Method for manufacturing coating of insoluble electrode for manufacturing electrolytic copper foil

Abstract

The present invention relates to a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil and, more specifically, to a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, the method allowing an anode to have resistance to oxygen evolution such that the efficiency and lifetime of the electrode are maximized. In order to accomplish the objective, the present invention provides the method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, comprising the steps of: pretreating an electrode substrate; preparing a coating solution for coating the pretreated electrode substrate; and coating the electrode substrate with the prepared coating solution so as to manufacture an insoluble electrode, wherein the electrode substrate is made of a titanium material, and applying, drying and heat-treating a preset amount of the coating solution are repeatedly performed several times so as to form a coating layer.

Description

Method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil

[0001] The present invention relates to a method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, and more specifically, to a method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil to maximize the efficiency and lifespan of the electrode by providing resistance to oxygen generation at the anode.

[0002]

[0003] Electrolytic copper foil is a product produced by forming copper into a thin foil form through an electroplating process. It is primarily used in the manufacture of electronic devices and batteries, and is particularly widely utilized as a core material for negative electrode current collectors in lithium-ion batteries or for printed circuit boards (PCBs). In particular, electrolytic copper foil is utilized as an important material in the advanced electronic device and battery industries due to its excellent conductivity and the advantage of being thin and capable of precise thickness control.

[0004] In the manufacture of such electrolytic copper foil, insoluble electrodes are used as anodes. Specifically, the electrode is responsible for the oxygen evolution reaction during the electrolysis process; it does not dissolve in the electrolyte and contributes to maintaining the stability of the reaction. In other words, the insoluble electrode enables the continuous participation of the electrochemical reaction without being consumed, thereby facilitating the smooth production of electrolytic copper foil.

[0005] However, conventional insoluble electrodes have limitations in terms of durability and efficiency. In particular, maintaining high electrode performance is crucial during the electrolytic copper foil manufacturing process, as electrode performance directly affects copper quality and the efficiency of electrochemical reactions. However, current electrodes degrade over time, leading to increased production costs and reduced overall production efficiency.

[0006] Furthermore, electrodes commonly used in the fabrication process struggle to maintain a uniform thickness during coating and plating, resulting in uneven activation of the electrode surface. This led to a decrease in the electrochemical reactivity of the electrodes, which in turn resulted in non-uniform electrode performance during production.

[0007] Furthermore, the electrochemical reactions occurring during the manufacturing process of electrolytic copper foil involve a complex process in which hydrogen is generated at the cathode and oxygen is generated at the anode. These reactions can cause corrosion or failure of the electrodes and reduce the reliability of the production process. In particular, conventional anode materials lacked resistance to oxygen generation, leading to performance degradation during prolonged use.

[0008]

[0009] <Prior Art Literature>

[0010] Korean Registered Patent No. 10-1409750

[0011]

[0012] The objective of the present invention, which aims to solve the above-mentioned problems, is to provide a method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil to maximize the efficiency and lifespan of the electrode by providing resistance to oxygen generation at the anode.

[0013] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art to which the present invention belongs from the description below.

[0014]

[0015] The present invention provides a method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, comprising the steps of: performing a pretreatment on an electrode substrate; preparing a coating solution for coating the pretreated electrode substrate; and coating the electrode substrate with the prepared coating solution to produce an insoluble electrode, wherein the electrode substrate is provided with a titanium material and the coating layer is formed by repeating the process of applying, drying, and heat-treating the coating solution in a predetermined amount multiple times.

[0016] In an embodiment of the present invention, the step of pre-treating the substrate may be characterized by comprising: a step of performing a sandblasting process on the electrode substrate to create an uneven surface; a step of performing a first cleaning on the electrode substrate with the uneven surface created; a step of performing etching on the cleaned electrode substrate; a step of performing a second cleaning on the etched electrode substrate; and a step of drying the electrode substrate that has undergone the second cleaning.

