JPWO2020059609A1 - An electrode body, an electrolytic capacitor having an electrode body, and a method for manufacturing the electrode body. - Google Patents
An electrode body, an electrolytic capacitor having an electrode body, and a method for manufacturing the electrode body. Download PDFInfo
- Publication number
- JPWO2020059609A1 JPWO2020059609A1 JP2020548410A JP2020548410A JPWO2020059609A1 JP WO2020059609 A1 JPWO2020059609 A1 JP WO2020059609A1 JP 2020548410 A JP2020548410 A JP 2020548410A JP 2020548410 A JP2020548410 A JP 2020548410A JP WO2020059609 A1 JPWO2020059609 A1 JP WO2020059609A1
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- Prior art keywords
- carbon
- graphite
- electrode body
- layer
- cathode
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Images
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- 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
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
電解コンデンサの初期静電容量のみならず、高温環境負荷後においても安定した静電容量を発現させることができる電極体、この電極体を備える電解コンデンサ、及びこの電極体の製造方法を提供する。電極体は、電解コンデンサの陰極に用いられ、弁作用金属により成る陰極箔と、この陰極箔に形成されたカーボン層とを備える。カーボン層は、黒鉛と球状炭素とを含む。 Provided are an electrode body capable of exhibiting not only the initial capacitance of an electrolytic capacitor but also a stable capacitance even after a high temperature environment load, an electrolytic capacitor provided with this electrode body, and a method for manufacturing the electrode body. The electrode body is used as a cathode of an electrolytic capacitor, and includes a cathode foil made of a valve acting metal and a carbon layer formed on the cathode foil. The carbon layer contains graphite and spherical carbon.
Description
本発明は、電極体、電極体を備える電解コンデンサ、及び電極体の製造方法に関する。 The present invention relates to an electrode body, an electrolytic capacitor including the electrode body, and a method for manufacturing the electrode body.
電解コンデンサは、タンタルあるいはアルミニウム等のような弁作用金属を陽極箔及び陰極箔として備えている。陽極箔は、弁作用金属を焼結体あるいはエッチング箔等の形状にすることで拡面化され、拡面化された表面に誘電体酸化皮膜層を有する。陽極箔と陰極箔の間には電解液が介在する。電解液は、陽極箔の凹凸面に密接し、真の陰極として機能する。この電解コンデンサは、誘電体酸化皮膜層の誘電分極作用により陽極側容量を得ている。 The electrolytic capacitor includes a valve acting metal such as tantalum or aluminum as an anode foil and a cathode foil. The anode foil is expanded by forming the valve acting metal into a shape such as a sintered body or an etching foil, and has a dielectric oxide film layer on the expanded surface. An electrolytic solution is interposed between the anode foil and the cathode foil. The electrolyte is in close contact with the uneven surface of the anode foil and functions as a true cathode. This electrolytic capacitor obtains the capacitance on the anode side by the dielectric polarization action of the dielectric oxide film layer.
電解コンデンサは陽極側と陰極側に容量が発現する直列コンデンサと見做すことができる。従って、陽極側容量を効率良く活用するには陰極側容量も非常に重要である。陰極箔もエッチング処理により表面積を増大させているが、陰極箔の厚みの観点から陰極箔の拡面化にも限界がある。 The electrolytic capacitor can be regarded as a series capacitor in which capacitance is developed on the anode side and the cathode side. Therefore, the cathode side capacitance is also very important in order to efficiently utilize the anode side capacitance. The surface area of the cathode foil is also increased by etching, but there is a limit to the expansion of the surface area of the cathode foil from the viewpoint of the thickness of the cathode foil.
そこで、窒化チタン等の金属窒化物の皮膜を陰極箔に形成した電解コンデンサが提案されている（特許文献１参照）。窒素ガス環境下で、イオンプレーティング法の一種である真空アーク蒸着法によってチタンを蒸発させ、陰極箔の表面に窒化チタンを堆積させる。金属窒化物は不活性であり、自然酸化皮膜が形成され難い。また蒸着皮膜は微細な凹凸が形成されて陰極の表面積が拡大する。 Therefore, an electrolytic capacitor in which a metal nitride film such as titanium nitride is formed on a cathode foil has been proposed (see Patent Document 1). In a nitrogen gas environment, titanium is evaporated by a vacuum arc vapor deposition method, which is a kind of ion plating method, and titanium nitride is deposited on the surface of the cathode foil. The metal nitride is inert, and it is difficult for a natural oxide film to be formed. In addition, fine irregularities are formed on the vapor-deposited film, and the surface area of the cathode is expanded.
また、活性炭を含む多孔質のカーボン層を陰極箔に形成した電解コンデンサも知られている（特許文献２参照）。この電解コンデンサの陰極側容量は、分極性電極と電解質との境界面に形成される電気二重層の蓄電作用により発現する。電解質のカチオンが多孔質カーボン層との界面に整列し、多孔質カーボン層内の電子と極めて短い距離を隔てて対を成し、陰極に電位障壁が形成される。この多孔質カーボン層が形成された陰極箔は、多孔質カーボンを分散させた水溶性バインダー溶液を混練してペースト状にし、当該ペーストを陰極箔の表面に塗布し、高温下に晒して乾燥させることで作製される。 Further, an electrolytic capacitor in which a porous carbon layer containing activated carbon is formed on a cathode foil is also known (see Patent Document 2). The cathode-side capacitance of this electrolytic capacitor is expressed by the storage action of the electric double layer formed on the interface between the polar electrode and the electrolyte. Electrolyte cations are aligned at the interface with the porous carbon layer and paired with electrons in the porous carbon layer at very short distances, forming a potential barrier at the cathode. The cathode foil on which the porous carbon layer is formed is kneaded with a water-soluble binder solution in which porous carbon is dispersed to form a paste, the paste is applied to the surface of the cathode foil, and the paste is exposed to a high temperature to be dried. It is made by.
金属窒化物の蒸着プロセスは複雑であり、電解コンデンサのコスト高を招く。しかも、近年の電解コンデンサは、例えば車載用途等のように、極低温環境下から高温環境下まで幅広い温度帯域で使用されることも想定される。しかしながら、金属窒化物の皮膜を陰極箔に形成した電解コンデンサは、高温に長時間晒されることで静電容量が大きく低下してしまう。そうすると、電解コンデンサの静電容量は当初想定されていた静電容量と大きく異なるものとなってしまう。活性炭を含む多孔質カーボン層をペーストの塗布により陰極箔に形成した電解コンデンサは、金属窒化物の皮膜を陰極箔に形成した電解コンデンサと比べて更に、高温環境下で静電容量が大きく低下してしまう。 The process of vapor deposition of metal nitrides is complicated and leads to high cost of electrolytic capacitors. Moreover, recent electrolytic capacitors are expected to be used in a wide temperature band from a cryogenic environment to a high temperature environment, for example, for in-vehicle applications. However, the capacitance of an electrolytic capacitor in which a metal nitride film is formed on a cathode foil is greatly reduced by being exposed to a high temperature for a long time. Then, the capacitance of the electrolytic capacitor will be significantly different from the initially assumed capacitance. An electrolytic capacitor in which a porous carbon layer containing activated carbon is formed on a cathode foil by applying a paste has a significantly lower capacitance in a high temperature environment than an electrolytic capacitor in which a metal nitride film is formed on the cathode foil. It ends up.
本発明は、上記課題を解決するために提案されたものであり、その目的は、高温環境負荷後においても安定した静電容量を発現させることができる電極体、この電極体を備える電解コンデンサ、及びこの電極体の製造方法を提供することにある。 The present invention has been proposed to solve the above problems, and an object of the present invention is an electrode body capable of developing a stable capacitance even after a high temperature environment load, an electrolytic capacitor provided with this electrode body, and the like. And a method for manufacturing this electrode body.
本発明者らは、鋭意研究の結果、黒鉛と球状炭素とを含むカーボン層を陰極箔に形成すると、その電極体を用いた電解コンデンサは、低周波領域での使用において、初期静電容量と高温環境負荷後の静電容量との差が小さくなることを見出した。即ち、高温環境下に長時間晒されても静電容量の低下が抑制されることを見出した。 As a result of diligent research, the present inventors have formed a carbon layer containing graphite and spherical carbon on the cathode foil, and the electrolytic capacitor using the electrode body has an initial capacitance when used in a low frequency region. It was found that the difference from the capacitance after high temperature environment load becomes small. That is, it has been found that the decrease in capacitance is suppressed even when exposed to a high temperature environment for a long time.
本発明は、この知見に基づき完成されたものであり、上記課題を解決すべく、電解コンデンサの陰極に用いられる電極体であって、弁作用金属により成る陰極箔と、前記陰極箔に形成されたカーボン層と、を備え、前記カーボン層は、黒鉛と球状炭素とを含むこと、を特徴とする。 The present invention has been completed based on this finding, and is an electrode body used for a cathode of an electrolytic capacitor, which is formed on a cathode foil made of a valve acting metal and the cathode foil in order to solve the above problems. A carbon layer is provided, and the carbon layer contains graphite and spherical carbon.
また、従来、電気二重層作用には周波数特性上の解決すべき問題があり、電解コンデンサにおいて高周波領域での使用を目指す場合、カーボン層を陰極箔に形成することは考えられていなかった。しかも、低周波領域において、黒鉛やアセチレンブラックなどのＢＥＴ比表面積の小さいカーボンは他の炭素材料に対して容量の点で劣ることが多い。しかしながら、本発明者らの鋭意研究の結果、低周波領域では他のカーボンブラックに対して容量の点で劣ることも多い黒鉛やＢＥＴ比表面積の小さい球状炭素を組み合わせると、高周波領域においては立場を逆転させて容量の点で優位になるとの知見が得られた。この知見に基づき、前記球状炭素は、例えばアセチレンブラックなどのＢＥＴ比表面積が２００ｍ２／ｇ以下のカーボンブラックであるようにしてもよい。Further, conventionally, the electric double layer action has a problem to be solved in terms of frequency characteristics, and when aiming at use in a high frequency region in an electrolytic capacitor, it has not been considered to form a carbon layer on a cathode foil. Moreover, in the low frequency region, carbon having a small BET specific surface area such as graphite or acetylene black is often inferior in capacity to other carbon materials. However, as a result of diligent research by the present inventors, when graphite and spherical carbon having a small BET specific surface area, which are often inferior in capacity to other carbon blacks in the low frequency region, are combined, they are in a position in the high frequency region. It was found that it can be reversed to give an advantage in terms of capacity. Based on this finding, the spherical carbon may be carbon black having a BET specific surface area of 200 m 2 / g or less, such as acetylene black.
前記黒鉛は、粒度分布における平均粒径が６μｍ以上１０μｍ以下であるようにしてもよい。 The graphite may have an average particle size of 6 μm or more and 10 μm or less in the particle size distribution.
前記黒鉛は、粒度分布における平均粒径が６μｍ以下であるようにしてもよい。 The graphite may have an average particle size of 6 μm or less in the particle size distribution.
