TW202416307A - Winding electrolytic capacitor - Google Patents
Winding electrolytic capacitor Download PDFInfo
- Publication number
- TW202416307A TW202416307A TW112111497A TW112111497A TW202416307A TW 202416307 A TW202416307 A TW 202416307A TW 112111497 A TW112111497 A TW 112111497A TW 112111497 A TW112111497 A TW 112111497A TW 202416307 A TW202416307 A TW 202416307A
- Authority
- TW
- Taiwan
- Prior art keywords
- foil
- anode foil
- cathode
- anode
- acid
- Prior art date
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Abstract
Description
本發明是有關於一種將陽極箔與陰極箔捲繞而成的捲繞型電解電容器。The present invention relates to a wound electrolytic capacitor formed by winding an anode foil and a cathode foil.
電解電容器是藉由靜電電容進行電荷的蓄電及放電的被動元件。電解電容器包括如鉭或鋁等般的閥作用金屬作為陽極箔及陰極箔。陽極箔及陰極箔是閥作用金屬的箔體。在陽極箔的箔表面形成有介電質氧化皮膜。在陽極箔與陰極箔之間介隔存在有電解液。Electrolytic capacitors are passive components that store and discharge electric charge by electrostatic capacitance. Electrolytic capacitors include valve metals such as tantalum or aluminum as anode foil and cathode foil. Anode foil and cathode foil are foil bodies of valve metal. A dielectric oxide film is formed on the foil surface of the anode foil. An electrolyte is interposed between the anode foil and the cathode foil.
電解液與陽極箔的介電質氧化皮膜密接,作為真正的陰極發揮功能。電解液與陽極箔的介電質氧化皮膜的接觸程度會對電解電容器的電容出現率帶來影響。電容出現率是電解電容器的實測靜電電容相對於理論靜電電容的比例(實測靜電電容/理論靜電電容×100)。The electrolyte is in close contact with the dielectric oxide film of the anode foil, and functions as a true cathode. The degree of contact between the electrolyte and the dielectric oxide film of the anode foil affects the capacitance appearance rate of the electrolytic capacitor. The capacitance appearance rate is the ratio of the measured electrostatic capacitance of the electrolytic capacitor to the theoretical electrostatic capacitance (measured electrostatic capacitance/theoretical electrostatic capacitance×100).
理論靜電電容是將電解電容器看作陽極側與陰極側串聯而成的電容器的合成靜電電容,可利用將陽極側靜電電容與陰極側靜電電容的相乘結果除以陽極側靜電電容與陰極側靜電電容之和的算出式((陽極側靜電電容×陰極側靜電電容)/(陽極側靜電電容+陰極側靜電電容))來獲得。Theoretical electrostatic capacitance is the resultant electrostatic capacitance when the electrolytic capacitor is regarded as a capacitor with the anode side and the cathode side connected in series. It can be obtained by dividing the product of the anode side electrostatic capacitance and the cathode side electrostatic capacitance by the sum of the anode side electrostatic capacitance and the cathode side electrostatic capacitance ((anode side electrostatic capacitance × cathode side electrostatic capacitance) / (anode side electrostatic capacitance + cathode side electrostatic capacitance)).
陽極側靜電電容與陰極側靜電電容是以如下方式進行測量,即:自箔切出規定面積的試驗片,在陽極側靜電電容中以鉑板作為相向電極,在陰極側靜電電容中使用兩張試驗片彼此作為相向電極,並浸漬於玻璃製的測定槽內的靜電電容測定液中,使用靜電電容計,按照日本電子資訊技術產業協會(Japan Electronic Information Technology Association,JEITA)標準RC-2364A進行測量。The anode side electrostatic capacitance and cathode side electrostatic capacitance are measured in the following manner: a test piece of a specified area is cut out from the foil, a platinum plate is used as an opposing electrode in the anode side electrostatic capacitance, and two test pieces are used as opposing electrodes in the cathode side electrostatic capacitance, and the test pieces are immersed in an electrostatic capacitance measurement solution in a glass measurement tank, and the measurement is performed using an electrostatic capacitance meter in accordance with the Japan Electronic Information Technology Association (JEITA) standard RC-2364A.
近年來,伴隨著巨量資料的活用等的伺服器電源的大輸出化或電波基站的大輸出化急速推進。電解電容器亦被要求高電容化的場景增多。陽極箔藉由將閥作用金屬製成燒結體或蝕刻箔等形狀而經擴面化,在經擴面化的表面形成介電質氧化皮膜。藉此,電解電容器能夠實現高電容化。In recent years, the high output of server power supplies and radio base stations has been rapidly advancing with the utilization of massive amounts of data. The number of scenarios where electrolytic capacitors are required to have higher capacitance has increased. The anode foil is expanded by forming a valve metal into a sintered body or an etched foil, and a dielectric oxide film is formed on the expanded surface. This allows electrolytic capacitors to have higher capacitance.
另外,伴隨設備的大輸出化,對電解電容器要求的耐電壓亦變高。為了提高電解液的火花電壓,在電解液中添加耐壓提高劑。作為耐壓提高劑,可列舉聚乙烯醇或聚乙二醇等聚合物系化合物、或者二氧化矽或氧化鋁等無機微粒子等(例如參照專利文獻1)。 [現有技術文獻] [專利文獻] In addition, as the output of equipment increases, the withstand voltage required of electrolytic capacitors also increases. In order to increase the spark voltage of the electrolyte, a withstand voltage enhancer is added to the electrolyte. Examples of withstand voltage enhancers include polymer compounds such as polyvinyl alcohol or polyethylene glycol, or inorganic microparticles such as silicon dioxide or aluminum oxide (for example, see Patent Document 1). [Prior Art Document] [Patent Document]
[專利文獻1]日本專利特開2011-176102號公報[Patent Document 1] Japanese Patent Publication No. 2011-176102
[發明所欲解決之課題][The problem that the invention wants to solve]
如此對電解電容器要求高電容化,本發明在於提供一種具有良好的電容出現率的電解電容器,以可實現更高電容化。 [解決課題之手段] As such, electrolytic capacitors are required to have higher capacitance, and the present invention provides an electrolytic capacitor with a good capacitance appearance rate so as to achieve higher capacitance. [Means for solving the problem]
為了解決所述課題,本實施方式的電解電容器包括具有介電質氧化皮膜的陽極箔、與所述陽極箔相向的陰極箔、介隔存在於所述陽極箔與所述陰極箔之間的隔板、捲繞有所述隔板、所述陽極箔及所述陰極箔的電容器元件、以及含浸於所述電容器元件中的電解液,所述電解液中包含聚氧乙烯甘油,所述陽極箔的沿著所述電容器元件的卷軸的帶寬超過37 mm。To solve the above-mentioned problem, the electrolytic capacitor of the present embodiment includes an anode foil having a dielectric oxide film, a cathode foil facing the anode foil, a separator interposed between the anode foil and the cathode foil, a capacitor element wound with the separator, the anode foil and the cathode foil, and an electrolyte impregnated in the capacitor element, wherein the electrolyte contains polyoxyethylene glycerol, and the strip width of the anode foil along the winding axis of the capacitor element exceeds 37 mm.
所述陽極箔的沿著所述電容器元件的卷軸的帶寬可為150 mm以下。The strip width of the anode foil along the winding axis of the capacitor element may be 150 mm or less.
所述隔板的平均密度可為0.85 g/cm 3以上。 The average density of the separator may be greater than 0.85 g/cm 3 .
所述陰極箔可包括積層於該陰極箔上的碳層。 [發明的效果] The cathode foil may include a carbon layer laminated on the cathode foil. [Effect of the invention]
根據本發明,電解電容器的電容出現率得到良好地維持,容易實現大電容化。According to the present invention, the capacitance appearance rate of the electrolytic capacitor is well maintained, and the capacitance can be easily increased.