[0017] In an embodiment of the present invention, in the step where a sandblasting process is performed on the electrode substrate to create an uneven surface, the sandblasting process may be characterized by using an alumina oxide abrasive.

[0018] In an embodiment of the present invention, the first washing and the second washing are arranged so as to perform high-pressure water washing and ultrasonic washing on the electrode substrate, and the ultrasonic washing may be characterized by being performed for 30 to 60 minutes at a frequency of 30 to 40 kHz while the electrode substrate is immersed in a cleaning solution diluted with an alkaline cleaning agent and hot water.

[0019] In an embodiment of the present invention, in the step of etching the washed electrode substrate, the electrode substrate may be characterized by being prepared to be etched for 10 to 25 minutes at a concentration of 25 to 30% in a temperature range of 30 to 80 degrees using an etching solution comprising oxalic acid and hydrochloric acid (HCl) or sulfuric acid (H2SO4).

[0020] In an embodiment of the present invention, the step of drying the electrode substrate after the secondary washing may be characterized in that the electrode substrate is completely dried at a temperature of 70 to 150 degrees for at least 20 minutes.

[0021] In an embodiment of the present invention, the step of preparing a coating solution for coating the pretreated electrode substrate may be characterized by comprising: a step of forming a mixture by mixing two or more elements among the platinum group elements, iridium oxide (Ir), ruthenium chloride (Ru), platinum (Pt), and tantalum chloride (Ta); a step of stirring the mixture with alcohol and dissolving the elements; and a step of preparing the coating solution by irradiating the dissolved elements with ultrasound.

[0022] In an embodiment of the present invention, the step of stirring and dissolving the mixture with alcohol may be characterized by stirring at a temperature of 30 to 50 degrees at 260 to 550 RPM for 2 to 4 hours.

[0023] In an embodiment of the present invention, the alcohol may be characterized as being provided as one or more of isopropyl alcohol, chlorine, butanol, and ethanol.

[0024] In an embodiment of the present invention, the step of manufacturing an insoluble electrode by coating the electrode substrate with the prepared coating solution may be characterized by comprising: a step of applying the coating solution to the pretreated electrode substrate; a step of drying the electrode substrate to which the coating solution is applied; a step of performing heat treatment on the dried electrode substrate; a step of sequentially repeating the steps of applying the coating solution, drying the electrode substrate, and performing heat treatment until a coating layer of a predetermined thickness is formed; and a step of manufacturing the insoluble electrode by performing a heat sintering process when the coating layer of the predetermined thickness is formed.

[0025]

[0026] The effect of the present invention according to the above configuration is that the speed and efficiency of the electrochemical reaction can be increased by using an insoluble titanium substrate coated with a platinum compound. This can improve productivity by increasing the electrodeposition rate of copper during the production of electrolytic copper foil.

[0027] In addition, according to the present invention, corrosion or performance degradation of the electrode can be minimized by coating the anode with iridium oxide, which has resistance to oxygen generation. This ensures the stability of the electrode during the electrolytic copper foil manufacturing process, enabling long-term use.

[0028] Furthermore, according to the present invention, the quality of the electrolytic copper foil produced is improved thanks to the high reactivity and stability of the insoluble electrode. High-quality copper foil enhances applicability in the electronic device and battery industries and contributes to maximizing the performance of the final product.

[0029] Furthermore, according to the present invention, in addition to the production of electrolytic copper foil, it can be applied to various fields such as brine electrolysis, wastewater treatment, and electrochemical cleaning. This versatility increases the potential for commercialization of the technology and can promote its utilization in various industrial sectors.

[0030] The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description of the invention or the claims.

[0031]

[0032] FIG. 1 is a process example diagram of a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil according to an embodiment of the present invention.

[0033] FIG. 2 is a flowchart of a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil according to an embodiment of the present invention.

[0034] FIG. 3 is a flowchart of the steps for pre-processing an electrode substrate according to an embodiment of the present invention.

