JPS63306614A - Manufacture of aluminum electrode for electrolytic capacitor - Google Patents
Manufacture of aluminum electrode for electrolytic capacitorInfo
- Publication number
- JPS63306614A JPS63306614A JP14276287A JP14276287A JPS63306614A JP S63306614 A JPS63306614 A JP S63306614A JP 14276287 A JP14276287 A JP 14276287A JP 14276287 A JP14276287 A JP 14276287A JP S63306614 A JPS63306614 A JP S63306614A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- titanium
- electrolytic capacitor
- ion plating
- aluminum electrode
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- 239000003990 capacitor Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 238000007733 ion plating Methods 0.000 claims abstract description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims description 8
- 238000007743 anodising Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 206010010219 Compulsions Diseases 0.000 abstract 2
- 239000010408 film Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
本発明は電解コンデンサに用いられるアルミニウム電極
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing aluminum electrodes used in electrolytic capacitors.
従来の技術
電解コンデンサの電極には、非常に薄い誘電体皮膜が電
気化学的に生成されるような金属が用いられ、現在はア
ルミニウムとタンタルが電極材料として工業化されてい
る。BACKGROUND OF THE INVENTION The electrodes of electrolytic capacitors use metals in which very thin dielectric films are electrochemically produced, and aluminum and tantalum are currently being industrialized as electrode materials.
このうちアルミニウム電極の誘電体であるＡｌｚＯ３の
比誘電率はおよそ７〜１０であり、他の弁作用金属の比
誘電率よりも決して大きな値ではない。Among these, the relative permittivity of AlzO3, which is the dielectric material of the aluminum electrode, is about 7 to 10, which is by no means larger than the relative permittivity of other valve metals.
たとえばＴａｚｏｓは比誘電率ε＝２５．２であり、Ｔ
ｉｅ、のε−６６，１である。このためアルミニウム電
解コンデンサに用いられるアルミニウム箔は静電容量増
大のために高倍率エツチング処理を行い、表面積を増大
させている。For example, Tazos has a dielectric constant ε=25.2 and T
ie, ε-66,1. For this reason, aluminum foil used in aluminum electrolytic capacitors is subjected to high-magnification etching treatment to increase the surface area in order to increase the capacitance.
このエツチング処理は箔厚を考慮し幾何学的に最も表面
積増大になるべく形状、すなわち理想エツチング状態に
すべく電気化学的あるいは化学的なエツチング方法の研
究が行われている。しかしながらエツチング技術はかな
り進歩し、現時点において現在の表面拡大率の２倍、３
倍とすることは単に表面を微細化させるのみでは不可能
になってきている。In this etching process, studies are being conducted on electrochemical or chemical etching methods in order to take the foil thickness into consideration and achieve a shape that geometrically maximizes the surface area, that is, an ideal etching state. However, etching technology has progressed considerably, and at present the current surface magnification rate can be doubled or tripled.
It is becoming impossible to double the size simply by making the surface finer.
発明が解決しようとする問題点
また仮により微細化することに成功したとしても、高い
電圧になるとエツチング孔のいわゆる目詰り現象によっ
てエツチング形状は生かせず、静電容量の低下を招く。Problems to be Solved by the Invention Even if it is possible to achieve finer etching, the etched shape cannot be maintained due to the so-called clogging phenomenon of the etched holes at high voltages, resulting in a decrease in capacitance.
さらに電解コンデンサを作成した時も電解液との界面接
触が低下し、箔抵抗の増大、ｔａｎδの増大、インピー
ダンス特性の低下など様々な緒特性の低下につながる。Furthermore, when an electrolytic capacitor is produced, the interfacial contact with the electrolyte decreases, leading to a decrease in various mechanical properties such as an increase in foil resistance, an increase in tan δ, and a decrease in impedance characteristics.
