DE4127743C2 - Surface-enlarged aluminum foil for electrolytic capacitors and vacuum coating processes for their production - Google Patents
Surface-enlarged aluminum foil for electrolytic capacitors and vacuum coating processes for their productionInfo
- Publication number
- DE4127743C2 DE4127743C2 DE19914127743 DE4127743A DE4127743C2 DE 4127743 C2 DE4127743 C2 DE 4127743C2 DE 19914127743 DE19914127743 DE 19914127743 DE 4127743 A DE4127743 A DE 4127743A DE 4127743 C2 DE4127743 C2 DE 4127743C2
- Authority
- DE
- Germany
- Prior art keywords
- aluminum
- coating
- foil
- aluminum foil
- layer
- 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.)
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Links
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 49
- 229910052782 aluminium Inorganic materials 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 34
- 239000011888 foil Substances 0.000 title claims description 31
- 239000003990 capacitor Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000001771 vacuum deposition Methods 0.000 title claims description 4
- 150000002500 ions Chemical class 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 4
- 239000011574 phosphorus Substances 0.000 claims 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 3
- 239000011651 chromium Substances 0.000 claims 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 3
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CNRZQDQNVUKEJG-UHFFFAOYSA-N oxo-bis(oxoalumanyloxy)titanium Chemical compound O=[Al]O[Ti](=O)O[Al]=O CNRZQDQNVUKEJG-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/225—Oblique incidence of vaporised material on substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physical Vapour Deposition (AREA)
Description
Die Erfindung betrifft eine Aluminiumfolie mit erhöhter spezifischer Oberflächenkapazität mit einer beidseitig aufgebrachten Schicht, die als Katode in Elektrolytkondensatoren eingesetzt wird und das Verfahren zu deren Herstellung durch beidseitige Vakuumbeschichtung mit Aluminium.The invention relates to an aluminum foil with increased specific Surface capacity with a layer applied on both sides, which acts as a cathode in electrolytic capacitors is used and the process for their production by bilateral Vacuum coating with aluminum.
Es ist allgemein bekannt, in Elektrolytkondensatoren eingesetzte Aluminiumfolien zur Gewährleistung einer hohen spezifischen Flächenkapazität auf beiden Seiten aufzurauhen. Dieses Aufrauhen und damit das Vergrößern der Oberfläche durch chemisches oder elektrochemisches Herauslösen von metallischem Aluminium aus der Folienoberfläche erfolgt durch dessen Umwandlung in beispielsweise Aluminiumhydroxid oder Aluminiumchlorid. Nachteilig ist dabei, daß die Aufarbeitung der verwendeten aggressiven Ätzlösungen aus Gründen des Umweltschutzes einen hohen Aufwand erfordert. Darüber hinaus müssen die Folien nach dem Ätzen ausreichend mit Wasser gespült werden, so daß außerdem eine umfangreiche Wasserver- und entsorgung notwendig ist. Weiterhin sind zur Erzeugung einer hohen spezifischen Kapazität spezielle Vorbehandlungen der Ausgangsglattfolie oder legierungstechnische Maßnahmen erforderlich.It is well known to be used in electrolytic capacitors Aluminum foils to ensure a high specific Roughen area capacity on both sides. This roughening and thus enlarging the surface by chemical or electrochemical removal of metallic aluminum from the Foil surface is done by converting it into, for example Aluminum hydroxide or aluminum chloride. The disadvantage is doing the workup of the aggressive used Etching solutions for reasons of environmental protection a lot of effort required. In addition, the foils need to be etched be rinsed sufficiently with water so that a extensive water supply and disposal is necessary. Farther are special for generating a high specific capacity Pretreatments of the initial smooth foil or alloy technology Measures required.
Weiterhin ist ein Verfahren bekannt, bei dem die Rauhigkeit einer bereits geätzten Folie durch Aufdampfen von Ti noch verstärkt wird (EP 0 272 926 A2). Infolge der Notwendigkeit eines Ätzprozesses vor dem Bedampfen werden auch bei diesem Verfahren die obengenannten Nachteile nicht vermieden.A method is also known in which the roughness of a already etched foil reinforced by evaporation of Ti (EP 0 272 926 A2). Due to the need for one Etching process before vapor deposition are also used in this process the disadvantages mentioned above are not avoided.