[0035] FIG. 4 is a flowchart of the steps for preparing a coating solution for coating a pretreated electrode substrate according to an embodiment of the present invention.

[0036] FIG. 5 is a flowchart of the steps for manufacturing an insoluble electrode by coating an electrode substrate with a coating solution prepared according to an embodiment of the present invention.

[0037] Figure 6 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 200x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0038] Figure 7 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 500x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0039] Figure 8 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 2,000x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0040] Figure 9 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 10,000x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0041] FIG. 10 is a graph showing the qualitative or quantitative analysis of elements on the surface of a material using an Energy Dospersive Spectroscope for an insoluble substrate according to the present invention.

[0042] FIG. 11 is an image taken at a magnification of 5,000x with a scanning electron microscope to confirm the elemental composition of an insoluble substrate according to the present invention.

[0043] FIG. 12 is an image taken to confirm the molecular structure and crystal structure of a mixture of insoluble substrates according to the present invention.

[0044] Figures 13 and 14 are images taken to confirm the molecular structure and crystal structure of iridium and tantalum when mixed together.

[0045] Figures 15 to 17 are images of an insoluble substrate taken by an X-ray photoelectron spectrometer.

[0046] Figure 18 is a table to show the effect of pretreatment on the electrode substrate.

[0047] Figure 19 is a table to show the effect of the coating solution on the electrode substrate.

[0048] Figure 20 is a table to show the effects of drying and heat treatment on the electrode substrate.

[0049]

[0050] A most preferred embodiment according to the present invention comprises: a step of pre-treating an electrode substrate; a step of preparing a coating solution for coating the pre-treated electrode substrate; and a step of coating the electrode substrate with the prepared coating solution to produce an insoluble electrode, wherein the electrode substrate is provided with a titanium material and is configured such that a coating layer is formed by repeating the process of applying, drying, and heat-treating the coating solution in a predetermined amount several times.

[0051]

[0052] The present invention will be described below with reference to the attached drawings. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein. Furthermore, in order to clearly explain the present invention in the drawings, parts unrelated to the explanation have been omitted, and similar parts throughout the specification have been given similar reference numerals.

[0053] Throughout the specification, when it is stated that a part is "connected (connected, in contact, combined)" with another part, this includes not only cases where they are "directly connected," but also cases where they are "indirectly connected" with other members interposed between them. Furthermore, when it is stated that a part "includes" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but rather allows for the inclusion of additional components.

[0054] The terms used herein are merely for describing specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising” or “having” are intended to indicate the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0055] Additionally, terms such as "...part," "...unit," and "...module" described in the specification refer to a unit that processes at least one function or operation, and this may be implemented in hardware, software, or a combination of hardware and software.

[0056] Additionally, in this specification, when a step is described as being located "before" or "after" another step, this includes not only cases where a step is in a direct chronological relationship with another step, but also cases where there is an indirect chronological relationship in which the chronological order of the two steps may change, such as a mixing step following each step.

[0057] Embodiments of the present invention will be described in detail below with reference to the attached drawings.

[0058] FIG. 1 is a process example diagram of a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil according to an embodiment of the present invention, and FIG. 2 is a flowchart of a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil according to an embodiment of the present invention.

[0059] Referring to FIGS. 1 and 2, a method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil may include a step (S10) of pre-treating an electrode substrate, a step (S20) of preparing a coating solution for coating the pre-treated electrode substrate, and a step (S30) of coating the electrode substrate with the prepared coating solution to produce an insoluble electrode.

[0060] FIG. 3 is a flowchart of the steps for pre-processing an electrode substrate according to an embodiment of the present invention.

[0061] Referring to FIG. 3, the step (S10) of pre-treating the electrode substrate may include a step (S11) of creating an uneven surface by performing a sandblasting process on the electrode substrate, a step (S12) of performing a first cleaning on the electrode substrate with the created uneven surface, a step (S13) of performing etching on the cleaned electrode substrate, a step (S14) of performing a second cleaning on the etched electrode substrate, and a step (S15) of drying the electrode substrate that has undergone the second cleaning.

