WO2021148318A1 - Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition - Google Patents
Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition Download PDFInfo
- Publication number
- WO2021148318A1 WO2021148318A1 PCT/EP2021/050794 EP2021050794W WO2021148318A1 WO 2021148318 A1 WO2021148318 A1 WO 2021148318A1 EP 2021050794 W EP2021050794 W EP 2021050794W WO 2021148318 A1 WO2021148318 A1 WO 2021148318A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- composition
- aluminum
- composition according
- dissolving
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/18—Polishing of light metals
- C25F3/20—Polishing of light metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys and uses of this composition
- the present invention relates to a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or
- the workpieces to be polished are normally immersed in an electrolyte, the polishing bath, removed from the electrolyte after a certain electrochemical reaction time has elapsed and then cleaned of the respective electrolyte, for example by rinsing in various rinsing baths.
- the choice of a suitable electrolyte depends, among other things, on the material of the workpiece to be machined. From DE 10320 909 A1, DE 26 18 313 A1, DE 11 2005 002 414 T5 and AT 520 365 A1, for example, various electrolyte compositions are known which are based on (aqueous) mixtures of concentrated acids and alcohols and / or ethers .
- electrochemical windows of these electrolytes i.e. the voltage ranges in which electrochemical reactions can be carried out in these electrolytes without the electrolyte itself decomposing, are comparatively small, ionic liquids have been used in electrochemical reactions since the turn of the millennium examined.
- Ionic liquids are well suited as electrolytes for the deposition and electropolishing of metals.
- Ionic liquids i.e. molten salts with melting points below 100 ° C, which are mostly formed from organic cations, such as pyrrolidinium or imidazolium ions, and comparatively large complex anions, such as tetrafluoroborate or trifluoromethanesulfonate, are also environmentally friendly due to their very low vapor pressure and high polarity Solvents in preparative chemistry and catalysis but also as electrolytes in other electrochemical applications, e.g. in batteries, fuel cells and photovoltaic systems.
- the present invention is based on the object of providing a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys which is improved compared to the prior art and which enables the formation of as smooth, homogeneous metal or alloy surfaces as possible at comparatively high removal rates.
- composition according to the invention as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprises butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ).
- the composition further comprises an acid.
- Such a composition not only enables a rapid dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, and thereby a rapid detachment from the surfaces of corresponding metallic workpieces, it is also used for Treatment of 3-D printing plates, in particular 3-D printing plates based on an aluminum-magnesium-silicon alloy, is suitable and advantageously reduces, in particular, the formation of a passivation layer on the workpiece surface.
- An embodiment of the invention has proven itself in which the composition butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (Nun BTA) and 0.1-2.0% by weight, preferably 0.2-1, 2% by weight %, particularly preferably 1.0% by weight KAIF 4 .
- KAIF 4 in the specified quantity range advantageously increases the rate of dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, on the surfaces of corresponding metallic workpieces in comparison to
- the composition also contains 0.1-2.0% by volume, preferably 0.8-1.2% by volume, particularly preferably 1.0% by volume, H 2 as the acid S0 4 includes.
- An addition of acid, in particular sulfuric acid also advantageously increases the rate of dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, on the surfaces of corresponding metallic workpieces in comparison to
- a content of 1.0% by weight of KAIF 4 and a content of 1.0% by volume of H 2 S0 4 have proven particularly useful.
- composition according to the invention can in particular be used as an electrolyte for dissolving aluminum and / or aluminum oxide or
- composition according to the invention is also suitable for use as an electrolyte in (electro) chemical energy stores for both stationary and mobile use, in particular also for use in stationary or mobile emergency power units.
- the composition according to the invention can also be used advantageously as an electrolyte in batteries for land, air and / or water vehicles.
- composition according to the invention can also be used as an electrolyte in the deposition of base metals, in particular in the deposition of aluminum.
- composition according to the invention is also suitable for use as an electrolyte in the coating of 3D printed components, in particular metallic 3D printed components.
- Example 1 Dissolution of aluminum or aluminum oxide from the surface of an aluminum plate by electrochemical dissolution
- EMIM OTf 1-ethyl-3-methylimidazolium trifluoromethanesulfonate
- EMIM BTA 1- Ethyl-3-methylimidazolium bis- (trifluoromethylsulfonyl) imide
- PMPyrr BTA 1- methyl-1-propylpyrrolidinium bis- (trifluoromethylsulfonyl) imide
- EMIM HS0 4 1-ethyl-3-methylimidazolium hydrogen sulfate
- PropPy BF 4 1-propylpyridinium tetrafluoroborate
- Example 2 Electropolishing of aluminum 3D printing plates
- a comparison of experiments nos. 11 and 12 with experiments nos. 7 to 10 shows that regardless of whether the electropolishing is carried out with the aid of a pulse program or by applying a direct voltage, in particular a composition comprising butyltrimethylammonium-bis (trifluoromethylsulfon-yl) imid (N 1114 BTA), 1 wt .-% potassium aluminum fluoride (KAIF 4 ) and 1 vol .-% sulfuric acid (H 2 S0 4 ) under the specified conditions advantageous for the strongest dissolution of the top metal or metal oxide layer on the respective material surface and thus the best smoothing with the lowest blackening at the same time.
