Electrolytic treatment of substrates containing copper and / or its alloys

Abstract

The present invention relates to a method for pretreatment of a substrate containing copper and / or its alloys, comprising at least step 1), i.e., contacting at least one surface of at least one substrate (the surface being made of copper and / or at least one of its alloys) with an aqueous composition in at least a portion thereof, thereby forming a film on at least a portion thereof, wherein the aqueous composition comprises water and at least one of components a1) and a2), i.e., as component a1), at least one of zirconium cation, titanium cation, and hafnium cation, each calculated as a metal in the respective case, preferably in an amount in the range of 5 to 2000 mg / L, and / or as component a2), at least one organosilane and / or at least one hydrolysate and / or condensate thereof, wherein the contact step 1) is performed in an electrolytic cell apparatus in which the substrate made of copper and / or its alloys serves as the cathode during the execution of step 1). The present invention also relates to a method for applying at least one coating film onto the surface of a pre-treated substrate, a substrate that can be obtained by any of these methods, a current collector, conductor, copper-clad laminate, anode material, and battery cell that can be obtained from the substrate, and a method for using the aforementioned aqueous composition for electrolytically forming a film on a substrate made of copper and / or its alloy.

Description

[Technical Field]

[0001] The present invention relates to a method for pre-treating a substrate containing copper and / or its alloys using a chemical pre-treatment composition, a method for applying at least one coating film to the surface of a chemically pre-treated substrate, a substrate obtainable by any of the above methods, a current collector, conductor, copper-clad laminate, anode material, and battery cell obtainable from such a substrate, and a method for using a chemical pre-treatment composition applied in a pre-treatment method for forming a coating film on a substrate containing copper and / or its alloys. [Background technology]

[0002] Copper substrates, such as copper foil, have advantages such as excellent thermal and electrical conductivity, and are widely used, for example, as connections in electronic circuits and as current collectors for battery electrodes.

[0003] Copper foils used in these applications must be protected from corrosion and / or heat. This has traditionally been achieved by forming a plating layer on the surface. For example, EP 2 544 282 A1 discloses a copper foil having two plating layers, each composed of copper metal, where the first plating layer is obtained by cathode electroplating using, for example, a copper sulfate electrolyte, and the second plating layer is applied by smooth copper plating. The resulting plated foil can be used, for example, in the negative electrode current collector of lithium-ion batteries (LIBs) and printed circuit boards (PCBs). While this method generally increases the surface roughness of the foil and consequently improves the adhesion of subsequent coating layers, the presence of such copper metal plating layers on the foil often hinders the transmission of high-frequency currents, which is undesirable. Furthermore, the application of the copper plating layer disclosed in EP 2 544 282 A1 is disadvantageous for economic and ecological reasons because it requires additional processes. Furthermore, the additional plating layer present on the copper foil used as the anode current collector foil increases the thickness of the copper foil. This negatively impacts the resulting battery capacity-to-volume ratio and further complicates the recycling process.

[0004] Furthermore, instead of simply forming a metal plating layer as a protective layer on the surface of copper foil, surface treatment is known to be applied. For example, copper foil having a surface coating layer made of chromium, molybdenum, nickel, and zinc is disclosed in EP 3 882 378 A1. Furthermore, WO 2015 / 108191 A1 discloses a surface-treated copper foil obtained by forming a surface treatment layer on copper foil and further etching the surface opposite to the surface on which the surface treatment layer is formed. The surface treatment layer can be a chromate treatment layer in particular. Furthermore, CN 112921311 A discloses a method for coating the surface of copper foil using an antioxidant solution to prevent discoloration of the copper foil. The antioxidant solution used contains anhydrous chromium. However, particularly for ecological reasons, the application of chromium-containing coating layers, such as those disclosed in EP 3 882 378 A1, WO 2015 / 108191 A1, and CN 112921311 A, is undesirable and should be avoided whenever possible. Furthermore, when chromium in different oxidation states, such as Cr(III) and Cr(VI), is present in such layers in both states, a non-uniform distribution is often observed on the foil surface, which is also undesirable.

[0005] Furthermore, it is known to provide copper foil with a chromium-free surface treatment. For example, CN 103114315 A relates to a chromate-free passivation method for copper foil. For this purpose, an aqueous tin-containing, i.e., stanate-containing electrodeposition solution is used, and a chromate-free passivation layer is formed on the surface of the copper foil by electrotreatment. However, the use of tin in the coating layer described in CN 103114315 A is also environmentally undesirable. Moreover, the resulting layer is similar to a tin-containing plating layer, which is generally undesirable because the presence of metals other than copper negatively affects the electrical conductivity to be achieved, and in the case of tin in particular, it complicates the recycling of the material. Furthermore, the use of tin can lead to the formation of so-called "metallic whiskers," which is undesirable. In addition, tin-containing solutions often lose their storage stability over time.

[0006] Additional surface treatment methods applicable to copper substrates are also known from CN 111118488 A, CN 112144049 A, CN 111364032, JP 2011-023303 A, and WO 2007 / 105800 A1. CN 111118488 A discloses a method for corrosion-preventive passivation of copper materials, including the use of a passivation solution containing an organic solvent prepared from ethyl alcohol and polyethylene glycol, in particular. However, for environmental reasons, for example, the use of organic solvents in the passivation solution, particularly the relatively large amount of organic solvent used according to the method disclosed in CN 111118488 A, is disadvantageous. CN 112144049 A discloses an organic inhibitor-containing layer prepared using a chromium-free passivating agent, i.e., at least one triazole derivative, for passivating the surface of a copper substrate. However, the presence of such an organic coating layer on the copper substrate surface often adversely affects the adhesion of subsequent coating layers, and therefore, such organic layers need to be removed later and, in some cases, replaced with other adhesion-promoting layers. This removal requires pickling of the foil and / or the use of relatively large amounts of organic solvents, both of which are undesirable. CN 111364032 A relates to surface treatment agents for copper foil, and in particular includes various silane coupling agents present in solvents such as alcohol, namely alkenyl, mercapto, and isocyanate-silane coupling agents. However, the use of the surface treatment agents disclosed in CN 111364032 A has the disadvantage of being undesirable from an environmental and safety standpoint because it requires the use of relatively large amounts of alcohol such as methanol and / or ethanol. Furthermore, due to the presence of isocyanate-silane coupling agents, these surface treatment agents have relatively low storage stability. In addition, when using the surface treatment agents of CN 111364032 A, insufficient adhesion with the subsequently applied coating layer is often observed, especially when the substrate surface roughness is low. JP 2011-023303 A discloses copper foil for current collectors in lithium-ion batteries.The surface of copper foil is subjected to silane coupling treatment, at least partially, by methods such as immersion or spraying in a non-electrolytic process. This method requires relatively high temperatures for curing, and even requires washing off excess silane after the heat treatment. However, from an economic and environmental standpoint in particular, the implementation of such high-temperature curing processes and the mandatory additional washing process after surface treatment are disadvantageous. Finally, WO 2007 / 105800 A1 discloses a surface treatment solution for copper materials by a non-electrolytic process using a copper oxide etchant, such as HMnO4 or H2O2. In addition to the aforementioned oxide etchant, this solution includes a compound containing at least one (semi)metallic element selected from Ti, Zr, and Si, and a fluorine compound as an HF source. The copper material can be immersed in the surface treatment solution, and at least one (semi)metallic element can be deposited by the oxidation means. However, the use of oxidizing agents described in WO 2007 / 105800 A1 has drawbacks, as such oxidizing agents are often hazardous and can cause significant contamination of the surrounding environment, and / or can be depleted relatively quickly. Furthermore, using too much of the oxidizing agent can excessively erode the surface of the copper material. On the other hand, using too little can lead to instability of the titanium, zirconium, and silicon fluorides produced in the surface treatment solution, especially in acidic environments.

