KR102655553B1 - Electrode body, electrolytic capacitor having electrode body, and method for manufacturing the electrode body - Google Patents
Electrode body, electrolytic capacitor having electrode body, and method for manufacturing the electrode body Download PDFInfo
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- KR102655553B1 KR102655553B1 KR1020217005036A KR20217005036A KR102655553B1 KR 102655553 B1 KR102655553 B1 KR 102655553B1 KR 1020217005036 A KR1020217005036 A KR 1020217005036A KR 20217005036 A KR20217005036 A KR 20217005036A KR 102655553 B1 KR102655553 B1 KR 102655553B1
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- South Korea
- Prior art keywords
- carbon
- graphite
- electrode body
- layer
- cathode
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—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
-
- 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
Landscapes
- 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)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
전해 콘덴서의 초기 정전 용량뿐만 아니라, 고온 환경 부하 후에 있어서도 안정된 정전 용량을 발현시킬 수 있는 전극체, 이 전극체를 구비하는 전해 콘덴서, 및 이 전극체의 제조 방법을 제공한다. 전극체는, 전해 콘덴서의 음극에 사용되고, 밸브 작용 금속에 의해 이루어지는 음극박과, 이 음극박에 형성된 카본층을 구비한다. 카본층은, 흑연과 구상(球狀) 탄소를 포함한다.An electrode body capable of developing not only the initial capacitance of an electrolytic capacitor but also a stable capacitance even after a high-temperature environmental load, an electrolytic capacitor including this electrode body, and a method of manufacturing this electrode body are provided. The electrode body is used for the 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
본 발명은, 전극체, 전극체를 구비하는 전해 콘덴서, 및 전극체의 제조 방법에 관한 것이다.The present invention relates to an electrode body, an electrolytic capacitor having the electrode body, and a method of manufacturing the electrode body.
전해 콘덴서는, 탄탈럼 혹은 알루미늄 등과 같은 밸브 작용 금속을 양극박 및 음극박으로서 구비하고 있다. 양극박은, 밸브 작용 금속을 소결체 혹은 에칭박 등의 형상으로 함으로써 확면화(擴面化)되고, 확면화된 표면에 유전체 산화 피막층을 갖는다. 양극박과 음극박 사이에는 전해액이 개재(介在)한다. 전해액은, 양극박의 요철면에 밀접하여, 참음극으로서 기능한다. 이 전해 콘덴서는, 유전체 산화 피막층의 유전 분극 작용에 의해 양극측 용량을 얻고 있다.The electrolytic capacitor is equipped with a valve metal such as tantalum or aluminum as an anode foil and a cathode foil. The anode foil is enlarged by shaping the valve metal into a sintered body or etched foil, and has a dielectric oxide film layer on the enlarged surface. An electrolyte solution is interposed between the anode foil and the cathode foil. The electrolyte solution is in close contact with the uneven surface of the anode foil and functions as a true cathode. This electrolytic capacitor obtains the anode side capacitance through the dielectric polarization effect of the dielectric oxide film layer.
전해 콘덴서는 양극측과 음극측에 용량이 발현하는 직렬 콘덴서라고 간주할 수 있다. 따라서, 양극측 용량을 효율적으로 활용하려면 음극측 용량도 매우 중요하다. 음극박도 에칭 처리에 의해 표면적을 증대시키고 있지만, 음극박의 두께의 관점에서 음극박의 확면화에도 한계가 있다.An electrolytic capacitor can be considered a series capacitor in which capacitance is developed on the anode side and the cathode side. Therefore, in order to efficiently utilize the anode side capacity, the cathode side capacity is also very important. The surface area of the cathode foil is also increased by etching, but there is a limit to the expansion of the cathode foil from the viewpoint of the thickness of the cathode foil.
그래서, 질화티타늄 등의 금속 질화물의 피막을 음극박에 형성한 전해 콘덴서가 제안되어 있다(특허문헌 1 참조). 질소 가스 환경 하에서, 이온 플레이팅법의 일종인 진공 아크 증착법에 의해 티타늄을 증발시키고, 음극박의 표면에 질화티타늄을 퇴적시킨다. 금속 질화물은 불활성이며, 자연 산화 피막이 형성되기 어렵다. 또한 증착 피막은 미세한 요철이 형성되어 음극의 표면적이 확대된다.Therefore, an electrolytic capacitor in which a film of metal nitride 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 vacuum arc deposition, a type of ion plating method, and titanium nitride is deposited on the surface of the cathode foil. Metal nitrides are inert, and it is difficult for a natural oxide film to form. Additionally, fine irregularities are formed in the deposited film, thereby increasing the surface area of the cathode.
또한, 활성탄을 포함하는 다공질의 카본층을 음극박에 형성한 전해 콘덴서도 알려져 있다(특허문헌 2 참조). 이 전해 콘덴서의 음극측 용량은, 분극성 전극과 전해질과의 경계면에 형성되는 전기 이중층의 축전 작용에 의해 발현된다. 전해질의 양이온이 다공질 카본층과의 계면(界面)에 정렬하여, 다공질 카본층 내의 전자와 매우 짧은 거리를 두고 쌍을 이루고, 음극에 전위 장벽이 형성된다. 이 다공질 카본층이 형성된 음극박은, 다공질 카본을 분산시킨 수용성 바인더 용액을 혼련(混練)하여 페이스트상(狀)으로 하고, 당해 페이스트를 음극박의 표면에 도포하고, 고온 하에 노출하여 건조시킴으로써 제작된다.Additionally, 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 capacity of this electrolytic capacitor is expressed by the capacitance effect of the electric double layer formed at the interface between the polarizable electrode and the electrolyte. Cations in the electrolyte are aligned at the interface with the porous carbon layer and pair with electrons in the porous carbon layer at a very short distance, forming a potential barrier at the cathode. The cathode foil with this porous carbon layer formed is produced by kneading a water-soluble binder solution in which porous carbon is dispersed to form a paste, applying the paste to the surface of the cathode foil, and drying it by exposure to high temperature. .
금속 질화물의 증착 프로세스는 복잡하며, 전해 콘덴서의 고비용을 초래한다. 게다가, 최근의 전해 콘덴서는, 예를 들면 차재 용도 등과 같이, 극저온 환경 하에서 고온 환경 하까지 폭넓은 온도대역으로 사용되는 것도 상정된다. 그러나, 금속 질화물의 피막을 음극박에 형성한 전해 콘덴서는, 고온에 장시간 노출됨으로써 정전 용량이 크게 저하해 버린다. 그러면, 전해 콘덴서의 정전 용량은 당초 상정되어 있던 정전 용량과 크게 다른 것이 되어 버린다. 활성탄을 포함하는 다공질 카본층을 페이스트의 도포에 의해 음극박에 형성한 전해 콘덴서는, 금속 질화물의 피막을 음극박에 형성한 전해 콘덴서에 비해 고온 환경 하에서 정전 용량이 더 크게 저하해 버린다.The metal nitride deposition process is complex and results in high cost of electrolytic capacitors. Furthermore, it is assumed that recent electrolytic capacitors are used in a wide temperature range from extremely low temperature environments to high temperature environments, such as in vehicle applications, for example. However, electrolytic capacitors in which a metal nitride film is formed on a cathode foil have greatly reduced electrostatic capacity when exposed to high temperatures for a long period of time. Then, the electrolytic capacitance of the electrolytic capacitor becomes significantly different from the capacitance originally assumed. Electrolytic capacitors in which a porous carbon layer containing activated carbon is formed on a cathode foil by applying a paste have a greater decrease in capacitance in a high-temperature environment compared to electrolytic capacitors in which a film of metal nitride is formed on the cathode foil.
본 발명은, 상기 과제를 해결하기 위해 제안된 것이며, 그 목적은, 고온 환경 부하 후에 있어서도 안정된 정전 용량을 발현시킬 수 있는 전극체, 이 전극체를 구비하는 전해 콘덴서, 및 이 전극체의 제조 방법을 제공하는 것에 있다.The present invention has been proposed to solve the above problems, and its purpose is to provide an electrode body capable of developing stable electrostatic capacity even after a high-temperature environmental load, an electrolytic capacitor provided with this electrode body, and a manufacturing method for this electrode body. It is about providing.
본 발명자들은, 예의 연구의 결과, 흑연과 구상(球狀) 탄소를 포함하는 카본층을 음극박에 형성하면, 그 전극체를 사용한 전해 콘덴서는, 저주파 영역에서의 사용에 있어서, 초기 정전 용량과 고온 환경 부하 후의 정전 용량과의 차가 작아지는 것을 발견했다. 즉, 고온 환경 하에 장시간 노출되어도 정전 용량의 저하가 억제되는 것을 발견했다.As a result of extensive research, the present inventors have found that when a carbon layer containing graphite and spherical carbon is formed on a cathode foil, an electrolytic capacitor using the electrode body has an initial capacitance and It was found that the difference with electrostatic capacity after high-temperature environmental load became smaller. In other words, it was discovered that the decline in electrostatic capacity was suppressed even when exposed to a high temperature environment for a long time.
본 발명은, 이 지견(知見)에 의거하여 완성된 것이며, 상기 과제를 해결하기 위해, 전해 콘덴서의 음극에 사용되는 전극체로서, 밸브 작용 금속에 의해 이루어지는 음극박과, 상기 음극박에 형성된 카본층을 구비하고, 상기 카본층은, 흑연과 구상 탄소를 포함하는 것을 특징으로 한다.The present invention was completed based on this knowledge, and in order to solve the above problems, it is an electrode body used for the cathode of an electrolytic condenser, comprising a cathode foil made of a valve metal and carbon formed on the cathode foil. layer, and the carbon layer is characterized in that it contains graphite and spherical carbon.
또한, 종래, 전기 이중층 작용에는 주파수 특성상의 해결해야 할 문제가 있어, 전해 콘덴서에 있어서 고주파 영역에서의 사용을 목표로 할 경우, 카본층을 음극박에 형성하는 것은 생각되고 있지 않았다. 게다가, 저주파 영역에 있어서, 흑연이나 아세틸렌 블랙 등의 BET 비표면적이 작은 카본은 다른 탄소 재료에 대하여 용량의 점에서 뒤떨어지는 경우가 많다. 그러나, 본 발명자들의 예의 연구의 결과, 저주파 영역에서는 다른 카본 블랙에 대하여 용량의 점에서 뒤떨어지는 경우도 많은 흑연이나 BET 비표면적이 작은 구상 탄소를 조합하면, 고주파 영역에 있어서는 입장을 역전시켜 용량의 점에서 우위가 된다는 지견이 얻어졌다. 이 지견에 의거하여, 상기 구상 탄소는, 예를 들면 아세틸렌 블랙 등의 BET 비표면적이 200㎡／g 이하인 카본 블랙이도록 해도 된다.In addition, conventionally, the electric double layer action has problems with frequency characteristics that need to be solved, and it has not been considered to form a carbon layer on the cathode foil when aiming at use in a high frequency range in electrolytic capacitors. Furthermore, in the low-frequency region, carbon with a small BET specific surface area, such as graphite or acetylene black, is often inferior to other carbon materials in terms of capacity. However, as a result of intensive research by the present inventors, when graphite, which is often inferior to other carbon blacks in terms of capacity in the low frequency range, and spherical carbon with a small BET specific surface area are combined, the situation is reversed in the high frequency range, increasing the capacity. Knowledge was gained that it had an advantage in this respect. Based on this knowledge, the spherical carbon may be, for example, carbon black such as acetylene black with a BET specific surface area of 200 m 2 /g or less.
상기 흑연은, 입도(粒度) 분포에 있어서의 평균 입경이 6㎛ 이상 10㎛ 이하이도록 해도 된다.The graphite may have an average particle size of 6 μm or more and 10 μm or less in particle size distribution.
상기 흑연은, 입도 분포에 있어서의 평균 입경이 6㎛ 이하이도록 해도 된다.The graphite may have an average particle size of 6 μm or less in the particle size distribution.
상기 흑연과 상기 카본 블랙의 혼합비는, 90:10 내지 25:75이도록 해도 된다.The mixing ratio of the graphite and the carbon black may be 90:10 to 25:75.
상기 음극박은, 확면층이 형성되고, 상기 카본층은, 상기 확면층 상에 형성되어 있도록 해도 된다.The cathode foil may be formed with an expanded surface layer, and the carbon layer may be formed on the expanded surface layer.
상기 확면층과 상기 카본층은 압접(壓接)하고 있도록 해도 된다.The expanded surface layer and the carbon layer may be pressure-welded.