- a direct voltage in particular a composition comprising butyltrimethylammonium-bis (trifluoromethylsulfon-yl) imid (N 1114 BTA), 1 wt .-% potassium aluminum fluoride (KAIF 4 ) and 1 vol .-% sulfuric acid (H 2 S0 4 ) under the specified conditions advantageous for the strongest dissolution
- the present invention relates to a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprising: butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ), and optionally an acid. It also relates to the use of this composition as an electrolyte in (electro) chemical energy storage devices, in particular for stationary or mobile applications, as an electrolyte in the deposition of base metals and as an electrolyte in the coating of 3D printed components.
- a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprising: butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ), and optionally an acid. It also relates to the use of this composition as an
- composition according to the invention advantageously enables metals and / or metal oxides, in particular aluminum and aluminum oxide, to dissolve rapidly from corresponding metallic workpieces. It is also suitable for treating 3D printing plates, in particular 3D printing plates based on an aluminum-magnesium-silicon alloy, and advantageously reduces the formation of a passivation layer on the workpiece surface.
Abstract
The invention relates to a composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, comprising: butyltrimethylammonium-bis(trifluormethylsulfon-yl)imid (N1114 BTA), potassium aluminum fluoride (KAlF4), and optionally an acid. The invention additionally relates to the use of said composition as an electrolyte in (electro)chemical energy storage units, in particular for stationary or mobile applications, as an electrolyte when separating non-precious metals, and as an electrolyte when coating 3D printed components. The composition according to the invention advantageously allows metals and/or metal oxides, in particular aluminum and aluminum oxide, to be quickly dissolved from corresponding metal workpieces. The invention is also suitable for treating 3D printing plates, in particular 3D printing plates based on an aluminum-magnesium-silicon alloy, in the process advantageously reducing the formation of a passivation layer on the workpiece surface.
Description
Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oder Metalllegierungen sowie Verwendungen dieser Zusammensetzung Composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys and uses of this composition
Die vorliegende Erfindung betrifft eine Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oderThe present invention relates to a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or
Metalllegierungen sowie deren weitere Verwendung. Metal alloys and their further uses.
Im Bereich der Oberflächen(nach)behandlung von metallischen Werkstücken nimmt das elektrochemische Polieren von Metalloberflächen eine wichtige fertigungstechnische Stellung zur Erzielung glatter, glänzenderIn the area of surface (post) treatment of metallic workpieces, the electrochemical polishing of metal surfaces plays an important role in production technology to achieve smoother, shinier ones
Werkstückoberflächen ein. Beim Elektropolieren werden die zu polierenden Werkstücke normalerweise in einen Elektrolyt, das Polierbad, getaucht, nach Ablauf einer gewissen elektrochemischen Reaktionszeit wieder aus dem Elektrolyt entfernt und anschließend beispielsweise durch Spülung in verschiedenen Spülbädern vom jeweiligen Elektrolyt gereinigt. Die Wahl eines geeigneten Elektrolyten hängt dabei unter anderem vom Material des zu bearbeitenden Werkstücks ab. Aus der DE 10320 909 A1, der DE 26 18 313 A1, der DE 11 2005 002 414 T5 und der AT 520 365 A1 sind dazu beispielsweise verschiedene Elektrolytzusammensetzungen bekannt, welche auf (wässrigen) Mischungen aus konzentrierten Säuren und Alkoholen und/oder Ethern basieren. Da die sog. elektrochemischen Fenster dieser Elektrolyte, also der Spannungsbereiche, in denen elektrochemische Reaktionen in diesen Elektrolyten durchgeführt werden können, ohne dass sich der Elektrolyt selbst zersetzt, vergleichsweise klein sind, wurden ungefähr seit der Jahrtausendwende ionische Flüssigkeit auf ihre Verwendbarkeit in elektrochemischen Reaktionen hin untersucht. Workpiece surfaces. In electropolishing, the workpieces to be polished are normally immersed in an electrolyte, the polishing bath, removed from the electrolyte after a certain electrochemical reaction time has elapsed and then cleaned of the respective electrolyte, for example by rinsing in various rinsing baths. The choice of a suitable electrolyte depends, among other things, on the material of the workpiece to be machined. From DE 10320 909 A1, DE 26 18 313 A1, DE 11 2005 002 414 T5 and AT 520 365 A1, for example, various electrolyte compositions are known which are based on (aqueous) mixtures of concentrated acids and alcohols and / or ethers . Since the so-called electrochemical windows of these electrolytes, i.e. the voltage ranges in which electrochemical reactions can be carried out in these electrolytes without the electrolyte itself decomposing, are comparatively small, ionic liquids have been used in electrochemical reactions since the turn of the millennium examined.
