JPH04196305A - Manufacture of electrode foil for aluminum electrolytic capacitor - Google Patents
Manufacture of electrode foil for aluminum electrolytic capacitorInfo
- Publication number
- JPH04196305A JPH04196305A JP2326361A JP32636190A JPH04196305A JP H04196305 A JPH04196305 A JP H04196305A JP 2326361 A JP2326361 A JP 2326361A JP 32636190 A JP32636190 A JP 32636190A JP H04196305 A JPH04196305 A JP H04196305A
- Authority
- JP
- Japan
- Prior art keywords
- boric acid
- foil
- aqueous solution
- aluminum foil
- voltage
- 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.)
- Granted
Links
- 239000011888 foil Substances 0.000 title claims abstract description 59
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 43
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003990 capacitor Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004327 boric acid Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- -1 aliphatic saturated dicarboxylic acid Chemical class 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 23
- 238000002048 anodisation reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001384 succinic acid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 20
- 238000005530 etching Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 11
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000028161 membrane depolarization Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアルミニウム電解コンデンサ用電極箔の製造方
法に舅するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to a method of manufacturing an electrode foil for an aluminum electrolytic capacitor.
一般に、この種の電極箔は次のようにして衿られでいる
。まず、エツチングされたアルミニウム箔を用意し、こ
のアルミニウム箔を燐酸や硼酸等の水溶液に浸漬し、一
定の電圧を印加して所望厚さの酸化皮膜を生成させる。Generally, this type of electrode foil is wrapped in the following manner. First, an etched aluminum foil is prepared, the aluminum foil is immersed in an aqueous solution of phosphoric acid, boric acid, etc., and a constant voltage is applied to form an oxide film of a desired thickness.
そして、数１００℃の高温雰囲気中に数分間放置する熱
処理工程を数回繰返す。Then, a heat treatment step of leaving the product in a high temperature atmosphere of several 100° C. for several minutes is repeated several times.
しかしながら、この方法では静電容量を高めるのに限度
があり、最近とみに要望されているより一層の小形かつ
高容量化に応えることができない。However, this method has a limit in increasing the capacitance, and cannot meet the recent demands for further miniaturization and higher capacitance.
本発明はこのような事情に鑑みなされたもので、より高
い静電容量が得られることができるようにしたアルミニ
ウム電解コンデンサ用電極箔の製造方法を提供すること
にある。The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for manufacturing an electrode foil for an aluminum electrolytic capacitor, which enables higher capacitance to be obtained.
上記した目的を達成するため、本発明においては、まず
エツチングされたアルミニウム箔を高温の純水中に所定
時間浸漬し、しかる後本化成工程として、少なくとも脂
肪族飽和ジカルボン酸もしくはその塩を含有する硼酸水
溶液中にそのアルミニウム箔を浸漬し、所定時間電圧を
印加して陽極酸化を行い、再化成工程においては、上記
アルミニウム箔を硼酸またはその塩を含む硼酸水溶液中
に浸漬し、所定時間電圧を印加して再陽極酸化を行なう
ようにしている。なお、本化成工程において、まず最初
にアルミニウム箔を硼酸水溶液中に浸漬し、所定時間電
圧を印加して第１の陽極酸化を行ない、引き続きそのア
ルミニウム箔を脂肪族飽和ジカルボン酸またはその塩を
含む硼酸水溶液中に浸漬し、所定時間電圧を印加して第
２の陽極酸化を行なうようにして多段陽極酸化してもよ
い。In order to achieve the above object, in the present invention, an etched aluminum foil is first immersed in high-temperature pure water for a predetermined period of time, and then, in the main chemical conversion step, an etched aluminum foil containing at least an aliphatic saturated dicarboxylic acid or a salt thereof is added. The aluminum foil is immersed in a boric acid aqueous solution and a voltage is applied for a predetermined time to perform anodic oxidation. In the reconversion step, the aluminum foil is immersed in a boric acid aqueous solution containing boric acid or a salt thereof, and a voltage is applied for a predetermined time. This is applied to perform re-anodization. In this chemical conversion step, first, the aluminum foil is immersed in a boric acid aqueous solution, a voltage is applied for a predetermined period of time to perform first anodic oxidation, and then the aluminum foil is immersed in an anodic oxidation solution containing an aliphatic saturated dicarboxylic acid or a salt thereof. Multi-stage anodization may be performed by immersing the substrate in a boric acid aqueous solution and applying a voltage for a predetermined period of time to perform the second anodic oxidation.