前記黒鉛と前記カーボンブラックの混合比は、９０：１０から２５：７５であるようにしてもよい。 The mixing ratio of the graphite and the carbon black may be 90:10 to 25:75.
前記陰極箔は、拡面層が形成され、前記カーボン層は、前記拡面層上に形成されているようにしてもよい。 The cathode foil may have a surface expansion layer formed on the cathode foil, and the carbon layer may be formed on the surface expansion layer.
前記拡面層と前記カーボン層とは圧接しているようにしてもよい。 The surface expansion layer and the carbon layer may be in pressure contact with each other.
前記拡面層は、凹凸面と当該凹凸面から前記陰極箔の深部に向けて形成される細孔とから形成され、前記球状炭素は、細孔に入り込み、前記黒鉛は、前記球状炭素が入り込んだ前記細孔を覆っているようにしてもよい。 The enlarged surface layer is formed of an uneven surface and pores formed from the uneven surface toward the deep part of the cathode foil, the spherical carbon enters the pores, and the graphite penetrates the spherical carbon. However, it may cover the pores.
前記球状炭素は、前記カーボン層の圧接により前記細孔に入り込んでいるようにしてもよい。 The spherical carbon may be made to enter the pores by pressure welding of the carbon layer.
前記黒鉛は、前記拡面層の前記凹凸面に沿うように変形しているようにしてもよい。 The graphite may be deformed along the uneven surface of the expansion layer.
この電極体を陰極に備える電解コンデンサも本発明の一態様である。 An electrolytic capacitor having this electrode body as a cathode is also an aspect of the present invention.
また、上記課題を解決すべく、本発明の電極体の製造方法は、電解コンデンサの陰極に用いられる電極体の製造方法であって、弁作用金属により成る陰極箔に、黒鉛と球状炭素とを含むカーボン層を形成すること、を特徴とする。 Further, in order to solve the above problems, the method for manufacturing an electrode body of the present invention is a method for manufacturing an electrode body used for a cathode of an electrolytic capacitor, in which graphite and spherical carbon are added to a cathode foil made of a valve acting metal. It is characterized by forming a carbon layer containing the mixture.
前記カーボン層は、前記黒鉛と球状炭素を含むスラリーを陰極箔に塗布、乾燥後、圧接して形成されるようにしてもよい。 The carbon layer may be formed by applying a slurry containing graphite and spherical carbon to a cathode foil, drying the slurry, and then pressing the carbon layer.
本発明によれば、陰極体は、高温環境負荷後においても安定した静電容量を発現させることができる。 According to the present invention, the cathode body can develop a stable capacitance even after a high temperature environmental load.
本発明の実施形態に係る電極体及びこの電極体を陰極に用いた電解コンデンサについて説明する。本実施形態では、電解液を有する電解コンデンサを例示して説明するが、これに限定されるものではなく。電解液、導電性ポリマーなどの固体電解質層、ゲル電解質、又は固体電解質層とゲル電解質に対して電解液を併用した電解質を有する電解コンデンサの何れにも適用できる。 An electrode body according to an embodiment of the present invention and an electrolytic capacitor using this electrode body as a cathode will be described. In the present embodiment, an electrolytic capacitor having an electrolytic solution will be described as an example, but the present invention is not limited thereto. It can be applied to any of an electrolytic solution, a solid electrolyte layer such as a conductive polymer, a gel electrolyte, or an electrolytic capacitor having an electrolyte in which an electrolytic solution is used in combination with the solid electrolyte layer and the gel electrolyte.
（電解コンデンサ）
電解コンデンサは、静電容量に応じた電荷の蓄電及び放電を行う受動素子である。この電解コンデンサは、巻回型又は積層型のコンデンサ素子を有する。コンデンサ素子は、電極体をセパレータを介して対向させ、電解液が含浸されて成る。この電解コンデンサは、陰極側に用いられた電極体と電解液との界面に生じる電気二重層作用によって陰極側容量が生じ、また誘電分極作用による陽極側容量が陽極側に用いられた電極体に生じる。以下、陰極側に用いられた電極体を陰極体といい、陽極側に用いられた電極体を陽極箔と称する。(Electrolytic capacitor)
The electrolytic capacitor is a passive element that stores and discharges electric charges according to the capacitance. This electrolytic capacitor has a wound type or a laminated type capacitor element. The capacitor element is formed by impregnating an electrode body with an electrolytic solution so as to face each other via a separator. In this electrolytic capacitor, the cathode side capacitance is generated by the electric double layer action generated at the interface between the electrode body used on the cathode side and the electrolytic solution, and the anode side capacitance due to the dielectric polarization action is applied to the electrode body used on the anode side. Occurs. Hereinafter, the electrode body used on the cathode side is referred to as a cathode body, and the electrode body used on the anode side is referred to as an anode foil.
陽極箔の表面には、誘電分極作用が生じる誘電体酸化皮膜層が形成されている。陰極体の表面には、電解液との界面に電気二重層作用を生じさせるカーボン層が形成されている。電解液は、陽極箔と陰極体の間に介在し、陽極箔の誘電体酸化皮膜層と陰極体のカーボン層に密接する。セパレータは、陽極箔と陰極体のショートを防止すべく、陽極箔と陰極体との間に介在し、また電解液を保持する。 A dielectric oxide film layer that causes a dielectric polarization action is formed on the surface of the anode foil. On the surface of the cathode body, a carbon layer that causes an electric double layer action is formed at the interface with the electrolytic solution. The electrolytic solution is interposed between the anode foil and the cathode body, and is in close contact with the dielectric oxide film layer of the anode foil and the carbon layer of the cathode body. The separator is interposed between the anode foil and the cathode body and holds the electrolytic solution in order to prevent a short circuit between the anode foil and the cathode body.
（陰極体）
この陰極体は、陰極箔とカーボン層の２層構造を有する。陰極箔は集電体となり、その表面には拡面層が形成されていることが好ましい。カーボン層は主材として炭素材を含む。このカーボン層が拡面層と密着することで、陰極箔とカーボン層の２層構造となる。(Cathode)
This cathode body has a two-layer structure of a cathode foil and a carbon layer. It is preferable that the cathode foil serves as a current collector and a surface expansion layer is formed on the surface thereof. The carbon layer contains a carbon material as a main material. When this carbon layer is in close contact with the expansion layer, it has a two-layer structure of a cathode foil and a carbon layer.
陰極箔は、弁作用金属を材料とする長尺の箔体である。弁作用金属は、アルミニウム、タンタル、ニオブ、チタン、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス及びアンチモン等である。純度は、９９％程度以上が望ましいが、ケイ素、鉄、銅、マグネシウム、亜鉛等の不純物が含まれていても良い。陰極箔としては、例えばＪＩＳ規格Ｈ０００１で規定される調質記号がＨであるアルミニウム材、いわゆるＨ材や、ＪＩＳ規格Ｈ０００１で規定される調質記号がＯであるアルミニウム材、いわゆるＯ材を用いてもよい。Ｈ材からなる剛性が高い金属箔を用いると、後述するプレス加工による陰極箔の変形を抑制できる。 The cathode foil is a long foil body made of a valve acting metal. The valve acting metal is aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like. The purity is preferably about 99% or more, but impurities such as silicon, iron, copper, magnesium, and zinc may be contained. As the cathode foil, for example, an aluminum material having a tempering symbol of H specified in JIS standard H0001, a so-called H material, or an aluminum material having a tempering symbol of O specified in JIS standard H0001, a so-called O material, is used. You may. When a highly rigid metal foil made of H material is used, deformation of the cathode foil due to press working, which will be described later, can be suppressed.
この陰極箔は、弁作用金属が延伸された金属箔に拡面処理が施されている。拡面層は、電解エッチングやケミカルエッチング、サンドブラスト等により形成され、又は金属箔に金属粒子等を蒸着若しくは焼結することにより形成される。電解エッチングとしては、直流エッチング又は交流エッチング等の手法が挙げられる。また、ケミカルエッチングでは、金属箔を酸溶液やアルカリ溶液に浸漬させる。形成された拡面層は、箔表面から箔芯部へ向けて掘り込まれたトンネル状のエッチングピット、又は海綿状のエッチングピットを有する層領域である。尚、エッチングピットは、陰極箔を貫通するように形成されていてもよい。 In this cathode foil, a surface-expanding treatment is applied to a metal foil in which a valve acting metal is stretched. The surface expansion layer is formed by electrolytic etching, chemical etching, sandblasting, or the like, or by depositing or sintering metal particles or the like on a metal foil. Examples of the electrolytic etching include methods such as DC etching and AC etching. In chemical etching, the metal foil is immersed in an acid solution or an alkaline solution. The formed expanded layer is a layer region having a tunnel-shaped etching pit or a sponge-shaped etching pit dug from the foil surface toward the foil core portion. The etching pit may be formed so as to penetrate the cathode foil.
カーボン層において、炭素材は、黒鉛と球状炭素の混合である。黒鉛としては、天然黒鉛、人造黒鉛、又は黒鉛化ケッチェンブラック等が挙げられ、鱗片状、鱗状（塊状）、土状、球状又は薄片状の形態を有する。黒鉛は、エッチングピットを押し潰してカーボン層と陰極箔との密着性を高めるためにも、鱗片状又は薄片状であり、その短径と長径とのアスペクト比が１：５〜１：１００の範囲のものを用いるのが好ましい。球状炭素としては例えばカーボンブラックが挙げられる。カーボンブラックとしては、ケッチェンブラック、アセチレンブラック、チャネルブラック及びサーマルブラック等が挙げられ、好ましくは一次粒子径が平均１００ｎｍ以下であり、また好ましくはＢＥＴ理論により計算される比表面積（以下、ＢＥＴ比表面積という）が２００ｍ２／ｇ以下である。ＢＥＴ比表面積が２００ｍ２／ｇ以下のカーボンブラックは例えばアセチレンブラックである。In the carbon layer, the carbon material is a mixture of graphite and spherical carbon. Examples of graphite include natural graphite, artificial graphite, graphitized Ketjen black and the like, and have scaly, scaly (lumpy), earthy, spherical or flaky morphology. Graphite is scaly or flaky in order to crush the etching pits and improve the adhesion between the carbon layer and the cathode foil, and the aspect ratio between the minor axis and the major axis is 1: 5 to 1: 100. It is preferable to use one in the range. Examples of spherical carbon include carbon black. Examples of carbon black include Ketjen black, acetylene black, channel black, thermal black, etc., preferably having a primary particle size of 100 nm or less on average, and preferably having a specific surface area calculated by the BET theory (hereinafter, BET ratio). The surface area) is 200 m 2 / g or less. A carbon black having a BET specific surface area of 200 m 2 / g or less is, for example, acetylene black.
