Method and system for subtractive and additive manufacturing of patterned foil

Abstract

Provided herein are tools and methods for continuously patterning conductive foils using a roller-to-roller electroetching and / or electrodeposition system that includes a circumferentially closed tape mask that presents an array of holes arranged in a perforation pattern or a through-hole pattern.

Description

TECHNICAL FIELD

[0001] The present invention, in some embodiments thereof, relates to the manufacturing of patterned metal or metal-containing foils, and more particularly, but not exclusively, to metal foils patterned (e.g., perforated) by a seamless repeating pattern. BACKGROUND

[0002] Patterned metal foils are widely used in various industrial applications, such as, but not limited to, printed circuit boards and batteries, and for decorative purposes.

[0003] When it comes to perforated patterns, thin metal foils perforated by a pattern of very fine holes can be used in various applications, such as in the aerospace industry for weight reduction and noise reduction, in the energy storage and conversion industry for elements of energy storage and generation devices, in sensing and biosensing applications, and in the filtration industry for filtering very fine particles. In addition, they can be used in the medical industry for implantable devices, and in the electronics industry for shielding and heat dissipation.

[0004] In some applications, it is required that the pattern of the metal foil is precise and accurate over a relatively large area of the foil, in order to provide similar conditions over the area. An exemplary application requiring such precision and accuracy is the use of perforated and / or three-dimensional metal foils as current collectors in rechargeable battery electrodes.

[0005] For example, a current collector can include a base layer and a patterned coating of a battery active material required for the specific assembly of the active material on the current collector. The patterned metal layer on the current collector can further increase the surface roughness, enhancing the adhesion of the battery active material to the CC and increasing the contact area with the active material layer. The patterned surface of the current collector can further improve the stability of the electrode during charge and / or discharge cycles. Perforated patterning of the current collector foil can reduce the weight of the current collector and facilitate ion transport between the two sides of the current collector, to enable balanced cycling and improve power density.

[0006] In some industrial fields, such as the battery electrode industry, the production of electrodes is performed using very long metal foils, typically provided in the form of rolls of several hundred and sometimes several thousand meters long. In such applications, the uniformity of the foils is essential for the repeatability and optimal performance of the resulting electrodes. When the foils are perforated / patterned, this uniformity requirement also applies to the perforations or their surface and / or bulk structural elements, meaning that the patterned foils should exhibit a repeating pattern without irregularities.

[0007] While "piercing dies" with multiple rows of needles that punch through metal sheets with a punch press cannot provide fine perforations (limited to the span of the die) with high precision (limited to the die span) and high density of holes (limited to holes larger than 100 pm), other methods such as laser perforation and electron beam emission can produce perforated metal foils with high precision (typically limited to about 30% variation in hole size) to some extent. Similar to other energy beam methods, laser methods can produce complex geometries with precise dimensions by consistently and accurately burning small holes, leaving a reinforcing ring around each hole; however, one major drawback of energy beam perforation such as laser perforation is high cost and time-consuming, especially when hundreds and thousands of meters of perforated metal foils need to be produced. Other methods for producing thin metal foils with fine perforation patterns based on semiconductor lithography techniques have one or more of the above-mentioned drawbacks and further limit their ability to perforate thin metal foils with a thickness of less than 100 pm.

[0008] Perforated foils can optionally be prepared by an electro-etching method. Electro-etching through a mask (also referred to herein as "electrochemical etching") is a common method used to create precise patterns or designs in metal foils, which is often used to produce filters, screens, and decorative items. The method includes placing a mask (a template mask) on at least one face of a pre-made metal foil and applying an electric current using electrodes while the template covers areas that should not be etched. The electric current causes the metal foil to corrode and etch away, physically subtracting metal atoms from the foil, and more likely to form through-holes or perforations in the material.

[0009] Masks for metal electro-etching can be made of various materials such as photoresist, rubber, or metal. Etching occurs in the areas of the foil that are not covered by the mask, thereby templating the pattern of the mask and producing a perforation pattern or design on the foil. Unlike chemical etching, electro-etching allows a high level of control over the size, shape, and spacing of individual through-holes in the perforation pattern, which can be controlled, among other things, by adjusting the electric current, the duration of the etching method, the temperature, the electrolyte composition, and the distance between the electrodes. Once the etching process is complete, the mask is removed, and the perforated metal foil is rinsed to remove any residue. However, prior art electrochemical etching methods are not configured for producing seamless patterns in long patterned foils and / or roll-to-roll foil configurations.

[0010] Thin and long metal foils can be produced industrially using electroforming methods such as electrodeposition (also referred to herein as "electrolytic deposition" or "electroplating"). Electrodeposition is a method of preparing metal foils by immersing an anode and a moving electroplating surface in an electrolyte containing a solution of metal ions and applying an electric current between the anode and the electroplating surface, thereby depositing a metal layer on the electroplating surface by reducing the metal ions to zero-valent metal species.

[0011] There is a need for cost and time efficient tools and methods to produce (a) seamless, repeating patterned metal foils with pores or through-holes, and (b) patterned metal foils with seamless, repeating patterns, wherein the foils are produced in a roll-to-roll configuration over an infinite length of the foil. SUMMARY

[0012] The present disclosure provides a roll-to-roll foil patterning system. The system can include an electro-patterning unit. The system can include an input roll. The system can include an output roll configured to collect the patterned foil. The system can include a power source.

[0013] The electro-patterning unit can be configured to transform the starting foil into the patterned foil upon application of an electric current and / or voltage. The electro-patterning unit can be configured to transform the starting foil into the patterned foil upon application of an electric current. The electro-patterning unit can be configured to transform the starting foil into the patterned foil upon application of a voltage. The electro-patterning unit can include an electrode. The electro-patterning unit can include an elastic mask. The electro-patterning unit can include two or more shafts. The electro-patterning unit can include a reservoir for containing and / or circulating a liquid electrolyte composition. The electro-patterning unit can include a fluid delivery unit.

[0014] The starting foil can be electrically conductive. The patterned foil can be electrically conductive.

[0015] The mask can have the form of a circumferentially closed band. The circumferentially closed band mask can have an electrically insulating outer surface. The mask can include a contact section positioned to contact a corresponding contact section of the starting foil, such that the contact section of the mask can have a curved shape that can conform to a curvature of the contact section of the starting foil. The contact section of the mask can be located between the electrode and the contact section of the starting foil.

[0016] The fluid delivery unit can be configured to direct a flow of the electrolyte composition. The fluid delivery unit can be configured to direct a flow of the electrolyte composition supplied by the reservoir. The fluid delivery unit can be configured to direct the flow of the electrolyte composition supplied by the reservoir tangentially to the outer surface of the mask. The fluid delivery unit can be configured to direct the flow of the electrolyte composition supplied by the reservoir to be parallel to the outer surface of the mask substantially along an entire length of the contact portion of the mask.

[0017] The fluid delivery unit can be configured to direct the flow of the electrolyte composition supplied by the reservoir parallel to the outer surface of the mask. The fluid delivery unit can be configured to direct the flow of the electrolyte composition supplied by the reservoir to be parallel to the outer surface of the mask substantially along an entire length of the contact portion of the mask.

[0018] The two or more shafts can hold the mask under tension.

[0019] The fluid delivery unit can be in fluid flow connection with the reservoir.

[0020] The input roller can be configured to feed the starting foil into the electro patterning unit.

[0021] The output roller can be configured to collect the patterned foil.

[0022] The mask and the starting foil can be configured to move in coordination while the starting foil is in contact with the mask while feeding the starting foil by the input roller and / or collecting the patterned foil by the output roller. The mask and the starting foil can be configured for coordinated movement while the starting foil is in contact with the mask while feeding the starting foil by the input roller. The mask and the starting foil can be configured to move in coordination while the starting foil is in contact with the mask while collecting the patterned foil by the output roller.

[0023] The power source can be configured to apply a voltage and / or a current between the electrode and the contact section of the starting foil in the presence of the electrolyte composition. The power source can be configured to apply a current between the electrode and the contact section of the starting foil in the presence of the electrolyte composition. The power source can be configured to apply a voltage between the electrode and the contact section of the starting foil in the presence of the electrolyte composition.

[0024] The electro patterning unit can comprise a washing unit. The washing unit can be connected to a source of washing liquid. The washing unit can comprise at least one nozzle facing a portion of the elastic mask. The washing unit can be configured to flush the portion of the elastic mask with washing liquid.

[0025] The liquid medium can comprise water. The washing unit can comprise two nozzles. The washing unit can be configured to wash the portion of the mask with pressurized water.

[0026] The fluid delivery unit can be positioned between the electrode and the mask in the contact area. The fluid delivery unit can be positioned between the starting foil and the mask before the contact area.

[0027] The electrode can be divided into two substantially equal sections. The fluid delivery unit can be positioned between the two sections facing the mask.

[0028] The system can further comprise an ultrasonic cleaning device. The ultrasonic cleaning device can comprise an ultrasonic transducer. The ultrasonic transducer can face the contact section of the starting foil. The ultrasonic transducer can be configured to emit ultrasound thereto.

[0029] The system can further comprise a counter electrode. The counter electrode can be located in proximity to the contact section.

[0030] The system can further comprise a liquid pump. The liquid pump can be configured to circulate the electrolyte composition in a flow path between the electrode and the counter electrode. The liquid pump can be configured to circulate the electrolyte composition in a flow path between the electrode and the starting foil.

[0031] The system can further include a filter. The filter can be positioned within the flow path. The filter can be configured to filter solid particles from the electrolyte composition.

[0032] The mask can include a hydrophilic material. The mask can be composed of a polymer or a polymer-coated metal. The mask can include a hydrophilic polymer or a hydrophilic polymer-coated metal. The mask can include a polyamide film.

[0033] The starting foil can be pressed against the mask while the starting foil is fed by an input roller and / or the patterned foil is collected by an output roller. Each possibility represents a separate embodiment of the application. The starting foil can be pressed against the mask while the starting foil is fed by an input roller and the patterned foil is collected by an output roller. The input roller, the output roller, or both can be configured to transfer the starting foil in a direction from the input roller to the output roller. Each possibility represents a separate embodiment of the application. The pressing and the transferring of the starting foil can be a drag mask. The pressing and the transferring of the starting foil can be a drag mask such that the starting foil can be configured to move in coordination with the mask. The drag can be affected by friction.

[0034] At least one of the input roller and the output roller can be a convex roll. Both the input roller and the output roller can be convex rolls. The convex roll can be configured to maintain the alignment of the starting roll with the mask in a lateral direction perpendicular to the direction of movement of the mask and the starting foil. The lateral direction can be substantially parallel to the surface of the mask and the starting foil.

[0035] The electrode can have a curved active surface having a curvature. The curvature can be in line with the curvature of the contact section of the starting foil.

[0036] The electrical patterning unit can include an element having a curved surface. The element can be configured to contact the starting foil on a first side of the contact section of the starting foil. The contact section of the mask can be configured to contact the starting foil on a second side of the contact section of the starting foil.

[0037] The mask can be configured to move towards the element prior to implementing the electrical patterning method. The mask can be configured to move towards the element prior to implementing the electrical patterning method, thereby forming an electrical patterning region between the contact section of the starting foil and the electrode.

[0038] The surface can form part of a lateral surface of a rotatable drum or part of a surface of an endless belt conveyor.

[0039] The electrode can be a cathode. The curved surface can be electrically insulating. The starting foil can be connected to a positive pole of a power source via an electrically conductive shaft. The electrically conductive shaft can be located outside the electrical patterning region.

[0040] The electrode can be an anode. The curved surface can be electrically insulating. The starting foil can be connected to the negative terminal of the power source via a conductive shaft. The conductive shaft can be located outside the electrically patterned region.

[0041] The mask can be configured to move toward the starting foil. The mask can be configured to move toward the starting foil to form an electrically patterned region between the contact segment of the starting foil and the electrode.

[0042] The mask can surround the electrode.

[0043] The system may also include a computerized control unit.

[0044] The mask can be elastic and tensioned between two or more axes.

[0045] This system can be a roll-to-roll foil electro-etching system. The electro-patterning unit can be an electro-etching unit. The electro-etching unit can be configured to transform the starting foil into an electro-etched foil when a current and / or voltage is applied. The electro-etching unit can be configured to transform the starting foil into an electro-etched foil when a current is applied. The electro-etching unit can be configured to transform the starting foil into an electro-etched foil when a voltage is applied. The electrode can be a cathode.

[0046] The electro-etching unit can be configured to transform a conductive foil into an electro-etched foil using an electro-etching method. The electro-etching method can impart a pattern to the foil.

[0047] The mask can be an SRP stencil mask. The mask can have a seamless repeating pattern (SRP) with through-holes. The through-holes can have an opening size of approximately 10-2,000 μm. The through-holes can have a pitch of approximately 50-2,500 μm, including each value and subrange within the specified range.

[0048] The mask can have a thickness ranging from about 5 μm to about 100 μm, including each value and subrange within the specified range.

[0049] The foil can be selected from aluminum foil and copper foil. The foil can be aluminum foil.

[0050] The mask can be configured to move toward the element prior to the electro-etching method, thereby forming an electro-etched area between the contact section of the starting foil and the cathode.

[0051] The curved surface can be conductive, and the starting foil can be connected to the negative terminal of the power source via the curved surface.

[0052] This system can be a roll-to-roll foil electrodeposition system. The electropatching unit can be an electrodeposition unit. The electrodeposition unit can be configured to pattern the foil by transforming a starting metal foil into a metal deposited electrochemically when a current and / or voltage is applied. The electrode can be an anode.

[0053] The mask can be an SRP stencil mask. The mask can have a seamless repeating pattern (SRP) of through-holes. The through-holes can have an opening size of approximately 10–2,000 μm, including each value and sub-range within the specified range. The horizontal distance between the centers of two adjacent through-holes can be in the range of approximately 50–2,500 μm, including each value and sub-range within the specified range.

[0054] The mask can have a thickness ranging from about 20 μm to about 300 μm, including each value and subrange within the specified range.

[0055] The mask can be configured to move toward the element prior to the implementation of the electrodeposition method, thereby forming an electrodeposition region between the contact section of the starting foil and the anode.

[0056] The curved surface can be conductive, and the starting foil can be connected to the negative terminal of the power source via the curved surface.

[0057] This disclosure also provides an electro-etching method for patterning a starting metal foil.

[0058] The method may include feeding a foil into an electro-etching unit. The electro-etching unit may include a mask and a cathode. At least one contact segment of the foil may be arranged within the electro-etching unit.

[0059] The method may include contacting a contact segment of a mask with a contact segment of a foil. The contact may form a contact area. The contact segment of the mask may be located between the contact segments of the cathode and the foil.

[0060] The method may include guiding an electrolyte composition tangentially to the outer surface of a mask. The method may also include guiding the electrolyte composition substantially tangentially to the outer surface of the mask along the entire length of a contact segment of the mask.

[0061] The method may include applying a current, voltage, or both between the cathode and the foil. Each possibility represents a separate embodiment of the invention. The method may include applying a current, voltage, or both between the cathode and the foil while advancing the foil through an electro-etching unit. Each possibility represents a separate embodiment of the invention. The application of current, voltage, or both and / or the advancement of the foil may require electro-etching the foil. Each possibility represents a separate embodiment of the invention. Electro-etching the foil may require forming an electro-etched foil. Electro-etching the foil may require forming a metal salt.

[0062] This propulsion can be coordinated with the movement of the mask.

[0063] This method may include collecting electro-etched foil.

[0064] Masks can be in the form of circumferentially closed bands. Masks can have electrically insulating outer surfaces.

[0065] The contact area can be curved.

[0066] The method may include using a cleaning solution to remove salts from the metal from the mask.

[0067] The applied current and / or voltage may be affected in the presence of the electrolyte composition. The electrolyte composition may contain an electrolyte. The electrolyte may be supplied to the electroetched region formed between the cathode and the contact area.

[0068] The method may include positioning a mask between a cathode and a starting metal foil.

[0069] The method may include positioning a foil between a mask and an anode. An electrolyte may be in contact with both the anode and cathode.

[0070] The method may include applying a current, voltage, or both between the cathode and anode. The method may include reversing the polarity of the anode and cathode. The method may include applying a reverse pulsed current, voltage, or both between the cathode and anode. Each possibility represents a separate embodiment of the invention. The reverse pulsed current, voltage, or both may at least partially remove metal salts from the electro-etched foil and / or from the contact sections of the mask.

[0071] The electrolyte composition may be in the form of an aqueous solution contained in a container.

[0072] The method may include circulating an aqueous solution between the anode and cathode or between the foil and the cathode.

[0073] The method may include guiding an electrolyte composition tangentially to the outer surface of a mask. The method may also include guiding the electrolyte composition substantially tangentially to the outer surface of the mask along the entire length of a contact segment of the mask.

[0074] Circulation can be performed under pressure. Circulation may include using a liquid pump to flow the aqueous solution. Circulation may include using a liquid pump to flow the aqueous solution in a closed path. The closed path may contact any of the anode and foil, cathode, and contact area. Circulation may achieve forced and / or directional flow thereto. Each possibility represents a separate embodiment of the invention.

[0075] The foil can be selected from aluminum foil and copper foil. The foil can be aluminum foil.

[0076] Making contact between the contact section of the mask and the contact section of the foil may require pressing one of the mask and foil onto the other at the contact section. Advancing the initial foil may require dragging the mask at a similar rate. Advancing the initial foil may require dragging the mask at a similar rate to create coordinated movement between the foil and the mask.

[0077] The method may include preventing relative movement between the starting foil and the mask in a direction perpendicular to the direction of travel. This direction may be parallel to the surface of the starting foil.

[0078] The thickness of the starting metal can range from 5 μm to 100 μm, including values ​​and subranges within the specified range.

[0079] Electro-etched foils may require the formation of metal salts and electro-etched foils with multiple etched perforations.

[0080] Multiple etched holes can have an average diameter of no more than 100 μm.

[0081] Multiple etched perforations in an electro-etched foil can have an opening area of ​​at least 15% of the total area of ​​the electro-etched foil.

[0082] Masks can be flexible.

[0083] This method may include tensioning a mask between two or more axes.

[0084] The method may include contacting a contact section of the foil with the side surface of a roller or with the surface of an annular belt conveyor. The method may include contacting a contact section of the foil with the side surface of a roller. The method may include contacting a contact section of the foil with the surface of an annular belt conveyor.

[0085] Feeding can be achieved by a feed roller. Collection can be done on an output roller, or both.

[0086] This method may include rinsing the electro-etched foil. The method may include rinsing the electro-etched foil prior to collection. Rinsing may be performed with water.

[0087] This method may include washing away salts from the metal using a cleaning solution. The cleaning solution may include water. The cleaning can be performed continuously.

[0088] Contact may include moving a rigid circular mask toward the contact section of the starting foil.

[0089] Propulsion may include the coordinated rotation of at least one of the two or more axes with the rigid circular mask.

[0090] This disclosure also provides a method, which includes, The conductive starting foil is fed into the electrodeposition unit; Make the contact section of the mask contact the contact section of the foil; Applying current, voltage, or both between the anode and the foil while simultaneously advancing the foil through an electro-etching unit, thereby electrodepositing metal onto the starting metal foil; and Collect patterned foil, The method may include guiding the electrolyte composition tangentially to the outer surface of the mask. The guiding electrolyte composition may be tangential to the outer surface of the mask substantially along the entire length of the contact section of the mask.

[0091] Masks can be in the form of circumferentially closed bands. Masks can have electrically insulating outer surfaces.

[0092] The contact area can be curved.

[0093] The electrodeposition unit may include a mask and an anode, such that at least one contact segment of the foil may be arranged within the electrodeposition unit.

[0094] A contact area can be formed by bringing the contact section of the mask into contact with the contact section of the foil. The contact section of the mask can be located between the contact sections of the anode and the foil.

[0095] This propulsion can be coordinated with the movement of the mask.

[0096] This disclosure also provides a metal component. The metal component may include a base foil and a plurality of raised textured elements on the surface of the base foil.

[0097] Multiple raised texture elements can be arranged into a seamless repeating pattern.

[0098] The width of the metal component can be at least 0.1m. The length of the metal component can be at least 0.5m.

[0099] Metal components can be prepared using the methods disclosed herein.

[0100] The pattern can cover 10 to 95% of the continuous area of ​​the surface that constitutes the base foil.

[0101] Raised texture elements can be electrodeposited on a substrate foil.

[0102] The raised texture elements can have a base size in the range of approximately 10-2,000 μm. The horizontal distance between the centers of two adjacent raised texture elements can be in the range of approximately 50-2,500 μm.

[0103] The height of the raised textured element can range from approximately 5 to 300 μm.

[0104] A seamless repeating pattern can be characterized by a uniformity of at least 15%.

[0105] The substrate foil may comprise a metal selected from copper, nickel, gold, silver, iron, tin, aluminum, palladium, and any alloys and combinations thereof. Each possibility represents a separate embodiment of the invention.

[0106] The raised texture element may include metals selected from copper, nickel, gold, silver, iron, tin, aluminum, palladium, and any alloys and combinations thereof. Each possibility represents a separate embodiment of the invention.

[0107] The substrate foil can be 3-100µm thick.

[0108] The height of the raised textured element from the top side of the substrate foil can be in the range of approximately 1 to 100 μm.

[0109] This disclosure also provides a roller comprising a cylindrical core and a metal member, as disclosed herein, wound around the core.

[0110] The width of the metal components can be at least 0.1 to 5 m.

[0111] The length of the metal components in the roller can be at least 0.5-10,000m.

[0112] This disclosure also provides a current collector. The current collector may include at least one metallic component disclosed herein.

[0113] This disclosure also provides an electrode that includes the current collector disclosed herein.

[0114] This disclosure also provides a battery including at least one electrode according to this disclosure. This disclosure also provides an electrical device including at least one battery according to this disclosure. Attached Figure Description

[0115] Preferred embodiments of the invention will now be described in detail with reference to the accompanying drawings, emphasizing that the details shown are by way of example and are intended to illustrate embodiments of the invention. In this regard, the description taken in conjunction with the drawings will make it clear to those skilled in the art how to practice embodiments of the invention.