また、第１の陽極酸化工程と第２の陽極酸化工程とを入
九替えても効果がある。It is also effective to alternate the first anodizing step and the second anodizing step.
脂肪族飽和ジカルボン酸は、
Ｘ○○Ｃ−（ＣＨ２）ｎ−Ｃ００Ｘ
なる化学式（但し、ＸはＨ＋またはＮＨ４”、ｎ＝１〜
１２好ましくはｎ ＝ １〜８）で表わされ、その代表
例としては、コハク酸、グルタル酸、アジピン酸、ピメ
リン酸、スペリン酸、アゼライン酸、セバシン酸などが
ある。Aliphatic saturated dicarboxylic acid has the chemical formula:
12 (preferably n = 1 to 8), typical examples of which include succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid.
本化成時のＩｉｌ！酸水溶液のＰＨは３〜９、好ましく
は４．５〜７に設定される。この硼酸水溶液中における
脂肪族飽和ジカルボン酸の濃度は０．００２〜１．０％
、液温は７０〜１００℃が好適である。また、再化成時
の硼酸またはその塩の濃度は０．５〜ｌ０ｗｔ％、液温
は７０〜１００℃であることが好ましい。Iil at the time of this formation! The pH of the acid aqueous solution is set to 3-9, preferably 4.5-7. The concentration of aliphatic saturated dicarboxylic acid in this boric acid aqueous solution is 0.002 to 1.0%
The liquid temperature is preferably 70 to 100°C. Moreover, it is preferable that the concentration of boric acid or its salt at the time of reconstitution is 0.5 to 10 wt%, and the liquid temperature is 70 to 100°C.
これによれば、従来法に比べて静電容量が約６〜１１％
以上増大する。なお１本化成後の減極処理にはｐＨ７〜
９で液温７０℃のアンモニア水、またはｐＨ４〜８の燐
酸水溶液などが用いられ、その浸漬時間は１〜５分程度
とされる。また、熱処理は４００〜５００℃で１〜３分
程度が好ましい。According to this, the capacitance is approximately 6 to 11% lower than that of the conventional method.
or more. In addition, for depolarization treatment after one-piece chemical formation, pH 7~
9, ammonia water with a liquid temperature of 70° C. or a phosphoric acid aqueous solution with a pH of 4 to 8 is used, and the immersion time is about 1 to 5 minutes. Further, the heat treatment is preferably performed at 400 to 500°C for about 1 to 3 minutes.
〔実施例１〕
（Ａ）まず、純度９９．９９％で厚さ１００μｍのアル
ミニウムエツチング箔を用意した。この場合、そのエツ
チング倍率はエツチングしていない平坦箔に対して２０
倍である。[Example 1] (A) First, an aluminum etched foil with a purity of 99.99% and a thickness of 100 μm was prepared. In this case, the etching magnification is 20
It's double.
（Ｂ）このアルミニウムエツチング箔を液温９８℃以上
の純水中で１５分間ボイル処理した。(B) This aluminum etched foil was boiled for 15 minutes in pure water at a liquid temperature of 98°C or higher.
（Ｃ）次に、硼酸２０ｇ／純水１１２にコハク酸アンモ
ニウムをＯ，１ｇ添加した硼酸水溶液、液温８５℃の中
にアルミニウムエツチング箔を浸漬し、電流密度１０ｍ
Ａ／Ｃｉの電流を流し、化成電圧６００ Ｖまで上昇さ
せ、同電圧を４０分間印加して本化成を行なった。(C) Next, the aluminum etching foil was immersed in a boric acid aqueous solution containing 20 g of boric acid and 1 g of ammonium succinate added to 112 g of pure water at a temperature of 85°C, and the etching foil was etched with a current density of 10 m.
