TW201513151A - Electrode material for aluminum electrolytic capacitor, and production method thereof - Google Patents
Electrode material for aluminum electrolytic capacitor, and production method thereof Download PDFInfo
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- TW201513151A TW201513151A TW103126581A TW103126581A TW201513151A TW 201513151 A TW201513151 A TW 201513151A TW 103126581 A TW103126581 A TW 103126581A TW 103126581 A TW103126581 A TW 103126581A TW 201513151 A TW201513151 A TW 201513151A
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- aluminum
- electrode material
- powder
- electrolytic capacitor
- particle diameter
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 160
- 239000007772 electrode material Substances 0.000 title claims abstract description 72
- 239000003990 capacitor Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002245 particle Substances 0.000 claims abstract description 149
- 239000000843 powder Substances 0.000 claims abstract description 83
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 238000005530 etching Methods 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 22
- 238000007743 anodising Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011888 foil Substances 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
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- 239000011347 resin Substances 0.000 description 11
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 9
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 8
- 239000001741 Ammonium adipate Substances 0.000 description 8
- 235000019293 ammonium adipate Nutrition 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
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Abstract
Description
本發明係有關於一種鋁電解電容器所使用之電極材，特別是低壓用之鋁電解電容器所使用之陽極用電極材及其製造方法。 The present invention relates to an electrode material for use in an aluminum electrolytic capacitor, particularly an electrode material for an anode used in an aluminum electrolytic capacitor for low voltage, and a method for producing the same.
鋁電解電容器由於能以低價獲得高容量而被廣泛地使用於各種區域。一般是使用鋁鉑來作為鋁電解電容器用電極材。 Aluminum electrolytic capacitors are widely used in various regions because they can obtain high capacity at low prices. Aluminum platinum is generally used as an electrode material for an aluminum electrolytic capacitor.
鋁箔藉由進行蝕刻處理來形成蝕孔，可藉以使表面積增大。接著，藉由對其表面施予陽極氧化處理，形成氧化皮膜，以此作為介電體發揮效用。因此，藉由將鋁箔蝕刻處理，並於其表面視使用電壓而以各種電壓施予陽極氧化處理，可製造適於各用途之電解電容器用鋁電極箔(陽極箔)。 The aluminum foil is etched to form an etched hole, whereby the surface area can be increased. Next, an anodized film is applied to the surface to form an oxide film, thereby functioning as a dielectric. Therefore, an aluminum electrode foil (anode foil) for an electrolytic capacitor suitable for each application can be produced by etching the aluminum foil and applying anodizing treatment to various voltages depending on the applied voltage.
在鋁箔的蝕刻處理中，是為了形成因應陽極氧化電壓最適合的蝕孔之蝕刻處理。具體而言，在中高壓用之電容器用途上，有形成厚氧化皮膜之必要。因此，為了不讓蝕孔被厚氧化皮膜埋沒，主要藉由進行直流蝕刻將蝕 孔形狀形成隧道型，處理成順應陽極氧化電壓之粗度。另一方面，在低壓用之電容器用途上，需要細的蝕孔，主要藉由交流蝕刻而形成海綿狀的蝕孔。 In the etching process of the aluminum foil, it is an etching process for forming an etching hole which is most suitable for the anodization voltage. Specifically, in the use of a capacitor for medium and high voltage, it is necessary to form a thick oxide film. Therefore, in order to prevent the etched holes from being buried by the thick oxide film, the etch is mainly performed by DC etching. The shape of the hole is formed into a tunnel type and processed to conform to the thickness of the anodization voltage. On the other hand, in the use of a capacitor for low voltage, fine etching is required, and a sponge-like etching hole is mainly formed by alternating current etching.
在蝕刻處理中，主要使用於鹽酸中添加有硫酸、磷酸、硝酸等之鹽酸水溶液。然而，鹽酸因在環境面上負荷大之故，開發不牽涉到蝕刻處理之鋁箔的表面積增大方法受到期待。 In the etching treatment, an aqueous hydrochloric acid solution containing sulfuric acid, phosphoric acid, nitric acid or the like is mainly used in hydrochloric acid. However, since hydrochloric acid has a large load on the environmental surface, it has been expected to develop a method for increasing the surface area of an aluminum foil which does not involve etching treatment.
有關於此，在專利文獻1中提出一種使用了令表面附著有微細鋁粉末之鋁箔的鋁電解電容器。又，在專利文獻2中，揭示有一種使用了下述電極箔的電解電容器，該電極箔是在箔厚15μm以上且小於35μm之平滑鋁箔的單面或雙面上附著有微粒子之凝聚物者，該微粒子係由在2μm至0.01μm之長度範圍內呈自相似之鋁及/或於表面形成有氧化鋁層之鋁所構成。 In connection with this, Patent Document 1 proposes an aluminum electrolytic capacitor using an aluminum foil having a fine aluminum powder adhered to its surface. Further, Patent Document 2 discloses an electrolytic capacitor using an electrode foil which is agglomerated with fine particles attached to one surface or both surfaces of a smooth aluminum foil having a foil thickness of 15 μm or more and less than 35 μm. The fine particles are composed of aluminum which is self-similar in a length range of 2 μm to 0.01 μm and/or aluminum which is formed with an aluminum oxide layer on the surface.
然而，該等的文獻中，由於是利用電鍍及/或蒸鍍使鋁粉末等附著於鋁箔之故，至少，無法說是足以作為中高壓用之電容器用途之粗蝕孔的代用者。 However, in these documents, aluminum powder or the like is adhered to the aluminum foil by electroplating and/or vapor deposition, and at least, it cannot be said that it is a substitute for a rough etching hole for a capacitor for medium and high voltage.
又，在專利文獻3中揭示有一種鋁電解電容器用電極材，其特徵在於該電極材是由鋁及鋁合金中至少1種的燒結體所構成，且確認其可獲得超出以習知之蝕刻處理所獲得之電極材的性能。 Further, Patent Document 3 discloses an electrode material for an aluminum electrolytic capacitor, characterized in that the electrode material is composed of at least one sintered body of aluminum and aluminum alloy, and it is confirmed that it can be obtained by a conventional etching treatment. The properties of the obtained electrode material.
然而，專利文獻3中所揭示之電極材雖在中高壓用之電容器用途上發揮優異的性能，但在低壓區域使用的情況中，卻無法發揮超越以習知之蝕刻處理所獲得之電極 材的性能。 However, the electrode material disclosed in Patent Document 3 exhibits excellent performance in the use of a capacitor for medium and high voltage, but in the case of use in a low pressure region, it cannot exhibit an electrode which is superior to that obtained by a conventional etching treatment. Material properties.
為了即便是在低壓區域使用的情況下也能發揮超越以習知之蝕刻處理所獲得之電極材的性能，雖有考慮過例如在將鋁及鋁合金中至少1種的粉末燒結時，盡可能抑制過度的縮頸(過燒結)，並盡可能減少粉末彼此間的接觸面積，藉以確保有效表面積，但目前解決了此課題之電極材尚未被提出。 In order to exhibit the performance of an electrode material obtained by a conventional etching treatment even when it is used in a low-pressure region, it is considered that, for example, when at least one powder of aluminum and an aluminum alloy is sintered, it is suppressed as much as possible. Excessive necking (over-sintering) and minimizing the contact area of the powders with each other to ensure an effective surface area, but electrode materials that have solved this problem have not yet been proposed.
專利文獻1：日本專利特開平2-267916號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 2-267916
專利文獻2：日本專利特開2006-108159號公報 Patent Document 2: Japanese Patent Laid-Open No. 2006-108159
專利文獻3：日本專利特開2008-98279號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-98279
本發明之目的在於提供一種鋁電解電容器用電極材，其具有鋁及鋁合金中至少1種之粉末的燒結層；該電極材即便是在用於低壓用電容器用途的情況下，也能確保優異的靜電容量。 An object of the present invention is to provide an electrode material for an aluminum electrolytic capacitor comprising a sintered layer of at least one of aluminum and an aluminum alloy; and the electrode material can be excellent even when used for a low-voltage capacitor application. The electrostatic capacity.
本發明人為了達成上述目的反覆致力研究的結果，發現將鋁及鋁合金中至少1種的粉末與特定物質一起燒結來形成燒結層時，可達成上述目的，終至完成了本發明。 In order to achieve the above object, the present inventors have found that the above object can be attained by sintering at least one powder of aluminum and aluminum alloy together with a specific substance to form a sintered layer, and the present invention has been completed.
亦即，本發明係有關於下述的鋁電解電容器用電極材及其製造方法。 That is, the present invention relates to an electrode material for an aluminum electrolytic capacitor described below and a method for producing the same.
