JPH01212733A - Aluminum-alloy foil for electrolytic capacitor cathode - Google Patents
Aluminum-alloy foil for electrolytic capacitor cathodeInfo
- Publication number
- JPH01212733A JPH01212733A JP3839188A JP3839188A JPH01212733A JP H01212733 A JPH01212733 A JP H01212733A JP 3839188 A JP3839188 A JP 3839188A JP 3839188 A JP3839188 A JP 3839188A JP H01212733 A JPH01212733 A JP H01212733A
- Authority
- JP
- Japan
- Prior art keywords
- foil
- etching
- alloy
- alloy foil
- electrolytic capacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011888 foil Substances 0.000 title claims abstract description 45
- 239000003990 capacitor Substances 0.000 title claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 31
- 229910045601 alloy Inorganic materials 0.000 abstract description 22
- 239000000956 alloy Substances 0.000 abstract description 22
- 238000000137 annealing Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、銅（以下Ｃｕとする）、マグネシウム（以下
Ｍｇとする）、及びコバルト（以下Ｃ。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applicable to copper (hereinafter referred to as Cu), magnesium (hereinafter referred to as Mg), and cobalt (hereinafter referred to as C).
とする）及び／又はニッケル（以下Ｎｉとする）を合金
成分とする新規な組成の電解コンデンサ陰極用アルミニ
ウム（以下ＡＱとする）合金箔に関する。The present invention relates to an aluminum (hereinafter referred to as AQ) alloy foil for electrolytic capacitor cathodes having a novel composition containing nickel (hereinafter referred to as Ni) and/or nickel (hereinafter referred to as Ni) as an alloy component.
従来技術とその問題点
電解コンデンサの静電容量（Ｃ）を増大させるためには
、陽極部の静電容量（ＣＡ）のみならず、陰極部（ｃｏ
）をも増大させる必要がある。Prior art and its problems In order to increase the capacitance (C) of an electrolytic capacitor, it is necessary to increase not only the capacitance (CA) of the anode part but also the cathode part (CO).
) also needs to be increased.
従来からも、エツチングによってＡΩ箔の表面積を拡大
させ、陰極部の静電容量を増大させることが行われてい
る。例えば、特開昭４４−２５０１６号公報は、Ｃｕを
０．１〜０．５％（本明細書においては、“％゛とある
のは、全て“重囲％”を表す）含有する電解コンデンサ
用ＡＱ合金箔を開示している。しかしながら、電解コン
デンサを使用する各種分野での急速な技術の進歩に伴っ
て、電解コンデンサの陰極部の静電容量についても、更
に一段の改善が望まれている。Conventionally, etching has been used to expand the surface area of AΩ foil and increase the capacitance of the cathode portion. For example, Japanese Patent Application Laid-Open No. 44-25016 discloses an electrolytic capacitor containing 0.1 to 0.5% of Cu (in this specification, all "%" represents "overlapping %"). However, with the rapid advancement of technology in various fields where electrolytic capacitors are used, further improvements in the capacitance of the cathode portion of electrolytic capacitors are desired. There is.
すなわち、現在使用されている陰極箔は、エツチング前
に焼鈍による調質を行うことが多いが、この焼鈍時に形
成される箔表面の酸化皮膜が、通常強固で且つ不均一で
あるため、化学反応を主体とするエツチングにおいては
、エツチングが十分に進行しなかったり、均一なエツチ
ングが行われなかったりする。従って、箔の酸化皮膜が
薄く且つ均一な状態でエツチングを行うために、酸素濃
度の極めて低い条件下に箔の焼鈍を行ったり、或いはエ
ツチングに先立って箔から酸化皮膜を除去する前処理を
行ったりしている。In other words, the cathode foils currently in use are often tempered by annealing before etching, but the oxide film formed on the foil surface during this annealing is usually strong and non-uniform, so chemical reactions may occur. In etching based on etching, the etching may not progress sufficiently or may not be etched uniformly. Therefore, in order to perform etching with a thin and uniform oxide film on the foil, the foil is annealed under extremely low oxygen concentration conditions, or a pretreatment is performed to remove the oxide film from the foil prior to etching. I'm doing it.