Ionischen Flüssigkeiten eignen sich aufgrund ihres vergleichsweise breiten elektrochemischen Fensters gut als Elektrolyte zum Abscheiden sowie zum Elektropolieren von Metallen. Ionische Flüssigkeiten, also geschmolzenen Salze
mit Schmelzpunkten unter 100 °C, welche meist aus organischen Kationen, wie bspw. Pyrrolidinium- oder Imidazolium-Ionen, und vergleichsweise großen komplexen Anionen, wie z.B. Tetrafluoroborat oder Trifluormethansulfonat, gebildet werden finden aufgrund ihres sehr niedrigen Dampfdrucks und ihrer hohen Polarität zudem als umweltfreundliche Lösungsmittel in der präparativen Chemie und Katalyse aber auch als Elektrolyte innerhalb anderer elektrochemischer Anwendungen bspw. in Batterien, Brennstoffzellen und Photovoltaikanalgen, Verwendung. Aus der US 2004/0097755 A1 sind dazu beispielsweise eine Reihe von Verbindungen auf Basis von quartären Ammonium-Ionen bekannt, welche durch Bildung von Wasserstoffbrückenbindungen zu verschiedenen organischen Molekülen ionische Flüssigkeiten bilden und unter anderem als Lösungsmittel bei Polymerisationsreaktionen aber auch bei der Elektropolitur von Edelstahl eingesetzt werden können. Due to their comparatively wide electrochemical window, ionic liquids are well suited as electrolytes for the deposition and electropolishing of metals. Ionic liquids, i.e. molten salts with melting points below 100 ° C, which are mostly formed from organic cations, such as pyrrolidinium or imidazolium ions, and comparatively large complex anions, such as tetrafluoroborate or trifluoromethanesulfonate, are also environmentally friendly due to their very low vapor pressure and high polarity Solvents in preparative chemistry and catalysis but also as electrolytes in other electrochemical applications, e.g. in batteries, fuel cells and photovoltaic systems. From US 2004/0097755 A1, for example, a number of compounds based on quaternary ammonium ions are known, which form ionic liquids by forming hydrogen bonds to various organic molecules and are used, among other things, as solvents in polymerization reactions but also in the electropolishing of stainless steel can be.
Ausgehend davon liegt der vorliegenden Erfindung nun die Aufgabe zugrunde, eine im Vergleich zum Stand der Technik verbesserte Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oder Metalllegierungen bereitzustellen, welche die Bildung möglichst glatter, homogener Metall- bzw. Legierungsoberflächen bei vergleichsweise hohen Abtragungsgeschwindigkeiten ermöglicht. Proceeding from this, the present invention is based on the object of providing a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys which is improved compared to the prior art and which enables the formation of as smooth, homogeneous metal or alloy surfaces as possible at comparatively high removal rates.
Diese Aufgabe wird durch eine Zusammensetzung mit den Merkmalen des unabhängigen Patentanspruchs 1 gelöst. This object is achieved by a composition with the features of independent claim 1.
Die erfindungsgemäße Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oder Metalllegierungen umfasst dabei Butyltrimethylammonium-bis(trifluormethylsulfonyl)imid (N1114 BTA) und Kaliumaluminiumfluorid (KAIF4). Gegebenenfalls umfasst die Zusammensetzung ferner eine Säure. Eine derartige Zusammensetzung ermöglicht nicht nur eine schnelle Auflösung von Metallen und/oder Metalloxiden, insbesondere von Aluminium und Aluminiumoxid, und dadurch eine schnelle Ablösung von den Oberflächen entsprechender metallischer Werkstücken, sie ist auch zur
Behandlung von 3D-Druckplatten, insbesondere von 3D-Druckplatten auf Basis einer Aluminium-Magnesium-Silicium-Legierung, geeignet und vermindert dabei vorteilhaft insbesondere die Bildung einer Passivierungsschicht an der Werkstückoberfläche. The composition according to the invention as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprises butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ). Optionally the composition further comprises an acid. Such a composition not only enables a rapid dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, and thereby a rapid detachment from the surfaces of corresponding metallic workpieces, it is also used for Treatment of 3-D printing plates, in particular 3-D printing plates based on an aluminum-magnesium-silicon alloy, is suitable and advantageously reduces, in particular, the formation of a passivation layer on the workpiece surface.
Dabei hat sich eine Ausgestaltung der Erfindung bewährt, bei der die Zusammensetzung Butyltrimethylammonium-bis-(trifluormethylsulfonyl)-imid (Nun BTA) und 0,1 - 2,0 Gew.-%, bevorzugt 0,2 - 1 ,2 Gew.-%, besonders bevorzugt 1 ,0 Gew.-% KAIF4 umfasst. Die Zugabe von KAIF4 im angegebenen Mengenbereich erhöht vorteilhaft die Auflösungsgeschwindigkeit von Metallen und/oder Metalloxiden, insbesondere von Aluminium und Aluminiumoxid, an den Oberflächen entsprechender metallischer Werkstücke im Vergleich zurAn embodiment of the invention has proven itself in which the composition butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (Nun BTA) and 0.1-2.0% by weight, preferably 0.2-1, 2% by weight %, particularly preferably 1.0% by weight KAIF 4 . The addition of KAIF 4 in the specified quantity range advantageously increases the rate of dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, on the surfaces of corresponding metallic workpieces in comparison to
Verwendung von reinem N1114 BTA als Elektrolyt. Use of pure N 1114 BTA as electrolyte.