[0062] First, in the step (S11) where a sandblasting process is performed on the electrode substrate to create an uneven surface, the electrode substrate (10) may be made of titanium material. For example, the electrode substrate (10) may be made of ASME B265-Gr.1.

[0063] In addition, an uneven surface (20) can be created on the electrode substrate (10) by a sandblasting process. At this time, the sandblasting process can be performed using an alumina oxide abrasive. In addition, the brown alumina particle size can be #80, #100, and #150 so that a uniform roughness within an error range of 8 to 15 Ra can be applied to each substrate.

[0064] Next, in the step (S12) where a first cleaning is performed on the electrode substrate with the uneven surface, high-pressure water cleaning and ultrasonic cleaning of the electrode substrate (10) may be performed.

[0065] At this time, the ultrasonic cleaning may be arranged so that the electrode substrate (10) is immersed in a cleaning solution diluted with an alkaline cleaning agent and hot water, and the cleaning is performed at a frequency of 30 to 40 kHz for 30 to 60 minutes.

[0066] In addition, the above cleaning solution may be prepared by diluting an alkaline cleaning agent with hot water at a ratio of 1:30.

[0067] This primary cleaning can remove the alumina that has penetrated during the sandblasting process of the electrode substrate (10).

[0068] Next, in the step (S13) where etching is performed on the cleaned electrode substrate, the electrode substrate (10) may be etched.

[0069] In particular, etching is performed to create a pattern and structure of the electrode substrate (10), and appropriate temperature, chemical concentration, and pressure must be maintained in the etching chamber so that uniform and accurate etching is performed.

[0070] To this end, the electrode substrate (10) may be prepared to be etched for 10 to 25 minutes at a concentration of 25 to 30% in a temperature range of 30 to 80 degrees by an etching solution containing oxalic acid and hydrochloric acid (HCl) or sulfuric acid (H2SO4).

[0071] At this time, since the titanium metal surface may melt if the etching time is too long, a chemical reaction is induced between 10 and 25 minutes to obtain an appropriate roughness, and at the same time, a uniform roughness within an error range of 8 to 15 Ra can be obtained.

[0072] As such, the electrode substrate that has undergone acid etching is additionally given fine roughness along the roughness formed by sandblasting treatment, thereby improving the contact area between the electrode substrate and the coating layer.

[0073] Next, in the step (S14) where a second cleaning is performed on the electrode substrate that has been etched, high-pressure water cleaning and ultrasonic cleaning of the electrode substrate (10) may be performed.

[0074] At this time, the ultrasonic cleaning may be arranged so that the electrode substrate (10) is immersed in a cleaning solution diluted with an alkaline cleaning agent and hot water, and the cleaning is performed at a frequency of 30 to 40 kHz for 30 to 60 minutes.

[0075] In addition, the above cleaning solution may be prepared by diluting an alkaline cleaning agent with hot water at a ratio of 1:30.

[0076] As such, ultrasonic cleaning performed with a cleaning solution containing an alkaline cleaning agent can dissolve and remove contaminants.

[0077] Next, in the step (S15) where the electrode substrate that has undergone the second washing is dried, the electrode substrate (10) that has undergone the second washing can be completely dried. Specifically, the electrode substrate (10) that has undergone the second washing can be arranged to be completely dried in an oven at a temperature of 70 to 150 degrees for at least 20 minutes.

[0078] FIG. 4 is a flowchart of the steps for preparing a coating solution for coating a pretreated electrode substrate according to an embodiment of the present invention.