상기 확면층은, 요철면과 당해 요철면으로부터 상기 음극박의 심부(深部)를 향하여 형성되는 세공(細孔)으로부터 형성되고, 상기 구상 탄소는, 세공에 들어가고, 상기 흑연은, 상기 구상 탄소가 들어간 상기 세공을 덮고 있도록 해도 된다.The expanded surface layer is formed from an uneven surface and pores formed from the uneven surface toward the deep portion of the cathode foil, the spherical carbon enters the pores, and the graphite contains the spherical carbon. The pores may be covered.
상기 구상 탄소는, 상기 카본층의 압접에 의해 상기 세공에 들어가 있도록 해도 된다.The spherical carbon may be allowed to enter the pores by pressure welding the carbon layer.
상기 흑연은, 상기 확면층의 상기 요철면을 따르도록 변형해 있도록 해도 된다.The graphite may be deformed so as to follow the uneven surface of the expanded surface layer.
이 전극체를 음극에 구비하는 전해 콘덴서도 본 발명의 일 태양이다.An electrolytic capacitor having this electrode body at the cathode is also an aspect of the present invention.
또한, 상기 과제를 해결하기 위해, 본 발명의 전극체의 제조 방법은, 전해 콘덴서의 음극에 사용되는 전극체의 제조 방법으로서, 밸브 작용 금속에 의해 이루어지는 음극박에, 흑연과 구상 탄소를 포함하는 카본층을 형성하는 것을 특징으로 한다.In addition, in order to solve the above problems, the method of manufacturing an electrode body of the present invention is a method of manufacturing an electrode body used for a cathode of an electrolytic capacitor, wherein a cathode foil made of a valve-acting metal contains graphite and spherical carbon. It is characterized by forming a carbon layer.
상기 카본층은, 상기 흑연과 구상 탄소를 포함하는 슬러리를 음극박에 도포, 건조 후, 압접하여 형성되도록 해도 된다.The carbon layer may be formed by applying a slurry containing the graphite and spherical carbon to a cathode foil, drying it, and then pressure-welding it.
본 발명에 의하면, 음극체는, 고온 환경 부하 후에 있어서도 안정된 정전 용량을 발현시킬 수 있다.According to the present invention, the cathode body can develop stable electrostatic capacity even after a high-temperature environmental load.
도 1은 세퍼레이터에 첩착(貼着)한 점착 테이프의 사진.
도 2는 음극체의 단면을 나타내는 SEM 사진.
도 3은 실시예 3과 참고예 1의 음극체의 단면의 SEM 사진.
도 4는 실시예 5와 참고예 2의 음극체의 단면의 SEM 사진.1 is a photograph of an adhesive tape attached to a separator.
Figure 2 is an SEM photograph showing a cross section of the cathode body.
Figure 3 is an SEM photograph of a cross section of the cathode body of Example 3 and Reference Example 1.
Figure 4 is an SEM photograph of a cross section of the cathode body of Example 5 and Reference Example 2.
본 발명의 실시형태에 따른 전극체 및 이 전극체를 음극에 사용한 전해 콘덴서에 대해서 설명한다. 본 실시형태에서는, 전해액을 갖는 전해 콘덴서를 예시하여 설명하지만, 이것에 한정되는 것이 아니다. 전해액, 도전성 폴리머 등의 고체 전해질층, 겔 전해질, 또는 고체 전해질층과 겔 전해질에 대하여 전해액을 병용한 전해질을 갖는 전해 콘덴서 중 어느 것에도 적용할 수 있다.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 this embodiment, an electrolytic capacitor having an electrolyte solution is exemplified and explained, but it is not limited to this. It can be applied to any of electrolytic capacitors having an electrolyte solution, a solid electrolyte layer such as a conductive polymer, a gel electrolyte, or an electrolyte using a solid electrolyte layer and an electrolyte solution in combination with the gel electrolyte.
(전해 콘덴서)(Electrolytic Capacitors)
전해 콘덴서는, 정전 용량에 따른 전하의 축전 및 방전을 행하는 수동 소자이다. 이 전해 콘덴서는, 권회형 또는 적층형의 콘덴서 소자를 갖는다. 콘덴서 소자는, 전극체를 세퍼레이터를 개재하여 대향시키고, 전해액이 함침되어 이루어진다. 이 전해 콘덴서는, 음극측에 사용된 전극체와 전해액과의 계면에 생기는 전기 이중층 작용에 의해 음극측 용량이 생기고, 또한 유전 분극 작용에 의한 양극측 용량이 양극측에 사용된 전극체에 생긴다. 이하, 음극측에 사용된 전극체를 음극체라고 하고, 양극측에 사용된 전극체를 양극박이라고 한다.An electrolytic capacitor is a passive element that stores and discharges charge according to electrostatic capacity. This electrolytic capacitor has a wound type or laminated type condenser element. The capacitor element is formed by opposing electrode bodies with a separator interposed between them and impregnating them with an electrolyte solution. In this electrolytic capacitor, the cathode side capacitance is generated by the electric double layer action that occurs at the interface between the electrode body used on the cathode side and the electrolyte solution, and the anode side capacitance is created by the dielectric polarization action in the electrode body used on the anode side. Hereinafter, the electrode body used on the cathode side is called a cathode body, and the electrode body used on the anode side is called an anode foil.
양극박의 표면에는, 유전 분극 작용이 생기는 유전체 산화 피막층이 형성되어 있다. 음극체의 표면에는, 전해액과의 계면에 전기 이중층 작용을 생기게 하는 카본층이 형성되어 있다. 전해액은, 양극박과 음극체의 사이에 개재하고, 양극박의 유전체 산화 피막층과 음극체의 카본층에 밀접한다. 세퍼레이터는, 양극박과 음극체의 쇼트를 방지하기 위해, 양극박과 음극체와의 사이에 개재하고, 또한 전해액을 유지한다.On the surface of the anode foil, a dielectric oxide film layer that produces a dielectric polarization effect is formed. On the surface of the cathode body, a carbon layer is formed that creates an electric double layer effect at the interface with the electrolyte solution. The electrolyte solution is interposed between the anode foil and the cathode body and is close to 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 to prevent short circuit between the anode foil and the cathode body, and also maintains the electrolyte solution.
(음극체)(cathode body)
이 음극체는, 음극박과 카본층의 2층 구조를 갖는다. 음극박은 집전체가 되고, 그 표면에는 확면층이 형성되어 있는 것이 바람직하다. 카본층은 주재(主材)로서 탄소재를 포함한다. 이 카본층이 확면층과 밀착함으로써, 음극박과 카본층의 2층 구조가 된다.This cathode body has a two-layer structure of a cathode foil and a carbon layer. The cathode foil serves as a current collector, and preferably has an expanded surface layer formed on its surface. The carbon layer contains carbon material as the main material. As this carbon layer comes into close contact with the expanded surface layer, a two-layer structure of the cathode foil and the carbon layer is formed.
음극박은, 밸브 작용 금속을 재료로 하는 장척(長尺)의 박체(箔體)이다. 밸브 작용 금속은, 알루미늄, 탄탈럼, 니오브, 티타늄, 하프늄, 지르코늄, 아연, 텅스텐, 비스무트 및 안티몬 등이다. 순도는, 99％ 정도 이상이 바람직하지만, 규소, 철, 구리, 마그네슘, 아연 등의 불순물이 포함되어 있어도 된다. 음극박으로서는, 예를 들면 JIS 규격 H0001로 규정되는 조질(調質) 기호가 H인 알루미늄재, 소위 H재나, JIS 규격 H0001로 규정되는 조질 기호가 O인 알루미늄재, 소위 O재를 사용해도 된다. H재로 이루어지는 강성(剛性)이 높은 금속박을 사용하면, 후술하는 프레스 가공에 의한 음극박의 변형을 억제할 수 있다.Cathode foil is a long thin body made of valve metal. Metals that act as valves include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth and antimony. The purity is preferably about 99% or more, but impurities such as silicon, iron, copper, magnesium, and zinc may be included. As the cathode foil, for example, an aluminum material with a tempering symbol of H specified in JIS standard H0001, or so-called H material, or an aluminum material with a tempering symbol of O specified in JIS standard H0001, or a so-called O material, may be used. . If a metal foil made of H material and having high rigidity is used, deformation of the cathode foil due to press processing, which will be described later, can be suppressed.
이 음극박은, 밸브 작용 금속이 연신(延伸)된 금속박에 확면 처리가 실시되어 있다. 확면층은, 전해 에칭이나 케미칼 에칭, 샌드 블라스트 등에 의해 형성되고, 또는 금속박에 금속 입자 등을 증착 혹은 소결함으로서 형성된다. 전해 에칭으로서는, 직류 에칭 또는 교류 에칭 등의 방법을 들 수 있다. 또한, 케미칼 에칭에서는, 금속박을 산 용액이나 알칼리 용액에 침지(浸漬)시킨다. 형성된 확면층은, 박 표면으로부터 박 심부(芯部)를 향하여 파고든 터널상의 에칭 피트, 또는 해면상(海綿狀)의 에칭 피트를 갖는 층 영역이다. 또, 에칭 피트는, 음극박을 관통하도록 형성되어 있어도 된다.This cathode foil is a metal foil in which valve metal is stretched and subjected to surface expansion treatment. The expanded surface layer is formed by electrolytic etching, chemical etching, sandblasting, etc., or by depositing or sintering metal particles on the metal foil. Examples of electrolytic etching include methods such as direct current etching or alternating current etching. Additionally, in chemical etching, the metal foil is immersed in an acid solution or an alkaline solution. The formed expanded surface layer is a layer area having tunnel-shaped etching pits or sea-surface etching pits dug from the foil surface toward the core of the foil. Additionally, the etching pit may be formed to penetrate the cathode foil.
카본층에 있어서, 탄소재는, 흑연과 구상 탄소의 혼합이다. 흑연으로서는, 천연 흑연, 인조 흑연, 또는 흑연화 케첸 블랙 등을 들 수 있고, 인편상(鱗片狀), 인상(鱗狀)(괴상(塊狀)), 토상(土狀), 구상 또는 박편상의 형태를 갖는다. 흑연은, 에칭 피트를 압궤(壓潰)하여 카본층과 음극박과의 밀착성을 높이기 위해서도, 인편상 또는 박편상이며, 그 단경과 장경과의 아스펙트비가 1:5∼1:100의 범위의 것을 사용하는 것이 바람직하다. 구상 탄소로서는 예를 들면 카본 블랙을 들 수 있다. 카본 블랙으로서는, 케첸 블랙, 아세틸렌 블랙, 채널 블랙 및 서멀 블랙 등을 들 수 있고, 바람직하게는 일차 입자경이 평균 100㎚ 이하이며, 또한 바람직하게는 BET 이론에 의해 계산되는 비표면적(이하, BET 비표면적이라고 함)이 200㎡／g 이하이다. BET 비표면적이 200㎡／g 이하인 카본 블랙은 예를 들면 아세틸렌 블랙이다.In the carbon layer, the carbon material is a mixture of graphite and spherical carbon. Examples of graphite include natural graphite, artificial graphite, and graphitized Ketjen black, and may be in the form of scales, lumps, spheroids, or flakes. It has a shape. Graphite is in the form of scales or flakes in order to crush etching pits and improve adhesion between the carbon layer and the cathode foil, and its aspect ratio between the minor axis and major axis is in the range of 1:5 to 1:100. It is desirable to use Examples of spherical carbon include carbon black. Examples of carbon black include Ketjen black, acetylene black, channel black, and thermal black. Preferably, the primary particle size is 100 nm or less on average, and the specific surface area calculated by BET theory (hereinafter, BET ratio) is preferred. (referred to as surface area) is less than 200㎡/g. Carbon black with a BET specific surface area of 200 m2/g or less is, for example, acetylene black.
이 흑연과 구상 탄소의 혼합으로 구성된 카본층은, 흑연과 구상 탄소를 활물질로 하여, 음극측 용량을 발현시키는 전기 이중층 활물질층이 된다. 흑연과 구상 탄소의 조합은, 저주파 영역에서 전해 콘덴서를 사용할 경우, 전해 콘덴서의 초기 정전 용량과 고온 환경 부하 후에 있어서의 정전 용량과의 차를 작게 한다. 즉, 흑연과 구상 탄소의 조합에 의해, 전해 콘덴서가 고온 환경 하에 장시간 노출되어도 정전 용량의 저하는 억제되어, 전해 콘덴서의 열안정성이 향상한다. 또, 초기 정전 용량은, 전해 콘덴서를 조립하여 에이징 처리한 후의 예를 들면 20℃ 등의 상온 부근에서의 정전 용량이며, 고온 환경 부하 후에 있어서의 정전 용량은, 예를 들면 125℃ 등의 고온 환경에 260시간 등의 장시간 노출한 후의 정전 용량이다.This carbon layer composed of a mixture of graphite and spherical carbon uses graphite and spherical carbon as active materials, and becomes an electric double layer active material layer that develops the cathode side capacity. The combination of graphite and spherical carbon reduces the difference between the initial capacitance of the electrolytic capacitor and the electrolytic capacitance after high-temperature environmental load when using the electrolytic capacitor in the low-frequency region. In other words, 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 the thermal stability of the electrolytic capacitor improves. In addition, the initial capacitance is the capacitance at around room temperature, such as 20°C, after the electrolytic capacitor is assembled and subjected to aging treatment, and the capacitance after load in a high-temperature environment is, for example, the capacitance in a high-temperature environment such as 125°C. This is the electrostatic capacity after long-term exposure, such as 260 hours.