この黒鉛と球状炭素の混合で構成されたカーボン層は、黒鉛と球状炭素を活物質として、陰極側容量を発現させる電気二重層活物質層となる。黒鉛と球状炭素の組み合わせは、低周波領域で電解コンデンサを使用する場合、電解コンデンサの初期静電容量と高温環境負荷後における静電容量との差を小さくする。即ち、黒鉛と球状炭素の組み合わせによって、電解コンデンサが高温環境下に長時間晒されても静電容量の低下は抑制され、電解コンデンサの熱安定性が向上する。尚、初期静電容量は、電解コンデンサを組み立ててエージング処理した後の例えば２０℃等の常温近辺での静電容量であり、高温環境負荷後における静電容量は、例えば１２５℃等の高温環境に２６０時間等の長時間晒した後の静電容量である。 The carbon layer composed of a mixture of graphite and spheroidal carbon becomes an electric double layer active material layer in which graphite and spheroidal carbon are used as active materials to develop a cathode side capacity. The combination of graphite and spherical carbon reduces the difference between the initial capacitance of the electrolytic capacitor and the capacitance after a high temperature environmental load when the electrolytic capacitor is used in the low frequency region. That is, the combination of graphite and spherical carbon suppresses a decrease in capacitance even when the electrolytic capacitor is exposed to a high temperature environment for a long time, and improves the thermal stability of the electrolytic capacitor. The initial capacitance is the capacitance near room temperature such as 20 ° C. after the electrolytic capacitor is assembled and aged, and the capacitance after the high temperature environment load is a high temperature environment such as 125 ° C. It is the capacitance after long-term exposure such as 260 hours.
特に、黒鉛とＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素との混合により成るカーボン層は、高周波領域で使用する場合、電解コンデンサの初期静電容量と高温環境負荷後の静電容量との差を顕著に縮める。一般的には、ＢＥＴ比表面積が小さいと電解コンデンサの静電容量は小さくなる。しかしながら、電解コンデンサを高周波領域で使用する場合、黒鉛とＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素との混合により成るカーボン層は、活性炭等のＢＥＴ比表面積が大きい炭素材との立場を逆転させ、高い静電容量を発現させる。即ち、黒鉛とＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素との混合により成るカーボン層は、高周波領域での使用において、電解コンデンサの熱安定性を高めるとともに、高い静電容量を発現させるため、好ましいものである。In particular, the carbon layer made of a mixture of graphite and spherical carbon having a BET specific surface area of 200 m 2 / g or less has the initial capacitance of the electrolytic capacitor and the capacitance after a high temperature environment load when used in a high frequency region. Significantly reduce the difference. Generally, the smaller the BET specific surface area, the smaller the capacitance of the electrolytic capacitor. However, when the electrolytic capacitor is used in the high frequency region, the carbon layer formed by mixing graphite and spherical carbon having a BET specific surface area of 200 m 2 / g or less reverses the position of a carbon material having a large BET specific surface area such as activated carbon. To develop a high capacitance. That is, the carbon layer made of a mixture of graphite and spherical carbon having a BET specific surface area of 200 m 2 / g or less enhances the thermal stability of the electrolytic capacitor and develops a high capacitance when used in a high frequency region. , Which is preferable.
更に、黒鉛とＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素との混合により成るカーボン層は、低周波領域での使用においても、電解コンデンサの初期静電容量と高温環境負荷後の静電容量との差を顕著に縮める。従って、黒鉛とＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素との混合により成るカーボン層は、低周波領域での使用においても、高周波領域での使用においても、幅広い周波数領域で熱安定性が高く、電解コンデンサを汎用的なものとする。Further, the carbon layer made of a mixture of graphite and spherical carbon having a BET specific surface area of 200 m 2 / g or less has an initial capacitance of an electrolytic capacitor and a capacitance after a high temperature environment load even when used in a low frequency region. The difference with is significantly reduced. Therefore, the carbon layer made of a mixture of graphite and spherical carbon having a BET specific surface area of 200 m 2 / g or less has thermal stability in a wide frequency range, both in the low frequency region and in the high frequency region. High and general purpose electrolytic capacitors.
黒鉛は、高温環境負荷後における静電容量の安定性の観点において、長径を基準とした粒度分布における平均粒径が６μｍ以上１０μｍ以下であることが好ましい。ここでいう平均粒径はメジアン径、所謂Ｄ５０である。平均粒径が６μｍ以上１０μｍ以下であると、高温環境負荷後であっても初期静電容量と同等の静電容量が発現する。換言すると、初期静電容量と高温環境負荷後の静電容量に差が無い。 From the viewpoint of capacitance stability after a high temperature environmental load, graphite preferably has an average particle size of 6 μm or more and 10 μm or less in the particle size distribution based on the major axis. The average particle size referred to here is the median diameter, so-called D50. When the average particle size is 6 μm or more and 10 μm or less, a capacitance equivalent to the initial capacitance appears even after a high temperature environment load. In other words, there is no difference between the initial capacitance and the capacitance after high temperature environmental load.
また黒鉛は、静電容量の大きさという点においては粒度分布における平均粒径（Ｄ５０）が６μｍ以下であることが好ましい。平均粒径が６μｍ以下であれば、黒鉛の粒径を小さくすればするほど、電解コンデンサの初期静電容量と高温環境負荷後の静電容量との差を小さく維持したまま、電解コンデンサの静電容量を増加させることができる。 Further, graphite preferably has an average particle size (D50) of 6 μm or less in the particle size distribution in terms of the magnitude of capacitance. If the average particle size is 6 μm or less, the smaller the particle size of graphite, the smaller the difference between the initial capacitance of the electrolytic capacitor and the capacitance after a high temperature environment load, and the static electricity of the electrolytic capacitor. The capacitance can be increased.
まず平均粒径が６μｍ程度であると、平均粒径が１０μｍである場合と比べて静電容量自体が大幅に改善し、電解コンデンサの熱安定性と良好な静電容量を両立する。また、平均粒径が６μｍ程度であると、高温環境負荷後については、窒化チタンの皮膜を陰極箔に形成した電解コンデンサと遜色の無い大きさの静電容量を発現する。 First, when the average particle size is about 6 μm, the capacitance itself is significantly improved as compared with the case where the average particle size is 10 μm, and both the thermal stability of the electrolytic capacitor and the good capacitance are compatible. Further, when the average particle size is about 6 μm, after a high temperature environment load, a capacitance having a size comparable to that of an electrolytic capacitor having a titanium nitride film formed on a cathode foil is exhibited.
次に、平均粒径が４μｍ程度となると、高温環境負荷後において低周波領域及び高周波領域の両方の静電容量が、窒化チタンの皮膜を陰極箔に形成した電解コンデンサを凌駕する。即ち、平均粒径が４μｍ程度となると、高温環境下での使用が想定される電解コンデンサとしては、窒化チタンの皮膜を陰極箔に形成した電解コンデンサよりも汎用的となる。 Next, when the average particle size is about 4 μm, the capacitance in both the low frequency region and the high frequency region exceeds that of the electrolytic capacitor in which the titanium nitride film is formed on the cathode foil after a high temperature environmental load. That is, when the average particle size is about 4 μm, the electrolytic capacitor that is expected to be used in a high temperature environment is more general than the electrolytic capacitor in which a titanium nitride film is formed on the cathode foil.
更に、平均粒径が１μｍまで小さくなると、初期静電容量であっても、高温環境負荷後の静電容量であっても、低周波領域及び高周波領域の両方の静電容量が、窒化チタンの皮膜を陰極箔に形成した電解コンデンサはおろか、電気二重層の活物質として一般的である活性炭を活物質として陰極箔に用いた電解コンデンサをも凌駕し、更に汎用的となる。 Furthermore, when the average particle size is reduced to 1 μm, the capacitance in both the low frequency region and the high frequency region becomes that of titanium nitride, regardless of whether it is the initial capacitance or the capacitance after a high temperature environment load. Not to mention the electrolytic capacitor in which the film is formed on the cathode foil, it surpasses the electrolytic capacitor using activated charcoal as the active material, which is generally used as the active material of the electric double layer, and becomes more versatile.
また、平均粒径が６μｍ以下であると、黒鉛をカーボン層内に留め置き易くなるという知見が得られた。そのため、平均粒径が６μｍ以下であると、カーボン層内に黒鉛を留め置くためのバインダーを少量にでき、陰極体の低抵抗化及び電解コンデンサの等価直列抵抗（ＥＳＲ）を低減できる点でも好ましい。 Further, it was found that when the average particle size is 6 μm or less, graphite can be easily retained in the carbon layer. Therefore, when the average particle size is 6 μm or less, the amount of binder for retaining graphite in the carbon layer can be reduced, which is also preferable in that the resistance of the cathode body can be lowered and the equivalent series resistance (ESR) of the electrolytic capacitor can be reduced. ..
尚、黒鉛Ｇと球状炭素Ｃの質量比は、Ｇ：Ｃ＝９０：１０〜２５：７５の範囲が好ましい。黒鉛の質量比が９０ｗｔ％超となると、電解コンデンサの初期静電容量と高温環境負荷後における電解コンデンサの静電容量との差が大きくなってしまう。また、球状炭素Ｃのみとすると、低周波領域での使用であっても、高周波領域での使用であっても、静電容量が小さくなってしまう。 The mass ratio of graphite G to spherical carbon C is preferably in the range of G: C = 90: 10 to 25:75. When the mass ratio of graphite exceeds 90 wt%, the difference between the initial capacitance of the electrolytic capacitor and the capacitance of the electrolytic capacitor after a high temperature environmental load becomes large. Further, if only spherical carbon C is used, the capacitance will be small regardless of whether it is used in a low frequency region or a high frequency region.
図２は、陰極体の断面を示すＳＥＭ写真である。図２に示すように、拡面層の表面は、うねりの大きな凹凸面２１と、この凹凸面２１から陰極箔の深部へ向けて形成される細孔２２により形成されている。黒鉛１１は、凹凸面２１に沿って変形しつつ、凹凸面２１上に積み重なっていることが好ましい。また、球状炭素１２は、細孔２２に入り込んでいることが好ましい。換言すると、黒鉛１１は、細孔２２に球状炭素１２が入り込んだ状態で、細孔２２を覆っている。また、球状炭素１２は、凹凸面２１上に積み重なった黒鉛１１の間を埋めるように、黒鉛１１間に充填されていることが好ましい。
FIG. 2 is an SEM photograph showing a cross section of the cathode body. As shown in FIG. 2, the surface of the expansion layer is formed by a concavo-
このようなカーボン層の態様は、拡面層にカーボン層が食い込んで密着性を高め、カーボン層と拡面層との間の界面抵抗を下げる。即ち、このようなカーボン層の態様は、拡面層の凹凸面２１において、拡面層とカーボン層との密着性を高める。また、このようなカーボン層の態様は、黒鉛１１が押圧蓋となって、球状炭素２２を細孔へ入り込ませて押し留め、拡面層の細孔２２において、拡面層のカーボン層との密着性を高める。
In such an aspect of the carbon layer, the carbon layer bites into the expansion layer to enhance the adhesion and reduce the interfacial resistance between the carbon layer and the expansion layer. That is, such an aspect of the carbon layer enhances the adhesion between the expanded surface layer and the carbon layer on the
このような陰極体は、カーボン層の材料が含まれるスラリーを作製し、また陰極箔に拡面層を形成しておき、拡面層にスラリーを塗布して乾燥及びプレスをすればよい。拡面層に関しては、典型的には、硝酸、硫酸、塩酸等の酸性水溶液中で直流又は交流を印加する直流エッチング又は交流エッチングにより形成される。 For such a cathode body, a slurry containing a carbon layer material may be prepared, a surface expansion layer may be formed on the cathode foil, and the slurry may be applied to the surface expansion layer to be dried and pressed. The surface expansion layer is typically formed by direct current etching or alternating current etching in which direct current or alternating current is applied in an acidic aqueous solution such as nitric acid, sulfuric acid, or hydrochloric acid.