[0007] Therefore, it is necessary to be able to efficiently provide a surface treatment layer on a copper substrate such as copper foil in a way that is more advantageous than conventional techniques. In particular, it is necessary to be able to efficiently form a surface treatment layer on a copper substrate such as copper foil in a simple, uncomplicated, economical, and environmentally advantageous way that is thin, easily recyclable, achieves excellent electrical conductivity, and enables good adhesion to a subsequent coating layer applied to the surface-treated copper substrate. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] EP 2 544 282 A1 [Patent Document 2] EP 3 882 378 A1 [Patent Document 3] WO 2015 / 108191 A1 [Patent Document 4] CN 112921311 A [Patent Document 5] CN 103114315 A [Patent Document 6] CN 111118488 A [Patent Document 7] CN 112144049 A [Patent Document 8] CN 111364032 [Patent Document 9] JP 2011-023303 A [Patent Document 10] WO 2007 / 105800 A1 [Overview of the project] [Problems that the invention aims to solve]

[0009] Therefore, the fundamental objective of the present invention is to efficiently provide a surface treatment layer on a copper or copper alloy-containing substrate, such as copper foil, in a manner that is more advantageous than the prior art. In particular, the aim has been to efficiently provide a surface treatment layer on a copper or copper alloy-containing substrate, such as copper foil, in a simple, uncomplicated, and economically and environmentally advantageous manner. This layer is thin, facilitates the recycling of the substrate, achieves excellent electrical conductivity, and enables good adhesion with a subsequent coating layer applied to the surface-treated copper or copper alloy substrate. [Means for solving the problem]

[0010] This objective is addressed by the subject matter of the claims of this application and its preferred embodiments disclosed herein, i.e., the subject matter described herein.

[0011] The first subject of the present invention is a method for pretreating a substrate containing copper and / or at least one of its alloys, the method comprising at least step 1), and optionally step 2) and / or 3), namely 1) a step of bringing at least one surface of at least one substrate into contact with an aqueous composition at least in part, thereby forming a film on at least part of said surface, wherein said surface optionally has at least one plating layer, and (i) at least one of said surfaces of said substrate and (ii) optionally at least one of the existing plating layers is made of copper and / or at least one of its alloys, preferably at least one of said surfaces of said substrate is made of copper and / or at least one of its alloys, said aqueous composition preferably contains at least 70% by mass of water based on its total mass, and in addition to water, at least one of different components a1) and a2), namely as component a1), at least one of zirconium cations, titanium cations, and hafnium cations, in each case calculated as the metal, preferably in an amount in the range of 5 to 2000 mg / L, and / or as component a2), at least one organic silane and / or at least one of its hydrolyzates and / or condensates a step comprising, and 2) optionally, a step of rinsing the film obtained after step 1) with water, and / or 3) optionally, a step of drying the film obtained after step 1) or after any step 2) comprising, the contacting step 1) is carried out in an electrolytic cell device in which the substrate containing copper and / or at least one of its alloys serves as the cathode during the implementation of step 1).

[0012] A further subject of the present invention is a method for applying at least one coating film to at least one surface of a substrate, the method comprising at least step 1) as defined above with respect to the pretreatment method, and optionally step 2) and / or step 3), and further step 4), namely, 4) As described above regarding the pretreatment method, the step of applying a coating material composition containing at least one film-forming polymer onto the film obtained after step 1), or after any of steps 2) and / or 3). Includes.

[0013] A further subject of the present invention is a substrate obtained by the aforementioned pretreatment method or by applying the aforementioned at least one coating film.

[0014] Further subject of the present invention is a component obtained from the aforementioned substrate, preferably selected from a current collector, conductor, copper-clad laminate, and anode material, or preferably a rechargeable battery cell obtained from the anode material, which is used in a battery cell such as a rechargeable battery cell.

[0015] A further subject of the present invention is a method for using the aqueous composition defined above in relation to a contact step 1) of a pretreatment method to electrolytically form a film on at least a portion of the surface of a substrate, wherein the surface optionally has at least one plating layer, and (i) at least one of the at least one surface of the substrate and (ii) at least one of the optionally present plating layers are made of copper and / or at least one alloy thereof, preferably the at least one surface of the substrate is made of copper and / or at least one alloy thereof, and the substrate functions as a cathode for electrolytic application.

[0016] Particularly surprising, it was found that films such as chemical conversion coatings applied in step 1) of the pretreatment method, and especially layers such as the conversion layer obtained after the drying step 3), can be applied to passivate the surface of copper and / or copper alloy substrates such as copper foil in an efficient, easy, and uncomplicated manner, and in an economically and ecologically advantageous way. These films and layers have been found to effectively protect the surface of the substrate and the substrate itself during transportation and storage.

[0017] Even more surprisingly, these films and layers have been found to be applicable with relatively thin dry layer thicknesses. For example, this dry layer thickness is determined in each case as trace elements such as Ti, Zr, and / or Si by XRF measurements using the method disclosed in the "Methods" section of this document, ranging from 0.5 to 500 mg / m². 2 , 1-400 mg / m² 2 , or 2-350 mg / m² 2 This corresponds to the coating mass in that range.

[0018] In particular, it has been found that substrates containing copper and / or copper alloys can be used as negative electrodes, i.e., cathodes, in electrolytic cell layouts while in contact with / during contact with the aqueous composition used in step 1) of the pretreatment method as a chemical pretreatment composition, and that films / layers can be applied to the surfaces of these substrates, respectively.