특히, 흑연과 BET 비표면적이 200㎡／g 이하인 구상 탄소와의 혼합에 의해 이루어지는 카본층은, 고주파 영역에서 사용할 경우, 전해 콘덴서의 초기 정전 용량과 고온 환경 부하 후의 정전 용량과의 차를 현저하게 줄인다. 일반적으로는, BET 비표면적이 작으면 전해 콘덴서의 정전 용량은 작아진다. 그러나, 전해 콘덴서를 고주파 영역에서 사용할 경우, 흑연과 BET 비표면적이 200㎡／g 이하인 구상 탄소와의 혼합에 의해 이루어지는 카본층은, 활성탄 등의 BET 비표면적이 큰 탄소재와의 입장을 역전시켜, 높은 정전 용량을 발현시킨다. 즉, 흑연과 BET 비표면적이 200㎡／g 이하인 구상 탄소와의 혼합에 의해 이루어지는 카본층은, 고주파 영역에서의 사용에 있어서, 전해 콘덴서의 열안정성을 높임과 함께, 높은 정전 용량을 발현시키기 때문에, 바람직한 것이다.In particular, the carbon layer formed by mixing graphite with spherical carbon with a BET specific surface area of 200 m2/g or less significantly reduces the difference between the initial capacitance of the electrolytic capacitor and the capacitance after high-temperature environmental load when used in the high frequency range. Reduce. Generally, the smaller the BET specific surface area, the smaller the electrolytic capacitance of the electrolytic capacitor. However, when an electrolytic capacitor is used in a high frequency range, the carbon layer formed by mixing graphite with spherical carbon with a BET specific surface area of 200 m2/g or less reverses the position of carbon materials with a large BET specific surface area such as activated carbon. , develops high electrostatic capacity. That is, the carbon layer formed by mixing graphite with spherical carbon with a BET specific surface area of 200 m2/g or less not only increases the thermal stability of the electrolytic capacitor when used in the high frequency range, but also develops high electrostatic capacity. , it is desirable.
또한, 흑연과 BET 비표면적이 200㎡／g 이하인 구상 탄소와의 혼합에 의해 이루어지는 카본층은, 저주파 영역에서의 사용에 있어서도, 전해 콘덴서의 초기 정전 용량과 고온 환경 부하 후의 정전 용량과의 차를 현저하게 줄인다. 따라서, 흑연과 BET 비표면적이 200㎡／g 이하인 구상 탄소와의 혼합에 의해 이루어지는 카본층은, 저주파 영역에서의 사용에 있어서도, 고주파 영역에서의 사용에 있어서도, 폭넓은 주파수 영역에서 열안정성이 높고, 전해 콘덴서를 범용적인 것으로 한다.In addition, the carbon layer formed by mixing graphite with spherical carbon with a BET specific surface area of 200 m2/g or less reduces the difference between the initial capacitance of the electrolytic capacitor and the capacitance after high-temperature environmental load even when used in a low-frequency range. Reduce significantly. Therefore, the carbon layer formed by mixing graphite with spherical carbon with a BET specific surface area of 200 m2/g or less has high thermal stability in a wide frequency range, both when used in the low-frequency range and when used in the high-frequency range. , the electrolytic capacitor is made general-purpose.
흑연은, 고온 환경 부하 후에 있어서의 정전 용량의 안정성의 관점에 있어서, 장경을 기준으로 한 입도 분포에 있어서의 평균 입경이 6㎛ 이상 10㎛ 이하인 것이 바람직하다. 여기에서 말하는 평균 입경은 메디안경, 소위 D50이다. 평균 입경이 6㎛ 이상 10㎛ 이하이면, 고온 환경 부하 후여도 초기 정전 용량과 동등한 정전 용량이 발현된다. 환언하면, 초기 정전 용량과 고온 환경 부하 후의 정전 용량에 차가 없다.From the viewpoint of stability of electrostatic capacity after 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 size, so-called D50. If the average particle diameter is 6 μm or more and 10 μm or less, a capacitance equivalent to the initial capacitance is developed even after a high-temperature environmental load. In other words, there is no difference between the initial capacitance and the capacitance after high-temperature environmental load.
또한 흑연은, 정전 용량의 크기라는 점에 있어서는 입도 분포에 있어서의 평균 입경(D50)이 6㎛ 이하인 것이 바람직하다. 평균 입경이 6㎛ 이하이면, 흑연의 입경을 작게 하면 할수록, 전해 콘덴서의 초기 정전 용량과 고온 환경 부하 후의 정전 용량과의 차를 작게 유지한 채, 전해 콘덴서의 정전 용량을 증가시킬 수 있다.In terms of electrostatic capacity, graphite preferably has an average particle size (D50) of 6 μm or less in the particle size distribution. If the average particle size is 6 μm or less, the smaller the graphite particle size is, the more the electrolytic capacitance of the electrolytic capacitor can be increased while keeping the difference between the initial capacitance of the electrolytic capacitor and the capacitance after high-temperature environmental load small.
우선 평균 입경이 6㎛ 정도이면, 평균 입경이 10㎛일 경우에 비해 정전 용량 자체가 대폭 개선하여, 전해 콘덴서의 열안정성과 양호한 정전 용량을 양립한다. 또한, 평균 입경이 6㎛ 정도이면, 고온 환경 부하 후에 대해서는, 질화티타늄의 피막을 음극박에 형성한 전해 콘덴서와 손색이 없는 크기의 정전 용량을 발현한다.First, when the average particle diameter is about 6㎛, the electrostatic capacity itself is greatly improved compared to the case where the average particle diameter is 10㎛, thereby achieving both thermal stability of the electrolytic capacitor and good electrostatic capacity. In addition, when the average particle diameter is about 6 μm, after a high-temperature environmental load, a capacitance comparable to that of an electrolytic capacitor in which a titanium nitride film is formed on a cathode foil is developed.
다음으로, 평균 입경이 4㎛ 정도가 되면, 고온 환경 부하 후에 있어서 저주파 영역 및 고주파 영역의 양쪽의 정전 용량이, 질화티타늄의 피막을 음극박에 형성한 전해 콘덴서를 능가한다. 즉, 평균 입경이 4㎛ 정도가 되면, 고온 환경 하에서의 사용이 상정되는 전해 콘덴서로서는, 질화티타늄의 피막을 음극박에 형성한 전해 콘덴서보다도 범용적이 된다.Next, when the average particle diameter is about 4 μm, the capacitance in both the low-frequency region and the high-frequency region after high-temperature environmental load exceeds that of an electrolytic capacitor in which a titanium nitride film is formed on a cathode foil. That is, when the average particle diameter is about 4 μm, the electrolytic capacitor expected to be used in a high temperature environment becomes more versatile than the electrolytic capacitor in which a titanium nitride film is formed on a cathode foil.
또한, 평균 입경이 1㎛까지 작아지면, 초기 정전 용량이어도, 고온 환경 부하 후의 정전 용량이어도, 저주파 영역 및 고주파 영역의 양쪽의 정전 용량이, 질화티타늄의 피막을 음극박에 형성한 전해 콘덴서는 물론, 전기 이중층의 활물질로서 일반적인 활성탄을 활물질로서 음극박에 사용한 전해 콘덴서도 능가하여, 더 범용적이 된다.In addition, when the average particle size decreases to 1㎛, even if it is the initial capacitance or the capacitance after high-temperature environmental load, the capacitance in both the low-frequency region and the high-frequency region is as high as that of an electrolytic capacitor in which a titanium nitride film is formed on a cathode foil. , it surpasses electrolytic capacitors that use common activated carbon as an active material in a cathode foil as an active material for an electric double layer, making it more versatile.
또한, 평균 입경이 6㎛ 이하이면, 흑연을 카본층 내에 유치(留置)하기 쉬워진다는 지견이 얻어졌다. 그 때문에, 평균 입경이 6㎛ 이하이면, 카본층 내에 흑연을 유치하기 위한 바인더를 소량으로 할 수 있고, 음극체의 저저항화 및 전해 콘덴서의 등가 직렬 저항(ESR)을 저감할 수 있는 점에서도 바람직하다.In addition, the knowledge was obtained that when the average particle size is 6 μm or less, it becomes easy to retain graphite in the carbon layer. Therefore, if the average particle diameter is 6 μm or less, the binder for attracting graphite in the carbon layer can be used in a small amount, and the resistance of the cathode body can be reduced and the equivalent series resistance (ESR) of the electrolytic capacitor can be reduced. desirable.
또, 흑연(G)과 구상 탄소(C)의 질량비는, G:C＝90:10∼25:75의 범위가 바람직하다. 흑연의 질량비가 90wt％ 초과되면, 전해 콘덴서의 초기 정전 용량과 고온 환경 부하 후에 있어서의 전해 콘덴서의 정전 용량과의 차가 커져 버린다. 또한, 구상 탄소(C)만으로 하면, 저주파 영역에서의 사용이어도, 고주파 영역에서의 사용이어도, 정전 용량이 작아져 버린다.Moreover, the mass ratio of graphite (G) and 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 high-temperature environmental load increases. Additionally, if spherical carbon (C) is used alone, the electrostatic capacity becomes small whether it is used in a low frequency range or a high frequency range.
도 2는, 음극체의 단면(斷面)을 나타내는 SEM 사진이다. 도 2에 나타내는 바와 같이, 확면층의 표면은, 웨이브가 큰 요철면(21)과, 이 요철면(21)으로부터 음극박의 심부를 향하여 형성되는 세공(22)에 의해 형성되어 있다. 흑연(11)은, 요철면(21)을 따라 변형하면서, 요철면(21) 상에 겹쳐쌓여 있는 것이 바람직하다. 또한, 구상 탄소(12)는, 세공(22)에 들어가 있는 것이 바람직하다. 환언하면, 흑연(11)은, 세공(22)에 구상 탄소(12)가 들어간 상태에서, 세공(22)을 덮고 있다. 또한, 구상 탄소(12)는, 요철면(21) 상에 겹쳐쌓인 흑연(11)의 사이를 채우도록, 흑연(11)간에 충전되어 있는 것이 바람직하다.Figure 2 is an SEM photograph showing a cross section of the cathode body. As shown in FIG. 2, the surface of the expanded layer is formed by an uneven surface 21 with large waves and pores 22 formed from this uneven surface 21 toward the core of the cathode foil. The graphite 11 is preferably stacked on the uneven surface 21 while being deformed along the uneven surface 21 . Additionally, it is preferable that the spherical carbon 12 is contained in the pores 22 . In other words, the graphite 11 covers the pores 22 with the spherical carbon 12 entering the pores 22 . In addition, the spherical carbon 12 is preferably filled between the graphites 11 so as to fill the space between the graphites 11 stacked on the uneven surface 21.
이러한 카본층의 태양은, 확면층에 카본층이 파고 들어가 밀착성을 높이고, 카본층과 확면층과의 사이의 계면 저항을 낮춘다. 즉, 이러한 카본층의 태양은, 확면층의 요철면(21)에 있어서, 확면층과 카본층과의 밀착성을 높인다. 또한, 이러한 카본층의 태양은, 흑연(11)이 압압(押壓) 덮개가 되어, 구상 탄소(22)를 세공에 들어가게 하여 눌러 막아, 확면층의 세공(22)에 있어서, 확면층의 카본층과의 밀착성을 높인다.This aspect of the carbon layer causes the carbon layer to penetrate into the expanded surface layer, increases adhesion, and lowers the interfacial resistance between the carbon layer and the expanded surface layer. That is, this aspect of the carbon layer increases the adhesion between the expanded surface layer and the carbon layer on the uneven surface 21 of the expanded surface layer. In addition, in this aspect of the carbon layer, the graphite 11 serves as a pressure cover, and the spherical carbon 22 is pressed into the pores to block them, and in the pores 22 of the expanded surface layer, the carbon of the expanded surface layer is blocked. Increases adhesion to the layer.