A current of A/Ci was applied, the chemical formation voltage was increased to 600 V, and the same voltage was applied for 40 minutes to perform main chemical formation.
（Ｄ）化成後のアルミニウムエツチング箔を液温７０℃
、ＰＨ７〜９に調整したアンモニア水に３分間浸漬し、
減極処理を行なった。(D) Aluminum etching foil after chemical treatment at a liquid temperature of 70℃
, immersed in ammonia water adjusted to pH 7-9 for 3 minutes,
Depolarization treatment was performed.
（Ｅ）５００℃の加熱雰囲気中で２分間熱処理した。(E) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｆ）純水１Ｑあたり硼酸２０ｇと硼酸アンモニウム０
．５ ｇを溶解した水溶液、液温８５℃中に再度浸漬し
、電流密度１０ｍＡ ／ ｃｉの電流を流し、化成電圧
６００Ｖまで上昇させ、同電圧を１３分間印加して再化
成した。(F) 20g of boric acid and 0 ammonium borate per 1Q of pure water
．． The sample was immersed again in an aqueous solution containing 5 g of the sample at a temperature of 85° C., a current with a current density of 10 mA/ci was applied, the chemical formation voltage was increased to 600 V, and the same voltage was applied for 13 minutes to re-form the sample.
（Ｇ）Ｊ−記（Ｅ）と同じく、５００℃の加熱雰囲気中
で２分間熱処理した。(G) J-Same as (E), heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｈ）再度、純水ＩＱあたり硼酸２０ｇと硼酸アンモニ
ウム０．５ｇを溶解した水溶液、液温８５℃中に浸漬し
、電流密度１０ｍＡ ／ ｃｉの電流を流し、化成電圧
６００■まで上昇させ、同電圧を１３分間印加して再化
成した。(H) Again, immerse it in an aqueous solution containing 20 g of boric acid and 0.5 g of ammonium borate per pure water IQ at a temperature of 85°C, apply a current with a current density of 10 mA/ci, raise the formation voltage to 600 μ, and A voltage was applied for 13 minutes to reconstitute.
（Ｉ）水洗し、乾燥させて化成箔の静電容量を測定した
ところ、 ０．４５８μＦ／ｄであった。(I) After washing with water and drying, the capacitance of the chemically formed foil was measured and found to be 0.458 μF/d.
（Ｊ）この化成ｍ （１５ｍ Ｘ ２７０ａｎ ）を陽
極とし、−方純度９９．２％で厚さ２０μｍ、エツチン
グ倍率５０倍のアルミニウム箔（１５ｍ Ｘ ３００ｎ
＊ ）を陰極とし、セパレータを介して巻回して、コン
デンサ素子を作成した。そして、このコンデンサ素子に
電解液を含浸させ、ケース内に封入し、定格４００Ｖ、
１６μＦの電解コンデンサを作成したところ、その静
電容量は１８．２μＦであった。(J) This chemically formed m (15 m x 270 an) was used as an anode, and an aluminum foil (15 m x 300 nm) with a purity of 99.2%, a thickness of 20 μm, and an etching magnification of 50 times was used as an anode.
*) was used as a cathode and wound through a separator to create a capacitor element. Then, this capacitor element is impregnated with electrolyte, sealed in a case, and rated at 400V.
When a 16 μF electrolytic capacitor was created, its capacitance was 18.2 μF.
なお、上記工程（Ｈ）と工程（Ｉ）との間に、８５ｗｔ
％の燐酸２５ｍβ／ρの水溶液であって、アンモニア水
でｐＨ６，５に調整した液温３０℃の水溶液に４分間浸
漬処理を行う工程を介在させてもよい。この工程を追加
した電解コンデンサは、例えば１０５℃、１０００時間
の高温貯蔵試験における製品の漏れ電流による劣化を防
止できる。In addition, between the above step (H) and step (I), 85wt
% of phosphoric acid 25 mβ/ρ at a temperature of 30° C. and adjusted to pH 6.5 with aqueous ammonia, a step of immersion treatment for 4 minutes may be included. An electrolytic capacitor added with this process can prevent deterioration due to leakage current in a high temperature storage test at 105° C. for 1000 hours, for example.