1.一種鋁電解電容器用電極材，其特徵在於具有燒結層，且該燒結層係使鋁及鋁合金中至少1種的粉末隔著電絕緣性粒子燒結而成者。 An electrode material for an aluminum electrolytic capacitor, comprising: a sintered layer obtained by sintering at least one powder of aluminum and an aluminum alloy through electrical insulating particles.
2.如上述項1之鋁電解電容器用電極材，其中前述粉末與前述電絕緣性粒子之含量的重量比為1：2至200：1。 2. The electrode material for an aluminum electrolytic capacitor according to item 1, wherein a weight ratio of the powder to the content of the electrically insulating particles is from 1:2 to 200:1.
3.如上述項1或2之鋁電解電容器用電極材，其中前述粉末的長徑比為1至1000。 3. The electrode material for an aluminum electrolytic capacitor according to item 1 or 2 above, wherein the powder has an aspect ratio of from 1 to 1,000.
4.如上述項1至3中任一項之鋁電解電容器用電極材，其中前述粉末的平均粒徑為1至80μm。 4. The electrode material for an aluminum electrolytic capacitor according to any one of the above items 1 to 3, wherein the powder has an average particle diameter of from 1 to 80 μm.
5.如上述項1至4中任一項之鋁電解電容器用電極材，其中前述粉末的平均厚度為0.01至80μm。 The electrode material for an aluminum electrolytic capacitor according to any one of the above items 1 to 4, wherein the powder has an average thickness of 0.01 to 80 μm.
6.如上述項1至5中任一項之鋁電解電容器用電極材，其中前述電絕緣性粒子為金屬氧化物或金屬氮化物。 The electrode material for aluminum electrolytic capacitors according to any one of the above items 1 to 5, wherein the electrically insulating particles are metal oxides or metal nitrides.
7.如上述項1至6中任一項之鋁電解電容器用電極材，其中前述電絕緣性粒子為選自於由氧化鋁、氧化鈦、氧化鋯及氧化矽所構成群組中之至少1種。 The electrode material for an aluminum electrolytic capacitor according to any one of the above items 1 to 6, wherein the electrically insulating particles are at least one selected from the group consisting of alumina, titania, zirconia and cerium oxide. Kind.
8.如上述項1至7中任一項之鋁電解電容器用電極材，其中前述電絕緣性粒子的平均粒徑為0.01至10μm。 The electrode material for an aluminum electrolytic capacitor according to any one of the above items 1 to 7, wherein the electrically insulating particles have an average particle diameter of 0.01 to 10 μm.
9.如上述項1至8中任一項之鋁電解電容器用電極材，其中前述燒結層的平均厚度為5至1000μm。 The electrode material for an aluminum electrolytic capacitor according to any one of the above items 1 to 8, wherein the sintered layer has an average thickness of 5 to 1000 μm.
10.如上述項1至9中任一項之鋁電解電容器用電極材，其具有支持前述燒結層的基材。 10. The electrode material for an aluminum electrolytic capacitor according to any one of items 1 to 9, which has a substrate supporting the sintered layer.
11.一種鋁電解電容器用電極材之製造方法，其特徵在於包含以下步驟：第1步驟，形成由糊狀組成物構成之皮膜，其中該糊狀組成物含有鋁及鋁合金中至少1種的粉末以及電絕緣性粒子；及第2步驟，藉由將前述皮膜以400至660℃之溫度燒結來形成燒結層；且前述製造方法不含蝕刻步驟。 A method for producing an electrode material for an aluminum electrolytic capacitor, comprising the steps of: forming a film composed of a paste composition containing at least one of aluminum and an aluminum alloy; a powder and electrically insulating particles; and a second step of forming the sintered layer by sintering the film at a temperature of 400 to 660 ° C; and the aforementioned manufacturing method does not include an etching step.
12.如上述項11之製造方法，其進一步具有將前述燒結層進行陽極氧化處理之第3步驟。 12. The method of claim 11, further comprising the third step of anodizing the sintered layer.
以下，就本發明之電極材及其製造方法作詳細地說明。 Hereinafter, the electrode material of the present invention and a method for producing the same will be described in detail.
本發明之鋁電解電容器用電極材以具有下述燒結層為特徵，該燒結層係使鋁及鋁合金中至少1種之粉末隔著電絕緣性粒子(發揮作為間隔物之作用)燒結而成者。以下，將鋁及鋁合金中至少1種的粉末僅以「粉末」稱之。 The electrode material for an aluminum electrolytic capacitor of the present invention is characterized in that it has a sintered layer in which at least one of aluminum and an aluminum alloy is sintered by electrically insulating particles (acting as a spacer) By. Hereinafter, at least one of the aluminum and the aluminum alloy powder is referred to as "powder".
由於具有上述特徵之本發明的鋁電解電容器用電極材，是藉由將鋁及鋁合金中至少1種的粉末隔著電絕緣性粒子燒結來形成燒結層，故可盡可能抑制燒結層中之前述粉末彼此間過度縮頸(過燒結)，並盡可能減少粉末彼此間的接觸面積而確保有效表面積。因此，本發明之鋁電 解電容器用電極材，即便在用於100V以下之低電壓下所使用之低壓用的電容器用途的情況中，也能發揮超越利用習知之蝕刻處理所獲得之電極材的性能。 In the electrode material for an aluminum electrolytic capacitor of the present invention having the above-described characteristics, a sintered layer is formed by sintering at least one powder of aluminum and an aluminum alloy via electrically insulating particles, so that the sintered layer can be suppressed as much as possible. The aforementioned powders are excessively necked (over-sintered) with each other, and the contact area of the powders with each other is minimized to ensure an effective surface area. Therefore, the aluminum battery of the present invention In the case of a capacitor for low-voltage use used for a low voltage of 100 V or less, the electrode material for a capacitor can exhibit performance superior to that of an electrode material obtained by a conventional etching process.
作為原料的鋁粉末，例如，以鋁純度99.8重量%以上的鋁粉末為佳。又，作為原料的鋁合金粉末，宜為例如含有矽(Si)、鐵(Fe)、銅(Cu)、錳(Mn)、鎂(Mg)、鉻(Cr)、鋅(Zn)、鈦(Ti)、釩(V)、鎵(Ga)、鎳(Ni)、硼(B)、鋯(Zr)等元素之1種或2種以上的合金。鋁合金中該等元素的含量宜設定為個別在100重量ppm以下，特宜為在50重量ppm以下。 As the aluminum powder as a raw material, for example, an aluminum powder having an aluminum purity of 99.8% by weight or more is preferable. Further, the aluminum alloy powder as a raw material preferably contains, for example, bismuth (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium (Cr), zinc (Zn), or titanium ( One or two or more alloys of elements such as Ti), vanadium (V), gallium (Ga), nickel (Ni), boron (B), and zirconium (Zr). The content of the elements in the aluminum alloy is preferably set to be 100 ppm by weight or less, particularly preferably 50 ppm by weight or less.
作為前述粉末，以平均粒徑為1至80μm者為佳。特別是在前述粉末的平均粒徑為1至10μm的情況下，所獲得之電極材可作為100V以下之低壓用途之鋁電解電容器的電極材而適宜地利用。 As the powder, those having an average particle diameter of from 1 to 80 μm are preferred. In particular, when the average particle diameter of the powder is from 1 to 10 μm, the electrode material obtained can be suitably used as an electrode material of an aluminum electrolytic capacitor for low-voltage use of 100 V or less.
再者，本說明書之燒結前之前述粉末的平均粒徑是藉由雷射繞射法來求得粒徑與對應於其粒徑之粒子數所獲得之粒度分布曲線中全粒子數之50%處所對應之粒子的粒子徑。又，燒結後之前述粉末的平均粒徑是將燒結層的截面利用掃描型電子顯微鏡觀察來測定。在上述截面觀察中，將前述各粉末粒子之最大徑(長徑)設為該粉末的粒徑，測定任意50個粉末的粒徑，並將該等的算術平均設為燒結後之前述粉末的平均粒徑。 Furthermore, the average particle diameter of the powder before sintering in the present specification is 50% of the total particle number in the particle size distribution curve obtained by the laser diffraction method to obtain the particle diameter and the number of particles corresponding to the particle diameter thereof. The particle diameter of the particle corresponding to the location. Further, the average particle diameter of the powder after sintering was measured by observing the cross section of the sintered layer by a scanning electron microscope. In the cross-sectional observation, the maximum diameter (long diameter) of each of the powder particles is defined as the particle diameter of the powder, and the particle diameter of any 50 powders is measured, and the arithmetic mean of these is the powder after sintering. The average particle size.