[0116] In the attached diagram: FIGS. 1A-1BA schematic diagram of an electro-etching unit 10 according to some embodiments of the present invention is shown, illustrating a circumferentially closed band mask 11 wound and tensioned between tension shafts 12a and 12b, surrounding a concave cathode 13 and located near a cylindrical mandrel constituting an anode 14, with a foil 15 tightly wound around the mandrel and covering a portion of the convex surface of the anode 14, wherein... FIG. 1A The electro-etching unit 10 is shown during the loading phase, before the mask 11 contacts the foil 15 and before electrical energy is applied. FIG. 1B The diagram shows an electro-etching unit 10 during the electro-etching stage where the mask 11 contacts the foil 15, and... FIG. 1B The dashed rectangle in the figure marks the contact area between the mask 11 and the foil 15, including the contact section 11a of the mask 11 and the contact section 15a of the foil 15. Contact is achieved by moving the tension shafts 12a and 12b toward the anode 14, moving the anode 14 toward the tension shafts 12a and 12b, or a combination thereof, while the tension shafts 12a and 12b can rotate in coordination with the anode 14. During this period, the electrolyte flows between the cathode 13 and the anode 14 (not shown), and electrical energy is applied to the cathode 13 and the anode 14 to achieve the electro-etching of the foil 15. FIG. 1C Some embodiments of the present invention are shown. FIGS. 1A-1B The schematic diagram of the electro-etching unit 10 shown shows that the concave cathode 13 is a split cathode including cathode portion 13a and cathode portion 13b, wherein the electrolyte can flow between cathode portion 13b and cathode portion 13b and anode 14, and wherein the circumferential closed strip mask 11 is wound and tensioned between three tensioning shafts 12a, 12b and 12b. FIG. 1D Some embodiments of the present invention are shown. FIGS. 1A-1B The schematic diagram of the electro-etching unit 10 shown also includes a cleaning unit comprising a cleaning head 16 including one or more nozzles pointing toward the closed strip mask 11, a cleaning tray 17 positioned to collect cleaning fluid from the closed strip mask 11, and a wiper 18 that prevents the cleaning fluid from contacting the foil 15; and also includes a roller 19 configured to stretch the closed strip mask 11, thereby exposing its area to the nozzles. FIGS. 2A-2B A schematic diagram of an electro-etching unit 20 according to some embodiments of the present invention is shown, illustrating a circumferentially closed strip mask 21 wound and tensioned between tension shafts 22a and 22b, surrounding a concave cathode 23 and located near an electrically insulating cylindrical mandrel 24, with foil 25 tightly wound around a portion of the convex surface of the mandrel 24 and a conductive tension shaft 26, wherein... FIG. 2A The electro-etching unit 20 is shown during the loading phase, before the mask 21 contacts the foil 25 and before electrical energy is applied. FIG. 2BThe diagram shows an electro-etching unit 20 during the electro-etching stage, wherein a mask 21 is in contact with a foil 25, and... FIG. 2B The dashed rectangle in the figure marks the contact area between the mask 21 and the foil 25, including the contact section 21a of the mask 21 and the contact section 25a of the foil 25. Meanwhile, the tensioning shafts 22a and 22b can rotate in coordination with the mandrel 24 and optionally the tensioning roller or annular belt conveyor 26. During this period, the electrolyte flows between the cathode 23 and the foil 25 (not shown), and electrical energy is applied to the cathode 23 and the tensioning roller or annular belt conveyor 26, which is connected to the positive terminal of the power supply (not shown), so that the foil 25 maintains a positive voltage relative to the cathode 23 and achieves the electro-etching of the foil 25. FIGS. 3A-3B A schematic diagram of an electro-etching unit 30 according to some embodiments of the present invention is shown, illustrating a circumferentially closed strip mask 31 wound and tensioned between tension shafts 32a and 32b, surrounding a concave cathode 33 and located near a fixed anode 34 having a curved active surface, a foil 35 tightly wound on the convex surface of the curved active surface, and a tension roller or annular belt 36, wherein... FIG. 3A The electro-etching unit 30 is shown in the loading phase before the mask 31 contacts the foil 35 and before electrical energy is applied. FIG. 3B An electro-etching unit 30 is shown in the electro-etching stage, wherein tension rollers 32a and 32b move toward the anode 34 to allow contact between the mask 31 and the foil 35, while tensioning shafts 32a and 32b can rotate in coordination with the rotating shaft 36. During this period, electrolyte flows between the cathode 33 and the fixed anode 34 and applies electrical energy to the cathode 33 and the fixed anode 34, thereby achieving electro-etching of the foil 35. FIGS. 4A-4B A schematic diagram of an electro-etching unit 40 according to some embodiments of the present invention is shown, illustrating a rigid circumferentially closed strip mask 41 with a cylindrical shape, viewed from top, surrounding a rotating cathode 43 and located near a foil 45 wound on tension / rotation shafts 26a and 26b, wherein the tension shaft 26a is conductive, and the contact sections of the mask, cathode, and starting foil are immersed in an electrolyte solution (not shown). FIG. 4A The electro-etching unit 40 is shown in the loading phase, before the mask 41 contacts the foil 45 and before electrical energy is applied. FIG. 4BAn electro-etching unit 40 is shown in the electro-etching stage, wherein a mask 41 contacts a foil 45. This contact can be achieved by moving tension shafts 46a and 46b toward the mask 41, moving the mask 41 toward tension rollers 46b and 46b, or a combination thereof. The tension shafts 46a and 46b can rotate in coordination with the mask 41, applying electrical energy to the cathode 43 and the tension shaft 46a, which is connected to the positive terminal of a power source (not shown). This maintains a positive voltage on the foil 45 relative to the cathode 43, and electro-etches the foil 45 as the cathode 43 rotates, facilitating the flow of electrolyte between the cathode 43 and the foil 45. The anode 43 has a central portion 43a and curved blades 43b and 43c connected to the central portion 43a, the outer surfaces of which constitute the active surface of the anode 43. The curved blades 43b and 43c are shaped to match the mask 41 to provide a constant distance between the active surface of the anode 43 and the contact segment of the initial foil 45.

[0117] FIGS. 5A-5D A figure illustrating an electro-etching system 500 according to some embodiments of the present invention ( FIG. 5A Side view and FIGS. 5B-5D The cross-section of the image includes an electro-etching unit comprising a circumferentially closed strip mask 51 wound and tensioned between tension shafts 52a, 52b and 53c, surrounding a concave cathode 53 and located near an electrically insulating cylindrical mandrel 54, on which a foil 55 is tightly wound on a portion of the convex surface of the mandrel 54 and located on a conductive tension shaft 56, wherein the foil 55 is fed into the electro-etching unit via an input (feed) roller 57a and collected on an output roller 57b, and wherein an electrolyte is introduced into the electro-etching unit via an electrolyte inlet 58. FIG. 6 This is a schematic diagram of an exemplary mask or SRP template mask according to an embodiment of the present invention, showing a circumferential closed band (loop) that presents a seamless repeating pattern, illustrated by an exemplary diagram of hexagonal holes shown in an enlarged circle; FIG. 7 A schematic diagram of two tapered holes in a mask with local thickness is shown, indicating that the diameter of the hole on the outer side (d1) is smaller than the diameter of the hole on the inner side (d2) of the mask; FIG. 8 This is a flowchart illustrating the basic steps of a method for continuous subtractive manufacturing (roll-to-roll construction) of a very long patterned foil, which involves electro-etching a very long raw foil through holes in a mask with a repeating hole pattern to form a repeating pattern of through holes in the foil. FIG. 9 This is a photograph of an exemplary mask used in this example, showing an SRP with circular holes of 100 μm diameter, spaced 150 μm apart, and arranged in a hexagonal stacked pattern; and FIG. 10The image shows a perforated aluminum foil obtained by the method provided in this paper, displaying SRP with circular through-holes of 100 μm in diameter and spaced 150 μm apart; FIGS. 11A-11B A schematic diagram of an electrodeposition unit 110 according to some embodiments of the present invention is shown, including a circumferentially closed band mask 111 wound and tensioned between tension shafts 112a and 112b, surrounding a concave anode 113 and located near a cylindrical mandrel constituting a cathode 114, the mandrel having a convex surface on which a starting foil 115 is wound, wherein... FIG. 11A The electrodeposition unit 110 in the loading stage is shown. FIG. 11B An electrodeposition unit 110 in the electrodeposition stage is shown; FIGS. 12A-12B A schematic diagram of an electrodeposition unit 120 according to some embodiments of the present invention is shown, including a circumferentially closed strip mask 121 wound and tensioned between tension shafts 122a and 122b, surrounding a concave anode 123, an electrically insulating cylindrical mandrel 124 having a convex surface on which a starting foil 125 is wound, and a conductive tension shaft 126, wherein... FIG. 12A The electrodeposition unit 120 in the loading stage is shown. FIG. 12B An electrodeposition unit 120 in the electrodeposition stage is shown; FIGS. 13A-13B A schematic diagram of an electrodeposition unit 130 according to some embodiments of the present invention is shown, including a circumferentially closed belt mask 131 wound and tensioned between tension shafts 132a and 132b, surrounding the mask 131, a concave anode 133, a fixed cathode 134 having a convex surface on which a starting foil 135 is wound, and a tensioning roller or annular belt conveyor 136, wherein... FIG. 13A The electrodeposition unit 130 in the loading stage is shown. FIG. 13B An electrodeposition unit 130 in the electrodeposition stage is shown; FIGS. 14A-14B This is a schematic diagram of an electrodeposition unit 140 according to some embodiments of the present invention, showing a cylindrical rigid circumferentially closed strip mask 141, a rotating anode 143, and a starting foil 145 wound on tension / rotation shafts 146a and 146b, as viewed from top. FIG. 14A The electrodeposition unit 140 in the loading stage is shown. FIG. 14B An electrodeposition unit 140 in the electrodeposition stage is shown; FIGS. 15A-15D A figure illustrating an electrodeposition system 1500 according to some embodiments of the present invention ( FIG. 15A Side view and FIG. 15B( -45D cross-section), which includes an electrodeposition unit comprising a circumferentially closed band mask 151 wound and tensioned between tension shafts 152a, 152b and 153c, surrounding an anode 153 and located near an electrically insulating cylindrical mandrel 154 on which a starting foil 155 is tightly wound on a portion of the convex surface of the mandrel 154 and located near a conductive tension shaft 156, wherein the starting foil 155 is fed into the electrodeposition unit via an input (feed) roller 157a and collected on an output roller 157b, and wherein an electrolyte is introduced into the electrodeposition unit via an electrolyte inlet 158; FIG. 16 This is a flowchart illustrating the basic steps of a process for continuous additive manufacturing (roll-to-roll construction), in which metal is electrodeposited on a very long starting foil through holes in a mask with a repeating hole pattern to form a seamless, repeating pattern of protruding elements on the starting foil; and FIGS. 17A-17B Microscopic images are shown of exemplary copper foils including copper textured elements electrodeposited on their surfaces, produced by the methods provided herein. These elements are tapered textured elements spaced approximately 150 μm apart, with a height of about 10 to 20 μm and a base diameter of 100 μm. FIG. 9 A shows a top view magnified 20 times, and FIG. 9 B shows a tilted side view magnified 20 times. Detailed Implementation

[0118] In some embodiments, the present invention relates to the manufacture of patterned conductive (e.g., metal or metal-containing) foils, and more specifically (but not exclusively) to metal foils patterned by seamless repeating patterns.

[0119] Before explaining at least one embodiment of the invention in detail, it should be understood that the invention is not necessarily limited to the details set forth in the following description or illustrated by way of example. This disclosure is intended to include other embodiments or to be practiced or implemented in various ways.

[0120] In some aspects and embodiments, the present invention provides a system for performing electro-etching of conductive (e.g., metal or metal-coated polymer) foil in a roll-to-roll configuration to create indentations or holes or perforations within the foil. In some aspects and embodiments, the present invention provides a system for electrodepositing metal on a conductive starting foil, such as a metal, metal-coated polymer, graphite, carbon, or conductive polymer foil, in a roll-to-roll configuration to produce a foil with patterned surface or bulk structures, such as voids within the foil and / or surface elements protruding from the foil surface. Furthermore, the present invention provides a tool that allows the formation of patterned foils with seamlessly repeating patterns over an extended length, which is limited only by practical considerations and not by method.

[0121] Electroetching is a metal etching method that uses an electrolyte solution, an anode, and a cathode. The metal sheet to be etched is connected to the positive terminal of a power source. Another metal sheet, called the cathode, is connected to the negative terminal. To minimize undesirable effects, the anode and cathode can be made of the same metal. The electrolyte can also contain the same metal cations. When a current or voltage is applied between the anode and cathode, the metal at the anode undergoes an oxidation reaction, dissolving the metal cations and releasing them into the electrolyte. Simultaneously, the cations in the electrolyte undergo a reduction reaction, being converted into metal and deposited on the cathode. Depending on the voltage and electrolyte concentration, other complex electrochemical effects can occur, but the main effects involve oxidation / dissolution at the anode and reduction / deposition at the cathode.

[0122] In the context of this invention, the term "electro-etching" refers to a method in which a conductive material, such as a metal, maintains a positive potential relative to a counter electrode and undergoes oxidation, for example, through contact with counter electrode ions via an electrolyte, such that the material is dissolved and the ions of the material are released into the electrolyte.

[0123] While putting this invention into practice, the inventors have demonstrated an electro-etching system comprising a mask configured as a circumferentially closed band or ring, wherein the mask is used as a template for a repeating pattern designed to create desired pores or holes within a conductive foil, including seamless repeating patterns. An aspect of the invention provides a roll-to-roll structure capable of producing continuous porous or perforated foils with pre-designed patterns. Tools and methods according to various aspects and embodiments of the invention provide control over the electro-etching process, allowing perforation of foils of varying thicknesses (e.g., battery-grade aluminum foil) while achieving high precision (low variation) in hole area, even with relatively small holes and / or relatively high opening areas for perforations. Therefore, the invention allows for the production of continuous thin metal foils suitable for industrial manufacturing methods, exhibiting seamless repeating patterns (SRPs) of fine indentations or through-hole elements that are substantially uniform in length (e.g., at least 1 meter), i.e., exhibiting uniformity of fine patterns substantially along and across the entire area of ​​the foil.

[0124] Regarding electrodeposition, electrodeposition systems according to various aspects and embodiments of the invention include a mask configured as a circumferentially closed band or ring, wherein the mask is used as a template for repeating patterns, designed to produce metal foils with specific configurations of voids and / or protruding surface elements, including seamless repeating patterns as specified by the mask. Aspects of the invention provide roll-to-roll structures capable of producing continuously patterned foils with pre-designed patterns. Tools and methods according to various aspects and embodiments of the invention provide control over the electrodeposition process, thereby allowing the production of patterned foils of varying thicknesses, which can be assembled in rolls, such as battery-grade copper foil, while achieving high precision (low variation) in pattern shape and size. Therefore, the invention allows for the production of continuous thin metal foils suitable for industrial manufacturing methods, which can exhibit seamless repeating patterns (SRPs) of fine indentations or protruding elements, substantially uniform in length of the foil (e.g., at least 1 meter), i.e., exhibiting uniformity of fine patterns substantially along and across the entire area of ​​the foil. The systems and methods of the present invention allow for the manufacture of metal foils composed of a single metal type (e.g., when copper is electrodeposited on a copper-starting foil) or a combination of metals (e.g., when copper is electrodeposited on a nickel-starting foil). In other words, the disclosed systems and methods allow for the patterning of metal foils with different metals, for example, for forming functional or decorative textured coatings.

[0125] Roll-to-roll electro-etching system: As is known in the art, electro-etching is a method of etching metal from a metal substrate surface by using an electric current to oxidize the metal into metal ions. Electro-etching can be used to transfer a pattern from a mask to a metal surface. A mask is placed on the surface of a metal substrate. An electric current is passed through an electrolyte solution, and the metal dissolves only on the surfaces not covered by the mask, thereby transferring the mask pattern to the metal surface and / or bulk structure (depending on the duration and conditions of the electro-etching method). Under certain method conditions, transferring the pattern to the metal surface results in surface changes, while more aggressive or longer electro-etching methods can form holes in the metal starting foil. Masks are typically made of materials inert to the electrolyte solution and the general conditions of the method, including during the current flow.

[0126] In some embodiments of the invention, an electro-etching system is provided for forming recesses or vias in a raw conductive foil, configured to produce very long (at least 1 meter and preferably more than 100 meters) patterned foil (metallic component) in a roll-to-roll configuration. The system includes an input (feed) roller for feeding the raw foil to an electro-etching unit (EU) and an output roller for collecting the etched (patterned) foil. In the electro-etching unit, patterns can be seamlessly repeated to etch recesses or vias in the foil, the electro-etching unit comprising a mask in the form of a circumferentially closed band presenting the via pattern. A section of the mask is located between a cathode and a section of the foil, the foil maintaining a positive voltage relative to the cathode by physical contact with the anode or electrical contact with the positive terminal of a power source, wherein the cathode is connected to the negative terminal of the power source. When a voltage is applied to the electrodes (i.e., the cathode and the foil or the anode), the portion of the foil in contact with the mask is etched, wherein the electrodes are ionically contacted, for example, by an electrolyte solution flowing therebetween. Therefore, the dents or vias are essentially formed in the foil in areas not covered (masked) by the masking material; that is, the dents or vias are formed in the foil according to the holes in the mask.

[0127] In the context of this invention, the term "cathode" refers to the electrode in which a reduction reaction occurs within the electro-etching unit, while the term "anode" refers to the electrode in which an oxidation reaction (i.e., electro-etching) occurs. Therefore, the cathode is connected to the negative terminal of the power supply, and the anode is connected to the positive terminal. The polarity of the electrodes can be reversed when the process involves applying a reverse pulse voltage and / or current for a specific time period.

[0128] In the context of this invention, the terms “starting foil,” “original metal foil,” “original foil,” and “substrate foil” refer to a foil prior to undergoing an electro-etching method in which holes such as indentations or through-holes are formed in the foil, and / or metal is electrodeposited on the foil to form a plurality of raised texture elements.

[0129] Patterned foil can be porous foil, i.e., containing pores. In the context of this invention, the term "pore" refers to a hollow structure formed within the foil that does not extend through the entire thickness of the foil, such as an indentation, recess, or groove, as well as a hollow structure that extends through the entire thickness of the foil, also referred to herein as a "through-hole." Through-holes are particularly useful for creating desired patterns or electro-etching within the raw foil and for cutting the raw foil into discrete sheets after collection on an output roller.

[0130] In the context of this invention, the terms "porous metal foil," "porous foil," "patterned metal foil," and "patterned foil" refer to conductive foils in which a pattern of pores is presented, particularly including through-holes. In some embodiments, the pattern of the pores follows a seamless repeating pattern.

[0131] In the context of this invention, the terms "perforated metal foil," "perforated foil," and "metal component" refer to a metal foil in which a through-hole pattern is presented. In some embodiments, the through-hole pattern follows a seamless repeating pattern.

[0132] When “foil” or “metal foil” is used herein and throughout, it means both the original state and the patterned (e.g., perforated) state of the metal foil before, during, and after the electro-etching process. It is noted here that metal foil is conductive foil because it is made of metal, regardless of whether it is perforated. As used herein, the term “conductive foil” is intended to cover metal foil and metal alloy foil, as well as foil made of composite materials or material compositions, wherein at least one of said materials is conductive, for example, in the form of a metal layer disposed on an electrically insulating substrate such as a polymer, or having metallic regions dispersed throughout the electrically insulating material, said metallic regions being at least partially present on the surface of the foil.

[0133] The original foil can be solid (non-porous), porous, or perforated, even prior to electro-etching methods, which enhance its porosity by creating additional pores and / or increasing the volume (e.g., depth) of existing pores.

[0134] Typically, when electro-etching metal foil using a mask with holes, the mask must be in direct contact with the foil to produce precise patterns in a controlled manner. For dynamic and continuous electro-etching methods, maintaining continuous contact between the mask and the foil presents mechanical, electrical, and chemical challenges to the system and method. In the context of this invention, the contact sections between the mask and the foil are preferably in contact to achieve high stencil printing fidelity of the pattern from the mask to the holes in the foil, as defined and explained below.

[0135] In the context of this invention, the term "stencil printing fidelity" refers to the accuracy of the pattern produced when a stencil is used, with the mask acting as the stencil. High stencil printing fidelity means that the pattern in the mask is reproduced in the foil, with a high level of control over the precision and consistency of production, and with little or no distortion or loss of detail.

[0136] To provide long and patterned foils, the foil can be continuously passed through the electro-etching unit, and the mask can be rotated such that specific sections of the mask are always located between the cathode and new sections of the foil. The mask extends over the foil to eliminate contact between areas of the foil not configured for etching and the electrolyte. To provide constant contact between the mask sections, the foil, and the electrolyte, the advancement of the foil through the electro-etching unit can be coordinated with the rotation of the mask. The flow of the electrolyte can be restricted to the contact area between the foil and the mask. Typically, in electro-etching methods, the electrolyte is configured not only to provide ionic contact between the electrodes but also to remove the etched material from its surface and to help remove bubbles that can form as a byproduct of metal dissolution. When bubbles are present on the metal surface, they can hinder metal dissolution due to increased resistance. Bubbles may further penetrate the area between the metal and the mask, loosening the contact between them and thus reducing the stencil printing fidelity of the mask. The system of the present invention may be particularly advantageous in electro-etching media containing bubbles because the mask is configured to maintain close and constant contact with the moving foil throughout the electro-etching process.

[0137] To provide controlled electro-etching according to a (templated) mask pattern, and to provide a perforation pattern in the foil faithful to the mask pattern, at least one segment of the foil is configured to be in close proximity or contact with at least one segment of a closed-band mask during the electro-etching method. The segment of the mask that contacts or is in close proximity to a corresponding segment of the foil, and the segment of the foil that contacts or is in close proximity to a corresponding segment of the mask, are also referred to herein as “contact segments,” and the areas in contact with each other are referred to as “contact regions” or “perforation regions.” It should be understood that during a continuous electro-etching method, the foil is passed into an electro-etching unit to be electro-etched, and the unetched portions of the original foil continuously become contact segments to allow seamless etching of the entire foil length, wherein the contact segments on the mask are circumferentially closed bands that continuously change and collectively span the entire circumference of the mask. Alternatively, the mask can be considered as comprising a finite number of contact segments, the number of which depends on the length of the contact segments of the foil and the total length of the mask (its perimeter).

[0138] In the context of the electro-etching method according to various aspects and embodiments of the present invention, the term "continuous" refers to an electro-etching method comprising a continuous (long) foil, preferably constructed in a roll-to-roll manner, wherein the foil can be advanced through the electro-etching unit in a continuous manner (at a constant or varying rate) or incremental manner, wherein the duration of steps during foil advancement, the advancement rate and the waiting time between steps can be adjusted according to the electro-etching conditions.

[0139] According to some embodiments, the contact segments in the foil and the corresponding contact segments in the mask are in substantially physical contact with each other over the entire contact segment, except for the area of ​​the holes (voids) in the mask. Since the system operates in continuous motion, at least in the foil and mask, this means the contact segments are continuously varying. The phrase "substantially over the entire contact segment" describes the dynamic state of the contact segments, indicating that at any given point in time during the method, most areas of the contact segments are in physical contact (zero distance), while some small areas of the contact segments may be very close to each other, and these areas are dynamically changing. In some embodiments, the contact segments of the foil and the corresponding contact segments or portions of the mask are very close to each other, where "very close" means a distance of 0 to 0.5 mm. In some embodiments, in the context of the contact area, the term "contact" means a range of states from complete physical contact over the entire area of ​​the contact segment, via complete physical contact over substantially the entire contact segment, to very close proximity over the entire area of ​​the contact segment.