〔実施例２〕
使用したアルミニウムエツチング箔およびボイル工程に
ついては、上記実施例１の（Ａ）（Ｂ）に同じ。[Example 2] The aluminum etching foil used and the boiling process were the same as those in Example 1 (A) and (B) above.
（Ｃ）硼酸２０ｇ／純水ＩＱにアジピン酸アンモニウム
を０．１ｇ添加した硼酸水溶液、液温８５℃の中にアル
ミニウムエツチング箔を浸漬し、電流密度１０＋ａＡ
／ （ｄの電流を流し、化成電圧６００Ｖまで上昇させ
、同電圧を４０分間印加して本化成を行なった。(C) An aluminum etching foil was immersed in a boric acid aqueous solution prepared by adding 0.1 g of ammonium adipate to 20 g of boric acid/pure water IQ at a temperature of 85°C, and the current density was 10+aA.
/ (d current was applied, the chemical formation voltage was increased to 600 V, and the same voltage was applied for 40 minutes to perform main chemical formation.
（Ｄ）化成後のアルミニウムエツチング箔を液温７０℃
、ＰＨ７〜９に調整したアンモニア水に３分間浸漬し、
減極処理を行なった。(D) Aluminum etching foil after chemical treatment at a liquid temperature of 70℃
, immersed in ammonia water adjusted to pH 7-9 for 3 minutes,
Depolarization treatment was performed.
（Ｅ ）５００℃の加熱雰囲気中で２分間熱処理した。(E) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｆ）純水ＩＱあたり硼酸２０ｇと硼酸アンモニウム０
．５ ｇを溶解した水溶液、液温８５℃中に再度浸漬し
、電流密度１０ＩＩＡ／ｄの電流を流し、化成電圧６０
０ Ｖまで上昇させ、同電圧を１３分間印加して再化成
した。(F) 20g of boric acid and 0 ammonium borate per pure water IQ
．． 5 g dissolved in an aqueous solution at a temperature of 85° C., a current with a current density of 10 IIA/d was applied, and the chemical formation voltage was 60
The voltage was increased to 0 V, and the same voltage was applied for 13 minutes to reconform.
（Ｇ ）５００℃の加熱雰囲気中で２分間熱処理した。(G) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｈ）再度、純水ＩＱあたり硼酸２０ｇと硼酸アンモニ
ウム０．５ｇを溶解した水溶液、液温８５℃中に浸漬し
、電流密度１０ＩＩＡ／ｄの電流を流し、化成電圧６０
０■まで上昇させ、同電圧を１３分間印加して再化成し
た。(H) Again, immerse in an aqueous solution containing 20 g of boric acid and 0.5 g of ammonium borate per pure water IQ at a temperature of 85°C, apply a current with a current density of 10 IIA/d, and apply a formation voltage of 60
The voltage was raised to 0 ■, and the same voltage was applied for 13 minutes to reconform.
（Ｉ）水洗し、乾燥させて化成箔の静電容量を測定した
ところ、０．４４８μＦ／ｃｄであった。(I) After washing with water and drying, the capacitance of the chemically formed foil was measured and found to be 0.448 μF/cd.
（Ｊ）この化成箔（１５ｍｍ ｘ ２７０ｗｎ ）を陽
極として、実施例１と同様、定格４００Ｖ、 １６μＦ
の電解コンデンサを作成したところ、その静電容量は１
７．８μＦであった・
〔実施例３〕
使用したアルミニウムエツチング箔およびボイル工程に
ついては、上記実施例１の（Ａ）（Ｂ）に同じ。(J) Using this chemically formed foil (15 mm x 270 wn) as an anode, the rating was 400 V and 16 μF as in Example 1.