前述粉末的形狀並無特別限定，可適宜地使用球狀、不定形狀、鱗片狀(薄片狀)、纖維狀等之中任一 者。一般而言，在使用鱗片狀粉末的情況下，雖易發生過燒結而難以確保電極材之有效表面積，但在本發明中藉由隔著電絕緣性粒子來燒結，即便在使用鱗片狀粉末時也易於抑制過燒結而確保電極材的有效表面積。 The shape of the powder is not particularly limited, and any of a spherical shape, an indefinite shape, a scaly shape (flaky shape), and a fibrous shape can be suitably used. By. In general, when a flaky powder is used, it is easy to cause sintering, and it is difficult to secure an effective surface area of the electrode material. However, in the present invention, sintering is performed by electrically insulating particles, even when scaly powder is used. It is also easy to suppress over-sintering to ensure an effective surface area of the electrode material.
前述粉末可使用藉由公知的方法所製造者。例如，可列舉原子化法、融熔紡絲法、旋轉圓盤法、旋轉電極法、急冷凝固法等，但就工業上生產而言，是以原子化法，特別是氣體原子化法為佳。亦即，希望使用藉由將熔融金屬原子化所獲得之粉末。 The above powder can be produced by a known method. For example, an atomization method, a melt spinning method, a rotating disk method, a rotating electrode method, a rapid solidification method, etc. may be mentioned, but in terms of industrial production, it is preferably an atomization method, particularly a gas atomization method. . That is, it is desirable to use a powder obtained by atomizing a molten metal.
前述粉末的平均粒徑，以球狀粒子而言宜為1至80μm，特別是，以1至10μm為較佳。在平均粒徑較1μm小的情況下，會有無法獲得所期望之耐電壓的疑慮。又，在平均粒徑較80μm大的情況下，會有無法獲得所期望之靜電容量的疑慮。 The average particle diameter of the powder is preferably from 1 to 80 μm in terms of spherical particles, and particularly preferably from 1 to 10 μm. When the average particle diameter is smaller than 1 μm, there is a fear that a desired withstand voltage cannot be obtained. Moreover, when the average particle diameter is larger than 80 μm, there is a concern that a desired electrostatic capacitance cannot be obtained.
在前述粉末為不定形狀、鱗片狀(薄片狀)或纖維狀的情況下，長徑比(平均粒徑/平均厚度)宜為1至1000。在長徑比較1000大的情況下，容易在後述製造方法之第1步驟中發生皮膜乾燥不良或在脫脂步驟中發生不良的情況。上述長徑比中，特別是在100至1000的情況下，即便是在低壓區域也能獲得較藉習知之蝕刻處理所獲得之電極材高的靜電容量之故而為佳。前述粉末的平均厚度可藉由利用掃描型電子顯微鏡所得之前述粉末的截面觀察來測定。燒結前，是將前述粉末與適宜樹脂或溶媒混合後形成塗膜，並進行該塗膜的截面觀察。又，燒結後，是進行 燒結層的截面觀察。在該等截面觀察中，是將各粉末的最小徑設為該粉末的厚度，測定任意50個粉末的厚度，並將該等的算術平均設為前述粉末的平均厚度。前述粉末的平均厚度宜為0.01至80μm。在粉末的平均厚度較0.01μm小的情況下，會有無法獲得所期望之耐電壓的疑慮。又，在前述粉末的平均厚度較80μm大的情況下，會有無法獲得所期望之靜電容量的疑慮。 In the case where the powder is in an indefinite shape, a scaly shape (flaky shape) or a fibrous shape, the aspect ratio (average particle diameter / average thickness) is preferably from 1 to 1,000. When the length of the long diameter is 1000, it is easy to cause a film drying failure or a defect in the degreasing step in the first step of the manufacturing method described later. Among the above aspect ratios, particularly in the case of 100 to 1000, it is preferable to obtain a higher electrostatic capacitance than the electrode material obtained by the conventional etching treatment even in a low pressure region. The average thickness of the above powder can be measured by cross-sectional observation of the aforementioned powder obtained by a scanning electron microscope. Before the sintering, the powder is mixed with a suitable resin or a solvent to form a coating film, and the cross section of the coating film is observed. Also, after sintering, it is carried out Cross section observation of the sintered layer. In the cross-sectional observation, the minimum diameter of each powder was set to the thickness of the powder, and the thickness of any 50 powders was measured, and the arithmetic mean of these was set to the average thickness of the said powder. The aforementioned powder preferably has an average thickness of from 0.01 to 80 μm. When the average thickness of the powder is smaller than 0.01 μm, there is a fear that a desired withstand voltage cannot be obtained. Further, when the average thickness of the powder is larger than 80 μm, there is a concern that a desired electrostatic capacity cannot be obtained.
作為前述電絕緣性粒子，只要是可在前述粉末燒結時作為間隔物夾雜於粉末之間來抑制前述粉末彼此間之過燒結，能確保電極材之有效表面積及靜電容量之粒子即可。作為這樣的電絕緣性粒子，例如，以金屬化合物粒子(氧化物、氮化物等)為佳；具體而言，宜為選自氧化鋁、氧化鈦、氧化鋯及氧化矽之至少1種金屬化合物粒子。 The electrically insulating particles may be particles which can be prevented from being excessively sintered between the powders by interposing the separators between the powders during the sintering of the powder, thereby ensuring an effective surface area and an electrostatic capacity of the electrode material. As such electrically insulating particles, for example, metal compound particles (oxides, nitrides, and the like) are preferable; specifically, at least one metal compound selected from the group consisting of alumina, titania, zirconia, and cerium oxide is preferable. particle.
該等粒子具有電絕緣性及高熔點(2000℃左右)，其自身不會與粉末燒結，在粉末燒結時可作為間隔物夾雜其中，且沒有對電極材之電氣特性帶來壞影響的疑慮，因此而受到青睞。 These particles have electrical insulation and high melting point (about 2000 ° C), do not sinter themselves with the powder, can be contained as a spacer during powder sintering, and have no doubt that the electrical properties of the electrode material are adversely affected. Therefore, it is favored.
前述電絕緣性粒子的平均粒徑雖無限定，但以0.01至10μm為佳，特別是以0.1至1μm為較佳。前述電絕緣性粒子之平均粒徑可使用與前述粉末相同的方法來測定。 The average particle diameter of the electrically insulating particles is not limited, but is preferably 0.01 to 10 μm, particularly preferably 0.1 to 1 μm. The average particle diameter of the electrically insulating particles can be measured by the same method as the above powder.
燒結層中之前述粉末與前述電絕緣性粒子之含量的重量比並無限制，但以例如前述粉末：前述電絕緣性粒子=1：2至200：1為佳；以2：1至20：1為較佳；以3：1 至10：1為特佳。就前述粉末與前述電絕緣性粒子之含量的體積比而言，以前述粉末：前述電絕緣性粒子=3：4至300：1為佳；以3：1至30：1為較佳；以9：2至15：1為特佳。 The weight ratio of the aforementioned powder to the content of the above electrically insulating particles in the sintered layer is not limited, but is preferably, for example, the aforementioned powder: the electrically insulating particles = 1:2 to 200:1; and 2:1 to 20: 1 is preferred; 3:1 It is especially good to 10:1. The volume ratio of the powder to the content of the electrically insulating particles is preferably the powder: the electrically insulating particles = 3:4 to 300:1; preferably 3:1 to 30:1; 9:2 to 15:1 is especially good.
藉由將含量的比(重量比、體積比)設定在該範圍內，可容易地確保電極材的有效表面積。再者，前述粉末之長徑比在3至1000的情況下，前述重量比以1：2至200：1之範圍為佳；在前述粉末之長徑比小於3(即1以上且小於3)的情況下，前述重量比以2：1至200：1之範圍為佳。一般認為這是由於使前述粉末之長徑比在3以上時前述電絕緣性粒子之容許含量會增加之故。 By setting the ratio (weight ratio, volume ratio) of the content within this range, the effective surface area of the electrode material can be easily ensured. Further, in the case where the aspect ratio of the powder is from 3 to 1,000, the aforementioned weight ratio is preferably in the range of 1:2 to 200:1; and the aspect ratio of the powder is less than 3 (i.e., 1 or more and less than 3). In the case of the above, the weight ratio is preferably in the range of 2:1 to 200:1. It is considered that this is because the allowable content of the electrically insulating particles is increased when the aspect ratio of the powder is 3 or more.