[0019] Furthermore, and particularly surprisingly, the pre-treated substrate, e.g., foil, obtained after step 1) or any step 2) and / or 3) of the pre-treatment method, exhibits a resistance of 10 mΩ / cm², especially when the pre-treated substrate, e.g., pre-treated foil, is incorporated into a battery cell, such as a rechargeable battery cell, particularly in the form of its anode (active) material. 2 Less than 3 mΩ / cm², preferably 3 mΩ / cm² 2 We discovered that it has an interfacial resistance of less than 100%, while also providing excellent electrical conductivity.

[0020] Furthermore, and particularly surprisingly, the pre-treated substrates obtained by the pre-treatment method were found to be relatively easy to recycle and to be free of elements and / or compounds that are especially ecological and / or environmentally problematic.

[0021] Finally, it was found to be particularly surprising that the pre-treated substrates obtained by the pre-treatment method provide good adhesion to subsequent coating films, such as plastic layers, composite layers, and other materials used particularly in rechargeable battery cells, applied on the pre-treated copper and / or copper alloy substrates. Furthermore, the pre-treated substrates have excellent corrosion-resistant properties. [Modes for carrying out the invention]

[0022] Detailed description of the invention In the present invention, the term "includes" preferably means "of which" in relation to the aqueous compositions used in the present invention. For example, with respect to the aforementioned compositions, in addition to all the essential components present therein, one or more additional optional components described below may also be included. All components may be present in each case in the preferred embodiments specified below.

[0023] The percentages and amounts of each component shown below in terms of mass percentage (mass%) are based on the total mass of each composition in each case, and the sum of these amounts to 100% by mass in each composition.

[0024] Pretreatment method including chemical pretreatment step 1) The first subject of the present invention is a method for pretreatment of a substrate containing copper and / or an alloy thereof, preferably a substrate made from copper and / or an alloy thereof. The method comprises at least step 1), and optionally further steps 2) and / or 3). The method may include further steps performed before step 1) and / or after each of steps 1), 2), and 3).

[0025] The term “pretreatment” as used herein is preferably used in accordance with the term “surface pretreatment” as defined in Roempp Lexikon, “Lacke und Druckfarben” (Publisher: Ulrich Zorll, Editor: Hans-Juergen P. Adler-Stuttgart; New York: Thieme, 1998; Terminology: “Oberflaechenvorbehandlung” p. 417). For metal substrates or substrates having a metal surface, the first step of surface treatment is often one or more (chemical) cleaning steps using an aqueous or non-aqueous cleaning composition (also called “surface preparation steps”), in accordance with DIN 50902:1994-07. Accordingly, as described below, this method may include one or more additional optional steps performed before step 1).

[0026] The term "chemical pretreatment" is used in accordance with EN ISO 4618:2006 (E / F / D) (Term: 2.41 "Chemical pretreatment"), and it refers to any chemical process applied to a surface before the application of a coating material. According to this standard, for example, processes such as chromating and phosphate treatment, which are included in the term "conversion treatment," belong to chemical pretreatment and are therefore distinguished from the (subsequent) coating process, i.e., the process of applying coating materials such as powder coating compositions, electrodeposition coating compositions, aqueous or non-aqueous liquid coating materials, i.e., coating compositions. In addition to conversion treatments such as chromating and phosphate treatment, chemical surface pretreatment is generally achieved by passivation compositions and film-forming compositions, including aqueous-containing compositions which are essentially used as chemical pretreatment compositions in step 1). Therefore, step 1) of this method represents the chemical pretreatment process, and the aqueous composition used therein represents the chemical pretreatment composition.

[0027] In accordance with the above internationally valid definition of "pretreatment" of metal substrates, the pretreatment method according to the present invention preferably includes a surface preparation cleaning step in addition to the chemical pretreatment step 1).

[0028] Preferably, the pretreatment method does not include any steps involving treatment with chromium ions such as Cr(VI) ions and / or Cr(III) ions.

[0029] Preferably, chemical pretreatment step 1) is the only chemical pretreatment step in the pretreatment method. Therefore, preferably, no chemical pretreatment compositions other than the aqueous composition applied in step 1) are used.

[0030] Preferably, the film obtained after step 1) or any step 2) and / or 3) contains 0.5 to 500 mg / m² of trace elements such as Ti, Zr, and / or Si, as determined in each case by XRF measurement using the method disclosed in the "Methods" section of this document. 2 More preferably 1-400 mg / m² 2 More preferably 2-350 mg / m² 2 This corresponds to the coating mass in that range.

[0031] Base material The substrate has at least one surface, where at least the at least one surface and / or at least one plating layer optionally present on the surface is made of copper and / or at least one alloy thereof. Preferably, the substrate itself is made of copper and / or an alloy thereof, more preferably a copper alloy. In the case of an alloy, copper is the main component based on the total mass of the alloy. Other alloy components include nickel, tin, zinc, and / or chromium. Examples of commercially available substrates include Furukawa Electric's copper foils NC-WS and FT-UP, Circuit Foil's copper foils BFL-NN and BF-PLSP, or JX Nippon Mining & Metals' copper alloy foil HS1200.

[0032] The substrate may be plated or unplated, that is, optionally, it may have at least one plating layer made of at least one metal and / or its alloy on at least one of its surfaces, particularly the surface that comes into contact with the aqueous composition in step 1) of the method. The optionally present at least one plating layer is preferably made of at least one of copper, zinc, nickel, tin, and / or one or more alloys of the said metals. One, two, or more plating layers may be present. For example, particularly if the substrate is foil and suitable for use in printed circuit board (PCB) applications, at least one surface of the substrate may have at least one plating layer to provide sufficient thermal protection.

[0033] The base material can have any shape or geometric structure, such as a coil, sheet, foil, or other component, for example, a rod-shaped component. Preferably, the base material is in the form of a foil, coil, or substantially flat component. Preferably, the foil has a thickness ranging from 1 μm or 2 μm to 10 mm, 8 mm, or 5 mm. More preferably, the foil has a thickness ranging from 1 μm or 2 μm to 4 mm or 6 mm.

[0034] Any step performed before step 1) Before step 1), one or more of the following optional steps may be performed in this order: Step A-1): A step of cleaning the surface of the substrate and optionally rinsing it afterward. Step B-1): The substrate surface is subjected to acid pickling, i.e., etching, supported by one or more oxidizing agents, and then the substrate surface is rinsed. Step C-1): A step of contacting the substrate surface with an aqueous composition containing at least one mineral acid, or alternatively, an alkaline aqueous composition or a pH-neutral aqueous composition, wherein each of these compositions is different from the aqueous composition used in Step 1), Step D-1): A step of rinsing the surface of the substrate obtained after contact according to Step C-1) and / or B-1).