Darüber hinaus hat es sich bewährt, wenn die Zusammensetzung ferner als Säure 0,1 - 2,0 Vol.-%, bevorzugt 0,8 - 1 ,2 Vol.-%, besonders bevorzugt 1 ,0 Vol.-%, H2S04 umfasst. Auch eine Zugabe von Säure, insbesondere Schwefelsäure, erhöht vorteilhaft die Auflösegeschwindigkeit von Metallen und/oder Metalloxiden, insbesondere von Aluminium und Aluminiumoxid, an den Oberflächen entsprechender metallischer Werkstücke im Vergleich zurIn addition, it has proven useful if the composition also contains 0.1-2.0% by volume, preferably 0.8-1.2% by volume, particularly preferably 1.0% by volume, H 2 as the acid S0 4 includes. An addition of acid, in particular sulfuric acid, also advantageously increases the rate of dissolution of metals and / or metal oxides, in particular aluminum and aluminum oxide, on the surfaces of corresponding metallic workpieces in comparison to
Verwendung von reinem N1114 BTA als Elektrolyt. Use of pure N 1114 BTA as electrolyte.
Erfindungsgemäß besonders bevorzugt ist dabei eine Zusammensetzung auf Basis von Butyltrimethylammonium-bis(trifluormethylsulfonyl)imid (N1114 BTA) und Kaliumaluminiumfluorid (KAIF4), die auch eine Säure, insbesondere Schwefelsäure (H2S04), umfasst. Besonders bewährt hat sich dabei ein Gehalt von 1,0 Gew.-% KAIF4 und ein Gehalt von 1 ,0 Vol.-% H2S04. According to the invention, a composition based on butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ), which also includes an acid, in particular sulfuric acid (H 2 S0 4 ), is particularly preferred. A content of 1.0% by weight of KAIF 4 and a content of 1.0% by volume of H 2 S0 4 have proven particularly useful.
Die erfindungsgemäße Zusammensetzung kann insbesondere als Elektrolyt zum Auflösen von Aluminium und/oder Aluminiumoxid bzw. vonThe composition according to the invention can in particular be used as an electrolyte for dissolving aluminum and / or aluminum oxide or
Aluminiumlegierungen und darunter insbesondere von Aluminium-Magnesium- Silicium-Legierungen verwendet werden.
Die erfindungsgemäße Zusammensetzung eignet sich zudem auch zur Verwendung als Elektrolyt in (elektro-)chemischen Energiespeichern sowohl für eine stationäre als auch für eine mobile Anwendung, hierbei insbesondere auch zur Verwendung in stationären oder mobilen Notstromaggregaten. Im Rahmen einer mobilen Anwendung kann die erfindungsgemäße Zusammensetzung auch vorteilhaft als Elektrolyt in Akkumulatoren von Land-, Luft- und/oder Wasserfahrzeugen verwendet werden. Aluminum alloys and including in particular aluminum-magnesium-silicon alloys are used. The composition according to the invention is also suitable for use as an electrolyte in (electro) chemical energy stores for both stationary and mobile use, in particular also for use in stationary or mobile emergency power units. In the context of a mobile application, the composition according to the invention can also be used advantageously as an electrolyte in batteries for land, air and / or water vehicles.
Darüber hinaus kann die erfindungsgemäße Zusammensetzung auch als Elektrolyt bei der Abscheidung unedler Metalle, insbesondere bei der Abscheidung von Aluminium, Verwendung finden. In addition, the composition according to the invention can also be used as an electrolyte in the deposition of base metals, in particular in the deposition of aluminum.
Schließlich eignet sich die erfindungsgemäße Zusammensetzung auch zur Verwendung als Elektrolyt bei der Beschichtung von 3D- Druckbauteilen, insbesondere von metallischen 3D-Druckbauteilen. Finally, the composition according to the invention is also suitable for use as an electrolyte in the coating of 3D printed components, in particular metallic 3D printed components.
Nachfolgend wird die Erfindung anhand von nicht-einschränkenden Ausführungsbeispielen näher erläutert. The invention is explained in more detail below on the basis of non-limiting exemplary embodiments.
Beispiel 1 : Auflösung von Aluminium bzw. Aluminiumoxid von der Oberfläche einer Aluminiumplatte durch elektrochemische Auflösung Example 1: Dissolution of aluminum or aluminum oxide from the surface of an aluminum plate by electrochemical dissolution
Die im Folgenden aufgeführten Auflöseversuche wurden mit einem Potentiostat/Galvanostat-Modul vom Typ Autolab der Firma Metrohm, Filderstadt durchgeführt. Als untersuchtes Werkstück sowie als Gegenelektrode wurden Aluminiumplatten verwendet, die Temperierung der elektrochemischen Zelle erfolgte mittels eines Ölbades. The dissolution tests listed below were carried out with a potentiostat / galvanostat module of the Autolab type from Metrohm, Filderstadt. Aluminum plates were used as the examined workpiece and as the counter electrode, and the temperature of the electrochemical cell was controlled using an oil bath.
Neben Butyltrimethylammonium bis-(trifluormethylsulfonyl)imid (N1114 BTA) wurden auch 1-Ethyl-3-methylimidazolium trifluormethansulfonat (EMIM OTf); 1- Ethyl-3-methylimidazolium bis-(trifluormethylsulfonyl)imid (EMIM BTA) und 1- Methyl-1-propylpyrrolidinium bis-(trifluormethylsulfonyl)imid (PMPyrr BTA) als ionische Flüssigkeiten getestet.