當上述重量比超過1：2而電絕緣性粒子變多時，恐有電絕緣性粒子的比例變得太高而使粉末彼此間的燒結變得困難之虞。又，粉末變多到上述重量比高達250：1左右時，電絕緣性粒子變得太少而有無法充分獲得提高靜電容量的效果之疑慮。 When the weight ratio exceeds 1:2 and the number of electrically insulating particles increases, the ratio of the electrically insulating particles may become too high, and sintering of the powders may become difficult. Further, when the powder is increased to a weight ratio of about 250:1, the electrically insulating particles are too small, and there is a fear that the effect of increasing the electrostatic capacity cannot be sufficiently obtained.
如前所述，迄今，一般認為在使用了鱗片狀粉末(鋁薄片)的情況下，相較於球狀粉末，其比表面積較大，且在塗布含有鋁薄片的糊後之鋁薄片彼此的定向性較易形成面接觸，因此在燒結時容易過燒結，而難以確保有效比表面積。然而，如下所述，藉由隔著電絕緣性粒子來燒結，可在燒結時抑制過燒結。 As described above, it has been conventionally considered that, in the case where a flaky powder (aluminum flake) is used, the specific surface area is larger than that of the spherical powder, and the aluminum flakes after coating the paste containing the aluminum flakes are mutually The orientation is easier to form a surface contact, so that it is easy to over-sinter during sintering, and it is difficult to secure an effective specific surface area. However, as described below, by sintering through the electrically insulating particles, over-sintering can be suppressed at the time of sintering.
將使用了鋁薄片之習知燒結層(不含電絕緣性粒子)的截面之掃描型電子顯微鏡觀測圖像表示於圖1。又， 將使用了鋁薄片及電絕緣性粒子之本發明之電極材的燒結層截面的掃描型電子顯微鏡觀測圖像表示於圖2。 A scanning electron microscope observation image of a cross section of a conventional sintered layer (excluding electrically insulating particles) using an aluminum foil is shown in Fig. 1 . also, A scanning electron microscope observation image of a cross section of a sintered layer of the electrode material of the present invention using an aluminum foil and electrically insulating particles is shown in Fig. 2 .
在圖1中，鋁薄片間的間隙崩塌，而呈現未充分活用鋁薄片之表面積的狀態。另一方面，在圖2中，可確認於鋁薄片間置入電絕緣性粒子，而在薄片間保有適度空間的樣子。藉此，變得能有效率地活用鋁薄片之大比表面積，即便在用於低壓用途的情況下亦能大幅提高靜電容量。再者，將電絕緣性粒子作為間隔物使用而能提高靜電容量的效果，並不限於使用鱗片狀電絕緣性粒子作為粉末的情況，在使用各種形狀之粉末時效果亦獲得確認。 In Fig. 1, the gap between the aluminum sheets collapses, and the surface area of the aluminum sheets is not sufficiently utilized. On the other hand, in Fig. 2, it was confirmed that electrically insulating particles were placed between the aluminum sheets, and an appropriate space was maintained between the sheets. Thereby, the large specific surface area of the aluminum foil can be utilized effectively, and the electrostatic capacitance can be greatly improved even when used for low-pressure use. In addition, the effect of improving the electrostatic capacitance by using the electrically insulating particles as a spacer is not limited to the case where scaly electrically insulating particles are used as the powder, and the effect is also confirmed when powders of various shapes are used.
前述燒結層的形狀並無特別限制，但一般而言是以平均厚度5至1000μm，特別是5至50μm之箔狀為佳。平均厚度是以測微計測定10點之測定值的平均。 The shape of the sintered layer is not particularly limited, but is generally a foil shape having an average thickness of 5 to 1000 μm, particularly 5 to 50 μm. The average thickness is an average of the measured values of 10 points measured by a micrometer.
本發明的電極材亦可具有支持燒結層的基材。作為基材係可適宜地使用例如鋁箔。 The electrode material of the present invention may also have a substrate supporting the sintered layer. As the substrate, for example, an aluminum foil can be suitably used.
作為基材的鋁箔並無特別限定，可使用純鋁或鋁合金。本發明所使用之鋁箔，包含在必要範圍內添加了矽(Si)、鐵(Fe)、銅(Cu)、錳(Mn)、鎂(Mg)、鉻(Cr)、鋅(Zn)、鈦(Ti)、釩(V)、鎵(Ga)、鎳(Ni)、硼(B)中之至少1種合金元素以為其組成的鋁合金，或限定了上述不可避免的不純物元素之含量的鋁。 The aluminum foil as the substrate is not particularly limited, and pure aluminum or an aluminum alloy can be used. The aluminum foil used in the present invention comprises cerium (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium (Cr), zinc (Zn), titanium added to the extent necessary. At least one of (Ti), vanadium (V), gallium (Ga), nickel (Ni), and boron (B) is an aluminum alloy composed thereof, or aluminum having a content of the above-mentioned unavoidable impurity element .
鋁箔的厚度並無特別限定，但宜設定在5至100μm，特別是10至50μm的範圍內。 The thickness of the aluminum foil is not particularly limited, but is preferably set in the range of 5 to 100 μm, particularly 10 to 50 μm.
上述的鋁箔可使用藉由公知的方法所製造者。 例如，調製具有上述之預定組成的鋁或鋁合金之熔融金屬，鑄造之並將所獲得的鑄塊進行適切地均質化處理。其後，藉由對該鑄塊施予熱軋製與冷軋製可製得鋁箔。 The above aluminum foil can be produced by a known method. For example, a molten metal of aluminum or an aluminum alloy having the predetermined composition described above is prepared, cast, and the obtained ingot is subjected to appropriate homogenization treatment. Thereafter, an aluminum foil can be obtained by applying hot rolling and cold rolling to the ingot.
再者，亦可在上述冷軋製步驟的過程中，於50至500℃、特別是150至400℃的範圍內施予中間退火處理。又，亦可在上述冷軋製步驟之後，於150至650℃、特別是350至550℃之範圍內施予退火處理而製成軟質箔。 Further, an intermediate annealing treatment may be applied in the range of 50 to 500 ° C, particularly 150 to 400 ° C, during the above cold rolling step. Further, after the cold rolling step, annealing treatment may be performed at 150 to 650 ° C, particularly 350 to 550 ° C, to obtain a soft foil.
本發明的電極材在用於基材時，燒結層是形成於基材之單面或雙面。在將燒結層形成於基材的雙面之情況，宜將上述平均厚度的燒結層分別於基材的雙面以呈對稱形的方式來形成。 When the electrode material of the present invention is used for a substrate, the sintered layer is formed on one side or both sides of the substrate. In the case where the sintered layer is formed on both sides of the substrate, it is preferred that the sintered layers having the above average thickness are formed symmetrically on both sides of the substrate.
本發明之電極材即便是用於在100V以下之低電壓下使用之低壓用電容器用途時，也能發揮超越習知之蝕刻處理所獲得之電極材的性能，因此可適宜地利用於低壓用鋁電解電容器之用途。 When the electrode material of the present invention is used for a low-voltage capacitor used at a low voltage of 100 V or less, the electrode material can exhibit performance superior to that of the conventional etching process, and therefore can be suitably used for low-voltage aluminum electrolysis. The use of capacitors.
本發明之電極材每次作為鋁電解電容器用電極使用時，不需將該電極材進行蝕刻處理就能使用。亦即，本發明之電極材不需進行蝕刻處理就可直接或藉由陽極氧化處理作為電極(電極箔)來使用。 When the electrode material of the present invention is used as an electrode for an aluminum electrolytic capacitor, it can be used without etching the electrode material. That is, the electrode material of the present invention can be used as an electrode (electrode foil) directly or by anodizing treatment without performing an etching treatment.
將使用了本發明之電極材的陽極箔與陰極箔隔著分離器而積層，捲繞而形成電容器元件，使該電容器元件含浸於電解液，將包含電解液之電容器元件收納於外部殼套中，並藉由以封口體將殼套封口來製得電解電容器。 The anode foil and the cathode foil using the electrode material of the present invention are laminated via a separator, wound to form a capacitor element, and the capacitor element is impregnated into the electrolytic solution, and the capacitor element including the electrolytic solution is housed in the outer casing. And an electrolytic capacitor is produced by sealing the casing with a sealing body.
本發明之鋁電解電容器用電極材的製造方法之特徵在於包含以下步驟：第1步驟，形成由糊狀組成物構成之皮膜，該糊狀組成物含有鋁及鋁合金中至少1種的粉末以及電絕緣性粒子；及第2步驟，藉由將前述皮膜以400至660℃之溫度燒結來形成燒結層；且，前述製造方法不含蝕刻步驟。 The method for producing an electrode material for an aluminum electrolytic capacitor according to the present invention includes the step of forming a film composed of a paste composition containing at least one powder of aluminum and an aluminum alloy, and a first step The electrically insulating particles; and the second step, the sintered film is formed by sintering the film at a temperature of 400 to 660 ° C; and the manufacturing method does not include an etching step.