[0079] Referring to FIG. 4, the step (S20) of manufacturing an insoluble electrode by coating an electrode substrate with a manufactured coating solution may include a step (S21) of mixing two or more elements among platinum group elements, iridium oxide (Ir), ruthenium chloride (Ru), platinum (Pt), and tantalum chloride (Ta) to form a mixture, a step (S22) of stirring the mixture with alcohol and dissolving the elements, and a step (S23) of irradiating the dissolved elements with ultrasound to manufacture the coating solution.

[0080] First, in the step (S21) of forming a mixture by mixing two or more elements among the platinum group elements, iridium oxide (Ir), ruthenium chloride (Ru), platinum (Pt), and tantalum chloride (Ta), the method may be configured to form a mixture by mixing two or more elements among the platinum group elements, iridium oxide (Ir), ruthenium chloride (Ru), platinum (Pt), and tantalum chloride (Ta).

[0081] Here, when making electrodes with iridium chloride (IrCl3, IrCl4, IrCl5) and iridium oxide (IrO2, IrO3, IrO5), iridium can be used as a mixture of two or more of tantalum chloride (TaCl2, TaCl3, TaCl4, TaCl5), tantalum oxide (TaO2, TaO3, TaO4, TaO5) and ruthenium chloride (Ru) to increase the life of the electrode in a corrosive environment.

[0082] Iridium chlorides (IrCl3, IrCl4, IrCl5) are relatively resistant to corrosive environments and possess high electrochemical reactivity, characterized by oxygen generation and low voltage, allowing for both direct and indirect reactions with contaminants.

[0083] Next, in the step (S22) where the mixture is stirred with alcohol and the element is dissolved, the mixture may be stirred with alcohol to dissolve the element.

[0084] For example, iridium, which is the main catalyst of the coating solution, and tantalum, which is the binder, can be prepared to be dissolved in alcohol in weight ratios of 70:30, 60:40, and 50:50.

[0085] At this time, the mixture may be prepared to be dissolved by stirring at 260 to 550 RPM at a temperature of 30 to 50 degrees in the alcohol for 2 to 4 hours.

[0086] In addition, the above alcohol may be prepared as one or more of isopropyl alcohol, chlorine, butanol, and ethanol.

[0087] In addition, if the viscosity of the mixed metal oxide coating solution used in the present invention is high, the coating power is good, but the bonding strength of the surface area of ​​the pretreated electrode substrate (10) is lowered, and if the viscosity of the coating solution is low, the problem of spreading occurs in the coating phenomenon, so the optimal viscosity of the coating solution can be manufactured to have 5,000 to 8,000 cps (centipoise).

[0088] Next, in the step (S23) where a coating solution is prepared by irradiating the dissolved elements with ultrasound, each dissolved element may be irradiated with ultrasound of 20 kHz to 50 kHz through ultrasonic dispersion to undergo the steps of particle dispersion, cell crushing, particle grinding, and homogenization by repeatedly applying intense pressure and depressurization.

[0089] At this time, the usage period and usage conditions are determined by the irradiation time, interval, and frequency according to the components of the solution, and can be arranged to make the particle size ultrafine, such as nano-size and smaller.

[0090] And, in the step (S23) where the coating solution is prepared by irradiating the dissolved element with ultrasound, the coating solution may be prepared by irradiating the dissolved element with ultrasound 2 to 5 times repeatedly at a frequency of 20 to 50 kHz for 20 to 60 minutes.

[0091] FIG. 5 is a flowchart of the steps for manufacturing an insoluble electrode by coating an electrode substrate with a coating solution prepared according to an embodiment of the present invention.

[0092] Referring to FIG. 5, the step (S30) of manufacturing an insoluble electrode by coating an electrode substrate with a manufactured coating solution may include: a step (S31) of applying a coating solution to a pretreated electrode substrate; a step (S32) of drying the electrode substrate coated with the coating solution; a step (S33) of performing heat treatment on the dried electrode substrate; a step (S34) of sequentially repeating the steps of applying the coating solution, drying the electrode substrate, and performing heat treatment until a coating layer of a preset thickness is formed; and a step (S35) of manufacturing an insoluble electrode by performing a heat sintering process when a coating layer of a preset thickness is formed.

