Continuous plating device for metal foil, continuous plating method for metal foil, and method for managing electrolyte solution in continuous plating device

Abstract

The present invention relates to a manufacturing device and a manufacturing method thereof, which can manufacture metal foils such as iron-nickel alloy foils, nickel foils and copper foils with high quality through continuous plating. The metal foil continuous plating apparatus according to the present invention comprises: an electrolytic bath for accommodating an electrolyte; a positive electrode disposed inside the electrolytic cell; a negative electrode disposed at a predetermined interval from the positive electrode to face the positive electrode; and a power supply device for applying a current to the positive electrode and the negative electrode, in which an electrolyte is supplied to one side of a space formed between the positive electrode and the negative electrode, and the electrolyte is discharged from the other side of the space; wherein a height of one side where the electrolyte is supplied is higher than a height of the other side such that the electrolyte flows through a space formed between the positive electrode and the negative electrode by means of a potential difference between the one side and the other side, and when the electrolyte passes through the space formed between the positive electrode and the negative electrode, metal ions contained in the electrolyte are electrodeposited on the negative electrode, thus, a metal foil is formed.

Description

Technical Field

[0001] The present invention relates to a metal foil continuous plating device, a metal foil continuous plating method and a method for managing an electrolyte of a continuous plating device, and more specifically, to a continuous plating device capable of manufacturing metal foils such as iron-nickel alloy foil, nickel foil and copper foil with high quality through a continuous plating method, a continuous plating method and a method for managing an electrolyte of a continuous plating device. Background Art

[0002] Invar alloy is an alloy having a very low coefficient of thermal expansion, and is a material used in various fields such as precision instruments, bimetallic devices, shadow masks, lead frames of integrated circuits, display sealants, and metal masks of organic light emitting diodes.

[0003] In order to increase the resolution of an OLED applied to a smartphone, it is necessary to reduce the thickness of a fine metal mask (FMM) used in a deposition process.

[0004] This fine metal mask is manufactured by a top-down method through casting-rolling-etching, but since it is difficult to achieve a fine metal mask with a thickness of less than 10 μm by the top-down method, attempts have been made to use a method in which a thin Invar alloy foil is manufactured by an electroforming method and then etched, or a fine metal mask having a pattern formed thereon is directly manufactured by an electroforming method.

[0005] On the other hand, since Invar is composed of an iron-nickel alloy, it is difficult to achieve the physical properties required for a metal mask if the uniformity of the alloy composition is not maintained in the plating solution. Therefore, so much research and development has been conducted to maintain the uniformity of the alloy composition, but to date, Invar foil manufactured by electroforming technology has not yet met the physical properties required for a fine metal mask.

[0006] In addition, an organic component such as saccharin or thiourea is added to the Invar electrolyte to increase the density of the plated Invar alloy foil or control the internal stress, and the organic component may be co-deposited into the crystal during the plating process, or may also be precipitated in the form of FeS or the like at the grain boundary (particularly near the triple point) during the heat treatment process. The co-deposition of impurities as described above may cause adverse effects such as increasing the thermal expansion coefficient of the manufactured Invar alloy foil and increasing brittleness. Therefore, in order to improve the properties of the Invar alloy foil manufactured by continuous plating, an electrolyte management technology for reducing factors causing the thermal expansion coefficient is required, but few technologies have been developed in this regard. Summary of the invention

[0007] Technical issues

[0008] An object of the present invention is to provide a metal foil continuous plating apparatus capable of manufacturing metal foils such as nickel foil and copper foil, and alloy foils such as Fe-Ni alloy foil with high quality.

[0009] Another object of the present invention is to provide a metal foil continuous plating method which can produce metal foils such as nickel foil and copper foil, and alloy foils such as Fe-Ni alloy foil with high quality.

[0010] Still another object of the present invention is to provide a method of managing an electrolyte that is capable of maintaining uniform physical properties of a metal foil formed during continuous plating and minimizing factors that adversely affect the physical properties.

[0011] Technical Solution

[0012] One aspect of the present invention provides a metal foil continuous plating device, which includes: an electrolytic cell for accommodating an electrolyte; a positive electrode arranged in the electrolytic cell; a negative electrode arranged at a predetermined interval from the positive electrode to face the positive electrode; and a power supply device for applying current to the positive electrode and the negative electrode, wherein the electrolyte is supplied to one side of a space formed between the positive electrode and the negative electrode, and the electrolyte is discharged from the other side of the space, wherein the height of the one side to which the electrolyte is supplied is formed to be higher than the height of the other side, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of the potential energy difference between the one side and the other side, and the electrolyte passes through the space formed between the positive electrode and the negative electrode, during which time the metal ions contained in the electrolyte are electrodeposited on the negative electrode, thereby forming a metal foil.

[0013] Another aspect of the present invention provides a continuous metal foil plating method, which is a method for: supplying an electrolyte between a positive electrode and a negative electrode, wherein the negative electrode is arranged at a predetermined interval with the positive electrode to face the positive electrode; applying an electric current to the positive electrode and the negative electrode, thereby forming a metal foil on the surface of the negative electrode, wherein the height of one side of the space formed between the positive electrode and the negative electrode is formed to be higher than the height of the other side thereof, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of the potential energy difference between the one side and the other side, and passes through the space formed between the positive electrode and the negative electrode.

[0014] Another aspect of the present invention provides a method for managing an electrolyte, the method comprising: collecting electrolyte from a plating tank or an electrolyte storage tank that supplies the electrolyte; selectively diluting the electrolyte with a diluent solution at a predetermined ratio, thereby adjusting the concentration of the electrolyte to an undiluted state or a diluted state of a predetermined ratio; irradiating the electrolyte with the adjusted concentration with light to analyze the light absorption characteristics of the electrolyte with the adjusted concentration, thereby analyzing the composition of the electrolyte; and adjusting the composition of the electrolyte of the plating tank based on the difference between the analyzed composition of the electrolyte and the preset composition of the electrolyte, wherein, if the light absorption characteristic analysis is performed for the ultraviolet region, the analysis is performed in a state where the electrolyte is diluted with the diluent solution at a predetermined ratio.