以下，分各步驟來進行說明。 Hereinafter, each step will be described.
第1步驟是形成由糊狀組成物構成的皮膜，且該糊狀組成物含有鋁及鋁合金中至少1種的粉末以及電絕緣性粒子。 In the first step, a film composed of a paste composition is formed, and the paste composition contains at least one powder of aluminum and an aluminum alloy and electrically insulating particles.
作為鋁及鋁合金的組成(成分)，可使用前述所揭示者。作為前述粉末，例如，宜使用鋁純度99.8重量%以上之純鋁粉末。又，作為電絕緣性粒子，可使用前述所揭示者。進一步而言，在形成皮膜時使用基材的情況下，可使用前述所揭示者。 As the composition (component) of aluminum and aluminum alloy, those disclosed above can be used. As the powder, for example, a pure aluminum powder having an aluminum purity of 99.8% by weight or more is preferably used. Further, as the electrically insulating particles, those disclosed above can be used. Further, in the case where a substrate is used in forming a film, the above-described ones can be used.
前述糊組成物，除了粉末及電絕緣性粒子以外，亦可視需要含有樹脂黏合劑、溶劑、燒結助劑、界面活性劑等。該等中任一者皆可使用公知或市售物。尤其宜令其含有樹脂黏合劑及溶劑之至少1種來作成糊狀組成物使用，藉此可更加有效率地形成皮膜。 The paste composition may contain, in addition to the powder and the electrically insulating particles, a resin binder, a solvent, a sintering aid, a surfactant, and the like. Any of these may be known or commercially available. In particular, it is preferable to use at least one of a resin binder and a solvent to form a paste composition, whereby the film can be formed more efficiently.
樹脂黏合劑並無限定，例如可適宜地使用：羧基改質聚烯烴樹脂、乙酸乙烯酯樹脂、氯乙烯樹脂、鹽乙 酸乙烯酯共聚樹脂、乙烯醇樹脂、丁醛樹脂、氟乙烯樹脂、丙烯酸樹脂、聚酯樹脂、胺甲酸乙酯樹脂、環氧樹脂、尿素樹脂、酚樹脂、丙烯腈樹脂、纖維素樹脂、石蠟、聚乙烯蠟等的合成樹脂或蠟、焦油、膠、清漆、松脂、蜜蠟等的天然樹脂或蠟。 The resin binder is not limited, and for example, a carboxyl group-modified polyolefin resin, a vinyl acetate resin, a vinyl chloride resin, or a salt B can be suitably used. Acid vinyl ester copolymer resin, vinyl alcohol resin, butyral resin, vinyl fluoride resin, acrylic resin, polyester resin, urethane resin, epoxy resin, urea resin, phenol resin, acrylonitrile resin, cellulose resin, paraffin wax A synthetic resin such as polyethylene wax or a natural resin or wax such as wax, tar, glue, varnish, turpentine or beeswax.
該等的樹脂黏合劑依分子量、樹脂的種類等，有加熱時揮發者，與因熱分解而其殘渣與鋁粉末一起殘存者；可視所期望之靜電特性等分別使用之。 These resin binders are volatilized when heated, depending on the molecular weight, the type of the resin, etc., and the residue remains together with the aluminum powder due to thermal decomposition, and can be used depending on the desired electrostatic properties and the like.
又，溶媒亦可使用公知者。例如，除了水之外，亦可使用乙醇、甲苯、酮類、酯類等的有機溶劑。 Further, a known one can be used as the solvent. For example, an organic solvent such as ethanol, toluene, ketone or ester may be used in addition to water.
形成皮膜時，除了可將糊組成物使用例如輥、刷毛、噴灑、浸浴等的塗布方法來形成皮膜之外，也可藉由絹印孔版印刷等公知的印刷方法來形成。 When the film is formed, the paste composition may be formed by a coating method such as a roll, a bristles, a spray, or a bath to form a film, or may be formed by a known printing method such as stencil printing.
在使用基材的情況下，皮膜形成於基材的單面或雙面。在形成於雙面的情況下，宜將皮膜夾著基材以對稱方式配置。皮膜的厚度雖無特別限定，但以形成為燒結後所獲得之燒結層的平均厚度在5至1000μm，特別是5至50μm之箔狀為佳。 In the case of using a substrate, the film is formed on one side or both sides of the substrate. In the case of being formed on both sides, it is preferred to arrange the film in a symmetrical manner with the substrate interposed therebetween. Although the thickness of the film is not particularly limited, it is preferable that the sintered layer obtained after sintering has an average thickness of 5 to 1000 μm, particularly 5 to 50 μm.
可視需要使皮膜在20至300℃範圍內之溫度下乾燥。 The film may be dried at a temperature in the range of 20 to 300 ° C as needed.
第2步驟係藉由將皮膜以400至660℃之溫度燒結來形成燒結層。 The second step forms a sintered layer by sintering the film at a temperature of 400 to 660 °C.
燒結溫度設為400至660℃，宜為450至600℃。 燒結時間雖視燒結溫度等而異，但通常可在5至24小時左右的範圍內適宜決定。 The sintering temperature is set to 400 to 660 ° C, preferably 450 to 600 ° C. Although the sintering time varies depending on the sintering temperature, etc., it can be suitably determined in the range of about 5 to 24 hours.
燒結氣體環境並無特別限制，例如可為真空環境、惰性氣體環境、氧化性氣體環境(大氣)、還原性氣體環境等任一者皆可；特別是以真空環境或還原性氣體環境為佳。又，壓力條件係可為常壓、減壓或加壓之任一者皆可。 The sintering gas atmosphere is not particularly limited, and may be, for example, a vacuum atmosphere, an inert gas atmosphere, an oxidizing gas atmosphere (atmosphere), a reducing gas atmosphere, or the like; in particular, a vacuum atmosphere or a reducing gas atmosphere is preferred. Further, the pressure conditions may be any of normal pressure, reduced pressure, or pressurized.
再者，第1步驟後、第2步驟前宜預先進行在100至600℃之溫度範圍且保持時間在5小時以上之加熱處理(脫脂處理)。加熱處理環境並無特別限定，例如可在真空環境、惰性氣體環境或氧化性氣體環境中任一者皆可。又，壓力條件亦可為常壓、減壓或加壓中任一者。 Further, it is preferable to perform a heat treatment (degreasing treatment) in a temperature range of 100 to 600 ° C and a holding time of 5 hours or more before the first step and before the second step. The heat treatment environment is not particularly limited, and may be, for example, a vacuum atmosphere, an inert gas atmosphere, or an oxidizing gas atmosphere. Further, the pressure condition may be any of normal pressure, reduced pressure, or pressure.
在前述之第2步驟中，可獲得本發明之電極材。這表示，不實施蝕刻處理，就能直接作為鋁電解電容器用電極(電極箔)來使用。另一方面，前述電極材可視需要施行陽極氧化處理作為第3步驟，藉以形成介電體，並能將之作為電極。 In the second step described above, the electrode material of the present invention can be obtained. This means that it can be directly used as an electrode (electrode foil) for an aluminum electrolytic capacitor without performing an etching treatment. On the other hand, the electrode material may be subjected to anodizing treatment as a third step, whereby a dielectric body is formed and can be used as an electrode.
陽極氧化處理條件並無限定，通常是在濃度0.01莫耳以上且5莫耳以下、溫度30℃以上且100℃以下的硼酸溶液或己二酸銨水溶液中，將10mA/cm2以上400mA/cm2左右的電流施加5分鐘以上即可。 The anodizing treatment conditions are not limited, and are usually 10 mA/cm 2 or more and 400 mA/cm in a boric acid solution or an aqueous ammonium adipate solution having a concentration of 0.01 mol or more and 5 mol or less and a temperature of 30 ° C or more and 100 ° C or less. The current of about 2 can be applied for 5 minutes or more.
本發明之鋁電解電容器用電極材係將鋁及鋁合金中至少1種的粉末隔著電絕緣性粒子進行燒結藉以形成 燒結層，故可極力抑制燒結層中之前述粉末彼此間過度縮頸(過燒結)，並盡可能地減低粉末彼此間的接觸面積而確保有效表面積。因此，本發明之鋁電解電容器用電極材即便是用於在100V以下之低電壓下使用之低壓用電容器用途時，也能發揮超越利用習知之蝕刻處理所獲得之電極材的性能。 In the electrode material for an aluminum electrolytic capacitor of the present invention, at least one powder of aluminum and aluminum alloy is sintered by electrically insulating particles to form a powder. By sintering the layer, it is possible to suppress the excessive shrinkage (over-sintering) of the aforementioned powders in the sintered layer as much as possible, and to reduce the contact area between the powders as much as possible to ensure an effective surface area. Therefore, even when the electrode material for an aluminum electrolytic capacitor of the present invention is used for a low-voltage capacitor used at a low voltage of 100 V or less, it can exhibit performance superior to that of an electrode material obtained by a conventional etching treatment.