[0093] First, in the step (S31) where a coating solution is applied to a pretreated electrode substrate, a coating solution prepared by the method described above may be applied to the pretreated electrode substrate (10).

[0094] At this time, application methods can be achieved using techniques such as spraying, brushing, rolling, and dipping.

[0095] Spray coating is an economical method that allows for uniform and stable coating on the surface by spraying the coating solution onto the electrode substrate (10) with a spray nozzle in nano-sized particles, and is suitable for mass production with minimal loss of solution.

[0096] Brushing coating is a method of applying a coating solution to an electrode substrate (10) with a brush. Although the coating method is simple and cost-effective, the material of the brush and the skill level of the operator are required to obtain a certain quality and depending on the product.

[0097] Rolling coating is a method of applying a solution to an electrode substrate (10) with a roller. Although the coating method is simple and cost-effective, the material of the roller and the skill of the operator are required to ensure consistent quality and the desired product.

[0098] Dipping coating is a method of obtaining a coating film by immersing an electrode substrate in a coating solution to form a precursor layer on the surface of the material and then firing it at a suitable temperature. It is used for relatively small products and is one of the economical methods because, compared to spray coating, the surface is relatively uniform and the loss of coating solution can be reduced.

[0099] In the step (S31) where a coating solution is applied to the pretreated electrode substrate, the coating solution prepared may be applied or sprayed onto the surface of the pretreated electrode substrate (10) using any one of these methods.

[0100] At this time, 2g / m² of the coating solution is applied once. 2 Thickness greater than or equal to this can be applied.

[0101] Next, in the step (S32) where the electrode substrate coated with the coating solution is dried, the electrode substrate (10) coated or sprayed with the coating solution may be dried. At this time, the drying temperature may be set to a temperature of 60 to 90°C and may be set to be dried for 10 to 20 minutes.

[0102] Next, in the step (S33) where heat treatment is performed on the dried electrode substrate, the dried electrode substrate (10) may be heat-treated within a temperature range of 400 to 650 degrees.

[0103] Next, in the step (S34) in which the steps of applying a coating solution, drying an electrode substrate, and performing heat treatment are repeated sequentially until a coating layer of a preset thickness is formed, the steps of applying a coating solution to a pretreated electrode substrate (S31), drying an electrode substrate with the applied coating solution (S32), and performing heat treatment on a dried electrode substrate (S33) may be arranged to be repeated sequentially 5 to 10 times until a coating layer of a preset thickness is formed.

[0104] At this time, the preset final coating thickness can be set to a range of 3 to 6 μm.

[0105] Next, in the step (S35) where a coating layer of a predetermined thickness is formed and a heat sintering process is performed to manufacture an insoluble electrode, if the predetermined final coating thickness is satisfied, the coating liquid application, drying, and heat treatment processes for the electrode substrate (10) may be stopped and the final heat sintering may be performed to manufacture the insoluble electrode (20).

[0106] At this time, the heat sintering process may be arranged to be carried out for 30 to 90 minutes within a temperature range of 550°C to 850°C.

[0107] The lifespan of the insoluble electrode (20) prepared in this way can be measured in the following way.

[0108] First, a specimen with a width of 25 mm x a height of 25 mm is prepared, and the electrolytic solution is an electrolytic cell with a sulfuric acid concentration of 20% or less. The specimen spacing is set to 20 mm, the current density is 500 ASD or less, the operating temperature is 70°C or less, and the voltage is 10 V or less, so that the lifespan of the insoluble electrode (20) can be checked. The lifespan test is conducted until a rapid reaction occurs in the voltage graph, and when a rapid reaction occurs, it can be determined that the lifespan has ended.