[0140] To provide a sufficiently large contact area between the closed-loop mask and the foil in a continuous manner, the contact sections of the mask and the corresponding contact sections of the foil are not flat, but preferably smoothly curved into curved surfaces, for example, following the curvature of arched, circular, or elliptical sections, wherein the shape of the contact section of the mask is configured to conform to the shape of the contact section of the foil (or vice versa). For example, the contact section of the foil may be convex (i.e., extending toward the contact section of the mask), while the contact section of the mask may be concave (i.e., curved inward from the contact section of the foil). In another example, the contact section of the foil may be concave, while the contact section of the mask may be convex.

[0141] According to some embodiments of the invention, the electro-etching method occurs in a curved contact region. As defined above, the contact region or perforation region is provided when the mask is pressed against the original foil, and the curved contact region is provided when at least one of the mask and foil has a curved surface or is pressed against a curved surface. Preferably, the curved surface, and thus the resulting curved contact region or the aforementioned contact segment of the foil and mask, is curved to match (conform to) the curvature of the active surface of the cathode. For example, the shape of the contact segment of the mask and foil may further correspond to the shape of the active surface of the cathode and / or the curvature of the curved surface forming a portion of the side surface of a cylindrical or spherical anode (see...). FIG. 1A -B、 FIG. 2A -B、 FIG. 3A -B and FIG. 4A -B). The region formed between the cathode and the contact area between the foil and the mask is referred to here as the "electro-etched zone," where electro-etching occurs when the cathode and foil are in electrical contact and an electrolyte is present therebetween.

[0142] According to some aspects and embodiments of the present invention, a roll-to-roll foil electro-etching system is provided, comprising: An electro-etching unit configured to transform a starting foil into an electro-etched foil when a current and / or voltage is applied; An input roller, configured to feed a starting foil into an electro-etching unit; and The output roller is configured to collect patterned foil. The electro-etching unit includes: cathode Elastic mask; Two or more axes that hold the mask under tension; Containers for holding and / or circulating liquid electrolyte compositions; A fluid delivery unit fluidly connected to the container; and power supply, The starting foil and the patterned foil are conductive; The mask has the form of a circumferentially closed band with an electrically insulating outer surface. The mask includes a contact section, which is positioned as a corresponding contact section of the contact foil, such that the contact section of the mask has a curved shape that conforms to the curvature of the contact section of the starting foil. The contact section of the mask is positioned between the contact section of the cathode and the contact section of the starting foil. The fluid delivery unit is configured to guide the flow of the electrolyte composition supplied by the container to be substantially tangent to the outer surface of the mask along the entire length of the contact portion of the mask; During the feeding of the starting foil via the input roller and / or the collection of the patterned foil via the output roller, the mask and the starting foil are configured to move in tandem while the starting foil contacts the mask; and The power source is configured to apply voltage and / or current between the contact section of the cathode and the starting foil in the presence of the electrolyte composition.

[0143] As used herein, the term "mask" refers to a perforated layer (i.e., a layer with through-holes) that has an electrically insulating surface and is resistant to electrical etching.

[0144] As detailed herein, according to some embodiments, the system includes a fluid delivery unit in fluid communication with a container. According to some embodiments, the fluid delivery unit is configured to guide a flow of the electrolyte composition supplied by the container tangentially to the outer surface of the mask. According to some embodiments, the fluid delivery unit is configured to guide a flow of the electrolyte composition supplied by the container parallel to the outer surface of the mask.

[0145] Specifically, it was surprisingly found that guiding and controlling the electrolyte flow (potentially under pressure) into the area between the foil and mask assembly and the cathode allows for the removal of etched metal from the foil surface and the mask. Therefore, it also allows for the formation of perforations on thick foils. Previous systems designed to guide electrolyte flow through perforations were less successful with smaller mask holes because the electrolyte flow was insufficient to remove these bubbles and / or etched metal salts from the mask holes, thus clogging the mask holes.

[0146] It was also found that perforation of thick foil is not permissible in the absence of flowing electrolyte.

[0147] Specifically, according to some embodiments, the system includes means for guiding and controlling the flow of electrolyte into the contact section of the starting foil and the mask. According to some embodiments, the system includes a liquid pump configured to circulate the electrolyte composition in a flow path between the electrode and the counter electrode. According to some embodiments, the liquid pump is configured to generate fluid pressure. According to some embodiments, the fluid pressure guides the flow of the electrolyte composition tangentially to the outer surface of the mask. According to some embodiments, the fluid pressure directs the flow of the electrolyte composition to the contact section of the foil and the mask.

[0148] According to some embodiments, the system includes a liquid pump configured to circulate the electrolyte composition in a flow path between the electrode and the counter electrode along substantially the entire length of the contact portion of the mask. The phrase "substantially the entire length of the contact portion of the mask" means at least 80%, at least 90%, or at least 95% of the mask length. Each possibility represents a separate embodiment of the invention.

[0149] It has also been found that a split cathode can be used to improve contact between the electrolyte composition and the cathode. According to some embodiments, the cathode is divided into two or more parts. According to some embodiments, the cathode is divided into two sections. According to some embodiments, the cathode is divided into two substantially equal segments. According to some embodiments, a fluid delivery unit is configured to guide the electrolyte flow between the two segments facing the mask.

[0150] The electrode can be divided into two parts, with the electrolyte flowing between them. In this case, the entire system can be rotated 90° counterclockwise, so that the cathode and mask are located below the foil, and the foil is pulled horizontally through the patterned area. This is illustrated in Figure 3C of this document.

[0151] In some embodiments, an electro-etching method imparts a seamless repeating pattern of vias to a conductive foil. In some embodiments, the system is configured to etch a seamless repeating pattern of vias into a continuous conductive foil in a roll-to-roll configuration.

[0152] Advantageously, this electro-etching system and method allows for the formation of small perforations (e.g., less than 6 mm in diameter). According to some embodiments, the system is configured to form perforations with an average diameter less than 6 mm, less than 5 mm, less than 4 mm, less than 3 mm, less than 2 mm, or less than 1 mm. Each possibility represents a separate embodiment of the invention.

[0153] According to some embodiments, at least one of the input roll and the output roll is a convex roll. According to some embodiments, the convex roll is configured to maintain the alignment of the starting roll with the mask in a transverse direction perpendicular to the direction of movement of the mask and the starting foil.

[0154] A convex coating roll is a roll with an arc-shaped surface that sweeps across its surface from the ends outward toward the center of the roll surface. The ends of the roll surface have the smallest diameter, while the roll diameter increases in equal increments across its surface toward the center. Convex coating rolls can be made from a variety of materials, such as steel, aluminum, stainless steel, or electroplated aluminum or steel, and can be covered with rubber.

[0155] In some embodiments, the active surface of the cathode conforms to the curvature of the contact section of the foil. In other embodiments, the active surface of the cathode is curved.

[0156] The term "active surface," which is related to the cathode or anode, refers to the surface of the contact section facing the foil during the electro-etching process.

[0157] The cathode of the electro-etching unit can be connected to the negative terminal of a power supply. The contact section of the conductive foil can be connected to the positive terminal of the power supply. As is known in the art, an electrical connection to the positive terminal can be achieved, for example, through an electrical conductor. The electro-etching unit may also include an anode. For example, the contact section of the foil can physically contact the anode, thereby connecting to the positive terminal of the power supply and maintaining a positive potential relative to the cathode to allow electro-etching at the contact area of ​​the foil. In some embodiments, the contact section of the foil is electrically connected to the positive terminal of the power supply without directly contacting the anode. For example, a portion of the metal foil that is not a contact section can be connected to the positive terminal of the power supply, for example, by winding the foil onto a conductive shaft, roller, or annular belt conveyor, wherein the conductive shaft / roller / conveyor is connected to the positive terminal. In some embodiments, the conductive foil itself constitutes the anode in the electro-etching method.

[0158] In some embodiments, the electro-etching unit includes a curved surface. In some embodiments, the curved surface is conductive, and a conductive foil is connected to the positive terminal of a power source via the curved surface. In some such embodiments, the curved surface may constitute the anode. In some embodiments, both the conductive foil and the curved surface are connected to the positive terminal of the power source.

[0159] In some embodiments, the curved surface forms part of the side surface of a cylindrical or annular belt conveyor or a large sphere (e.g., with a diameter of 3 meters or more). In some embodiments, the roller or conveyor element is rotatable and configured to move in coordination with the mask (see [link to relevant documentation]). FIGS. 1A-1B ).

[0160] As described above, the contact sections of the closed-band mask have a curved shape corresponding to the contact sections of the conductive foil, which means that the contact sections of the foil can also have curved surfaces. The terms “corresponding,” “belonging to,” “conforming to,” and “conforming to” as used herein in describing curved shapes refer to complementary curvatures, i.e., combinations of convex and concave shapes or surfaces. It should be understood that both the mask and the foil are in thin film form, i.e., either continuous, as in the case of the foil, or closed-band, as in the case of the mask, and therefore can be permanently or temporarily shaped to form the corresponding curved contact sections.

[0161] The radius of curvature of the contact segments of the mask and foil can be selected to provide the desired length of the contact area and the electro-etched area, and can range from about 10 cm to about 1,000 cm or greater. The radius of curvature can also be adjusted according to the thickness and material properties of the mask and foil, such as elongation, for example, below the elongation at break value of the material.

[0162] The contact section of the foil can be held within the electro-etching unit by being wound around a stationary or moving object with a curved surface. In some embodiments, the foil is wound around a stationary or moving object having a convex surface facing the foil. For example, the contact section of the foil may be wound around a portion of the outer (convex) surface of a mandrel, also referred to herein as a “cylindrical mandrel,” “cylindrical cylinder,” or “roller.” The terms “cylinder,” “roller,” and “mandrel” are used interchangeably herein to refer to a curved surface on which the foil may be wound or rolled to provide a curved shape for the contact section of the foil. The curved surface of the mandrel may also be part of a large sphere. The mandrel may rotate in a manner that cooperates with the mask to allow the foil to roll continuously within the electro-etching unit.

[0163] According to some embodiments, the mask and the starting foil are configured for coordinated movement. According to some embodiments, the mask and the starting foil are configured to move coordinatedly when the starting foil contacts the mask. According to some embodiments, the mask and the starting foil are configured for coordinated movement when the starting foil is fed via an input roller and / or when the patterned foil is collected via an output roller.

[0164] According to some embodiments, the starting foil is pressed against the mask. According to some embodiments, an input roller, an output roller, or both are configured to transfer the starting foil in the direction from the input roller to the output roller. According to some embodiments, the input roller is configured to transfer the starting foil in the direction from the input roller to the output roller. According to some embodiments, the output roller is configured to change the starting foil in the direction from the input roller to the output roller.

[0165] According to some implementations, the initial foil is pressed and the mask is dragged. According to some implementations, dragging enables the foil and mask to move in tandem.

[0166] The contact section of the foil can be wound around the convex surface of a non-rotating object. In some embodiments, continuous rolling of the foil is facilitated by providing one or more rotating shafts on which the foil can be wound. The non-rotating object can be stationary or can move in a linear motion, for example, to establish a desired distance between the foil and the active surfaces of the mask and / or cathode. The rotating shaft, also known as a rotating roller, is a mechanical part of the machine used to allow a plate or line to slide on it while passively rotating due to the movement of the plate or line (passive rotating shaft), or to move the plate or line by means of the motorized axial rotation of the shaft and the friction therebetween.

[0167] To further improve the removal of etched metal from the foil surface and / or from the mask, designated units for removing the etched metal from the electro-etching system can be employed. In particular, etched metal particles can accumulate in the apertures of the mask and inhibit further electro-etching through these apertures, thus negatively impacting the SRP of the perforations etched in the foil. This is especially important when manufacturing perforated foils with high open area (e.g., 15% or more) or when the mask aperture diameter is relatively small (e.g., less than 100 μm). For example, when electrolytically etching aluminum foil, the etched metal may include alumina or aluminum hydroxide. Due to the limited solubility of these salts in electrolyte solutions, they often precipitate as particles that can accumulate in the foil, mask, or other parts of the system. It has been found that without washing, the aperture size distribution is wide and the aperture shape is non-uniform (not conforming to the mask aperture shape).

[0168] Therefore, according to some embodiments, the system includes means for removing etched metal from an electro-etching system. According to some embodiments, the system includes means for removing etched metal from a foil, a mask, or both.

[0169] According to some implementations, the electro-etching unit includes means for removing etched metal from the mask.

[0170] According to some implementation schemes, an online mask cleaning unit can be added to the system to ensure that the apertures of the mask are free of etched metal salts before contacting the foil.

[0171] According to some embodiments, the electropatterning unit includes a cleaning unit. According to some embodiments, it can be connected to a cleaning fluid source. According to some embodiments, the liquid is a cleaning liquid. According to some embodiments, the liquid includes water. According to some embodiments, the liquid is an aqueous composition. According to some embodiments, the aqueous composition is an aqueous solution.

[0172] According to some embodiments, the cleaning unit includes at least one nozzle facing a portion of the elastic mask and configured to rinse that portion of the starting foil with a cleaning fluid.

[0173] According to one embodiment, the cleaning unit includes at least one nozzle. According to one embodiment, the cleaning unit includes at least two nozzles. According to one embodiment, the cleaning unit includes two nozzles.

[0174] According to some embodiments, the cleaning unit is configured to clean this portion of the mask with pressurized water. According to some embodiments, this portion of the mask is offset from the contact section between the mask and the foil. According to some embodiments, this portion of the mask is exposed and offset from the contact section between the mask and the foil and from the tensioning shaft. According to some embodiments, this portion of the mask is positioned between two tensioning shafts.

[0175] According to some implementations, the cleaning unit includes a cleaning head configured to spray pressurized liquid toward that portion of the mask.

[0176] According to some embodiments, the cleaning unit also includes an electro-etched metal collection tray located in the inlet of the liquid reservoir, positioned to collect the electro-etched metal to be cleaned. It should be understood that the collection tray is positioned such that it can collect the water sprayed or misted from the cleaning mask.

[0177] According to some embodiments, the system includes an electro-etched foil cleaning device. According to some embodiments, the electro-etching unit includes an electro-etched foil cleaning device. According to some embodiments, the apparatus for removing etched metal from the foil includes an electro-etched foil cleaning unit.

[0178] The electro-etched foil cleaning unit can be similar to the mask cleaning unit, and each relevant embodiment of the mask cleaning unit, except for its positioning, can be similarly applied to the electro-etched foil cleaning unit. Specifically, the electro-etched foil cleaning unit is positioned such that the electro-etched foil cleaning apparatus can clean a portion of the electro-etched foil with pressurized water. According to some embodiments, this portion of the electro-etched foil is offset from the contact section between the mask and the foil. According to some embodiments, this portion of the mask is positioned between the contact section between the mask and the foil and the output roller.

[0179] According to some embodiments, the system includes an ultrasonic cleaning device. According to some embodiments, the electro-etching unit includes an ultrasonic cleaning device. According to some embodiments, the apparatus for removing etched metal from a foil, mask, or both includes an ultrasonic cleaning device.

[0180] According to some implementation schemes, ultrasonic cleaning devices include ultrasonic transducers.

[0181] The ultrasonic cleaning device can be configured to transmit ultrasonic waves to a mask and / or an electro-etched foil. Furthermore, according to some embodiments, two ultrasonic cleaning devices or an ultrasonic cleaning device with two transducers can be combined. Each possibility represents a separate embodiment of the invention.

[0182] According to some embodiments, the ultrasonic transducer may face a portion of the mask. The portion of the mask that the ultrasonic transducer may face can be as described for a portion of the mask cleaned by a cleaning unit. Therefore, each embodiment associated with a cleaning portion of the mask can be similarly applied to an ultrasonically irradiated portion of the mask. According to some embodiments, the cleaning portion of the mask and the ultrasonically irradiated portion of the mask may be the same portion of different portions of the mask, as defined above.

[0183] According to some embodiments, the ultrasonic transducer may be directed toward a portion of the electro-etched foil. The portion of the electro-etched foil that the ultrasonic transducer may be directed toward may be as described for the portion of the electro-etched foil being cleaned by the cleaning unit. Therefore, each embodiment associated with the cleaning portion of the electro-etched foil can be similarly applied to the ultrasonically irradiated portion of the electro-etched foil. According to some embodiments, the cleaning portion of the mask and the ultrasonically irradiated portion of the electro-etched foil may be the same portion of the different portions of the electro-etched foil as defined above.

[0184] According to some embodiments, another device for removing etched metal from a foil, mask, or both includes a filter. As detailed herein, according to some embodiments, the system may include an anode positioned adjacent to the contact segment.

[0185] According to some embodiments, the system may further include a liquid pump configured to circulate the electrolyte composition in a flow path between the electrode and the counter electrode. As described above, according to some embodiments, over time, an electro-etched metal (e.g., Al(OH)3) may precipitate into the electrolyte composition. Therefore, according to some embodiments, the system may further include a filter comprising a membrane configured to filter undissolved solid particles from the electrolyte composition.

[0186] A tensioning shaft or roller can be used to maintain tension on a closed belt mask by being mounted on a spring or other mechanism that allows it to move slightly against a counterforce (e.g., a resistance spring). As the closed belt begins to roll, the tensioning shaft moves to compensate for changes in tension in the belt, thereby keeping the belt taut.

[0187] A cylindrical mandrel can serve as the anode, i.e., connected to the positive terminal of a power source. In some embodiments, at least a portion of the curved surface of the mandrel is conductive. In some embodiments, the cylindrical mandrel is made of a conductive material. The mandrel can be made of a solid conductive material, i.e., its body is filled with said material. Alternatively, the mandrel can be a hollow conductive mandrel.

[0188] In some embodiments, the body of the cylindrical mandrel is made of an electrically insulating material, and its curved surface is made of a conductive material. For example, a conductive sleeve may be mounted on the curved surface of the electrically insulating mandrel. Alternatively, the curved surface of the electrically insulating mandrel may be coated with a conductive material, for example, by electrodeposition.

[0189] In some embodiments, the body and / or curved surface of the cylindrical mandrel are made of alternating conductive and electrically insulating portions. For example, the mandrel may be made primarily of an electrically insulating material while including inserts of conductive material extending radially from the central axis of the mandrel toward its curved surface and present on the curved surface. Without wishing to be constrained by theory or mechanism of action, such a configuration is expected to improve current distribution during the electro-etching process.

[0190] In some embodiments, the cylindrical mandrel is electrically insulated. In some embodiments, the foil may be electrically connected to the positive terminal of a power source by means of a conductive roller, which is electrically connected to the positive terminal and contacts the foil outside the contact area.

[0191] Non-limiting examples of conductive and electrically insulating materials that can be used in spindles include metals, electroplated metals and metal alloys such as Al, Ni, Cu, Mg, Ti, steel, stainless steel, chromium-coated steel; polymers such as polytetrafluoroethylene (PTFE, e.g., TEFLON™) and polyaryletherketones such as PEEK™; carbon and / or graphite; ceramics; and polymer-coated metals.

[0192] The cathode may have an active surface facing the contact section of the mask, the shape of which corresponds to or conforms to the shape of the contact section of the mask and / or the contact section of the foil. For example, the cathode may have a concave active surface facing the contact section of the mask. In some embodiments, the mask surrounds the cathode, and the cathode-mask assembly may be moved as a whole toward the foil to press the contact section of the mask against the curved contact section of the foil.

[0193] The cathode can be a dynamic cathode, such as a rotating cathode. Rotation of the cathode can facilitate the flow of the electrolyte solution through the electro-etching unit during the electro-etching process. The cathode can further be used, for example, to deliver the electrolyte solution to the contact area via spraying.

[0194] In some implementations, the length of the effective region of the cathode is less than the length of the contact region. Without being bound by any particular theory or mechanism of action, it is anticipated and assumed that limiting the length of the cathode active region relative to the contact region can help prevent undesirable electro-etching of the foil in areas not in contact with the mask, such as before such contacts are established within the electro-etching system. This can be particularly important when the foil, mask, and cathode are immersed in an electrolyte solution and when controlling the contact area between the foil and the electrolyte solution is difficult.

[0195] The cathode can be made of any conductive material that is inert to the conditions of the electro-etching medium and the electro-etching method when used as a cathode. In some embodiments, the cathode is made of the same material as the conductive foil, for example, aluminum when patterned aluminum foil, or copper when patterned copper foil. Non-limiting examples of cathode materials that can be used in combination with different types of conductive foil include graphite, glassy carbon, stainless steel, and platinum.

[0196] According to some embodiments, the cathode can be made of conductive and non-conductive segments. According to some embodiments, this segmented configuration of the cathode allows the cathode current density to be closer to the anode current density. This configuration may be advantageous, for example, in copper etching.

[0197] Masks can be either elastic or rigid. In the context of masks, the term "elastic" refers to the ability of a mask to stretch and contract without breaking when rotated, tensioned, flexed, twisted, and relaxed. The elasticity of a mask gives it the ability to return to its original shape after being deformed, bent, and relaxed by external forces. In the same context, the term "rigid" refers to the ability of a mask to maintain its shape under load and refers to a mask that does not have the ability to stretch and return to its original dimensions, wherein in some embodiments, a rigid mask can still be bent and rolled around an axis and driven by the axis. According to some embodiments of the invention, a mask can be both elastic and flexible (bendable), as in the case of some polymer masks, only flexible, i.e., substantially non-stretchable but bendable and twistable, as in the case of tough metal strips, or rigid, having a predetermined and constant shape, as in the case of circular hard / rigid metal masks. Thus, a bendable mask can be temporarily or permanently shaped (e.g., bent or stretched) to form curved contact sections without necessarily being circular along its entire perimeter. On the other hand, the rigid mask should be pre-formed to have a circular shape in order to continuously provide curved contact segments during rotation.

[0198] In some implementations, the mask is a resilient mask. Thus, the mask can be wound between two or more tension axes and / or rotation axes to achieve its continuous drive and / or rolling. The resilient mask can also be tensioned between the two or more tension axes.

[0199] In some implementations, the resilient mask is temporarily shaped to form corresponding curved contact sections. For example, a contact section of a mask wound between two or more tension shafts can be pushed against and pressed against a contact section of a foil with a convex shape. Alternatively, a contact section of a foil with a convex shape can be pushed against and pressed against a contact section of a mask wound between two or more tension shafts. The convex shape of the contact section of the foil can be provided by winding the contact section around the convex surface of a stationary or moving object (e.g., a cylindrical mandrel).