[0015] Beneficial Effects

[0016] According to the present invention, by using the potential energy difference caused by the height difference between the side where the electrolyte is supplied and the side where the electrolyte is discharged, the electrolyte is supplied by controlling the electrolyte to pass between the positive electrode and the negative electrode, so that the amount of electrolyte supplied between the positive electrode and the negative electrode and the amount of electrolyte discharged are both achieved in a stable state or a state very close to a stable state, which can significantly improve the uniformity of the composition of the electrolyte in contact with the negative electrode during electrodeposition compared to the prior art.

[0017] Therefore, the Fe-Ni alloy foil produced by the apparatus of the present invention is expected to satisfy the characteristics required for a fine metal mask.

[0018] Furthermore, if the apparatus or method according to the present invention is used to manufacture pure metal foils such as nickel foil and copper foil, the density of the formed foil is further increased, thereby obtaining a metal foil having improved properties compared to a metal foil manufactured using a typical plating apparatus. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a perspective view of a metal foil continuous plating apparatus according to an embodiment of the present invention.

[0020] Figure 2 1 is a partially exploded perspective view of a metal foil continuous plating apparatus according to an embodiment of the present invention.

[0021] Figure 3 is a cross-sectional view of a metal foil continuous plating apparatus according to an embodiment of the present invention.

[0022] Figure 4 is a cross-sectional view of a metal foil continuous plating apparatus according to another embodiment of the present invention.

[0023] Figure 5 FIG. 4 is a schematic diagram of a metal foil continuous plating device according to another embodiment of the present invention.

[0024] Figure 6 FIG. 4 is a schematic diagram of a metal foil continuous plating device according to another embodiment of the present invention.

[0025] Figure 7 Shows the results of UV-visible spectra measured when the iron-nickel electrolyte was diluted with ultrapure water.

[0026] Figure 8 a shows the results of UV-visible spectra measured when 97 g / L NiSO4 solution was diluted with ultrapure water, Figure 8 b shows the result of UV-visible spectrum measured when 85 g / L FeSO4 solution was diluted with ultrapure water.

[0027] Fig. 9 a shows the results of UV-visible spectra measured after exposing 85 g / L FeSO4 solution to air for 24 hours and then diluting the solution with ultrapure water, Fig. 9 b shows the results of UV-visible spectra measured after exposing a 85 g / L FeSO4 solution to air for 24 hours, removing the precipitate, and then diluting the solution with ultrapure water.

[0028] Fig.10 a shows the result of UV-visible spectrum measured when 2 g / L ascorbic acid solution was diluted with ultrapure water, Fig.10 b shows the result of UV-visible spectrum measured when 2.6 g / L saccharin solution was diluted with ultrapure water.

[0029] Fig.11 Shown is the UV-Vis spectrum of a standard plating solution (97 g / L Ni, 85 g / L FeSO4, 2.6 g / L saccharin, 1.0 g / L ascorbic acid, 25 g / L boric acid and 0.2 g / L lauryl) analyzed using a short path cell (transmission length: 0.1 mm), as well as the UV-Vis spectrum of a plating solution analyzed using a normal cell (transmission length: 10 mm) after the plating solution was diluted to 1 / 100.

[0030] Fig.12 Results of UV-visible spectra of 30 g / L of sodium chloride, 0.2 g / L of sodium dodecyl sulfate (hereinafter, referred to as "lauryl"), and 25 g / L of boric acid are shown.

[0031] Fig.13 a shows the results of UV-visible spectra of the case where NiSO4 and various additives are mixed, Fig.13 b shows the results of UV-visible spectra of the case where FeSO4 and various additives are mixed.

[0032] Fig.14 a shows that by adding a predetermined amount of Fe3+ The results of UV-visible spectra obtained by adding 1.0 g / L ascorbic acid and diluting the mixture to 1 / 200 in ultrapure water, Fig.14 b shows that by adding a predetermined amount of Fe 3+ UV-Vis spectra obtained in an undiluted state with addition to 1.0 g / L ascorbic acid.

[0033] Fig.15 Schematic diagram of a plating solution analysis process according to one embodiment of the present invention.

[0034] Fig.16 Displays the training and validation sets used for the partial least squares analysis algorithm.

[0035] Fig.17 Display by Fig.16 Results of UV-Vis spectra obtained for each solution are shown, wherein the solution was diluted to 1 / 200 in the 200-500 nm region and in an undiluted state in the 500 nm-1000 nm region.

[0036] Fig.18 Display usage Fig.16 and Fig.17 The data are calibrated from partial least squares analysis. DETAILED DESCRIPTION

[0037] Hereinafter, the configuration and operation of the embodiments of the present invention will be described with reference to the drawings.

[0038] When describing the present invention, when it is determined that the detailed description may unnecessarily obscure the gist of the present invention, the detailed description of the related known functions or configurations will be omitted. In addition, when a part is referred to as "comprising" any component, it means that the part may further include other components rather than excluding other components, unless otherwise specified.

[0039] In the present invention, the “steady state” refers to a state in which the amount of the electrolyte solution flowing into the space between the positive electrode and the negative electrode is the same as the amount of the electrolyte solution discharged from the space between the positive electrode and the negative electrode.