[0109] Figure 6 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 200x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0110] Figure 7 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 500x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0111] Figure 8 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 2,000x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0112] Figure 9 is an image of SE (Secondary Electrons) and BSE (Backscattered Electrons) taken with a scanning electron microscope at 10,000x magnification to confirm the microstructure and elemental composition of the insoluble substrate according to the present invention.

[0113] Referring to Figures 6 to 9, the microstructure and composition of the specimen surface were confirmed using a scanning electron microscope. The analysis conditions were Acc. Voltage: 3kV, Current: 1.6nA, and Magnification 200x / 500x / 2000x / 5000x / 10000x. At this time, it can be seen that different morphologies were observed in each region at 2,000x and 10,000x magnification.

[0114] FIG. 10 is a graph showing the qualitative or quantitative analysis of elements on the surface of a material using an Energy Dospersive Spectroscope for an insoluble substrate according to the present invention.

[0115] Referring to Fig. 10, elements on the surface of the material were qualitatively or quantitatively analyzed using an Energy Dospersive Spectroscope. The analysis conditions were surface analysis and depth profile, with an etching time of 5 sec / 5 times.

[0116] FIG. 11 is an image taken at 5,000x magnification with a scanning electron microscope to confirm the elemental composition of the insoluble substrate according to the present invention, and FIG. 12 is an image taken to confirm the molecular structure and crystal structure of the mixture of the insoluble substrate according to the present invention.

[0117] Figures 13 and 14 are images taken to confirm the molecular structure and crystal structure of iridium and tantalum when mixed together.

[0118] Referring to Figures 11 to 14, to confirm the molecular structure and crystal structure when iridium and tantalum are mixed, 2400g of paper and 2400g of slide glass were measured, and the analysis conditions were Laser: 532nm, Exposure time: 0.3s, Number of accumulation: 10, Accumulation cycle: 1s, ND Filter: 10%.

[0119] Figures 15 to 17 are images of an insoluble substrate taken by an X-ray photoelectron spectrometer.

[0120] Referring to FIGS. 15 to 17, the X-ray Photoelectron Spectroscope (XPS) is used to determine the composition and chemical bonding state of a sample surface and to measure the depth profile of each element by measuring the energy of photoelectrons emitted after X-rays are incident on the surface of a sample.

[0121] The analysis conditions were surface analysis and depth profile, and etching time: 5 sec / 5 times.

[0122] Figure 18 is a table showing the effect of pretreatment on the electrode substrate, Figure 19 is a table showing the effect of coating solution on the electrode substrate, and Figure 20 is a table showing the effect of drying and heat treatment on the electrode substrate.

[0123] The effect of the present invention according to the above configuration is that the speed and efficiency of the electrochemical reaction can be increased by using an insoluble titanium substrate coated with a platinum compound. This can improve productivity by increasing the electrodeposition rate of copper during the production of electrolytic copper foil.

[0124] In addition, according to the present invention, corrosion or performance degradation of the electrode can be minimized by coating the anode with iridium oxide, which has resistance to oxygen generation. This ensures the stability of the electrode during the electrolytic copper foil manufacturing process, enabling long-term use.

[0125] In addition, according to the present invention, the quality of the electrolytic copper foil produced is improved due to the high reactivity and stability of the insoluble electrode (20). High-quality copper foil increases applicability in the electronic device and battery industries and contributes to maximizing the performance of the final product.

[0126] Furthermore, according to the present invention, in addition to the production of electrolytic copper foil, it can be applied to various fields such as brine electrolysis, wastewater treatment, and electrochemical cleaning. This versatility increases the potential for commercialization of the technology and can promote its utilization in various industrial sectors.

[0127] Although the foregoing description of the present invention has been illustrated with reference to the drawings, it is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single unit may be implemented in a distributed manner, and components described as distributed may likewise be implemented in a combined form. Furthermore, the described techniques may be performed in a different order than the described method.