問題点を解決するための手段
本発明者は、上記の如き技術の現状に鑑みて鋭意研究を
重ねた結果、ＡＱに特定量のＣｕ、Ｍｇ並びにＣｏ及び
／又はＮｉを配合した合金が、電解コンデンサ陰極用Ａ
Ｑ合金箔として優れた特性を具備していることを見出し
た。すなわち、本発明は、ＣｕＯ，１〜０．７％、Ｍｇ
０．００５〜１．０％及びＣｏ並びにＮｉの少なくとも
一種０．００５〜１．０％を含有する電解コンデンサ陰
極用Ａ９合金箔を提供するものである。Means for Solving the Problems As a result of extensive research in view of the current state of the technology as described above, the present inventor discovered that an alloy containing specific amounts of Cu, Mg, Co and/or Ni in AQ can be used in electrolysis. A for capacitor cathode
It has been found that it has excellent properties as a Q alloy foil. That is, the present invention provides an A9 alloy foil for an electrolytic capacitor cathode containing 1 to 0.7% of CuO, 0.005 to 1.0% of Mg, and 0.005 to 1.0% of at least one of Co and Ni. This is what we provide.
化学反応を主体とするＡＱ箔のエツチングにおいては、
所定のエツチング溶液に対するＡＱ箔の化学反応力を高
めるために、以下の条件を満たす必要がある：
（１）箔表面に形成された酸化皮膜の耐蝕性を適度に低
下させる。In the etching of AQ foil, which mainly involves chemical reactions,
In order to increase the chemical reactivity of AQ foil to a given etching solution, it is necessary to satisfy the following conditions: (1) Corrosion resistance of the oxide film formed on the foil surface should be moderately reduced.
（２）エツチング開始点となる拠点を増加させる。(2) Increase the number of bases that serve as etching starting points.
（３）箔の厚さ方向の中心に向かってエツチングが進行
し易くする。(3) Etching progresses easily toward the center of the foil in the thickness direction.
上記の条件（１）に関しては、主としてＭｇが大きく寄
与する。すなわち、Ｍｇが０．００５〜１％の範囲内に
ある場合には、エツチング前に行われる焼鈍による調質
時に、Ｍｇが１箔の表面に拡散して濃縮し、焼鈍により
形成される酸化皮膜の耐蝕性を低下させるので、エツチ
ングが円滑に進行する。Ｍｇの量が１％を上回る場合に
は、焼鈍時のＡＱ箔間の密着が強固となり、巻戻しが困
難となる。Ｍｇが０．００５％未満の場合には、添加の
効果がほとんど認められない。Regarding the above condition (1), Mg mainly makes a large contribution. That is, when Mg is in the range of 0.005 to 1%, Mg diffuses and concentrates on the surface of one foil during tempering by annealing performed before etching, and an oxide film is formed by annealing. Since the corrosion resistance of the material is reduced, etching progresses smoothly. If the amount of Mg exceeds 1%, the adhesion between the AQ foils during annealing becomes strong and unwinding becomes difficult. When Mg is less than 0.005%, almost no effect of addition is observed.