Es ist ein weiteres Verfahren unter Verwendung von Ti für die Schichtherstellung bekannt, indem mit dem Aluminium Titanoxid aufgedampft wird. Der Prozeß wird im Katoden-Bogen ausgeübt (JP 3-147 3121 A. In: Patents Abstr. of Japan, Sect. E. Vol. 15 (1991), Nr. 371 (E-1113)). Mit diesem Verfahren wird keine hohe Produktivität erreicht, so daß es zu teuer ist, um größere Mengen, wie es bei der Herstellung von Kondensatorfolien nötig ist, zu beschichten. It is another method using Ti for that Layer production is known by using the aluminum titanium oxide is evaporated. The process is carried out in the cathode arc (JP 3-147 3121 A. In: Patents Abstr. of Japan, Sect. E. Vol. 15 (1991), No. 371 (E-1113)). With this method, there is no high productivity achieved so that it is too expensive to handle larger quantities as in the production of capacitor foils is necessary to coat.
Es ist auch ein Verfahren bekannt, bei dem zum Vermeiden dieser Nachteile die notwendige Oberflächenvergrößerung durch Aufdampfen einer porösen Schicht auf Al- oder Kunststoffolien erfolgt (DE 30 29 171 A1). Die Porosität wird dadurch erreicht, daß das Aufdampfen unter einem möglichst kleinen Winkel gegen die Substratoberfläche erfolgt. Poröse Filme haben jedoch den Nachteil, daß die Grenzfläche zwischen dem Substrat und dem aufgedampften Film eine Schwachstelle der Haftung darstellt, und die aufgedampfte Schicht unter Einwirken des Betriebselektrolyten leicht abgelöst wird und somit eine geringe Stabilität aufweist.A method is also known in which to avoid this Disadvantages the necessary surface enlargement by vapor deposition a porous layer on aluminum or plastic foils (DE 30 29 171 A1). The porosity is achieved by the evaporation at the smallest possible angle against the substrate surface he follows. However, porous films have the disadvantage that the Interface between the substrate and the evaporated film Represents the weak point of liability, and the evaporated layer is easily detached under the influence of the operating electrolyte and thus has a low stability.
Schließlich ist es auch noch bekannt, die Aluminiumfolien für Elektrolytkondensatoren doppelseitig mit Titan zu beschichten (US 4 970 626). Das Aufdampfen von Titan erfolgt in üblichen Bandbedampfungsanlagen über einer Kühlwalze, so daß der Auftreffwinkel der Dampfteilchen sehr groß bis senkrecht zur Ebene ist. Damit werden die bereits den anderen bekannten Verfahren anhaftenden Mängel nicht beseitigt. Außerdem ist die dazu erforderliche Menge Ti sehr teuer, so daß das Verfahren unwirtschaftlich ist.Finally, it is also known that the aluminum foils for electrolytic capacitors are double-sided to be coated with titanium (US 4,970,626). The evaporation of titanium takes place in a conventional band steaming plant over one Cooling roller, so that the angle of incidence of the steam particles is very large is perpendicular to the plane. With that they already become the other Defects inherent in known methods are not eliminated. Furthermore the amount of Ti required for this is very expensive, so that Procedure is uneconomical.
Der Erfindung liegt die Aufgabe zugrunde, eine Aluminiumfolie für Elektrolytkondensatoren mit hoher spezifischer Flächenkapazität und hoher Stabilität sowie ein Verfahren zu deren Herstellung zu schaffen, wobei chemische bzw. elektrochemische Prozesse bei der Herstellung vermieden werden sollen. Das Verfahren soll umweltfreundlich sein. Das Verfahren soll mit konventionellen Vakuum-Beschichtungsanlagen, d. h. Bedampfungsanlagen, ausführbar sein.The invention has for its object an aluminum foil for Electrolytic capacitors with a high specific surface capacity and high stability and a process for their production create, whereby chemical or electrochemical processes in the Manufacturing should be avoided. The process is said to be environmentally friendly his. The process is said to use conventional vacuum coating systems, i. H. Steaming systems, be executable.