電解電容器是藉由靜電電容進行電荷的蓄電及放電的被動元件。電解電容器包括隔著隔板使陽極箔與陰極箔相向的電容器元件。在陽極箔的箔表面形成有介電質氧化皮膜。該電容器元件包含電解液。電解液介隔存在於陽極箔與陰極箔之間,與陽極箔的介電質氧化皮膜密接,成為真正的陰極。An electrolytic capacitor is a passive element that stores and discharges electric charge by electrostatic capacitance. An electrolytic capacitor includes a capacitor element in which an anode foil and a cathode foil are placed opposite each other via a separator. A dielectric oxide film is formed on the foil surface of the anode foil. The capacitor element contains an electrolyte. The electrolyte exists between the anode foil and the cathode foil as a separator, and is in close contact with the dielectric oxide film of the anode foil, becoming a true cathode.
該電解電容器為捲繞型。電容器元件是將陽極箔與陰極箔呈螺旋狀捲入而構成。陽極箔與陰極箔是以閥作用金屬為材料的長條的箔體。電容器元件的卷軸與陽極箔及陰極箔的短邊的延伸方向、即帶寬方向一致。陽極箔與陰極箔具有沿著短邊延伸的卷軸,以長邊被弄圓的方式沿著長邊方向捲入,從而形成電容器元件。The electrolytic capacitor is of a wound type. The capacitor element is formed by spirally winding an anode foil and a cathode foil. The anode foil and the cathode foil are long foil bodies made of valve-acting metal. The winding axis of the capacitor element is consistent with the extension direction of the short sides of the anode foil and the cathode foil, that is, the width direction. The anode foil and the cathode foil have a winding axis extending along the short sides, and are wound along the long side direction in a manner that the long sides are rounded, thereby forming a capacitor element.
陽極箔的短邊、即沿著電容器元件的卷軸的帶寬超過37 mm。陰極箔的短邊較佳為與陽極箔的短邊為相同長度或為相同長度以上,以便無法在陽極箔形成與陰極箔非相向的區域。關於陰極箔的長邊,亦較佳為與陽極箔的長邊為相同長度或為相同長度以上,以便無法在陽極箔形成與陰極箔非相向的區域。隔板較佳為較陽極箔及陰極箔的長邊長,以便可先行捲繞而形成卷軸。The short side of the anode foil, i.e., the width of the strip along the winding axis of the capacitor element, exceeds 37 mm. The short side of the cathode foil is preferably the same length as or longer than the short side of the anode foil so that no area that is not facing the cathode foil can be formed on the anode foil. As for the long side of the cathode foil, it is also preferably the same length as or longer than the long side of the anode foil so that no area that is not facing the cathode foil can be formed on the anode foil. The separator is preferably longer than the long sides of the anode foil and the cathode foil so that it can be wound up first to form a winding axis.
在使電解液含浸於電容器元件中時,電解液自與電容器元件的周面正交且平坦的端面朝向電容器元件的中心方向浸透。在電解液的含浸步驟中,根據需要施加減壓處理或加壓處理。含浸於電容器元件中的電解液中含有聚氧乙烯甘油(以下稱為POEG(polyoxyethylene glycerin))。POEG與聚乙烯醇或聚乙二醇相同,原本作為耐壓提高劑發揮功能。When the electrolyte is impregnated into the capacitor element, the electrolyte penetrates from the flat end surface perpendicular to the peripheral surface of the capacitor element toward the center of the capacitor element. In the electrolyte impregnation step, a pressure reduction treatment or a pressure increase treatment is applied as needed. The electrolyte impregnated into the capacitor element contains polyoxyethylene glycerin (hereinafter referred to as POEG (polyoxyethylene glycerin)). POEG, like polyvinyl alcohol or polyethylene glycol, originally functions as a withstand voltage enhancer.
該電解電容器滿足電容器元件為捲繞型、陽極箔的卷軸方向上的長度超過37 mm、及電解液中包含POEG此三個條件。當將該些結構組合時,與其他結構相比,電解電容器的電容出現率相對變得良好,容易使電解電容器大電容化。再者,作為其他結構,雖然為捲繞型,但陽極箔的卷軸方向上的長度為27 mm以上且80 mm的範圍,以電解液中含有POEG以外的耐壓提高劑的電解電容器為比較對象。The electrolytic capacitor satisfies three conditions: the capacitor element is a winding type, the length of the anode foil in the winding direction exceeds 37 mm, and the electrolyte contains POEG. When these structures are combined, the capacitance appearance rate of the electrolytic capacitor becomes relatively good compared with other structures, and it is easy to make the electrolytic capacitor large in capacitance. Furthermore, as another structure, although it is a winding type, the length of the anode foil in the winding direction is greater than 27 mm and within the range of 80 mm, and the electrolyte contains a voltage-resistant improver other than POEG as a comparison object.
陽極箔的沿著卷軸的帶寬較佳為70 mm以下。藉由至70 mm為止滿足為捲繞型、使陽極箔的卷軸方向上的長度超過37 mm、及電解液中包含POEG此三個條件,與其他結構相比,電解電容器的電容出現率亦維持高而為超過95%。The width of the anode foil along the winding axis is preferably 70 mm or less. By satisfying the three conditions of being wound to 70 mm, making the length of the anode foil in the winding axis direction exceed 37 mm, and containing POEG in the electrolyte, the capacitance appearance rate of the electrolytic capacitor is also maintained high and exceeds 95% compared with other structures.
另外,陽極箔的沿著卷軸的帶寬較佳為超過70 mm。雖然為捲繞型,但陽極箔的卷軸方向上的長度為超過70 mm的範圍,電解液中含有POEG以外的耐壓提高劑的電解電容器的電容出現率會顯著降低。然而,藉由滿足陽極箔的卷軸方向的長度超過70 mm、且為捲繞型、及電解液中包含POEG此三個條件,電解電容器的電容出現率的降低得到抑制,與在電解液中含有POEG以外的耐壓提高劑的電解電容器相比,電容出現率更有優勢。In addition, the strip width of the anode foil along the winding axis is preferably more than 70 mm. Although it is a wound type, if the length of the anode foil in the winding axis direction is more than 70 mm, the capacitance appearance rate of the electrolytic capacitor containing a voltage-resistant enhancer other than POEG in the electrolyte will be significantly reduced. However, by satisfying the three conditions that the length of the anode foil in the winding axis direction exceeds 70 mm, it is a wound type, and POEG is contained in the electrolyte, the decrease in the capacitance appearance rate of the electrolytic capacitor is suppressed, and the capacitance appearance rate is more advantageous than that of the electrolytic capacitor containing a voltage-resistant enhancer other than POEG in the electrolyte.
此處,在日本工業標準(Japanese Industrial Standards,JIS)標準(JIS C 5101-4-1)中,靜電電容的容許誤差被規定為較佳為±20%。在符合該規定的情況下,關於陽極箔的沿著卷軸的帶寬的上限,較佳為150 mm以下。陽極箔的卷軸方向上的長度為150 mm以下的電解電容器進一步為捲繞型,若電解液中包含POEG,則可簡便地達成80%的電容維持率。Here, in the Japanese Industrial Standards (JIS) standard (JIS C 5101-4-1), the permissible error of electrostatic capacitance is preferably specified as ±20%. In compliance with this specification, the upper limit of the width of the anode foil along the winding axis is preferably 150 mm or less. If the length of the anode foil in the winding axis direction is 150 mm or less and the electrolytic capacitor is further a wound type, a capacitance retention rate of 80% can be easily achieved if POEG is included in the electrolyte.