[0035] Alternatively, any steps A-1) and B-1) may be carried out in a single step. Any step C-1) preferably aims to remove oxides from the substrate surface, thereby activating the surface for subsequent treatment in step 1). Preferably, at least one mineral acid in the composition of step C-1) is sulfuric acid and / or nitric acid, more preferably sulfuric acid. Any rinsing, which is part of rinsing steps D-1) and A-1), is preferably carried out using deionized water or tap water. Preferably, step D-1) is carried out using deionized water.

[0036] Process 1) According to step 1) of the pretreatment method, at least one surface of at least one substrate is brought into contact with an aqueous composition at least partially, thereby forming at least partially a film on the surface. The contact step 1) is carried out in an electrolytic cell apparatus in which a substrate made of copper and / or at least one alloy thereof serves as the cathode (negative electrode in an electrolytic cell) during the execution of step 1).

[0037] By performing step 1), a chemical conversion film is formed on the substrate surface that has come into contact with the aqueous composition. Therefore, the film formed by the contact step 1) preferably represents a chemical conversion film and can also be considered a passivation film.

[0038] The term "at least a portion" in this context, according to the general understanding of the term, means that it may be desirable or sufficient to have the entire surface of the substrate in contact with the chemical pretreatment composition, rather than the entire surface. When only a portion of the surface is in contact with the composition, it is usually the same portion throughout the entire process. The surface of the substrate or the substrate itself may be, for example, completely immersed or only partially immersed. In the latter case, the aqueous composition is applied only to the immersed area. However, generally, it is desirable to have the entire surface of the substrate in contact with each composition.

[0039] The "contact" in step 1) can be a dipping or roll coating process. The contact technique used only needs to enable the formation of an electrical circuit that functions as the cathode (negative electrode) of the electrolytic cell arrangement in which the substrate is formed in step 1).

[0040] At least one surface of at least one substrate can be brought into direct contact with the power supply, for example, using one or more clamps. Alternatively, a conductive holding system can be used for this purpose. One or more counter electrodes can be installed on one or both sides of the substrate, preferably parallel to the substrate. The counter electrodes can be made from any conductive material, preferably metal. If a fluoride-containing composition is used as the aqueous composition in step 1), the resistance to the composition must be taken into consideration and addressed accordingly.

[0041] Step 1) can be carried out continuously or discontinuously. For example, when step 1) is carried out continuously in the form of bringing a coil or foil into contact with the aqueous composition, contact can be achieved using a conductive roller. Preferably, the coil or foil moves parallel to one or more counter electrodes that are at least partially immersed in the pretreatment bath obtained from the aqueous composition.

[0042] During step 1), the pretreatment bath obtained from the aqueous composition is either not stirred or, preferably, stirred. If stirred, it is preferable to stir so that the pretreatment liquid present in the pretreatment bath around the substrate to be treated is in a quasi-laminar flow state.

[0043] The processing time, i.e., the period during which the surface is in contact with the aqueous composition in step 1), is preferably 1 second to 5 minutes, more preferably 2 seconds, 2.5 minutes, or 1 minute, and most preferably 2 seconds to 30 seconds.

[0044] The temperature of the aqueous composition used in step 1) is preferably 5 to 90°C, more preferably 15 to 70°C, and most preferably 20 to 60°C.

[0045] Preferably, after step 1), the film obtained after drying by any optional step 3) is determined as trace elements such as Ti, Zr, and / or Si in each case by XRF measurement by the method disclosed in the "Method" section of this specification, calculated as each metal or element, 0.5 to 500 mg / m 2 more preferably 1 to 400 mg / m 2 more preferably 2 to 350 mg / m 2 more preferably 3 to 300 mg / m 2 and has a coating mass determined by XRF (X-ray fluorescence analysis) of silicon, zirconium, titanium and / or hafnium ions.

[0046] Preferably, the electrolytic treatment in step 1) is carried out with direct current, more preferably using a voltage in the range of 2 to 10 V, even more preferably using a voltage in the range of 3 to 8 V, preferably generating a current density in the range of 2 to 30 A / m 2 more preferably in the range of 3 to 20 A / m 2 while being carried out.

[0047] The aqueous composition used in step 1) The aqueous composition used in step 1), also referred to hereinafter or above as the "pretreatment composition" or "chemical pretreatment composition", in addition to water, contains at least one of different components a1) and a2), namely at least one of zirconium cation, titanium cation and hafnium cation as component a1), and / or at least one organic silane and / or at least one of its hydrolysis products and / or condensation products as component a2).

[0048] In relation to the compositions used in the present invention, the term "aqueous" preferably means that the aqueous composition contains at least 50% by mass, preferably at least 60% by mass, more preferably at least 70% by mass, particularly preferably at least 80% by mass, and most preferably at least 90% by mass of water, based on the total content of water-containing organic solvents and inorganic solvents. Therefore, the composition may contain at least one organic solvent in addition to water, but in amounts less than the amount of water present. However, as will be described later, aqueous compositions do not contain or substantially contain organic solvents.

[0049] Preferably, the aqueous composition contains, based on its total mass, at least 50% by mass, preferably at least 60% by mass, more preferably at least 70% by mass, particularly preferably at least 80% by mass, and most preferably at least 90% by mass of water.

[0050] Preferably, the pretreatment composition does not contain or substantially contains organic solvents. "Substantially contained" means that organic solvents are not intentionally added, but the possibility of their presence as impurities is not ruled out. Preferably, the amount of organic solvent present in the aqueous composition is 5% by mass or less, more preferably 2.5% by mass or less, even more preferably less than 2.0% by mass, most preferably a maximum of 1.0% by mass, a maximum of 0.5% by mass, or a maximum of 0.1% by mass, based on the total mass of the composition in each case.

[0051] Preferably, the pH value of the aqueous composition used in step 1) is in the range of 1.0 to 9.0, more preferably 1.5 to 7.0, and even more preferably 2.0 to 6.5. Preferably, the pH value is measured at room temperature (23°C). Preferably, the aqueous composition used in step 1) is acidic, i.e., has a pH value of less than 7.0, more preferably less than 6.5. The pH value of the aqueous composition is preferably adjusted as needed using at least one acid such as nitric acid, or at least one alkaline inducer such as aqueous ammonia and / or sodium carbonate.

[0052] Preferably, the aqueous composition is an aqueous solution. Solubility is measured at 20°C and atmospheric pressure (1.013 bar).

[0053] Preferably, the pretreatment composition does not contain, or substantially contains, chromium ions such as Cr(VI) ions and / or Cr(III) ions. In this context, "substantially contained" means that chromium ions are not intentionally added, but the possibility of either of these being present as impurities is not ruled out. Preferably, the amount of chromium ions present in the aqueous composition does not exceed 100 mg / L when calculated as metal.

