うことにより、巻回素子における陽極箔の切り口や、外部引き出し電極取り付け部の、誘電体酸化皮膜が欠損した部分が修復される。この化成処理においては、化成液として、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または無機溶媒に溶解した化成液が使用され、溶質にアジピン酸アンモニウムを主体とした水溶媒に溶解させ、濃度０．１～２重量％の化成液（例えば、リン酸化成液やホウ酸化成液）を用いることが好ましく、誘電体酸化皮膜の化成電圧値に似した電圧を印加して化成処理を行う。
強靭な誘電体酸化皮膜を形成するには、熱処理と化成処理を数回繰り返すことが好ましく、この際、熱処理は２００℃以下の温度範囲で数分～数十分程度行うのが一般的である。
Then, the cut cross section of the anode foil and the attachment portion with the tab terminal are subjected to chemical conversion treatment.
By performing such a chemical conversion treatment, the cut end of the anode foil in the winding element and the portion of the external extraction electrode mounting portion where the dielectric oxide film is missing are repaired. In this chemical conversion treatment, a chemical conversion solution obtained by dissolving a solute of an organic acid salt having a carboxylic acid group or an inorganic acid salt such as phosphoric acid in an organic solvent or an inorganic solvent is used as the chemical conversion solution, and ammonium adipate is mainly used as the solute. It is preferable to dissolve in a water solvent and use a chemical conversion solution having a concentration of 0.1 to 2% by weight (for example, a phosphorylation solution or a booxide solution), and a voltage similar to the chemical conversion voltage value of the dielectric oxide film. Is applied to perform the chemical conversion treatment.
In order to form a tough dielectric oxide film, it is preferable to repeat the heat treatment and the chemical conversion treatment several times. At this time, the heat treatment is generally performed in a temperature range of 200 ° C. or lower for several minutes to several tens of minutes. ..
次に、上記の化成処理を行った後の巻回素子に導電性高分子層を形成するが、導電性高分子層の形成方法は限定されるものではなく、例えば、導電性高分子を水に分散させた分散体高分子溶液に、化成処理後の巻回素子を浸漬含浸させた後、巻回素子を引き上げ乾燥する方法が挙げられる。
上記の巻回素子を分散体高分子溶液に含浸させる際の浸漬深さは、巻回素子の１／２～２／３とすることが好ましく、浸漬を行った後に減圧含浸を実施することが好ましい。また、この減圧含浸時の減圧度としては９０～９５ｋＰａの範囲が好ましく、大気開放と減圧を合計３回程度行うことが好ましい。
導電性高分子層を形成する際に使用される導電性高分子としては、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）や、自己ドープ型ポリエチレンジオキシチオフェン、ポリピロール、ポリアニリンなどが挙げられる。
Next, a conductive polymer layer is formed on the wound element after the above chemical conversion treatment, but the method for forming the conductive polymer layer is not limited, and for example, the conductive polymer is water-based. There is a method of dipping and impregnating the wound polymer solution after the chemical conversion treatment in the dispersion polymer solution dispersed in the above, and then pulling up and drying the winding element.
The immersion depth when impregnating the above-mentioned winding element with the dispersion polymer solution is preferably 1/2 to 2/3 of that of the winding element, and it is preferable to carry out vacuum impregnation after the immersion. .. The degree of decompression at the time of impregnation with reduced pressure is preferably in the range of 90 to 95 kPa, and it is preferable to open the atmosphere and reduce the pressure about three times in total.
Examples of the conductive polymer used for forming the conductive polymer layer include polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), self-doped polyethylene dioxythiophene, polypyrrole, polyaniline and the like. ..
そして、導電性高分子層を形成した巻回素子に密閉するための封口部材を取り付ける。この際、封口部材としては、弾性のあるゴム、例えばブチルゴム等からなり、外部引き出し端子が貫通する貫通孔を備えたものを用いる。なお、巻回素子への封口部材の取り付けは、巻回素子に電解液を含浸した後でもよい。 Then, a sealing member for sealing is attached to the winding element on which the conductive polymer layer is formed. At this time, the sealing member is made of elastic rubber such as butyl rubber and has a through hole through which the external extraction terminal penetrates. The sealing member may be attached to the winding element after the winding element is impregnated with the electrolytic solution.