電解液自與電容器元件的周面正交的平坦的端面朝向電容器元件的中心方向浸透,並滲入至隔板而得到保持。隔板的平均密度較佳為0.85 g/cm 3以上。當電解電容器滿足為捲繞型、使陽極箔的卷軸方向上的長度超過37 mm、及電解液中包含POEG此三個條件,則即便提高隔板的密度,電容出現率亦保持得高。 The electrolyte penetrates from the flat end surface perpendicular to the peripheral surface of the capacitor element toward the center of the capacitor element and is maintained by infiltrating the separator. The average density of the separator is preferably above 0.85 g/ cm3 . When the electrolytic capacitor meets the three conditions of being a winding type, making the length of the anode foil in the winding direction exceed 37 mm, and containing POEG in the electrolyte, the capacitance appearance rate is maintained high even if the density of the separator is increased.
若可使隔板薄壁化,則可延長能夠捲繞於一定外徑的電容器元件的陽極箔及陰極箔的帶長。若可延長陽極箔及陰極箔的帶長,則電極面積變大。藉由滿足三個條件而達成的高電容出現率與利用隔板的薄壁化達成的大電極面積相互作用,而使該電解電容器的靜電電容進一步增大。If the separator can be made thinner, the length of the anode foil and cathode foil that can be wound around a capacitor element with a certain outer diameter can be extended. If the length of the anode foil and cathode foil can be extended, the electrode area becomes larger. The high capacitance appearance rate achieved by satisfying the three conditions and the large electrode area achieved by thinning the separator interact with each other, further increasing the electrostatic capacitance of the electrolytic capacitor.
再者,POEG較佳為在常溫下為液體狀態。若POEG的分子量例如為1000左右,則POEG在常溫下為液體狀態。於將POEG在常溫下設為固體狀態的情況下,可藉由利用加熱使POEG溶解於溶液中而添加至電解液中。但是,關於常溫下為液體狀態的POEG,即便溶媒經時性地揮發亦不易析出,從而良好地保持電解電容器的靜電電容。Furthermore, POEG is preferably in a liquid state at room temperature. If the molecular weight of POEG is, for example, about 1000, POEG is in a liquid state at room temperature. When POEG is in a solid state at room temperature, it can be dissolved in a solution by heating and added to an electrolyte. However, POEG in a liquid state at room temperature is not easily precipitated even if the solvent evaporates over time, thereby maintaining the electrostatic capacitance of the electrolytic capacitor well.
在此種電解電容器中,陽極箔、陰極箔、電解液及隔板可應用公知者,並無特別限定。In such an electrolytic capacitor, the anode foil, cathode foil, electrolyte and separator can be any known ones and are not particularly limited.
例如,陽極箔及陰極箔中使用的閥作用金屬為鋁、鉭、鈮、鈦、鉿、鋯、鋅、鎢、鉍及銻等。理想的是純度高,但亦可包含矽、鐵、銅、鎂、鋅等雜質。For example, valve metals used in anode foil and cathode foil are aluminum, tantalum, niobium, titanium, uranium, zirconium, zinc, tungsten, bismuth, and antimony. They are ideally of high purity, but may contain impurities such as silicon, iron, copper, magnesium, and zinc.
形成於陽極箔及陰極箔的擴面層是對閥作用金屬的粉體進行燒結而成的燒結體、或對經延伸的箔實施了蝕刻處理而成的蝕刻層,且包含隧道狀的坑(pit)、海綿狀的坑、或密集的粉體間的空隙。隧道狀的坑可貫穿設置於箔。介電質氧化皮膜典型而言為形成於陽極箔的表層的氧化皮膜,若陽極箔為鋁製,則為使擴面層的表面氧化而成的氧化鋁層。陰極箔可具有自然氧化皮膜,亦可藉由化學合成處理形成薄的介電質氧化皮膜(1 V~10 V左右)。The diffusion layer formed on the anode foil and cathode foil is a sintered body formed by sintering the powder of the valve metal, or an etched layer formed by etching the stretched foil, and includes tunnel-shaped pits, sponge-shaped pits, or gaps between dense powders. The tunnel-shaped pits can be set through the foil. The dielectric oxide film is typically an oxide film formed on the surface of the anode foil. If the anode foil is made of aluminum, it is an aluminum oxide layer formed by oxidizing the surface of the diffusion layer. The cathode foil can have a natural oxide film, or a thin dielectric oxide film (about 1 V to 10 V) can be formed by chemical synthesis.
在陰極箔的表面可形成包含碳原材料作為主要材料的碳層。即,陰極側亦可為該陰極箔與碳層積層而成的陰極箔。在陰極箔積層有碳層、陰極側為陰極體、與本電解電容器的三個條件相互作用,以如下方式達成電解電容器的大電容化。A carbon layer containing a carbon raw material as a main material may be formed on the surface of the cathode foil. That is, the cathode side may also be a cathode foil formed by laminating the cathode foil and the carbon layer. The three conditions of the cathode foil being laminated, the cathode side being a cathode body, and the present electrolytic capacitor interact with each other to achieve a large capacitance of the electrolytic capacitor in the following manner.
即,當碳層積層於陰極箔上時,電解電容器內的氫氣產生總量得到抑制。推測氫氣產生總量得到抑制的理由在於,在陰極溶解氧的還原反應較氫離子的還原反應更有優勢。若可利用陰極側的措施抑制氫氣產生總量,則對成為氫氣產生機制的開端的介電質氧化皮膜進行修復時的漏電流的增加多少得到容許。That is, when the carbon layer is deposited on the cathode foil, the total amount of hydrogen gas generated in the electrolytic capacitor is suppressed. The reason why the total amount of hydrogen gas generated is suppressed is presumed to be that the reduction reaction of dissolved oxygen in the cathode is more advantageous than the reduction reaction of hydrogen ions. If the total amount of hydrogen gas generated can be suppressed by measures on the cathode side, the increase in leakage current when repairing the dielectric oxide film that is the start of the hydrogen gas generation mechanism can be tolerated to some extent.
若容許漏電流的增加,則能夠實現降低陽極箔的耐電壓的介電質氧化皮膜的薄壁化。當介電質氧化皮膜經薄壁化時,極間距離變窄,電解電容器的電容提高標準。因此,當在陰極箔積層碳層時,電容出現率的增加與電容的提高標準相互作用,從而達成電解電容器的大電容化。If the leakage current is allowed to increase, the dielectric oxide film can be thinned to reduce the withstand voltage of the anode foil. When the dielectric oxide film is thinned, the distance between the electrodes becomes narrower, and the capacitance of the electrolytic capacitor is improved. Therefore, when a carbon layer is stacked on the cathode foil, the increase in the capacitance appearance rate and the increase in the capacitance interact with each other, thereby achieving a larger capacitance of the electrolytic capacitor.
碳層中含有的碳原材料為石墨、碳黑、活性炭、碳奈米角、纖維狀碳或該些的混合。作為石墨,可列舉天然石墨、人造石墨、石墨化科琴黑等。作為碳黑,可列舉科琴黑、乙炔黑、槽黑及熱碳黑等。活性炭以椰子殼等天然植物組織、苯酚等合成樹脂、煤炭、焦炭、瀝青等源自化石燃料者為原料。作為纖維狀碳,可列舉碳奈米管(以下,為CNT(carbon nanotube))、碳奈米纖維(以下,為CNF(carbon nanofiber))等。The carbon raw materials contained in the carbon layer are graphite, carbon black, activated carbon, carbon nanotubes, fibrous carbon or a mixture of these. Examples of graphite include natural graphite, artificial graphite, graphitized Ketjen black, etc. Examples of carbon black include Ketjen black, acetylene black, channel black, and thermal black, etc. Activated carbon is made from natural plant tissues such as coconut shells, synthetic resins such as phenol, coal, coke, asphalt, etc., which are derived from fossil fuels. Examples of fibrous carbon include carbon nanotubes (hereinafter referred to as CNT (carbon nanotube)), carbon nanofibers (hereinafter referred to as CNF (carbon nanofiber)), etc.