이러한 음극체는, 카본층의 재료가 포함되는 슬러리를 제작하고, 또한 음극박에 확면층을 형성해 두고, 확면층에 슬러리를 도포하여 건조 및 프레스를 하면 된다. 확면층에 관해서는, 전형적으로는, 질산, 황산, 염산 등의 산성 수용액 중에서 직류 또는 교류를 인가(印加)하는 직류 에칭 또는 교류 에칭에 의해 형성된다.To make such a cathode body, a slurry containing a carbon layer material is produced, an expanded layer is formed on the cathode foil, the slurry is applied to the expanded surface layer, and then dried and pressed. As for the expanded surface layer, it is typically formed by direct current etching or alternating current etching by applying direct current or alternating current in an acidic aqueous solution such as nitric acid, sulfuric acid, or hydrochloric acid.
카본층에 관해서는, 흑연과 구상 탄소의 분말을 용매 중에서 분산시키고, 바인더를 더하여 슬러리를 제작한다. 이 슬러리 제작 전에 흑연의 평균 입경을 비즈 밀이나 볼 밀 등의 분쇄 수단으로 분쇄함으로써 조정해 두어도 된다. 용매는, 메탄올, 에탄올이나 2-프로판올 등의 알코올, 탄화수소계 용매, 방향족계 용매, N-메틸-2-피롤리돈(NMP)이나 N,N-디메틸포름아미드(DMF) 등의 아미드계 용매, 물 및 이들 혼합물 등이다. 분산 방법으로서는, 믹서, 제트 믹싱(분류(噴流) 충합), 또는, 초원심 처리, 그 외 초음파 처리 등을 사용한다. 분산 공정에서는, 혼합 용액 중의 흑연과 구상 탄소와 바인더가 세분화 및 균일화하고, 용액 중에 분산된다. 바인더로서는, 예를 들면 스티렌부타디엔 고무, 폴리불화비닐리덴, 또는 폴리테트라플루오로에틸렌을 들 수 있다.Regarding the carbon layer, powders of graphite and spherical carbon are dispersed in a solvent and a binder is added to produce a slurry. Before producing this slurry, the average particle size of the graphite may be adjusted by grinding it with a grinding means such as a bead mill or ball mill. Solvents include alcohols such as methanol, ethanol and 2-propanol, hydrocarbon solvents, aromatic solvents, and amide solvents such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF). , water and mixtures thereof, etc. As a dispersion method, a mixer, jet mixing (jet mixing), ultracentrifugation, ultrasonic treatment, etc. are used. In the dispersion process, the graphite, spherical carbon, and binder in the mixed solution are subdivided and homogenized, and dispersed in the solution. Examples of the binder include styrene-butadiene rubber, polyvinylidene fluoride, or polytetrafluoroethylene.
다음으로, 슬러리를 확면층에 도포하고, 건조시킨 후, 소정 압력으로 프레스함으로써, 카본층의 흑연 및 구상 탄소를 빈틈없이 깔아 정렬시킨다. 또한, 프레스함으로써, 카본층의 흑연이 확면층의 요철면을 따르도록 변형한다. 또한, 프레스함으로써, 확면층의 요철면을 따라 변형한 흑연에 압접의 응력이 가해져, 흑연과 확면층과의 사이의 구상 탄소가 세공 내에 압입(押入)된다. 이에 따라, 카본층과 확면층의 밀착성을 담보(擔保)시킨다.Next, the slurry is applied to the expanded surface layer, dried, and pressed at a predetermined pressure to spread the graphite and spherical carbon of the carbon layer tightly and align them. Additionally, by pressing, the graphite in the carbon layer is deformed to follow the uneven surface of the expanded surface layer. In addition, by pressing, the stress of pressure welding is applied to the graphite deformed along the uneven surface of the expanded surface layer, and the spherical carbon between the graphite and the expanded surface layer is pressed into the pores. Accordingly, the adhesion between the carbon layer and the expanded surface layer is ensured.
또, 흑연 및 구상 탄소에, 부활(賦活) 처리나 개구 처리 등의 다공질화 처리를 실시할 경우, 가스 부활법, 약제 부활법 등의 종래 공지의 부활 처리를 이용할 수 있지만, 구상 탄소의 BET 비표면적은 200㎡／g 이하에 그치도록 하면 된다. 가스 부활법에 사용하는 가스로서는, 수증기, 공기, 일산화탄소, 이산화탄소, 염화수소, 산소 또는 이들을 혼합한 것으로 이루어지는 가스를 들 수 있다. 또한, 약제 부활법에 사용하는 약제로서는, 수산화나트륨, 수산화칼륨 등의 알칼리 금속의 수산화물, 수산화칼슘 등의 알칼리 토류 금속의 수산화물, 붕산, 인산, 황산, 염산 등의 무기산류, 또는 염화아연 등의 무기염류 등을 들 수 있다. 이 부활 처리 시에는 필요에 따라 가열 처리가 실시된다.In addition, when performing porous nitriding treatment such as activation treatment or opening treatment on graphite and spherical carbon, conventionally known activation treatment such as gas activation method or chemical activation method can be used, but the BET ratio of spherical carbon The surface area should be limited to 200㎡/g or less. Gases used in the gas activation method include water vapor, air, carbon monoxide, carbon dioxide, hydrogen chloride, oxygen, or a mixture of these. In addition, the drugs used in the drug revitalization method include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, inorganic acids such as boric acid, phosphoric acid, sulfuric acid, and hydrochloric acid, or inorganic acids such as zinc chloride. Salts, etc. can be mentioned. During this resurrection treatment, heat treatment is performed as necessary.
(양극박)(anodized foil)
다음으로, 양극박은, 밸브 작용 금속을 재료로 하는 장척의 박체이다. 순도는, 양극박에 관하여 99.9％ 정도 이상이 바람직하다. 이 양극박은, 연신된 박에 에칭 처리를 실시하여 이루어지거나, 또는 밸브 작용 금속의 분체(粉體)를 소결하여 이루어지고, 또는 금속 입자 등의 피막을 박에 증착시켜 피막을 실시하여 이루어진다. 양극박은, 에칭층 또는 다공질 구조층을 표면에 갖는다.Next, the anode foil is a long thin body made of valve metal. The purity of the anode foil is preferably about 99.9% or more. This anode foil is made by etching the stretched foil, sintering the powder of the valve metal, or depositing a film of metal particles on the foil. The anode foil has an etching layer or a porous structure layer on its surface.
양극박에 형성되는 유전체 산화 피막층은, 전형적으로는, 양극박의 표층에 형성되는 산화 피막이며, 양극박이 알루미늄제이면, 다공질 구조 영역을 산화시킨 산화알루미늄층이다. 이 유전체 산화 피막층은, 붕산암모늄, 인산암모늄, 아디프산암모늄 등의 산 혹은 이들 산의 수용액 등의 할로겐 이온 부재의 용액 중에서 전압 인가하는 화성(化成) 처리에 의해 형성된다. 또, 음극박에는, 자연 산화 피막층이 형성될 수 있고, 의도적으로 유전체 산화 피막층을 마련해도 된다.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, it is an aluminum oxide layer in which the porous structural region is oxidized. This dielectric oxide film layer is formed by chemical conversion by applying a voltage in a halogen ion-free solution such as an acid such as ammonium borate, ammonium phosphate, or ammonium adipate, or an aqueous solution of these acids. Additionally, a natural oxide film layer may be formed on the cathode foil, or a dielectric oxide film layer may be intentionally provided.
(세퍼레이터)(separator)
세퍼레이터는, 크래프트, 마닐라삼, 에스파르토, 헴프(hemp), 레이온 등의 셀룰로오스 및 이들 혼합지, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 그들 유도체 등의 폴리에스테르계 수지, 폴리테트라플루오로에틸렌계 수지, 폴리불화비닐리덴계 수지, 비닐론계 수지, 지방족 폴리아미드, 반방향족 폴리아미드, 전방향족 폴리아미드 등의 폴리아미드계 수지, 폴리이미드계 수지, 폴리에틸렌 수지, 폴리프로필렌 수지, 트리메틸펜텐 수지, 폴리페닐렌설파이드 수지, 아크릴 수지 등을 들 수 있고, 이들 수지를 단독으로 또는 혼합하여 사용할 수 있고, 또한 셀룰로오스와 혼합하여 사용할 수 있다.The separator is made of cellulose such as kraft, Manila hemp, esparto, hemp, and rayon, and mixed papers thereof, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and their derivatives, and polyester resin. Polyamide-based resins such as tetrafluoroethylene-based resin, polyvinylidene fluoride-based resin, vinylon-based resin, aliphatic polyamide, semi-aromatic polyamide, wholly aromatic polyamide, polyimide-based resin, polyethylene resin, polypropylene resin, Trimethylpentene resin, polyphenylene sulfide resin, acrylic resin, etc. can be mentioned, and these resins can be used individually or in combination, and can also be used by mixing with cellulose.
(전해액)(electrolyte)
전해액은, 용매에 대하여 용질을 용해하고, 또한 필요에 따라 첨가제가 첨가된 혼합액이다. 용매는 프로톤성의 극성 용매 또는 비프로톤성의 극성 용매 중 어느 것이어도 된다. 프로톤성의 극성 용매로서, 1가 알코올류, 및 다가 알코올류, 옥시알코올 화합물류, 물 등을 대표적으로 들 수 있다. 비프로톤성의 극성 용매로서는, 설폰계, 아미드계, 락톤류, 환상(環狀) 아미드계, 니트릴계, 옥사이드계 등을 대표적으로 들 수 있다.The electrolyte solution is a mixed solution in which a solute is dissolved in a solvent and additives are added as necessary. The solvent may be either a protic polar solvent or an aprotic polar solvent. Representative examples of protic polar solvents include monohydric alcohols, polyhydric alcohols, oxyalcohol compounds, and water. Representative aprotic polar solvents include sulfone-based, amide-based, lactone-based, cyclic amide-based, nitrile-based, and oxide-based solvents.
1가 알코올류로서는, 에탄올, 프로판올, 부탄올, 펜탄올, 헥산올, 시클로부탄올, 시클로펜탄올, 시클로헥산올, 벤질알코올 등을 들 수 있다. 다가 알코올류 및 옥시알코올 화합물류로서는, 에틸렌글리콜, 프로필렌글리콜, 글리세린, 메틸셀로솔브, 에틸셀로솔브, 메톡시프로필렌글리콜 디메톡시프로판올 등을 들 수 있다. 설폰계로서는, 디메틸설폰, 에틸메틸설폰, 디에틸설폰, 설포란, 3-메틸설포란, 2,4-디메틸설포란 등을 들 수 있다. 아미드계로서는, N-메틸포름아미드, N,N-디메틸포름아미드, N-에틸포름아미드, N,N-디에틸포름아미드, N-메틸아세트아미드, N,N-디메틸아세트아미드, N-에틸아세트아미드, N,N-디에틸아세트아미드, 헥사메틸포스포르아미드 등을 들 수 있다. 락톤류, 환상 아미드계로서는, γ-부티로락톤, γ-발레로락톤, δ-발레로락톤, N-메틸-2-피롤리돈, 에틸렌카보네이트, 프로필렌카보네이트, 부틸렌카보네이트, 이소부틸렌카보네이트 등을 들 수 있다. 니트릴계로서는, 아세토니트릴, 3-메톡시프로피오니트릴, 글루타로니트릴 등을 들 수 있다. 옥사이드계로서는 디메틸설폭시드 등을 들 수 있다. 용매로서, 이들이 단독으로 사용되어도 되고, 또한 2종류 이상을 조합해도 된다.Examples of monohydric alcohols include ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, and benzyl alcohol. Examples of polyhydric alcohols and oxyalcohol compounds include ethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol dimethoxypropanol, etc. Examples of sulfone systems include dimethylsulfone, ethylmethylsulfone, diethylsulfone, sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane. As an amide type, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethyl. Acetamide, N,N-diethylacetamide, hexamethylphosphoramide, etc. can be mentioned. Lactones and cyclic amides include γ-butyrolactone, γ-valerolactone, δ-valerolactone, N-methyl-2-pyrrolidone, ethylene carbonate, propylene carbonate, butylene carbonate, and isobutylene carbonate. etc. can be mentioned. Examples of nitrile series include acetonitrile, 3-methoxypropionitrile, and glutaronitrile. Examples of oxide-based examples include dimethyl sulfoxide. As a solvent, these may be used individually, or two or more types may be combined.