一方陽臘酸化方法（化成方法）による静電容量の増大も
試みられている。これは純水ボイル処理によるベーマイ
ト皮膜と電気化学的生成皮膜との複合皮膜、ホウ酸溶液
による化成皮膜とリン酸溶液による化成皮膜との複合皮
膜、化成前処理に特殊薄膜を作成させ、該薄膜と電気化
学的皮膜との複合皮膜など様々な検討が行われている。On the other hand, attempts have also been made to increase the capacitance by a positive oxidation method (chemical conversion method). This is a composite film of a boehmite film and an electrochemically generated film by boiling in pure water, a composite film of a chemical conversion film using a boric acid solution and a chemical conversion film using a phosphoric acid solution, and a special thin film created by a pre-chemical treatment. A variety of studies are being conducted, including composite coatings with electrochemical coatings and electrochemical coatings.
しかしながら大幅な静電容量の増加方法は見出されてい
ない。However, no method has been found to significantly increase capacitance.
このように現時点に使用されている９９．９９％あるい
は９９．９％の高純度アルミニウム箔を用いた改良では
大幅な静電容量の増大にはかなりの困難に直面している
。無理をして静電容量の増大を図っても漏れ電流の増大
、耐圧の低下を起こし良好な結果は得られない。As described above, improvements using 99.99% or 99.9% high-purity aluminum foil currently in use face considerable difficulties in significantly increasing capacitance. Even if the capacitance is increased by force, the leakage current increases and the withstand voltage decreases, and good results cannot be obtained.
問題点を解決するための手段
本発明はこのような背景をもとに無理なく大きな静電容
量が得られる電解コンデンサ用アルミニウム電極の製造
方法を提供しようとするものである。Means for Solving the Problems Based on this background, the present invention aims to provide a method for manufacturing aluminum electrodes for electrolytic capacitors, which allows reasonably large capacitance to be obtained.
最近イオン−ブレーティングを始めとするイオン注入法
の技術は大幅に進歩し、現在その実用例として半導体工
学において、基板物質に微量の不純物を高度に制御した
条件で混入させる等有効に用いられている。イオン−ブ
レーティング法は高エネルギー粒子の侵入により基板物
質の化学結合や結晶構造の破壊が起こるが、それと同時
に再結晶を生じ、表層中に準安定物が形成される。この
プロセスは衝突というランダムな過程で進行するため、
基板物質と添加元素の組合せは任意に選択できる。この
ことから金属へのイオン注入では通常の熱平衡での溶解
性を無視した組成からなる合金を作成することができる
。Recently, ion implantation techniques such as ion-blating have made great progress, and are currently being used effectively in semiconductor engineering to mix minute amounts of impurities into substrate materials under highly controlled conditions. There is. In the ion-blating method, the chemical bonds and crystal structure of the substrate material are destroyed due to the penetration of high-energy particles, but at the same time, recrystallization occurs and metastable substances are formed in the surface layer. This process proceeds through random processes called collisions, so
The combination of substrate material and additive elements can be selected arbitrarily. Therefore, by ion implantation into metals, it is possible to create alloys with compositions that ignore solubility in normal thermal equilibrium.
すなわち、本発明はアルミニウムにチタンをイオンプレ
ーティングすることによりアルミニウム表面にアルミ−
チタン合金を形成させ、これを陽極酸化によりアルミと
チタンの混在複合誘電体膜を生成し、大幅に静電容量を
増大することができる電解コンデンサ用アルミニウム電
極の製造方法である。That is, the present invention applies aluminum to the aluminum surface by ion plating titanium on aluminum.
This is a method for manufacturing aluminum electrodes for electrolytic capacitors that can significantly increase capacitance by forming a titanium alloy and then anodizing it to produce a composite dielectric film containing aluminum and titanium.