關於活性炭或纖維狀碳,由於π電子非定域化,比表面積大,因此作為碳層中含有的碳原材料而言較佳。亦可對碳原材料實施活化處理或開口處理等多孔質化處理。Activated carbon or fibrous carbon is preferred as a carbon material to be contained in the carbon layer because of its large specific surface area due to the delocalization of π electrons. The carbon material may be subjected to a porosity treatment such as activation treatment or opening treatment.
為了提高碳層與陰極箔的密接性,亦可在陰極箔的表面形成擴面層,在擴面層上形成碳層。另外,為了提高碳層與陰極箔的密接性,較佳為對形成有碳層的陰極箔進行壓製加工。在壓製加工中,例如利用壓製輥夾持碳層與陰極箔,施加壓製線壓。壓製壓力理想的是0.01 t/cm~100 t/cm左右。當碳層與陰極箔經壓接時,碳原材料進入擴面層的細孔中,另外碳原材料沿著擴面層的凹凸面變形,碳層與陰極箔的密接性及固著性進一步提高。In order to improve the adhesion between the carbon layer and the cathode foil, a diffusion layer may be formed on the surface of the cathode foil, and the carbon layer may be formed on the diffusion layer. In addition, in order to improve the adhesion between the carbon layer and the cathode foil, it is preferred to perform a press process on the cathode foil formed with the carbon layer. During the press process, for example, the carbon layer and the cathode foil are clamped by a pressing roller, and a pressing line pressure is applied. The pressing pressure is ideally about 0.01 t/cm to 100 t/cm. When the carbon layer and the cathode foil are pressed, the carbon raw material enters the pores of the diffusion layer, and the carbon raw material is deformed along the concave and convex surface of the diffusion layer, and the adhesion and fixation between the carbon layer and the cathode foil are further improved.
碳層中含有的碳原材料並無特別限定,但作為球狀碳的碳黑亦較佳。在形成於陰極箔的表面的擴面層為蝕刻坑的情況下,當使用粒徑較蝕刻坑的開口直徑小的碳黑時,容易進入蝕刻坑的更深部,使得碳層與陰極箔密接。The carbon raw material contained in the carbon layer is not particularly limited, but carbon black as spherical carbon is also preferred. When the expansion layer formed on the surface of the cathode foil is an etched pit, when using carbon black with a smaller particle size than the opening diameter of the etched pit, it is easy to enter the deeper part of the etched pit, so that the carbon layer and the cathode foil are in close contact.
另外,碳層中含有的碳原材料亦可為鱗片狀或鱗狀的石墨與作為球狀碳的碳黑。鱗片狀或鱗狀的石墨較佳為短徑與長徑的縱橫比為1:5~1:100的範圍。作為球狀碳的碳黑較佳為一次粒徑為平均100 nm以下。在將含有該組合的碳原材料的碳層積層於陰極箔的情況下,碳黑容易藉由石墨研碎混入至擴面層的細孔中。石墨容易沿著擴面層的凹凸面變形,容易積層於凹凸面上。並且,石墨成為按壓蓋而阻止研碎混入至細孔中的球狀碳。因此,碳層與陰極箔的密接性及固著性進一步提高。In addition, the carbon raw material contained in the carbon layer may also be flaky or scaly graphite and carbon black as spherical carbon. The flaky or scaly graphite preferably has an aspect ratio of the short diameter to the long diameter in the range of 1:5 to 1:100. The carbon black as spherical carbon preferably has an average primary particle size of 100 nm or less. When the carbon layer containing the carbon raw material of this combination is stacked on the cathode foil, the carbon black is easily ground into the pores of the diffusion layer by the graphite. Graphite is easily deformed along the concave and convex surface of the diffusion layer and is easily stacked on the concave and convex surface. In addition, the graphite becomes a pressing cover to prevent the spherical carbon from being ground and mixed into the pores. Therefore, the adhesion and fixation between the carbon layer and the cathode foil are further improved.
電解液除含有POEG以外,亦含有陰離子成分及陽離子成分。作為電解液的溶媒,可列舉質子性的有機極性溶媒或非質子性的有機極性溶媒,可單獨使用或組合兩種以上。關於質子性的有機極性溶媒,可列舉一元醇類、多元醇類及含氧醇化合物類等,例如為乙二醇、丙二醇或甘油等。關於非質子性的有機極性溶媒,可列舉碸系、醯胺系、內酯系、環狀醯胺系、腈系、亞碸系等作為代表,例如為γ-丁內酯、碳酸伸乙酯、碳酸伸丙酯、乙腈等。In addition to POEG, the electrolyte also contains anionic components and cationic components. As the solvent of the electrolyte, protic organic polar solvents or non-protic organic polar solvents can be listed, and they can be used alone or in combination of two or more. Regarding protic organic polar solvents, monohydric alcohols, polyhydric alcohols and oxygen-containing alcohol compounds can be listed, such as ethylene glycol, propylene glycol or glycerol. Regarding non-protic organic polar solvents, sulfone series, amide series, lactone series, cyclic amide series, nitrile series, sulfone series, etc. can be listed as representatives, such as γ-butyrolactone, ethyl carbonate, propyl carbonate, acetonitrile, etc.
作為成為陰離子成分的有機酸,可列舉:草酸、琥珀酸、戊二酸、庚二酸、辛二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、馬來酸、己二酸、苯甲酸、甲苯酸(toluic acid)、庚酸(enanthic acid)、丙二酸、1,6-癸烷二羧酸、1,7-辛烷二羧酸、壬二酸、間苯二酚酸、2,4,6-三羥基苯甲酸(phloroglucinic acid)、沒食子酸、龍膽酸(gentisic acid)、原兒茶酸(protocatechuic acid)、兒茶酚甲酸(pyrocatechuic acid)、偏苯三甲酸、均苯四甲酸等羧酸、或酚類、磺酸。另外,作為成為陰離子成分的無機酸,可列舉:硼酸、磷酸、亞磷酸、次磷酸、碳酸、矽酸等。作為成為陰離子成分的有機酸與無機酸的複合化合物,可列舉:硼合二水楊酸、硼合二草酸、硼合二甘醇酸、硼合二丙二酸、硼合二琥珀酸、硼合二己二酸、硼合二壬二酸、硼合二苯甲酸、硼合二馬來酸、硼合二乳酸、硼合二蘋果酸、硼合二酒石酸、硼合二檸檬酸、硼合二鄰苯二甲酸、硼合二(2-羥基)異丁酸、硼合二間苯二酚酸、硼合二甲基水楊酸、硼合二萘甲酸、硼合二苦杏仁酸及硼合二(3-羥基)丙酸等。Examples of organic acids that serve as anionic components include carboxylic acids such as oxalic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, benzoic acid, toluic acid, enanthic acid, malonic acid, 1,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, azelaic acid, resorcinolic acid, 2,4,6-trihydroxybenzoic acid (phloroglucinic acid), gallic acid, gentisic acid, protocatechuic acid, pyrocatechuic acid, trimellitic acid, and pyromellitic acid, or phenols and sulfonic acids. In addition, examples of inorganic acids that serve as anionic components include boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, and silicic acid. Examples of complex compounds of organic acids and inorganic acids that serve as anionic components include borodihydroxysalicylic acid, borodioxalic acid, borodiglycolic acid, borodimalonic acid, borodisucinic acid, borodiadipic acid, borodiazelaic acid, borodibenzoic acid, borodimaleic acid, borodilactic acid, borodimalic acid, boroditartaric acid, borodicitric acid, borodiphthalic acid, borodi(2-hydroxy)isobutyric acid, borodiresorcinolic acid, borodimethylsalicylic acid, borodinaphthoic acid, borodimandelic acid, and borodi(3-hydroxy)propionic acid.