圖1所示者係使用了鱗片狀粉末(鋁薄片)之習知燒結層(不含電絕緣性粒子)之截面的掃描型電子顯微鏡觀測圖像。 Fig. 1 shows a scanning electron microscope observation image of a cross section of a conventional sintered layer (excluding electrically insulating particles) using a scaly powder (aluminum foil).
圖2所示者係使用了鱗片狀粉末(鋁薄片)及電絕緣性粒子之本發明之燒結層截面的掃描型電子顯微鏡觀測圖像。 Fig. 2 shows a scanning electron microscope observation image of a cross section of the sintered layer of the present invention using scaly powder (aluminum flake) and electrically insulating particles.
以下，例示實施例及比較例來具體地說明本發明。惟，本發明並不受實施例所限定。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the invention is not limited by the examples.
用使平均粒徑為3μm的鋁粉末(99.99%以上之高純度鋁粉末、長徑比(平均粒徑/平均厚度)1)與平均粒徑為0.5μm之氧化鋁粒子以下述比例均勻分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。平均粒徑的測定是使用日機裝股份有限公司製MICROTRAC來進行。 Aluminum powder having an average particle diameter of 3 μm (high-purity aluminum powder of 99.99% or more, aspect ratio (average particle diameter/average thickness) 1) and alumina particles having an average particle diameter of 0.5 μm were uniformly dispersed in the following ratio. A coating film having a thickness of 50 μm on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil) was obtained. The measurement of the average particle diameter was carried out using a MICROTRAC manufactured by Nikkiso Co., Ltd.
又，使用己二酸銨水溶液實施了陽極氧化處理。陽極氧化處理的條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2的電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁粉末與氧化鋁粒子之比(鋁粉末：氧化鋁粒子) Ratio of aluminum powder to alumina particles (aluminum powder: alumina particles)
實施例1-1 200：1(重量比)、300：1(體積比) Example 1-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例1-2 20：1(重量比)、30：1(體積比) Example 1-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例1-3 10：1(重量比)、15：1(體積比) Example 1-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例1-4 5：1(重量比)、15：2(體積比) Example 1-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例1-5 2：1(重量比)、3：1(體積比) Example 1-5 2:1 (weight ratio), 3:1 (volume ratio)
比較例1-1(空白試驗：以下稱「BL」)鋁粉末100% Comparative Example 1-1 (blank test: hereinafter referred to as "BL") aluminum powder 100%
將各電極材之靜電容量表示於下述表1。 The electrostatic capacitance of each electrode material is shown in Table 1 below.
鋁粉末：氧化鋁粒子之重量比在2：1至200：1之範圍，與BL相較之下，在所有的電壓區域皆顯示較高容量。 The aluminum powder: alumina particles have a weight ratio ranging from 2:1 to 200:1, and exhibit higher capacity in all voltage regions than BL.
用使平均粒徑為80μm的鋁粉末(99.99%以上的高純度鋁粉末、長徑比(平均粒徑/平均厚度)1)與平均粒徑 為5μm的氧化鋁粒子以下述比例均勻分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層100μm之燒結體。 Aluminum powder having an average particle diameter of 80 μm (high-purity aluminum powder of 99.99% or more, aspect ratio (average particle diameter / average thickness) 1) and average particle diameter A coating film obtained by uniformly dispersing alumina particles of 5 μm in the following ratio was obtained, and a sintered body having a thickness of 100 μm on both sides of a 20 μm aluminum foil substrate (high-purity aluminum foil of 99.99% or more) was obtained.
又，使用己二酸銨水溶液，實施了陽極氧化處理。陽極氧化處理的條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，且施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁粉末與氧化鋁粒子之比(鋁粉末：氧化鋁粒子) Ratio of aluminum powder to alumina particles (aluminum powder: alumina particles)
實施例2-1 200：1(重量比)、300：1(體積比) Example 2-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例2-2 20：1(重量比)、30：1(體積比) Example 2-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例2-3 10：1(重量比)、15：1(體積比) Example 2-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例2-4 5：1(重量比)、15：2(體積比) Example 2-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例2-5 2：1(重量比)、3：1(體積比) Example 2-5 2:1 (weight ratio), 3:1 (volume ratio)
比較例2-1(BL)鋁粉末100% Comparative Example 2-1 (BL) aluminum powder 100%
將各電極材之靜電容量表示於下述表2。 The electrostatic capacitance of each electrode material is shown in Table 2 below.
即便是改變了粒徑、積層厚度之燒結體，也會得到與實施例1-1至1-5相同的傾向。 Even in the case of a sintered body in which the particle diameter and the thickness of the layer were changed, the same tendency as in Examples 1-1 to 1-5 was obtained.
用使平均粒徑為5μm、長徑比(平均粒徑/平均厚度)=5(5μm/1μm)之鋁薄片，與平均粒徑為0.5μm的氧化鋁粒子以下述比例均勻地分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 An aluminum flake having an average particle diameter of 5 μm and an aspect ratio (average particle diameter/average thickness) = 5 (5 μm / 1 μm) was uniformly dispersed in the following ratio with alumina particles having an average particle diameter of 0.5 μm. By coating a film, a sintered body of 50 μm each of which was laminated on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil) was obtained.
又，使用己二酸銨水溶液，實施了陽極氧化處理。陽極氧化處理之條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁薄片與氧化鋁粒子之比(鋁薄片：氧化鋁粒子) Ratio of aluminum flakes to alumina particles (aluminum flakes: alumina particles)
實施例3-1 200：1(重量比)、300：1(體積比) Example 3-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例3-2 20：1(重量比)、30：1(體積比) Example 3-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例3-3 10：1(重量比)、15：1(體積比) Example 3-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例3-4 5：1(重量比)、15：2(體積比) Example 3-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例3-5 2：1(重量比)、3：1(體積比) Example 3-5 2:1 (weight ratio), 3:1 (volume ratio)
實施例3-6 1：1(重量比)、3：2(體積比) Example 3-6 1:1 (weight ratio), 3:2 (volume ratio)
實施例3-7 1：2(重量比)、3：4(體積比) Example 3-7 1:2 (weight ratio), 3:4 (volume ratio)
比較例3-1(BL)鋁薄片100% Comparative Example 3-1 (BL) aluminum flakes 100%
將各電極材之靜電容量表示於下述表3。 The electrostatic capacitance of each electrode material is shown in Table 3 below.
使用了鋁薄片時係自BL提高了最大80%左右的容量。可看出使用鱗片狀粉末(鋁薄片)的情況下相較於使用球狀粉末時，其併用電絕緣性粒子(氧化鋁粒子)的效果較大。 When aluminum flakes are used, the capacity is increased by up to about 80% from BL. It can be seen that when a scaly powder (aluminum flake) is used, the effect of using electrically insulating particles (alumina particles) is larger than when a spherical powder is used.
用使平均粒徑為5μm、長徑比(平均粒徑/平均厚度)=100(5μm/0.05μm)的鋁薄片，與平均粒徑為0.01μm之氧化鋁粒子以下述比例均勻地分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 An aluminum flake having an average particle diameter of 5 μm and an aspect ratio (average particle diameter/average thickness) = 100 (5 μm/0.05 μm) was uniformly dispersed in the following ratio with alumina particles having an average particle diameter of 0.01 μm. The coated film was obtained by laminating a sintered body of 50 μm on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil).
又，使用己二酸銨水溶液，實施了陽極氧化處理。陽極氧化處理的條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁薄片與氧化鋁粒子之比(鋁薄片：氧化鋁粒子) Ratio of aluminum flakes to alumina particles (aluminum flakes: alumina particles)
實施例4-1 200：1(重量比)、300：1(體積比) Example 4-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例4-2 20：1(重量比)、30：1(體積比) Example 4-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例4-3 10：1(重量比)、15：1(體積比) Example 4-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例4-4 5：1(重量比)、15：2(體積比) Example 4-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例4-5 2：1(重量比)、3：1(體積比) Example 4-5 2:1 (weight ratio), 3:1 (volume ratio)
實施例4-6 1：1(重量比)、3：2(體積比) Example 4-6 1:1 (weight ratio), 3:2 (volume ratio)
實施例4-7 1：2(重量比)、3：4(體積比) Example 4-7 1:2 (weight ratio), 3:4 (volume ratio)
比較例4-1(BL)鋁薄片100% Comparative Example 4-1 (BL) aluminum flakes 100%
將各電極材的靜電容量表示於下述表4。 The electrostatic capacitance of each electrode material is shown in Table 4 below.