Erfindungsgemäß wird diese Aufgabe nach den Merkmalen der Ansprüche 1 und 3 gelöst. Weitere Ausgestaltungen beinhalten die Unteransprüche.According to the invention, this task according to the characteristics of Claims 1 and 3 solved. Further configurations include the Subclaims.
Die geforderten Eigenschaften der Aluminiumfolie werden im wesentlichen dann erreicht, wenn das aufgebrachte Aluminium in der Schicht in Form von stengelförmigen Kristalliten vorliegt, die vom Aluminiumoxid eingehüllt und voneinander elektrisch isoliert sind.The required properties of the aluminum foil are in the essentially achieved when the applied aluminum in the layer is in the form of columnar crystallites, which are enveloped by aluminum oxide and are electrically insulated from one another.
Durch die mäanderförmige Anordnung der Kristallite, die durch Oxidphasen voneinander isoliert sind, wird offenbar eine große "innere" Oberfläche erzeugt, die die große spezifische Flächenkapazität erzeugt. Verstärkt wird dieser Effekt noch durch eine gewisse Mikrorauhigkeit der Oberfläche infolge der stengelförmigen Kristallite. Durch den erfindungsgemäßen Schichtaufbau und das Vermeiden der Porosität wird eine hohe Adhäsion der Schicht gegenüber der Grundfolie aus Aluminium gewährleistet.Through the meandering Arrangement of crystallites separated by oxide phases are isolated, apparently a large "inner" surface that creates the large specific area capacity. This effect is reinforced by a certain micro-roughness the surface due to the stalk-shaped crystallites. By the layer structure according to the invention and the avoidance of Porosity is a high adhesion of the layer to the Base foil made of aluminum guaranteed.
Das Einbringen von Ventilmetallen, wie Ti, Ta, Zr bzw. deren Verbindungen, dient zu einer weiteren Erhöhung der spezifischen Oberflächenkapazität, und das Zusetzen von Stabilisierungselementen, wie P oder Cr bzw. deren Verbindungen, erhöht die Beständigkeit der Schicht gegenüber dem Betriebselektrolyten.The introduction of valve metals such as Ti, Ta, Zr or their Connections serves to further increase the specific Surface capacity, and the addition of stabilizing elements, such as P or Cr or their compounds, increases the resistance the layer opposite the operating electrolyte.
Ein wesentliches Merkmal des Verfahrens zur Herstellung der Aluminiumfolie ist der Auftreffwinkel des Aluminiumdampfes relativ zur Folienoberfläche zu Beginn der Beschichtung. Der Auftreffwinkel darf nicht zu klein sein, denn ein Aufdampfen mit zu kleinem Winkel zu Beginn der Schichtbildung führt zu porösen Schichten und unzureichender Schichthaftung (siehe DE 30 29 171 A1). Es wurde gefunden, daß bei der genannten Ioneneinwirkung der Auftreffwinkel zu Beginn der Schichtbildung mehr als 30° betragen muß. Ohne Ioneneinwirkung muß der Auftreffwinkel zu Beginn der Schichtbildung sogar mehr als 60° betragen. Die Ioneneinwirkung hat weiterhin den Vorteil, daß trotz des ungewöhnlich hohen Sauerstoffpartialdruckes und der ungewöhnlich hohen Bedampfungsrate der Sauerstoff chemisch mit dem Aluminiumdampf reagiert und nicht nur physikalisch in die Schicht eingebaut wird. Die durch die Ioneneinwirkung angeregten bzw. ionisierten Aluminium- und Sauerstoffatome verbinden sich beim Kondensationsprozeß mit hoher Reaktivität zu Aluminiumoxid, welches sich an den Korngrenzen der Kristallite anreichert, so daß sich zwischen den Kristalliten eine dünne isolierende Oxidhaut bildet.An essential feature of the process for producing the Aluminum foil is the angle of incidence of the aluminum vapor relative to the film surface at the beginning of the coating. Of the Impact angle must not be too small, because a vapor deposition with too small an angle at the beginning of the layer formation leads to porous Layers and insufficient layer adhesion (see DE 30 29 171 A1). It was found that with the aforementioned ion action the impact angle at the beginning of the layer formation is more than 30 ° must be. Without the influence of ions, the angle of incidence must be increased Beginning of the layer formation may even be more than 60 °. The Ion exposure has the further advantage that despite the unusual high oxygen partial pressure and the unusual high vapor deposition rate of the oxygen chemically with the aluminum vapor reacts and not just physically built into the layer becomes. The excited or ionized by the action of ions Aluminum and oxygen atoms combine in the Condensation process with high reactivity to aluminum oxide, which accumulates at the grain boundaries of the crystallites, so that there is a thin insulating oxide skin between the crystallites forms.