本発明では、上記により作製されたコンデンサ素子を有底筒状の金属ケース内に収納した後に、当該金属ケースの容量に応じた量の電解液が注入されるが、この際使用される電解液は５ｋΩ・ｃｍ以上の比抵抗を有するものであり、５～１００ｋΩ・ｃｍの範囲であるものがより好ましく、２０～４０ｋΩ・ｃｍの範囲のものが特に好ましい。本発明において電解液の比抵抗が５ｋΩ・ｃｍ以上に限定されるのは、５ｋΩ・ｃｍ未満の場合には、導電性高分子と反応して、導電性高分子の脱ドープによるＥＳＲ増大を引き起こすからである。電解液の比抵抗の上限値については特に限定されないが、１００ｋΩ・ｃｍを極端に超える場合には、誘電体酸化皮膜の修復性能が低下し漏れ電流が大きくなる傾向があるので好ましくない。なお、本明細書において示されている比抵抗はマルチ水質計（東亜ディーケーケー株式会社製）に従って、３０℃±０．５℃の条件にて測定された値である。 In the present invention, after the capacitor element produced as described above is housed in a bottomed tubular metal case, an electrolytic solution corresponding to the capacity of the metal case is injected, and the electrolytic solution used at this time is injected. Has a specific resistance of 5 kΩ · cm or more, more preferably in the range of 5 to 100 kΩ · cm, and particularly preferably in the range of 20 to 40 kΩ · cm. In the present invention, the specific resistance of the electrolytic solution is limited to 5 kΩ · cm or more, when it is less than 5 kΩ · cm, it reacts with the conductive polymer and causes an increase in ESR due to dedoping of the conductive polymer. Because. The upper limit of the specific resistance of the electrolytic solution is not particularly limited, but if it exceeds 100 kΩ · cm extremely, the repair performance of the dielectric oxide film tends to decrease and the leakage current tends to increase, which is not preferable. The resistivity shown in the present specification is a value measured under the condition of 30 ° C. ± 0.5 ° C. according to a multi-water quality meter (manufactured by DKK-TOA CORPORATION).
本発明では、上記の電解液中に含まれる溶媒が、ジオール類およびラクトン類からなるグループより選ばれたものであることが好ましく、溶質としては、ジカルボン酸、ポリカルボン酸、リン酸、亜リン酸、次亜リン酸およびアミン類からなるグループより選ばれたものが好ましい。また、上記電解液中の溶質濃度は０．５～１５重量％であることが好ましく、１～１３重量％がより好ましい。上記の溶媒および溶質を含む電解液は低蒸散性であるために、電解液の比抵抗を５ｋΩ・ｃｍ以上とすることで、エージング前の熱処理によりリフロー後の漏れ電流の増大を抑制することが可能となる。
本発明においては、上記電解液を注入した後、素子内への電解液浸透性を高めるために、減圧度９０～９５ｋＰａの減圧環境下で含浸を行うことが好ましい。
In the present invention, the solvent contained in the above electrolytic solution is preferably selected from the group consisting of diols and lactones, and the solutes are dicarboxylic acid, polycarboxylic acid, phosphoric acid, and subphosphoric acid. Those selected from the group consisting of acids, hypophosphoric acids and amines are preferred. The solute concentration in the electrolytic solution is preferably 0.5 to 15% by weight, more preferably 1 to 13% by weight. Since the electrolytic solution containing the above solvent and solute has low transpiration, by setting the specific resistance of the electrolytic solution to 5 kΩ · cm or more, it is possible to suppress the increase in leakage current after reflow by the heat treatment before aging. It will be possible.
In the present invention, after injecting the electrolytic solution, it is preferable to impregnate the electrolytic solution in a reduced pressure environment with a reduced pressure of 90 to 95 kPa in order to enhance the permeability of the electrolytic solution into the device.