[0040] [First embodiment]

[0041] A first embodiment of the present invention is a metal foil continuous plating device, comprising: an electrolytic cell for accommodating an electrolyte; a positive electrode arranged in the electrolytic cell; a negative electrode arranged at a predetermined interval from the positive electrode to face the positive electrode; and a power supply device for applying current to the positive electrode and the negative electrode, wherein the electrolyte is supplied to one side of a space formed between the positive electrode and the negative electrode, and the electrolyte is discharged from the other side of the space, wherein the height of the one side to which the electrolyte is supplied is formed to be higher than the height of the other side, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of a potential energy difference between the one side and the other side, and the electrolyte passes through the space formed between the positive electrode and the negative electrode, during which time metal ions contained in the electrolyte are electrodeposited on the negative electrode, thereby forming a metal foil.

[0042] As described above, if the electrolyte is made to flow by means of the potential energy difference between the position where the electrolyte is supplied and the position where the electrolyte is discharged, it is advantageous that the electrolyte is maintained in a stable state or a state very close to the stable state in the space between the positive electrode and the negative electrode, thereby maintaining the composition of the electrolyte uniform between the positive electrode and the negative electrode where electrodeposition occurs, and also reducing the generation of bubbles or eddies during the flow of the electrolyte, so that a metal foil with excellent uniformity can be obtained. Therefore, in the case of alloy plating, the uniformity of the composition over the entire metal foil can be increased, and in the case of single metal plating, the density can be increased.

[0043] The electrolyte level H on the electrolyte supply side 入 The electrolyte level H on the electrolyte discharge side 出 The difference between 入 -H 出 There is no particular limitation as long as the electrolyte can flow through the potential energy. 入 -H 出 It can be greater than 0, or can be set to a value greater than or equal to the interval between the positive electrode and the negative electrode. In addition, the difference H can be adjusted differently according to the required flow rate of the electrolyte. 入 -H 出 For example, if the flow rate increases, the height difference may increase, and if the flow rate decreases, the height difference may decrease.

[0044] In the first embodiment, an electrolyte guide member may be further included, which is disposed on the electrolyte supply side of the positive electrode and guides the electrolyte to be supplied to the space formed between the positive electrode and the negative electrode at a predetermined angle and rate.

[0045] The electrolyte guiding member helps the electrolyte to enter between the positive electrode and the negative electrode at a predetermined angle and rate while maintaining a laminar flow, which advantageously implements the electrolyte supplied between the positive electrode and the negative electrode in a stable state or a state very close to a stable state.

[0046] In the first embodiment, an electrolyte storage tank may be further included, which recovers the electrolyte discharged through the space formed between the positive electrode and the negative electrode, and processes the recovered electrolyte. The processing of the electrolyte includes removing impurities generated during the electrodeposition process, or adding necessary components of the electrolyte to maintain the composition in the initial state.

[0047] In the first embodiment, the electrolyte supplied through the electrolyte storage tank may be supplied to a lower portion of one side of the electrolyte guide member and rise to an upper portion of the electrolyte guide member to be supplied to a space between the positive electrode and the negative electrode.

[0048] In the first embodiment, as the electrolyte, various electrolytes for forming metal foils can be used, such as an electrolyte for forming an iron-nickel alloy foil, an electrolyte for forming a nickel foil, and an electrolyte for forming a copper foil. For example, the electrolyte for forming an Fe-Ni alloy foil may be iron sulfate (FeSO4.7H2O), nickel sulfate hexahydrate (NiSO4.6H2O), boric acid (H3BO3), sodium saccharin (C7H4NO3SNa), sodium dodecyl sulfate (C7H4NO3SNa), and sodium sulphate (C7H4NO3SNa). 12 H 25 More specifically, based on 1 part by weight of ferric sulfate, the electrolyte may include 0.49 to 0.94 parts by weight of nickel sulfate hexahydrate, 0.20 to 0.31 parts by weight of boric acid, 0.009 to 0.044 parts by weight of saccharin sodium, 0.0009 to 0.0033 parts by weight of sodium lauryl sulfate, and 0.23 to 0.37 parts by weight of sodium chloride.

[0049] In the first embodiment, the positive electrode can be formed into a plate shape having a downwardly concave arc, and as the positive electrode material, any material can be used without particular limitation as long as it has the characteristics that can be used as a positive electrode. In addition, the shape of the positive electrode can be variously adjusted according to the shape of the negative electrode arranged to face the positive electrode.

[0050] In the first embodiment, the negative electrode may be formed in a drum shape having a circular cross section.

[0051] In the first embodiment, the drum-shaped negative electrode is composed of a clad metal having two or more layers, wherein the surface layer may be composed of a first metal such as titanium, a titanium alloy, or stainless steel, and the inner layer may be composed of copper (Cu), silver (Ag), aluminum (Al), or an alloy thereof (copper alloy, silver alloy, or aluminum alloy) having excellent conductivity. The clad metal may be manufactured by various methods, such as welding two thin plates, bonding them with a bonding material, electroplating, or coating.

[0052] In the first embodiment, irregularities (or patterns) may be formed on the surface of the negative electrode so as to make the surface roughness of the metal foil formed on the negative electrode within a predetermined value range.

[0053] In the first embodiment, the electrolyte guide may have a flat shape inclined at a predetermined angle, or may be curved, and by adjusting the shape (inclination or curvature) of the electrolyte guide member, the entrance angle of the electrolyte supplied to the space formed between the positive electrode and the negative electrode may be adjusted.

[0054] In the first embodiment, an auxiliary guide (cover) for leveling the height of the electrolyte may be arranged on the upper side of the electrolyte guide member.

[0055] By means of the auxiliary guide (cover), the height of the electrolyte can be kept constant with respect to the entire drum-type negative electrode.

[0056] The entry angle of the electrolyte may be adjusted differently, for example, to be substantially the same as the curvature of the positive and negative electrodes.