[0200] Now for reference FIGS. 1A-1B It shows a schematic diagram of an electro-etching unit 10 according to some embodiments of the present invention, showing a circumferentially closed band mask 11 wound and tensioned between tension shafts 12a and 12b, surrounding a concave cathode 13 and located near a cylindrical mandrel constituting an anode 14, with a foil 15 tightly wound on the mandrel and covering a portion of the convex surface of the anode 14, wherein... FIG. 1A The electro-etching unit 10 is shown during the loading phase, before the mask 11 contacts the foil 15 and before electrical energy is applied. FIG. 1B The diagram shows an electro-etching unit 10 during the electro-etching stage where the mask 11 contacts the foil 15, and... FIG. 1B The dashed rectangle in the figure marks the contact area between the mask 11 and the foil 15, including the contact segment 11a of the mask 11 and the contact segment 15a of the foil 15. Contact is achieved by moving the tension shafts 12a and 12b toward the anode 14, moving the anode 14 toward the tension shafts 12a and 12b, or a combination thereof, while the tension shafts 12a and 12b can rotate in coordination with the anode 14. During this period, an electrolyte flows between the cathode 13 and the anode 14 (not shown), and electrical energy is applied to the cathode 13 and the anode 14 to achieve the electro-etching of the foil 15.

[0201] As from FIGS. 1A-1BUnderstandably, the electro-etching unit is configured to form patterned indentations or vias in the foil. This pattern is templated (stencil printing) by a mask pattern as a result of applying electrical energy between the cathode and anode while continuously passing the tensioned foil through the electro-etching unit. The movement of the foil is coordinated with the movement of the mask, and the electrolyte solution flows at least through the portion of the electro-etching unit where the foil and mask are located between the electrodes. Specifically, as a result of the coordinated rotational movement of the tensioning rollers 12a and 12b with the anode 14, new segments of the foil 15 and mask 11 come into contact, forming new contact segments 15a and 11a respectively between the electrodes and in the electrolyte solution, allowing for continuous electro-etching of the foil according to the mask pattern. In this exemplary illustration, the electro-etching unit includes a curved surface on which curved perforation regions are formed; this curved surface is the curved surface of the anode 14.

[0202] Now for reference FIGS. 2A-2B It shows a schematic diagram of an electro-etching unit 20 according to some embodiments of the present invention, illustrating a circumferentially closed strip mask 21 wound and tensioned between tension shafts 22a and 22b, surrounding a concave cathode 23 and located near an electrically insulating cylindrical mandrel 24, with foil 25 tightly wound around a portion of the convex surface of the mandrel 24 and a conductive tension shaft 26, wherein... FIG. 2A The electro-etching unit 20 is shown during the loading phase, before the mask 21 contacts the foil 25 and before electrical energy is applied. FIG. 2B The diagram shows an electro-etching unit 20 during the electro-etching stage, wherein a mask 21 is in contact with a foil 25, and... FIG. 2B The dashed rectangle in the figure marks the contact area between the mask 21 and the foil 25, including the contact section 21a of the mask 21 and the contact section 25a of the foil 25. Meanwhile, the tensioning shafts 22a and 22b can rotate in coordination with the mandrel 24 and optionally the tensioning roller 26. During this period, the electrolyte flows between the cathode 23 and the foil 25 (not shown), and electrical energy is applied to the cathode 23 and the tensioning roller 26, which is connected to the positive terminal of the power supply (not shown), so that the foil 25 maintains a positive voltage relative to the cathode 23 and achieves the electro-etching of the foil 25.

[0203] FIG. 1C Some embodiments of the present invention are shown. FIGS. 1A-1B The schematic diagram of the electro-etching unit 10 shown indicates that the concave cathode 13 is a split cathode including cathode portion 13a and cathode portion 13b, wherein the electrolyte can flow between cathode portion 13b and cathode portion 13b and anode 14, and wherein the circumferential closed strip mask 11 is wound and tensioned between three tensioning shafts 12a, 12b and 12b.

[0204] FIG. 1D Some embodiments of the present invention are shown. FIGS. 1A-1BThe schematic diagram of the electro-etching unit 10 shown also includes a cleaning unit comprising a cleaning head 16 with one or more nozzles pointing toward the closed strip mask 11, a cleaning tray 17 positioned to collect cleaning fluid from the closed strip mask 11, and a wiper 18 to prevent the cleaning fluid from contacting the foil 15; and a roller 19 configured to stretch the closed strip mask 11, thereby exposing its area to the nozzles. The roller 19 also helps to center the mask and prevent its axial movement. Thus, according to some embodiments, the roller 19 may be a convex roller. The roller 19 may be configured to stretch the mask 11, exposing its area to the nozzles of the cleaning head 16. The wiper 18 may be configured to prevent the cleaning fluid from contacting the foil.

[0205] As from FIGS. 2A-2B As can be seen, the electro-etching unit is configured to form patterned indentations or through-holes in the foil. This pattern is templated by a mask pattern as a result of applying electrical energy between the cathode and the foil while simultaneously causing the tensioned foil to continuously pass through the electro-etching unit. The movement of the foil is coordinated with the movement of the mask, and the electrolyte solution flows at least through the portion of the mask of the electro-etching unit located between the cathode and the foil. In this exemplary illustration, the electro-etching unit includes a curved surface on which a curved perforation region is formed. This curved perforation region is the curved surface of the cylindrical mandrel 24.

[0206] Now for reference FIGS. 3A-3B It shows a schematic diagram of an electro-etching unit 30 according to some embodiments of the present invention, showing a circumferentially closed strip mask 31 wound and tensioned between tension shafts 32a and 32b, which surrounds a concave cathode 33 and is located near a fixed anode 34 having a curved active surface, a foil 35 tightly wound on the convex surface of the curved active surface and a tension roller 36, wherein... FIG. 3A The electro-etching unit 30 is shown in the loading phase before the mask 31 contacts the foil 35 and before electrical energy is applied. FIG. 3B An electro-etching unit 30 is shown in the electro-etching stage, wherein tension rollers 32a and 32b move toward the anode 34, allowing contact between the mask 31 and the foil 35, while tensioning shafts 32a and 32b can rotate in coordination with the rotating shaft 36. During this period, electrolyte flows between the cathode 33 and the fixed anode 34 and electrical energy is applied to the cathode 33 and the fixed anode 34, thereby achieving electro-etching of the foil 35.

[0207] exist FIGS. 3A-3B In the exemplary illustration, the electro-etching unit includes a curved surface on which a curved perforation region is formed, the curved perforation region being a curved active surface of the fixed anode 34.

[0208] In some embodiments, the circumferentially closed strip mask is a rigid mask. A rigid mask can have a constant shape and does not necessarily need to be wound on a tension roller. A rigid mask can be in the form of a cylinder with side surfaces that serve as curved surfaces. In some embodiments, the foil can be wound on two or more tension / rolling shafts such that, during the electro-etching process, the contact sections of the mask have a convex shape, and the contact sections of the foil are concave, with two corresponding contact sections contacting each other to form a contact area.

[0209] Now for reference FIG. 4A -B, which shows a schematic diagram of an electro-etching unit 40 according to some embodiments of the present invention, showing a rigid circumferentially closed strip mask 41 with a cylindrical shape viewed from top, surrounding a rotating cathode 43 and located near a foil 45 wound on tension / rotation shafts 26a and 26b, wherein the tension shaft 26a is conductive, and the contact section of the mask, cathode, and starting foil is immersed in an electrolyte solution (not shown), wherein FIG. 4A The electro-etching unit 40 is shown in the loading phase, before the mask 41 contacts the foil 45 and before electrical energy is applied. FIG. 4B An electro-etching unit 40 is shown in the electro-etching stage, wherein a mask 41 contacts a foil 45. This contact can be achieved by moving tension shafts 46a and 46b toward the mask 41, moving the mask 41 toward tension rollers 46b and 46b, or a combination thereof. The tension shafts 46a and 46b can rotate in coordination with the mask 41, and electrical energy is applied to the cathode 43 and the tension shaft 46a, which is connected to the positive terminal of a power source (not shown). This maintains a positive voltage on the foil 45 relative to the cathode 43, and electro-etches the foil 45 as the cathode 43 rotates to facilitate the flow of electrolyte between the cathode 43 and the foil 45. The anode 43 has a central portion 43a and curved blades 43b and 43c connected to the central portion 43a, the outer surfaces of which constitute the active surface of the anode 43. The curved blades 43b and 43c are shaped to match the shape of the mask 41 to provide a constant distance between the active surface of the anode 43 and the contact segment of the initial foil 45.

[0210] In this exemplary illustration, curved perforated areas are formed on a rigid mask 41, which constitutes the curved surface of the electro-etching unit.

[0211] The speed of the linear and rotational motion of the tensioning and rotating shafts, as well as the speed of the rotational anode and the electrolyte flow rate, can determine the uniformity of the etching method and therefore can be monitored and / or controlled throughout the process. Electroetching method conditions can also be controlled, such as parameters of the applied voltage or current, including but not limited to amplitude, type (DC, pulse, AC, etc.), waveform, frequency and step size, distance between electrodes (or between the cathode and the foil), and the temperature and / or composition and properties of the electrolyte solution.

[0212] An electro-etching system may include a computer control unit (CCU). The electro-etching method affected by the electro-etching system can be controlled by the CCU (a computer and multiple sensors and actuators, as known in the art), which monitors the voltage and / or current between the electrodes and / or foils, and can also adjust the speed of the roller movement and the flow rate of the electrolyte to achieve the desired result. Typically, a computer control unit (CCU) is a device that uses a computer to control the system. The computer in the CCU is typically an embedded computer specifically designed for the tasks of controlling the system. The CCU may also include multiple sensors and actuators. Sensors are devices that measure physical quantities such as electrical parameters, temperature, pH, conductivity, pressure, or flow rate, as well as chemical composition and concentration. Actuators are devices that can change physical quantities, such as the position of a valve or the speed of a motor. The computer in the CCU can use data from the sensors to determine the current state of the system. The computer can then use this information to control the actuators to maintain the system in the desired state.

[0213] The CCU can be used to control the voltage and / or current between the electrodes and / or the starting foil. The voltage and / or current can determine the rate at which the foil is etched, with higher voltage and current generally resulting in a faster etching rate.

[0214] CCUs can also control the flow rate of the electrolyte used in electro-etching methods. Consistent flow of fresh electrolyte produces a more uniform etched pattern. As used herein, the term "electrolyte" refers to an ionicly conductive and electrically insulating medium, typically an aqueous solution. The type of electrolyte used can depend on the materials of the foil and mask, as well as other considerations such as toxicity, corrosiveness, and environmental impact.

[0215] In some embodiments, the electrolyte may comprise an aqueous solution. As used herein, the terms “aqueous electrolyte” and “aqueous solution” are intended to cover liquid compositions containing water as the sole solvent and containing organic solvents or additives, wherein the water content of the liquid phase is at least about 70% (w / w).

[0216] The components of an exemplary electrolyte solution may include one or more of the following: Salts of the metal to be electro-etched, such as copper sulfate or copper chloride for electro-etching copper, zinc sulfate for electro-etching zinc, and ferrous sulfate for electro-etching mild steel. Chloride salts (such as sodium chloride, potassium chloride, or ammonium chloride) increase the conductivity of electrolyte solutions, which allows current to flow more easily; Acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, citric acid, or perchloric acid, are used to facilitate the etching process; Water, which acts as a carrier (solvent) for salts and optionally acids, and also helps regulate the temperature of electrolyte solutions; and Organic solvents, such as, but not limited to, isopropanol, ethanol, and ethylene glycol.

[0217] According to some implementation schemes, when electro-etching copper, sodium nitrate can be used instead of sodium chloride to adjust the electrolyte composition to prevent the formation of copper chloride, which is a fine dispersion that easily adheres to the cathode, thereby reducing the distance between the cathode and the foil.

[0218] In addition to these components, some electrolyte solutions may also contain other additives, such as dispersants, surfactants, buffers, and organic compounds. These additives can improve the etching process and enhance the quality of the resulting electro-etched foil, or prevent the formation of corrosion products. The specific composition and concentration of the electrolyte solution used for electro-etching will depend on the composition of the foil and the desired etching result.

[0219] Non-limiting examples of suitable electrolyte solutions include ferric chloride acidified with hydrochloric acid and dissolved in water; sodium chloride and citric acid dissolved in water; and sodium chloride and a dispersant dissolved in water and ethanol.

[0220] The electro-etching unit may further include a container for holding and / or circulating the electrolyte. In some embodiments, the power source is configured to apply voltage and / or current between the contact sections of the cathode and the foil in the presence of the electrolyte. Therefore, the contact sections of the foil, the contact sections of the mask, and the cathode may be immersed in the electrolyte solution, or the electrolyte solution may flow from the container to the electro-etching area.

[0221] When using an electrolyte bath, immersing the foil in the electrolyte solution only at the contact section of the foil, i.e., after the initial contact point with the mask, prevents the electrolyte from contacting the foil in exposed areas (i.e., areas not in contact with the mask's contact section). When using a circulating electrolyte, introducing the electrolyte into the electro-etching system at a point after the initial contact between the foil and the mask prevents the electrolyte from contacting the foil in exposed areas (i.e., areas not in contact with the mask's contact section).

[0222] The system may include a single electrolyte inlet or multiple electrolyte inlets. In some embodiments, the system includes a single electrolyte inlet located within the contact region between the cathode and the foil-mask assembly. The electrolyte inlet may be configured to supply electrolyte solution across the entire width of the foil. Electrolyte diffusion may be aided by foil and mask movement. The system may also include two or more seals at the periphery of the contact region (i.e., along or outside the outer edge of the foil and / or mask) to restrict electrolyte flow into the contact region and / or prevent electrolyte flow outside the region. The seals may be dynamic seals that do not interfere with the movement of the foil and / or mask.

[0223] The system may also include an electrolyte circulation unit that carries the electrolyte to the perforation area throughout the process and can further control the temperature and possible chemical composition of the electrolyte. The electrolyte circulation unit may optionally be configured to filter the electrolyte to remove debris and purify it from excess dissolved gases generated during the process. Dissolved gases that have turned into bubbles may remain in the EU, adversely acting as insulators and stopping the electro-etching process at least at the location of the bubbles. The electrolyte circulation unit may also include a reservoir, waste tank, various pumps, chemical sensors (pH, ionic strength, viscosity, optical density), piping, and other technologies.

[0224] The system may also include a patterned foil cleaning station, in which electrolytes and debris are rinsed off the patterned foil, and optionally dried in preparation for rewinding on the output roll. In some embodiments, the electro-etching system also includes an upstream foil cleaning station for preparing the foil for the electro-etching method.

[0225] The system may also include various motorized or passive shafts and cylinders, linear motion actuators, and various sensors to help control the continuous process.

[0226] Now for reference FIGS. 5A-5D It shows a side view of an electro-etching system 500 according to some embodiments of the present invention. FIG. 5A ) and cross-sectional view ( FIGS. 5B-5D The electro-etching unit includes an electro-etching unit comprising a circumferentially closed strip mask 51 wound and tensioned between tension shafts 52a, 52b and 53c, surrounding a concave cathode 53 and located near an electrically insulating cylindrical mandrel 54, on which a foil 55 is tightly wound on a portion of the convex surface of the mandrel 54 and located on a conductive tension shaft 56, wherein the foil 55 is fed into the electro-etching unit via an input (feed) roller 57a and collected on an output roller 57b, and wherein an electrolyte is introduced into the electro-etching unit via an electrolyte inlet 58.

[0227] FIG. 5C The dashed line marks the contact area between mask 51 and foil 55. FIG. 5D The dashed lines schematically illustrate the electrolyte path through the electro-etching unit. It can be seen that after point 59, the electrolyte is introduced into the electro-etching unit, establishing a contact between mask 51 and foil 55 at point 59. In other words, the electrolyte is introduced into the contact area between mask 51 and foil 55. It can be further seen that the length of the active surface of cathode 53 is less than the length of the contact area. Therefore, the electro-etching reaction is confined to the area of ​​the foil covered by the mask, thus allowing controlled etching of the foil according to the mask perforation pattern.

[0228] The electrolyte inlet 58 can be connected via a pipe to a container for holding and / or circulating the electrolyte. According to some embodiments, the pipe may be orthogonal to the plane of its cross-section.

[0229] The electro-etching system 500 may include one or more gaskets 511. The gaskets 511 prevent the electrolyte from flowing upward. Thus, the electrolyte is sealed off from three sides and dragged downward by gravity.

[0230] For clarity, element 512 indicates the volume filled with the electrolyte composition.

[0231] Roll-to-roll electrodeposition system: As is known in the art, electrodeposition is a method of depositing metal from a solution containing metal ions onto a conductive substrate surface by using an electric current to reduce metal ions to metal. Electrodeposition can be used to form solid, uniform foils, as well as foils having predetermined patterns on or within a metal surface.

[0232] In the context of this invention, the term "electrodeposition" refers to a method in which a conductive surface, such as a metal, maintains a negative potential relative to a counter electrode and is contacted with the counter electrode ions by an electrolyte containing metal ions, such that the metal ions are reduced on the surface of the conductive surface and a solid metal is deposited thereon.

[0233] In some embodiments of the invention, an electrodeposition system is provided, configured to produce very long (at least 1 meter, preferably more than 100 meters) patterned foils (metallic components) in a roll-to-roll configuration. The system includes an input (feed) roller that feeds a conductive starting foil into an electrodeposition unit (EU); and an output roller for collecting the electrodeposited (patterned) foil, wherein the foil is supported on the starting foil. The electrodeposition method may include patterning the starting foil in the electrodeposition unit, comprising an electrically insulating mask in the form of a circumferentially closed strip with a perforated pattern. A section of the mask is located between the anode and a section of the starting foil, and the starting foil is held at a negative voltage relative to the anode by physical contact with the cathode or electrical contact with the negative terminal of a power source, wherein the anode is connected to its positive terminal. When a voltage is applied to the electrodes (i.e., the anode and foil or cathode), the portion of the starting foil that is in contact with that section of the mask but not covered by the mask material (i.e., the starting foil exposed through the holes in the mask) serves as the substrate for electrodepositing the metal. The electrodes are ionically contacted, for example, by flowing an electrolyte solution between them, and the electrolyte contains ions of the metal to be deposited on the starting foil. The voltage or current is adjusted based on the type of metal to be deposited and the anode. Thus, the metal is essentially electrodeposited on the starting foil in the area not covered (masked) by the mask material forming the raised pattern, while the covered area of ​​the starting foil remains uncovered, thereby creating voids in the electrodeposited layer within the mask-covered area. The shape of the raised pattern formed on the starting foil directly corresponds to the perforation pattern of the mask and conversely to the negative space of the mask perforation (i.e., the material around the holes). In turn, the pattern of the voids in the electrodeposited foil is inversely related to the perforation pattern of the mask (or directly related to the negative space of the mask hole pattern).

[0234] The electrodeposition system disclosed in this specification is similar to the electroetching system disclosed in this specification and has the same components and features. Therefore, except for the details specifically discussed herein with reference to the electrodeposition system, the electrodeposition system may include any features described for the electroetching system. First, since electrodeposition and electroetching involve opposite current flows, the cathode and anode are opposite in function and location; therefore, statements relating to the cathode in an electroetching system may apply to the anode in an electrodeposition system, and statements relating to the anode in an electroetching system may apply to the cathode in an electrodeposition system. References to negative / positive electrodes may also be reversed in meaning.

[0235] The starting metal foil can be solid (without holes), porous, or perforated, wherein its perforation pattern can be selected to provide a patterned foil including raised elements with perforations therebetween, thereby enhancing the wrinkles of the patterned foil.

[0236] In the context of this invention, the terms "electrodeposited foil," "patterned foil," "patterned metal foil," "porous foil," "porous metal foil," and "metal component" refer to a foil formed on a starting foil during the electrodeposition process, and encompass an assembly of the electrodeposited metal and the starting foil. The terms and phrases "a plurality of raised textured elements arranged in a pattern," "pattern of raised protrusions," "seamless repeating pattern of raised protrusions," "electrodeposited layer," "patterned layer," "porous layer," "electrodeposited coating," "electrodeposited pattern," "electrodeposited textured element," "patterned coating," and "porous coating" specifically refer to metal deposited on a starting foil.

[0237] The patterned foil can be a porous foil, i.e., containing pores. In the context of this invention, the terms "pore" and "void" are used interchangeably to refer to a hollow structure formed within the foil that does not extend through the entire thickness of the foil, such as a notch, recess, or groove. Voids can be formed between two or more electrodeposited texture elements protruding from the surface of the starting foil. In some embodiments, the pattern of the voids and / or the electrodeposited texture elements follows a seamless repeating pattern.

[0238] In the context of this invention, the terms “structural element,” “surface element,” “protruding element,” “surface structure,” and “protruding structure” are used interchangeably as to refer to an electrodeposited foil and are intended to cover metallic material deposited on a starting foil in an area not covered by the mask material, i.e., metal deposited between gaps caused by the mask.

[0239] In the case of electrodeposition, high stencil printing fidelity means reproducing the pattern in the mask in the electrodeposited foil with a high level of control over the accuracy and consistency of production and with little or no distortion or loss of detail, wherein the pattern generated on the starting foil is inversely correlated with the pattern in the mask (i.e., vias are converted into raised texture elements).

[0240] To provide a long, patterned foil, on which electrodeposition occurs, a starting foil can be continuously passed through the electrodeposition unit, and the mask can be rotated such that specific portions of the mask are always positioned between the anode and a new region of the starting foil. The mask is stretched over the starting foil to eliminate contact between certain regions of the starting foil and the electrolyte, said regions being configured to create voids in the electrodeposited metal. Exposed portions of the starting foil need to be in contact with the electrolyte to allow metal ions to deposit from the electrolyte onto the starting foil. To provide constant contact between the mask segments, the foil, and the electrolyte, the advancement of the foil through the electrodeposition unit can be coordinated with the rotation of the mask. Electrolyte flow can be restricted to the contact area between the foil and the mask.

[0241] The shape of the contact section of the mask and the starting foil may further correspond to the shape of the active surface of the anode and / or the curvature of the curved surface forming part of the side surface of the cylindrical or spherical cathode (see [reference]). FIGS. 11A-11B , FIGS. 12A-12B , FIGS. 13A-13B and FIGS. 14A-14B The region formed between the contact area of ​​the anode and the foil and mask is called the “electrodeposition zone”, where electrodeposition occurs when the anode and the starting foil are in electrical contact and an electrolyte is present therebetween.