[0054] Preferably, the pretreatment composition does not contain nickel ions or is substantially free of them. In this context, "substantially free" means that nickel ions are not intentionally added, but the possibility of their presence as impurities is not ruled out. Preferably, the amount of nickel ions present in the aqueous solution composition is 0.2 g / L or less, more preferably 0.1 g / L or less, more preferably less than 0.1 g / L, and most preferably 0.05 g / L or less, calculated as metal in each case, for example, in the range of 0 or 0.001 to 0.05 g / L.

[0055] Preferably, the pretreatment composition does not contain or substantially contains tin ions. In this context, "substantially contained" means that tin ions are not intentionally added, but the possibility of their presence as impurities is not ruled out. Preferably, the amount of tin ions present in the aqueous composition is 0.2 g / L or less, more preferably 0.1 g / L or less, more preferably less than 0.1 g / L, and most preferably 0.05 g / L or less, for example, in the range of 0.001 to 0.05 g / L, calculated as metal in each case.

[0056] Component a1) If the aqueous composition contains (preferably) at least one component a1), the component a1) is selected from zirconium cations, titanium cations, hafnium cations, and mixtures thereof. Preferably, the aqueous composition contains at least one of zirconium cations and titanium cations as component a1), and more preferably at least one zirconium cation.

[0057] Preferably, the aqueous composition contains at least one component a1) in an amount ranging from 5 to 2000 mg / L, more preferably 7.5 to 1500 mg / L, even more preferably 10 to 1000 mg / L, and even more preferably 15 to 500 mg / L, calculated as a metal in each case.

[0058] Preferably, a precursor metal compound is used to generate at least one metal cation present as component a1). Preferably, the precursor metal compound is water-soluble. Solubility is measured at 20°C and atmospheric pressure (1.013 bar). Particularly preferred zirconium, titanium, and / or hafnium compounds used as precursor compounds are complex fluorides of these metals. The term “complex fluoride” includes single and multiple protonated forms and deprotonated forms. It is also possible to use mixtures of such complex fluorides. In the present invention, a complex fluoride refers to a complex of a metal cation such as a zirconium cation, titanium cation, and / or hafnium cation and a fluoride ion, formed, for example, by the coordination of a fluoride anion to a zirconium cation, titanium cation, and / or hafnium cation in the presence of water. The content of at least one metal cation can be monitored and measured by ICP-OES (inductively coupled plasma atomic emission spectroscopy). The method is described in the “Methods” section below. When a complex fluoride of at least one zirconium cation, titanium cation, and / or hafnium cation is used as a precursor compound, the aqueous composition further comprises a fluoride anion as component a3).

[0059] Component a2) If the aqueous composition contains at least one component a2), then component a2) is selected from at least one organosilane and / or at least one hydrolysate and / or condensate thereof, and mixtures thereof.

[0060] Preferably, the aqueous composition comprises at least one of the following as component a2): an organic alkoxysilane, an organic silanol, a polyorganosilanol, and a mixture thereof. More preferably, component a2) comprises at least one organic silane and / or its hydrolysate and / or condensate. Preferably, component a2) is selected from silane, silanol, siloxane, and / or polysiloxane. Preferably, component a2) has at least one functional group selected from (meth)acrylate group, alkylaminoalkyl group, alkylamino group, alkyl disulfide group, alkyltotetrasulfide group, amino group, aminoalkyl group, carboxyl group, epoxy group, glycidoxy group, hydroxyl group, isocyanate group, mercaptoalkyl group, succinic anhydride group, and / or ureid group.

[0061] Examples include, for instance, (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, bis(3-triethoxysilylpropyl)disulfide), bis(3-trimethoxysilylpropyl)tetrasulfide), 1,2-bis(triethoxysilyl)ethane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3-methylaminopropyl)triethoxysilane, (3-methylaminopropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane and / or (3-glycidyloxypropyl)triethoxysilane and / or vinyltrimethoxysilane. Organic silanes are preferably present in hydrolyzed forms.

[0062] Preferably, the aqueous composition contains at least one component a2) in an amount calculated as elemental silicon in each case, ranging from 5 to 20,000 mg / L, more preferably 10 to 15,000 mg / L, even more preferably 20 to 10,000 mg / L, even more preferably 30 to 8,000 mg / L, and even more preferably 50 to 5,000 mg / L.

[0063] Any other component including component a3) All other components optionally present in the aqueous composition, such as component a3), are different from each other and are also different from both components a1) and a2).

[0064] Optionally, and preferably, the aqueous composition contains a fluoride anion containing a complex fluoride anion as component a3). However, the aqueous composition may be free of or substantially free of fluoride anions.

[0065] Preferably, the aqueous composition contains at least one component a3) in an amount of 0 or 10 to 2000 mg / L, more preferably 0 or 15 to 1500 mg / L, even more preferably 0 or 20 to 1000 mg / L, even more preferably 0 or 25 to 500 mg / L, and even more preferably 0 or 25 to 500 mg / L, calculated as fluorine in each case. As described later and as mentioned above, preferably, complex fluorides such as complexes of zirconium, titanium and / or hafnium formed with fluoride ions are present in the aqueous composition, for example, by the coordination of fluoride anions to zirconium, titanium and / or hafnium cations in the presence of water. Alternatively, fluoride anions may be generated by adding other water-soluble fluorine compounds, such as fluorides (other than complex fluorides of Ti, Zr, and / or Hf) and hydrofluoric acid to the composition. The free fluoride content is measured using a fluoride ion-sensitive electrode according to the method disclosed in the "Methods" section.

[0066] Optionally, preferably, the aqueous composition contains as component a3) a fluoride anion that exists as a complex fluoride anion coordinated to at least one of the zirconium, titanium, and hafnium cations present in the composition as component a1).

[0067] In particular, the following combinations of essential components can be used: a) Hexafluorozirconate b) Zirconium nitrate c) Hexafluorozirconate and zirconium nitrate d) Hexafluorotitanium acid e) Hexafluorozirconate and hexafluorotitanium acid f) Hexafluorotitanium acid and zirconium nitrate g) Hexafluorozirconate, hexafluorotitanium acid, and zirconium nitrate h) Organosilane compounds (one or more) i) Organosilane compounds and hexafluorozirconic acid.

[0068] Optionally, the aqueous composition may also contain further components, such as other metal cations (other than Zr, Ti, and / or Hf), and / or at least one water-soluble polymer having at least one functional group selected from acidic groups, hydroxyl groups, and mixtures thereof. Preferably, if at least one water-soluble polymer is present, it is a homopolymer or copolymer obtained by polymerization of at least one ethylene unsaturated monomer, wherein at least a portion of the monomer has at least one functional group selected from acidic groups, hydroxyl groups, and mixtures thereof. More preferably, it is a homopolymer or copolymer obtained by polymerization of at least one vinyl monomer and / or (meth)acrylic monomer, wherein at least a portion of the monomer has at least one functional group selected from acidic groups, hydroxyl groups, and mixtures thereof.