Als saurer Vergleichselektrolyt wurde zudem eine Mischung aus 49,5 Gew.-% 1- Ethyl-3-methylimidazolium hydrogensulfat (EMIM HS04), 49,5 Gew.-% 1- Propylpyridinium tetrafluoroborat (PropPy BF4) und 1 Gew.-% KAIF4 untersucht. In addition to butyltrimethylammonium bis- (trifluoromethylsulfonyl) imide (N 1114 BTA), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM OTf); 1- Ethyl-3-methylimidazolium bis- (trifluoromethylsulfonyl) imide (EMIM BTA) and 1- methyl-1-propylpyrrolidinium bis- (trifluoromethylsulfonyl) imide (PMPyrr BTA) tested as ionic liquids. A mixture of 49.5% by weight of 1-ethyl-3-methylimidazolium hydrogen sulfate (EMIM HS0 4 ), 49.5% by weight of 1-propylpyridinium tetrafluoroborate (PropPy BF 4 ) and 1% by weight was also used as an acidic comparative electrolyte. % KAIF 4 examined.
Tabelle 1 fasst die Ergebnisse der Auflöseversuche zusammen:
Table 1 summarizes the results of the dissolution tests:
Wie insbesondere ein Vergleich der Versuche Nr. 3 bis 6 zeigt, ermöglicht eine Zusammensetzung umfassend Butyltrimethylammonium-bis(trifluormethyl- sulfonyl)imid (N1114 BTA), 1 Gew.-% Kaliumaluminiumfluorid (KAIF4) und 1 Vol.-% Schwefelsäure (H2S04) unter den angegebenen Bedingungen die beste (schnellste) Auflösung von Aluminium bzw. Aluminiumoxid, was vorteilhaft zur stärksten Ablösung der obersten Metall- bzw. Metalloxidschicht von der jeweiligen Werkstoffoberfläche führt. Dabei übertreffen die Ergebnisse unter Verwendung der angegebenen Zusammensetzung (Versuch Nr. 6) auch vorteilhaft die Ergebnisse von Auflöseversuchen unter Verwendung eines Pulsprogramms (vgl. Versuche Nr. 3 und Nr. 4). As a comparison of experiments No. 3 to 6 shows in particular, a composition comprising butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA), 1% by weight of potassium aluminum fluoride (KAIF 4 ) and 1% by volume of sulfuric acid ( H 2 S0 4 ) the best (fastest) dissolution of aluminum or aluminum oxide under the specified conditions, which advantageously leads to the strongest detachment of the uppermost metal or metal oxide layer from the respective material surface. The results using the specified composition (test no. 6) also advantageously exceed the results of dissolution tests using a pulse program (cf. tests no. 3 and 4).
Beispiel 2: Elektropolitur von Aluminium-3D-Druckplatten Example 2: Electropolishing of aluminum 3D printing plates
Bei der additiven Fertigung von Metallteilen („3D-Druck“) stellt sich häufig das Problem, dass die erhaltenen Bauteile prozessbedingt wellige und/oder raue
Oberflächen aufweisen. Eine mechanische Nachbearbeitung dieser 3D- gedruckten Bauteile ist dabei oft unwirtschaftlich bzw. aufgrund komplexer Bauteilgeometrien sehr schwer praktisch durchzuführen. Die Elektropolitur derartiger Bauteile stellt eine bekannte Lösung der genannten Probleme dar. In the additive manufacturing of metal parts (“3D printing”), the problem often arises that the resulting components are wavy and / or rough due to the process Have surfaces. Mechanical post-processing of these 3D-printed components is often uneconomical or very difficult to carry out in practice due to complex component geometries. The electropolishing of such components represents a known solution to the problems mentioned.
Im Rahmen der Herstellung von Aluminium 3D-Druck-Bauteilen, welche gewöhnlich nicht aus reinem Aluminium, sondern aus einer Aluminium- Magnesium-Silicium-Legierung hergestellt werden, ergibt sich bei der anschließenden Elektropolitur allerdings das zusätzliche Problem, dass bei Verwendung gängiger Elektrolyte eine Schwarzfärbung der Bauteiloberfläche zu beobachten ist. Diese Schwarzfärbung kann auf die Anreicherung von Silicium an der Werkstoffoberfläche in Form einer Passivierungsschicht zurückgeführt werden, welche nur durch Behandlung des Werkstücks mit der schwer zu handhabenden Chemikalie Fluorwasserstoff (HF) wieder entfernt werden kann. In the context of the production of aluminum 3D-printed components, which are usually not made from pure aluminum but from an aluminum-magnesium-silicon alloy, the subsequent electropolishing, however, results in the additional problem that when common electrolytes are used, they turn black the component surface can be observed. This black coloration can be traced back to the accumulation of silicon on the material surface in the form of a passivation layer, which can only be removed again by treating the workpiece with the difficult-to-use chemical hydrogen fluoride (HF).