When I created an electrolytic capacitor, its capacitance was 1
It was 7.8 μF. [Example 3] The aluminum etching foil used and the boiling process were the same as in (A) and (B) of Example 1 above.
（Ｃ）硼酸２０ｇノ純水ＩＱにセバシン酸アンモニウム
を０．１ｇ添加した硼酸水溶液、液温８５℃の中にアル
ミニウムエツチング箔を浸漬し、電流密度１０ｍＡ ／
（ｄの電流を流し、化成電圧６００■まで上昇させ、
同電圧を４０分間印加して本化成を行なった。(C) An aluminum etching foil was immersed in a boric acid aqueous solution containing 20 g of boric acid and 0.1 g of ammonium sebacate added to pure water IQ at a temperature of 85°C, and a current density of 10 mA/
(A current of d is applied and the formation voltage is increased to 600■,
The main chemical formation was performed by applying the same voltage for 40 minutes.
（Ｄ）化成後のアルミニウムエツチング箔を液温７０℃
、ｐＨ７〜９に調整したアンモニア水に３分間浸漬し、
減極処理を行なった。(D) Aluminum etching foil after chemical treatment at a liquid temperature of 70℃
, immersed in ammonia water adjusted to pH 7-9 for 3 minutes,
Depolarization treatment was performed.
（Ｅ）５００℃の加熱雰囲気中で２分間熱処理した。(E) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｆ）純水ＩＱあたり硼酸２０ｇと硼酸アンモニウムｏ
、ｓ ｇを溶解した水溶液、液温８５℃中に再度浸漬し
、電流密度１０ｍＡ／ ｄの電流を流し、化成電圧６０
０■まで上昇させ、同電圧を１３分間印加して再化成し
た。(F) 20g of boric acid and ammonium borate per pure water IQ
, sg dissolved in an aqueous solution at a temperature of 85°C, a current with a current density of 10 mA/d was applied, and a formation voltage of 60 mA/d was applied.
The voltage was raised to 0 ■, and the same voltage was applied for 13 minutes to reconform.
（Ｇ ）５００℃の加熱雰囲気中で２分間熱処理した。(G) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（Ｈ）再度、純水ＩＱあたり硼酸２０ｇと硼酸アンモニ
ウム０．５ｇを溶解した水溶液、液温８５℃中に浸漬し
、電流密度１Ｏ１ｌＡ／ｄの電流を流し、化成電圧６０
０Ｖまで上昇させ、同電圧を１３分間印加して再化成し
た。(H) Once again, the pure water IQ was immersed in an aqueous solution containing 20 g of boric acid and 0.5 g of ammonium borate at a temperature of 85°C, and a current with a current density of 1O11A/d was passed, and the formation voltage was 60.
The voltage was increased to 0V and the same voltage was applied for 13 minutes to perform reconversion.
（Ｉ）水洗し、乾燥させて化成箔の静電容量を測定した
ところ、０．４６０μＦ／ｄであった。(I) After washing with water and drying, the capacitance of the chemically formed foil was measured and found to be 0.460 μF/d.
（Ｊ）二〇化成箔（１５ｍＸ ２７０ａＩ１１）を陽極
として、実施例１と同様、定格４００Ｖ、 １６μＦの
電解コンデンサを作成したところ、その静電容量は１８
．３μＦであった。(J) When an electrolytic capacitor with a rating of 400 V and 16 μF was made in the same manner as in Example 1 using a chemically formed foil (15 m x 270 a I11) as an anode, its capacitance was 18
．． It was 3μF.
く比較例１〉
（ａ）（ｂ）使用したアルミニウムエツチング箔および
ボイル工程については、上記実施例１の（Ａ）（Ｂ）に
同じ。Comparative Example 1 (a) (b) The aluminum etching foil used and the boiling process were the same as in (A) and (B) of Example 1 above.