[0069] Optionally, the aqueous composition may contain further components, such as surfactants, pH adjusters, such as inorganic acids and their salts, organic acids and their salts, and / or rheological additives.

[0070] Optional step 2) In an optional step 2), the film obtained after step 1) is rinsed with water, preferably deionized water or tap water, more preferably deionized water. Here, "rinse" preferably means, in accordance with the general understanding of this term, the removal of any excess aqueous composition that came into contact with the surface in the step immediately preceding the rinsing step.

[0071] Optional step 3) In any step 3), the film obtained after step 1) or any step 2) is dried.

[0072] Drying can be carried out in step 4), described later, for example, when the coating material composition is subsequently applied. However, step 3) is merely an optional step, and therefore, it is also possible to carry out further method steps such as step 4) without drying the obtained film. In particular, in step 4), described later, it is also possible to apply the coating material composition onto the wet film obtained after carrying out step 1).

[0073] Drying step 3) is carried out, for example, at a temperature preferably in the range of 15°C to 100°C, more preferably in the range of 18°C ​​to 95°C, and particularly in the range of 20°C to 90°C. In this invention, "drying" specifically refers to physical drying by evaporation of water originally present in the composition used. Once the film is dried, the resulting product can be considered as a layer.

[0074] Substrate having a chemically pre-treated surface obtained by a pre-treatment method A further subject of the present invention is a substrate obtained by the aforementioned pretreatment method, that is, a pretreated, and in particular chemically pretreated, substrate.

[0075] All preferred embodiments of the pretreatment method and its preferred embodiments described herein are also preferred embodiments of the substrate obtained by this method.

[0076] How to apply at least one coating film A method for applying at least one coating film to at least one surface of a substrate comprises at least step 1), optionally step 2) and / or step 3), and further step 4), as described above in relation to the pretreatment method, i.e. 4) A step of applying a coating material composition containing at least one film-forming polymer onto the film obtained after step 1), or after any of steps 2) and / or 3), as defined above with respect to the pretreatment method. Includes.

[0077] The pretreatment method, the substrate obtained by this method, and all preferred embodiments described herein in relation to each preferred embodiment are also preferred embodiments of a method for applying at least one coating film.

[0078] Substrate obtained by a method of applying at least one coating film A further subject of the present invention is a substrate obtained by the method described above, to which at least one coating film is applied.

[0079] The pretreatment method, the substrate obtained by this method, and the method for applying at least one coating film, and all preferred embodiments described herein in relation to each preferred embodiment, are also preferred embodiments of the substrate obtained by the latter method.

[0080] Components such as current collectors, conductors, copper-clad laminates, anode materials, and battery cells obtained from the aforementioned anode material. A further subject of the present invention is a component obtained from the substrate, preferably selected from a rechargeable battery cell, which is used in a battery cell such as a rechargeable battery cell, including a current collector, a conductor, a copper-clad laminate, and an anode material, or preferably a rechargeable battery cell obtained from the anode material.

[0081] All preferred embodiments described herein with respect to the pretreatment method, the substrate obtained by this method, the method of applying at least one coating film, the substrate obtained by this method, and each preferred embodiment are also preferred embodiments of the resulting anode material and battery cell.

[0082] Method for using aqueous compositions for electrolytic treatment A further subject of the present invention is a method for using the aqueous composition defined above in relation to a contact step 1) of a pretreatment method to electrolytically form a film on at least a portion of the surface of a substrate, wherein the surface optionally has at least one plating layer, and (i) at least one of the at least one surface of the substrate and (ii) at least one of the optionally present plating layers are made of copper and / or at least one alloy thereof, and the substrate functions as a cathode for electrolytic application.

[0083] All preferred embodiments described herein with respect to the pretreatment method, the substrate obtained by this method, the method of applying at least one coating film, the substrate obtained by this method, the aforementioned components, and each preferred embodiment are also preferred embodiments of the aforementioned method of use of the present invention.

[0084] method 1. Determination of free fluoride content The free fluoride content is determined by a fluoride ion selective electrode. The electrode is calibrated using at least three standard solutions with known fluoride concentrations. A calibration curve is constructed through the calibration process. This curve is then used to determine the fluoride content.

[0085] 2. ICP-OES The content of specific elements such as zirconium, titanium, and hafnium in the sample to be analyzed is determined using inductively coupled plasma atomic emission spectroscopy (ICP-OES) in accordance with DIN EN ISO 11885 (dated: September 1, 2009). The sample is thermally excited in an argon plasma generated by a radio frequency field, and the light emitted by electronic transitions is visualized as spectral lines of the corresponding wavelengths and analyzed using an optical system. A linear relationship exists between the intensity of the emitted light and the concentration of the target element. Calibration measurements are performed using known elemental standards (reference standards) according to the sample to be analyzed before the procedure. These calibrations can be used to determine the concentrations of unknown solutions, such as the concentrations of titanium, zirconium, and hafnium.

[0086] 3. Coating mass XRF (X-ray fluorescence analysis) is used to determine the coating mass (mg / m²) of specific (trace) elements such as Ti, Zr, and / or Si in layers such as chemically converted layers obtained by applying a chemical pretreatment composition to a substrate. 2 It is used to measure ).

[0087] 4.Adhesiveness Adhesion was determined by a wrap shear test using a two-component epoxy adhesive in accordance with DIN 1465 (07-2009) on a copper-containing substrate that had undergone chemical pretreatment. The adhesive strength was then evaluated by comparing it with the results of the same test using a copper-containing substrate that had not undergone chemical pretreatment.

[0088] Alternatively, the adhesive properties were determined by a tensile strength test in accordance with ISO 15754 on a copper-containing substrate that had undergone chemical pretreatment, using a calendered graphite anode active material used in lithium-ion batteries, and compared with the results of the same test using a copper-containing substrate that had not undergone chemical pretreatment.

[0089] 5.Interfacial resistivity The interfacial resistivity was measured using the HIOKI Multipin System.

[0090] 6. Potentiodynamic scanning In accordance with ISO 17475, potentiodynamic scanning using a GAMRY Instrument was performed on a chemically pre-treated copper-containing substrate at a neutral pH, with a scanning range of -250 to 300 mV and a scanning speed of 5 mV / s. The passivation efficiency was measured and compared with the results of the same test using an unpre-treated copper-containing substrate. [Examples]

[0091] The following embodiments further illustrate the present invention, but do not limit its scope.

[0092] 1. Chemical pretreatment composition Several exemplary chemical pretreatment compositions, namely compositions A1-A4, B1, B2, and C, were prepared.