[0057] In the first embodiment, the shape of the position for discharging the electrolyte can be a shape that allows the electrolyte to be discharged directly into the electrolyte storage tank after passing between the positive electrodes and the positive electrodes facing each other, or to be discharged into the electrolyte storage tank after passing through a discharge guide of a flat shape, a concave shape, a convex shape, etc.

[0058] In the first embodiment, the electrolyte may be provided with a member for suppressing the occurrence of an eddy current to suppress the generation of bubbles during the process of discharging the electrolyte into the electrolyte storage tank.

[0059] In the first embodiment, the surface of the negative electrode may have a predetermined pattern consisting of an area where electrodeposition occurs and an area where electrodeposition does not occur. The pattern of the negative electrode is transferred to a metal foil formed by the negative electrode having the pattern, so that the metal foil can be immediately molded into a shape such as a metal mesh or a fine metal mask.

[0060] [Second Embodiment]

[0061] A second embodiment of the present invention is a metal foil continuous plating method, which is used for the following method: an electrolyte is supplied between a positive electrode and a negative electrode, and a current is applied to the positive electrode and the negative electrode to form a metal foil on the surface of the negative electrode, wherein the negative electrode is arranged at a predetermined interval with the positive electrode so as to face the positive electrode, wherein the height of one side of the space formed between the positive electrode and the negative electrode is formed to be higher than the height of the other side thereof, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of the potential energy difference between the one side and the other side, and passes through the space formed between the positive electrode and the negative electrode, during which the metal foil is formed on the surface of the negative electrode.

[0062] [Third Embodiment]

[0063] A third embodiment of the present invention is a method for managing an electrolyte, the method comprising: collecting electrolyte from a plating tank or an electrolyte storage tank that supplies electrolyte; selectively diluting the electrolyte with a diluent solution at a predetermined ratio, thereby adjusting the concentration of the electrolyte to an undiluted state or a diluted state at a predetermined ratio; irradiating the electrolyte with the adjusted concentration with light to analyze the light absorption characteristics of the electrolyte with the adjusted concentration, thereby analyzing the composition of the electrolyte; and adjusting the composition of the electrolyte of the plating tank based on the difference between the analyzed composition of the electrolyte and the preset composition of the electrolyte, wherein, if the light absorption characteristic analysis is performed for the ultraviolet region, the analysis is performed in a state where the electrolyte is diluted with the diluent solution at a predetermined ratio.

[0064] In the electrolyte analysis method of the present invention, when analyzing the composition of the electrolyte, the electrolyte diluted with a diluent at a predetermined ratio is analyzed instead of the undiluted electrolyte, thereby improving the analysis accuracy.

[0065] In a third embodiment, the dilution solution preferably contains water (H2O), has no light absorption in the wavelength range of 200nm to 500nm, and has a dilution ratio of 1 / 2 to 1 / 400 between the electrolyte and the dilution solution. Here, the absence of absorption in the wavelength range of 200nm to 500nm not only means that no absorption is achieved at all, but also means that the absorption is achieved at a noise level that does not affect the analysis.

[0066] This is because if the dilution ratio of the electrolyte is less than 1 / 2, or greater than 1 / 400, it is difficult to improve the accuracy of the absorption characteristic analysis of the components detected in the ultraviolet region. Here, a dilution ratio of 1 / 2 refers to a dilution solution of a mixture of electrolyte equivalent to twice the volume, and 1 / 400 refers to a dilution solution of a mixture of electrolyte equivalent to 400 times the volume. More preferably, the dilution ratio of the electrolyte can be 1 / 50 to 1 / 200.

[0067] In the third embodiment, when the absorption characteristic analysis is performed, if the wavelength region of 300 nm to 1000 nm is analyzed, the electrolyte solution can be analyzed in an undiluted state without being diluted.

[0068] This is because, if the visible light region or the wavelength region of 300 nm to 1000 nm close to the visible light region is analyzed, the analysis accuracy can be improved when the electrolyte is analyzed in an undiluted state rather than in a diluted state.

[0069] In a third embodiment, the spectrum analysis may include a first spectrum analysis for analyzing with respect to a wavelength range of 10 nm to 500 nm, and a second spectrum analysis for analyzing with respect to a wavelength range of 300 nm to 1000 nm.

[0070] By UV-visible spectroscopy, the composition of various components contained in the iron-nickel electrolyte can be analyzed.

[0071] In the third embodiment, the electrolyte mainly contains Fe 2+ 、Ni 2+ and saccharin.

[0072] In a third embodiment, electrolyte composition analysis may include processing data obtained by absorption characteristics analysis through multivariate calibration.

[0073] In particular, various metal ions and organic components contained in the iron-nickel electrolyte can be rapidly analyzed with high reliability through multivariate calibration.

[0074] Multivariate calibration may be performed, for example, by a partial least squares (PLS) algorithm.

[0075] By using the partial least squares (PLS) algorithm, highly reliable analysis results can be obtained for the composition of various components contained in the iron-nickel electrolyte.

[0076] In a third embodiment, a partial least squares algorithm can be optimized to analyze the Ni 2+ , Fe 2+ , Fe 3+ , stress relaxants, antioxidants or iron ion precipitates, but the present invention is not limited to the above components.

[0077] In the third embodiment, the stress relaxant may include saccharin, and the antioxidant may include ascorbic acid, but the present invention is not limited to the analysis of the electrolyte including the above stress relaxant or antioxidant.

[0078] In the third embodiment, the wavelength of the light may be 10 nm to 1000 nm.

[0079] Through the above, the ultraviolet-visible-near infrared region can be analyzed, so that various components contained in the electrolyte can be analyzed.

[0080] <Example 1>

[0081] Figure 1 is a perspective view of a metal foil continuous plating device according to Example 1 of the present invention, Figure 2 is a partially exploded perspective view of a metal foil continuous plating device according to Example 1 of the present invention, Figure 3 4 is a cross-sectional view of a metal foil continuous plating apparatus according to Example 1 of the present invention.