条件（２）に関しては、０．００５〜１％の範囲で含有
されるＣＯおよび／またはＮｉが、主として効果を発揮
する。これらの元素は、ＡＱマトリックス中にほとんど
固溶せず、ＡＲ−Ｃｏ化合物またはＡｌ２−Ｎｉ化合物
として析出する。これらの化合物は、ＡＱに対して貴で
あるので、該化合物とＡＱ・マトリックスとの間の電位
差が高まる。従って、この様な化合物を均一に分散させ
た状態でＡＱ合金箔をエツチングに供する場合には、Ａ
Ｑ・マトリックス中にエツチング開始点を多数発生させ
ることが出来る。Ｃｏおよび／またはＮｉの足が０．０
０５％未満の場合には、添加の効果があまり無く、一方
、１％を超える場合には、エツチングのコントロールが
困難となる。Regarding condition (2), CO and/or Ni contained in the range of 0.005 to 1% mainly exhibits the effect. These elements hardly dissolve in solid solution in the AQ matrix and precipitate as AR-Co compounds or Al2-Ni compounds. Since these compounds are noble to AQ, the potential difference between them and the AQ matrix increases. Therefore, when etching AQ alloy foil with such compounds uniformly dispersed, AQ
Many etching starting points can be generated in the Q-matrix. Co and/or Ni foot is 0.0
If it is less than 0.5%, the effect of addition is not so great, while if it exceeds 1%, it becomes difficult to control etching.
条件（３）に関しては、０．１〜０．７％の範囲で含有
されるＣｕが主に効果を発揮する。Ｃｕは、ＡＱ・マト
リックス中に固溶し易く、マトリックスの腐蝕電位を高
め、化学的溶解を促進するため、エツチングビットが成
長し易くなる。Ｃｕの量が０．１％未満では、添加の効
果があまり認められず、一方、０．７％を上回る場合に
は、やはりエツチングのコントロールが困難となる。Regarding condition (3), Cu contained in the range of 0.1 to 0.7% mainly exhibits the effect. Cu easily forms a solid solution in the AQ matrix, increases the corrosion potential of the matrix, and promotes chemical dissolution, making it easier for etching bits to grow. If the amount of Cu is less than 0.1%, the effect of addition is not so noticeable, while if it exceeds 0.7%, it becomes difficult to control etching.
なお、本発明ＡＱ合金箔は、夫々０．５％までのＦ ６
％ Ｓ ｔ ｓまた夫々０．０５％までのＭ ｎ 。The AQ alloy foil of the present invention contains up to 0.5% F6, respectively.
% S t s and M n up to 0.05% each.
ＺｎＳＴｉなどの微量の不可避不純物を含んでいても良
い。It may contain a trace amount of unavoidable impurities such as ZnSTi.
発明の効果 本発明によれば、以下の如き効果が達成される。Effect of the invention According to the present invention, the following effects are achieved.
（イ）焼鈍時にＡＱ箔表面に形成される酸化皮膜の耐蝕
性が低いので、エツチングがスムースに進行する。(a) Since the oxide film formed on the surface of the AQ foil during annealing has low corrosion resistance, etching progresses smoothly.
（ロ）エツチング時の反応性が高いので、エツチング箔
の表面積が著しく拡大される。(b) Since the reactivity during etching is high, the surface area of the etching foil is significantly expanded.
（ハ）電解コンデンサ陰極箔としての静電容世が高い。(c) High electrostatic capacity as an electrolytic capacitor cathode foil.
（ニ）エツチング後の箔の強度が高い。(d) The strength of the foil after etching is high.
実施例
以下実施例を示し、本発明の特徴とするところをより一
層明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
実施例１
一次電解ＡＱ地金に所定量の添加成分を加えて、溶解し
、ＡＱ合金スラブを鋳造した。Example 1 A predetermined amount of additional components were added to a primary electrolytic AQ ingot and melted to cast an AQ alloy slab.
得られたスラブを通常の熱間圧延及び冷間圧延に供して
、厚さ５０μｍの合金箔を得た後、真空下に４００°Ｃ
で５時間焼鈍を行い、次いで冷却した。The obtained slab was subjected to normal hot rolling and cold rolling to obtain an alloy foil with a thickness of 50 μm, and then heated at 400°C under vacuum.
Annealing was carried out for 5 hours, and then cooled.
かくして得られた合金箔のＡＱ以外の合金成分含有量（
％）を第１表に示す。The alloy component content other than AQ of the alloy foil thus obtained (
%) are shown in Table 1.