[0093] Composition A1 A hexafluorozirconium acid-containing composition was diluted with deionized water to achieve a zirconium concentration of 500 ppm (calculated as Zr). Diluted sodium carbonate solution was added to adjust the pH to 3.6–3.8, obtaining a free fluoride concentration of 48–55 ppm. The measured conductivity was 1400–1500 μS / cm.

[0094] Composition A2 A zirconium nitrate-containing composition was diluted with deionized water to achieve a zirconium concentration of 270 ppm (calculated as Zr). Diluted sodium carbonate solution was added to adjust the pH value of the fluoride-free composition to 2.8-3.0.

[0095] Composition A3 A composition containing hexafluorozirconium acid, ammonium molybdate, and poly(meth)acrylic acid polymer was diluted with deionized water to achieve a zirconium concentration of 380 ppm (calculated as Zr) and a molybdenum concentration of 40 ppm (calculated as Mo). Diluted ammonium difluoride solution was added to adjust the pH to 3.5–3.7, resulting in a free fluoride concentration of 70–80 ppm and an electrical conductivity of 1250–1300 μS / cm. The poly(meth)acrylic acid polymer had a mass-average molecular weight of approximately 250,000 g / mol and was a commercially available product.

[0096] Composition A4 A composition containing hexafluorotitanium acid, ammonium molybdate, and poly(meth)acrylic acid polymer was diluted with deionized water to achieve a titanium concentration of 250 ppm (calculated as Ti) and a molybdenum concentration of 40 ppm (calculated as Mo). Diluted ammonium difluoride solution was added to adjust the pH to 3.6-3.8, resulting in a free fluoride concentration of 70-80 ppm and an electrical conductivity of 1250-1300 μS / cm. The poly(meth)acrylic acid polymer had a mass-average molecular weight of approximately 250,000 g / mol and was a commercially available product.

[0097] Composition B1 A pre-condensate prepared from aminosilane and bifunctional silane was diluted with deionized water to achieve a silicon concentration of 4000 ppm (calculated as Si). Diluted ammonium bicarbonate solution was added to adjust the pH to 6.0-6.4. The measured conductivity was 1870-2140 μS / cm.

[0098] Composition B2 Pre-condensates prepared from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and bis[3-(trimethoxysilyl)propyl]amine were diluted with deionized water to achieve a silicon concentration of 300 ppm (calculated as Si). Diluted sodium carbonate solution was added to adjust the pH to 3.9–4.2. The measured conductivity was 300–1400 μS / cm.

[0099] Composition C A mixture of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, and hexafluorozirconic acid-containing compositions was diluted with deionized water to achieve a silicon concentration of 150 ppm (Si equivalent) and a zirconium concentration of 20 ppm (Zr equivalent). A diluted sodium carbonate solution was added to adjust the pH to 3.3-3.5. The measured conductivity was 1400-1500 μS / cm.

[0100] 2. Pretreatment including chemical pretreatment methods 2.1 Copper workpieces (thin foil or rod-shaped) were used as the base material. Specifically, the following base materials were used: Base material S1: Copper foil made of a copper alloy with a copper content of over 98%, unplated, 6 μm thick. Substrate S2: Pure copper foil, nickel and zinc plated, 18 μm thick. Base material S3: Pure copper foil, unplated, 10 μm thick. Substrate S4: Pure copper foil, unplated, 18 μm thick, and Base material S5: Copper rod made of copper alloy with a copper content of over 98%, nickel and zinc plated, 3mm thick.

[0101] 2.2 The substrate S5 was cleaned by immersing it in a cleaning bath prepared from Gardoclean® S5176 aqueous cleaning solution manufactured by Chemetall GmbH at 70°C for 10 minutes, and then rinsing it with deionized water for 1 minute before proceeding to the pickling process described below.

[0102] 2.3 Surface-cleaned substrates S5 and S1-S4 were acid-washed at room temperature for 5-60 seconds using a solution containing sulfuric acid (20% by mass) and hydrogen peroxide (0.9-3.0% by mass), then rinsed with deionized water for 1 minute, followed by deacidification treatment at room temperature for approximately 30 seconds using a solution containing sulfuric acid (5% by mass), and then rinsed with deionized water for 1 minute. After that, drying was performed with compressed air. The success of the cleaning was confirmed by the water drainage behavior when removing the substrate from the final deionized water rinse. For each substrate type, the least aggressive and successful acid-washing conditions were selected in preliminary tests.

[0103] 2.4 Next, the substrate was immersed in one of the chemical pretreatment baths A1-A4, B1, B2, and C, with a portion of the workpiece protruding from the bath in each case. For foils, a non-conductive sample holder made of polyamide was used. The bath was maintained at room temperature of 20-23°C. Counter electrodes made of stainless steel or platinum-plated niobium were similarly immersed in the bath with a portion protruding from the bath. These counter electrodes were placed parallel to each other, and the copper workpiece to be treated was also placed parallel to the center of the counter electrodes. When chemical pretreatment was applied to only one side (surface) of the copper workpiece, one parallel counter electrode was sufficient. When there were two counter electrodes, they were connected with a stainless steel holder or electrical cable so that the applied current flowed equally through both electrodes. In all experiments shown, both sides of the substrate were pretreated. A counter electrode larger than the copper workpiece to be treated was connected to a laboratory power supply as the positive electrode (also called the anode in an electrolytic cell). A copper workpiece was connected as the negative electrode (also called the cathode in an electrolytic cell). All connections were made via electrical cables with clamps above the surface of the treatment liquid. The bath was either agitated or unagitated, so that the composition present in the bath around the copper workpiece to be treated was in a quasi-laminar flow state. The copper workpiece to be treated was immersed with the current off, then a low current was applied for a predetermined time, and then the current was cut off. After this treatment, the copper workpiece was removed from the treatment bath and subjected to either deionized water treatment (rinsing and / or immersion) and / or forced drying with clean compressed air, or both, to remove residual treatment liquid. To remove residual moisture, the copper substrate was dried in a convection oven at 40°C for 20 minutes. However, for composition B1, 85°C was used instead of 40°C.

[0104] Table 1 summarizes the conditions used in each experiment (run). Runs 4, 5, 12, and 13 were comparison runs (no current was applied).

[0105] [Table 1]

[0106] 3. Characterization of the obtained chemically pretreated substrates 3.1 The coating mass of the layer present on the surface of each substrate was determined according to the method disclosed in the Methods section. The results are summarized in Table 2. Runs 4, 5, 12, and 13 are comparison runs (no current was applied). For Zr and Ti coating masses, the calculations were performed as metals in each case. For Si coating masses, the calculations were performed as Si (element) in each case.