[0082] Reference Figures 1 to 3 The metal foil continuous plating device according to Example 1 of the present invention includes a plating tank 100, an electrolyte guide member 200 disposed in the plating tank 100, a positive electrode 300 connected to one side of the upper surface of the electrolyte guide member 200, a negative electrode 400 arranged at a predetermined interval with the positive electrode 300, and an electrolyte storage tank 500 arranged at a lower portion of the plating tank 100.

[0083] The plating tank 100 is composed of a container in which a space is formed, and in an embodiment of the present invention, although the container is not equipped with a lid for covering its upper portion, a lid for covering the upper portion may also be equipped. In addition, the space is formed in a generally rectangular shape, but is not limited to this shape, and the space may be formed in various shapes, such as a rectangular shape, a circular shape, and an elliptical shape.

[0084] like Figure 2 As shown, the electrolyte guiding member 200 is formed by including a positive electrode attachment portion 210 and an electrolyte guiding portion 220, wherein the positive electrode attachment portion 210 is recessed downward and attached to the positive electrode, and the electrolyte guiding portion 220 guides the electrolyte supplied from the electrolyte storage tank 500 into the space between the positive electrode 300 and the negative electrode 400 at a controlled angle and rate.

[0085] The positive electrode attachment portion 210 is formed to be recessed downward to correspond to the shape of the positive electrode.

[0086] The electrolyte guide 220 has a gently convex shape. In the embodiment of the present invention, the electrolyte guide 220 is formed in a gently convex shape, but it can also be formed in various shapes, such as an inclined shape. Figure 3 As shown in the upper part of , the electrolyte guide 220 affects the angle of entry and rate of the electrolyte, and for installation, the angle can be adjusted to various angles (θ1, θ2, θ3, θ4, etc.) according to the plating conditions.

[0087] The left end portion of the positive electrode attachment portion 210 in the figure is formed to be open to allow the electrolyte that has passed between the positive electrode and the negative electrode to be directly discharged downward.

[0088] The maximum height of the electrolyte guide 220 is the height of the position where the electrolyte is supplied, and is formed to be higher than the height of the position where the electrolyte is discharged. Therefore, there is a potential difference between the position where the electrolyte is supplied to the electrolyte guide 220 and the position where the electrolyte is discharged, so that when the electrolyte is supplied to the upper part of the electrolyte guide 220, the electrolyte can flow to the position where the electrolyte is discharged by its own weight without a force applied from the outside.

[0089] In addition, the electrolyte guide member 200 forms a partition wall 230 for partitioning a space (first space) for supplying electrolyte and a space (second space) for discharging electrolyte in the plating tank 100 so that the supplied electrolyte and the discharged electrolyte are not mixed with each other.

[0090] The electrolyte dropped from the position where the electrolyte is discharged is recovered to the electrolyte storage tank 500 through the inlet 510 of the electrolyte storage tank 500 in the second space, and the electrolyte discharged through the outlet 520 is supplied to the first space.

[0091] The positive electrode 300 may be formed in a plate shape having a cross section approximately in an arc shape, but is not necessarily limited to the plate shape and is not particularly limited as long as the positive electrode has an opposing surface maintaining a predetermined interval with the negative electrode 400 .

[0092] For example, the positive electrode 300 itself may be in a shape supported within the plating tank 100 without being attached to the electrolyte guide member 200 .

[0093] The negative electrode 400 is formed in a roll shape extending a predetermined length in a length direction for continuous electroplating. The negative electrode 400 is formed on a rotating shaft 410 and is rotationally driven by a driving device (not shown).

[0094] The negative electrode may be formed of copper and titanium-coated materials having excellent conductivity, and the coating material is preferably used to form a uniform current density throughout the negative electrode by quickly transferring a current applied from the outside to the entire negative electrode via copper.

[0095] It may be preferred that the interval between the positive electrode 300 and the negative electrode 400 is always maintained at the same interval to allow the electrolyte to maintain a stable state. According to the need to control the composition of the electrolyte or control the composition of the formed foil, the interval between the positive electrode 300 and the negative electrode 400 may be gradually increased or decreased from the supply side of the electrolyte toward the discharge side thereof.

[0096] The electrolyte storage tank 500 is located at the lower part of the plating tank 100 to recover the electrolyte on which the electrodeposition treatment has been performed through the electrolyte recovery port 120 connected to the second space S2 of the plating tank 100, and to supply the treated electrolyte to the first space S1 through the electrolyte supply port 110 connected to the first space S1 of the plating tank 100.

[0097] Meanwhile, in Embodiment 1 of the present invention, the electrolyte storage tank 500 is installed at the lower portion of the plating tank 100 , but may also be installed at a different position, such as parallel to the plating tank 100 , or installed at the upper portion of the plating tank 100 .

[0098] In addition, the electrolyte recovery tank and the electrolyte supply tank may be used separately, instead of treating the electrolyte through the electrolyte storage tank 500 and supplying the treated electrolyte to the plating tank 100. In this case, the electrolyte recovered in the electrolyte recovery tank may be processed, such as impurity removal, composition control, etc., and then supplied to the electrolyte supply tank.

[0099] Using the metal foil continuous plating apparatus 10 as described above, a metal foil can be manufactured as follows.

[0100] Reference Figure 3 , the electrolyte stored in the electrolyte storage tank 500 is supplied to the lower part of the first space S1 through the electrolyte supply port 110. When the electrolyte is supplied, the electrolyte fills the first space S1, and when the liquid level of the electrolyte is higher than the upper end of the electrolyte guide 220, the electrolyte flows downward into the space between the positive electrode 300 and the negative electrode 400 by its own weight, and the flowing electrolyte passes through the space between the positive electrode 300 and the negative electrode 400 and is discharged to the second space S2.