전해액에 포함되는 용질은, 음이온 및 양이온의 성분이 포함되고, 전형적으로는, 유기산 혹은 그 염, 무기산 혹은 그 염, 또는 유기산과 무기산과의 복합 화합물 혹은 그 이온 해리성이 있는 염이며, 단독 또는 2종 이상을 조합하여 사용된다. 음이온이 되는 산 및 양이온이 되는 염기를 용질 성분으로서 별개로 전해액에 첨가해도 된다.The solute contained in the electrolyte solution includes anionic and cationic components and is typically an organic acid or a salt thereof, an inorganic acid or a salt thereof, a complex compound of an organic acid and an inorganic acid, or a salt capable of ion dissociation, either alone or It is used in combination of two or more types. The acid that becomes an anion and the base that becomes a cation may be separately added to the electrolyte solution as solute components.
전해액 중에서 음이온 성분이 되는 유기산으로서는, 옥살산, 숙신산, 클루타르산, 피멜린산, 수베르산, 세바스산, 프탈산, 이소프탈산, 테레프탈산, 말레산, 아디프산, 벤조산, 톨루일산, 에난트산, 말론산, 1,6-데칸디카르복시산, 1,7-옥탄디카르복시산, 아젤라산, 운데칸이산, 도데칸이산, 트리데칸이산 등의 카르복시산, 페놀류, 설폰산을 들 수 있다. 또한, 무기산으로서는, 붕산, 인산, 아인산, 차아인산, 탄산, 규산 등을 들 수 있다. 유기산과 무기산의 복합 화합물로서는, 보로디살리실산, 보로디옥살산, 보로디글리콜산 등을 들 수 있다.Organic acids that become anionic components in the electrolyte include oxalic acid, succinic acid, clutaric acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, toluic acid, enanthic acid, Examples include carboxylic acids such as malonic acid, 1,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid, phenols, and sulfonic acids. Additionally, examples of the inorganic acid include boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, and silicic acid. Examples of complex compounds of organic acids and inorganic acids include borodisalicylic acid, borodioxalic acid, and borodiglycolic acid.
또한, 유기산, 무기산, 그리고 유기산과 무기산의 복합 화합물의 적어도 1종의 염으로서, 암모늄염, 4급 암모늄염, 4급화 아미디늄염, 아민염, 나트륨염, 칼륨염 등을 들 수 있다. 4급 암모늄염의 4급 암모늄 이온으로서는 테트라메틸암모늄, 트리에틸메틸암모늄, 테트라에틸암모늄 등을 들 수 있다. 4급화 아미디늄으로서는, 에틸디메틸이미다졸리늄, 테트라메틸이미다졸리늄 등을 들 수 있다. 아민염의 아민으로서는, 1급 아민, 2급 아민, 3급 아민을 들 수 있다. 1급 아민으로서는, 메틸아민, 에틸아민, 프로필아민 등, 2급 아민으로서는, 디메틸아민, 디에틸아민, 에틸메틸아민, 디부틸아민 등, 3급 아민으로서는, 트리메틸아민, 트리에틸아민, 트리부틸아민, 에틸디메틸아민, 에틸디이소프로필아민 등을 들 수 있다.In addition, examples of at least one salt of an organic acid, an inorganic acid, and a complex compound of an organic acid and an inorganic acid include ammonium salt, quaternary ammonium salt, quaternized amidinium salt, amine salt, sodium salt, potassium salt, etc. Examples of the quaternary ammonium ion of the quaternary ammonium salt include tetramethylammonium, triethylmethylammonium, and tetraethylammonium. Examples of quaternized amidinium include ethyldimethylimidazolinium and tetramethylimidazolinium. Examples of amine salts include primary amines, secondary amines, and tertiary amines. Primary amines include methylamine, ethylamine, propylamine, etc., secondary amines include dimethylamine, diethylamine, ethylmethylamine, dibutylamine, etc., and tertiary amines include trimethylamine, triethylamine, and tributyl. Amine, ethyldimethylamine, ethyldiisopropylamine, etc. can be mentioned.
또한, 전해액에는 다른 첨가제를 첨가할 수도 있다. 첨가제로서는, 폴리에틸렌글리콜, 붕산과 다당류(만니트, 소르비트 등)와의 착화합물, 붕산과 다가 알코올과의 착화합물, 붕산에스테르, 니트로 화합물(o-니트로벤조산, m-니트로벤조산, p-니트로벤조산, o-니트로페놀, m-니트로페놀, p-니트로페놀 등), 인산에스테르, 콜로이달실리카 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.Additionally, other additives may be added to the electrolyte solution. As additives, polyethylene glycol, complexes of boric acid and polysaccharides (mannit, sorbit, etc.), complexes of boric acid and polyhydric alcohols, boric acid esters, nitro compounds (o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o -nitrophenol, m-nitrophenol, p-nitrophenol, etc.), phosphoric acid ester, colloidal silica, etc. These may be used individually, or two or more types may be used in combination.
이상, 전해액을 사용한 전해 콘덴서를 설명했지만, 고체 전해질을 사용했을 경우는, 집전체와 접촉한 카본층에 의해 고체 전해질과 도통하게 되어, 유전 분극 작용에 의한 양극측 용량에 의해 전해 콘덴서의 정전 용량이 구성된다. 또한, 고체 전해질을 사용할 경우는, 폴리에틸렌디옥시티오펜 등의 폴리티오펜이나, 폴리피롤, 폴리아닐린 등의 도전성 폴리머를 들 수 있다.Above, an electrolytic capacitor using an electrolyte solution has been described. However, when a solid electrolyte is used, the carbon layer in contact with the current collector becomes conductive with the solid electrolyte, and the electrolytic capacitance of the electrolytic capacitor is increased by the anode side capacitance due to the dielectric polarization effect. This is composed. Additionally, when using a solid electrolyte, polythiophene such as polyethylenedioxythiophene, and conductive polymer such as polypyrrole and polyaniline may be used.
(실시예)(Example)
이하, 실시예에 의거하여 본 발명을 더 상세히 설명한다. 또, 본 발명은 하기 실시예에 한정되는 것이 아니다.Hereinafter, the present invention will be described in more detail based on examples. Additionally, the present invention is not limited to the following examples.
(실시예 1)(Example 1)
다음과 같이 해서 실시예 1의 전해 콘덴서를 제작했다. 우선, 음극체에 관한 것으로, 탄소재인 인편상의 흑연의 분말 및 구상 탄소의 분말, 바인더인 스티렌부타디엔 고무(SBR), 및 분산제 함유 수용액으로서 카르복시메틸셀룰로오스나트륨(CMC-Na) 수용액을 혼합하여 혼련함으로써 슬러리를 제작했다. 탄소재와 바인더와 분산제 함유 수용액의 배합비는, 중량비로 84:10:6으로 했다. 별도, 전극 리드판을 인출한 알루미늄박을 음극박으로서 준비하고, 이 음극박에 슬러리를 균일하게 도포했다. 이 알루미늄박에는, 미리, 염산 중에서 전압을 인가함으로써, 에칭층을 형성해 두었다. 슬러리는, 그 에칭층에 도포했다. 그리고, 슬러리를 건조시킨 후, 150kN㎝-2의 압력으로 수직 프레스를 걸고, 카본층을 음극박 상에 정착시켰다.The electrolytic capacitor of Example 1 was manufactured as follows. First, regarding the cathode body, powder of flaky graphite and spherical carbon as carbon materials, styrenebutadiene rubber (SBR) as a binder, and sodium carboxymethyl cellulose (CMC-Na) as an aqueous solution containing a dispersant are mixed and kneaded. Slurry was produced. The mixing ratio of the carbon material, binder, and dispersant-containing aqueous solution was set to 84:10:6 in weight ratio. Separately, the aluminum foil from which the electrode lead plate was taken out was prepared as a cathode foil, and the slurry was uniformly applied to this cathode foil. An etching layer was previously formed on this aluminum foil by applying a voltage in hydrochloric acid. The slurry was applied to the etching layer. Then, after drying the slurry, a vertical press was applied at a pressure of 150 kN cm -2 to fix the carbon layer on the cathode foil.
또한, 알루미늄박에 에칭 처리를 실시하여, 공칭 화성 전압이 4Vfs가 되도록 유전체 산화 피막을 형성하고, 투영 면적이 2.1㎠의 크기의 알루미늄박을 얻어, 이것을 양극박으로 했다. 이 양극박의 용량은 386μF㎝-2였다. 그리고, 이 음극체와 양극체를 레이온제의 세퍼레이터를 개재하여 대향시키고, 전해액을 함침시켜, 라미네이트 셀로 하고, 공통의 재(再)화성 처리를 실시했다. 전해액으로서는, 프탈산테트라메틸이미다졸리늄을 용질로 하고, γ-부티로락톤을 용매로 하여 제작되었다. 재화성 시에는, 전(全)전해 콘덴서 모두 105℃의 환경 하에서, 3.35V의 전압을 60분간 인가했다.Additionally, an etching treatment was performed on the aluminum foil to form a dielectric oxide film so that the nominal chemical conversion voltage was 4V fs , an aluminum foil with a projected area of 2.1 cm2 was obtained, and this was used as an anode foil. The capacity of this anode foil was 386μF㎝ -2 . Then, the cathode body and the anode body were placed opposite each other through a rayon separator, and were impregnated with an electrolyte solution to form a laminated cell, and a common re-chemical treatment was performed. The electrolyte solution was produced using tetramethylimidazolinium phthalate as the solute and γ-butyrolactone as the solvent. When re-igniting, a voltage of 3.35 V was applied to all electrolytic capacitors for 60 minutes in an environment of 105°C.
실시예 1의 전해 콘덴서에 있어서는, 평균 입경이 10㎛인 인편상의 흑연을 사용하고, 구상 탄소로서 아세틸렌 블랙(AB)을 사용했다. 이 아세틸렌 블랙의 일차 입자경이 평균 50㎚이며, 또한 BET 비표면적은 39㎡／g이다. 또한 흑연과 아세틸렌 블랙의 혼합비는 75:25로 했다.In the electrolytic capacitor of Example 1, flaky graphite with an average particle diameter of 10 μm was used, and acetylene black (AB) was used as spherical carbon. The primary particle size of this acetylene black is 50 nm on average, and the BET specific surface area is 39 m2/g. Additionally, the mixing ratio of graphite and acetylene black was 75:25.
(실시예 2, 3 및 10)(Examples 2, 3 and 10)
실시예 1의 전해 콘덴서와 동일 조건으로 실시예 2, 3 및 10의 전해 콘덴서를 제작했다. 단, 실시예 2의 전해 콘덴서에서는, 구상 탄소로서 아세틸렌 블랙을 사용하고, 흑연과 아세틸렌 블랙의 혼합비를 75:25로 했지만, 평균 입경이 6㎛인 인편상의 흑연을 사용했다. 또한, 실시예 3의 전해 콘덴서에서는, 흑연과 아세틸렌 블랙의 혼합비를 75:25로 했지만, 평균 입경이 4㎛인 인편상의 흑연을 사용했다. 또한, 실시예 10의 전해 콘덴서에서는, 흑연과 아세틸렌 블랙의 혼합비를 75:25로 했지만, 평균 입경이 0.5㎛인 인편상의 흑연을 사용했다. 즉, 실시예 2, 3 및 10은, 실시예 1에 대하여 인편상의 흑연의 평균 입경이 변경되어 있다.Electrolytic capacitors of Examples 2, 3, and 10 were manufactured 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, the mixing ratio of graphite and acetylene black was 75:25, and flaky graphite with an average particle diameter of 6 μm was used. Additionally, in the electrolytic capacitor of Example 3, the mixing ratio of graphite and acetylene black was 75:25, but flaky graphite with an average particle diameter of 4 μm was used. In addition, in the electrolytic capacitor of Example 10, the mixing ratio of graphite and acetylene black was 75:25, but flaky graphite with an average particle diameter of 0.5 μm was used. That is, in Examples 2, 3, and 10, the average particle size of flaky graphite was changed compared to Example 1.