另外,作為有機酸、無機酸以及有機酸與無機酸的複合化合物的至少一種的鹽,例如可列舉銨鹽、四級銨鹽、四級化脒鹽、胺鹽、鈉鹽、鉀鹽等。作為四級銨鹽的四級銨離子,可列舉四甲基銨、三乙基甲基銨、四乙基銨等。作為四級化脒鹽,可列舉乙基二甲基咪唑鎓、四甲基咪唑鎓等。作為胺鹽,可列舉一級胺、二級胺、三級胺的鹽。作為一級胺,可列舉甲胺、乙胺、丙胺等,作為二級胺,可列舉二甲胺、二乙胺、乙基甲胺、二丁胺等,作為三級胺,可列舉三甲胺、三乙胺、三丁胺、乙基二甲胺、乙基二異丙胺等。In addition, as salts of at least one of organic acids, inorganic acids, and complex compounds of organic acids and inorganic acids, for example, ammonium salts, quaternary ammonium salts, quaternary amidine salts, amine salts, sodium salts, potassium salts, etc. can be listed. As quaternary ammonium ions of quaternary ammonium salts, tetramethylammonium, triethylmethylammonium, tetraethylammonium, etc. can be listed. As quaternary amidine salts, ethyldimethylimidazolium, tetramethylimidazolium, etc. can be listed. As amine salts, salts of primary amines, secondary amines, and tertiary amines can be listed. Examples of the primary amine include methylamine, ethylamine, and propylamine, examples of the secondary amine include dimethylamine, diethylamine, ethylmethylamine, and dibutylamine, and examples of the tertiary amine include trimethylamine, triethylamine, tributylamine, ethyldimethylamine, and ethyldiisopropylamine.
亦可在電解液中添加其他添加劑。作為添加劑,可列舉包含磷酸的磷酸化合物、包含硼酸的硼酸化合物、硼酸與甘露醇或山梨糖醇等糖醇的錯合物、膠體二氧化矽及矽油等。Other additives may be added to the electrolyte. Examples of the additives include phosphoric acid compounds including phosphoric acid, boric acid compounds including boric acid, complexes of boric acid and sugar alcohols such as mannitol or sorbitol, colloidal silicon dioxide, and silicone oil.
作為電解質,除電解液以外,亦可併用固體電解質。固體電解質例如為導電性高分子。導電性高分子是由分子內的摻雜劑分子摻雜的自摻雜型或由外部摻雜劑分子摻雜的共軛系高分子。共軛系高分子是藉由對具有π共軛雙鍵的單體或其衍生物進行化學氧化聚合或電解氧化聚合而獲得。共軛系高分子或摻雜劑可並無特別限定地使用公知者。As an electrolyte, a solid electrolyte may be used in addition to an electrolyte solution. The solid electrolyte is, for example, a conductive polymer. The conductive polymer is a self-doped polymer doped with a dopant molecule within the molecule or a conjugated polymer doped with an external dopant molecule. The conjugated polymer is obtained by chemical oxidation polymerization or electrolytic oxidation polymerization of a monomer having a π-conjugated double bond or a derivative thereof. The conjugated polymer or dopant may be a known one without particular limitation.
作為導電性高分子,特佳為摻雜有被稱為PSS(polystyrene sulfonate)的聚苯乙烯磺酸的被稱為PEDOT(Poly(3,4-ethylenedioxythiophene))的聚(3,4-伸乙基二氧噻吩)。固體電解質是藉由將電容器元件浸漬於固體電解質分散在溶媒中而成的分散液中並使其乾燥而形成。可將陽極箔、陰極箔及隔板在裝配前分別浸漬於分散液中,亦可進行滴加塗佈、噴塗等。電解液只要於在電容器元件形成有固體電解質的層後,含浸於電容器元件中即可。As a conductive polymer, poly(3,4-ethylenedioxythiophene) called PEDOT (Poly(3,4-ethylenedioxythiophene)) doped with polystyrene sulfonic acid called PSS (polystyrene sulfonate) is particularly preferred. The solid electrolyte is formed by immersing the capacitor element in a dispersion in which the solid electrolyte is dispersed in a solvent and drying it. The anode foil, cathode foil and separator can be immersed in the dispersion before assembly, or they can be dripped, sprayed, etc. The electrolyte can be impregnated in the capacitor element after the solid electrolyte layer is formed in the capacitor element.
為了防止陽極箔與陰極箔或陰極體的短路,隔板介隔存在於陽極箔與陰極箔之間並保持電解液。隔板可列舉牛皮紙、馬尼拉麻(Manila hemp)、西班牙草(esparto)、麻(hemp)、嫘縈等纖維素及該些的混合紙、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、該些的衍生物等聚酯系樹脂、聚四氟乙烯系樹脂、聚偏二氟乙烯系樹脂、維尼綸(vinylon)系樹脂、脂肪族聚醯胺、半芳香族聚醯胺、全芳香族聚醯胺等聚醯胺系樹脂、聚醯亞胺系樹脂、聚乙烯樹脂、聚丙烯樹脂、三甲基戊烯樹脂、聚苯硫醚樹脂、丙烯酸樹脂等,該些樹脂可單獨使用或者混合使用,且可與纖維素混合使用。In order to prevent short circuit between the anode foil and the cathode foil or the cathode body, a separator is interposed between the anode foil and the cathode foil and retains the electrolyte. Examples of the partition include kraft paper, Manila hemp, esparto, hemp, rayon and other cellulose and mixed papers thereof, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and derivatives thereof, polytetrafluoroethylene resins, polyvinylidene fluoride resins, vinylon resins, aliphatic polyamides, semi-aromatic polyamides, wholly aromatic polyamides and other polyamide resins, polyimide resins, polyethylene resins, polypropylene resins, trimethylpentene resins, polyphenylene sulfide resins, acrylic resins and the like. These resins can be used alone or in combination and can be mixed with cellulose.
此處,對於電解電容器,除要求高耐電壓以外,亦要求高電容化。為了實現高電容化,除陽極箔的擴面化以外,亦需要增大陽極箔。因此,電解電容器的沿著電容器元件的卷軸的帶寬存在變大的傾向。在伺服器電源中,供配置電解電容器的框體小型化,伴隨於此,搭載於框體的電解電容器亦被要求薄型化或基板中的專用面積的減少。因此,出於薄型化的目的而橫向配置電解電容器逐漸成為主流,為了使該電解電容器高電容化,延長製品成為必然。另外,與並列使用多個長度短的電解電容器相比,要求延長電解電容器的長度以確保靜電電容,減少所搭載的電解電容器的個數。Here, in addition to requiring high withstand voltage, electrolytic capacitors are also required to have high capacitance. In order to achieve high capacitance, in addition to expanding the area of the anode foil, the anode foil also needs to be enlarged. Therefore, the band width of the electrolytic capacitor along the winding axis of the capacitor element tends to increase. In server power supplies, the frame for configuring electrolytic capacitors is miniaturized, and along with this, the electrolytic capacitors mounted on the frame are also required to be thinner or the dedicated area on the substrate is reduced. Therefore, horizontally configuring electrolytic capacitors for the purpose of thinning has gradually become the mainstream, and in order to increase the capacitance of the electrolytic capacitor, it is inevitable to extend the product. In addition, compared with using a plurality of short electrolytic capacitors in parallel, it is required to extend the length of the electrolytic capacitor to ensure the electrostatic capacitance and reduce the number of electrolytic capacitors to be mounted.