[0101] Then, when the amount of electrolyte supplied to the space between the positive electrode 300 and the negative electrode 400 and the amount of electrolyte discharged reach a steady state or a state very close to the steady state, the negative electrode 400 is rotationally driven and power is applied to allow electrodeposition to occur on the negative electrode 400. Of course, the negative electrode 400 may be rotationally driven while the electrolyte is supplied or before reaching a steady state.

[0102] <Example 2>

[0103] Figure 4 is a cross-sectional view of a metal foil continuous plating device according to another embodiment of the present invention.

[0104] The metal foil continuous plating device according to Example 2 is different from the metal foil continuous plating device according to Example 1 in that an electrolyte discharge guide portion 240 extending in a curved manner to the outside of the negative electrode is formed on one side of the electrolyte discharge portion in the same manner as on one side of the electrolyte supply portion, thereby allowing the electrolyte to be discharged to be discharged smoothly, and therefore, having a structure that is conducive to maintaining laminar flow (or steady state) on the discharge side.

[0105] <Example 3>

[0106] Figure 5 FIG. 4 is a schematic diagram of a metal foil continuous plating device according to another embodiment of the present invention.

[0107] The metal foil continuous plating apparatus according to Embodiment 3 is an example of an apparatus that performs plating by arranging in parallel the metal foil continuous plating apparatus according to Embodiment 1. In Embodiment 3, two metal foil continuous plating apparatuses are arranged, but three or more apparatuses may be arranged and used if necessary.

[0108] The metal foil continuous plating apparatus according to Example 3 shows a process in which an electrodeposited foil is peeled off from a first metal foil continuous plating apparatus 10 and then introduced into a second metal foil continuous plating apparatus 10 ′ to allow two-layer electrodeposition to be performed continuously.

[0109] If the metal foil formed in the first metal foil continuous plating device 10 is thin, additional plating is partially required, or a different type of metal needs to be plated, the metal foil continuous plating device according to Embodiment 3 uses a method of electroplating by the second metal foil continuous plating device 10'. In the case where additional plating is partially required, the surface of the negative electrode formed in the second metal foil continuous plating device 10' can be divided into an area where electrodeposition occurs and an area where electrodeposition does not occur.

[0110] In addition, since the first metal foil continuous plating apparatus 10 and the second metal foil continuous plating apparatus 10' have separate plating tanks, electrolytes of different compositions can be used, in which case metal foils having different compositions in the thickness direction can also be manufactured.

[0111] <Example 4>

[0112] Figure 6 FIG. 4 is a schematic diagram of a metal foil continuous plating device according to another embodiment of the present invention.

[0113] The metal foil continuous plating apparatus according to Example 4 is different from the metal foil continuous plating apparatus according to Example 3 in that two metal foil continuous plating apparatuses are arranged in one plating tank, and if necessary, three or more metal foil continuous plating apparatuses may be arranged in one plating tank.

[0114] <Example 5>

[0115] Example 5 relates to a method for managing an electrolyte used in the above-mentioned metal foil continuous plating apparatus.

[0116] The Fe-Ni electrolyte was subjected to spectral analysis using a light source having a wavelength of 200 nm to 1000 nm. At this time, UV-visible light analysis was performed in a scanning mode at room temperature, and the scanning rate was 10 nm / s.

[0117] refer to Figure 7 , light absorption peaks were observed at 200nm to 300nm, about 400nm, about 650nm, about 725nm, and about 1000nm. Among them, the absorption peak observed between 200nm and 300nm was observed in a form exceeding the detection limit, but it was confirmed that the peak became a normal peak form as the dilution ratio of the electrolyte increased.

[0118] Reference Figure 8 a, Ni was observed at about 400 nm, about 650 nm, about 725 nm, and about 1000 nm 2+ Characteristic peaks of ions. Figure 8 b, Fe was observed around 900 nm 2+ The characteristic peaks of ions. Figure 8 The peak observed between 200 nm and 300 nm in a appears to be Fe contained as an impurity in FeSO4. 3+ characteristic peaks.

[0119] refer to Fig. 9 a,Fe 2+ The peak of the ions changes with the exposure time in air, which seems to be due to the Fe 2+ Ions are oxidized to Fe 3+ and precipitate formation. Fig. 9 b Spectra before and after the removal of the precipitate, Fe was observed around 325 nm 3+ The characteristic peak of , and the absorption of the precipitate was widely observed in 200nm to 1000nm.

[0120] refer to Fig.10 a and Fig.10 b, when saccharin and ascorbic acid are included, absorption is observed in the region of 200nm to 300nm. At this time, the intensity of the absorption is strong, so when the analysis is performed in an undiluted state, a peak in the form of noise exceeding the detection limit is observed. However, when the solution containing saccharin and ascorbic acid is diluted to 1 / 10, a normal peak form is observed, and a characteristic peak is observed in the region of 200nm to 300nm for saccharin, and a characteristic peak is observed at about 270nm for ascorbic acid.

[0121] Fig.11 Show the UV-Vis spectrum of the standard plating solution (Ni of 97g / L, FeSO of 85g / L, saccharin of 2.6g / L, ascorbic acid of 1.0g / L, boric acid of 25g / L and lauryl of 0.2g / L) analyzed using short light path cell (transmission length: 0.1mm). Also be shown in the UV-Vis spectrum result of the plating solution analyzed using common tank (transmission length: 10mm) after the electroplating solution is diluted to 1 / 100. In two cases where the short light path cell is used and the plating solution is diluted, the peaks of saccharin and ascorbic acid are observed in the ultraviolet region. In both cases, the peak size and shape of saccharin are similar, but the peak size and position of ascorbic acid are different from each other. As can be seen from the above, it is advantageous to analyze by diluting the plating solution in terms of component analysis, because compared with the situation of using the short light path cell, a peak with higher sensitivity can be obtained.