(실시예 4 내지 9)(Examples 4 to 9)
실시예 1의 전해 콘덴서와 동일 조건으로 실시예 4 내지 9의 전해 콘덴서를 제작했다. 단, 실시예 4 내지 9의 전해 콘덴서에서는, 평균 입경이 1㎛인 인편상의 흑연을 사용했다. 이들 실시예 4 내지 9의 전해 콘덴서는, 흑연과 아세틸렌 블랙의 혼합비가 다르다. 실시예 4에서는 흑연과 아세틸렌 블랙의 혼합비를 95:5로 하고, 실시예 5에서는 흑연과 아세틸렌 블랙의 혼합비를 흑연의 비율을 떨어뜨려 90:10으로 하고, 실시예 6에서는 흑연과 아세틸렌 블랙의 혼합비를 흑연의 비율을 더 떨어뜨려 85:15로 하고, 실시예 7에서는 흑연과 아세틸렌 블랙의 혼합비를 흑연의 비율을 더 떨어뜨려 75:25로 하고, 실시예 8에서는 흑연과 아세틸렌 블랙의 혼합비를 흑연의 비율을 더 떨어뜨려 50:50으로 하고, 실시예 9에서는 흑연과 아세틸렌 블랙의 혼합비를 흑연의 비율을 더 떨어뜨려 25:75로 했다.Electrolytic capacitors of Examples 4 to 9 were manufactured under the same conditions as the electrolytic capacitor of Example 1. However, in the electrolytic capacitors of Examples 4 to 9, flaky graphite with an average particle diameter of 1 μm was used. The electrolytic capacitors of these Examples 4 to 9 had different mixing ratios of graphite and acetylene black. In Example 4, the mixing ratio of graphite and acetylene black was set to 95:5, in Example 5, the mixing ratio of graphite and acetylene black was reduced to 90:10 by lowering the ratio of graphite, and in Example 6, the mixing ratio of graphite and acetylene black was set to 90:10. The ratio of graphite was further reduced to 85:15, and in Example 7, the mixing ratio of graphite and acetylene black was further reduced to 75:25, and in Example 8, the mixing ratio of graphite and acetylene black was reduced to 75:25. The ratio was further reduced to 50:50, and in Example 9, the mixing ratio of graphite and acetylene black was further reduced to 25:75.
(비교예 3 및 참고예 1)(Comparative Example 3 and Reference Example 1)
실시예 4 내지 9의 전해 콘덴서와의 대비로서, 비교예 3 및 참고예 1의 전해 콘덴서를 제작했다. 단, 비교예 3에서는, 구상 탄소를 더하지 않고, 평균 입경 1㎛의 흑연만을 탄소재로 하여 카본층을 형성했다. 참고예 1에서는, 인편상의 흑연을 더하지 않고, 아세틸렌 블랙만을 탄소재로 하여 카본층을 형성했다. 그 밖의 조건은, 실시예 4 내지 9와 동일하다.As a comparison with the electrolytic capacitors of Examples 4 to 9, the electrolytic capacitors of Comparative Example 3 and Reference Example 1 were produced. However, in Comparative Example 3, no spherical carbon was added and a carbon layer was formed using only graphite with an average particle diameter of 1 μm as the carbon material. In Reference Example 1, a carbon layer was formed using only acetylene black as a carbon material without adding flaky graphite. Other conditions are the same as Examples 4 to 9.
(실시예 11 및 12)(Examples 11 and 12)
실시예 2의 전해 콘덴서와 동일 조건으로 실시예 11 및 12의 전해 콘덴서를 제작했다. 단, 실시예 11의 전해 콘덴서에서는, 구상 탄소로서 케첸 블랙을 사용한 점에서 실시예 2와 다르지만, 인편상의 흑연의 평균 입경이 6㎛인 점, 및 인편상의 흑연과 구상 탄소의 혼합비가 75:25인 점에서 동일하다. 케첸 블랙의 일차 입자경이 평균 40㎚이며, 또한 BET 비표면적은 800㎡／g이다. 실시예 12의 전해 콘덴서에서는, 실시예 11에 비해 인편상의 흑연의 혼합비를 떨어뜨려, 50:50으로 했다.The electrolytic capacitors of Examples 11 and 12 were manufactured under the same conditions as the electrolytic capacitors of Example 2. However, the electrolytic capacitor of Example 11 differs from Example 2 in that Ketjen black was used as spherical carbon, but the average particle size of flaky graphite was 6 μm and the mixing ratio of flaky graphite and spherical carbon was 75:25. It is the same in that it is The primary particle size of Ketjen Black is 40 nm on average, and the BET specific surface area is 800 m2/g. In the electrolytic capacitor of Example 12, the mixing ratio of flaky graphite was lowered compared to Example 11, and was set to 50:50.
(실시예 13 및 14)(Examples 13 and 14)
실시예 11 및 12의 전해 콘덴서와 동일 조건으로 실시예 13 및 14의 전해 콘덴서를 제작했다. 단, 실시예 13의 전해 콘덴서는 실시예 11에 대해, 또한 실시예 14의 전해 콘덴서는 실시예 12에 대해, 인편상의 흑연의 평균 입경이 1㎛인 점에서 다르다.The electrolytic capacitors of Examples 13 and 14 were manufactured under the same conditions as the electrolytic capacitors of Examples 11 and 12. However, the electrolytic capacitor of Example 13 differs from Example 11, and the electrolytic capacitor of Example 14 differs from Example 12 in that the average particle size of flaky graphite is 1 μm.
(비교예 1 및 2)(Comparative Examples 1 and 2)
마지막으로, 이들 실시예 1 내지 14의 전해 콘덴서와의 대비로서, 비교예 1 및 비교예 2의 전해 콘덴서를 제작했다. 비교예 1의 전해 콘덴서에 관해서는, 에칭 미처리의 알루미늄박을 집전체로서 사용하고, 전자 빔 증착법에 의해 질화티타늄층을 형성하고, 이 질화티타늄층을 형성한 알루미늄박을 음극체로서 사용했다. 또한, 비교예 2의 전해 콘덴서에 관해서는, 에칭 미처리의 알루미늄박을 집전체로서 사용하고, 평균 입경이 5㎛인 활성탄과 아세틸렌 블랙을 혼합한 카본층을 형성하고, 이 카본층을 형성한 알루미늄박을 음극체로서 사용했다. 활성탄의 BET 비표면적은 1500㎡／g이다. 또한 비교예 2에서 사용한 아세틸렌 블랙의 BET 비표면적은 39㎡／g이다. 비교예 1 및 2의 전해 콘덴서에 있어서의 양극박, 세퍼레이터 및 전해액의 조성, 제작 공정 및 제작 조건은, 각 실시예의 전해 콘덴서와 같다.Finally, as a comparison with the electrolytic capacitors of Examples 1 to 14, electrolytic capacitors of Comparative Examples 1 and 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 electron beam evaporation, and the aluminum foil on which this titanium nitride layer was formed was used as a cathode body. In addition, regarding the electrolytic capacitor of Comparative Example 2, an unetched aluminum foil was used as a current collector, a carbon layer was formed by mixing activated carbon and acetylene black with an average particle diameter of 5 μm, and the aluminum foil forming this carbon layer was formed. Foil was used as a cathode. The BET specific surface area of activated carbon is 1500㎡/g. Additionally, the BET specific surface area of the acetylene black used in Comparative Example 2 was 39 m2/g. The composition, manufacturing process, and manufacturing conditions of the anode foil, separator, and electrolyte solution in the electrolytic capacitors of Comparative Examples 1 and 2 were the same as those of the electrolytic capacitors in each Example.
(제품 시험)(Product Test)
이상의 실시예 1 내지 14, 비교예 1 내지 3, 그리고 참고예 1의 전해 콘덴서의 정전 용량(Cap)을 측정했다. 이 제품 시험에서는, 20℃에서 120㎐ 및 10㎑ 충방전 시의 정전 용량(Cap)을 초기 정전 용량으로서 측정했다. 또한, 125℃인 고온 환경 하에 260시간 노출하고, 그 후, 20℃에서 120㎐ 및 10㎑ 충방전 시의 정전 용량(Cap)을 고온 환경 부하 후 정전 용량으로서 측정했다. 그 결과를 하기 표 1에 나타낸다. 또한, 표 1에는, 초기 정전 용량에 대한 고온 환경 부하 후 정전 용량의 변화율(ΔCap)을 주파수마다 기재했다.The electrostatic capacitance (Cap) of the electrolytic capacitors of Examples 1 to 14, Comparative Examples 1 to 3, and Reference Example 1 above was measured. In this product test, the capacitance (Cap) during charging and discharging at 120 Hz and 10 kHz at 20°C was measured as the initial capacitance. Additionally, it was exposed to a high-temperature environment of 125°C for 260 hours, and then the electrostatic capacity (Cap) during charging and discharging at 120 Hz and 10 kHz at 20°C was measured as the electrostatic capacity after high-temperature environmental load. The results are shown in Table 1 below. Additionally, in Table 1, the rate of change (ΔCap) of capacitance after high-temperature environmental load relative to the initial capacitance is listed for each frequency.
(표 1)(Table 1)
표 1에 나타내는 바와 같이, 저주파 영역인 120㎐에서 전해 콘덴서를 사용하면, 실시예 1 내지 14의 전해 콘덴서는, 초기 정전 용량에 대한 고온 환경 부하 후 정전 용량의 변화율(ΔCap)에 있어서, 비교예 1 및 2의 전해 콘덴서에 대하여 양호했다. 이들 실시예 1 내지 14는, 흑연과 아세틸렌 블랙 또는 케첸 블랙과 같은 구상 탄소를 혼합하여 음극체의 카본층을 형성한 것이다. 한편, 비교예 3의 전해 콘덴서와 같이, 흑연만으로 음극체의 카본층을 형성하면, 비교예 1 및 2에 비해 초기 정전 용량의 현저한 저하가 보여, 고온 환경 부하 후 정전 용량의 저하도 큰 것을 확인할 수 있고, 10㎑에서의 사용에 있어서도 정전 용량이 현저하게 낮다. 또, 참고예 1의 전해 콘덴서는, 본 제품 시험에 있어서 비교적 양호하기는 하지만, 후술하는 바와 같이 계면 저항이 뒤떨어져 있다.As shown in Table 1, when electrolytic capacitors are used in the low-frequency region of 120 Hz, the electrolytic capacitors of Examples 1 to 14 have a change rate (ΔCap) of capacitance after high-temperature environmental load with respect to the initial capacitance of the comparative example. It was good for electrolytic capacitors 1 and 2. In these Examples 1 to 14, the carbon layer of the cathode body was formed by mixing graphite and spherical carbon such as acetylene black or Ketjen black. 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, a significant decrease in initial capacitance is observed compared to Comparative Examples 1 and 2, confirming that the decrease in capacitance after high temperature environmental load is also large. Even when used at 10 kHz, the capacitance is significantly low. In addition, although the electrolytic capacitor of Reference Example 1 was relatively good in this product test, its interface resistance was inferior, as will be described later.
이에 따라, 흑연과 구상 탄소를 혼합하여 음극체의 카본층을 형성함으로써, 전해 콘덴서는, 120㎐와 같은 저주파 영역에서의 사용에 있어서, 초기 정전 용량뿐만 아니라, 고온 환경 부하 후에 있어서도 비교적 안정된 정전 용량을 갖는 것이 확인되었다.Accordingly, by mixing graphite and spherical carbon to form the carbon layer of the cathode body, the electrolytic capacitor has not only an initial capacitance but also a relatively stable capacitance even after a high-temperature environmental load when used in a low frequency range such as 120 Hz. It was confirmed to have.
다음으로, 실시예 1 내지 10의 전해 콘덴서는, 구상 탄소로서 아세틸렌 블랙을 사용한 것이지만, 고주파 영역인 10㎑에서 전해 콘덴서를 사용해도, 초기 정전 용량에 대한 고온 환경 부하 후 정전 용량의 변화율(ΔCap)에 있어서 양호한 것이 확인되었다. 즉, 흑연과 아세틸렌 블랙을 혼합하여 이루어지는 카본층을 음극체에 형성한 전해 콘덴서는, 고온 환경 부하 후의 정전 용량의 관점에서, 저주파 영역에서의 사용에 있어서도, 고주파 영역에서의 사용에 있어서도, 폭넓은 주파수 영역에서 안정적인 정전 용량을 갖고 있어 범용적인 것이 확인되었다.Next, the electrolytic capacitors of Examples 1 to 10 used acetylene black as the spherical carbon, but even if the electrolytic capacitor was used in the high frequency range of 10 kHz, the rate of change in capacitance after high temperature environmental load with respect to the initial capacitance (ΔCap) It was confirmed that it was good. In other words, electrolytic capacitors in which a carbon layer made of a mixture of graphite and acetylene black is formed on the cathode body have a wide range of uses in both low-frequency and high-frequency areas from the viewpoint of electrostatic capacity after high-temperature environmental load. It was confirmed that it has stable capacitance in the frequency domain and is therefore universal.