Zur Durchführung der nachfolgend beschriebenen Versuche wurde wiederum ein Potentiostat/Galvanostat-Modul vom Typ Autolab der Firma Metrohm, Filderstadt verwendet. Wie aus den Daten der nachfolgenden Tabelle 2 ersichtlich, kann bei Verwendung der erfindungsgemäßen Zusammensetzung als Elektrolyt bei der Elektropolitur von Aluminium 3D-Druck-Bauteilen die erwähnte Schwarzfärbung nun vorteilhaft bereits während des Elektropolierens reduziert werden. Tabelle 2 fasst die Ergebnisse zur Elektropolitur von Aluminium 3D-Druck- Bauteilen zusammen:
A potentiostat / galvanostat module of the Autolab type from Metrohm, Filderstadt, was again used to carry out the experiments described below. As can be seen from the data in Table 2 below, when the composition according to the invention is used as an electrolyte in the electropolishing of aluminum 3D-printed components, the blackening mentioned can now advantageously already be reduced during the electropolishing. Table 2 summarizes the results for the electropolishing of aluminum 3D printed components:
Ein Vergleich der Versuche Nr. 11 und 12 mit den Versuchen Nr. 7 bis 10 zeigt, dass unabhängig davon, ob die Elektropolitur mit Hilfe eines Pulsprogamms oder durch Anlegen einer Gleichspannung durchgeführt wird, insbesondere eine Zusammensetzung umfassend Butyltrimethylammonium-bis(trifluormethylsulfon- yl)imid (N1114 BTA), 1 Gew.-% Kaliumaluminiumfluorid (KAIF4) und 1 Vol.-% Schwefelsäure (H2S04) unter den angegebenen Bedingungen vorteilhaft zur stärksten Auflösung der obersten Metall- bzw. Metalloxidschicht an der jeweiligen Werkstoffoberfläche und somit besten Glättung bei gleichzeitig geringster Schwarzfärbung führt. A comparison of experiments nos. 11 and 12 with experiments nos. 7 to 10 shows that regardless of whether the electropolishing is carried out with the aid of a pulse program or by applying a direct voltage, in particular a composition comprising butyltrimethylammonium-bis (trifluoromethylsulfon-yl) imid (N 1114 BTA), 1 wt .-% potassium aluminum fluoride (KAIF 4 ) and 1 vol .-% sulfuric acid (H 2 S0 4 ) under the specified conditions advantageous for the strongest dissolution of the top metal or metal oxide layer on the respective material surface and thus the best smoothing with the lowest blackening at the same time.
Die vorliegende Erfindung betrifft eine Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oder Metalllegierungen umfassend: Butyltrimethylammonium-bis(trifluormethylsulfon- yl)imid (N1114 BTA) und Kaliumaluminiumfluorid (KAIF4), sowie gegebenenfalls eine Säure. Sie betrifft zudem die Verwendung dieser Zusammensetzung als Elektrolyt in (elektro-) chemischen Energiespeichern, insbesondere für stationäre oder mobile Anwendungen, als Elektrolyt bei der Abscheidung von unedlen Metallen sowie als Elektrolyt bei der Beschichtung von 3D-Druckbauteilen. Die erfindungsgemäße Zusammensetzung ermöglicht vorteilhaft eine schnelle Auflösung von Metallen und/oder Metalloxiden, insbesondere von Aluminium und Aluminiumoxid, von entsprechenden metallischen Werkstücken. Sie ist auch zur Behandlung von 3D-Druckplatten, insbesondere von 3D-Druckplatten auf Basis einer Aluminium-Magnesium-Silicium-Legierung, geeignet und vermindert dabei vorteilhaft die Bildung einer Passivierungsschicht an der Werkstückoberfläche.
The present invention relates to a composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprising: butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and potassium aluminum fluoride (KAIF 4 ), and optionally an acid. It also relates to the use of this composition as an electrolyte in (electro) chemical energy storage devices, in particular for stationary or mobile applications, as an electrolyte in the deposition of base metals and as an electrolyte in the coating of 3D printed components. The composition according to the invention advantageously enables metals and / or metal oxides, in particular aluminum and aluminum oxide, to dissolve rapidly from corresponding metallic workpieces. It is also suitable for treating 3D printing plates, in particular 3D printing plates based on an aluminum-magnesium-silicon alloy, and advantageously reduces the formation of a passivation layer on the workpiece surface.
Claims
Patentansprüche 1. Zusammensetzung als Elektrolyt zum Auflösen und/oder Abscheiden von Metallen, Metalloxiden und/oder Metalllegierungen umfassend: Claims 1. Composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys comprising:
- Butyltrimethylammonium-bis(trifluormethylsulfonyl)imid (N1114 BTA) und - Butyltrimethylammonium bis (trifluoromethylsulfonyl) imide (N 1114 BTA) and
- Kaliumaluminiumfluorid (KAIF4). - Potassium aluminum fluoride (KAIF 4 ).
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass die Zusammensetzung 0,1 - 2,0 Gew.-%, bevorzugt 0,2 - 1,2 Gew.-%, besonders bevorzugt 1,0 Gew.-% KAIF4 umfasst. 2. Composition according to claim 1, characterized in that the composition comprises 0.1-2.0% by weight, preferably 0.2-1.2% by weight, particularly preferably 1.0% by weight of KAIF 4 .
3. Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Zusammensetzung ferner eine Säure umfasst. 3. Composition according to claim 1 or 2, characterized in that the composition further comprises an acid.
4. Zusammensetzung nach Anspruch 3, dadurch gekennzeichnet, dass die Zusammensetzung als Säure 0,1 - 2,0 Vol.-%, bevorzugt 0,8 - 1 ,2 Vol.- %, besonders bevorzugt 1,0 Vol.-%, Schwefelsäure (H2S04) umfasst. 4. Composition according to claim 3, characterized in that the composition as acid 0.1-2.0% by volume, preferably 0.8-1.2% by volume, particularly preferably 1.0% by volume, Sulfuric acid (H 2 S0 4 ) includes.
5. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 4 als Elektrolyt zum Auflösen von Aluminium und/oder Aluminiumoxid. 5. Use of a composition according to any one of claims 1 to 4 as an electrolyte for dissolving aluminum and / or aluminum oxide.
6. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis6. Use of a composition according to any one of claims 1 to
4 als Elektrolyt zum Auflösen von Aluminiumlegierungen, insbesondere von Aluminium-Magnesium-Silicium-Legierungen. 4 as an electrolyte for dissolving aluminum alloys, in particular aluminum-magnesium-silicon alloys.
7. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 4 als Elektrolyt in (elektro-)chemischen Energiespeichern. 7. Use of a composition according to any one of claims 1 to 4 as an electrolyte in (electro) chemical energy storage devices.
8. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 4 als Elektrolyt in (elektro-)chemischen Energiespeichern für stationäre oder mobile Anwendungen, insbesondere für stationäre oder mobile
Notstromaggregate und/oder für Akkumulatoren von Land-, Luft- und/oder Wasserfahrzeugen. 8. Use of a composition according to one of claims 1 to 4 as an electrolyte in (electro) chemical energy storage devices for stationary or mobile applications, in particular for stationary or mobile applications Emergency power generators and / or for accumulators for land, air and / or water vehicles.
9. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 4 als Elektrolyt bei der Abscheidung von unedlen Metallen, insbesondere Aluminium. 9. Use of a composition according to one of claims 1 to 4 as an electrolyte in the deposition of base metals, in particular aluminum.
10. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 4 als Elektrolyt bei der Beschichtung von 3D-Druckbauteilen, insbesondere von metallischen 3D-Druckbauteilen.
10. Use of a composition according to one of claims 1 to 4 as an electrolyte in the coating of 3D printed components, in particular of metallic 3D printed components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102020200815.9 | 2020-01-23 | ||
| DE102020200815.9A DE102020200815A1 (en) | 2020-01-23 | 2020-01-23 | Composition as an electrolyte for dissolving and / or depositing metals, metal oxides and / or metal alloys and uses of this composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021148318A1 true WO2021148318A1 (en) | 2021-07-29 |
Family
ID=74285449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2021/050794 WO2021148318A1 (en) | 2020-01-23 | 2021-01-15 | Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE102020200815A1 (en) |
| WO (1) | WO2021148318A1 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE729836C (en) * | 1937-02-27 | 1943-01-04 | Feldmuehle Papier Und Zellstof | Process for the production of items from pure chrome by electroplating |
| DE2618313A1 (en) | 1975-04-30 | 1976-12-09 | Oxy Metal Industries Corp | ELECTROPOLISHING ALUMINUM AND ALUMINUM ALLOYS |
| EP0121817A1 (en) * | 1983-03-15 | 1984-10-17 | Kawasaki Steel Corporation | Method for producing tin-free steel sheets having improved lacquer adhesion |
| US20040097755A1 (en) | 2000-09-27 | 2004-05-20 | Abbott Andrew P. | Ionic liquids and their use as solvents |
| DE10320909A1 (en) | 2003-05-09 | 2004-11-18 | Poligrat Holding Gmbh | Electrolyte for the electrochemical polishing of metal surfaces |
| DE112005002414T5 (en) | 2004-10-06 | 2007-09-27 | Basf Ag | An electropolishing electrolyte and method of planarizing a metal layer using the same |
| WO2014124428A1 (en) * | 2013-02-11 | 2014-08-14 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University, Las Vegas, Nv | Room temperature electrodeposition of actinides from ionic solutions |
| AT520365A1 (en) | 2017-08-29 | 2019-03-15 | Hirtenberger Eng Surfaces Gmbh | ELECTROLYTE FOR ELECTROPOLISHING METAL SURFACES |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0606016D0 (en) | 2006-03-25 | 2006-05-03 | Ionic Polymer Solutions Ltd | Quaternary ammonium compounds and their uses |
| US20140017571A1 (en) | 2012-07-16 | 2014-01-16 | Nthdegree Technologies Worldwide Inc. | Printable Ionic Gel Separation Layer for Energy Storage Devices |
| DE102013226533A1 (en) | 2013-12-18 | 2015-06-18 | MAHLE Behr GmbH & Co. KG | Cleaner for an aluminum component and a process for cleaning aluminum components |