作用
イオン−ブレーティング法では上記したように合金組成
を自由に選択することが可能であるため、イオン−ブレ
ーティングによって打ち込むチタン量の調整ができ、静
電容量のコントロールが可能である。またエツチングさ
れたアルミニウムに対しても有効であり、かなりの静電
容量の増加が図れた。In the active ion-blating method, the alloy composition can be freely selected as described above, so the amount of titanium implanted can be adjusted by ion-blating, and the capacitance can be controlled. It was also effective against etched aluminum, and a considerable increase in capacitance was achieved.
“ さらに従来まで試みられていたアルミニウム上へ
のチタン蒸着法や塗膜熱分解法では陽極酸化条件をかな
り限定しないと、直列に配した複合誘電体層となってし
まったり、大幅な静電容量低下を招いたり、チタンの陽
極酸化中の剥がれが誘発され、かなり困難な点があった
が、本発明法によるイオンプレーティングによる表面合
金では上述の問題は全く発生しない。また誘電体となる
べき金属酸化物の付着と異なり、付着する際の厚みを全
く気にしないですむという利点も有している。“Furthermore, the titanium vapor deposition method and film pyrolysis method on aluminum that have been attempted so far require very limited anodic oxidation conditions, resulting in composite dielectric layers arranged in series, or a large capacitance. However, the above-mentioned problems do not occur at all with the surface alloy formed by ion plating according to the method of the present invention. Unlike the attachment of metal oxides, it also has the advantage that there is no need to worry about the thickness when attaching.
すなわち、アルミニウム金属上にチタンをイオンプレー
ティングするとチタン薄膜が生成するのではなく、アル
ミ−チタン合金が形成され、そこに陽極酸化を行うと酸
化アルミニウムと酸化チタンの混在複合皮膜が形成され
、高容量が得られる。In other words, when titanium is ion plated on aluminum metal, an aluminum-titanium alloy is formed instead of a thin titanium film, and when anodized, a mixed composite film of aluminum oxide and titanium oxide is formed, resulting in a high Capacity is obtained.
実施例
純度９９．９９％、厚み７０μｍのアルミニウム箔を塩
酸を主体としたエツチング液を用い、電Ｍエツチングを
行い約２０倍の表面積を有するエツチング箔を作成した
。EXAMPLE An aluminum foil having a purity of 99.99% and a thickness of 70 μm was subjected to electric M etching using an etching solution mainly containing hydrochloric acid to produce an etched foil having a surface area approximately 20 times larger.
次いで該表面上の約５〜１０μｍの部分にＡ （ｌ ｑ
。Ｔｉ、。になるようにＴｉのイオンプレーティング処
理して試料Ａを作成し、また
Ａ （ｌ ｓ。Ｔｉ５゜になるようにＴｉのイオンプレ
ーティング処理して試料Ｂを作成した。Then, A (l q
. Ti,. Sample A was prepared by ion plating Ti so that the angle became A (l s. Ti5°), and sample B was prepared by ion plating Ti so that A (l s. Ti5°).
上記試料Ａ、Ｂと、Ｔｉのイオンプレーティングを行わ
ないもの（試料Ｃ）を各々ｐＨ＝６．５のリン酸アンモ
ニウム溶液で８０Ｖ陽極酸化を行い、皮膜特性を測定し
た。その結果を表に示す。The above-mentioned samples A and B and a sample without Ti ion plating (sample C) were each anodized at 80V with an ammonium phosphate solution having a pH of 6.5, and the film properties were measured. The results are shown in the table.
静電容量はｐＨ＝６．５のリン酸アンモニウム溶液中で
１２０１１ｚにて測定し、皮膜耐圧は上記化成液中で電
流密度０．１ｍＡ／ｃａｌを通電した時の電圧一時間特
性を測り、電圧上昇停止点を皮膜耐圧とした。The capacitance was measured at 12011z in an ammonium phosphate solution with pH = 6.5, and the film breakdown voltage was measured by measuring the voltage characteristics for one hour when a current density of 0.1 mA/cal was applied in the above chemical solution. The point at which the rise stopped was defined as the film withstand pressure.