또한, 실시예 1 및 2의 전해 콘덴서는, 고주파 영역에서 사용하든, 저주파 영역에서 사용하든, 초기 정전 용량에 대하여 고온 환경 부하 후 정전 용량이 떨어지지 않는 것이 확인되었다. 즉, 흑연의 평균 입경을 6㎛ 이상 10㎛ 이하로 하고, 구상 탄소로서 아세틸렌 블랙을 선택하면, 전해 콘덴서의 열안정성이 우수하여, 폭넓은 온도 환경 하에 걸쳐 매우 안정적으로 동작하는 것이 확인되었다. 또한, 실시예 2의 전해 콘덴서는, 실시예 1에 비하면 정전 용량 자체가 대폭 향상하고, 고온 환경 부하 후에 관해서는 질화티타늄의 피막을 음극박에 형성한 비교예 1의 전해 콘덴서와 손색이 없는 크기의 정전 용량을 발현하고 있다. 즉, 흑연의 평균 입경을 6㎛ 정도(±2㎛)로 하면, 고온 환경에 있어서도 고용량이며 또한 안정적인 것이 확인되었다.In addition, it was confirmed that the electrolytic capacitors of Examples 1 and 2, regardless of whether they were used in a high-frequency range or a low-frequency range, did not have a drop in capacitance after being subjected to a high-temperature environmental load with respect to the initial capacitance. In other words, it was confirmed that when the average particle size of graphite is set to 6 μm or more and 10 μm or less and acetylene black is selected as the spherical carbon, the electrolytic capacitor has excellent thermal stability and operates very stably under a wide temperature environment. In addition, the electrolytic capacitor of Example 2 has a significantly improved electrostatic capacity compared to Example 1, and its size is comparable to that of the electrolytic capacitor of Comparative Example 1 in which a titanium nitride film was formed on the cathode foil after high-temperature environmental load. A capacitance of . In other words, it was confirmed that if the average particle size of graphite was about 6㎛ (±2㎛), it had high capacity and was stable even in a high temperature environment.
또한, 실시예 3 내지 10의 전해 콘덴서는, 고주파 영역에서 사용하든, 저주파 영역에서 사용하든, 비교예 1 및 비교예 2의 전해 콘덴서의 초기 정전 용량뿐만 아니라, 고온 환경 부하 후 정전 용량에 필적 혹은 능가하는 것이 확인되었다. 즉, 흑연의 평균 입경을 6㎛ 미만으로 하고, 구상 탄소로서 아세틸렌 블랙을 선택하면, BET 비표면적이 39㎡／g인 아세틸렌 블랙을 사용하고 있음에도 불구하고, BET 비표면적이 1500㎡／g인 활성탄을 사용한 비교예 2에 필적하고, 또한 평균 입경을 1㎛로 하면, 이 비교예 2를 능가하여, 전해 콘덴서의 정전 용량을 높일 수 있는 것이 확인되었다. 더욱이는, 고온 환경 부하 후의 정전 용량의 저하를 억제하는 것이 가능해져, 열안정성이 우수한 것에 더해, 넓은 주파수 영역에 있어서 매우 안정적으로 동작하는 것이 확인되었다.In addition, the electrolytic capacitors of Examples 3 to 10, whether used in the high-frequency region or the low-frequency region, not only have the initial capacitance of the electrolytic capacitors of Comparative Examples 1 and 2, but also have comparable or comparable capacitances after high-temperature environmental load. It has been confirmed that it surpasses In other words, if the average particle size of graphite is set to less than 6㎛ and acetylene black is selected as the spherical carbon, activated carbon with a BET specific surface area of 1500㎡/g is obtained even though acetylene black with a BET specific surface area of 39㎡/g is used. It was confirmed that the electrolytic capacitance of the electrolytic capacitor could be increased, comparable to Comparative Example 2 using , and surpassing Comparative Example 2 when the average particle diameter was set to 1 μm. Furthermore, it became possible to suppress the decline in capacitance after high-temperature environmental load, and it was confirmed that in addition to excellent thermal stability, it operates very stably over a wide frequency range.
(계면 저항)(interface resistance)
여기에서, 실시예 3 및 참고예 1의 전해 콘덴서에 있어서, 음극체의 단면을 주사형 전자 현미경으로 촬영하고, 또한 카본층과 확면층의 계면 저항값을 측정했다. 도 3은, 음극체의 단면의 SEM 사진이며, (a)는 실시예 3에 따른 10,000배, (b)는 참고예 1에 따른 10,000배, (c)는 실시예 3에 따른 25,000배, (d)는 참고예 1에 따른 25,000배이다. 계면 저항값은, 전극 저항 측정 시스템(히오키덴키 가부시키가이샤제; 형번 RM2610)으로 측정했다. 또, 실시예 3은, 흑연과 카본 블랙에 의해 카본층이 되고, 이에 대하여, 참고예 1은, 흑연을 포함하지 않고, 카본 블랙에 의해 카본층이 되고, 실시예 3과 참고예 1은, 그 외에 대해 동일하다.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 interface resistance value of the carbon layer and the expanded surface layer was measured. Figure 3 is an SEM photograph of the cross section of the cathode body, (a) is 10,000 times according to Example 3, (b) is 10,000 times according to Reference Example 1, (c) is 25,000 times according to Example 3, ( d) is 25,000 times according to Reference Example 1. The interface resistance value was measured with an electrode resistance measurement system (Hioki Denki Co., Ltd.; model number RM2610). In addition, in Example 3, a carbon layer is formed by graphite and carbon black. In contrast, Reference Example 1 does not contain graphite and forms a carbon layer by carbon black, and Example 3 and Reference Example 1 have, Other than that, it's the same.
도 3의 (a) 및 (c)에 나타내는 바와 같이, 실시예 3의 음극체에서는, 흑연이 확면층의 요철면을 따라 변형하여 빈틈없이 깔리고, 카본층과 확면층이 요철면에 있어서 밀착해 있는 것을 알 수 있다. 또한, 실시예 3의 음극체에서는, 흑연이 압압 덮개가 되어 확면층의 세공에 카본 블랙을 압입하고 있으며, 카본층과 확면층이 세공에 있어서도 밀착해 있는 것을 알 수 있다. 또한, 흑연이 굴곡하고, 굴곡 각도가 국소적으로 90° 정도까지 꺾여 구부러진다. 이와 같이 굴곡한 흑연에 의해, 압접의 압력이 직접 전해지기 어려운 요철면의 측면이나 심부의 세공까지 카본 블랙을 효율적으로 압입하고 있다.As shown in Figures 3 (a) and (c), in the cathode body of Example 3, the graphite is deformed along the uneven surface of the expanded surface layer and spread tightly, and the carbon layer and the expanded surface layer are in close contact with the uneven surface. You can see that it exists. Additionally, in the cathode body of Example 3, graphite serves as a pressure cover to press carbon black into the pores of the expanded surface layer, and it can be seen that the carbon layer and the expanded surface layer are in close contact even in the pores. Additionally, the graphite bends, and the bending angle locally bends to about 90°. By bending the graphite in this way, carbon black is efficiently press-fitted into the pores of the sides and deep portions of the uneven surface where pressure from pressure contact is difficult to be transmitted directly.
이와 같이, 실시예 3의 음극체에서는, 확면층에 카본층이 파고 들어가 있는 것을 알 수 있다. 이에 대하여, 참고예 1의 음극체에서는, 카본 블랙이 확면층의 요철면에 쌓여 있지만, 카본층과 요철면과의 사이의 곳곳에 공극(空隙)이 생겨 있다. 또한, 참고예 1의 음극체에서는, 확면층의 세공에 들어가 있는 카본 블랙이 상대적으로 적어, 세공 내의 공극이 많이 발생하여 있다.In this way, in the cathode body of Example 3, it can be seen that the carbon layer is penetrated into the expanded surface layer. In contrast, in the cathode body of Reference Example 1, carbon black was accumulated on the uneven surface of the expanded surface layer, but voids were formed in various places between the carbon layer and the uneven surface. Additionally, in the cathode body of Reference Example 1, there was relatively little carbon black contained in the pores of the expanded surface layer, and many voids within the pores were generated.
이 결과, 실시예 3의 음극체의 계면 저항값은, 1.78mΩ㎠였지만, 참고예 1의 음극체의 계면 저항값은, 2.49mΩ㎠가 되어 버렸다. 즉, 흑연과 구상 탄소의 양쪽을 카본층에 포함하는 실시예 1 내지 14는, 고온 환경 부하 후에 있어서도 안정된 정전 용량을 발현시킬 수 있는 점에 더해, 낮은 계면 저항값이 얻어지는 것이 확인되었다.As a result, the interface resistance value of the cathode body of Example 3 was 1.78 mΩcm2, but the interface resistance value of the cathode body of Reference Example 1 was 2.49 mΩcm2. That is, it was confirmed that Examples 1 to 14, which contain both graphite and spherical carbon in the carbon layer, were able to develop stable electrostatic capacity even after high-temperature environmental load and, in addition, low interface resistance values were obtained.
(프레스 효과 시험)(Press effect test)
여기에서, 150kN㎝-2의 압력으로 수직 프레스를 건 실시예 3의 음극체와의 비교 대상으로서, 프레스 공정을 생략한 참고예 2의 음극체를 제작했다. 참고예 2의 음극체는, 프레스의 유무를 제외하고 실시예 3과 동일 조건으로 제작되었다. 그리고, 실시예 3의 음극체와 참고예 2의 음극체의 단면을 주사형 전자 현미경으로 촬영했다. 촬영 결과를, 도 4에 나타낸다. 도 4는, 음극체의 단면의 SEM 사진이며, (a)는 실시예 3에 따른 10,000배, (b)는 참고예 2에 따른 10,000배, (c)는 실시예 3에 따른 25,000배, (d)는 참고예 2에 따른 25,000배이다.Here, as an object of comparison with the cathode body of Example 3, which was vertically pressed at a pressure of 150 kN cm -2 , the cathode body of Reference Example 2, in which the pressing process was omitted, was produced. The cathode body of Reference Example 2 was manufactured under the same conditions as Example 3, except for the presence or absence of a press. Then, 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 imaging results are shown in Figure 4. Figure 4 is an SEM photograph of the cross section of the cathode body, (a) is 10,000 times according to Example 3, (b) is 10,000 times according to Reference Example 2, (c) is 25,000 times according to Example 3, ( d) is 25,000 times according to Reference Example 2.
도 4의 (a) 및 (c)에 나타내는 바와 같이, 실시예 3의 음극체에서는, 흑연이 확면층의 요철면을 따라 변형하여 빈틈없이 깔려, 카본층과 확면층이 요철면에 있어서 밀착해 있는 것을 알 수 있다. 또한, 실시예 3의 음극체에서는, 흑연이 압압 덮개가 되어 확면층의 세공에 카본 블랙을 압입하고 있으며, 카본층과 확면층이 세공에 있어서도 밀착해 있는 것을 알 수 있다. 이와 같이, 실시예 3의 음극체에서는, 확면층에 카본층이 파고 들어가 있는 것을 알 수 있다.As shown in Figures 4 (a) and (c), in the cathode body of Example 3, the graphite is deformed along the uneven surface of the expanded surface layer and spread tightly, and the carbon layer and the expanded surface layer are in close contact with the uneven surface. You can see that it exists. Additionally, in the cathode body of Example 3, graphite serves as a pressure cover to press carbon black into the pores of the expanded surface layer, and it can be seen that the carbon layer and the expanded surface layer are in close contact even in the pores. In this way, in the cathode body of Example 3, it can be seen that the carbon layer is penetrated into the expanded surface layer.
한편, 참고예 2의 음극체에서는, 흑연이 확면층의 요철면을 따라 변형해 있지 않고, 카본층과 요철면과의 사이의 곳곳에 공극이 생겨 있다. 또한, 참고예 2의 음극체에서는, 확면층의 세공에 들어가 있는 카본 블랙이 상대적으로 적어, 세공 내의 공극이 많이 발생하여 있다.On the other hand, in the cathode body of Reference Example 2, the graphite was not deformed along the concavo-convex surface of the expanded layer, and voids were formed in various places between the carbon layer and the concave-convex surface. Additionally, in the cathode body of Reference Example 2, there was relatively little carbon black contained in the pores of the expanded surface layer, and many voids within the pores were generated.