カーボン層に関しては、黒鉛と球状炭素の粉末を溶媒中で分散させ、バインダーを加えてスラリーを作製する。このスラリー作製前に黒鉛の平均粒径をビーズミルやボールミル等の粉砕手段にて粉砕することで調整しておいてもよい。溶媒は、メタノール、エタノールや２−プロパノールなどのアルコール、炭化水素系溶媒、芳香族系溶媒、Ｎ−メチル−２−ピロリドン（ＮＭＰ）やＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）などのアミド系溶媒、水及びこれらの混合物などである。分散方法としては、ミキサー、ジェットミキシング（噴流衝合）、または、超遠心処理、その他超音波処理などを使用する。分散工程では、混合溶液中の黒鉛と球状炭素とバインダーが細分化及び均一化し、溶液中に分散する。バインダーとしては、例えばスチレンブタジエンゴム、ポリフッ化ビニリデン、又はポリテトラフルオロエチレンが挙げられる。 Regarding the carbon layer, graphite and spherical carbon powder are dispersed in a solvent, and a binder is added to prepare a slurry. Before preparing this slurry, the average particle size of graphite may be adjusted by pulverizing with a pulverizing means such as a bead mill or a ball mill. Solvents include methanol, alcohols such as ethanol and 2-propanol, hydrocarbon solvents, aromatic solvents, amide solvents such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF), Water and mixtures thereof. As the dispersion method, a mixer, jet mixing (jet collision), ultracentrifugation treatment, or other ultrasonic treatment is used. In the dispersion step, graphite, spherical carbon and the binder in the mixed solution are subdivided and homogenized and dispersed in the solution. Examples of the binder include styrene-butadiene rubber, polyvinylidene fluoride, and polytetrafluoroethylene.
次に、スラリーを拡面層に塗布し、乾燥させた後、所定圧力でプレスすることで、カーボン層の黒鉛及び球状炭素を敷き詰めて整列させる。また、プレスすることで、カーボン層の黒鉛が拡面層の凹凸面に沿うように変形する。また、プレスすることで、拡面層の凹凸面に沿って変形した黒鉛に圧接の応力が加わり、黒鉛と拡面層との間の球状炭素が細孔内に押し込まれる。これにより、カーボン層と拡面層の密着性が担保させる。 Next, the slurry is applied to the expansion layer, dried, and then pressed at a predetermined pressure to spread graphite and spherical carbon in the carbon layer and align them. Further, by pressing, the graphite of the carbon layer is deformed along the uneven surface of the expansion layer. Further, by pressing, pressure welding stress is applied to the graphite deformed along the uneven surface of the surface expansion layer, and spherical carbon between the graphite and the surface expansion layer is pushed into the pores. As a result, the adhesion between the carbon layer and the expansion layer is ensured.
尚、黒鉛及び球状炭素に、賦活処理や開口処理などの多孔質化処理を施す場合、ガス賦活法、薬剤賦活法などの従来公知の賦活処理を用いることができるが、球状炭素のＢＥＴ比表面積は２００ｍ２／ｇ以下に留めるようにすればよい。ガス賦活法に用いるガスとしては、水蒸気、空気、一酸化炭素、二酸化炭素、塩化水素、酸素またはこれらを混合したものからなるガスが挙げられる。また、薬剤賦活法に用いる薬剤としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、水酸化カルシウム等のアルカリ土類金属の水酸化物、ホウ酸、リン酸、硫酸、塩酸等の無機酸類、または塩化亜鉛などの無機塩類などが挙げられる。この賦活処理の際には必要に応じて加熱処理が施される。When graphite and spherical carbon are subjected to a porosification treatment such as an activation treatment or an opening treatment, conventionally known activation treatments such as a gas activation method and a chemical activation method can be used, but the BET specific surface area of the spherical carbon Should be kept below 200 m 2 / g. Examples of the gas used in the gas activation method include water vapor, air, carbon monoxide, carbon dioxide, hydrogen chloride, oxygen, or a gas composed of a mixture thereof. The chemicals used in the chemical activation method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, boric acid, phosphoric acid, sulfuric acid, and hydrochloric acid. Inorganic acids such as, or inorganic salts such as zinc chloride can be mentioned. During this activation treatment, heat treatment is performed as necessary.
（陽極箔）
次に、陽極箔は、弁作用金属を材料とする長尺の箔体である。純度は、陽極箔に関して９９．９％程度以上が望ましい。この陽極箔は、延伸された箔にエッチング処理を施して成り、または弁作用金属の粉体を焼結して成り、または金属粒子等の皮膜を箔に蒸着させて皮膜を施して成る。陽極箔は、エッチング層又は多孔質構造層を表面に有する。(Anode foil)
Next, the anode foil is a long foil body made of a valve acting metal. The purity is preferably about 99.9% or more with respect to the anode foil. The anode foil is formed by etching a stretched foil, by sintering powder of a valve acting metal, or by depositing a film of metal particles or the like on the foil to apply the film. The anode foil has an etching layer or a porous structural layer on the surface.
陽極箔に形成される誘電体酸化皮膜層は、典型的には、陽極箔の表層に形成される酸化皮膜であり、陽極箔がアルミニウム製であれば、多孔質構造領域を酸化させた酸化アルミニウム層である。この誘電体酸化皮膜層は、硼酸アンモニウム、リン酸アンモニウム、アジピン酸アンモニウム等の酸あるいはこれらの酸の水溶液等のハロゲンイオン不在の溶液中で電圧印加する化成処理により形成される。尚、陰極箔には、自然酸化皮膜層が形成され得るし、意図的に誘電体酸化皮膜層を設けてもよい。 The dielectric oxide film layer formed on the anode foil is typically an oxide film formed on the surface layer of the anode foil, and if the anode foil is made of aluminum, aluminum oxide obtained by oxidizing the porous structural region. It is a layer. This dielectric oxide film layer is formed by a chemical conversion treatment in which a voltage is applied in an acid such as ammonium borate, ammonium phosphate, ammonium adipate, or a solution in the absence of halogen ions such as an aqueous solution of these acids. A natural oxide film layer may be formed on the cathode foil, and a dielectric oxide film layer may be intentionally provided on the cathode foil.
（セパレータ）
セパレータは、クラフト、マニラ麻、エスパルト、ヘンプ、レーヨン等のセルロースおよびこれらの混合紙、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、それらの誘導体などのポリエステル系樹脂、ポリテトラフルオロエチレン系樹脂、ポリフッ化ビニリデン系樹脂、ビニロン系樹脂、脂肪族ポリアミド、半芳香族ポリアミド、全芳香族ポリアミド等のポリアミド系樹脂、ポリイミド系樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、トリメチルペンテン樹脂、ポリフェニレンサルファイド樹脂、アクリル樹脂等が挙げられ、これらの樹脂を単独で又は混合して用いることができ、またセルロースと混合して用いることができる。(Separator)
Separators include celluloses such as kraft, Manila hemp, esparto, hemp, and rayon, and mixed papers thereof, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polyester resins such as derivatives thereof, polytetrafluoroethylene resins, and polyfluorides. Examples include vinylidene resin, vinylon resin, aliphatic polyamide, semi-aromatic polyamide, polyamide resin such as total aromatic polyamide, polyimide resin, polyethylene resin, polypropylene resin, trimethylpentene resin, polyphenylene sulfide resin, acrylic resin and the like. These resins can be used alone or in combination, or mixed with cellulose.
（電解液）
電解液は、溶媒に対して溶質を溶解し、また必要に応じて添加剤が添加された混合液である。溶媒はプロトン性の極性溶媒又は非プロトン性の極性溶媒の何れでもよい。プロトン性の極性溶媒として、一価アルコール類、及び多価アルコール類、オキシアルコール化合物類、水などが代表として挙げられる。非プロトン性の極性溶媒としては、スルホン系、アミド系、ラクトン類、環状アミド系、ニトリル系、オキシド系などが代表として挙げられる。(Electrolyte)
The electrolytic solution is a mixed solution in which a solute is dissolved in a solvent and additives are added as needed. The solvent may be either a protic polar solvent or an aprotic polar solvent. Typical examples of the protic polar solvent include monohydric alcohols, polyhydric alcohols, oxyalcohol compounds, and water. Typical examples of aprotic polar solvents include sulfone-based, amide-based, lactones, cyclic amide-based, nitrile-based, and oxide-based solvents.
一価アルコール類としては、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロブタノール、シクロペンタノール、シクロヘキサノール、ベンジルアルコール等が挙げられる。多価アルコール類およびオキシアルコール化合物類としては、エチレングリコール、プロピレングリコール、グリセリン、メチルセロソルブ、エチルセロソルブ、メトキシプロピレングリコール、ジメトキシプロパノール等が挙げられる。スルホン系としては、ジメチルスルホン、エチルメチルスルホン、ジエチルスルホン、スルホラン、３−メチルスルホラン、２，４−ジメチルスルホラン等が挙げられる。アミド系としては、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−エチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−エチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等が挙げられる。ラクトン類、環状アミド系としては、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、Ｎ−メチル−２−ピロリドン、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、イソブチレンカーボネート等が挙げられる。ニトリル系としては、アセトニトリル、３−メトキシプロピオニトリル、グルタロニトリル等が挙げられる。オキシド系としてはジメチルスルホキシド等が挙げられる。溶媒として、これらが単独で用いられてもよく、また２種類以上を組み合わせても良い。 Examples of monohydric alcohols include ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzyl alcohol and the like. Examples of polyhydric alcohols and oxyalcohol compounds include ethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, dimethoxypropanol and the like. Examples of the sulfone system include dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane and the like. As the amide system, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N- Examples thereof include diethylacetamide and hexamethylphosphoricamide. Examples of lactones and cyclic amides include γ-butyrolactone, γ-valerolactone, δ-valerolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, and isobutylene carbonate. Examples of the nitrile type include acetonitrile, 3-methoxypropionitrile, glutaronitrile and the like. Examples of the oxide system include dimethyl sulfoxide and the like. As the solvent, these may be used alone, or two or more kinds may be combined.