なお、第１表において、試料Ｎ００１〜６は、本発明に
よるＡ９合金を示し、試料Ｎｏ、 ７〜１２は、比較Ａ
２合金を示す。In Table 1, samples Nos. 001 to 6 represent A9 alloys according to the present invention, and samples Nos. 7 to 12 represent comparative A
2 alloys are shown.
第１表
試料 Ｆｅ Ｓｉ Ｃｕ Ｍｇ Ｃｏ Ｎ
ｉＮｏ。Table 1 Samples Fe Si Cu Mg Co N
iNo.
１ ０．０７０．０４０．２００．０５０．０３−２
／／ ／／ ／／ ／／ Ｑ、１Ｑ−３／／
／／ ／／ ／／ Ｑ、３Ｑ−４／／ ／
／ ／／ ／／ ０．Ｑ３５ ／／ ／／
／／ ／／ Ｑ、ｌＱ６ ／／ ／／
／／ ／／ Ｑ、３Ｑ７ 〃” 〃０．０
００．１０−
８ ／／ ／／ ／／ ／／ Ｑ、ＩＱ９
０．１５’〆 〃０．０５−−
１０ ０．３００．１０ ” 〃−−１１ｌｌ”
” ０．００− −
１２ ０．０７０．０４０．０００．０５０．１０−得
られた箔を以下の２つの条件でエツチングした。1 0.070.040.200.050.03-2
// // // // // Q, 1Q-3//
// // // // Q, 3Q-4// /
／ ／／ ／／ 0. Q35 // //
// // Q, lQ6 // //
// // Q, 3Q7 〃” 〃0.0
00.10- 8 // // // // // Q, IQ9
0.15'〆 〃0.05-- 10 0.300.10"〃--11ll"
0.00--12 0.070.040.000.050.10-The obtained foil was etched under the following two conditions.
条件Ｉ：
１００℃に保持した１０％塩酸溶液に箔を１５秒間浸漬
し、化学エツチングを行った。次いで、５％ホウ酸溶液
中で３ｖの化成を行った後、８％ホウ酸アンモニウム液
中でＬＣＲメーターにより静電容量（Ｃａｐ：単位はμ
Ｆ／ｃ♂）を測定した。Condition I: Chemical etching was performed by immersing the foil in a 10% hydrochloric acid solution maintained at 100° C. for 15 seconds. Next, after performing 3V chemical conversion in a 5% boric acid solution, the capacitance (Cap: unit is μ) was measured using an LCR meter in an 8% ammonium borate solution.
F/c♂) was measured.
条件■：
条件Ｉと同一のエツチング液中で箔の溶解量が約４．０
ｍｇ／ｃｔｌとなるまでエツチングを行なった後、条件
Ｉと同様にして、静電容ｆｆ１（Ｃａｐ：単位はμＦ／
ｃＪ）を測定した。また、この時のエツチド箔の強度（
単位はｋｇ／ １ ｃｍ巾）を測定した。Condition ■: The amount of foil dissolved in the same etching solution as Condition I is approximately 4.0.
After etching until it reaches mg/ctl, the capacitance ff1 (Cap: unit is μF/
cJ) was measured. Also, the strength of the etched foil at this time (
The unit is kg/1 cm width).
結果は、第２表に示す通りである。The results are shown in Table 2.
第２表
Ｎα
１ ３７３ ４１０ １．８
２ ４２０ ４３０ ２．０
３ ４８５ ４４５ ２．１
４ ３５８ ４０３ １．８
５ ４０５ ４２５ ２．０
６ ４７２ ４３１ ２．２
７ ２４５ ３６６ １．６
８ ２６２ ３９２ １．７
９ ２５６ ３８９ １．９
１０ ２９８ ３７７ ２．０
１１ ２０１ ３４６ １．５
１２ １４２ １９３ ２．５
参考例１
実施例１の試料２合金箔と試料７合金箔のエツチング後
の断面の形状を同一倍率で顕微鏡観察したところ、それ
ぞれ第１図及び第２図に概要を示すようなピットの形成
状況が観察された。Table 2 Nα 1 373 410 1.8 2 420 430 2.0 3 485 445 2.1 4 358 403 1.8 5 405 425 2.0 6 472 431 2.2 7 245 366 1.6 8 262 392 1 .7 9 256 389 1.9 10 298 377 2.0 11 201 346 1.5 12 142 193 2.5 Reference Example 1 The cross-sectional shapes of Sample 2 alloy foil and Sample 7 alloy foil of Example 1 after etching are When observed under a microscope at the same magnification, pit formation was observed as outlined in FIGS. 1 and 2, respectively.