[0128] The embodiments described in this specification and the accompanying drawings are merely illustrative of some of the technical ideas included in the present invention. Accordingly, the scope of the present invention is defined by the claims set forth below, and all modifications or variations derived from the meaning and scope of the claims and equivalent concepts thereof should be interpreted as being included within the scope of the present invention.

[0129]

[0130] <Explanation of Symbols>

[0131] 10: Electrode substrate

[0132] 11: Uneven parts

[0133] 20: Insoluble electrode

Claims

1. A step in which pretreatment is performed on the electrode substrate; A step of preparing a coating solution for coating the pretreated electrode substrate; and The method includes the step of manufacturing an insoluble electrode by coating the electrode substrate with the manufactured coating solution, and A method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized in that the electrode substrate is provided with a titanium material, and the coating layer is formed by repeating the process of applying, drying, and heat treating the coating solution in a predetermined amount several times.

2. In Paragraph 1, The step of performing pretreatment on the above substrate is, A step in which a sandblasting process is performed on the electrode substrate to create an uneven surface; A step of performing a first cleaning of the electrode substrate on which the above-mentioned uneven portion is formed; A step of performing etching on the cleaned electrode substrate; A step of performing a secondary cleaning of the electrode substrate on which etching has been performed; and A method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized by including a step of drying the electrode substrate on which a second washing has been performed.

3. In Paragraph 2, In the step where a sandblasting process is performed on the electrode substrate to create an uneven surface, A method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, characterized in that the above sandblasting process is performed using an alumina oxide abrasive.

4. In Paragraph 2, The above first wash and the above second wash are, High-pressure water cleaning and ultrasonic cleaning are provided for the above electrode substrate, and A method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized in that the above ultrasonic cleaning is performed for 30 to 60 minutes at a frequency of 30 to 40 kHz while the electrode substrate is immersed in a cleaning solution diluted with an alkaline cleaning agent and hot water.

5. In Paragraph 2, In the step where etching is performed on the above-mentioned cleaned electrode substrate, A method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, characterized in that the electrode substrate is prepared to be etched for 10 to 25 minutes at a concentration of 25 to 30% in a temperature range of 30 to 80 degrees.

6. In Paragraph 2, The step of drying the electrode substrate after the above secondary washing is, A method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized in that the electrode substrate is arranged to be completely dried at a temperature of 70 to 150 degrees for at least 20 minutes.

7. In Paragraph 1, The step of preparing a coating solution for coating the pretreated electrode substrate is: A step of forming a mixture by mixing two or more elements among platinum group elements, iridium oxide (Ir), ruthenium chloride (Ru), platinum (Pt), and tantalum chloride (Ta); A step in which the above mixture is stirred with alcohol and the above element is dissolved; and A method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, characterized by including a step of irradiating the dissolved element with ultrasound to produce a coating solution.

8. In Paragraph 7, The step in which the above mixture is stirred and dissolved with alcohol is, A method for manufacturing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized by being arranged to be stirred at a temperature of 30 to 50 degrees at 260 to 550 RPM for 2 to 4 hours.

9. In Paragraph 7, The above alcohol is, A method for preparing a coating of an insoluble electrode for manufacturing electrolytic copper foil, characterized by being prepared from one or more of isopropyl alcohol, chlorine, butanol, and ethanol.

10. In Paragraph 1, The step of manufacturing an insoluble electrode by coating the electrode substrate with the manufactured coating solution is as follows: A step of applying the coating solution to the pretreated electrode substrate; A step of drying the electrode substrate coated with the above coating solution; A step of performing heat treatment on the dried electrode substrate; A step in which the steps of applying the coating solution, drying the electrode substrate, and performing the heat treatment are repeated sequentially until a coating layer of a predetermined thickness is formed; and A method for manufacturing a coating of an insoluble electrode for manufacturing an electrolytic copper foil, characterized by including a step in which, when a coating layer of the above-determined thickness is formed, a heat sintering process is performed to manufacture the above-determined insoluble electrode.

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