電解液に含まれる溶質は、アニオン及びカチオンの成分が含まれ、典型的には、有機酸若しくはその塩、無機酸若しくはその塩、又は有機酸と無機酸との複合化合物若しくはそのイオン解離性のある塩であり、単独又は２種以上を組み合わせて用いられる。アニオンとなる酸及びカチオンとなる塩基を溶質成分として別々に電解液に添加してもよい。 The solute contained in the electrolytic solution contains anionic and cationic components, and is typically an organic acid or a salt thereof, an inorganic acid or a salt thereof, or a composite compound of an organic acid and an inorganic acid or an ion dissociation thereof. A salt that is used alone or in combination of two or more. An acid as an anion and a base as a cation may be separately added to the electrolytic solution as solute components.
電解液中でアニオン成分となる有機酸としては、シュウ酸、コハク酸、グルタル酸、ピメリン酸、スベリン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、アジピン酸、安息香酸、トルイル酸、エナント酸、マロン酸、１，６−デカンジカルボン酸、１，７−オクタンジカルボン酸、アゼライン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸等のカルボン酸、フェノール類、スルホン酸が挙げられる。また、無機酸としては、ホウ酸、リン酸、亜リン酸、次亜リン酸、炭酸、ケイ酸等が挙げられる。有機酸と無機酸の複合化合物としては、ボロジサリチル酸、ボロジ蓚酸、ボロジグリコール酸等が挙げられる。 Organic acids that become anionic components in the electrolytic solution include oxalic acid, succinic acid, glutaric acid, piceric acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, and toluyl. Acids, enanthic acids, malonic acids, 1,6-decandicarboxylic acids, 1,7-octanedicarboxylic acids, azelaic acids, undecanedioic acids, dodecanedioic acids, tridecanedioic acids and other carboxylic acids, phenols and sulfonic acids are listed. Be done. Examples of the inorganic acid include boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, silicic acid and the like. Examples of the composite compound of an organic acid and an inorganic acid include borodisalicylic acid, borodioxalic acid, and borodiglycolic acid.
また、有機酸、無機酸、ならびに有機酸と無機酸の複合化合物の少なくとも１種の塩として、アンモニウム塩、四級アンモニウム塩、四級化アミジニウム塩、アミン塩、ナトリウム塩、カリウム塩等が挙げられる。四級アンモニウム塩の四級アンモニウムイオンとしてはテトラメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウム等が挙げられる。四級化アミジニウムとしては、エチルジメチルイミダゾリニウム、テトラメチルイミダゾリニウムなどが挙げられる。アミン塩のアミンとしては、一級アミン、二級アミン、三級アミンが挙げられる。一級アミンとしては、メチルアミン、エチルアミン、プロピルアミンなど、二級アミンとしては、ジメチルアミン、ジエチルアミン、エチルメチルアミン、ジブチルアミンなど、三級アミンとしては、トリメチルアミン、トリエチルアミン、トリブチルアミン、エチルジメチルアミン、エチルジイソプロピルアミン等が挙げられる。 Further, examples of at least one salt of the organic acid, the inorganic acid, and the composite compound of the organic acid and the inorganic acid include an ammonium salt, a quaternary ammonium salt, a quaternized amidinium salt, an amine salt, a sodium salt, and a potassium salt. Be done. Examples of the quaternary ammonium ion of the quaternary ammonium salt include tetramethylammonium, triethylmethylammonium, tetraethylammonium and the like. Examples of the quaternized amidinium include ethyldimethylimidazolinium and tetramethylimidazolinium. Examples of amines in amine salts include primary amines, secondary amines, and tertiary amines. Primary amines include methylamine, ethylamine, and propylamine, secondary amines include dimethylamine, diethylamine, ethylmethylamine, and dibutylamine, and tertiary amines include trimethylamine, triethylamine, tributylamine, and ethyldimethylamine. Ethyldiisopropylamine and the like can be mentioned.
さらに、電解液には他の添加剤を添加することもできる。添加剤としては、ポリエチレングリコール、ホウ酸と多糖類（マンニット、ソルビットなど）との錯化合物、ホウ酸と多価アルコールとの錯化合物、ホウ酸エステル、ニトロ化合物（ｏ−ニトロ安息香酸、ｍ−ニトロ安息香酸、ｐ−ニトロ安息香酸、ｏ−ニトロフェノール、ｍ−ニトロフェノール、ｐ−ニトロフェノールなど）、リン酸エステル、コロイダルシリカなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Further, other additives can be added to the electrolytic solution. Additives include polyethylene glycol, a complex compound of boric acid and polysaccharides (mannit, sorbit, etc.), a complex compound of boric acid and polyhydric alcohol, boric acid ester, nitro compound (o-nitrobenzoic acid, m). -Nitroboric acid, p-nitroboric acid, o-nitrophenol, m-nitrophenol, p-nitrophenol, etc.), phosphoric acid ester, colloidal silica and the like. These may be used alone or in combination of two or more.
以上、電解液を用いた電解コンデンサを説明したが、固体電解質を用いた場合は、集電体と接触したカーボン層によって固体電解質と導通することとなり、誘電分極作用による陽極側容量によって電解コンデンサの静電容量が構成される。また、固体電解質を用いる場合は、ポリエチレンジオキシチオフェンなどのポリチオフェンや、ポリピロール、ポリアニリンなどの導電性ポリマーが挙げられる。 The electrolytic capacitor using the electrolytic solution has been described above, but when a solid electrolyte is used, the carbon layer in contact with the current collector conducts the solid electrolyte, and the capacitance on the anode side due to the dielectric polarization action of the electrolytic capacitor Capacitance is configured. When a solid electrolyte is used, polythiophene such as polyethylene dioxythiophene and conductive polymers such as polypyrrole and polyaniline can be mentioned.
以下、実施例に基づいて本発明をさらに詳細に説明する。なお、本発明は下記実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail based on Examples. The present invention is not limited to the following examples.
（実施例１）
次のようにして実施例１の電解コンデンサを作製した。まず、陰極体に関し、炭素材である鱗片状の黒鉛の粉末及び球状炭素の粉末、バインダーであるスチレンブタジエンゴム（ＳＢＲ）、及び分散剤含有水溶液としてカルボキシメチルセルロースナトリウム（ＣＭＣ−Ｎａ）水溶液を混合して混練することでスラリーを作製した。炭素材とバインダーと分散剤含有水溶液の配合比は、重量比で８４：１０：６とした。別途、電極リード板を引き出したアルミニウム箔を陰極箔として用意し、この陰極箔にスラリーを均一に塗布した。このアルミニウム箔には、予め、塩酸中で電圧を印加することで、エッチング層を形成しておいた。スラリーは、そのエッチング層に塗布した。そして、スラリーを乾燥させた後、１５０ｋＮｃｍ−２の圧力で垂直プレスをかけ、カーボン層を陰極箔上に定着させた。(Example 1)
The electrolytic capacitor of Example 1 was produced as follows. First, regarding the cathode body, scaly graphite powder and spherical carbon powder as carbon materials, styrene butadiene rubber (SBR) as a binder, and sodium carboxymethyl cellulose (CMC-Na) aqueous solution as a dispersant-containing aqueous solution are mixed. And kneaded to prepare a slurry. The compounding ratio of the carbon material, the binder, and the dispersant-containing aqueous solution was 84:10: 6 by weight. Separately, an aluminum foil from which the electrode lead plate was pulled out was prepared as a cathode foil, and the slurry was uniformly applied to the cathode foil. An etching layer was formed on this aluminum foil in advance by applying a voltage in hydrochloric acid. The slurry was applied to the etching layer. Then, after the slurry was dried, a vertical press was applied at a pressure of 150 kNcm-2 to fix the carbon layer on the cathode foil.
また、アルミニウム箔にエッチング処理を施し、公称化成電圧が４Ｖｆｓとなるように誘電体酸化皮膜を形成し、投影面積が２．１ｃｍ２の大きさのアルミニウム箔を得て、これを陽極箔とした。この陽極箔の容量は３８６μＦｃｍ−２であった。そして、この陰極体と陽極体をレーヨン製のセパレータを介して対向させ、電解液を含浸させ、ラミネートセルとし、共通の再化成処理を施した。電解液としては、フタル酸テトラメチルイミダゾリニウムを溶質とし、γ−ブチロラクトンを溶媒として作製された。再化成の際には、全電解コンデンサとも１０５℃の環境下で、３．３５Ｖの電圧を６０分間印加した。Further, the aluminum foil is etched to form a dielectric oxide film so that the nominal chemical conversion voltage is 4 V fs, and an aluminum foil having a projected area of 2.1 cm 2 is obtained, which is used as an anode foil. bottom. The capacity of this anode foil was 386 μFcm- 2 . Then, the cathode body and the anode body were opposed to each other via a rayon separator, impregnated with an electrolytic solution to form a laminated cell, and subjected to a common re-chemical conversion treatment. The electrolytic solution was prepared using tetramethylimidazolinium phthalate as a solute and γ-butyrolactone as a solvent. At the time of regeneration, a voltage of 3.35 V was applied for 60 minutes in an environment of 105 ° C. for all electrolytic capacitors.
実施例１の電解コンデンサにおいては、平均粒径が１０μｍの鱗片状の黒鉛を用い、球状炭素としてアセチレンブラック（ＡＢ）を用いた。このアセチレンブラックの一次粒子径が平均５０ｎｍであり、またＢＥＴ比表面積は３９ｍ２／ｇである。また黒鉛とアセチレンブラックの混合比は７５：２５とした。In the electrolytic capacitor of Example 1, scaly graphite having an average particle size of 10 μm was used, and acetylene black (AB) was used as the spherical carbon. The primary particle size of this acetylene black is 50 nm on average, and the BET specific surface area is 39 m 2 / g. The mixing ratio of graphite and acetylene black was 75:25.
（実施例２、３及び１０）
実施例１の電解コンデンサと同一条件で実施例２、３及び１０の電解コンデンサを作製した。但し、実施例２の電解コンデンサでは、球状炭素としてアセチレンブラックを用い、黒鉛とアセチレンブラックの混合比を７５：２５としたものの、平均粒径が６μｍの鱗片状の黒鉛を用いた。また、実施例３の電解コンデンサでは、黒鉛とアセチレンブラックの混合比を７５：２５としたものの、平均粒径が４μｍの鱗片状の黒鉛を用いた。また、実施例１０の電解コンデンサでは、黒鉛とアセチレンブラックの混合比を７５：２５としたものの、平均粒径が０．５μｍの鱗片状の黒鉛を用いた。即ち、実施例２、３及び１０は、実施例１に対して鱗片状の黒鉛の平均粒径が変更されている。(Examples 2, 3 and 10)
The electrolytic capacitors of Examples 2, 3 and 10 were produced under the same conditions as the electrolytic capacitors of Example 1. However, in the electrolytic capacitor of Example 2, acetylene black was used as the spherical carbon, and although the mixing ratio of graphite and acetylene black was 75:25, scaly graphite having an average particle size of 6 μm was used. Further, in the electrolytic capacitor of Example 3, although the mixing ratio of graphite and acetylene black was set to 75:25, scaly graphite having an average particle size of 4 μm was used. Further, in the electrolytic capacitor of Example 10, although the mixing ratio of graphite and acetylene black was 75:25, scaly graphite having an average particle size of 0.5 μm was used. That is, in Examples 2, 3 and 10, the average particle size of the scaly graphite is changed from that of Example 1.