이 결과, 음극박에 슬러리를 균일하게 도포하여 건조시킨 후, 소정의 압력으로 프레스를 걸면, 흑연이 확면층의 요철면을 따라 용이하게 변형하여 빈틈없이 깔려, 카본층과 확면층이 요철면에 있어서 밀착하기 쉬워, 계면 저항값을 낮추기 쉬운 것이 확인되었다. 또한, 프레스에 의해, 흑연이 압압 덮개가 되어 확면층의 세공에 카본 블랙을 용이하게 압입하고, 카본층과 확면층이 세공에 있어서도 밀착하기 쉬워, 계면 저항값을 낮추기 쉬운 것이 확인되었다.As a result, when the slurry is uniformly applied to the cathode foil, dried, and then pressed at a predetermined pressure, the graphite is easily deformed along the concavo-convex surface of the expanded surface layer and spread tightly, and the carbon layer and the expanded surface layer are formed on the uneven surface. It was confirmed that it was easy to adhere closely and the interface resistance value could be easily lowered. In addition, it was confirmed that by pressing, graphite becomes a pressure cover and carbon black is easily pressed into the pores of the expanded surface layer, and the carbon layer and the expanded surface layer are easily brought into close contact even in the pores, making it easy to lower the interface resistance value.
(실시예 15 및 16)(Examples 15 and 16)
BET 비표면적이 39㎡／g인 아세틸렌 블랙을 사용한 실시예 7의 전해 콘덴서에 비해, BET 비표면적이 133㎡／g인 아세틸렌 블랙을 사용한 실시예 15의 전해 콘덴서를 제작했다. 그 밖의 조건은 실시예 7의 전해 콘덴서와 동일하다. 또한, BET 비표면적이 800㎡／g인 케첸 블랙을 사용한 실시예 13의 전해 콘덴서에 비해, BET 비표면적이 377㎡／g인 케첸 블랙을 사용한 실시예 16의 전해 콘덴서를 제작했다. 그 밖의 조건은 실시예 13의 전해 콘덴서와 동일하다.Compared to the electrolytic capacitor of Example 7 using acetylene black with a BET specific surface area of 39 m2/g, the electrolytic capacitor of Example 15 using acetylene black with a BET specific surface area of 133 m2/g was produced. Other conditions are the same as for the electrolytic capacitor in Example 7. Additionally, compared to the electrolytic capacitor of Example 13 using Ketjen Black with a BET specific surface area of 800 m2/g, the electrolytic capacitor of Example 16 using Ketjen Black with a BET specific surface area of 377 m2/g was produced. Other conditions are the same as for the electrolytic capacitor in Example 13.
이들 실시예 15 및 16의 전해 콘덴서에 관해서도, 초기 정전 용량 및 고온 환경 부하 후의 정전 용량에 대해서 각 주파수 영역의 조합으로 제품 시험을 행했다. 그 결과를 표 2에 나타낸다. 표 2에는, 참고적으로 실시예 7 및 13의 전해 콘덴서의 제품 시험의 결과도 나타낸다.Regarding the electrolytic capacitors of Examples 15 and 16, product tests were also conducted on the initial capacitance and capacitance after high-temperature environmental load in combinations of each frequency range. The results are shown in Table 2. Table 2 also shows the results of product testing of the electrolytic capacitors of Examples 7 and 13 for reference.
(표 2)(Table 2)
표 2에 나타내는 바와 같이, BET 비표면적이 200㎡／g 이하인 구상 탄소를 포함하는 카본층이 형성된 음극체를 사용한 실시예 7 및 15의 전해 콘덴서는, BET 비표면적이 200㎡／g 초과인 실시예 13 및 16의 전해 콘덴서에 비해, 120㎐ 및 10㎑의 양쪽에 있어서 고온 환경 부하 후 정전 용량의 변화율(ΔCap)이 양호한 것이 확인되었다. 즉, 아세틸렌 블랙뿐만 아니라, BET 비표면적이 200㎡／g 이하인 구상 탄소를 포함하는 카본층이 형성된 음극체를 사용함으로써, 초기 정전 용량뿐만 아니라, 고온 환경 부하 후에 있어서도, 폭넓은 주파수 영역에 있어서 안정적으로 정전 용량을 발현하는 것이 확인되었다.As shown in Table 2, the electrolytic capacitors of Examples 7 and 15 using a cathode body formed with a carbon layer containing spherical carbon with a BET specific surface area of 200 m2/g or less are the embodiments with a BET specific surface area of more than 200 m2/g. Compared to the electrolytic capacitors of Examples 13 and 16, it was confirmed that the rate of change in capacitance (ΔCap) after high-temperature environmental load was good at both 120 Hz and 10 kHz. In other words, by using a cathode body formed with a carbon layer containing not only acetylene black but also spherical carbon with a BET specific surface area of 200 m2/g or less, it is stable not only in the initial capacitance but also in a wide frequency range even after a high temperature environmental load. It was confirmed that electrostatic capacity was developed.
(탄소재 정착성 시험)(Carbon material fixation test)
흑연의 입자경이 10, 6, 4 및 1㎛인 실시예 1, 2, 3 및 7의 전해 콘덴서의 탄소재 정착성 시험을 행했다. 각 전해 콘덴서를 콘덴서 소자의 단계에서 분해하고, 세퍼레이터의 음극체측의 면에 점착 테이프(3M제 스카치 테이프: 형번 144JP 32-978)를 한번 첩부(貼付)하여 박리하고, 점착 테이프에의 부착물을 관찰했다. 그 결과를 도 1에 나타낸다. 도 1은, 실시예 1, 2, 3 및 7에 따른 박리 후의 점착 테이프를 촬영한 사진이다.A carbon material fixation test was conducted on the electrolytic capacitors of Examples 1, 2, 3, and 7 in which the graphite particle diameters were 10, 6, 4, and 1 μm. Each electrolytic capacitor was disassembled at the capacitor element stage, and adhesive tape (Scotch tape made by 3M: model number 144JP 32-978) was applied once to the surface of the separator on the cathode side, peeled off, and the adhesion to the adhesive tape was observed. did. The results are shown in Figure 1. Figure 1 is a photograph of the adhesive tape after peeling according to Examples 1, 2, 3, and 7.
일반적으로는 흑연의 입경이 작을수록, 카본층으로부터 흑연이 이탈하기 쉽다고 추측되는 것이지만, 도 1에 나타내는 바와 같이, 흑연의 입경이 작아질수록, 카본층으로부터 이탈한 흑연의 양이 적어져 있는 것을 확인할 수 있다. 특히, 흑연의 평균 입경이 6㎛ 이하인 실시예 2, 3 및 7은, 동(同) 10㎛의 실시예 1에 비해 점착 테이프에의 부착량이 적어져 있다. 이 때문에, 흑연의 평균 입경을 6㎛ 이하로 하면, 카본층 내에 탄소재를 유치하는 바인더의 양을 적게 할 수 있어, 음극체의 저항을 낮추고, 또한 전해 콘덴서의 ESR을 낮출 수 있는 것이 확인되었다.In general, it is assumed that the smaller the particle size of graphite, the easier it is for graphite to be separated from the carbon layer. However, as shown in Figure 1, as the particle size of graphite becomes smaller, the amount of graphite separated from the carbon layer decreases. You can check it. In particular, Examples 2, 3, and 7 in which the average particle diameter of graphite was 6 μm or less showed a smaller amount of adhesion to the adhesive tape compared to Example 1 in which the graphite had an average particle size of 10 μm. For this reason, it was confirmed that if the average particle size of graphite is set to 6 ㎛ or less, the amount of binder that holds the carbon material in the carbon layer can be reduced, lowering the resistance of the cathode body and lowering the ESR of the electrolytic capacitor. .
Claims (13)
밸브 작용 금속에 의해 이루어지는 음극박과,
상기 음극박에 형성된 카본층,
을 구비하고,
상기 카본층은, 흑연과 구상(球狀) 탄소를 포함하고,
상기 구상 탄소는, BET 비표면적이 200㎡／g 이하인 카본 블랙이며,
상기 흑연은, 인편상 또는 박편상이며, 그 단경과 장경과의 아스펙트비가 1:5∼1:100의 범위이고, 입도 분포에 있어서의 평균 입경이 6㎛ 이하이며,
상기 흑연과 상기 카본 블랙의 혼합비는, 90:10 내지 25:75인 것
을 특징으로 하는 전극체.As an electrode body used for the cathode of an electrolytic capacitor,
A cathode foil made of valve-acting metal,
A carbon layer formed on the cathode foil,
Equipped with
The carbon layer includes graphite and spherical carbon,
The spherical carbon is carbon black with a BET specific surface area of 200 m2/g or less,
The graphite is in the form of flakes or flakes, the aspect ratio between the minor axis and the major axis is in the range of 1:5 to 1:100, and the average particle size in the particle size distribution is 6 μm or less,
The mixing ratio of the graphite and the carbon black is 90:10 to 25:75.
An electrode body characterized by .
상기 음극박은, 확면층(擴面層)이 형성되고,
상기 카본층은, 상기 확면층 상에 형성되어 있는 것을 특징으로 하는 전극체.According to paragraph 1,
The cathode foil is formed with an expanded surface layer,
An electrode body characterized in that the carbon layer is formed on the expanded surface layer.
상기 확면층과 상기 카본층은 압접(壓接)하고 있는 것을 특징으로 하는 전극체.According to clause 6,
An electrode body characterized in that the expanded surface layer and the carbon layer are pressure-welded.
상기 확면층은, 요철면과 당해 요철면으로부터 상기 음극박의 심부(深部)를 향하여 형성되는 세공(細孔)으로 형성되고,
상기 구상 탄소는, 세공에 들어가고,
상기 흑연은, 상기 구상 탄소가 들어간 상기 세공을 덮고 있는 것을 특징으로 하는 전극체.According to clause 6,
The expanded surface layer is formed of an uneven surface and pores formed from the uneven surface toward the deep portion of the cathode foil,
The spherical carbon enters the pores,
An electrode body characterized in that the graphite covers the pores containing the spherical carbon.
상기 구상 탄소는, 상기 카본층의 압접에 의해 상기 세공에 들어가 있는 것을 특징으로 하는 전극체.According to clause 8,
An electrode body characterized in that the spherical carbon enters the pores by pressure welding the carbon layer.
상기 흑연은, 상기 확면층의 상기 요철면을 따르도록 변형하여 있는 것을 특징으로 하는 전극체.According to clause 8,
The electrode body is characterized in that the graphite is deformed to follow the concavo-convex surface of the expanded surface layer.
밸브 작용 금속에 의해 이루어지는 음극박에, 인편상 또는 박편상이며, 그 단경과 장경과의 아스펙트비가 1:5∼1:100의 범위이며, 입도 분포에 있어서의 평균 입경이 6㎛ 이하인 흑연과, BET 비표면적이 200㎡／g 이하인 카본 블랙인 구상 탄소를, 상기 흑연과 상기 카본 블랙의 혼합비가 90:10 내지 25:75로 포함하는 카본층을 형성하는 것을 특징으로 하는 전극체의 제조 방법.A method of manufacturing an electrode body used for a cathode of an electrolytic capacitor, comprising:
Graphite is a cathode foil made of a valve-acting metal, is in the form of flakes or flakes, has an aspect ratio between the minor axis and the major axis in the range of 1:5 to 1:100, and has an average particle size of 6 ㎛ or less in the particle size distribution. , A method for manufacturing an electrode body, comprising forming a carbon layer comprising spherical carbon, which is carbon black, with a BET specific surface area of 200 m2/g or less, and a mixing ratio of the graphite and the carbon black of 90:10 to 25:75. .
상기 카본층을, 상기 흑연과 상기 구상 탄소를 포함하는 슬러리를 음극박에 도포 및 건조 후, 압접하여 형성하는 것을 특징으로 하는 전극체의 제조 방법.According to clause 12,
A method of manufacturing an electrode body, characterized in that the carbon layer is formed by applying a slurry containing the graphite and the spherical carbon to a cathode foil, drying it, and then pressure-welding it.
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| JP2022039636A (en) * | 2020-08-28 | 2022-03-10 | 日本ケミコン株式会社 | Electrolytic capacitor and manufacturing method thereof |
| JP2022144278A (en) * | 2021-03-18 | 2022-10-03 | 日本ケミコン株式会社 | Solid electrolytic capacitor and method for manufacturing solid electrolytic capacitor |
| JP2023002276A (en) * | 2021-06-22 | 2023-01-10 | 日本ケミコン株式会社 | Electrolytic capacitor, cathode body, and manufacturing method for electrolytic capacitor |
| JP2023002273A (en) * | 2021-06-22 | 2023-01-10 | 日本ケミコン株式会社 | Electrolytic capacitor, cathode body, and manufacturing method for electrolytic capacitor |
| JP2023023117A (en) * | 2021-08-04 | 2023-02-16 | 日本ケミコン株式会社 | Electrolytic capacitor |
| TWI805224B (en) * | 2022-02-15 | 2023-06-11 | 中國鋼鐵股份有限公司 | Carbon material for energy storage, method for producing the same, electrode for supercapacitor and supercapacitor |
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