（ｃ）硼酸２０ｇ／純水ＩＱの水溶液、液温８５℃中に
アルミニウムエツチング箔を浸漬し、電流密度１０１１
Ａ／−の電流を流し、化成電圧６００■まで上昇させ、
同電圧を４０分間印加して本化成を行なった。(c) Aluminum etching foil was immersed in an aqueous solution of boric acid 20 g/pure water IQ at a temperature of 85°C, and the current density was 1011.
A current of A/- is applied and the formation voltage is increased to 600■,
The main chemical formation was performed by applying the same voltage for 40 minutes.
（ｄ）化成後のアルミニウムエツチング箔を液温７０℃
、ＰＨ７〜９に調整したアンモニア水に３分間浸漬し、
減極処理を行なった。(d) Aluminum etching foil after chemical treatment at a liquid temperature of 70°C.
, immersed in ammonia water adjusted to pH 7-9 for 3 minutes,
Depolarization treatment was performed.
（ｅ）５００℃の加熱雰囲気中で２分間熱処理した。(e) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（ｆ）上記（ｃ）と同じ条件の水溶液、すなわち硼酸２
０ｇ／純水１Ωの水溶液、液温８５℃中に再度浸漬し、
電流密度１０ａＡ ／ ｃｉの電流を流し、化成電圧６
００■まで上昇させ、同電圧を１３分間印加して再化成
した。(f) Aqueous solution under the same conditions as in (c) above, i.e. boric acid 2
0g/pure water 1Ω aqueous solution, immersed again in a liquid temperature of 85℃,
A current with a current density of 10 aA/ci was passed, and the formation voltage was 6.
00 ■, and the same voltage was applied for 13 minutes to reconform.
（ｇ）５００℃の加熱雰囲気中で２分間熱処理した。(g) Heat treated for 2 minutes in a heating atmosphere at 500°C.
（ｈ）再度、硼酸２０ｇ／純水ＩＱの水溶液、液温８５
℃中に浸漬し、電流密度１０ｍ１Ａ／ ｃａｌｆの電流
を流し、化成電圧６００Ｖまで上昇させ、同電圧を１３
分間印加して再化成した。(h) Again, an aqueous solution of boric acid 20g/pure water IQ, liquid temperature 85
℃, a current with a current density of 10 mA/calf was applied, the formation voltage was increased to 600 V, and the voltage was increased to 13
It was applied for a minute to reconstitute it.
（ｉ）水洗し、乾燥させて化成箔の容量を測定したとこ
ろ、０．２９６ μＦ／ ａ（であった。(i) The capacitance of the chemically formed foil was measured after washing with water and drying, and it was found to be 0.296 μF/a.
（ｊ）この化成箔（１５ｍ＋ Ｘ ２７０ｍｎ ）を陽
極として、実施例１と同様、定格４００Ｖ、 １６μＦ
の電解コンデンサを作成したところ、その静電容量は１
１．７μＦであった。(j) Using this chemically formed foil (15 m + x 270 mn) as an anode, the rating was 400 V and 16 μF as in Example 1.
When I created an electrolytic capacitor, its capacitance was 1
It was 1.7μF.
〈比較例２〉
（ａ）（ｂ）使用したアルミニウムエツチング箔および
ボイル工程については、上記実施例１の（Ａ）（Ｂ）に
同じ。<Comparative Example 2> (a) (b) The aluminum etching foil used and the boiling process were the same as in (A) and (B) of Example 1 above.
（ｃ）硼酸２０ｇ／純水ＩＱと硼酸アンモニウム０．５
ｇからなる水溶液、液温８５℃中にアルミニウムエツ
チング箔を浸漬し、電流密度１０ＩＩＡ／ｃｉの電流を
流し、化成電圧６００ Ｖまで上昇させ、同電圧を４０
分間印加して本化成を行なった。(c) Boric acid 20g/pure water IQ and ammonium borate 0.5
An aluminum etching foil was immersed in an aqueous solution consisting of 85°C at a temperature of 85°C, and a current with a current density of 10IIA/ci was applied to raise the formation voltage to 600V, and the voltage was increased to 40V.