長徑比極大(厚度薄，比表面積大)的鋁薄片在BL的狀態下容量低。這是由於燒結層之截面的狀態會變成如圖1所示的樣子。然而，藉由將氧化鋁粒子作為間隔物來使其分散，低壓容量(5V)最大甚至可達800倍。 The aluminum flake having a large aspect ratio (thickness and large specific surface area) has a low capacity in the state of BL. This is because the state of the cross section of the sintered layer becomes as shown in FIG. However, by dispersing the alumina particles as spacers, the low-pressure capacity (5 V) can be up to 800 times.
該容量係遠高於使用了以習知之蝕刻處理所得之鋁箔(以下稱為「經蝕刻箔」)的電極材的最大容量(5V、3600μF/10cm2)。 This capacity is much higher than the maximum capacity (5 V, 3600 μF/10 cm 2 ) of the electrode material using the aluminum foil obtained by the conventional etching treatment (hereinafter referred to as "etched foil").
100V容量的值會低，一般認為是厚度小於 0.2μm的鋁薄片，難以形成具有100V之耐電壓之充足厚度的氧化皮膜。 The value of 100V capacity will be low, generally considered to be less than the thickness. With an aluminum sheet of 0.2 μm, it is difficult to form an oxide film having a sufficient thickness of a withstand voltage of 100V.
用使平均粒徑為3μm、長徑比(平均粒徑/平均厚度)=3(3μm/1μm)之鋁薄片，與平均粒徑為0.5μm的氧化鋁粒子以下述比例均勻地分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 An aluminum flake having an average particle diameter of 3 μm and an aspect ratio (average particle diameter/average thickness) = 3 (3 μm / 1 μm) was uniformly dispersed in the following ratio with alumina particles having an average particle diameter of 0.5 μm. By coating a film, a sintered body of 50 μm each of which was laminated on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil) was obtained.
又，使用己二酸銨水溶液，實施了陽極氧化處理。陽極氧化處理之條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁薄片與氧化鋁粒子之比(鋁薄片：氧化鋁粒子) Ratio of aluminum flakes to alumina particles (aluminum flakes: alumina particles)
實施例5-1 200：1(重量比)、300：1(體積比) Example 5-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例5-2 20：1(重量比)、30：1(體積比) Example 5-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例5-3 10：1(重量比)、15：1(體積比) Example 5-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例5-4 5：1(重量比)、15：2(體積比) Example 5-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例5-5 2：1(重量比)、3：1(體積比) Example 5-5 2:1 (weight ratio), 3:1 (volume ratio)
實施例5-6 1：1(重量比)、3：2(體積比) Example 5-6 1:1 (weight ratio), 3:2 (volume ratio)
實施例5-7 1：2(重量比)、3：4(體積比) Example 5-7 1:2 (weight ratio), 3:4 (volume ratio)
比較例5-1(BL)鋁薄片100% Comparative Example 5-1 (BL) aluminum flakes 100%
即便是使用與實施例3-1至3-7相比之下平均粒徑較小的鋁薄片，也得到了相同的傾向。 Even when aluminum flakes having a smaller average particle diameter than those of Examples 3-1 to 3-7 were used, the same tendency was obtained.
用使平均粒徑為10μm、長徑比(平均粒徑/平均厚度)=10(10μm/1μm)之鋁薄片，與平均粒徑為0.5μm的氧化鋁粒子以下述比例均勻地分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 An aluminum flake having an average particle diameter of 10 μm and an aspect ratio (average particle diameter/average thickness)=10 (10 μm/1 μm) was uniformly dispersed in the following ratio with alumina particles having an average particle diameter of 0.5 μm. By coating a film, a sintered body of 50 μm each of which was laminated on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil) was obtained.
又，使用己二酸銨水溶液，實施了陽極氧化處理。陽極氧化處理之條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁薄片與氧化鋁粒子之比(鋁薄片：氧化鋁粒子) Ratio of aluminum flakes to alumina particles (aluminum flakes: alumina particles)
實施例6-1 200：1(重量比)、300：1(體積比) Example 6-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例6-2 20：1(重量比)、30：1(體積比) Example 6-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例6-3 10：1(重量比)、15：1(體積比) Example 6-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例6-4 5：1(重量比)、15：2(體積比) Example 6-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例6-5 2：1(重量比)、3：1(體積比) Example 6-5 2:1 (weight ratio), 3:1 (volume ratio)
實施例6-6 1：1(重量比)、3：2(體積比) Example 6-6 1:1 (weight ratio), 3:2 (volume ratio)
實施例6-7 1：2(重量比)、3：4(體積比) Example 6-7 1:2 (weight ratio), 3:4 (volume ratio)
比較例6-1(BL)鋁薄片100% Comparative Example 6-1 (BL) aluminum flakes 100%
即便是使用與實施例3-1至3-7相比之下平均粒徑較大的鋁薄片，也得到了相同的傾向。 Even when aluminum flakes having a larger average particle diameter than those of Examples 3-1 to 3-7 were used, the same tendency was obtained.
用使平均粒徑為5μm、長徑比(平均粒徑/平均厚度)=5(5μm/1μm)之鋁薄片，與平均粒徑為0.5μm的氧化鈦粒子以下述比例均勻地分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 An aluminum flake having an average particle diameter of 5 μm and an aspect ratio (average particle diameter/average thickness) = 5 (5 μm/1 μm) was uniformly dispersed in the following ratio with titanium oxide particles having an average particle diameter of 0.5 μm. By coating a film, a sintered body of 50 μm each of which was laminated on both sides of a 20 μm aluminum foil substrate (99.99% or more of high-purity aluminum foil) was obtained.
又，使用己二酸銨水溶液，實施了陽極氧化處 理。陽極氧化處理之條件設定成上述水溶液濃度為0.3莫耳、溫度為60℃，並施加25mA/cm2之電流10分鐘。 Further, an anodizing treatment was carried out using an aqueous solution of ammonium adipate. The conditions of the anodizing treatment were set such that the above aqueous solution concentration was 0.3 mol, the temperature was 60 ° C, and a current of 25 mA/cm 2 was applied for 10 minutes.
鋁薄片與氧化鈦粒子之比(鋁薄片：氧化鈦粒子) Ratio of aluminum flakes to titanium oxide particles (aluminum flakes: titanium oxide particles)
實施例7-1 200：1(重量比)、300：1(體積比) Example 7-1 200:1 (weight ratio), 300:1 (volume ratio)
實施例7-2 20：1(重量比)、30：1(體積比) Example 7-2 20:1 (weight ratio), 30:1 (volume ratio)
實施例7-3 10：1(重量比)、15：1(體積比) Example 7-3 10:1 (weight ratio), 15:1 (volume ratio)
實施例7-4 5：1(重量比)、15：2(體積比) Example 7-4 5:1 (weight ratio), 15:2 (volume ratio)
實施例7-5 2：1(重量比)、3：1(體積比) Example 7-5 2:1 (weight ratio), 3:1 (volume ratio)
實施例7-6 1：1(重量比)、3：2(體積比) Example 7-6 1:1 (weight ratio), 3:2 (volume ratio)
實施例7-7 1：2(重量比)、3：4(體積比) Example 7-7 1:2 (weight ratio), 3:4 (volume ratio)
比較例7-1(BL)鋁薄片100% Comparative Example 7-1 (BL) aluminum flakes 100%
容量之值與實施例3-1至3-7大致呈同等。可知即便不是氧化鋁粒子，只要是同粒徑下具有電絕緣性者，也能發揮作為間隔物的機能。 The values of the capacities are substantially the same as those of the examples 3-1 to 3-7. It is understood that even if it is not alumina particles, it can function as a spacer as long as it has electrical insulation at the same particle diameter.
用使下述鋁粉末(1)至(9)與平均粒徑0.01μm之氧化鋁粒子以10：1(重量比)之比率分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 A coating film obtained by dispersing the following aluminum powders (1) to (9) and alumina particles having an average particle diameter of 0.01 μm in a ratio of 10:1 (weight ratio) to obtain an aluminum foil substrate of 20 μm (99.99) A sintered body of 50 μm each of which is laminated on both sides of the high-purity aluminum foil of % or more.