本発明の製造方法においては、前記コンデンサ素子と、上記の比抵抗値を有する電解液を、有底筒状の金属ケース内に収容し、当該金属ケースの開口部を封止した後、エージング処理を行う前に、１５０～２１０℃で１０～３０分間の条件にて電圧を印加することなく熱処理を実施し、その後で、カテゴリ上限温度以下の条件にて定格電圧を印加し、エージング処理を行う。本発明では、このような処理を実施することによって、ＥＳＲの増大を引き起こすことなく、ＬＣの改善が可能なハイブリッドコンデンサが作製できる。 In the manufacturing method of the present invention, the capacitor element and the electrolytic solution having the above specific resistance value are housed in a bottomed tubular metal case, the opening of the metal case is sealed, and then an aging treatment is performed. Before performing the heat treatment at 150 to 210 ° C. for 10 to 30 minutes without applying a voltage, after that, the rated voltage is applied under the condition of the category upper limit temperature or less, and the aging treatment is performed. .. In the present invention, by carrying out such a process, a hybrid capacitor capable of improving LC can be manufactured without causing an increase in ESR.
本発明では、エージング処理を行う前に実施する熱処理温度は、１５０～２１０℃が好ましく、２００～２１０℃がより好ましい。なお、熱処理温度が２１０℃を超えるとリード線の表面に形成されためっきが再溶融する問題がある。 In the present invention, the heat treatment temperature carried out before the aging treatment is preferably 150 to 210 ° C, more preferably 200 to 210 ° C. If the heat treatment temperature exceeds 210 ° C., there is a problem that the plating formed on the surface of the lead wire is remelted.
本明細書中において、電解コンデンサの連続使用が可能な最高周囲温度を、当該電解コンデンサの「カテゴリ上限温度」と規定するものとする。かかる最高周囲温度は、一般的に、製造メーカ等により、実用に供される固体電解コンデンサの品質保証試験の際に、当該最高周囲温度で当該固体電解コンデンサに定格電圧を一定時間印加する等により決定され、例えば、８５℃、１０５℃、１２５℃、１３５℃、１５０℃等の温度が最高周囲温度として保証される。 In the present specification, the maximum ambient temperature at which an electrolytic capacitor can be continuously used is defined as the "category upper limit temperature" of the electrolytic capacitor. The maximum ambient temperature is generally determined by applying a rated voltage to the solid electrolytic capacitor at the maximum ambient temperature for a certain period of time at the time of quality assurance test of the solid electrolytic capacitor to be put into practical use by a manufacturer or the like. Determined, for example, temperatures such as 85 ° C, 105 ° C, 125 ° C, 135 ° C, 150 ° C, etc. are guaranteed as the maximum ambient temperature.
エージング工程前に熱処理を行う本発明の製造方法を用いることにより、ＬＣ（漏れ電流）改善が可能となる。
ＬＣ改善効果は、巻回素子の状態で熱処理を行った場合にも出現するが、組立工程での機械的ストレスによりＬＣが増大するため、組立後～エージング前に熱処理を行うことが最もＬＣ改善効果が大きい。
以下に、実施例に基づいて、本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。
LC (leakage current) can be improved by using the production method of the present invention in which heat treatment is performed before the aging step.
The LC improvement effect also appears when heat treatment is performed in the state of the wound element, but since LC increases due to mechanical stress in the assembly process, it is best to perform heat treatment after assembly and before aging. The effect is great.
Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
〔実施例：本発明の製造方法を用いた導電性高分子ハイブリッドアルミニウム電解コンデンサの製造例〕
陽極箔として、アルミニウム箔をエッチング処理にて粗面化した後、化成処理を施すことにより、誘電体酸化皮膜が形成されたものを準備し、陰極箔としては、表面がエッチング処理にて粗面化されているアルミニウム箔を準備し、セパレータとして、セルロース繊維を主体としたものを準備した。
そして、所定の幅に切断された上記陽極箔および陰極箔に、それぞれ外部引き出し電極用のリードタブ（アルミニウムで形成）を接続し、上記のセパレータを介して巻回することにより巻回素子を作製した。
[Example: Production example of a conductive polymer hybrid aluminum electrolytic capacitor using the production method of the present invention]
As the anode foil, an aluminum foil is roughened by etching, and then a chemical conversion treatment is performed to prepare a foil having a dielectric oxide film formed. As a cathode foil, the surface is roughened by etching. We prepared an aluminum foil that had been converted, and prepared a separator mainly made of cellulose fiber.