また、漏れ電流は上記測定液で５０Ｖ印加し２分後の値
を読み取った。Further, the leakage current was measured by applying 50V to the test solution and reading the value after 2 minutes.
表
発明の効果
表に示したように本発明法によって作成したアルミニウ
ム合金電極は大幅な静電容量の増大が測られ、電解コン
デンサの小型化に大きく寄与し、工業的かつ実用的価値
大なるものである。As shown in the Table of Effects of the Invention, the aluminum alloy electrode produced by the method of the present invention has a significant increase in capacitance, greatly contributes to the miniaturization of electrolytic capacitors, and has great industrial and practical value. It is.
Claims (2)
ーティング法により付着せしめ、表面にアルミ−チタン
合金層を形成させた後、陽極酸化処理してアルミ−チタ
ン混在酸化物誘電体層を形成させることを特徴とする電
解コンデンサ用アルミニウム電極の製造方法。(1) After adhering titanium to the surface of high-purity aluminum by ion plating to form an aluminum-titanium alloy layer on the surface, anodizing is performed to form an aluminum-titanium mixed oxide dielectric layer. A method for manufacturing an aluminum electrode for an electrolytic capacitor, characterized by:
、チタンをイオンプレーティング法により付着せしめる
ことを特徴とする特許請求の範囲第１項記載の電解コン
デンサ用アルミニウム電極の製造方法。(2) The method for manufacturing an aluminum electrode for an electrolytic capacitor according to claim 1, characterized in that after etching the high-purity aluminum, titanium is deposited by an ion plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14276287A JPS63306614A (en) | 1987-06-08 | 1987-06-08 | Manufacture of aluminum electrode for electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14276287A JPS63306614A (en) | 1987-06-08 | 1987-06-08 | Manufacture of aluminum electrode for electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63306614A true JPS63306614A (en) | 1988-12-14 |
Family
ID=15322989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14276287A Pending JPS63306614A (en) | 1987-06-08 | 1987-06-08 | Manufacture of aluminum electrode for electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63306614A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008166602A (en) * | 2006-12-28 | 2008-07-17 | Sachiko Ono | Aluminum material for electrolytic capacitor electrode, its manufacturing method, electrode material for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| JP2012094914A (en) * | 2012-02-03 | 2012-05-17 | Sachiko Ono | Aluminum material for electrolytic capacitor electrode, its manufacturing method, electrode material for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| JP2012124347A (en) * | 2010-12-09 | 2012-06-28 | Panasonic Corp | Electrode foil, method of manufacturing the same, and capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6215813A (en) * | 1985-07-12 | 1987-01-24 | 昭和アルミニウム株式会社 | Anode material for electrolytic capacitor |
| JPS6279610A (en) * | 1985-10-03 | 1987-04-13 | 日通工株式会社 | Anode for electrolytic condenser |
-
1987
- 1987-06-08 JP JP14276287A patent/JPS63306614A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6215813A (en) * | 1985-07-12 | 1987-01-24 | 昭和アルミニウム株式会社 | Anode material for electrolytic capacitor |
| JPS6279610A (en) * | 1985-10-03 | 1987-04-13 | 日通工株式会社 | Anode for electrolytic condenser |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008166602A (en) * | 2006-12-28 | 2008-07-17 | Sachiko Ono | Aluminum material for electrolytic capacitor electrode, its manufacturing method, electrode material for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| JP2012124347A (en) * | 2010-12-09 | 2012-06-28 | Panasonic Corp | Electrode foil, method of manufacturing the same, and capacitor |
| JP2012094914A (en) * | 2012-02-03 | 2012-05-17 | Sachiko Ono | Aluminum material for electrolytic capacitor electrode, its manufacturing method, electrode material for aluminum electrolytic capacitor and aluminum electrolytic capacitor |
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