（実施例４乃至９）
実施例１の電解コンデンサと同一条件で実施例４乃至９の電解コンデンサを作製した。但し、実施例４乃至９の電解コンデンサでは、平均粒径が１μｍの鱗片状の黒鉛を用いた。これら実施例４乃至９の電解コンデンサは、黒鉛とアセチレンブラックの混合比が異なる。実施例４では黒鉛とアセチレンブラックの混合比を９５：５とし、実施例５では黒鉛とアセチレンブラックの混合比を黒鉛の比率を落として９０：１０とし、実施例６では黒鉛とアセチレンブラックの混合比を黒鉛の比率を更に落として８５：１５とし、実施例７では黒鉛とアセチレンブラックの混合比を黒鉛の比率を更に落として７５：２５とし、実施例８では黒鉛とアセチレンブラックの混合比を黒鉛の比率を更に落として５０：５０とし、実施例９では黒鉛とアセチレンブラックの混合比を黒鉛の比率を更に落として２５：７５とした。(Examples 4 to 9)
The electrolytic capacitors of Examples 4 to 9 were produced under the same conditions as the electrolytic capacitors of Example 1. However, in the electrolytic capacitors of Examples 4 to 9, scaly graphite having an average particle size of 1 μm was used. The electrolytic capacitors of Examples 4 to 9 have different mixing ratios of graphite and acetylene black. In Example 4, the mixing ratio of graphite and acetylene black was 95: 5, in Example 5, the mixing ratio of graphite and acetylene black was reduced to 90:10, and in Example 6, the mixing ratio of graphite and acetylene black was reduced. The ratio was set to 85:15 by further reducing the ratio of graphite, the mixing ratio of graphite and acetylene black was further reduced to 75:25 in Example 7, and the mixing ratio of graphite and acetylene black was set to 75:25 in Example 8. The ratio of graphite was further reduced to 50:50, and in Example 9, the mixing ratio of graphite and acetylene black was further reduced to 25:75.
（比較例３及び参考例１）
実施例４乃至９の電解コンデンサとの対比として、比較例３及び参考例１の電解コンデンサを作製した。但し、比較例３では、球状炭素を加えず、平均粒径１μｍの黒鉛のみを炭素材としてカーボン層を形成した。参考例１では、鱗片状の黒鉛を加えず、アセチレンブラックのみを炭素材としてカーボン層を形成した。その他の条件は、実施例４乃至９と同一である。(Comparative Example 3 and Reference Example 1)
As a comparison with the electrolytic capacitors of Examples 4 to 9, the electrolytic capacitors of Comparative Example 3 and Reference Example 1 were prepared. However, in Comparative Example 3, the carbon layer was formed using only graphite having an average particle size of 1 μm as the carbon material without adding spherical carbon. In Reference Example 1, a carbon layer was formed using only acetylene black as a carbon material without adding scaly graphite. Other conditions are the same as in Examples 4 to 9.
（実施例１１及び１２）
実施例２の電解コンデンサと同一条件で実施例１１及び１２の電解コンデンサを作製した。但し、実施例１１の電解コンデンサでは、球状炭素としてケッチェンブラックを用いた点で実施例２と異なるが、鱗片状の黒鉛の平均粒径が６μｍである点、及び鱗片状の黒鉛と球状炭素の混合比が７５：２５である点で同一である。ケッチェンブラックの一次粒子径が平均４０ｎｍであり、またＢＥＴ比表面積は８００ｍ２／ｇである。実施例１２の電解コンデンサでは、実施例１１と比べて鱗片状の黒鉛の混合比を落とし、５０：５０とした。(Examples 11 and 12)
The electrolytic capacitors of Examples 11 and 12 were produced under the same conditions as the electrolytic capacitors of Example 2. However, the electrolytic capacitor of Example 11 is different from Example 2 in that Ketjen black is used as the spherical carbon, but the average particle size of the scaly graphite is 6 μm, and the scaly graphite and the spherical carbon. Is the same in that the mixing ratio of The primary particle size of Ketjen Black is 40 nm on average, and the BET specific surface area is 800 m 2 / g. In the electrolytic capacitor of Example 12, the mixing ratio of scaly graphite was reduced to 50:50 as compared with Example 11.
（実施例１３及び１４）
実施例１１及び１２の電解コンデンサと同一条件で実施例１３及び１４の電解コンデンサを作製した。但し、実施例１３の電解コンデンサは実施例１１に対し、また実施例１４の電解コンデンサは実施例１２に対し、鱗片状の黒鉛の平均粒径が１μｍである点で異なる。(Examples 13 and 14)
The electrolytic capacitors of Examples 13 and 14 were produced under the same conditions as the electrolytic capacitors of Examples 11 and 12. However, the electrolytic capacitor of Example 13 is different from that of Example 11, and the electrolytic capacitor of Example 14 is different from that of Example 12 in that the average particle size of the scaly graphite is 1 μm.
（比較例１及び２）
最後に、これら実施例１乃至１４の電解コンデンサとの対比として、比較例１及び比較例２の電解コンデンサを作製した。比較例１の電解コンデンサに関しては、エッチング未処理のアルミニウム箔を集電体として用い、電子ビーム蒸着法により窒化チタン層を形成し、この窒化チタン層を形成したアルミニウム箔を陰極体として用いた。また、比較例２の電解コンデンサに関しては、エッチング未処理のアルミニウム箔を集電体として用い、平均粒径が５μｍの活性炭とアセチレンブラックとを混合したカーボン層を形成し、このカーボン層を形成したアルミニウム箔を陰極体として用いた。活性炭のＢＥＴ比表面積は１５００ｍ２／ｇである。また比較例２で用いたアセチレンブラックのＢＥＴ比表面積は３９ｍ２／ｇである。比較例１及び２の電解コンデンサにおける陽極箔、セパレータ及び電解液の組成、作製工程及び作製条件は、各実施例の電解コンデンサと同じである。(Comparative Examples 1 and 2)
Finally, as a comparison with the electrolytic capacitors of Examples 1 to 14, the electrolytic capacitors of Comparative Example 1 and Comparative Example 2 were produced. Regarding the electrolytic capacitor of Comparative Example 1, an unetched aluminum foil was used as a current collector, a titanium nitride layer was formed by an electron beam vapor deposition method, and the aluminum foil on which the titanium nitride layer was formed was used as a cathode body. Regarding the electrolytic capacitor of Comparative Example 2, an unetched aluminum foil was used as a current collector to form a carbon layer in which activated carbon having an average particle size of 5 μm and acetylene black were mixed to form this carbon layer. Aluminum foil was used as the cathode body. The BET specific surface area of activated carbon is 1500 m 2 / g. The BET specific surface area of acetylene black used in Comparative Example 2 is 39 m 2 / g. The composition, manufacturing process, and manufacturing conditions of the anode foil, the separator, and the electrolytic solution in the electrolytic capacitors of Comparative Examples 1 and 2 are the same as those of the electrolytic capacitors of each example.
（製品試験）
以上の実施例１乃至１４、比較例１乃至３、並びに参考例１の電解コンデンサの静電容量（Ｃａｐ）を測定した。この製品試験では、２０℃で１２０Ｈｚ及び１０ｋＨｚ充放電時の静電容量（Ｃａｐ）を初期静電容量として測定した。また、１２５℃である高温環境下に２６０時間晒し、その後、２０℃で１２０Ｈｚ及び１０ｋＨｚ充放電時の静電容量（Ｃａｐ）を高温環境負荷後静電容量として測定した。その結果を下記表１に示す。更に、表１には、初期静電容量に対する高温環境負荷後静電容量の変化率（ΔＣａｐ）を周波数ごとに記した。(Product test)
The capacitance (Cap) of the electrolytic capacitors of Examples 1 to 14, Comparative Examples 1 to 3, and Reference Example 1 was measured. In this product test, the capacitance (Cap) at 120 Hz and 10 kHz charging / discharging at 20 ° C. was measured as the initial capacitance. Further, it was exposed to a high temperature environment of 125 ° C. for 260 hours, and then the capacitance (Cap) during charging / discharging at 120 Hz and 10 kHz at 20 ° C. was measured as the capacitance after loading in a high temperature environment. The results are shown in Table 1 below. Further, Table 1 shows the rate of change (ΔCap) of the capacitance after a high temperature environment load with respect to the initial capacitance for each frequency.
（表１）
表１に示すように、低周波領域である１２０Ｈｚで電解コンデンサを使用すると、実施例１乃至１４の電解コンデンサは、初期静電容量に対する高温環境負荷後静電容量の変化率（ΔＣａｐ）において、比較例１及び２の電解コンデンサに対して良好であった。これら実施例１乃至１４は、黒鉛とアセチレンブラック又はケッチェンブラックといった球状炭素を混合して陰極体のカーボン層を形成したものである。一方、比較例３の電解コンデンサのように、黒鉛のみで陰極体のカーボン層を形成すると、比較例１及び２と比べて初期静電容量の著しい低下が見られ、高温環境負荷後静電容量の低下も大きいことが確認でき、１０ｋＨｚでの使用においても静電容量が著しく低い。尚、参考例１の電解コンデンサは、本製品試験において比較的良好ではあるが、後述するように界面抵抗が劣っている。 As shown in Table 1, when an electrolytic capacitor is used at 120 Hz, which is a low frequency region, the electrolytic capacitors of Examples 1 to 14 have a change rate (ΔCap) of the capacitance after a high temperature environment load with respect to the initial capacitance. It was good for the electrolytic capacitors of Comparative Examples 1 and 2. In Examples 1 to 14, graphite and spherical carbon such as acetylene black or Ketjen black are mixed to form a carbon layer of a cathode body. On the other hand, when the carbon layer of the cathode body is formed only with graphite as in the electrolytic capacitor of Comparative Example 3, the initial capacitance is significantly reduced as compared with Comparative Examples 1 and 2, and the capacitance after a high temperature environment load is observed. It can be confirmed that the decrease in capacitance is large, and the capacitance is extremely low even when used at 10 kHz. The electrolytic capacitor of Reference Example 1 is relatively good in this product test, but has inferior interfacial resistance as will be described later.
これにより、黒鉛と球状炭素を混合して陰極体のカーボン層を形成することで、電解コンデンサは、１２０Ｈｚという低周波領域での使用において、初期静電容量のみならず、高温環境負荷後においても比較的安定した静電容量を有することが確認された。 As a result, graphite and spherical carbon are mixed to form a carbon layer of the cathode body, so that the electrolytic capacitor can be used not only in the initial capacitance but also after a high temperature environment load when used in the low frequency region of 120 Hz. It was confirmed that it has a relatively stable capacitance.