Then, a lead tab (formed of aluminum) for an external extraction electrode was connected to each of the anode foil and the cathode foil cut to a predetermined width, and the winding element was manufactured by winding the lead tab through the separator. ..
次いで、溶質にアジピン酸アンモニウムを主体とした水溶媒に溶解させ、濃度が２重量％の化成液を調製し、この化成液を用いて上記巻回素子に、誘電体酸化皮膜の化成電圧値に似した電圧を印加し、化成処理を行った。その後、熱処理（２００℃、３０分）と上記化成処理を数回繰り返すことにより、誘電体酸化皮膜を形成した。
その後、化成処理後の巻回素子を、減圧下で、ＰＥＤＯＴ／ＰＳＳを含む分散体高分子溶液に、浸漬深さが巻回素子の１／２～２／３までとなるようにして３～５分間浸漬させ、浸漬後に減圧度を９０～９５ｋＰａとし、大気開放と減圧を合計３回行った。そして、分散体高分子溶液から巻回素子を引き上げて乾燥し導電性高分子層を形成した。
Next, the solute was dissolved in an aqueous solvent mainly composed of ammonium adipate to prepare a chemical conversion solution having a concentration of 2% by weight, and this chemical conversion solution was used to apply the chemical conversion voltage value of the dielectric oxide film to the winding element. A similar voltage was applied and chemical conversion treatment was performed. Then, the heat treatment (200 ° C., 30 minutes) and the above chemical conversion treatment were repeated several times to form a dielectric oxide film.
Then, the wound element after the chemical conversion treatment is immersed in a dispersion polymer solution containing PEDOT / PSS under reduced pressure so that the immersion depth is 1/2 to 2/3 of that of the wound element, 3 to 5 The mixture was immersed for a minute, and after the immersion, the degree of decompression was set to 90 to 95 kPa, and the mixture was opened to the atmosphere and depressurized a total of 3 times. Then, the winding element was pulled up from the dispersion polymer solution and dried to form a conductive polymer layer.
その後、所定量の電解液（溶質：リシノール酸、亜リン酸、ジブチルアミン、溶媒：１，５－ペンタンジオール、γ－バレロラクトン、溶質濃度：１０．０重量％）を素子に注入した。この電解液の比抵抗は３２ｋΩ・ｃｍであった。
そして、上記の電解液を減圧環境下（９０～９５ｋＰａ）にて巻回素子に含浸させてコンデンサ素子を作製し、このコンデンサ素子に密封するための封口部材（ブチルゴム製）を取り付けて金属ケース内に収納し、金属ケースの開口部をカーリング加工して封止した。続いて、表１の前処理条件にて熱処理を加え、その後、カテゴリ上限温度以下の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（１２５℃、１時間）を施し、導電性高分子ハイブリッドアルミニウム電解コンデンサを５０個作製した。
Then, a predetermined amount of an electrolytic solution (solute: ricinoleic acid, phosphorous acid, dibutylamine, solvent: 1,5-pentanediol, γ-valerolactone, solute concentration: 10.0% by weight) was injected into the device. The specific resistance of this electrolytic solution was 32 kΩ · cm.
Then, the winding element is impregnated with the above electrolytic solution under a reduced pressure environment (90 to 95 kPa) to produce a capacitor element, and a sealing member (made of butyl rubber) for sealing is attached to the capacitor element to be inside the metal case. The opening of the metal case was curled and sealed. Subsequently, heat treatment is applied under the pretreatment conditions shown in Table 1, and then the rated voltage is applied to the capacitor under the conditions below the upper limit temperature of the category to perform aging treatment (125 ° C., 1 hour), and the conductive polymer hybrid is performed. 50 aluminum electrolytic capacitors were manufactured.