[0242] According to some aspects and embodiments of the present invention, a roll-to-roll foil electrodeposition system is provided, comprising: An electro-etching unit, which is an electrodeposition unit, is configured to transform a starting metal foil into a patterned foil by electrochemical deposition of metal when a current and / or voltage is applied. An input roller, configured to feed a starting foil into the electrodeposition unit; and The output roller is configured to collect patterned foil. The electrodeposition unit includes: electrode; Elastic mask; Two or more axes that hold the mask under tension; Containers for holding and / or circulating liquid electrolyte compositions; A fluid delivery unit fluidly connected to the container; and power supply, The starting foil and the patterned foil are conductive; The mask has the form of a circumferentially closed band with an electrically insulating outer surface. The mask includes a contact section, which is positioned as a corresponding contact section of the contact foil, such that the contact section of the mask has a curved shape that conforms to the curvature of the contact section of the starting foil. The contact section of the mask is positioned between the contact section of the electrode and the contact section of the starting foil. The fluid delivery unit is configured to guide the flow of the electrolyte composition supplied by the container to be substantially tangent to the outer surface of the mask along the entire length of the contact portion of the mask; During the feeding of the starting foil via the input roller and / or the collection of the patterned foil via the output roller, the mask and the starting foil are configured to move in tandem while the starting foil contacts the mask; and The power source is configured to apply voltage and / or current between the contact section of the electrode and the starting foil in the presence of the electrolyte composition.

[0243] As used herein, the term "conductive foil" refers to a metal or metal alloy foil; a composite foil; carbon and / or graphite; and a conductive polymer. A composite foil may contain a metal, for example, in the form of a metal layer disposed on an electrically insulating substrate (e.g., a polymer), or have metal regions dispersed throughout the electrically insulating material, wherein said metal regions are at least partially present on the surface of the foil. A conductive polymer, also referred to herein as an "intrinsically conductive polymer (ICP)," may be selected from linear backbone "polymer blacks," such as polyacetylene, polypyrrole, polyindole, and polyaniline, and copolymers thereof; and aromatic cyclic polymers, such as poly(p-phenylenevinylene) (PPV).

[0244] The mask can have an electrically insulating surface and be resistant to electrodeposition, that is, it prevents electrodeposition on the surface covered by the mask material.

[0245] The anode can be made of any conductive material, which, when used as an anode, is inert to the electrodeposition medium and the conditions of the electrodeposition method. In some embodiments, the anode is made of a material that does not participate in the electrodeposition process (i.e., cannot dissolve to deposit on the starting foil). In some embodiments, the anode is made of the same material as the electrodeposition metal, for example, copper when forming a patterned copper layer on the starting foil, or nickel when forming a patterned nickel layer on the starting foil. In some such embodiments, the anode can be at least partially dissolved during the electrodeposition process. In other words, such an anode can be a consumable anode. Non-limiting examples of anode materials that can be used for electrodeposition of various types of metals include carbon-based materials such as graphite or glassy carbon, and metals such as titanium, lead, tantalum, or niobium, as well as their ferrites and oxides.

[0246] In the electrodeposition systems and methods according to various aspects and embodiments of the present invention, the electrodeposited metal may be derived from metal ions present in the electrolyte and / or from a consumable anode.

[0247] The starting foil may be made of any conductive material known in the art, such as, but not limited to, metals, metal alloys, metal-containing composites, carbon-based materials, and conductive polymers.

[0248] In some embodiments, the system is configured to provide a metal foil or metal-containing foil with a patterned multilayer structure, wherein different layers include different structures and / or void arrangements (including substantially non-porous layers). Such a multilayer foil can be fabricated by changing the mask between electrodepositions of different layers.

[0249] See now FIGS. 1A-1BThe diagram illustrates an electrodeposition apparatus 110 according to some embodiments of the invention, showing a circumferentially closed band mask 111 wound and tensioned between tension shafts 112a and 112b, surrounding a concave anode 113 and located near the cylindrical mandrel constituting a cathode 114, with a foil 115 tightly wound around a portion of the convex surface of the cathode 114, wherein... FIG. 11A The electrodeposition apparatus 110 is shown in the loading phase before the mask 111 contacts the starting foil 115 and before electrical energy is applied. FIG. 11B An electrodeposition apparatus 110 is shown in the electrodeposition stage, wherein a mask 111 is in contact with a starting foil 115, and... FIG. 11B The dashed rectangle in the figure marks the contact area between the mask 111 and the starting foil 115, including the contact section 111a of the mask 111 and the contact section 115a of the starting foil 115. Contact is achieved by moving the tension shafts 112a and 112b toward the cathode 114, moving the cathode 114 toward the tension shafts 112a and 112b, or a combination thereof, while the tension shafts 112a and 112b can rotate in coordination with the cathode 114. During this period, electrical energy is applied to the anode 113 and the cathode 114, and an electrolyte containing the metal ions to be electrodeposited flows between the anode 113 and the cathode 114 to achieve the electrodeposition of the metal on the starting foil 115.

[0250] As from FIGS. 11A-11B It can be inferred that the electrodeposition unit is configured to form a metal layer on a starting foil in a contact region on a foil area not covered by the mask. Therefore, the metal layer is formed continuously with a pattern templated by perforations in the mask. While the tensioned starting foil continuously passes through the electrodeposition unit, electrical energy is applied between the cathode and anode, resulting in continuous electrodeposition, wherein the movement of the starting foil is coordinated with the movement of the mask, and the electrolyte solution flows at least through the portion of the electrodeposition unit where the starting foil and mask are located between the electrodes. Specifically, due to the coordinated rotational movement of the tensioning rollers 112a and 112b with the anode 114, new segments of the starting foil 115 and the mask 111 come into contact, thereby forming new contact segments 115a and 111a respectively located between the electrodes and in the electrolyte solution, allowing continuous electrodeposition on the foil according to the mask pattern. In this exemplary illustration, the electrodeposition unit includes a curved surface on which a curved contact region is formed, which is the curved surface of the cathode 114.

[0251] Now for reference FIGS. 12A-12BIt shows a schematic diagram of an electro-etching unit 120 according to some embodiments of the present invention, showing a circumferentially closed strip mask 121 wound and tensioned between tension shafts 122a and 122b, surrounding a concave anode 123 and located near an electrically insulating cylindrical mandrel 124, with foil 125 tightly wound on a portion of the convex surface of the mandrel 124 and a conductive tension shaft 126, wherein... FIG. 12A The electrodeposition unit 120 is shown during the loading phase, before the mask 121 contacts the foil 125 and before electrical energy is applied. FIG. 12B An electrodeposition apparatus 120 is shown in the electrodeposition stage, wherein a mask 121 is in contact with a starting foil 125, and FIG. 12B The dashed rectangle in the figure marks the contact area between the mask 121 and the starting foil 125, including contact segment 121a of the mask 121 and contact segment 125a of the starting foil 125. Meanwhile, tensioning shafts 122a and 122b can rotate in coordination with the mandrel 24 and optionally the tensioning roller 126. During this period, electrical energy is applied to the anode 123 and the tensioning roller 126, which is connected to the negative terminal of the power supply (not shown), thereby maintaining a negative voltage on the starting foil 125 relative to the anode 123. An electrolyte (not shown) containing metal ions to be electrodeposited flows between the anode 123 and the starting foil 125 to achieve electrodeposition of the metal on the starting foil 125. In this exemplary illustration, the electrodeposition unit includes a curved surface on which a curved contact area is formed. This curved surface is the curved surface of the cylindrical mandrel 124.

[0252] Now for reference FIGS. 13A-13B It shows a schematic diagram of an electrodeposition unit 130 according to some embodiments of the present invention, showing a circumferentially closed strip mask 131 wound and tensioned between tension shafts 132a and 132b, surrounding a concave anode 133 and located near a fixed cathode 134 having a curved active surface, a starting foil 135 tightly wound on the convex surface of the curved active surface and a tension roller 136, wherein... FIG. 13A The electrodeposition unit 130 is shown during the loading phase, before the mask 131 contacts the starting foil 135 and before electrical energy is applied. FIG. 13BAn electrodeposition unit 130 is shown in the electrodeposition stage, wherein tension rollers 132a and 132b move toward the cathode 134, allowing contact between the mask 31 and the starting foil 135, while tensioning shafts 32a and 132b can rotate in coordination with a rotation shaft 136. During this period, electrical energy is applied to the anode 133 and the stationary cathode 134, and electrolyte ions (not shown) of the metal to be electrodeposited flow between the anode 33 and the stationary cathode 134, thereby achieving electrodeposition of the metal on the foil 135. In this exemplary illustration, the electrodeposition unit includes a curved surface on which a curved contact region is formed, which is a curved active surface of the stationary cathode 134.

[0253] Now for reference FIGS. 14A-14B It shows a schematic diagram of an electrodeposition unit 140 according to some embodiments of the present invention, showing a rigid circumferentially closed strip mask 411 with a cylindrical shape, viewed from top, surrounding a rotating anode 143 and located near a starting foil 145 wound on tension / rotation shafts 146a and 146b, wherein tension shaft 126a is conductive, and the contact section of the mask, anode, and starting foil is immersed in an electrolyte solution (not shown) containing metal ions to be electrodeposited, wherein FIG. 14A The electrodeposition unit 140 is shown during the loading stage before the mask 141 contacts the starting foil 145 and before electrical energy is applied. FIG. 14B An electrodeposition unit 140 in the electrodeposition stage is shown, wherein a mask 141 contacts a starting foil 145, wherein the contact can be achieved by moving tension shafts 146a and 146b toward the mask 141, moving the mask 141 toward tension rollers 146b and 146b, or a combination thereof, while tension shafts 146a and 146b can rotate in coordination with the mask 141 and apply electrical energy to the anode 143 and tension shaft 146a, which is connected to the negative terminal of a power source (not shown), thereby maintaining a negative voltage on the starting foil 145 relative to the anode 143 and enabling the electrodeposition of metal ions in the electrolyte onto the starting foil 145, while rotating the anode 143 to promote the flow of electrolyte between the anode 143 and the starting foil 145. The anode 143 has a central portion 143a and curved blades 143b and 143c connected to the central portion 143a, the outer surfaces of which constitute the active surface of the anode 143. The curved blades 143b and 143c are shaped to conform to the shape of the mask 141 to provide a constant distance between the active surface of the anode 143 and the contact segment of the starting foil 145. In this exemplary illustration, a curved contact region is formed on the rigid mask 141 that constitutes the curved surface of the electrodeposition unit.

[0254] The components of an exemplary electrolyte solution suitable for electrodeposition may include one or more of the following: A salt of the metal to be electrodeposited, such as copper sulfate or copper tetrafluoroborate for electrodepositing copper, and nickel sulfate, nickel sulfamate, or nickel chloride for electrodepositing nickel. This salt can be obtained by dissolving the metal in a strong acid containing the salt anion; Chloride salts (such as sodium chloride, potassium chloride, or ammonium chloride) increase the conductivity of electrolyte solutions, which allows current to flow more easily; Acids, such as sulfuric acid, boric acid, fluoroboric acid, or aminosulfonic acid, are used to dissolve metals and / or assist in the deposition process; Water serves as a carrier (solvent) for salts and, optionally, acids, and also helps regulate the temperature of the electrolyte solution.

[0255] In addition to these components, some electrolyte solutions may contain other additives, such as dispersants, surfactants, buffers, and organic solvents and compounds. These additives can improve the deposition process and enhance the quality of the resulting electrodeposited foil, or prevent the formation of reaction byproducts. The specific composition and concentration of the electrolyte solution used for electrodeposition will depend on the composition of the foil and the desired coating result.

[0256] A non-limiting example of an electrolyte solution suitable for copper electrodeposition includes copper and chloride salts dissolved in sulfuric acid.

[0257] As is known in the art, the system may further include a passivation unit or a chemical treatment unit.

[0258] Now for reference FIGS. 15A-15D It shows a diagram (side view) of an electrodeposition system 1500 according to some embodiments of the present invention. FIG. 15A ) and cross-sectional view ( FIGS. 15B-15D The electrodeposition unit includes an electrodeposition unit comprising a circumferentially closed band mask 151 wound and tensioned between tension shafts 152a, 152b and 153c, surrounding a convex anode 153 and located near an electrically insulating cylindrical mandrel 154 on which a starting foil 155 is tightly wound on a portion of the convex surface of the mandrel 154 and located near a conductive tension shaft 156, wherein the starting foil 155 is fed into the electrodeposition unit via an input (feed) roller 157a and collected on an output roller 157b, and wherein an electrolyte is introduced into the electrodeposition unit via an electrolyte inlet 158. FIG. 15C The dashed line in the diagram marks the contact area between the mask 151 and the starting foil 155. FIG. 15DThe dashed lines schematically illustrate the electrolyte path through the electrodeposition unit. It can be seen that the electrolyte is introduced into the electrodeposition unit after contact is established at point 159 between the mask 151 and the starting foil 155. In other words, the electrolyte is introduced into the contact area between the mask 151 and the starting foil 155. It can be further seen that the length of the active surface of the cathode 153 is less than the length of the contact area. Therefore, the electrodeposition reaction is confined to the mask-covered area of ​​the starting foil, thereby allowing controlled metal deposition of the foil according to the mask perforation pattern.

[0259] SRP template mask: The uniformity of perforation / electrodeposited patterns in patterned foils is critical, especially when metal components are used as current collectors in lithium-ion batteries. Therefore, this invention provides a solution to address the problem of forming consistent, uniform, and seamlessly repeating patterns of vias or protruding elements and / or voids in very long conductive foils. Since industrial processes require metal components to be supplied in rolls of long, continuous components, and since the components should not exhibit breaks or gaps that are not part of the desired pattern, or unintended variations in the via, surface, and / or body pattern, the inventors have designed SRP template masks in the form of circumferentially closed strips or bands (rings) made of electrically insulating or composite materials that are substantially inert (electrochemically stable) under the operating conditions of the electropatinated cells, exhibiting seamlessly repeating hole patterns.

[0260] Therefore, according to one aspect of some embodiments of the present invention, a circumferentially closed gap mask having a seamless repeating hole pattern is provided, and is referred to herein as an "SRP stencil mask". Here and throughout the text, the term "mask" includes the term "SRP stencil mask", which is a mask that displays a seamless repeating pattern (SRP) of holes that can be used to form SRP on a substrate (e.g., a metal foil).

[0261] The terms "substantially inert" and "electrochemically stable material" refer to the properties of a material that do not undergo significant changes when exposed to an electrolyte or an electric current in the electrolyte. This is important for electro-etching masks, as the masks need to withstand electro-etching conditions without dissolving or corroding. The mask material is chosen to be substantially resistant to etching, dissolution, corrosion, and mechanical abrasion, thus enabling it to maintain long operating cycles under electro-etching / electrodeposition conditions.

[0262] In the case of a mask, a circumferentially closed band or strip is a shape without open ends. It is a continuous curve forming a loop. The closed band can have any width or length, but has no open ends.

[0263] FIG. 6This is a schematic diagram of an exemplary mask or SRP template mask according to an embodiment of the present invention, showing a circumferential closed band (loop) that presents a seamless repeating pattern, illustrated by an exemplary diagram of hexagonal holes shown in an enlarged circle.

[0264] The materials or composite materials used to manufacture the masks and the SRP template masks disclosed herein are electrochemically stable. Many materials can be used to form masks, such as the SRP template masks provided herein, including but not limited to: Kapton®: Kapton® is a trademark name for a polyimide known for its high-temperature resistance. It is commonly used in applications where materials require high-temperature resistance, such as aerospace and electronics applications. The generic name for Kapton® is polyimide.

[0265] Polyimide: Polyimide is a synthetic polymer known for its high strength, toughness, and chemical resistance. It is frequently used in applications requiring high performance and durability, such as the aerospace and electronics industries. Polyimide is a synthetic polymer made from two monomers, pyromellitic dianhydride (PMDA) and 4,4'-oxodiphenylamine (ODA). The monomers are linked together through a condensation reaction to form long-chain molecules.

[0266] PTFE: Polytetrafluoroethylene (PTFE), also known as Teflon, is another synthetic polymer with excellent electrical and chemical resistance. It is frequently used in applications requiring non-stick surfaces, such as cookware and medical implants.

[0267] Parylene: Parylene is a generic name for a group of polymer coating materials, optionally dielectrics, commonly used to protect electronic components, medical devices, and other objects from moisture, chemicals, and other contaminants. Parylene coatings are typically applied via chemical vapor deposition (CVD), meaning they are deposited from a gaseous state onto the surface of an object. This method allows for the production of thin, uniform coatings that conform to the surface of the object, even complex shapes.

[0268] Composite materials suitable for perimeter-closed strip masks, such as SRP template masks, include core-coating composites, i.e., base materials coated with highly resistant coating materials. Masks made of metals with low electrical resistance can be coated with electrically insulating and electrochemically stable materials, such as polymers, like parylene. A non-limiting example of a base material is stainless steel. Stainless steel is an alloy of iron containing chromium and other elements. It is known to have high strength, corrosion resistance, and a lasting luster. Stainless steel is commonly used in applications requiring durable and corrosion-resistant materials and can be further coated with polymers such as polyimide to improve its corrosion resistance.

[0269] Composite materials that can be used to construct SRP template masks include, but are not limited to, polymer-coated metals, such as parylene-coated nickel, layered composites of different metals and polymers, and some woven materials such as glass fibers.

[0270] The specific material or composite material used to manufacture masks, such as SRP stencil masks, will depend on the specific application. For example, if the mask is used for etching under corrosive conditions, a material with high chemical resistance, such as PTFE, would be a preferred choice for the mask or for mask coating. If the mask is used for etching at high temperatures, then a material with high-temperature resistance, for example, would be a preferred choice for the mask or for mask coating.

[0271] In some embodiments, the mask is made of a hydrophilic material. It is not desirable to be bound by theories or mechanisms of action; reducing the hydrophobicity of the mask is expected to improve one or more process parameters, such as stencil printing fidelity, lifetime, electrolyte flow, etc. For example, a hydrophilic surface of the mask can improve electrolyte flow within the orifices of the mask. As used herein, the term "hydrophilicity" refers to the wettability of the mask by a water or electrolyte solution and can be defined by the contact angle between the mask surface and the water or electrolyte. In some embodiments, the contact angle between the water or electrolyte and the mask surface is less than 90°. In some embodiments, the contact angle is less than 80°, less than 70°, or less than 60°. The mask can be made of a hydrophobic material that is treated to improve its wettability by an electrolyte. In some embodiments, the outer surface of the mask configured as a contact foil is made hydrophilic through surface treatments, such as, but not limited to, laser etching.

[0272] As mentioned above, masks can be elastic or rigid, i.e., have flexible or stable shapes. The choice of mask material can also be based on the desired elasticity of the mask.

[0273] According to some embodiments, the mask comprises a hydrophilic material. According to some embodiments, the mask is made of a polymer or a polymer-coated metal. According to some embodiments, the mask is made of a hydrophilic polymer or a hydrophilic polymer-coated metal. Each possibility represents a single embodiment of the invention. According to some embodiments, the polymer or polymer coating comprises a polyamide. According to some embodiments, the mask comprises a polyamide film. Without wishing to be bound by any theory of action, a hydrophilic mask may be important for electrolyte removal.

[0274] According to some embodiments, the mask includes at least one electrically insulating surface. According to some embodiments, the electrically insulating surface is the outer surface of the mask that is in contact with the foil.

[0275] The mask may have a substantially smooth outer surface, including at the edges of the through-holes. In some embodiments, the mask has a substantially smooth inner surface. As used herein, the term "substantially smooth" in some embodiments refers to a surface roughness (Ra) of 1 μm or less. In some embodiments, the surface roughness of the mask is less than 0.5 μm. It should be understood that the term "surface roughness" refers to structural irregularities on the surface of intentionally formed through-holes that are not part of the mask. In some embodiments, the surfaces of the through-hole walls within the mask are substantially smooth.

[0276] The thickness of a mask, such as an SRP stencil mask, is related to several factors affecting the method, such as mechanical properties and stencil printing fidelity. A mask that is too thin may have a short lifespan (short service life) and may be more difficult to control, drive, and manipulate around the various shafts and other moving parts of the drivetrain. A mask that is too thick may not be flexible enough to form a tight contact in the contact area, or may be more difficult to manipulate around the various shafts and other moving parts of the drivetrain. Additionally, a higher mask thickness can limit the diffusion of the etched foil material from the exposed area. Furthermore, a mask that is too thick can negatively impact stencil printing fidelity, i.e., reduce the similarity between the mask pattern and the pattern obtained on the perforated foil. The mask thickness can affect the local composition and properties of the electrolyte solution in the exposed areas of the starting foil (i.e., the areas not covered by the mask during electrodeposition in the contact area). However, a thicker mask can allow for the formation of a thicker patterned layer on the starting foil. Preferably, the thickness of the electrodeposited layer is substantially equal to or less than the mask thickness.

[0277] Masks suitable for the electrolysis systems and methods of the present invention, such as SRP template masks, can have a thickness ranging from about 5 μm to about 100 μm. In some embodiments, the mask thickness ranges from about 5 μm to about 80 μm. In another embodiment, the mask thickness ranges from about 5 μm to about 60 μm. Masks suitable for the electrodeposition systems and methods of the present invention, such as SRP template masks, can have a thickness ranging from about 20 μm to about 300 μm. In some embodiments, the mask thickness ranges from about 50 μm to about 200 μm. In some embodiments, the mask thickness is at least about 25 μm. In some embodiments, the mask thickness is at least about 50 μm.

[0278] According to some embodiments, the mask exhibits a seamless repeating pattern (SRP) of vias. According to some embodiments, the vias have an opening size of approximately 10-2,000 μm, including each value and subrange within a specified range. According to some embodiments, the openings have a mean diameter of less than 100 μm. According to some embodiments, the openings have a mean diameter of less than 80 μm. According to some embodiments, the openings have a mean diameter of less than 60 μm. According to some embodiments, the openings have a mean diameter of less than 40 μm. According to some embodiments, the openings have a mean diameter of less than 30 μm. According to some embodiments, the openings have a mean diameter of less than 100 μm. According to some embodiments, the openings have a mean diameter of less than 80 μm. According to some embodiments, the openings have a mean diameter of less than 60 μm. According to some embodiments, the openings have a mean diameter of less than 40 μm. According to some embodiments, the openings have a mean diameter of less than 30 μm.

[0279] It should be understood that when referring to the contact section of a mask, the term "contact section" includes both the continuous solid area of ​​the mask (without holes) and the area of ​​the mask with holes. This is to distinguish between the area within the contact area and the area outside the contact area, where there is no contact between the mask and the start foil due to the mask perforations, but there is physical contact between the mask and the start foil; and in the area outside the contact area, there is no physical contact between the mask and the start foil.

[0280] The mask can be wider than the starting foil, for example, at least about 1%, 5%, 10% or more. A wider mask prevents uncontrolled etching or electrodeposition at the foil edges. A wider mask can also be used to seal the electrically patterned cells, thus confining the electrolyte flow to the contact area.