[0107] [Table 2]

[0108] 3.2 The adhesive properties of some of the substrates that had undergone chemical pretreatment were also tested.

[0109] The substrates obtained after Experiment 16 were subjected to the adhesion strength test described in the Methods section. As a result, it was found that the substrates obtained after Experiment 16 showed a 44% increase in adhesion strength compared to the same substrates that had not undergone chemical pretreatment.

[0110] Furthermore, the substrate obtained after Experiment 1 was subjected to the tensile force test described in the Methods section. As a result, the adhesive strength (N / mm²) of the substrate obtained after Experiment 1 was 2 The amount (in units) was found to have increased by 12% compared to the same substrate that had not undergone chemical pretreatment.

[0111] 3.3 The interfacial resistivity of a portion of the chemically pretreated substrate was measured according to the method described in the Methods section. A graphite anode active material used in lithium-ion batteries was applied thereto and calendered. The interfacial resistivity of the substrate obtained after Experiment 1 was 3.3 mΩ / cm². 2 The following was measured. A graphite anode active material used in lithium-ion batteries was applied to it and calendered. The interfacial resistivity of the substrate obtained after Experiment 11 was 4.4 mΩ / cm². 2 It was measured as follows.

[0112] 3.4 Potentiodynamic scanning was performed on the chemically pretreated substrates obtained after Experiment 1. The passivation efficiency compared to the same substrate without chemical pretreatment was calculated by log i (corrosion current value). corr When evaluated using this method, it improved by 13%.

Claims

1. A method for pretreatment of a substrate comprising copper and / or at least one alloy thereof, comprising at least step 1), and optionally step 2) and / or 3), i.e. 1) A step of bringing at least one surface of at least one substrate into contact with an aqueous composition in at least a portion thereof, thereby forming a film on at least a portion of the surface, wherein the surface optionally has at least one plating layer, and the at least one surface of the substrate is made of copper and / or at least one alloy thereof. The aqueous composition contains at least 70% by mass of water based on its total mass, and in addition to water, at least one of the different constituent components a1) and a2), i.e. As component a1), at least one of zirconium cation, titanium cation, and hafnium cation, in an amount ranging from 5 to 2000 mg / L, calculated as a metal in each case, and / or Component a2) includes at least one organosilane and / or at least one hydrolysate and / or condensate thereof. Processes including, 2) Optionally, a step of rinsing the film obtained after step 1) with water, and / or 3) Optionally, a step to dry the film obtained after step 1) or after any step 2). Includes, A method wherein the contact step 1) is performed in an electrolytic cell apparatus in which a substrate containing copper and / or at least one alloy thereof serves as the cathode during the execution of step 1).

2. The method according to claim 1, wherein the aqueous composition contains, as component a1), at least one of zirconium cation, titanium cation, and hafnium cation, preferably at least zirconium cation, in an amount preferably in the range of 7.5 to 1500 mg / L, more preferably 10 to 1000 mg / L, and even more preferably 15 to 500 mg / L, calculated as a metal in each case.

3. The method according to claim 1 or 2, wherein the aqueous composition further contains, as component a3), a fluoride anion containing a complex fluoride anion, in an amount calculated as fluorine in each case, preferably 10 to 2000 mg / L, more preferably 15 to 1500 mg / L, even more preferably 20 to 1000 mg / L, and even more preferably 25 to 500 mg / L.

4. The method according to claim 3, wherein the aqueous composition contains a fluoride anion present as a component a3) as a complex fluoride anion, and the complex fluoride anion is preferably coordinated to at least one of a zirconium cation, a titanium cation, and a hafnium cation present in the composition as component a1).

5. The method according to claim 1 or 2, wherein the aqueous composition contains, as component a2), at least one organosilane and / or at least one hydrolysate and / or condensate thereof, in an amount calculated as elemental silicon in each case, ranging from 5 to 20,000 mg / L, preferably 10 to 15,000 mg / L, more preferably 20 to 10,000 mg / L, even more preferably 30 to 8,000 mg / L, and even more preferably 50 to 5,000 mg / L.

6. The electrolytic treatment in step 1) is performed using DC current, preferably with a voltage in the range of 2 to 10 V, more preferably in the range of 3 to 8 V, and preferably with an A / m² of 2 to 30 A / m². ２ A / m² is more preferably in the range of 3 to 20 A / m². ２ The method according to claim 1 or 2, which is carried out while generating a current density in the range of .

7. The method according to claim 1 or 2, wherein the processing time, i.e., the period during which the surface is in contact with the aqueous composition in step 1), is 1 second to 5 minutes, preferably 2 seconds or 2.5 minutes or 1 minute, most preferably 2 seconds to 30 seconds, and / or the temperature of the aqueous composition used in step 1) is 5 to 90°C, more preferably 15 to 70°C, most preferably 20 to 60°C.

8. The method according to claim 1 or 2, wherein the aqueous composition used in step 1) has a pH value in the range of 1.0 to 9.0, preferably 1.5 to 7.0, and more preferably 2.0 to 6.

5.

9. The film obtained after step 1), or after any steps 2) and / or 3), contains, in each case determined by XRF measurement, trace elements such as Ti, Zr, and / or Si, in a concentration of 0.5 to 500 mg / m². ２ Preferably 1 to 400 mg / m² ２ More preferably 2 to 350 mg / m² ２ The method according to claim 1 or 2, wherein the dry film thickness corresponds to a coating mass within the range of [specified range].

10. The method according to claim 1 or 2, wherein the optionally at least one plating layer is made of copper, zinc, nickel, tin, and / or an alloy of one or more of the aforementioned metals, preferably the aforementioned substrate itself is made of copper and / or at least one of its alloys.

11. The method according to claim 1 or 2, wherein the base material is in the form of a foil, a coil, or a substantially flat component.

12. A method for applying at least one coating film to at least one surface of a substrate, comprising at least step 1) as defined in claim 1, and optionally step 2) and / or step 3), and further step 4), i.e., 4) The step of applying a coating material composition comprising at least one film-forming polymer onto a film obtained after step 1) as defined in claim 1, or after any step 2) and / or 3). Methods that include...

13. A substrate that can be obtained by the pretreatment method described in claim 1, or the method described in claim 12.

14. A component that can be obtained from the substrate according to claim 13, preferably used in a rechargeable battery cell, which is selected from a rechargeable battery cell that can be obtained from the aforementioned anode material, including a current collector, a conductor, a copper-clad laminate, and an anode material.

15. A method of using an aqueous composition as defined in claim 1 or 2 in relation to a contact step 1) to electrolytically form a film on at least a portion of the surface of a substrate, wherein the surface optionally has at least one plating layer, at least one surface of the substrate is made of copper and / or at least one alloy thereof, and the aforementioned substrate functions as a cathode for electrolytic application.

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