〔比較例：熱処理を行わない場合（比較例１）、熱処理温度が１３０℃である場合（比較例２）〕
前記実施例におけるコンデンサ素子を金属ケース内に収納し、金属ケースの開口部を封止した後、表１の前処理条件を行う以外は、前記実施例１と同様にして、導電性高分子ハイブリッドアルミニウム電解コンデンサを５０個作製した。
[Comparative Example: When no heat treatment is performed (Comparative Example 1), when the heat treatment temperature is 130 ° C. (Comparative Example 2)]
The conductive polymer hybrid is the same as in Example 1 except that the capacitor element in the above embodiment is housed in the metal case, the opening of the metal case is sealed, and then the pretreatment conditions shown in Table 1 are performed. 50 aluminum electrolytic capacitors were manufactured.
〔従来例：電解液の比抵抗が５ｋΩ・ｃｍ未満である場合〕
前記実施例における電解液の代わりに、溶質がアミジン塩で、溶媒がエチレングリコールおよびγ-ブチロラクトンで、溶質濃度が２５．０重量％である電解液（比抵抗０．１ｋΩ・ｃｍ）を用いる以外は、前記実施例１と同様にして、導電性高分子ハイブリッドアルミニウム電解コンデンサを５０個作製した。
[Conventional example: When the specific resistance of the electrolytic solution is less than 5 kΩ · cm]
Instead of the electrolytic solution in the above example, an electrolytic solution (specific resistance 0.1 kΩ · cm) having a solute concentration of 25.0% by weight and an amidin salt as a solute and ethylene glycol and γ-butyrolactone as a solvent is used. Made 50 conductive polymer hybrid aluminum electrolytic capacitors in the same manner as in Example 1.
〔リフロー前後の電気特性比較〕
上記実施例、比較例および従来例で作製した電解コンデンサのそれぞれについて、リフロー前後の電気特性、即ち、周波数１００ｋＨｚにおける等価直列抵抗（ＥＳＲ）、および定格電圧を１分間印加した後の漏れ電流（ＬＣ）を測定し、比較を行った。なお、ＬＣ規格は３５．２８μＡ以下とした。
その結果を、以下の表１に示す。なお、実施例、比較例および従来例の電解コンデンサはいずれもサイズが直径１０ｍｍ×長さ１０ｍｍで、定格電圧が６３Ｖ、定格容量が５６μＦのものであり、Ｎ＝５０の平均値が示されている。
[Comparison of electrical characteristics before and after reflow]
For each of the electrolytic capacitors manufactured in the above examples, comparative examples, and conventional examples, the electrical characteristics before and after the reflow, that is, the equivalent series resistance (ESR) at a frequency of 100 kHz, and the leakage current (LC) after applying the rated voltage for 1 minute. ) Was measured and compared. The LC standard was 35.28 μA or less.
The results are shown in Table 1 below. The electrolytic capacitors of the examples, comparative examples, and conventional examples all have a diameter of 10 mm and a length of 10 mm, a rated voltage of 63 V, and a rated capacity of 56 μF, and an average value of N = 50 is shown. There is.
上記表１の結果から、実施例の電解コンデンサと、従来例の電解コンデンサを比較した場合、リフロー前後の両方において、エージング処理前に１５０～２１０℃、１０～３０分間の熱処理を追加することで、ＥＳＲを上昇させることなくＬＣの上昇が抑制でき、リフロー前後のＬＣ変動を安定化できることが確認された。また、熱処理を実施しないまたは熱処理温度が１３０℃とした場合には、サンプル毎のバラツキが非常に大きくＬＣ規格から外れるサンプルが発生することもわかった。 From the results in Table 1 above, when the electrolytic capacitor of the example and the electrolytic capacitor of the conventional example are compared, heat treatment at 150 to 210 ° C. for 10 to 30 minutes is added before the aging treatment both before and after the reflow. It was confirmed that the increase in LC can be suppressed without increasing the ESR, and the LC fluctuation before and after the reflow can be stabilized. It was also found that when the heat treatment was not performed or the heat treatment temperature was set to 130 ° C., the variation among the samples was very large and some samples deviated from the LC standard.