[0281] In the context of this invention, and as provided by the electropatterning system disclosed herein, a circumferentially closed strip mask is considered to be a ring / continuous strip without obvious ends, seams, stitching, or closure marks (unless intentionally introduced to create such seams on the starting foil). To impart a uniform and seamless pattern, such as multiple indentations, perforations, or protrusions, to the foil during the electropatterning process, the mask is an SRP stencil mask, characterized in particular by a non-random and deliberately designed seamless repeating pattern (SRP) of holes that essentially spans the entire area of ​​the strip (in some embodiments, except for the white border), closing into a strip or band, with no visible or tangible boundaries or irregular / arbitrary / random transitions between or within repeating pattern sequences. The SRP of the holes in the mask is also continuous, i.e., without start or end marks along the circumference of the strip (see...). FIG. 6 ).

[0282] As used herein, the terms “template,” “stencil,” and “patterning” in relation to masks refer to a deliberately designed and designed closed strip of holes (which may also be referred to interchangeably herein as “texture elements”) having regular shapes, regular spacing, and / or regular orientations in / on its surface.

[0283] As used herein, the phrase "seamless repeating pattern," abbreviated as "SRP," refers to a pattern that spans an undefined and infinite surface without any visible transition or boundary. An SRP is a continuous repeating pattern of textured elements arranged in a two-dimensional form, such as geometric shapes or decorative designs. SRPs continue infinitely in all directions, creating a seamless visual effect. This type of pattern is commonly used in textiles, wallpaper, flooring, and other decorative materials, as well as in graphic design, packaging, and trademarks. As discussed herein, an SRP can be defined by repeating pattern units, and placing multiple such units closely adjacent to each other (juxtaposing) will provide an SRP. Repeating units are referred to herein as tiles or motifs.

[0284] A motif is defined by one or more structural units, and each motif is mixed with adjacent motifs to obtain an SRP. In the context of this invention, a motif includes texture elements in the form of holes (i.e., through holes, perforations, apertures, through-windows), and the entire SRP may be defined by repeating motifs. In contrast to the random distribution of similar texture elements over similar regions, the arrangement of any given texture element in the seamless repeating pattern characterized by the SRP stencil mask provided herein is controlled (non-random); therefore, by definition, the SRP (and the resulting patterned metal components) characterized by the SRP stencil mask provided herein is non-random.

[0285] Using the SRP described above to cover a flat surface, such as the surface of an SRP template mask, essentially follows any standard tessellation or tiling method, using one or more non-overlapping and gapless geometries (tiles; sequences). Although some embodiments of the invention are drawn as flat surfaces, which are essentially two-dimensional solids regardless of thickness, it is noted that tessellation can be extended to higher dimensions and various geometries. In some embodiments, the SRP is provided by periodic tiling, while some embodiments include regular tiling with regular polygonal tiles, all of which have the same shape, and some embodiments include semi-regular tiling with regular tiles of more than one shape, and each corner is arranged identically.

[0286] As used herein, the term "motif" or "tile" refers to the smallest and simplest single texture element, or a non-repeating group of texture elements that repeat to form and define an SRP. In the context of this invention, a motif is closely related to a unit cell in a 3D lattice (crystal / lattice), and an SRP is formed by repeating a motif in any direction on the plane. Within a motif, there may be one or more texture elements. In some embodiments, a motif comprises more than one texture element associated with each other through symmetric operations in a 2D plane, such as translation, rotation, and reflection transformations. In some embodiments, a motif comprises more than one texture element arranged asymmetrically relative to each other, or more than one texture element having different sizes / shapes. It should be understood that within a single tile, texture elements should not necessarily be arranged in a symmetrical or ordered manner. The plane or SRP can be completely tiled (covered) with triangles, rectangles, and hexagonal polygons (tiles), each tile having one or more texture elements arranged therein. Rectangular and hexagonal tiles can be placed using the same tile orientation (translation only, no rotation), while triangular tiles are placed with a 60° rotation (translation and rotation).

[0287] An example of a simple motif is a dot, which can be represented by a hole, and its SRP can be a stack of square or hexagonal circles, wherein the circles are evenly spaced and, in the case of through holes, do not touch each other to allow for material continuity between them.

[0288] In practice, in some embodiments, the SRP stencil mask presents SRP from edge to edge over its entire area; in other embodiments, SRP is distributed throughout the main area of ​​the SRP stencil mask, leaving narrow white borders along its edges due to the technical / practical requirements of industrial processing machines. A white border refers to an area where the SRP stencil mask does not display SRP, where the SRP stencil mask can be complete or have a pattern different from the SRP. In some embodiments, the white border extends along each edge of the mask, and in some embodiments, the white border spans less than 1%, less than 2%, less than 5%, less than 10%, less than 20%, or less than 30% of the total width of the SRP stencil mask. In some embodiments, the white border extends along each edge of the mask, and in some embodiments, the white border spans at least 1%, at least 2%, at least 5%, at least 10%, at least 20%, or at least 30% of the total width of the SRP stencil mask. In some embodiments, one or more unpatterned strips are present near or at the center of the long axis of the SRP stencil mask, designed for practical and industrial purposes, such as cutting the resulting components into narrower strips. In such an implementation, the majority of the SRP stencil mask comprises SRP, while the narrow strips of the original mask separate the wide strips of the patterned mask.

[0289] A mask may include multiple different SRP patterns along its width and / or length. For example, when using a relatively wide mask and starting foil, different patterned foil segments can be created along the foil length. Patterned foils with different patterned segments can be used as is or cut into separate segments to obtain narrower, longer foils with a single type of pattern. Alternatively, when using a mask with a relatively large circumference, different patterned foil segments can be created along the foil width. Patterned foils with different patterned portions can be used as is or cut into separate portions to obtain wide and short foils with a single type of pattern.

[0290] According to some embodiments of the invention, the seamless repeating pattern is mathematically defined or constructed. In some embodiments, the SRP is generated via machine learning based on the expected requirements for the patterned foil.

[0291] It should be understood that the mask does not have to be an SRP mask. For example, when production is configured to cut a continuous patterned foil into discrete segments along its length, a seamless pattern is not required. Additionally, vias can be arranged asymmetrically (e.g., randomly) within the mask, however, this is predefined to produce the desired pattern structure on / within the starting foil.

[0292] Texture elements: In some embodiments, the textured element, such as an SRP stencil mask, is a small through-hole. According to embodiments of the invention, the hole can take any shape and orientation, including circular, elliptical, rectangular, triangular, polygonal, hexagonal, circular polygonal, rhomboid, or odd-shaped. Circular holes can be used to create rod-shaped or conical protrusions on the surface of the starting foil, while polygonal holes can be used to form truncated and / or enlarged pyramidal protrusions, etc. In some embodiments, the hole is circular, i.e., having a circular cross-section.

[0293] Regarding electrodeposition, the electrodeposition methods and tools described herein can also be used to provide patterned foils with raised patterns resembling those of steel-diamond plates (also known as checkerboard, deck, floor, anti-slip plate, or treads), a class of metal plates having a raised diamond-shaped pattern on one side and a smooth surface on the other. To provide such a pattern, the holes can have shapes such as slits, slots, notches, cracks, fissures, or fissures, with a width-to-length ratio up to 1:10,000. For example, slit-shaped holes impart elongated protrusions or bulges to the starting foil; such elongated texture features can also exhibit specific relative orientations to provide complex patterns, such as those seen in checkerboard corrugated metal plates. This type of pattern typically presents a series of raised angular and symmetrical diamond or linear ridges on the surface of a sheet or foil. A checkerboard corrugated metal plate is a sheet of metal with a checkerboard pattern of relatively oriented and spaced ridges. The height of the ridges and the width of the space between them can vary, and the texture characteristics of the resulting patterned metal foil can be characterized by the following: the ridges are the raised portions of the patterned foil and can exhibit a V-shaped vertical cross-section; the space is the area between the ridges, which is usually flat and smooth; and the ridges on such patterned foil are usually in two directions perpendicular to each other.

[0294] An optional definition of SRP describes an SRP stencil mask as a foil with a patterned surface, wherein the patterned surface is a porous surface with a designed hole location distribution (PLD), where the holes are through-holes. In some embodiments, the holes are located on the SRP stencil mask at regularly spaced intervals. In some embodiments, the SRP stencil mask has holes of different sizes at different locations on the SRP stencil mask. In some embodiments, the SRP stencil mask has holes of different types at different locations on the SRP stencil mask. In some embodiments, the SRP stencil mask has holes of different shapes at different locations on the SRP stencil mask. In some embodiments, the SRP stencil mask has holes aligned in a straight line. In some embodiments, the SRP stencil mask has holes arranged in a straight line, said line being inclined at an angle relative to the edge of the SRP stencil mask.

[0295] As used herein, the term "size" refers to a characteristic scale of an object, structural element, or texture element. When referring to the size of multiple objects, it means the average obtained by measuring the sizes of a representative group of objects. The size of a circular object can refer to the diameter of the object. In the case of a non-circular object, the size of the non-circular object can refer to the diameter of the corresponding circular object, wherein the corresponding circular object exhibits or has a specific set of derived or measurable properties that are substantially the same as those of the non-circular object. Alternatively or in combination, the size of a non-circular object can refer to the average of the various orthogonal dimensions of the object. Thus, for example, the size of an object with a conical cross-section (e.g., an ellipse) can refer to the average of the major and minor axes of the object. In some embodiments, the term "size" refers to the equivalent circular radius.

[0296] When a set of objects is referred to as having a specific size, it can be expected that the objects may have a size distribution around that specific size. Therefore, as used herein, the size of a set of objects can refer to the typical size of the size distribution, such as the average size, median size, or peak size.

[0297] As described above, the perforations of the SRP stencil mask follow a seamless repeating pattern or SRP, which can be defined by tangent tiles or sequences in which holes or texture elements are positioned. The SRP is formed by filling the plane with tiles. Tiles may include a portion of a (symmetrical) hole, a single hole or any shape, or more than one hole and / or portions thereof of the same or different shapes (a mixture of shapes).

[0298] In some embodiments, the through-hole may have parallel walls perpendicular to the plane of the mask (cylindrical hole). In some embodiments, the through-hole may have a tapered shape or sloping walls, such that one opening of the through-hole differs in size and shape from the opposite opening of the same hole (truncated conical hole).

[0299] FIG. 7 A schematic diagram of two tapered holes in a mask with local thickness is shown, indicating that the diameter of the hole on the outer side (d1) is smaller than the diameter of the hole on the inner side (d2) of the mask.

[0300] Masks, such as SRP stencil masks, can be constructed with tapered apertures. It is undesirable to be constrained by theory or mechanism of action; the tapered apertures are expected to improve one or more method parameters, such as stencil printing fidelity, lifetime, electrolyte hydraulic properties, etc. For example, the space defining a circular aperture (void) can have a truncated cone shape, and the space defining a rectangular aperture can have a trimmed pyramid shape. In some embodiments, the apertures in the mask, such as in an SRP stencil mask, are characterized by a tapered aperture diameter, or in other words, the aperture narrows from one surface side of the foil plane to the other. In some embodiments, the mask, such as an SRP stencil mask, has an outer side configured to contact the starting foil and an inner side configured to face the cathode, and the apertures in the mask are wider on the inner side than on the outer side of the mask; that is, the apertures gradually taper towards the same side of the mask (which is the outer side). In some embodiments, all apertures in the mask are wider on the inner side of the mask than on the outer side of the mask.

[0301] Without being bound by theories or mechanisms of action, it is anticipated that in electro-etching methods, the widening of the aperture from the foil outward (and toward the cathode) will facilitate the flow of electrolyte in the aperture compared to through-holes with parallel or tapered walls that taper toward the inner side of the mask facing the cathode, and in particular, improve the removal of bubbles from the foil surface.

[0302] According to some embodiments, the aperture diameter (aperture size) of the holes in the mask (e.g., the SRP stencil mask with a seamless repeating pattern of through-hole textured elements provided herein) can be as small as 1-200 μm. In some embodiments, the aperture size of the through-hole ranges from 10 μm to 5000 μm, or about 10-2000 μm, or about 10-1000 μm, or about 10-500 μm, or about 10-200 μm, or about 10-100 μm, or about 10-50 μm, or 20-100 μm, 30-100 μm, 40-100 μm, 50-100 μm, 60-100 μm, 70-100 μm, 80-100 μm, 90-200 μm, 90-300 μm, 90-400 μm, or about 90-500 μm. In some implementations, the aperture texture element (hole; hole) has an opening size of less than about 1,000 μm, less than about 750 μm, less than about 500 μm, less than about 250 μm, less than about 100 μm, less than 90 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, less than 15 μm, less than 10 μm, less than 9 μm, less than 8 μm, less than 7 μm, less than 6 μm, less than 5 μm, or less than 4 μm.

[0303] In some embodiments including any of the foregoing, the aperture has an opening (orifice; opening size) of about 1-100 μm × about 1-100 μm, about 1-50 μm × about 1-50 μm, about 20-30 μm × about 20-30 μm, about 40 μm × 50 μm, or about 52 μm × 52 μm.

[0304] In some embodiments, the aperture size is equal to or greater than the mask thickness. In other embodiments, the aperture size is at least about 10%, at least about 30%, at least about 50%, at least about 70%, or at least about 100% greater than the mask thickness.

[0305] The mask can have a single-peak, double-peak, triple-peak, or other multi-peak aperture size distribution. A single-peak aperture size distribution can be used when forming apertures / structural elements of substantially the same size in a starting foil. A mask with a multi-peak aperture distribution may be advantageous when producing metal foils patterned with apertures or texture elements of different sizes. The mask may have an aperture distribution in which at least 80% of the apertures are in the range of 0.9 to 1.1 times the average aperture. Preferably, more than 90% of the apertures have an aperture in this range. Even more preferably, more than 95% of the apertures have an aperture in this range.

[0306] The average aperture and aperture distribution of the mask can be measured using appropriate image analysis software via optical microscopy or scanning electron microscopy (SEM).

[0307] The horizontal distance between the centers of two adjacent holes, also referred to herein as the “pitch,” can be selected based on the desired pattern of the foil, provided that the adjacent holes do not coalesce. In some embodiments, the horizontal distance between the centers of two adjacent holes ranges from 10-5000 μm, or 10-2000 μm, or 50-2500 μm, or 10-1000 μm, or 20-500 μm, 30-500 μm, 40-500 μm, 50-250 μm, 60-250 μm, 70-250 μm, 80-250 μm, about 100-200 μm, or about 60-100 μm. In some embodiments, the horizontal distance between the centers of two through-holes (holes) in the mask is approximately 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or approximately 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm. 160μm, 170μm, 180μm, 190μm, 200μm, 210μm, 220μm, 230μm, 240μm, 250μm, 260μm, 2 70μm, 280μm, 290μm, 300μm, 310μm, 320μm, 330μm, 340μm, 350μm, 360μm, 370μm, 380 µm, 390 µm, or approximately 400 µm, 450 µm, 500 µm, 550 µm, 600 µm, 650 µm, 700 µm, 750 µm, 800 µm, 850 µm, 900 µm, 950 µm, or 1,000 µm.

[0308] The aperture density depends on the aperture size and the horizontal distance between adjacent apertures. In the context of this invention, the aperture density of a mask, such as an SRP stencil mask, is related to the number of through-holes per unit area. In some embodiments, the aperture density is related to the ratio between the area of ​​mask material per unit area and the area of ​​voids (apertures). According to some embodiments, the aperture density ranges from 30 apertures / 1 mm. 2 (square millimeters) to 200 holes / mm 2 .

[0309] The uniformity of SRP can be determined by any experimental method, such as photographing different portions of the SRP stencil mask or the resulting patterned foil, scanning predetermined areas in or between photographs, identifying and digitizing motifs in the scanned images, measuring the size and horizontal distance of a predetermined number of patterns in each scanned portion, and calculating the standard deviation of the motifs over the entire segment. In embodiments where the motif / patch contains a single hole, SRP uniformity relates to the standard deviation between the individual holes. In embodiments where the motif / patch contains more than one hole, SRP uniformity relates to the standard deviation between the motifs / patches. In some embodiments, the standard deviation of motif overlap ranges from 0-15%. In some embodiments, the standard deviation of motif overlap is less than 15%, less than 10%, or less than 5%.

[0310] Continuous subtractive manufacturing method: The subtractive processing method of this invention relates to this electro-etching system and process. The challenge of seamless and continuously repeatable patterning is addressed using a circumferentially closed-belt SRP stencil mask, based on a roll-to-roll architecture developed for continuous production. Currently available tools and methods for electro-etching use current and a mask under certain operating conditions to remove metal at predetermined locations in the original conductive foil. By choosing to perforate the original foil using electro-etching instead of chemical etching, the inventors have achieved control over the process parameters, and thus achieved uniform perforation patterns and high stencil printing fidelity.

[0311] The roll-to-roll electroetching system provided herein can be used as a method for manufacturing patterned metal foils (e.g., perforated metal foils (metal components) or composite foils) or metal-coated dielectric materials (e.g., polymers), suitable for producing continuous SRPs on or within a continuous original foil (also referred to herein as a starter / substrate foil); such methods are also known as continuous subtractive manufacturing methods. This invention provides inexpensive and rapid tools and methods for producing long perforated foils with high and uniform porosity, involving enhancing the functional porosity of thin foils so that these perforated metal foils provide the benefits of 3D structures (e.g., metal foams) while maintaining the uniformity, production speed, production cost, and roll availability benefits obtained from continuous production methods.

[0312] The present invention includes tools and methods for perforating a preformed thin metal foil to present SRP perforations in a single subtractive manufacturing step, i.e., by introducing perforations into the foil, metal components can be provided at any length (up to tens of kilometers, essentially limited by the original length of the input raw foil). The perforation step by electro-etching can be performed under SRP conditions and uniformity requirements. In some embodiments, the subtractive manufacturing technique is electro-etching, in which the conductive foil is subjected to etching conditions through a mask having holes arranged under SRP conditions (SRP stencil mask), such that etchable foil material, such as metal, is selectively removed through these holes, as described below. For example, a thin aluminum foil can be electro-etched through an SRP stencil mask having an ordered arrangement of holes. In the context of the present invention, this ordered arrangement is the stencil of SRP, and the mask serves as a template or mold for forming holes in the metal component. This step can form a fine, seamlessly repeating pattern of through-holes in the metal component, thereby stencil printing the arrangement of holes in the mask.

[0313] According to some aspects and embodiments of the present invention, an electro-etching method is provided for imparting a pattern to a starting metal foil. The method includes: The foil is fed into an electro-etching unit that includes a mask and a cathode, such that at least a contact section of the foil is disposed within the electro-etching unit; The contact section of the mask is brought into contact with the contact section of the foil to form a contact area, wherein the contact section of the mask is located between the contact sections of the cathode and the foil; The guiding electrolyte composition is substantially tangential to the outer surface of the mask along the entire length of the contact section of the mask; While advancing the foil through the electro-etching unit, a current, voltage, or both are applied between the cathode and the foil, thereby electro-etching the foil and forming an electro-etched foil and a salt of metal, wherein the advancement is coordinated with the movement of the mask; and Collect electro-etched foil, in: The mask has the form of a circumferentially closed band, which has an electrically insulating outer surface; and The contact area is curved.

[0314] As used herein, the phrase "applying current and / or voltage" also includes applying electrical power (which is the product of current and voltage), and the electro-etching method can be performed under controlled voltage, current, and / or power. Those skilled in the art will also readily recognize that applying current and / or voltage in an electrochemical system such as an electro-etching unit requires an electrolyte solution between the electrodes of the system or unit to establish ion contact therebetween.

[0315] One or more of the steps described above can be performed continuously to provide a conductive foil with a seamlessly repeating pattern. For example, the foil can be continuously or incrementally fed into an electro-etching unit and continuously (or incrementally) collected once it leaves the electro-etching unit. The method may further include contacting a contact segment of a mask with a contact segment of the foil throughout the continuous process and applying a constant current or voltage between the contact segments of the cathode and the metal film in the presence of an electrolyte. The electrolyte can be circulated within the electro-etching unit and, in particular, continuously flows between the contact segments of the cathode and the foil.

[0316] The etching time period, controlled by the speed at which the starting foil is fed into the electro-etching system or collected at the output rollers as patterned foil, is the time it takes for any portion of the foil to remain in the electro-etching unit and become a contact area. The etching time period (and effectively the foil feed rate) can be adjusted based on the thickness of the original foil, the length of the contact area along the workflow direction, the perforation density (representing the amount of foil material to be etched away), the composition and concentration of the electrolyte solution, and other factors. The etching time period can be determined experimentally and controlled by varying the speed of the coordinated movement of the mask and foil and / or the power parameters, where a sufficient etching time period is not less than the minimum time required to achieve the desired aperture depth of the foil at a given speed and power setting. Typical etching time periods range from 1 to 600 seconds. Alternatively, the speed at which the foil passes through the system along the workflow direction can be adjusted based on the length of the contact area (which in particular depends on the radius of curvature of the foil and / or mask) so that each axial portion of the foil entering the electro-etching unit is exposed to the cathode and electrolyte for a sufficient time (i.e., 1-600 seconds) for etching. In some implementations, the foil travels through the system at a speed ranging from about 1 to about 500 meters per hour in the workflow direction.

[0317] As described above, according to some embodiments, this system allows the electrolyte to be guided in a path connecting the two electrodes and the contact section of the foil with the mask. According to some embodiments, the guidance of the electrolyte composition requires guidance along substantially the entire length of the contact section of the mask in a path tangential to the outer surface of the mask.

[0318] According to some embodiments, the electrolyte composition is in the form of an aqueous solution contained in a container. According to some embodiments, the method includes circulating the aqueous solution between the anode and cathode. According to some embodiments, the method includes guiding the electrolyte composition substantially tangentially to the outer surface of the mask along the entire length of the contact section of the mask.

[0319] According to some embodiments, the circulation is carried out under pressure. According to some embodiments, the liquid pressure is provided by a liquid pump. According to some embodiments, the circulation involves using a liquid pump to flow an aqueous solution in a closed path, the closed path contacting the anode, cathode, and contact area, thereby achieving forced and directional flow thereto.

[0320] According to some implementation schemes, guiding the electrolyte flow also includes flowing between the two parts of the split cathode.

[0321] According to some embodiments, electro-etching forms an electro-etched (e.g., perforated) foil and an electro-etched metal salt. According to some embodiments, the starting foil comprises a metal. According to some embodiments, the metal includes aluminum. According to some embodiments, the electro-etched metal salt comprises aluminum oxide.

[0322] According to some embodiments, the method further includes cleaning the metal salts from the mask with a cleaning solution. According to some embodiments, cleaning is performed using a cleaning unit of the system disclosed herein. According to some embodiments, cleaning includes applying (e.g., rinsing) a flow of water to a portion of the mask. The location of that portion of the mask is defined here in relation to the cleaning unit. According to some embodiments, cleaning includes applying (e.g., rinsing) a flow of water to a portion of the electro-etched foil. The location of that portion of the electro-etched foil is defined here in relation to the cleaning unit. According to some embodiments, the method includes cleaning both the mask and the electro-etched foil.