Es wurde gefunden, daß die Abmessungen der entstehenden Kristallite um so kleiner sind, je höher der Aluminiumoxidgehalt der Schichten ist. It was found that the dimensions of the resulting crystallites the smaller the higher the alumina content of the Layers is.
Zur Erhöhung der Haftfestigkeit und Stabilität der Schicht im Betriebselektrolyten ist es vorteilhaft, außer dem Mindest-Auftreffwinkel zu Beginn der Schichtbildung und der Ioneneinwirkung bei der Beschichtung jede zu beschichtende Seite der Aluminiumfolie vor der Beschichtung einem Ionenätzprozeß zu unterwerfen. Dabei ist es wichtig, daß dieser in einem Vakuumdurchlauf vor der Beschichtung, d. h. ohne Zwischenbelüftung der Oberfläche erfolgt. Eine hohe Beschichtungsrate unter Ioneneinwirkung während der reaktiven Aluminiumbeschichtung wird vorteilhafterweise erreicht, indem das Aluminium mittels eines Elektronenstrahl- Linienverdampfers verdampft wird und die dabei rückgestreuten Elektronen zur Ionisierung von Aluminiumdampf und Sauerstoff genutzt werden. Dieser Ionisierungseffekt kann noch verstärkt werden, indem die rückgestreuten Elektronen durch ein Magnetfeld zwischen Verdampfertiegel und zu beschichtender Aluminiumfolie auf Kreisbahnen gezwungen werden, wodurch sich ihre Bahn innerhalb der Dampfwolke verlängert und sich somit die Ionisierungswahrscheinlichkeit erhöht.To increase the adhesive strength and stability of the layer in the Operating electrolytes are advantageous, except for the minimum impact angle at the beginning of layer formation and the influence of ions when coating each side of the aluminum foil to be coated subject to an ion etching process prior to coating. It is important that this in a vacuum pass before the Coating, d. H. without intermediate ventilation of the surface he follows. A high coating rate under the influence of ions during the reactive aluminum coating is advantageous achieved by aluminum using an electron beam Line evaporator is evaporated and the thereby backscattered electrons for ionizing aluminum vapor and Oxygen can be used. This ionization effect can still be amplified by the backscattered electrons by a Magnetic field between the evaporator crucible and the one to be coated Aluminum foil will be forced on circular orbits, causing their path within the cloud of steam lengthens and thus the Ionization probability increased.
Es ist weiterhin möglich, die Ionisierung von Aluminiumdampf und Sauerstoff durch Einwirkung einer an sich bekannten Ionen- oder Plasmaquelle im Bereich zwischen Verdampfertiegel und zu beschichtender Folie zu bewirken. Diese Ionisierungsquellen können zusätzlich zur Ionisierung durch rückgestreute Elektronen beim Elektronenstrahlverdampfer aber auch beim Aluminiumverdampfen nach anderen Verfahren eingesetzt werden. Eine weitere Verstärkung der Ioneneinwirkung während der Kondensation auf der Folienoberfläche ist dadurch möglich, daß die zu beschichtende Aluminiumfolie gegenüber dem Verdampfer auf eine Bias-Spannung gelegt wird. Dadurch werden die Ionen auf die Folienoberfläche beschleunigt und bewirken aufgrund ihrer höheren Energie eine weitere Erhöhung der Haftfestigkeit und Kompaktheit der aufwachsenden Schicht.It is also possible to ionize aluminum vapor and Oxygen by the action of a known ion or Plasma source in the area between the evaporator crucible and to effect coating film. These sources of ionization can in addition to ionization by backscattered electrons with electron beam evaporators but also with aluminum evaporation be used by other methods. Another Intensification of the influence of ions during the condensation on the Foil surface is possible in that the to be coated Aluminum foil towards the evaporator to a bias voltage is placed. This causes the ions to hit the film surface accelerates and cause a due to their higher energy further increase the adhesive strength and compactness of the growing Layer.