次に、実施例１乃至１０の電解コンデンサは、球状炭素としてアセチレンブラックを用いたものであるが、高周波領域である１０ｋＨｚで電解コンデンサを使用しても、初期静電容量に対する高温環境負荷後静電容量の変化率（ΔＣａｐ）において良好であることが確認された。即ち、黒鉛とアセチレンブラックとを混合して成るカーボン層を陰極体に形成した電解コンデンサは、高温環境負荷後の静電容量の観点で、低周波領域での使用においても、高周波領域での使用においても、幅広い周波数領域で安定的な静電容量を有していて汎用的であることが確認された。 Next, the electrolytic capacitors of Examples 1 to 10 use acetylene black as the spherical carbon, but even if the electrolytic capacitor is used at 10 kHz, which is a high frequency region, it is static after a high temperature environment load with respect to the initial capacitance. It was confirmed that the rate of change in capacitance (ΔCap) was good. That is, an electrolytic capacitor having a carbon layer formed by mixing graphite and acetylene black as a cathode body is used in a high frequency region even when used in a low frequency region from the viewpoint of capacitance after a high temperature environment load. It was also confirmed that it has a stable capacitance in a wide frequency range and is versatile.
また、実施例１及び２の電解コンデンサは、高周波領域で使用しようとも、低周波領域で使用しようとも、初期静電容量に対して高温環境負荷後静電容量が落ちないことが確認された。即ち、黒鉛の平均粒径を６μｍ以上１０μｍ以下とし、球状炭素としてアセチレンブラックを選択すると、電解コンデンサの熱安定性に優れ、幅広い温度環境下に亘って極めて安定に動作することが確認された。更に、実施例２の電解コンデンサは、実施例１と比べると静電容量自体が大幅に向上し、高温環境負荷後に関しては窒化チタンの皮膜を陰極箔に形成した比較例１の電解コンデンサと遜色の無い大きさの静電容量を発現している。即ち、黒鉛の平均粒径を６μｍ程度（±２μｍ）とすると、高温環境においても高容量で且つ安定的であることが確認された。 Further, it was confirmed that the electrolytic capacitors of Examples 1 and 2 did not lose their capacitance after a high temperature environment load with respect to the initial capacitance regardless of whether they were used in the high frequency region or the low frequency region. That is, it was confirmed that when the average particle size of graphite was 6 μm or more and 10 μm or less and acetylene black was selected as the spherical carbon, the electrolytic capacitor was excellent in thermal stability and operated extremely stably over a wide temperature environment. Further, the electrolytic capacitor of Example 2 has a significantly improved capacitance itself as compared with Example 1, and is inferior to the electrolytic capacitor of Comparative Example 1 in which a titanium nitride film is formed on the cathode foil after a high temperature environment load. It expresses a capacitance of a size that does not exist. That is, it was confirmed that when the average particle size of graphite is about 6 μm (± 2 μm), the volume is high and stable even in a high temperature environment.
また、実施例３乃至１０の電解コンデンサは、高周波領域で使用しようとも、低周波領域で使用しようとも、比較例１及び比較例２の電解コンデンサの初期静電容量のみならず、高温環境負荷後静電容量に匹敵或いは凌駕することが確認された。即ち、黒鉛の平均粒径を６μｍ未満とし、球状炭素としてアセチレンブラックを選択すると、ＢＥＴ比表面積が３９ｍ２／ｇであるアセチレンブラックを用いているにもかかわらず、ＢＥＴ比表面積が１５００ｍ２／ｇである活性炭を用いた比較例２に匹敵し、更に平均粒径を１μｍとすると、この比較例２を凌駕して、電解コンデンサの静電容量を高めることができることが確認された。更には、高温環境負荷後の静電容量の低下を抑制することが可能となり、熱安定性に優れることに加え、広い周波数領域において極めて安定に動作することが確認された。Further, the electrolytic capacitors of Examples 3 to 10 are used not only in the initial capacitance of the electrolytic capacitors of Comparative Examples 1 and 2 but also after a high temperature environment load regardless of whether they are used in a high frequency region or a low frequency region. It was confirmed that it was comparable to or surpassed the capacitance. That is, when the average particle size of graphite is less than 6 μm and acetylene black is selected as the spherical carbon, the BET specific surface area is 1500 m 2 / g even though acetylene black having a BET specific surface area of 39 m 2 / g is used. It was confirmed that when the average particle size is 1 μm, which is comparable to Comparative Example 2 using activated carbon, the capacitance of the electrolytic capacitor can be increased, surpassing that of Comparative Example 2. Furthermore, it has been confirmed that it is possible to suppress a decrease in capacitance after a high temperature environment load, and in addition to being excellent in thermal stability, it operates extremely stably in a wide frequency range.
（界面抵抗）
ここで、実施例３及び参考例１の電解コンデンサにおいて、陰極体の断面を走査型電子顕微鏡で撮影し、またカーボン層と拡面層の界面抵抗値を測定した。図３は、陰極体の断面のＳＥＭ写真であり、（ａ）は実施例３に係る１０，０００倍、（ｂ）は参考例１に係る１０，０００倍、（ｃ）は実施例３に係る２５，０００倍、（ｄ）は参考例１に係る２５，０００倍である。界面抵抗値は、電極抵抗測定システム（日置電機株式会社製；型番ＲＭ２６１０）にて測定した。尚、実施例３は、黒鉛とカーボンブラックによってカーボン層が成り、これに対して、参考例１は、黒鉛を含まず、カーボンブラックによってカーボン層が成り、実施例３と参考例１は、その他につき同一である。(Interfacial resistance)
Here, in the electrolytic capacitors of Example 3 and Reference Example 1, the cross section of the cathode body was photographed with a scanning electron microscope, and the interfacial resistance value between the carbon layer and the surface expansion layer was measured. FIG. 3 is an SEM photograph of a cross section of the cathode body, in which (a) is 10,000 times according to Example 3, (b) is 10,000 times according to Reference Example 1, and (c) is Example 3. 25,000 times, and (d) is 25,000 times according to Reference Example 1. The interfacial resistance value was measured by an electrode resistance measuring system (manufactured by Hioki Electric Co., Ltd .; model number RM2610). In Example 3, a carbon layer is formed of graphite and carbon black, whereas in Reference Example 1, a carbon layer is formed of carbon black without containing graphite, and Examples 3 and 1 are other. Is the same.
図３の（ａ）及び（ｃ）に示すように、実施例３の陰極体では、黒鉛が拡面層の凹凸面に沿って変形して敷き詰められ、カーボン層と拡面層が凹凸面において密着していることがわかる。また、実施例３の陰極体では、黒鉛が押圧蓋となって拡面層の細孔にカーボンブラックを押し込んでおり、カーボン層と拡面層が細孔においても密着していることがわかる。また、黒鉛が屈曲し、屈曲角度が局所的に９０°程度まで折れ曲がる。このように屈曲した黒鉛によって、圧接の圧力が直接伝わり難い凹凸面の側面や深部の細孔までカーボンブラックを効率的に押し込んでいる。 As shown in FIGS. 3A and 3C, in the cathode body of Example 3, graphite is deformed and spread along the uneven surface of the expansion layer, and the carbon layer and the expansion layer are spread on the uneven surface. It can be seen that they are in close contact with each other. Further, in the cathode body of Example 3, graphite acts as a pressing lid to push carbon black into the pores of the expansion layer, and it can be seen that the carbon layer and the expansion layer are also in close contact with each other in the pores. In addition, graphite bends and the bending angle is locally bent to about 90 °. With the graphite bent in this way, carbon black is efficiently pushed into the pores on the side surface and the deep part of the uneven surface where the pressure of pressure welding is difficult to be directly transmitted.
このように、実施例３の陰極体では、拡面層にカーボン層が食い込んでいることがわかる。これに対して、参考例１の陰極体では、カーボンブラックが拡面層の凹凸面に積もっているものの、カーボン層と凹凸面との間の所々に空隙が生まれている。更に、参考例１の陰極体では、拡面層の細孔に入り込んでいるカーボンブラックが相対的に少なく、細孔内の空隙が多く発生している。 As described above, in the cathode body of Example 3, it can be seen that the carbon layer bites into the expansion layer. On the other hand, in the cathode body of Reference Example 1, although carbon black is accumulated on the uneven surface of the expansion layer, voids are formed in some places between the carbon layer and the uneven surface. Further, in the cathode body of Reference Example 1, the amount of carbon black that has entered the pores of the expansion layer is relatively small, and many voids are generated in the pores.
この結果、実施例３の陰極体の界面抵抗値は、１．７８ｍΩｃｍ２であったが、参考例１の陰極体の界面抵抗値は、２．４９ｍΩｃｍ２となってしまった。即ち、黒鉛と球状炭素の両方をカーボン層に含む実施例１乃至１４は、高温環境負荷後においても安定した静電容量を発現させることができる点に加え、低い界面抵抗値が得られることが確認された。As a result, the interfacial resistance value of the cathode body of Example 3 was 1.78 mΩcm 2 , but the interfacial resistance value of the cathode body of Reference Example 1 was 2.49 mΩcm 2 . That is, in Examples 1 to 14 in which both graphite and spherical carbon are contained in the carbon layer, in addition to being able to develop a stable capacitance even after a high temperature environmental load, a low interfacial resistance value can be obtained. confirmed.
（プレス効果試験）
ここで、１５０ｋＮｃｍ−２の圧力で垂直プレスをかけた実施例３の陰極体との比較対象として、プレス工程を省いた参考例２の陰極体を作製した。参考例２の陰極体は、プレスの有無を除いて実施例３と同一条件で作製された。そして、実施例３の陰極体と参考例２の陰極体の断面を走査型電子顕微鏡で撮影した。撮影結果を、図４に示す。図４は、陰極体の断面のＳＥＭ写真であり、（ａ）は実施例３に係る１０，０００倍、（ｂ）は参考例２に係る１０，０００倍、（ｃ）は実施例３に係る２５，０００倍、（ｄ）は参考例２に係る２５，０００倍である。(Press effect test)
Here, as a comparison target with the cathode body of Example 3 which was vertically pressed at a pressure of 150 kNcm- 2, the cathode body of Reference Example 2 without the pressing step was prepared. The cathode body of Reference Example 2 was produced under the same conditions as in Example 3 except for the presence or absence of a press. Then, the cross sections of the cathode body of Example 3 and the cathode body of Reference Example 2 were photographed with a scanning electron microscope. The shooting results are shown in FIG. FIG. 4 is an SEM photograph of a cross section of the cathode body, in which (a) is 10,000 times according to Example 3, (b) is 10,000 times according to Reference Example 2, and (c) is Example 3. 25,000 times, and (d) is 25,000 times according to Reference Example 2.