相對於此,關於本實施方式的電解電容器,即便電容器元件的卷軸方向被延長,亦可將電容出現率保持得高。因此,具有相對於外徑而言卷軸方向長的細長電容器元件,可推進與安裝基板的擴展垂直的方向上的薄型化,較佳作為橫置用途。另外,由於能夠實現電解電容器的大電容化,因此可減少所搭載的電解電容器的個數。 [實施例] In contrast, the electrolytic capacitor of the present embodiment can maintain a high capacitance appearance rate even if the winding direction of the capacitor element is extended. Therefore, a thin and long capacitor element that is long in the winding direction relative to the outer diameter can promote thinning in a direction perpendicular to the expansion of the mounting substrate, and is preferably used for horizontal placement. In addition, since the capacitance of the electrolytic capacitor can be increased, the number of electrolytic capacitors mounted can be reduced. [Example]
以下,基於實施例對該電解電容器進一步進行詳細說明。再者,本發明並不限定於下述實施例。The electrolytic capacitor is further described in detail below based on the embodiments. Furthermore, the present invention is not limited to the following embodiments.
以如下方式製作了各參考例、各實施例及各比較例的電解電容器。使用帶狀的鋁箔作為陽極箔。陰極側作為積層有陰極箔與碳層而成的陰極體,陰極箔與陽極箔相同地使用帶狀的鋁箔。Electrolytic capacitors of each reference example, each embodiment, and each comparative example were produced as follows. A strip of aluminum foil was used as the anode foil. The cathode side was a cathode body formed by laminating cathode foil and carbon layer, and the cathode foil was a strip of aluminum foil similar to the anode foil.
對陽極側的鋁箔實施直流蝕刻處理,形成包含隧道狀的蝕刻坑的擴面層。在直流蝕刻處理中,使用形成坑的第一步驟與擴大坑的第二步驟,第一步驟是在包含氯離子的水溶液中以直流電流電化學地對鋁箔進行蝕刻處理。The aluminum foil on the anode side is subjected to a direct current etching process to form an expanded surface layer including tunnel-shaped etched pits. In the direct current etching process, a first step of forming pits and a second step of expanding the pits are used. The first step is to electrochemically etch the aluminum foil with a direct current in an aqueous solution containing chlorine ions.
在形成擴面層後,對陽極箔進行在擴面層表面形成介電質氧化皮膜的化學合成處理。具體而言,在液溫85℃、4 wt%的硼酸的化學合成溶液中施加650 V的電壓。After the expansion layer is formed, the anode foil is subjected to a chemical synthesis treatment to form a dielectric oxide film on the surface of the expansion layer. Specifically, a voltage of 650 V is applied in a chemical synthesis solution of 4 wt% boric acid at a liquid temperature of 85°C.
對陰極側的鋁箔實施交流蝕刻處理,在箔兩面形成包含海綿狀的蝕刻坑的擴面層。接著,對鋁箔實施化學合成處理,在擴面層的表面形成氧化皮膜。在化學合成處理中,在利用磷酸水溶液將進行交流蝕刻處理時附著的氯去除後,在磷酸二氫銨的水溶液內施加電壓。The aluminum foil on the cathode side is subjected to AC etching to form a diffusion layer containing sponge-like etching pits on both sides of the foil. Next, the aluminum foil is subjected to chemical synthesis to form an oxide film on the surface of the diffusion layer. In the chemical synthesis, chlorine attached during the AC etching treatment is removed with a phosphoric acid aqueous solution, and then a voltage is applied to an aqueous solution of ammonium dihydrogen phosphate.
在積層於陰極箔的碳層中含有碳黑作為碳原材料。首先,將碳黑的粉末、作為黏合劑的苯乙烯丁二烯橡膠(styrene butadiene rubber,SBR)、及作為含分散劑的水溶液的羧甲基纖維素銨(CMC(carboxymethyl cellulose)-NH 3)水溶液加以混合並進行混煉,藉此製作漿料。 The carbon layer laminated on the cathode foil contains carbon black as a carbon raw material. First, carbon black powder, styrene butadiene rubber (SBR) as a binder, and carboxymethyl cellulose ammonium (CMC (carboxymethyl cellulose)-NH 3 ) aqueous solution as an aqueous solution containing a dispersant are mixed and kneaded to prepare slurry.
將該漿料均勻地塗佈於陰極箔。在對漿料進行加熱乾燥而使溶媒揮發後,對陰極箔實施壓製加工。在壓製加工中,利用壓製輥夾入陰極箔,施加5.38 kN/cm的壓製線壓,使碳層固著於陰極箔上。The slurry is evenly applied to the cathode foil. After the slurry is heated and dried to volatilize the solvent, the cathode foil is pressed. During the pressing process, the cathode foil is sandwiched by pressing rolls and a pressing linear pressure of 5.38 kN/cm is applied to fix the carbon layer on the cathode foil.
作為隔板,將密度不同的隔板加以重疊而使用。具體而言,將包含密度0.85 g/cm 3、厚度15 μm的牛皮紙的隔板與密度0.95 g/cm 3、厚度25 μm的牛皮紙的隔板加以重疊而使用。電解液在包含耐壓提高劑的同時,亦包含乙二醇作為溶媒,包含壬二酸乙胺作為溶質。藉由在陽極箔與陰極箔之間夾著隔板進行捲繞而製作電容器元件,將電容器元件浸漬於電解液中,自電容器元件的兩端面方向含浸電解液。 As separators, separators with different densities are stacked and used. Specifically, a separator comprising kraft paper with a density of 0.85 g/cm 3 and a thickness of 15 μm and a separator comprising kraft paper with a density of 0.95 g/cm 3 and a thickness of 25 μm are stacked and used. The electrolyte contains a withstand voltage enhancer, ethylene glycol as a solvent, and ethylamine azelaic acid as a solute. The capacitor element is made by winding the separator between the anode foil and the cathode foil, and the capacitor element is immersed in the electrolyte, and the electrolyte is impregnated from both end faces of the capacitor element.
在陽極箔與陰極箔藉由冷壓焊法連接有鋁製的箔狀的引出端子。含浸有電解液後,將自電容器元件導出的引出端子連接於安裝在包含苯酚積層板的封口體的外部端子。之後,將電容器元件收容於鋁製的殼體中,利用封口體密封殼體的開口。利用封口體進行密封後,對電解電容器實施老化處理。老化處理是在常溫(30℃)下施加90分鐘的490 V的電壓。The anode foil and cathode foil are connected to an aluminum foil lead terminal by cold pressure welding. After being impregnated with electrolyte, the lead terminal from the capacitor element is connected to the external terminal mounted on the sealing body containing the phenol laminate. After that, the capacitor element is housed in an aluminum casing, and the opening of the casing is sealed with the sealing body. After sealing with the sealing body, the electrolytic capacitor is subjected to aging treatment. The aging treatment is to apply a voltage of 490 V for 90 minutes at room temperature (30°C).
各參考例、各實施例及各比較例中,電解液中包含的耐壓提高劑的種類與陽極箔的帶寬不同。將各參考例、各實施例及比較例的差異示於以下表1中。再者,陽極箔與陰極箔為相同長度,代表性地僅記載有陽極箔。In each reference example, each embodiment, and each comparative example, the type of withstand voltage enhancer contained in the electrolyte and the width of the anode foil are different. The differences among each reference example, each embodiment, and comparative example are shown in the following Table 1. In addition, the anode foil and the cathode foil have the same length, and only the anode foil is representatively shown.