The main chemical formation was performed by applying the voltage for a minute.
（ｄ）化成後のアルミニウムエツチング箔を液温７０℃
、ｐｌ（７〜９に調整したアンモニア水に３分間浸漬し
、減極処理を行なった。(d) Aluminum etching foil after chemical treatment at a liquid temperature of 70°C.
, pl (dipped in ammonia water adjusted to 7 to 9 for 3 minutes to perform depolarization treatment.
（ｅ）５００℃の加熱雰囲気中で２分間熱処理した。(e) Heat treatment was performed for 2 minutes in a heating atmosphere of 500°C.
（ｆ）硼ｒ！１２０ｇ／純水ＩＱと硼酸アンモニウム０
．５ ｇからなる水溶液、液温８５℃中に再度浸漬し、
電流密度１０＋＋＋Ａ／ｃｄの電流を流し、化成電圧６
００ Ｖまで上昇させ、同電圧を１３分間印加して再化
成した。(f) 硼r! 120g/pure water IQ and ammonium borate 0
．． 5 g of an aqueous solution at a temperature of 85°C,
A current with a current density of 10+++ A/cd was applied, and the formation voltage was 6.
The voltage was increased to 0.00 V, and the same voltage was applied for 13 minutes to perform reconversion.
（ｇ）５００℃の加熱雰囲気中で２分間熱処理した。(g) Heat treated for 2 minutes in a heating atmosphere at 500°C.
（ｈ）再度、硼酸２０ｇ／純水ｌρと＠酸アンモニウム
０．５ｇの水溶液、液温８５℃中に浸漬し、電流密度１
０ＷＬＡ／ａＪの電流を流し、化成電圧６００ Ｖまで
上昇させ、同電圧を１３分間印加して再化成した。(h) Immerse again in an aqueous solution of 20 g of boric acid/pure water lρ and 0.5 g of ammonium chloride at a temperature of 85°C, with a current density of 1
A current of 0 WLA/aJ was applied, the chemical formation voltage was increased to 600 V, and the same voltage was applied for 13 minutes to reform the metal.
＜ｊ）水洗し、乾燥させて化成箔の容量を測定したとこ
ろ、０．４２３μＦ／ｄであった。<j) The capacitance of the chemically formed foil was measured after washing with water and drying, and it was found to be 0.423 μF/d.
（ｊ）上記比較例１と同じ電解コンデンサを作成したと
ころ、その容量は１６．８μＦであった。(j) When the same electrolytic capacitor as in Comparative Example 1 was prepared, its capacitance was 16.8 μF.
参考までに、法衣に上記各実施例および各比較例で得ら
れた化成箔の箔容量とその化成箔を用いて試作した電解
コンデンサの静電容量を示す。For reference, the foil capacitance of the chemically formed foil obtained in each of the above Examples and Comparative Examples and the electrostatic capacitance of an electrolytic capacitor prototyped using the chemically formed foil are shown on the robe.
この表から明らかなように１本発明によると箔容鴬およ
び製品容量ともに、従来法による比較例に比べて約８〜
９％増大している。As is clear from this table, according to the present invention, both the foil volume and the product capacity are about 8 to
It has increased by 9%.
以上説明したように１本発明によれば、エツチングされ
たアルミニウム箔を純水ボイルし、次いで本化成工程と
して同アルミニウム箔を少なくとも脂肪族飽和ジカルボ
ン酸もしくはその塩を含む硼酸溶液中に浸漬し、所定時
間電圧を印加して陽極酸化を行い、その後の再化成工程
においては硼酸またはその塩を含む水溶液中に浸漬して
所定時間電圧を印加することにより、静電８鴬の高い電
極箔が製造される。As explained above, according to one aspect of the present invention, an etched aluminum foil is boiled in pure water, and then, as the main chemical conversion step, the aluminum foil is immersed in a boric acid solution containing at least an aliphatic saturated dicarboxylic acid or a salt thereof, Anodic oxidation is performed by applying a voltage for a predetermined period of time, and in the subsequent reconstitution process, electrode foil with a high electrostatic capacity is manufactured by immersing it in an aqueous solution containing boric acid or its salt and applying a voltage for a predetermined period of time. be done.