An einem Beispiel wird die Erfindung näher beschrieben. In der zugehörigen Zeichnung ist die Struktur der erfindungsgemäß erzeugten Schicht in 170 000facher Vergrößerung abgebildet. Die stengelförmigen Aluminium-Kristallite sind deutlich zu erkennen, die voneinander durch Aluminiumoxid-Phasen getrennt sind. Die aufgebrachte Schicht ist 2,4 µm dick und befindet sich auf einer 30 µm dicken Aluminiumfolie.The invention is described in more detail using an example. In the associated drawing is the structure of the invention generated layer shown in 170,000 times magnification. The stem-shaped aluminum crystallites are clearly closed recognize that separated from each other by alumina phases are. The applied layer is 2.4 µm thick and is located on a 30 µm thick aluminum foil.
Die spezifische Flächenkapazität einer derart beschichteten Aluminiumfolie wurde bei 100 Hz in verschiedenen Elektrolyten gemessen und mit einer nach bekannter Technologie elektrochemisch geätzten Folie gleicher Dicke verglichen.The specific surface capacity of such a coated Aluminum foil was at 100 Hz in various electrolytes measured and electrochemically using a known technology etched foil of the same thickness compared.
Die experimentell ermittelten Kapazitätswerte sind nur verständlich, wenn man annimmt, daß die Oberflächen der Kristallite maßgeblich zur Kapazitätsbildungg beitragen, obwohl eine exakte Erklärung dieses Phänomens bisher noch nicht möglich ist.The experimentally determined capacitance values are only understandable, if one assumes that the surfaces of the crystallites contribute significantly to capacity building, although an exact Explanation of this phenomenon is not yet possible.
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US6287673B1 (en) * | 1998-03-03 | 2001-09-11 | Acktar Ltd. | Method for producing high surface area foil electrodes |
US6865071B2 (en) | 1998-03-03 | 2005-03-08 | Acktar Ltd. | Electrolytic capacitors and method for making them |
DE19817405A1 (en) * | 1998-04-20 | 1999-10-21 | Becromal Spa | High dielectric constant electrolytic capacitor anode manufacturing method |
IT1307557B1 (en) * | 1999-04-14 | 2001-11-14 | Becromal Spa | ELECTRODES FOR ELECTROLYTIC CAPACITORS AND THEIR MANUFACTURING PROCESS BY VACUUM VAPORATION. |
IL173121A (en) | 2006-01-12 | 2011-07-31 | Dina Katsir | Electrodes, membranes, printing plate precursors and other articles including multi-strata porous coatings |
RU2339110C1 (en) | 2007-11-12 | 2008-11-20 | Ооо "Восток" | Multilayer anode |
KR101552746B1 (en) * | 2008-04-22 | 2015-09-11 | 도요 알루미늄 가부시키가이샤 | Electrode material for aluminum electrolytic capacitor and process for producing the electrode material |
WO2011114680A1 (en) * | 2010-03-16 | 2011-09-22 | パナソニック株式会社 | Electrode foil and capacitor using same |
EE05629B1 (en) * | 2010-09-06 | 2013-02-15 | O� Skeleton Technologies | Method for the preparation of an electrochemical system of a high power and energy density supercapacitor, a corresponding supercapacitor and a method for making it |
JPWO2012161158A1 (en) | 2011-05-26 | 2014-07-31 | 東洋アルミニウム株式会社 | Electrode material for aluminum electrolytic capacitor and method for producing the same |
JP5769528B2 (en) | 2011-07-15 | 2015-08-26 | 東洋アルミニウム株式会社 | Electrode material for aluminum electrolytic capacitor and method for producing the same |
KR102079032B1 (en) | 2012-02-10 | 2020-02-19 | 도요 알루미늄 가부시키가이샤 | Method for manufacturing electrode material for aluminium electrolytic capacitor |
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US4763229A (en) * | 1986-12-24 | 1988-08-09 | Showa Aluminum Kabushiki Kaisha | Aluminum capacitor plate for electrolytic capacitor and process for making the same |
WO1989001230A1 (en) * | 1987-07-30 | 1989-02-09 | Matsushita Electric Industrial Co., Ltd. | Electrolytic capacitor and production method thereof |
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