| US10487416B2 (en) | 2015-06-15 | 2019-11-26 | General Electric Company | Electrochemical machining employing electrical voltage pulses to drive reduction and oxidation reactions |
| KR20200101473A (en) | 2018-01-16 | 2020-08-27 | 프린티드 에너지 피티와이 리미티드 | Thin film-based energy storage device |
| EP3753059A4 (en) | 2018-03-20 | 2022-01-05 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
-
2020
- 2020-01-23 DE DE102020200815.9A patent/DE102020200815A1/en active Pending
-
2021
- 2021-01-15 WO PCT/EP2021/050794 patent/WO2021148318A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE729836C (en) * | 1937-02-27 | 1943-01-04 | Feldmuehle Papier Und Zellstof | Process for the production of items from pure chrome by electroplating |
| DE2618313A1 (en) | 1975-04-30 | 1976-12-09 | Oxy Metal Industries Corp | ELECTROPOLISHING ALUMINUM AND ALUMINUM ALLOYS |
| EP0121817A1 (en) * | 1983-03-15 | 1984-10-17 | Kawasaki Steel Corporation | Method for producing tin-free steel sheets having improved lacquer adhesion |
| US20040097755A1 (en) | 2000-09-27 | 2004-05-20 | Abbott Andrew P. | Ionic liquids and their use as solvents |
| DE10320909A1 (en) | 2003-05-09 | 2004-11-18 | Poligrat Holding Gmbh | Electrolyte for the electrochemical polishing of metal surfaces |
| DE112005002414T5 (en) | 2004-10-06 | 2007-09-27 | Basf Ag | An electropolishing electrolyte and method of planarizing a metal layer using the same |
| WO2014124428A1 (en) * | 2013-02-11 | 2014-08-14 | The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University, Las Vegas, Nv | Room temperature electrodeposition of actinides from ionic solutions |
| AT520365A1 (en) | 2017-08-29 | 2019-03-15 | Hirtenberger Eng Surfaces Gmbh | ELECTROLYTE FOR ELECTROPOLISHING METAL SURFACES |
Non-Patent Citations (1)
| Title |
|---|
| BEYERSDORFF T ET AL: "IONIC LIQUIDS TODAY", INTERNET CITATION, 11 October 2005 (2005-10-11), XP002382625, Retrieved from the Internet <URL:http://www.iolitec.de/download/newsletter/Ionic%20Liquids%20Today-03-05.pdf> [retrieved on 20060101] * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102020200815A1 (en) | 2021-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3048083C2 (en) | Process for the chemical removal of oxide layers from objects made of titanium or titanium alloys | |
| DE2432364B2 (en) | Process for coating aluminum or aluminum alloys | |
| DE2907875C2 (en) | Process for the electrolytic removal of tungsten carbide coatings on workpieces made of titanium or titanium alloys | |
| DE102016205815A1 (en) | Process for nickel-free phosphating of metallic surfaces | |
| DE4002700A1 (en) | ELECTROCHEMICALLY MACHINABLE WORKPIECE AND METHOD FOR ELECTROCHEMICALLY WORKING A METAL WORKPIECE | |
| EP1911862B1 (en) | Electropolishing method for niobium and tantalum | |
| DE4432591A1 (en) | Coating process for a nickel-titanium alloy component | |
| DE1094245B (en) | Lead dioxide electrode for use in electrochemical processes | |
| DE3020012C2 (en) | Method of exposing the silicon crystals on the surface of a body made of an aluminum alloy with a high silicon content | |
| EP2238280B1 (en) | Multifunctional coating of aluminium pieces | |
| DE3706711A1 (en) | METHOD FOR CLEANING SURFACES OF AN ALUMINUM OBJECT | |
| DE102016125244A1 (en) | Process for electropolishing a metallic substrate | |
| WO2021148318A1 (en) | Composition in the form of an electrolyte for dissolving and/or separating metals, metal oxides, and/or metal alloys, and uses of said composition | |
| EP2635724B1 (en) | Process for electroplating hard chromium from a cr(vi) free electrolyte | |
| DE925330C (en) | Process for the electrolytic etching of tantalum | |
| DE102021200338A1 (en) | Housing arrangement for an energy storage cell | |
| DE2836353C2 (en) | Process for obtaining hydrogen and sulfuric acid by electrochemical decomposition of an electrolyte and an electrode for carrying out the electrochemical decomposition | |
| EP0360863A1 (en) | Method and nickel-oxide electrode for applying a composite nickel-oxide coating to a metal carrier | |
| DE1496906B2 (en) | Aqueous bath for the electrolysis of iron and steel | |
| DE1944388B2 (en) | PROCESS FOR ELECTROLYTIC PICKLING AND DESCALING OF TIN-CONTAINING TITANIUM ALLOYS | |
| EP2975162B1 (en) | Method for providing a workpiece with a protective coating | |
| EP0011801B1 (en) | Process for electrochemically machining metal surfaces | |
| EP0911428B1 (en) | Process for producing bismuth compounds | |
| EP3502311A1 (en) | Method for the corrosion protection and cleaning pretreatment of metallic components | |
| DE4232636C2 (en) | Method for producing electrode foils for, in particular high-voltage, electrolytic capacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21701935 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21701935 Country of ref document: EP Kind code of ref document: A1 |