図４の（ａ）及び（ｃ）に示すように、実施例３の陰極体では、黒鉛が拡面層の凹凸面に沿って変形して敷き詰められ、カーボン層と拡面層が凹凸面において密着していることがわかる。また、実施例３の陰極体では、黒鉛が押圧蓋となって拡面層の細孔にカーボンブラックを押し込んでおり、カーボン層と拡面層が細孔においても密着していることがわかる。このように、実施例３の陰極体では、拡面層にカーボン層が食い込んでいることがわかる。 As shown in FIGS. 4A and 4C, in the cathode body of Example 3, graphite is deformed and spread along the uneven surface of the expansion layer, and the carbon layer and the expansion layer are spread on the uneven surface. It can be seen that they are in close contact with each other. Further, in the cathode body of Example 3, graphite acts as a pressing lid to push carbon black into the pores of the expansion layer, and it can be seen that the carbon layer and the expansion layer are also in close contact with each other in the pores. As described above, in the cathode body of Example 3, it can be seen that the carbon layer bites into the expansion layer.
一方、参考例２の陰極体では、黒鉛が拡面層の凹凸面に沿って変形しておらず、カーボン層と凹凸面との間の所々に空隙が生まれている。更に、参考例２の陰極体では、拡面層の細孔に入り込んでいるカーボンブラックが相対的に少なく、細孔内の空隙が多く発生している。 On the other hand, in the cathode body of Reference Example 2, graphite is not deformed along the uneven surface of the expansion layer, and voids are formed in some places between the carbon layer and the uneven surface. Further, in the cathode body of Reference Example 2, the amount of carbon black that has entered the pores of the expansion layer is relatively small, and many voids are generated in the pores.
この結果、陰極箔にスラリーを均一に塗布して乾燥させた後、所定の圧力でプレスをかければ、黒鉛が拡面層の凹凸面に沿って容易に変形して敷き詰められ、カーボン層と拡面層が凹凸面において密着し易く、界面抵抗値を下げ易いことが確認された。また、プレスにより、黒鉛が押圧蓋となって拡面層の細孔にカーボンブラックを容易に押し込み、カーボン層と拡面層が細孔においても密着し易く、界面抵抗値を下げ易いことが確認された。 As a result, if the slurry is uniformly applied to the cathode foil, dried, and then pressed at a predetermined pressure, the graphite is easily deformed and spread along the uneven surface of the expansion layer, and spreads with the carbon layer. It was confirmed that the surface layer easily adheres to the uneven surface and the interfacial resistance value can be easily lowered. In addition, it was confirmed by pressing that graphite acts as a pressing lid and easily pushes carbon black into the pores of the expansion layer, so that the carbon layer and the expansion layer easily adhere to each other even in the pores, and it is easy to lower the interfacial resistance value. Was done.
（実施例１５及び１６）
ＢＥＴ比表面積が３９ｍ２／ｇのアセチレンブラックを用いた実施例７の電解コンデンサと比べて、ＢＥＴ比表面積が１３３ｍ２／ｇのアセチレンブラックを用いた実施例１５の電解コンデンサを作製した。その他の条件は実施例７の電解コンデンサと同一である。また、ＢＥＴ比表面積が８００ｍ２／ｇのケッチェンブラックを用いた実施例１３の電解コンデンサと比べて、ＢＥＴ比表面積が３７７ｍ２／ｇのケッチェンブラックを用いた実施例１６の電解コンデンサを作製した。その他の条件は実施例１３の電解コンデンサと同一である。(Examples 15 and 16)
Compared with the electrolytic capacitor of Example 7 using acetylene black having a BET specific surface area of 39 m 2 / g, an electrolytic capacitor of Example 15 using acetylene black having a BET specific surface area of 133 m 2 / g was prepared. Other conditions are the same as those of the electrolytic capacitor of Example 7. Further, as compared with the electrolytic capacitor of Example 13 using Ketjen Black having a BET specific surface area of 800 m 2 / g, the electrolytic capacitor of Example 16 using Ketjen Black having a BET specific surface area of 377 m 2 / g was produced. bottom. Other conditions are the same as those of the electrolytic capacitor of Example 13.
これら実施例１５及び１６の電解コンデンサに関しても、初期静電容量および高温環境負荷後の静電容量について各周波数領域の組み合わせで製品試験を行った。その結果を表２に示す。表２には、参考的に実施例７及び１３の電解コンデンサの製品試験の結果も示す。 The electrolytic capacitors of Examples 15 and 16 were also subjected to product tests for the initial capacitance and the capacitance after a high temperature environment load in each frequency domain combination. The results are shown in Table 2. Table 2 also shows the results of product tests of the electrolytic capacitors of Examples 7 and 13 for reference.
（表２）
表２に示すように、ＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素を含むカーボン層が形成された陰極体を用いた実施例７及び１５の電解コンデンサは、ＢＥＴ比表面積が２００ｍ２／ｇ超である実施例１３及び１６の電解コンデンサと比べて、１２０Ｈｚ及び１０ｋＨｚの両方において高温環境負荷後静電容量の変化率（ΔＣａｐ）が良好であることが確認された。即ち、アセチレンブラックのみならず、ＢＥＴ比表面積が２００ｍ２／ｇ以下の球状炭素を含むカーボン層が形成された陰極体を用いることで、初期静電容量のみならず、高温環境負荷後においても、幅広い周波数領域において安定的に静電容量を発現することが確認された。As shown in Table 2, the electrolytic capacitors of Examples 7 and 15 using the cathode body on which the carbon layer containing spherical carbon having a BET specific surface area of 200 m 2 / g or less was formed had a BET specific surface area of 200 m 2 / g. It was confirmed that the rate of change (ΔCap) of the capacitance after a high temperature environment load was better at both 120 Hz and 10 kHz as compared with the electrolytic capacitors of Examples 13 and 16 which were super. That is, by using not only acetylene black but also a cathode body having a carbon layer containing spherical carbon having a BET specific surface area of 200 m 2 / g or less, not only the initial capacitance but also after a high temperature environment load. It was confirmed that the capacitance is stably expressed in a wide frequency range.
（炭素材定着性試験）
黒鉛の粒子径が１０、６、４及び１μｍの実施例１、２、３及び７の電解コンデンサの炭素材定着性試験を行った。各電解コンデンサをコンデンサ素子の段階で分解し、セパレータの陰極体側の面に粘着テープ（３Ｍ製スコッチテープ：型番１４４ＪＰ ３２−９７８）を一度貼り付けて剥離し、粘着テープへの付着物を観察した。その結果を図１に示す。図１は、実施例１、２、３及び７に係る剥離後の粘着テープを撮影した写真である。(Carbon material fixability test)
The carbon material fixability test of the electrolytic capacitors of Examples 1, 2, 3 and 7 having graphite particle sizes of 10, 6, 4 and 1 μm was performed. Each electrolytic capacitor was disassembled at the stage of the capacitor element, and an adhesive tape (3M Scotch tape: model number 144JP 32-978) was once attached to the surface of the separator on the cathode body side and peeled off, and the adhesion to the adhesive tape was observed. .. The result is shown in FIG. FIG. 1 is a photograph of the peeled adhesive tape according to Examples 1, 2, 3 and 7.
一般的には黒鉛の粒径が小さいほど、カーボン層から黒鉛が離脱し易いと推測されるのだが、図１に示すように、黒鉛の粒径が小さくなるほど、カーボン層から離脱した黒鉛の量が少なくなっていることが確認できる。特に、黒鉛の平均粒径が６μｍ以下の実施例２、３及び７は、同１０μｍの実施例１と比べて粘着テープへの付着量が少なくなっている。このため、黒鉛の平均粒径を６μｍ以下とすると、カーボン層内に炭素材を留め置くバインダーの量を少なくでき、陰極体の抵抗を下げ、また電解コンデンサのＥＳＲを下げられることが確認された。 Generally, it is presumed that the smaller the particle size of graphite, the easier it is for graphite to separate from the carbon layer. However, as shown in FIG. 1, the smaller the particle size of graphite, the more the amount of graphite separated from the carbon layer. Can be confirmed to be reduced. In particular, Examples 2, 3 and 7 having an average particle size of graphite having an average particle size of 6 μm or less have a smaller amount of adhesion to the adhesive tape than Example 1 having an average particle size of 10 μm. Therefore, it was confirmed that when the average particle size of graphite is 6 μm or less, the amount of the binder that retains the carbon material in the carbon layer can be reduced, the resistance of the cathode body can be lowered, and the ESR of the electrolytic capacitor can be lowered. ..
Claims (13)
弁作用金属により成る陰極箔と、
前記陰極箔に形成されたカーボン層と、
を備え、
前記カーボン層は、黒鉛と球状炭素とを含むこと、
を特徴とする電極体。An electrode body used for the cathode of an electrolytic capacitor.
Cathode foil made of valve acting metal and
The carbon layer formed on the cathode foil and
With
The carbon layer contains graphite and spherical carbon.
An electrode body characterized by.
を特徴とする請求項１記載の電極体。The spherical carbon is carbon black having a BET specific surface area of 200 m 2 / g or less.
The electrode body according to claim 1.
を特徴とする請求項２記載の電極体。The graphite has an average particle size of 6 μm or more and 10 μm or less in the particle size distribution.
2. The electrode body according to claim 2.
を特徴とする請求項２記載の電極体。The graphite has an average particle size of 6 μm or less in the particle size distribution.
2. The electrode body according to claim 2.
を特徴とする請求項２乃至４の何れかに記載の電極体。The mixing ratio of the graphite and the carbon black is 90:10 to 25:75.
The electrode body according to any one of claims 2 to 4.
前記カーボン層は、前記拡面層上に形成されていること、
を特徴とする請求項１乃至５記載の電極体。An enlarged surface layer is formed on the cathode foil.
The carbon layer is formed on the expansion layer.
The electrode body according to claim 1 to 5.
を特徴とする請求項６記載の電極体。The expansion layer and the carbon layer are in pressure contact with each other.
6. The electrode body according to claim 6.
前記球状炭素は、細孔に入り込み、
前記黒鉛は、前記球状炭素が入り込んだ前記細孔を覆っていること、
を特徴とする請求項６又は７記載の電極体。The surface expansion layer is formed of a concavo-convex surface and pores formed from the concavo-convex surface toward the deep part of the cathode foil.
The spherical carbon penetrates into the pores and
The graphite covers the pores in which the spherical carbon has entered.
The electrode body according to claim 6 or 7.
を特徴とする請求項８記載の電極体。The spherical carbon has entered the pores by pressure welding of the carbon layer.
8. The electrode body according to claim 8.
を特徴とする請求項８又は９記載の電極体。The graphite is deformed along the uneven surface of the expansion layer.
The electrode body according to claim 8 or 9.
を特徴とする電解コンデンサ。The cathode is provided with the electrode body according to any one of claims 1 to 10.
An electrolytic capacitor characterized by.
弁作用金属により成る陰極箔に、黒鉛と球状炭素とを含むカーボン層を形成すること、
を特徴とする電極体の製造方法。A method for manufacturing an electrode body used for a cathode of an electrolytic capacitor.
Forming a carbon layer containing graphite and spherical carbon on a cathode foil made of a valve acting metal,
A method for manufacturing an electrode body.
を特徴とする請求項１２に記載の電極体の製造方法。The carbon layer is formed by applying the graphite and the slurry containing the spherical carbon to the cathode foil, drying them, and then pressing them together.
The method for manufacturing an electrode body according to claim 12.
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