[0323] The foil and mask can be advanced either continuously or through discrete (incremental) steps. Voltage and / or current can be applied during and / or between advance steps. When advancing the foil incrementally, the step duration, advance rate, and interval between steps can be adjusted, if necessary, to adapt to the electro-etching rate controlled by the conditions described above, to provide a seamless pattern. For example, when the electro-etching process is relatively slow and voltage and / or current are applied in intervals, short-duration advance steps with a slow advance rate and short intervals will substantially resemble continuous slow movement of the foil and should not compromise the seamlessness of the electro-etched pattern. The form of foil movement can be selected based on the desired final pattern and practical considerations.

[0324] Advancement may include coordinated movement of the foil and the mask. According to some embodiments, coordinated movement may include pressing the foil against the mask and advancing the foil such that the mask and the foil move together (e.g., by frictional engagement).

[0325] According to some implementations, making the contact section of the mask contact the contact section of the foil requires pressing one of the mask and the foil onto the other in the contact section. According to some implementations, advancing the initial foil requires dragging the mask at a similar rate to form a synergy between the foil and the mask.

[0326] According to some embodiments, the method includes preventing relative displacement between the starting foils. According to some embodiments, displacement is prevented in a direction perpendicular to the feed direction. According to some embodiments, displacement is prevented in a direction parallel to the surface of the starting foil; or both. According to some embodiments, displacement is prevented by using a convex roll as an input roll, an output roll, or both. According to some embodiments, the input roll is a convex roll. According to some embodiments, the output roll is a convex roll.

[0327] It was found that parallel flow along the mask length allows for better replenishment of the electrolyte in the mask apertures, thereby allowing for the etching of smaller apertures and / or the formation of etched foils with larger opening areas.

[0328] The foil is fed into the electro-etching unit via an input roller and collected via an output roller as it leaves the unit. The foil leaving the electro-etching unit is also referred to herein as “etched foil,” “patterned foil,” “porous foil,” and “perforated foil.”

[0329] As described above, applying current and / or voltage between the contact section of the cathode and the foil can be done by connecting the foil to the positive terminal of a power source and the cathode to the negative terminal. The voltage and / or current can be DC, constant, pulsed, stepped, or AC, and the waveform, frequency, and step duration can be adjusted based on the desired electro-etching method configuration and results. When using pulsed voltage and / or current, the polarity of the electrodes can be reversed for a certain period of time, for example, to change the electrolyte composition near the etched surface.

[0330] According to some embodiments, the method includes applying a reverse pulsed current. According to some embodiments, the method includes positioning a mask between a cathode and a starting metal foil, and positioning the foil between the mask and an anode, wherein the electrolyte is in contact with the anode and cathode. According to some embodiments, the method includes applying a current, a voltage, or both between the cathode and anode. According to some embodiments, the method includes reversing the polarity of the anode and cathode, applying a reverse pulsed current, a voltage, or both between the cathode and anode.

[0331] According to some implementations, the reverse pulse forms bubbles, which at least partially remove the salts of the metal from the electro-etched foil.

[0332] Applying current and / or voltage between the contact sections of the cathode and the foil can further include establishing an ion contact between the foil and the cathode. For example, an ion contact can be established by immersing at least the contact section of the foil, the contact section of the mask, and the cathode in an electrolyte solution, or by allowing an electrolyte solution to flow at least through the contact sections of the foil, the contact sections of the mask, and the portion of the cathode located in the electro-etching unit.

[0333] For example, for aluminum electrolytic etching, an aqueous electrolyte solution with 0.5-3M NaCl and a pH range of 6-8 can be used. Electroetching can be performed at a constant or pulsed voltage in the range of 3-10V for etching times ranging from 1-600 seconds.

[0334] In some implementations of the methods provided herein, the mask is an SRP template mask.

[0335] The shape of the mask pattern and / or the conditions of the electro-etching method can be adjusted to provide the desired pattern on the foil, especially, for example, indentations or vias.

[0336] In some embodiments, the method includes electro-etching a raw copper foil, aluminum foil, titanium foil, or steel / stainless steel foil, and typically any metal or alloy, by applying a suitable current and / or voltage. In some embodiments, the method includes electro-etching a conductive composite foil containing metal, for example, in the form of a metal layer deposited on a polymer film.

[0337] In some embodiments, including any of the foregoing, the original foil is wrapped around an anode having a cylindrical shape. In some of these embodiments, the cylinder is made of Al, Ni, Cu, Mg, Ti, steel, stainless steel, steel coated with chromium, or steel of other suitable metals that are inert under the operating conditions of the anode in the electro-etching method.

[0338] In some embodiments, the raw foil is wrapped around a cylinder made of a dielectric material. In some such embodiments, before the foil is wound onto the cylinder, the raw foil can be electrically connected to the positive terminal of a power source by contacting the foil with a conductor electrically connected to the positive terminal, for example, but not limited to, by winding the foil onto a tension roller connected to the positive terminal. The cylinder can be made of any dimensionally stable electrically insulating (dielectric) material, such as polymers, ceramics, and polymer-coated metals. Non-limiting examples of suitable polymers include polytetrafluoroethylene (PTFE, such as TEFLON™) and polyaryletherketones, such as PEEK™.

[0339] In short, according to some embodiments of the invention, essentially as presented herein, the continuous electro-etching (subtractive manufacturing) method provided herein can be performed by providing a raw conductive foil roll and a circumferentially closed strip mask for etching holes in the foil (e.g., an SRP template mask showing a hole pattern corresponding to an SRP), and loading (feeding) the raw foil into an electro-etching unit of an electro-etching system. Elements of the electro-etching unit may include a cathode having a curved active surface, and optionally, a cathode having a correspondingly curved surface on which the foil and mask can be pressed against each other to form a contact area between the foil and mask, wherein the foil is connected to the contact area or serves as an anode.

[0340] The foil is loaded into the electro-etching unit such that the tip of the foil is advanced into the unit until at least one contact area of ​​the foil is positioned within the unit, which is already equipped with a cathode and a mask. For example, in some embodiments, feeding the foil into the electro-etching unit includes winding the foil around at least one segment of the circumference of a curved surface of a conductive cylindrical mandrel that serves as an anode in the electro-etching unit to form a conductive contact area in which the foil contacts the cylindrical anode.

[0341] A section of the mask is brought into contact with a contact section of the foil, such that the contact sections of the mask and the foil are substantially in contact over a region having a curved shape, and such that the contact section of the mask is located between the contact sections of the cathode and the foil. For example, a circumferentially closed strip mask can be brought into contact with a section of the foil wound on a curved anode, thereby forming a curved contact region therebetween, and such that the contact region of the mask is positioned between the foil and the cathode. In another example, a circumferentially closed strip mask is a rotatable rigid mask with a permanently stable circular shape that surrounds the cathode, and foil wound on two or more tension / rotation axes can be brought into contact with a contact section of the mask, thereby forming a curved contact region therebetween, and such that the contact region of the mask is positioned between the foil and the cathode.

[0342] Once the components of the electro-etching unit are in place and in contact, the method continues by applying current and / or voltage between the cathode and the contact section of the foil in the presence of an electrolyte. For example, once the foil, mask, and other components are brought together in the electro-etching unit, optionally with additional seals and walls (plates) to form a flow cell in which the electrolyte flows continuously, current / voltage is continuously applied between the anode and the contact section of the original foil, and associated tension and rotation shafts engage in coordinated motion, thereby continuously electro-etching the original foil essentially only through the apertures of the mask while continuously advancing the foil through the electro-etching unit, and the contact section of the mask is in constant contact with the contact section of the foil.

[0343] The method is complete once the input foil in the roll of raw foil has passed through the electro-etching system and the output patterned foil leaving the electro-etching unit has been collected on the output roller.

[0344] FIG. 8 This is a flowchart illustrating the basic steps of a method for continuous subtractive manufacturing (roll-to-roll construction) of very long patterned foil, which involves electro-etching very long original foil through holes in a mask with a repeating hole pattern to form a repeating pattern of through holes in the foil.

[0345] According to some embodiments, the method includes forming perforations with an average diameter of less than 6 mm, less than 5 mm, less than 4 mm, less than 3 mm, less than 2 mm, or less than 1 mm. Each possibility represents a separate embodiment of the invention.

[0346] Continuous additive manufacturing methods: The challenge of seamless and continuously repeatable patterning is addressed using a circumferentially closed strip SRP template mask, based on a roll-to-roll architecture developed for continuous production modes. Currently available tools and methods suitable for electrodeposition utilize current and a mask under specific operating conditions to deposit metal at predetermined locations on a conductive foil (starter foil).

[0347] The roll-to-roll electrodeposition system provided herein can be used to manufacture metal foils with patterns of raised protrusions on one side of a metal foil (metal component), composite foils comprising more than one substance (e.g., two metals), or metal-coated dielectric materials (e.g., polymers), methods adapted to produce continuous SRPs on or within a continuous initial foil (also referred to herein as a starting foil); such methods are also known as continuous additive manufacturing methods. This invention provides tools and methods for producing long patterned foils with uniform and optionally seamless surface or integral patterns, offering the benefits of 3D structures while retaining the uniformity and roll-readiness benefits obtained from continuous production methods.

[0348] The present invention includes tools and methods for patterning preformed thin metal foils to achieve SRP (Surface Mount Reinforced Plastic) in a single additive manufacturing step, i.e., by introducing a pattern into the foil, metal components can be provided at any length (up to tens of kilometers, substantially limited by the original length of the input starting foil). Patterning by electrodeposition can be performed under SRP conditions and uniformity requirements. In some embodiments, the additive manufacturing technique is electrodeposition, in which a conductive foil is subjected to an electrolyte solution containing metal ions and maintained at a negative potential relative to a counter electrode to achieve electrodeposition of the metal through a mask presenting holes arranged under SRP conditions (SRP template mask), thereby allowing the electrodeposited layer to grow selectively in the mask holes.

[0349] According to some aspects and embodiments of the present invention, an electrodeposition method is provided, comprising: A conductive starting foil is fed into an electrodeposition unit including a mask and an anode, such that at least a contact section of the foil is disposed within the electro-etching unit; The contact section of the mask is brought into contact with the contact section of the foil to form a contact area, wherein the contact section of the mask is located between the contact section of the anode and the contact section of the foil; The guiding electrolyte composition is substantially tangential to the outer surface of the mask along the entire length of the contact section of the mask; A current, voltage, or both are applied between the anode and the foil while simultaneously advancing the foil through the electro-etching unit, thereby electrodepositing metal on the starting metal foil, wherein the advancement is coordinated with the movement of the mask; and Collect patterned foil, in: The mask has the form of a circumferentially closed strip, the strip having an electrically insulating outer surface; and The contact area is curved.

[0350] The electrodeposition subtractive method disclosed herein shares similarities and components, steps, and features with the additive electro-etching method disclosed herein. Therefore, except for the details specifically referred to herein, the electrodeposition method may include any features described for the method system. First, since electrodeposition and electro-etching involve opposite current flows, the cathode and anode are opposite in function and location; therefore, statements relating to the cathode in an electro-etching system may apply to the anode in an electrodeposition system, and vice versa. References to negative / positive electrodes may also be reversed in meaning.

[0351] The starting foil can be fed into the electrodeposition unit via the input roller and collected via the output roller as it leaves the electrodeposition unit. As mentioned above, the starting foil leaving the electrodeposition apparatus is also referred to herein as “electrodeposited foil”, “patterned foil”, “patterned metal foil”, “porous foil”, and “porous metal foil”.

[0352] For copper electrodeposition, an aqueous electrolyte solution containing 10-25 g / L copper, 90-120 ml / L sulfuric acid, and 50-80 mg / L sodium chloride can be used. Electrodeposition can be carried out at a constant voltage of 5-10 A / dm³. 2 The current density is used for measurement.

[0353] In some embodiments, the method includes electrodepositing copper, nickel, cobalt, zinc, or any combination thereof, as well as any metal or alloy generally suitable for electrodeposition. In some embodiments, the method includes electrodepositing on a metal starting foil. The metal of the starting foil may be the same metal as the electrodepositing metal or a different metal. Alternatively, the method may include electrodepositing on a carbon-based or graphite-based foil or a conductive polymer foil.

[0354] In some embodiments, including any of the foregoing, the starting foil is wound around a cathode having a cylindrical shape. In some of these embodiments, the cylinder is made of Ti, steel, stainless steel, steel coated with chromium, or other suitable metal that is inert under the operating conditions of the cathode in the electrodeposition method.

[0355] In short, according to some embodiments of the invention, essentially as described herein, the continuous electrodeposition (additive manufacturing) method provided herein can be performed by providing a conductive starter foil roll and a circumferentially closed strip mask for patterning the starter foil (e.g., an SRP template mask presenting a hole pattern corresponding to an SRP), and loading (feeding) the starter foil into an electrodeposition unit of an electrodeposition system. Elements of the electrodeposition unit may include an anode having a curved active surface and optionally a correspondingly curved surface, on which the starter foil and the mask may be pressed against each other to form a contact area therebetween, the starter foil being connected to this contact area or used as a cathode.

[0356] FIG. 16 This is a flowchart illustrating the basic steps of a method for continuously electrodepositing (roll-to-roll structure) metal onto a very long starting foil through holes in a mask with a repeating hole pattern to form a repeating pattern of protruding structures on the surface of the starting foil.

[0357] Patterned foil: The electrodeposition system and method provided herein can be used to manufacture long, patterned metal foils in industrial environments. The patterned foil is characterized by a smooth bottom side and a pattern of raised textured elements (protrusions) on the other side (top side), arranged in a seamless repeating pattern, having a three-dimensional structure characterized by an infinite length, a given width, and a given thickness, the given thickness being the sum of the thickness of the base foil and the height of the raised protrusions.

[0358] The raised texture elements on the top side of the substrate foil are attached to the substrate foil by electrodeposition and arranged in a seamless repeating pattern to produce a uniform and consistent surface texture. The shape, size, and arrangement of the raised texture elements can vary depending on the specific design of the SRP stencil mask.

[0359] The raised texture elements are formed by electrodeposition; thus, the raised texture elements are fused to the substrate foil. This is because the electrodeposition process involves transferring metal ions from an electrolyte solution to the surface of the starting foil. The metal ions are deposited on the surface as raised texture elements, and the substrate of each element is bonded to the surface by metallic bonds. Metallic bonds are formed by the delocalization of electrons throughout the metal. Metal atoms lose their valence electrons, which become delocalized, meaning they do not associate with any single atom but move freely throughout the metal. The delocalized electrons are attracted to positively charged metal ions, which creates a strong attraction between the atoms. Metallic bonding is what makes the metallic components presented herein so unique, such as their high electrical conductivity, ductility, and malleability. Delocalized electrons allow the metal to conduct electricity and heat, and they also make the metal soft and easily deformable.

[0360] The bonding strength between the textured element and the substrate foil depends on several factors, including the metal type, electrolyte solution concentration, and applied voltage. Generally, stronger bonds are found in metals with high melting points and electrolyte solutions with high concentrations of metal ions. The applied voltage also affects bond strength, with higher voltages resulting in stronger bonds. The fusion properties of the textured element and substrate foil ensure that the textured element is firmly attached to the surface and does not loosen, and it prevents the textured element from being corroded or damaged by environmental factors. These fusion properties also allow the textured element to be used in a variety of applications, such as batteries, capacitors, circuits, sensors, actuators, and microelectronics.

[0361] In some implementations, two different metals are used, one for the base foil and the other for the raised texture, providing a variety of physical, chemical, and electrical characteristics. When two different metals are fused (juxtaposed), such as in an implementation where one type of metal is electrodeposited on different metals, phenomena that can be observed include, but are not limited to, contact potential difference, plating corrosion, thermoelectric effects, piezoelectric effects, and magnetic effects.

[0362] In short, a contact potential difference is observed when two different metals come into contact; a potential difference is generated between them at the contact interface. This potential difference is called the contact potential difference, and it is caused by the different electron affinities of the two metals. Electroplating corrosion is a type of corrosion that occurs when two different metals come into contact in the presence of an electrolyte. The more reactive metal (the metal with a lower standard reduction potential) will corrode, while the less reactive metal will be protected. Thermoelectric effect is the voltage generated when two different metals are placed in contact and a temperature difference exists between them; the voltage generated is proportional to the temperature difference. Piezoelectricity is the ability of certain materials to generate an electric charge when subjected to mechanical stress. The magnetism of a metal can be affected by the presence of other metals; for example, adding a small amount of cobalt or nickel to iron can make it more magnetic.

[0363] The height of the raised texture elements will also vary depending on the electrodeposition chemistry and electrical parameters, as well as the mask design. In some cases, the height of the raised elements can be relatively small, resulting in a fine raised texture on the surface (top side) of the substrate foil. In other cases, the height of the raised elements can be more pronounced, resulting in a more prominent texture.

[0364] Therefore, according to another aspect of some embodiments of the present invention, a metal component is provided, comprising a base foil and a plurality of raised textured elements located on the top side of the base foil, wherein the raised textured elements are arranged in a seamless repeating pattern; the metal component has a given width and an infinite length, or at least 0.1 m wide and at least 0.5 m long.

[0365] In some embodiments, a plurality of raised texture elements or patterns cover at least 10% of the continuous, uninterrupted, and unbroken area constituting the top side of the substrate foil. In some embodiments, SRP covers 10-95% and up to 100% of the continuous area constituting the top side of the substrate foil. When referring to pattern coverage of a surface, it means considering the entire area covered by the pattern, including flat areas between individual raised texture elements. In some embodiments, unpatterned areas (i.e., the surface of the substrate foil not covered by raised texture elements) include continuous strips of the substrate foil defining an edge along the foil's axis, or two strips along each of the two edges of the foil's long axis, or one or two strips between the edges of the foil. Such unpatterned strips can be used for additional post-production processes and operations of the metal components provided herein.

[0366] In some implementations, the raised textured elements are formed by electrodepositing metal on the top side of the substrate foil.

[0367] As discussed above, each of the raised texture elements inherits its basic shape and size from the apertures in the mask, since the texture elements are formed by electrodepositing metal through the apertures in the mask, and therefore the shape and size of the base of the structural element (the area of ​​the interface / contact between the base foil and the raised texture element) corresponds to the shape and size of the apertures in the mask. According to some embodiments, the base shape of the raised texture element has a size in the range of about 10-200 μm, and the horizontal distance between the centers of two adjacent raised texture elements is about 50-250 μm.

[0368] In some embodiments, the height of the raised textured element depends on the chemical and electrical conditions and parameters of the electrodeposition method, as well as the thickness of the mask. In some embodiments, the height of the raised textured element is in the range of approximately 5-300 μm.

[0369] As discussed above, each of the substrate foil and the raised texture element can be made of the same or different metals, each metal being independently selected from copper, nickel, gold, silver, iron, tin, aluminum, palladium, and any alloys and combinations thereof. The substrate foil can further be made of conductive materials such as carbon / graphite or conductive polymers. Those skilled in the art will understand the specific choices of materials and electrodeposition parameters suitable for each type of material and any particular combination of substrate material and deposited metal.

[0370] In some embodiments, the substrate foil is 3-100 μm thick. In some embodiments, the height of the raised textured elements is in the range of approximately 1-100 μm from the top side of the substrate foil.

[0371] Other aspects: According to another aspect of some embodiments of the present invention, a roll comprising a cylindrical core and a metal component provided herein wound on the core is provided.

[0372] In some embodiments, the width of the metal member in the roll is in the range of at least 0.1-5 m. In some embodiments, the length of the metal member in the roll is in the range of at least 0.5-10,000 m.

[0373] According to another aspect of some embodiments of the present invention, a current collector is provided, which includes at least one metal component as provided herein.

[0374] As used herein, the term "current collector" (CC) refers to a substrate that conducts electrons sufficiently to complete the circuitry at the cathode and anode in a battery or electrochemical cell. CCs are typically made of metals such as copper, aluminum, or nickel. Other metals, such as magnesium, tungsten, cobalt, iron, titanium, platinum, tungsten, and gold, and any alloys thereof, as well as alloys or combinations of metals, such as steel, may also be used. In the case of a secondary battery, the CC in the cathode conducts electrons from the external circuitry to the cathode during discharge and from the cathode to the external circuitry during charging, while in the anode, the CC conducts electrons from the external circuitry to the anode during charging and from the anode to the external circuitry during discharge.

[0375] The current collectors described herein may also include contacts and contact leads, terminals and other features common to and / or required as part of the current collector, or features required for its assembly and implementation in an electrical installation, and all or any selection of these additional features are included in the definition of a current collector as used herein.

[0376] The advantages gained by using the metal components provided herein as CCs include an increased amount of active material that can be loaded per unit area, an increased contact surface area between the current collector and the active material, improved electrical pathways within the active material, and all of these while maintaining low production costs and compatibility with mass production machines and methods.

[0377] The metal component and CC provided in this paper can help reduce the local current density by increasing the surface area of ​​the CC. Since reducing the current density at the anode of a lithium battery can delay the onset of lithium dendrite growth and slow down the growth rate, the CC provided in this paper can mitigate dendrite growth.

[0378] Advantageously, the components provided herein, as well as current collectors including or composed of the components, can be implemented in electrode production in the form of a continuous roll of feed foil, which is fed into an active material coating apparatus and subsequently cut into individual electrodes.

[0379] Therefore, according to one aspect of some embodiments of the present invention, an electrode is provided, for example in the case of a battery or capacitor, comprising at least one current collector and an active electrode material (also referred to as a coating material) disposed on a current collector (CC), wherein the current collector comprises at least one metal component provided herein or is composed of metal components provided herein. Herein, unless otherwise explicitly stated, the term "electrode" refers to both the anode and the cathode.

[0380] Electrode coating is a crucial part of the battery manufacturing process, significantly contributing to the final microstructure and thus relating to the function of the resulting electrode. According to embodiments of the invention, the coating of the metal components provided herein can be performed through various means, and the coating apparatus can be a scraper commonly used in research laboratories to produce small coatings, or for larger industrial applications, a roll-to-roll (also known as R2R or roll-to-roll) coater, the components currently disclosed being particularly suitable for this purpose. In roll-to-roll apparatuses, according to some embodiments of the invention, the geometry of the coater for coating the metal components can be a scraper (a fine blade positioned at a fixed gap from the CC), a comma bar (a comma-shaped geometry with a curved leading edge), a die (extruding coating from a groove onto the CC), a "knife-over-roll" (distributing coating onto the CC and then passing it through the blade and roller), a "reverse roller," or a "Meyer rod" (where the roller applies coating onto the CC, and then the Meyer rod measures the correct amount), these methods and apparatuses are known in the art. The coating can be applied while the current collector (CC) is supported by a roller, or it can be applied under tension to an unsupported CC; this is known as tension mesh coating. Other electrode coating methods known in the art can be used to coat the current collector described herein.