(1)實施例8-1 平均粒徑=3μm長徑比1的鋁粉末 (1) Example 8-1 Aluminum powder having an average particle diameter = 3 μm aspect ratio 1
(2)實施例8-2 平均粒徑=3μm長徑比3(3μm/1μm)的鋁薄片 (2) Example 8-2 Aluminum flakes having an average particle diameter = 3 μm aspect ratio 3 (3 μm / 1 μm)
(3)實施例8-3 平均粒徑=3μm長徑比25(3μm/0.12μm)的鋁薄片 (3) Example 8-3 Aluminum flakes having an average particle diameter = 3 μm aspect ratio 25 (3 μm / 0.12 μm)
(4)實施例8-4 平均粒徑=3μm長徑比60(3μm/0.05μm)的鋁薄片 (4) Example 8-4 Aluminum flakes having an average particle diameter of 3 μm and an aspect ratio of 60 (3 μm/0.05 μm)
(5)實施例8-5 平均粒徑=5μm長徑比5(5μm/1μm)的鋁薄片 (5) Example 8-5 Aluminum flakes having an average particle diameter = 5 μm aspect ratio 5 (5 μm / 1 μm)
(6)實施例8-6 平均粒徑=5μm長徑比100(5μm/0.05μm)的鋁薄片 (6) Example 8-6 Aluminum flakes having an average particle diameter of 5 μm and an aspect ratio of 100 (5 μm/0.05 μm)
(7)實施例8-7 平均粒徑=10μm長徑比25(10μm/0.4μm)的鋁薄片 (7) Example 8-7 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 25 (10 μm / 0.4 μm)
(8)實施例8-8 平均粒徑=10μm長徑比200(10μm/0.05μm)的鋁薄片 (8) Example 8-8 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 200 (10 μm/0.05 μm)
(9)實施例8-9 平均粒徑=10μm長徑比1000(10μm/0.01μm)的鋁薄片 (9) Example 8-9 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 1000 (10 μm/0.01 μm)
比較例8-1 經蝕刻箔最高程度的容量 Comparative Example 8-1 The highest degree of capacity of the etched foil
比較例8-2(BL)平均粒徑3μm長徑比1的鋁粉末(僅有鋁粉末之習知積層箔) Comparative Example 8-2 (BL) Aluminum powder having an average particle diameter of 3 μm and aspect ratio 1 (a conventional laminated foil of only aluminum powder)
相對於各種粒徑、長徑比之鋁粉末，使平均粒徑0.01μm之氧化鋁粒子分散可獲得高容量。又可知長徑比越大，就能獲得越大的效果。 The alumina powder having an average particle diameter of 0.01 μm is dispersed in a wide range of aluminum powders having various particle diameters and aspect ratios to obtain a high capacity. It can also be seen that the larger the aspect ratio, the greater the effect can be obtained.
在比較例8-2(BL)中雖未達經蝕刻箔的最高容量，但在實施例8-7中100V以下的電壓區域全部都超越經蝕刻箔的最高容量。在實施例8-3、8-4、8-6、8-8中，在10V以下具有優異的容量。如實施例8-9，鋁薄片的厚度若小於0.02μm，因未形成足夠厚度之耐電壓皮膜之故，即便在10V下容量也會變低。 Although the highest capacity of the etched foil was not obtained in Comparative Example 8-2 (BL), the voltage regions of 100 V or less in Example 8-7 all exceeded the maximum capacity of the etched foil. In Examples 8-3, 8-4, 8-6, and 8-8, it had an excellent capacity below 10V. As in the case of Example 8-9, if the thickness of the aluminum flakes is less than 0.02 μm, the capacity is lowered even at 10 V because a voltage-resistant film having a sufficient thickness is not formed.
關於實施例8-2及8-5，在100V區域呈超越經蝕刻箔之值。實施例8-1亦有較BL容量提高之傾向，例如在150V之容量值為51.2μF，確認有超越經蝕刻箔的容量(約48μF)。 With regard to Examples 8-2 and 8-5, the value in the 100 V region exceeded the value of the etched foil. Example 8-1 also has a tendency to increase the BL capacity, for example, a capacity value of 51.2 μF at 150 V, which is confirmed to have a capacity exceeding the etched foil (about 48 μF).
藉由選擇適合於各鋁粉末之電壓區域，在各電壓區域都能獲得較經蝕刻箔高容量的電極。再者，長徑比 超過1000的鋁薄片，容易在積層箔之製造步驟中發生塗布之乾燥不良或在熱處理時發生之脫脂不良，而難以獲得穩定的製品。 By selecting a voltage region suitable for each aluminum powder, an electrode having a higher capacity than the etched foil can be obtained in each voltage region. Furthermore, the aspect ratio When the aluminum foil exceeds 1,000, it is easy to cause poor drying of the coating in the production step of the laminated foil or poor degreasing which occurs during heat treatment, and it is difficult to obtain a stable product.
用使下述鋁粉末(1)至(9)與平均粒徑0.5μm之氧化鋁粒子以10：1(重量比)之比率分散而得之塗膜，製得在20μm之鋁箔基材(99.99%以上的高純度鋁箔)上雙面各積層50μm之燒結體。 A coating film obtained by dispersing the following aluminum powders (1) to (9) and alumina particles having an average particle diameter of 0.5 μm at a ratio of 10:1 (weight ratio) was used to prepare an aluminum foil substrate of 20 μm (99.99). A sintered body of 50 μm each of which is laminated on both sides of the high-purity aluminum foil of % or more.
(1)實施例9-1 平均粒徑=3μm長徑比1的鋁粉末 (1) Example 9-1 Aluminum powder having an average particle diameter = 3 μm aspect ratio 1
(2)實施例9-2 平均粒徑=3μm長徑比3(3μm/1μm)的鋁薄片 (2) Example 9-2 Aluminum flakes having an average particle diameter of 3 μm and an aspect ratio of 3 (3 μm / 1 μm)
(3)實施例9-3 平均粒徑=3μm長徑比25(3μm/0.12μm)的鋁薄片 (3) Example 9-3 Aluminum flakes having an average particle diameter of 3 μm and an aspect ratio of 25 (3 μm / 0.12 μm)
(4)實施例9-4 平均粒徑=3μm長徑比60(3μm/0.05μm)的鋁薄片 (4) Example 9-4 Aluminum flakes having an average particle diameter of 3 μm and an aspect ratio of 60 (3 μm/0.05 μm)
(5)實施例9-5 平均粒徑=5μm長徑比5(5μm/1μm)的鋁薄片 (5) Example 9-5 Aluminum flakes having an average particle diameter of 5 μm and an aspect ratio of 5 (5 μm / 1 μm)
(6)實施例9-6 平均粒徑=5μm長徑比100(5μm/0.05μm)的鋁薄片 (6) Example 9-6 Aluminum flakes having an average particle diameter of 5 μm and an aspect ratio of 100 (5 μm/0.05 μm)
(7)實施例9-7 平均粒徑=10μm長徑比25(10μm/0.4μm)的鋁薄片 (7) Example 9-7 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 25 (10 μm / 0.4 μm)
(8)實施例9-8 平均粒徑=10μm長徑比200(10μm/0.05μm)的鋁薄片 (8) Example 9-8 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 200 (10 μm/0.05 μm)
(9)實施例9-9平均粒徑=10μm長徑比1000(10μm/0.01μm)的鋁薄片 (9) Example 9-9 Aluminum flakes having an average particle diameter of 10 μm and an aspect ratio of 1000 (10 μm/0.01 μm)
比較例9-1 經蝕刻箔最高程度的容量 Comparative Example 9-1 The highest degree of capacity of the etched foil
比較例9-2(BL)平均粒徑3μm、長徑比1的鋁粉末(僅有鋁粉末之習知積層箔) Comparative Example 9-2 (BL) Aluminum powder having an average particle diameter of 3 μm and an aspect ratio of 1 (a conventional laminated foil of only aluminum powder)
使用了平均粒徑0.5μm之氧化鋁粒子時之結果亦與實施例8-1至8-9相同。 The results when alumina particles having an average particle diameter of 0.5 μm were used were also the same as in Examples 8-1 to 8-9.
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| CN109036852B (en) * | 2018-08-13 | 2020-09-18 | 浙江华义瑞东新材料有限公司 | Three-dimensional porous aluminum electrode foil and preparation method thereof |
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| CN113458143B (en) * | 2021-09-02 | 2021-11-23 | 西安稀有金属材料研究院有限公司 | Method for preparing aluminum electrolytic capacitor anode foil by using cold rolling mill |
| CN115083784B (en) * | 2022-07-15 | 2024-01-02 | 新疆众和股份有限公司 | Slurry for sintered foil, preparation method of sintered foil and aluminum electrolytic capacitor |
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