(表1)
如表1所示,在參考例1及參考例3以及實施例1至實施例6中,電解液中包含POEG作為耐壓提高劑。表1中,環氧丙烷&環氧乙烷(propylene oxideðylene oxide,PO&EO)加成甘油是在甘油的兩個羥基位置加成有環氧丙烷的聚合物(PO)與環氧乙烷的聚合物(EO)而成的甘油衍生物。在參考例2及參考例4以及比較例1至比較例6中,電解液中包含PO&EO加成甘油作為耐壓提高劑。添加至電解液中的耐電壓提高劑的濃度在各參考例、各實施例及各比較例中相同。As shown in Table 1, in Reference Example 1 and Reference Example 3 and Examples 1 to 6, POEG is included in the electrolyte as a withstand voltage enhancer. In Table 1, propylene oxide & ethylene oxide (PO & EO) added glycerol is a glycerol derivative obtained by adding a polymer of propylene oxide (PO) and a polymer of ethylene oxide (EO) to two hydroxyl positions of glycerol. In Reference Example 2 and Reference Example 4 and Comparative Examples 1 to 6, PO & EO added glycerol is included in the electrolyte as a withstand voltage enhancer. The concentration of the withstand voltage enhancer added to the electrolyte is the same in each reference example, each example and each comparative example.
對上表1所示的各參考例、各實施例及比較例的電解電容器的電容出現率進行測定。對電解電容器的實測靜電電容相對於理論靜電電容的比例(實測靜電電容/理論靜電電容×100)進行計算,將計算結果作為電容出現率。理論靜電電容是使用算出式((陽極側靜電電容×陰極側靜電電容)/(陽極側靜電電容+陰極側靜電電容))進行計算。The capacitance appearance rate of the electrolytic capacitors of each reference example, each embodiment and comparative example shown in Table 1 above was measured. The ratio of the measured electrostatic capacitance of the electrolytic capacitor to the theoretical electrostatic capacitance (measured electrostatic capacitance/theoretical electrostatic capacitance×100) was calculated, and the calculation result was used as the capacitance appearance rate. The theoretical electrostatic capacitance was calculated using the calculation formula ((anode side electrostatic capacitance×cathode side electrostatic capacitance)/(anode side electrostatic capacitance+cathode side electrostatic capacitance)).
陽極側靜電電容與陰極側靜電電容是以如下方式進行測量,即:將老化處理後的電解電容器加以分解,取出陽極箔與陰極箔,自箔切出試驗片,以鉑板作為相向電極,在陰極側靜電電容中使用兩張試驗片互相作為相向電極,並浸漬於玻璃製的測定槽內的靜電電容測定液中,使用靜電電容計按照JEITA標準RC-2364A進行測量。The anode side electrostatic capacitance and cathode side electrostatic capacitance are measured in the following manner: the electrolytic capacitor after aging treatment is disassembled, the anode foil and cathode foil are taken out, and test pieces are cut out from the foils. A platinum plate is used as a counter electrode. In the cathode side electrostatic capacitance, two test pieces are used as counter electrodes and immersed in the electrostatic capacitance measurement solution in a glass measurement tank. The electrostatic capacitance meter is used to measure according to JEITA standard RC-2364A.
將各參考例、實施例及比較例的電解電容器的電容出現率示於下表2中。
(表2)
另外,基於表2,製作了圖1的圖表。此處,將使用聚氧乙烯甘油的參考例1及參考例3以及實施例1至實施例6設為POEG系列。將使用PO&EO加成甘油的參考例2及參考例4以及比較例1至比較例6設為PO&EO加成甘油系列。並且,以橫軸為陽極箔的帶寬、以縱軸為電容出現率,將相同的系列包含於同一圖表中。包含實施例的POEG系列以圓形記號標繪的曲線表示,包含比較例的PO&EO加成甘油系列以x記號標繪的曲線表示。In addition, based on Table 2, the graph of Figure 1 was prepared. Here, Reference Examples 1 and 3 using polyoxyethylene glycerol and Examples 1 to 6 are set as the POEG series. Reference Examples 2 and 4 using PO&EO added glycerol and Comparative Examples 1 to 6 are set as the PO&EO added glycerol series. And, with the horizontal axis being the width of the anode foil and the vertical axis being the capacitance appearance rate, the same series are included in the same graph. The POEG series including the examples is represented by a curve marked with circular marks, and the PO&EO added glycerol series including the comparative examples is represented by a curve marked with x marks.
進而,基於表2製作了圖2的圖表。在圖2中,以PO&EO加成甘油系列內的各電容出現率為基準(100%),繪製了POEG系列的各電容出現率的比例。包含實施例的POEG系列以圓形記號標繪的曲線表示,包含比較例的PO&EO加成甘油系列以x記號標繪的曲線表示。Furthermore, a graph of FIG2 was prepared based on Table 2. In FIG2, the ratio of each capacitance appearance rate of the POEG series is plotted with the capacitance appearance rate of each PO&EO addition glycerol series as the standard (100%). The POEG series including the embodiment is represented by a curve marked with a circle, and the PO&EO addition glycerol series including the comparative example is represented by a curve marked with an x.
如表1、圖1及圖2所示,POEG系列在所有陽極箔的帶寬中,電容出現率均較PO&EO加成甘油系列高。並且,PO&EO加成甘油系列中,若陽極箔的帶寬超過37 mm,則電容出現率越發大幅降低,若到達62 mm則電容出現率急劇減少,進而若超過70 mm,則電容出現率顯著降低。相對於此,POEG系列在62 mm以下的所有陽極箔的帶寬下維持電容出現率,即便陽極箔的帶寬擴大至超過70 mm,電容出現率的降低亦得到抑制。As shown in Table 1, Figure 1, and Figure 2, the POEG series has a higher capacitance appearance rate than the PO&EO glycerol series in all anode foil widths. In addition, in the PO&EO glycerol series, if the anode foil width exceeds 37 mm, the capacitance appearance rate decreases significantly, and if it reaches 62 mm, the capacitance appearance rate decreases sharply, and if it exceeds 70 mm, the capacitance appearance rate decreases significantly. In contrast, the POEG series maintains the capacitance appearance rate at all anode foil widths below 62 mm, and even if the anode foil width is expanded to more than 70 mm, the decrease in capacitance appearance rate is suppressed.
因此,若陽極箔的帶寬超過37 mm,則會擴大POEG系列與PO&EO加成甘油系列的電容出現率之差,與PO&EO加成甘油系列相比POEG系列的電容出現率相對得到優化。而且,在陽極箔的帶寬例如為32 mm的情況下,POEG系列與PO&EO加成甘油系列的電容出現率之差為1.9%,若陽極箔的帶寬成為62 mm,則擴大至4.9%,POEG系列明顯更有優勢,進而若陽極箔的帶寬超過70 mm,則擴大至8.7%,POEG系列極有優勢。Therefore, if the width of the anode foil exceeds 37 mm, the difference in capacitance appearance rate between the POEG series and the PO&EO plus glycerol series will be enlarged, and the capacitance appearance rate of the POEG series will be relatively optimized compared with the PO&EO plus glycerol series. Moreover, when the width of the anode foil is, for example, 32 mm, the difference in capacitance appearance rate between the POEG series and the PO&EO plus glycerol series is 1.9%. If the width of the anode foil becomes 62 mm, it will be enlarged to 4.9%, and the POEG series will obviously have an advantage. Furthermore, if the width of the anode foil exceeds 70 mm, it will be enlarged to 8.7%, and the POEG series will have a great advantage.
藉此確認到,當將電容器元件製成捲繞型,使陽極箔的沿著卷軸的帶寬超過37 mm,使電解液中含有POEG時,電解電容器的電容出現率得到良好的維持,容易實現大電容化。This confirmed that when the capacitor element is made into a wound type, the strip width of the anode foil along the winding axis exceeds 37 mm, and POEG is contained in the electrolyte, the capacitance appearance rate of the electrolytic capacitor is well maintained and it is easy to achieve a large capacitance.