[0122] In addition, when the analysis is performed by dilution, the matrix effect can also be mitigated. Generally, when a plating solution is used, side reactions such as hydrogen generation reactions occur, resulting in changes in pH. Therefore, in order to analyze substances that show pH dependence, such as ascorbic acid, it is necessary to adjust the pH of the solution before analysis, but when the analysis is performed by dilution, accurate analysis results can be obtained without a pH adjustment process.

[0123] Reference Fig.12 , in the case of the electrolyte containing NaCl, boric acid, and lauryl, no characteristic peak was observed in the region of 200 nm to 1000 nm.

[0124] Fig.13 a shows the UV-visible spectrum analyzed by adding NaCl, boric acid, lauryl, etc. to a solution containing 97 g / L of NiSO4. Fig.13 As shown in a, the characteristic peak of NiSO4 is clearly observed, but no change in the characteristic peak is observed according to the addition of NaCl, boric acid, lauryl, etc. This means that Ni 2+ The ions do not interact with NaCl, boric acid, lauryl, etc. in the solution.

[0125] Fig.13 b shows the UV-visible spectrum analyzed by adding NaCl, boric acid, lauryl, etc. to a solution containing 85 g / LFeSO4. Fig.13 In case a, the characteristic peak of FeSO4 was clearly observed, but no change in the characteristic peak was observed due to the addition of NaCl, boric acid, lauryl, etc. This means that Fe 2+ The ions also do not interact with NaCl, boric acid, lauryl, etc.

[0126] Fig.14 It is shown that by 3+ UV-Vis spectra obtained by adding Fe 3+ With the addition of ascorbic acid, the peak observed near 270 nm gradually decreased. No additional Fe 3+ absorption, and observed that it was assumed to be Fe 2+ When ascorbic acid and Fe 3+ When the molar ratio of Fe to Mg reaches 1:2, the peak of ascorbic acid disappears completely, and the peak of Fe 3+ The peak caused by ascorbic acid and Fe 3+ When the molar ratio of Fe reaches 1:2.5, 3+ The peaks of ascorbic acid and Fe 3+ The reaction is in a 1:2 ratio, resulting in oxidation of ascorbic acid and conversion of Fe 3+ Reduction to Fe 2+ .

[0127] From the analysis results of the absorption characteristics of the above solutions, it can be seen that the Ni contained in the electrolyte 2+ , Fe 2+ , Fe 3 + , Fe precipitate, saccharin and ascorbic acid show absorption characteristics in the analysis of wavelengths of 200nm to 1000nm, but NaCl, boric acid, lauryl, etc. do not show absorption characteristics and also basically do not react with Ni 2+ and Fe 2+ Ionic interactions.

[0128] In addition, 2+ , Fe 2+ , Fe 3+ , Fe precipitates, etc. have different absorption characteristics in the visible light (partially including near infrared) region of 300nm to 1000nm, and organic substances such as saccharin and ascorbic acid have different absorption characteristics in the ultraviolet region of 200 to 300nm, where characteristic peaks are clearly observed in a diluted state at a predetermined ratio (e.g., 1 / 200).

[0129] Fe 3+ Reacts quickly with ascorbic acid and is reduced to Fe 2+ , the reaction ratio is ascorbic acid:Fe 3+ =1:2.

[0130] There is no separate peak for hydrogen ions, but the change in pH may change the intensity of the ascorbic acid peak. At this time, when the analysis is performed by dilution, the intensity of the ascorbic acid peak is greater than the case where a short path cell is used.

[0131] As can be seen from the above, when analyzing an iron-nickel electrolyte, it is preferred to analyze it in an undiluted state in the visible light range and in a diluted state in the UV range, so it is preferred to analyze the solution in an undiluted state and the solution in a diluted state during UV-visible analysis.

[0132] Additionally, since the peaks from each substance overlap, it can be seen that when performing the analysis, it is preferable to use a multivariate analysis algorithm. The chemical species that affects the spectrum is Fe 2+ , Fe 3+ 、Ni 2+ , saccharin, ascorbic acid, hydrogen ions, precipitates, etc., and among these substances, Fe 2+ , Fe 3+ 、Ni 2+ , saccharin and ascorbic acid can be calibrated with high accuracy.

[0133] Next, a multivariate calibration was performed using a partial least squares (PLS) algorithm to analyze the five materials with absorption characteristics (Fe 2+ , Fe 3+ 、Ni 2+ , ascorbic acid and saccharin).

[0134] Fig.15 Shows the process of collecting data for partial least squares analysis. The plating solution was collected in an undiluted state for analysis, and some of the solution was diluted to 1 / 200 in ultrapure water. The absorbance relative to the diluted plating solution was analyzed over a wavelength range of 200nm to 500nm, and the absorbance relative to the undiluted state was analyzed over a wavelength range of 500nm to 1000nm and integrated to form a single spectrum. A multivariate calibration was performed between the initial plating solution composition and the above spectra using partial least squares, and its accuracy was evaluated.

[0135] Fig.16 The training and validation sets used for the partial least squares analysis algorithm are shown. In the training and validation sets, the concentration of Fe was adjusted in the reaction between the two materials. 3+ and ascorbic acid concentrations.

[0136] like Fig.17 As shown, a UV-visible spectrum analysis is performed on each training set, and the spectrum of the electrolyte diluted to 1 / 200 is connected to the UV region, and the spectrum of the electrolyte in an undiluted state is connected to the visible region to determine x as the axis factor.

[0137] The analysis was performed using R software with the built-in PLS algorithm. Cross-validation was used for validation without individual data preprocessing.