特許出願人 エルナー株式会社Patent applicant: Elna Co., Ltd.
Claims (3)
に所定時間浸漬する純水ボイル工程と、しかるのち少な
くとも脂肪族飽和ジカルボン酸もしくはその塩を含有す
る硼酸水溶液中にそのアルミニウム箔を浸漬し、所定時
間電圧を印加して陽極酸化を行なう本化成工程と、硼酸
またはその塩を含む硼酸水溶液中に上記アルミニウム箔
を浸漬し、所定時間電圧を印加して再陽極酸化を行なう
再化成工程と含むことを特徴とするアルミニウム電解コ
ンデンサ用電極箔の製造方法。(1) A pure water boiling step in which the etched aluminum foil is immersed in high-temperature pure water for a predetermined time, and then the aluminum foil is immersed in an aqueous boric acid solution containing at least an aliphatic saturated dicarboxylic acid or a salt thereof; It includes a main chemical formation step in which a voltage is applied for a predetermined period of time to carry out anodization, and a re-formation step in which the aluminum foil is immersed in a boric acid aqueous solution containing boric acid or its salt, and a voltage is applied for a specified period of time to carry out re-anodization. A method for manufacturing an electrode foil for an aluminum electrolytic capacitor, characterized in that:
１〜１２）で表わされるものからなる請求項１記載のア
ルミニウム電解コンデンサ用電極箔の製造方法。(2) The aliphatic saturated dicarboxylic acid has the chemical formula: XOOC-(CH_z)n-COOX (where X is H^+ or NH_4^+, n=
2. The method for producing an electrode foil for an aluminum electrolytic capacitor according to claim 1, which comprises one of the following: 1 to 12).
硼酸水溶液中における陽極酸化が含まれる請求項１記載
のアルミニウム電解コンデンサ用電極箔の製造方法。(3) The method for manufacturing an electrode foil for an aluminum electrolytic capacitor according to claim 1, wherein the chemical formation step further includes anodization in a boric acid aqueous solution containing boric acid or a salt thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2326361A JPH07109815B2 (en) | 1990-11-28 | 1990-11-28 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2326361A JPH07109815B2 (en) | 1990-11-28 | 1990-11-28 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04196305A true JPH04196305A (en) | 1992-07-16 |
| JPH07109815B2 JPH07109815B2 (en) | 1995-11-22 |
Family
ID=18186940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2326361A Expired - Fee Related JPH07109815B2 (en) | 1990-11-28 | 1990-11-28 | Method for manufacturing electrode foil for aluminum electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07109815B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100361643B1 (en) * | 2000-01-13 | 2002-11-21 | 한국과학기술원 | Preparing Method for Anode Electrode for High Volt Electrolytic Capacitor |
| WO2006030922A1 (en) * | 2004-09-13 | 2006-03-23 | Showa Denko K.K. | Solid electrolytic capacitor element, solid electrolytic capacitor and production method thereof |
| JP2007036048A (en) * | 2005-07-28 | 2007-02-08 | Nichicon Corp | Manufacturing method of electrode foil for aluminum electrolytic capacitor |
-
1990
- 1990-11-28 JP JP2326361A patent/JPH07109815B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100361643B1 (en) * | 2000-01-13 | 2002-11-21 | 한국과학기술원 | Preparing Method for Anode Electrode for High Volt Electrolytic Capacitor |
| WO2006030922A1 (en) * | 2004-09-13 | 2006-03-23 | Showa Denko K.K. | Solid electrolytic capacitor element, solid electrolytic capacitor and production method thereof |
| JP2007036048A (en) * | 2005-07-28 | 2007-02-08 | Nichicon Corp | Manufacturing method of electrode foil for aluminum electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07109815B2 (en) | 1995-11-22 |
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