繼而,在圖1的圖表中,使用陽極箔的帶寬長度為52 mm以上的4點,設定了近似直線。將該近似直線的曲線示於圖3中。在圖3中,包含實施例的POEG系列亦以圓形記號的標繪表示,包含比較例的PO&EO加成甘油系列亦以x記號的標繪表示。如圖3所示,POEG系列的近似直線表示在陽極箔的帶寬長度為150 mm時電容出現率成為80%。即,確認到,當將電容器元件製成捲繞型,使電解液中含有POEG時,在陽極箔的沿著卷軸的帶寬為150 mm以下時,滿足對靜電電容容許誤差為±20%進行規定的JIS標準。Next, in the graph of FIG1 , an approximate straight line is set using four points where the width of the anode foil is 52 mm or more. The curve of the approximate straight line is shown in FIG3 . In FIG3 , the POEG series including the embodiment is also represented by a circular mark, and the PO&EO addition glycerol series including the comparative example is also represented by an x mark. As shown in FIG3 , the approximate straight line of the POEG series indicates that the capacitance appearance rate becomes 80% when the width of the anode foil is 150 mm. That is, it was confirmed that when the capacitor element is made into a winding type and POEG is contained in the electrolyte, when the width of the anode foil along the winding axis is less than 150 mm, the JIS standard that stipulates an allowable error of electrostatic capacitance of ±20% is satisfied.
接著,對於陽極箔的沿著卷軸的長度為62 mm且電解液中包含POEG的實施例4、及陽極箔的沿著卷軸的長度為62 mm且電解液中包含PO&EP加成甘油的比較例4,自殼體中取出電容器元件,並將所取出的電容器元件加以分解。將分解後的陽極箔的表面的照片示於圖3中。圖3的(a)是實施例4的陽極箔的照片,圖3的(b)是比較例4的陽極箔的照片。Next, for Example 4 in which the length of the anode foil along the reel is 62 mm and the electrolyte contains POEG, and Comparative Example 4 in which the length of the anode foil along the reel is 62 mm and the electrolyte contains PO&EP plus glycerol, the capacitor element is taken out from the casing and the taken out capacitor element is decomposed. A photograph of the surface of the decomposed anode foil is shown in FIG3. FIG3 (a) is a photograph of the anode foil of Example 4, and FIG3 (b) is a photograph of the anode foil of Comparative Example 4.
如圖3的(a)及(b)所示,在實施例4及比較例4的陽極箔中,在卷軸方向中心區域帶有沿著帶長度方向的線Le及線Lc。對構成實施例4的線Le及比較例4的線Lc的成分進行分析。其結果,線Le及線Lc均包含耐壓提高劑。As shown in (a) and (b) of Figure 3, in the anode foil of Example 4 and Comparative Example 4, the wire Le and the wire Lc along the length direction of the wire are provided in the center region in the winding direction. The components constituting the wire Le of Example 4 and the wire Lc of Comparative Example 4 were analyzed. As a result, the wire Le and the wire Lc both contain a withstand voltage improver.
但是,如對圖3的(a)與(b)進行比較可知般,實施例4的線Le細且淺。另一方面,與實施例4相比,比較例4的線Lc粗且深。即,在實施例4與比較例4的比較中,在比較例4中,PO&EP加成甘油偏向存在於陽極箔的卷軸方向中心區域。另一方面,在實施例4與比較例4的比較中,在實施例4中,偏向存在於陽極箔的卷軸方向中心區域的POEG少。However, as can be seen from a comparison between (a) and (b) of FIG. 3 , the line Le of Example 4 is thin and shallow. On the other hand, compared with Example 4, the line Lc of Comparative Example 4 is thick and deep. That is, in the comparison between Example 4 and Comparative Example 4, in Comparative Example 4, PO&EP-added glycerol tends to exist in the central area of the axial direction of the anode foil. On the other hand, in the comparison between Example 4 and Comparative Example 4, in Example 4, the amount of POEG tending to exist in the central area of the axial direction of the anode foil is small.
再者,可確認到,陽極箔的帶有線Le及線Lc的部分濕潤,含浸有電解液,電解液與陽極箔密接。據此推測,在比較例4中,在電容器元件的卷軸方向中心區域中,電解液亦與陽極箔密接,但由於耐壓提高劑的偏向存在,無法獲得和依據電解液與陽極箔密接而獲得的密接面積的靜電電容的理論值相近的值,電容出現率顯著降低。Furthermore, it can be confirmed that the part of the anode foil with the line Le and the line Lc is wet and impregnated with the electrolyte, and the electrolyte is in close contact with the anode foil. Based on this, it is speculated that in Comparative Example 4, the electrolyte is also in close contact with the anode foil in the center area of the winding axis direction of the capacitor element, but due to the bias of the withstand voltage improver, it is impossible to obtain a value close to the theoretical value of the electrostatic capacitance of the close contact area obtained by the close contact between the electrolyte and the anode foil, and the capacitance appearance rate is significantly reduced.
即,耐電壓提高劑的高濃度區域中,靜電電容的出現率下降。若耐電壓提高劑偏向存在的區域粗且深,則靜電電容的出現率下降的區域變寬,靜電電容的出現率的下降變大。因此,電解電容器整體上的電容出現率亦變低。推測與比較例1至比較例4相比,實施例1至實施例4的耐壓提高劑較均勻地分散於陽極箔整體中,靜電電容的出現率下降的區域少,靜電電容的出現率的下降小,且電容出現率得到了良好的維持。另外,此種現象在隔板的密度為0.85 g/cm 3以上的情況下顯著發生。 That is, in the high concentration area of the withstand voltage enhancer, the appearance rate of the electrostatic capacitance decreases. If the area where the withstand voltage enhancer tends to exist is coarse and deep, the area where the appearance rate of the electrostatic capacitance decreases becomes wider, and the decrease in the appearance rate of the electrostatic capacitance becomes greater. Therefore, the capacitance appearance rate of the electrolytic capacitor as a whole also becomes lower. It is speculated that compared with Comparative Examples 1 to 4, the withstand voltage enhancers of Examples 1 to 4 are more evenly dispersed in the entire anode foil, the area where the appearance rate of the electrostatic capacitance decreases is smaller, the decrease in the appearance rate of the electrostatic capacitance is small, and the capacitance appearance rate is well maintained. In addition, this phenomenon occurs significantly when the density of the separator is 0.85 g/ cm3 or more.
Le、Lc:線Le, Lc: line
圖1是以橫軸為陽極箔的帶寬、以縱軸為電容出現率的POEG系列與PO&EO加成甘油系列的圖表。 圖2是表示以PO&EO加成甘油系列的各電容出現率為基準的POEG系列的陽極箔的帶寬與電容出現率的關係的圖表。 圖3是表示PO&EO加成甘油系列與POEG系列的近似直線的圖表。 圖4的(a)是實施例4的陽極箔的照片,圖4的(b)是比較例4的陽極箔的照片。 FIG1 is a graph of the POEG series and the PO&EO addition glycerol series, with the horizontal axis being the width of the anode foil and the vertical axis being the capacitance appearance rate. FIG2 is a graph showing the relationship between the width of the anode foil and the capacitance appearance rate of the POEG series based on the capacitance appearance rates of the PO&EO addition glycerol series. FIG3 is a graph showing the approximate straight line of the PO&EO addition glycerol series and the POEG series. FIG4 (a) is a photograph of the anode foil of Example 4, and FIG4 (b) is a photograph of the anode foil of Comparative Example 4.
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