第１図に示す本発明合金による箔（試料２合金箔）の場
合には、第２図に示す比較合金による箔（試料７合金箔
）の場合に比して、より微細なピットが均一に発生して
いることが明らかである。In the case of the foil made of the invention alloy shown in Figure 1 (Sample 2 alloy foil), the finer pits are more uniform than in the case of the foil made of the comparative alloy (Sample 7 alloy foil) shown in Figure 2. It is clear that this is occurring.
第１図は、本発明ＡＱ合金による箔のエツチング後の断
面形状の概要を示す図面、第２図は、比較ＡＱ合金によ
る箔のエツチング後の断面形状の概要を示す図面である
。
（以上）
舅 １ 図FIG. 1 is a drawing showing an outline of the cross-sectional shape of a foil made of an AQ alloy of the present invention after etching, and FIG. 2 is a drawing showing an outline of a cross-sectional shape of a foil made of a comparative AQ alloy after etching. (more) Father-in-law 1 figure
Claims (1)
１．０％及びコバルト並びにニッケルの少なくとも一種
０．００５〜１．０％を含有する電解コンデンサ陰極用
アルミニウム合金箔。(1) Copper 0.1~0.7%, magnesium 0.005~
An aluminum alloy foil for an electrolytic capacitor cathode containing 1.0% and 0.005 to 1.0% of at least one of cobalt and nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3839188A JPH01212733A (en) | 1988-02-19 | 1988-02-19 | Aluminum-alloy foil for electrolytic capacitor cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3839188A JPH01212733A (en) | 1988-02-19 | 1988-02-19 | Aluminum-alloy foil for electrolytic capacitor cathode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01212733A true JPH01212733A (en) | 1989-08-25 |
Family
ID=12523984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3839188A Pending JPH01212733A (en) | 1988-02-19 | 1988-02-19 | Aluminum-alloy foil for electrolytic capacitor cathode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01212733A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07211593A (en) * | 1994-01-21 | 1995-08-11 | Showa Alum Corp | Aluminum foil for electrolytic-capacitor electrode and its etching method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133444A (en) * | 1980-03-22 | 1981-10-19 | Kobe Steel Ltd | Al alloy for cathode foil of electrolytic capacitor |
| JPS57126941A (en) * | 1981-01-28 | 1982-08-06 | Showa Alum Corp | Aluminum alloy foil for cathode of electrolytic capacitor |
| JPS62149858A (en) * | 1985-12-24 | 1987-07-03 | Toyo Alum Kk | Manufacture of aluminum alloy foil for cathode of electrolytic capacitor |
-
1988
- 1988-02-19 JP JP3839188A patent/JPH01212733A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133444A (en) * | 1980-03-22 | 1981-10-19 | Kobe Steel Ltd | Al alloy for cathode foil of electrolytic capacitor |
| JPS57126941A (en) * | 1981-01-28 | 1982-08-06 | Showa Alum Corp | Aluminum alloy foil for cathode of electrolytic capacitor |
| JPS62149858A (en) * | 1985-12-24 | 1987-07-03 | Toyo Alum Kk | Manufacture of aluminum alloy foil for cathode of electrolytic capacitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07211593A (en) * | 1994-01-21 | 1995-08-11 | Showa Alum Corp | Aluminum foil for electrolytic-capacitor electrode and its etching method |
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