以上、本発明の実施形態について実施例に基づいて説明したが、具体的な構成は、これらの実施形態に限定されるものでないと考えられるべきである。本発明の範囲は上記した説明ではなく特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれる。 Although the embodiments of the present invention have been described above based on the examples, it should be considered that the specific configuration is not limited to these embodiments. The scope of the present invention is shown by the scope of claims rather than the above description, and includes all modifications within the meaning and scope equivalent to the scope of claims.
なお、実施例では、ＰＥＤＯＴ／ＰＳＳを導電性高分子に用いたが、自己ドープ型ポリエチレンジオキシチオフェン、ポリピロール、ポリアニリン等の他の導電性高分子を用いた場合、これらを組み合わせて多層とした場合でも同様の効果が得られる。 In the examples, PEDOT / PSS was used as the conductive polymer, but when other conductive polymers such as self-doped polyethylene dioxythiophene, polypyrrole, and polyaniline were used, these were combined to form a multilayer. The same effect can be obtained even in the case.
本発明の製造方法によれば、エージング処理を行う前に、製品を封口した状態で熱処理を実施することによってＬＣを改善することができ、製造時の歩留りを大きく向上させることができ、本製法は、電解コンデンサ、特に導電性高分子ハイブリッドアルミニウム電解コンデンサの製造において有用である。 According to the manufacturing method of the present invention, LC can be improved by performing heat treatment in a state where the product is sealed before the aging treatment, and the yield at the time of manufacturing can be greatly improved. Is useful in the manufacture of electrolytic capacitors, especially conductive polymer hybrid aluminum electrolytic capacitors.
１ ハイブリッドコンデンサ
２ 外装ケース
３ コンデンサ素子
４ 封口体
１１ 陽極箔（陽極）
１２ 陰極箔（陰極）
１３ セパレータ
１４ テープ
２１,２２ リード端子
３１,３２ 孔
1
12 Cathode foil (cathode)
13
Claims (3)
前記電解液として、比抵抗が５ｋΩ・ｃｍ以上の電解液を使用すること、および
前記当該金属ケースの開口部を封止した後、エージング処理を行う前に、１５０～２１０℃で１０～３０分間の条件にて熱処理を実施することを特徴とする電解コンデンサの製造方法。 A winding element is manufactured by winding an anode foil to which a tab terminal for an external extraction electrode is connected and a cathode foil via a separator, and a cut cross section of the anode foil and a mounting portion with the tab terminal are formed. After chemical treatment is performed to form a conductive polymer layer to produce a capacitor element, the capacitor element to which the sealing member is attached and the electrolytic solution are stored in a bottomed tubular metal case, and the opening of the metal case is opened. In the method of manufacturing an electrolytic capacitor, which is subjected to aging treatment after sealing.
As the electrolytic solution, an electrolytic solution having a specific resistance of 5 kΩ · cm or more is used, and after sealing the opening of the metal case and before performing the aging treatment, the temperature is 150 to 210 ° C. for 10 to 30 minutes. A method for manufacturing an electrolytic capacitor, which comprises performing heat treatment under the above conditions.
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| JP2015002274A (en) * | 2013-06-17 | 2015-01-05 | テイカ株式会社 | Electrolytic capacitor and method for manufacturing the same |
| JP2020072132A (en) * | 2018-10-30 | 2020-05-07 | ニチコン株式会社 | Manufacturing method of electrolytic capacitor |
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| JP2003017369A (en) * | 2001-06-29 | 2003-01-17 | Nippon Chemicon Corp | Method for manufacturing solid electrolytic capacitor |
| JP2015002274A (en) * | 2013-06-17 | 2015-01-05 | テイカ株式会社 | Electrolytic capacitor and method for manufacturing the same |
| JP2020072132A (en) * | 2018-10-30 | 2020-05-07 | ニチコン株式会社 | Manufacturing method of electrolytic capacitor |
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