[0138] After training, the linear variable (LV) value at which the linear coefficient is minimized is determined, and the analysis results of the training set and the validation set measured in the corresponding LV are given in Fig.18 As shown in Fig.18 As shown, the high accuracy can be confirmed by the fact that the determined values ​​are very close to the actual concentrations.

[0139] [Description of Reference Numerals or Symbols]

[0140] 10: Metal foil continuous plating device

[0141] 100: Plating tank

[0142] 200: Electrolyte guiding component

[0143] 300: Positive

[0144] 400: Negative

[0145] 500: Electrolyte storage tank

Claims

1. A metal foil continuous plating device, comprising: an electrolytic cell for containing an electrolyte; a positive electrode, which is arranged in the electrolytic cell; a negative electrode arranged at a predetermined interval from the positive electrode to face the positive electrode; and a power supply device for applying current to the positive electrode and the negative electrode, The electrolyte is supplied to one side of a space formed between the positive electrode and the negative electrode, and the electrolyte is discharged from the other side of the space, wherein the height of the one side to which the electrolyte is supplied is formed to be higher than the height of the other side, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of a potential energy difference between the one side and the other side, and in the process of the electrolyte passing through the space formed between the positive electrode and the negative electrode, metal ions contained in the electrolyte are electrodeposited on the negative electrode, thereby forming a metal foil.

2. The metal foil continuous plating device according to claim 1, further comprising an electrolyte guiding member arranged to contact the positive electrode and guide the electrolyte to be supplied to a space formed between the positive electrode and the negative electrode at a predetermined angle and rate. 3 . The metal foil continuous plating device according to claim 1 , further comprising an electrolyte storage tank for recovering the electrolyte discharged through the space formed between the positive electrode and the negative electrode and processing the recovered electrolyte.

4. The metal foil continuous plating device according to claim 1, wherein: The electrolyte supplied through the electrolyte storage tank is supplied to a lower portion of one side of the electrolyte guide member and rises to an upper portion of the electrolyte guide member to be supplied to a space between the positive electrode and the negative electrode.

5. The metal foil continuous plating device according to claim 1, wherein: The electrolyte is an electrolyte for forming an iron-nickel alloy foil, an electrolyte for forming a nickel foil, or an electrolyte for forming a copper foil.

6. The metal foil continuous plating device according to claim 1, wherein: The positive electrode is formed into a plate shape having an arc shape that is concave downward; and The negative electrode is formed in a drum shape having a circular cross section.

7. The metal foil continuous plating device according to claim 1, wherein: The electrolyte guide member has a flat shape inclined at a predetermined angle or a convex shape having a predetermined curvature, and an entrance angle of the electrolyte supplied to a space formed between the positive electrode and the negative electrode is adjusted by the electrolyte guide member.

8. The metal foil continuous plating device according to claim 1, further comprising: An auxiliary guide on an upper side of the electrolyte guide member, the auxiliary guide being used to level a water level of the electrolyte.

9. A metal foil continuous plating device, comprising a group of a first metal foil continuous plating device and a second metal foil continuous plating device as described in claim 1, wherein a first metal foil manufactured by the first metal foil continuous plating device is introduced into the second metal foil continuous plating device to perform plating on the first metal foil by the second metal foil continuous plating device, thereby forming a second metal foil.

10. A method for manufacturing a metal foil, the method comprising: supplying an electrolyte between a positive electrode and a negative electrode, the negative electrode being arranged at a predetermined interval with the positive electrode to face the positive electrode; applying an electric current to the positive electrode and the negative electrode, thereby forming a metal foil on the surface of the negative electrode, wherein the height of one side of the space formed between the positive electrode and the negative electrode is formed to be higher than the height of the other side thereof, so that the electrolyte flows through the space formed between the positive electrode and the negative electrode by means of a potential energy difference between the one side and the other side, and passes through the space formed between the positive electrode and the negative electrode, during which the metal foil is formed on the surface of the negative electrode.

11. A method for managing an electrolyte, the method comprising: collecting electrolyte from a plating tank or an electrolyte storage tank that supplies electrolyte; selectively diluting the electrolyte with a diluting solution at a predetermined ratio, thereby adjusting the concentration of the electrolyte to an undiluted state or a diluted state at a predetermined ratio; irradiating the electrolyte having the adjusted concentration with light to analyze light absorption characteristics of the electrolyte having the adjusted concentration, thereby analyzing the composition of the electrolyte; as well as adjusting the composition of the electrolyte of the plating tank based on the difference between the analyzed composition of the electrolyte and the preset composition of the electrolyte, If the light absorption characteristic analysis is performed in the ultraviolet region, the analysis is performed in a state where the electrolyte is diluted with the diluent at a predetermined ratio.

12. The method according to claim 11, wherein: The dilution solution contains water (H 2 O), has no absorption in the wavelength range of 200 nm to 500 nm, and is diluted with the electrolyte solution at a volume ratio of 2 to 400 times.

13. The method according to claim 11, wherein: In the light absorption characteristic analysis, if the analysis is performed for a wavelength range of 300 nm to 1000 nm, the analysis is performed when the electrolyte is in an undiluted state.

14. The method according to claim 11, wherein: The light absorption characteristics analysis includes: A first spectral analysis for analyzing a wavelength range of 10 nm to 500 nm; and The second spectral analysis is used to analyze the wavelength range of 300nm to 1000nm.

15. The method according to claim 11, wherein: The electrolyte composition analysis includes processing data obtained by the light absorption characteristics analysis using a multivariate calibration.

16. The method according to claim 11, wherein: The electrolyte contains Fe 2+ 、Ni 2+ and saccharin.

17. The method according to claim 16, wherein: The electrolyte also contains an antioxidant.

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