[0381] Therefore, according to some embodiments of the invention, the electrodes are produced using rolls of the metal components provided herein by any known roll-to-roll (R2R) method.

[0382] In view of the foregoing, a cell or battery is provided comprising at least one electrode, wherein the electrode comprises at least one metal member as provided herein, or wherein the electrode comprises a current collector, the current collector comprising at least one metal member as provided herein or comprising or consisting of metal members as provided herein. It should be noted that although a cell is a single unit of a device for converting chemical energy into electrical energy, and a battery may comprise a collection of cells that convert chemical energy into electrical energy, the terms "cell" and "battery" are used interchangeably herein.

[0383] Accordingly, an electric device is provided, which includes a cell, cell array, battery, or battery array as provided herein.

[0384] In some embodiments, the cell or battery includes at least one electrode, which includes at least one current collector, wherein CC is the metallic component described herein.

[0385] The electrical equipment considered within the scope of this invention includes any electrical equipment that can use the cells or batteries provided herein as a primary, auxiliary, or secondary energy source. Alternatively, the electrical equipment is a device that includes at least one battery according to the invention, wherein the device uses electrical energy stored in the battery as its power source.

[0386] Examples of electrical equipment include, but are not limited to, electric vehicles used for transportation in the air, on land, in water and / or in space, smartphones, laptops, portable media players, power tools, toys, heating equipment, cooling equipment, items for lighting (e.g., flashlights), etc.

[0387] Batteries according to various embodiments of the present invention may also be present in energy storage and / or energy generation devices or systems.

[0388] It is anticipated that during the term of the patent granted in this application, many related tools and methods for continuous electrodeposition of conductive foils will be developed, and the scope of the phrase "tools and methods for continuous electrodeposition of conductive foils" is intended to include all these new technologies a priori.

[0389] It should be understood that certain features of this disclosure described in the context of individual embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features of the invention described in the context of individual embodiments for brevity may also be provided individually or in any suitable sub-combination or as suitably as in any other described embodiments of the invention. Certain features described in the context of various embodiments are not considered essential features of those embodiments unless the embodiment would be inoperable without those elements.

[0390] As used herein, the term “about” means ±10%. For example, the term “about 100 μm” includes the value 100 μm, as well as the values ​​90 μm, 91 μm, 92 μm, 93 μm, 94 μm, 95 μm, 96 μm, 97 μm, 98 μm, 99 μm, 100 μm, 101 μm, 102 μm, 103 μm, 104 μm, 105 μm, 106 μm, 107 μm, 108 μm, 109 μm, and 110 μm.

[0391] The terms “contains,” “includes,” “including,” “containing,” “having,” and their variations refer to “including but not limited to.”

[0392] The term "composed of" means "including and limited to".

[0393] The term "consistently made of" means that a composition, method, or structure may include additional ingredients, steps, and / or portions, but only if the additional ingredients, steps, and / or portions do not substantially alter the essential and novel characteristics of the claimed composition, method, or structure.

[0394] As used herein, the phrase “selected from the group consisting of” includes all members of the group, each member of the group, and all possible combinations thereof. For example, selected from A, B, and C, including only A, and B, only C, and only A and B, and A and C, and B and C, and A, B, and C.

[0395] As used herein, in the context of certain substances, the phrases “significantly free” and / or “substantially free” mean that a composition is completely free of the substance or includes a substance present in amounts of less than about 5%, 1%, 0.5%, or 0.1% by weight or volume of the composition. Alternatively, in the context of methods, properties, or characteristics, the phrases “significantly free” and / or “substantially free” mean that a method / method step, or a property or characteristic, or a method / method step of a method, composition, structure, or article is completely free of a method / method step where the method / method step is affected by less than about 5%, 1%, 0.5%, or 0.1% compared to a given standard method / method, or the property or characteristic is less than about 5%, 1%, 0.5%, or 0.1% compared to a given standard.

[0396] When applied to the original, desired, or provided properties of an object or composition, as used herein, the term “substantially retained” means that the properties in the processed object or composition change by no more than 20%, 10%, or more than 5%.

[0397] The term "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any embodiment described as "exemplary" should not be construed as being preferred or advantageous over other embodiments and / or excluding combinations of features from other embodiments.

[0398] The terms “optionally” or “alternatively” are used herein to mean “provided in some embodiments but not in others.” Any particular embodiment of the invention may include multiple “optional” features unless these features conflict.

[0399] As used herein, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly indicates otherwise. For example, the terms “a compound” or “at least one compound” can include multiple compounds, including mixtures thereof.

[0400] In this application, various embodiments of the invention may be presented in the form of a scope. It should be understood that the scope description is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention. Therefore, the scope description should be considered to specifically disclose all possible sub-scopes and individual numerical values ​​within those scopes. For example, a description of a scope such as 1 to 6 should be considered to specifically disclose sub-scopes such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., and individual numerical values ​​within those scopes such as 1, 2, 3, 4, 5, and 6. This is unrelated to the width of the scope.

[0401] Whenever a range of values ​​is indicated herein, it means any referenced number (fraction or integer) included within the indicated range. The phrases “range / scope between the first and second indicator numbers” and “range / scope from the first indicator number to the second indicator number” are used interchangeably herein and are intended to include the first and second indicator numbers and all fractions and integers in between.

[0402] As used herein, the terms “process” and “method” refer to the manner, means, techniques and procedures used to accomplish a given task, including but not limited to those manner, means, techniques and procedures known to or readily developed from known manner, means, techniques and procedures by practitioners in the fields of chemistry, materials, mechanics, computing and digital science.

[0403] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although similar or equivalent methods and materials to those described herein may be used in the practice or testing of embodiments of the invention, exemplary methods and / or materials will be described below. In case of conflict, the specification (including definitions) of this invention shall prevail. Furthermore, materials, methods, and embodiments are illustrative only and not restrictive.

[0404] As described above and as claimed in the claims section, various embodiments and aspects of the invention find experimental support in the following embodiments.

[0405] Example The following embodiments, together with the foregoing description, illustrate some implementations of the invention in a non-limiting manner.

[0406] Example 1 Foil perforation system The roll-to-roll electro-etching system used in this embodiment includes a foil feeding mechanism comprising an unfolding shaft (input roller), a rewinding shaft (output roller), and an electro-etching unit. The electro-etching unit comprises a 15 cm diameter stainless steel component coated with TEFLON. TMThe center roller, which corresponds to FIG. 2A The cylindrical mandrel 24 in -B corresponds to FIG. 2A -B contains the tensioning roller 26, which is connected to the positive terminal of the power supply, corresponding to... FIG. 2A -B contains a concave cathode 23, wherein the curvature of the cathode is reverse-matched to the curvature of the central roller in order to maintain a constant distance between the cathode and the central roller.

[0407] The electro-etching unit also includes a mask, which serves as a counterpart to... FIG. 2A The SRP template mask of mask 21 in -B is made by the corresponding FIG. 2A The two tensioning shafts 22a and 22bd in -B are tensioned and surround the cathode, wherein the mask presents a pattern of circular holes, each with a diameter of 100 μm, and arranged in a hexagonal 2D stacked manner with a hole center distance of 150 μm.

[0408] The system also includes an electrolyte flow and circulation mechanism, a perforated foil cleaning station, various guide idler rollers, tensioning and rotating shafts, and a CCU, all of which are not shown in the figure. The electrolyte is an aqueous solution of NaCl 3M containing a dispersant dissolved in ethanol.

[0409] The mask was made of a 45 μm thick and 94.2 cm long and 20 cm wide Kapton® film (DuPont's polyimide) to form closed bands, and was patterned with SRP as closed bands using a computer-guided laser beam. FIG. 9 This is a photograph of an exemplary mask used in this example, showing an SRP with circular holes of 100 μm in diameter, spaced 150 μm apart, and stacked in a hexagonal pattern.

[0410] A roll of raw (unperforated) aluminum foil, 19 cm wide, 13 μm thick, and 300 meters long, is loaded onto the system and used as the input roller for this method. The front end of the foil is pulled over and wound around the cathode-facing portion of the central roller, ensuring no wrinkles form in the foil. The foil is then further guided through the system's cleaning station and from there to the rewinding shaft (output roller).

[0411] The mechanism for tensioning the SRP template mask is moved toward the central roller to press the mask's contact area against the foil's contact area, thereby creating a perforated area (see...). FIG. 2A -B (dashed rectangle).

[0412] The cathode is positioned closer to the perforation area, creating a 0.2 mm gap between the tensioned SRP template mask and the concave surface of the cathode (e.g., see...). FIG. 2B ).

[0413] An electrolyte cycle is initiated, filling the perforated area with electrolyte (i.e., exposing the contact area to the perforated area), and the foil propulsion mechanism is moved, thereby driving the foil and mask in a coordinated motion.

[0414] According to some embodiments of the invention, a current of 280 amperes is applied to the electrode at a potential of 10V, and an electro-etching method is performed in the perforation area, essentially printing the SRP stencil of the mask onto / into the original foil as described above.

[0415] The resulting perforated aluminum foil is collected on the rewinding shaft.

[0416] FIG. 10 The image shows a perforated aluminum foil obtained by the method provided in this paper, displaying SRP with circular through-holes of 100 μm in diameter and spaced 150 μm apart.

[0417] Example 2 Electrodeposition system The roll-to-roll electrodeposition system used in this embodiment includes a foil feeding mechanism comprising an unfolding shaft (input roll), a rewinding shaft (output roll), and an electrodeposition unit. The electrodeposition unit comprises a 115 cm diameter stainless steel unit coated with TEFLON. TM The center roller, which corresponds to FIGS. 12A-12B The cylindrical mandrel 124 in the middle corresponds to FIGS. 12A-12B The tensioning roller 126 in the middle is a roller connected to the negative terminal of the power supply, corresponding to... FIGS. 12A-12B The concave anode 123 in the anode has a curvature that is opposite to that of the central roller in order to maintain a constant distance between the anode and the central roller.

[0418] The electrodeposition unit also includes a mask, which acts as an SRP-template mask and corresponds to FIGS. 12A-12B Mask 121 in the middle is made by the corresponding FIG. 12A The two tensioning shafts 122a and 122b in -B are tensioned and surround the anode, wherein the mask presents a pattern of circular holes, each with a diameter of 100 μm, and arranged in a 2D stack of hexagons with a center-to-center distance of 150 μm.

[0419] The system also includes an electrolyte flow and circulation mechanism, a patterned foil cleaning station, various guide idler rollers, tensioning and rotating shafts, and a CCU, all of which are not shown in the figure. The electrolyte contains 75 g / L copper sulfate and 100 g / L H2SO4. 4。

[0420] The mask was made of a 45 μm thick and 94.2 cm long and 20 cm wide Kapton® film (polyimide from DuPont), which was used to form the closed band and patterned as the closed band using a computer-guided laser beam.

[0421] A 30 μm thick starting copper foil is loaded onto the system and used as the input roller for this method. The leading edge of the starting foil is pulled over and wound around the anode-facing portion of the central roller, ensuring no wrinkles form in the starting foil. The starting foil is collected on the rewinding shaft (output roller).

[0422] The mechanism that tensions the SRP template mask moves towards the central roller to press the mask's contact area against the foil's contact area, thereby creating an electrodeposition zone (see...). FIGS. 2A-2B (The dashed rectangle in the middle).

[0423] The anode is positioned closer to the electrodeposition region, creating a 1-2 mm gap between the tensioned SRP template mask and the concave surface of the anode (see, for example). FIG. 2B ).

[0424] An electrolyte cycle is initiated to fill the electrodeposition area with electrolyte (i.e., to expose the contact area to the perforation area), and the foil propulsion mechanism is moved to drive the initiating foil and mask in a coordinated motion.

[0425] According to some embodiments of the present invention, essentially as described above, 6-8 amperes / dm 2 A direct current is applied to the electrodes, and the electrodeposition process is carried out within the electrodeposition area, printing the SRP inversion stencil of the mask onto / into the starting foil.

[0426] The resulting patterned foil is collected on the rewinding axis. FIGS. 17A-17B The image shows a microscopic image of the obtained patterned foil.

[0427] FIGS. 17A-17B A microscope image is shown of an exemplary copper foil including copper textured elements electrodeposited on its surface, produced by the method provided herein. The elements are tapered textured elements spaced about 150 μm apart, with a height of about 10 to 20 μm and a base diameter of 100 μm.

[0428] While the invention has been described in conjunction with specific embodiments thereof, it will be apparent to those skilled in the art that various substitutions, modifications, and variations will be readily apparent. Therefore, within the spirit and broad scope of the appended claims, all such substitutions, modifications, and variations are intended to be included.

[0429] The applicant intends that all publications, patents, and patent applications mentioned in this specification are incorporated herein by reference in their entirety, just as each individual publication, patent, or patent application is specifically and individually identified when cited and is incorporated herein by reference. Furthermore, any reference or identification in this application should not be construed as an admission that such references are prior art to the invention. The use of partial headings should not be construed as necessarily limiting. Additionally, any priority documents of this application are incorporated herein by reference in their entirety.

Claims

1. A roll-to-roll foil patterning system, comprising: An electrical patterning unit is configured to transform a starting foil into a patterned foil when a current and / or voltage is applied; An input roller is configured to feed the starting foil into the electrical patterning unit; as well as An output roller, configured to collect the patterned foil, is used. The electrical patterning unit includes: electrode; Elastic mask; Two or more axes that hold the mask under tension; Containers for holding and / or circulating liquid electrolyte compositions; A fluid delivery unit fluidly connected to the container; and power supply, The starting foil and the patterned foil are conductive; The mask has the form of a circumferentially closed band with an electrically insulating outer surface. The mask includes a contact section positioned to contact a corresponding contact section of the starting foil, such that the contact section of the mask has a curved shape that conforms to the curvature of the contact section of the starting foil. The contact section of the mask is positioned between the electrode and the contact section of the starting foil. The fluid delivery unit is configured to guide the flow of the electrolyte composition supplied by the container to be substantially tangent to the outer surface of the mask along the entire length of the contact portion of the mask; The mask and the starting foil are configured to move collaboratively while the starting foil is in contact with the mask, wherein the starting foil is fed through the input roller and / or the patterned foil is collected through the output roller; and The power source is configured to apply voltage and / or current between the contact segment of the electrode and the starting foil in the presence of the electrolyte composition.

2. The system according to claim 1, wherein, The electropatterning unit includes a cleaning unit connectable to a cleaning fluid source, wherein the cleaning unit includes at least one nozzle facing a portion of the elastic mask and configured to rinse the portion of the elastic mask with the cleaning fluid.

3. The system according to claim 2, wherein, The liquid includes water, and the cleaning unit includes two nozzles and is configured to clean the portion of the mask with pressurized water.

4. The system according to any one of claims 1-3, wherein, The fluid delivery unit is positioned within the contact area between the electrode and the mask.

5. The system according to any one of claims 1-4, wherein, The electrode is divided into two substantially equal sections, and the fluid delivery unit is located between the two sections facing the mask.

6. The system according to any one of claims 1-5 further includes an ultrasonic cleaning device, the ultrasonic cleaning device comprising an ultrasonic transducer facing the foil as the foil is wound around the input roller and the output roller, and configured to emit ultrasonic waves toward the foil.

7. The system according to any one of claims 1-6, further comprising a counter electrode located adjacent to the contact section.

8. The system of claim 7 further includes a liquid pump configured to circulate the electrolyte composition in a flow path between the electrode and the counter electrode.

9. The system of claim 8 further includes a filter located within the flow path and configured to filter solid particles from the electrolyte composition.

10. The system according to any one of claims 1-9, wherein, The mask contains a hydrophilic material; The mask is made of polymer or polymer-coated metal; Or both.

11. The system according to any one of claims 1-10, wherein, The mask comprises a polyamide film.

12. The system according to any one of claims 1-11, wherein, When the starting foil is fed through the input roller and / or the patterned foil is collected through the output roller, the starting foil presses against the mask, wherein the input roller, the output roller, or both are configured to transfer the starting foil in a direction from the input roller to the output roller, wherein the pressing and transfer of the starting foil drags the mask, such that the starting foil is configured to move in coordination with the mask.

13. The system according to any one of claims 1-12, wherein, At least one of the input roller and the output roller is a convex roller, which is configured to maintain the alignment of the starting roller with the mask in a transverse direction perpendicular to the direction of movement of the mask and the starting foil.

14. The system according to any one of claims 1-13, wherein, The electrode has a curved active surface with a curvature consistent with that of the contact segment of the starting foil.

15. The system according to any one of claims 1-14, wherein, The electrical patterning unit includes an element having a curved surface configured to contact the starting foil on a first side of the contact segment of the starting foil, and the contact segment of the mask configured to contact the starting foil on a second side of the contact segment of the starting foil.

16. The system according to claim 15, wherein, The mask is configured to move toward the element prior to implementing the electrical patterning method, thereby forming an electrically patterned region between the contact segment of the starting foil and the electrode.

17. The system according to any one of claims 14-16, wherein, The curved surface forms part of the side surface of a rotatable drum or part of the surface of an annular belt conveyor.

18. The system according to claim 17, wherein, The electrode is a cathode, wherein the curved surface is electrically insulating, and the starting foil is connected to the positive terminal of the power source via a conductive shaft positioned outside the electrically patterned region.

19. The system according to claim 17, wherein, The electrode is the anode, the curved surface is electrically insulating, and the starting foil is connected to the negative terminal of the power source via a conductive shaft positioned outside the electrically patterned region.

20. The system according to any one of claims 15-19, wherein, The mask is configured to move toward the element prior to implementing the electrical patterning method, thereby forming an electrically patterned region between the contact segment of the starting foil and the electrode.

21. The system according to any one of claims 15-20, wherein, The curved surface is conductive, and the initiation is connected to the pole of the power source via the curved surface.

22. The system according to any one of claims 1-21, wherein, The mask is configured to move toward the starting foil, thereby forming an electrically patterned region between the contact segment of the starting foil and the electrode.

23. The system according to any one of claims 1-22, wherein, The mask surrounds the electrode.

24. The system according to any one of claims 1-23 further includes a computerized control unit.

25. The system according to any one of claims 1-24, wherein it is a roll-to-roll foil electro-etching system, wherein: The electropatching unit is an electroetching unit configured to transform the starting foil into an electroetched foil upon application of current and / or voltage. The electrode is a cathode.

26. The system according to claim 25, wherein, The mask is an SRP stencil mask that exhibits a seamless repeating pattern (SRP) of through-holes, wherein the through-holes have an opening size of approximately 10-2,000 μm and a spacing of approximately 50-2,500 μm.

27. The system according to any one of claims 25-26, wherein, The mask has a thickness ranging from about 5 μm to about 100 μm.

28. The system according to any one of claims 1-24, wherein it is a roll-to-roll foil electrodeposition system, wherein: The electropatching unit is an electrodeposition unit configured to transform a starting metal foil into a patterned foil by electrochemical deposition of metal upon application of current and / or voltage. The electrode is an anode.

29. The system according to claim 28, wherein, The mask is an SRP template mask that exhibits a seamless repeating pattern (SRP) of through-holes, wherein the through-holes have an opening size of approximately 10–2,000 μm, and wherein the horizontal distance between the centers of two adjacent through-holes is in the range of approximately 50–2,500 μm.

30. The system according to any one of claims 28-29, wherein, The mask has a thickness ranging from about 20 μm to about 300 μm.

31. An electro-etching method for patterning a starting metal foil, the method comprising: The foil is fed into an electro-etching unit comprising a mask and a cathode, such that at least a contact section of the foil is disposed within the electro-etching unit; The contact section of the mask is brought into contact with the contact section of the foil to form a contact area, wherein the contact section of the mask is located between the cathode and the contact section of the foil; The guiding electrolyte composition is substantially tangential to the outer surface of the mask along the entire length of the contact section of the mask; While advancing the foil through the electro-etching unit, a current, a voltage, or both are applied between the cathode and the foil, thereby electro-etching the foil and forming an electro-etched foil and a salt of the metal, wherein the advancement is coordinated with the movement of the mask; as well as Collect the electro-etched foil, in: The mask has the form of a circumferentially closed strip, the strip having an electrically insulating outer surface; and The contact area is curved.

32. The method of claim 31, further comprising washing the mask from the salt of the metal with a washing solution.

33. The method according to any one of claims 27-32, wherein, The applied current and / or voltage are achieved in the presence of the electrolyte composition containing an electrolyte, wherein the electrolyte is supplied to the electro-etched region formed between the cathode and the contact region.

34. The method of claim 33, further comprising positioning the mask between the cathode and the starting metal foil, and positioning the foil between the mask and the anode, wherein the electrolyte is in contact with the anode and the cathode; A current, a voltage, or both are applied between the cathode and the anode; Reverse the polarity of the anode and the cathode; as well as A reverse pulse current, voltage, or both are applied between the cathode and the anode to at least partially remove the salt of the metal from the electro-etched foil and / or from the contact section of the mask.

35. The method of claim 34, wherein, The electrolyte composition is in the form of an aqueous solution contained in a container, and the method includes: The aqueous solution is circulated between the anode and the cathode, or between the foil and the cathode; and The electrolyte composition is guided to be substantially tangent to the outer surface of the mask along the entire length of the contact section of the mask.

36. The method according to claim 35, wherein, The cycle is carried out under pressure and includes using a liquid pump to flow the aqueous solution in a closed path that contacts any one of the anode and the foil, the cathode and the contact area, thereby achieving forced and directional flow thereto.

37. The method according to any one of claims 31-36, wherein, The foil is aluminum foil.

38. The method according to any one of claims 31-37, wherein, The mask is configured to move toward the element prior to performing the electro-etching method, thereby forming an electro-etched region between the contact segment of the starting foil and the cathode.

39. The method according to any one of claims 31-38, wherein: Making the contact section of the mask contact the contact section of the foil requires pressing one of the mask and the foil against the other in the contact section, wherein advancing the initial foil requires dragging the mask at a similar rate to form a coordinated movement of the foil and the mask; The method includes preventing relative movement between the starting foil and the mask in a direction perpendicular to the advance direction and parallel to the surface of the starting foil; Or both.

40. The method according to any one of claims 31-39, wherein, The starting metal has a thickness ranging from 5 μm to 100 μm.

41. The method according to any one of claims 31-40, wherein, Electro-etching the foil requires forming a salt of the metal and an electro-etched foil having multiple etched perforations, wherein The plurality of etched holes have an average diameter of no more than 100 μm; The opening area of ​​the plurality of perforations in the electro-etched foil is at least 15% based on the total area of ​​the electro-etched foil; Or both.

42. The method according to any one of claims 31-3841, wherein, The mask is elastic, and the method includes: Tensioning the mask between two or more axes; and The contact section of the foil is brought into contact with the side surface of the roller or the surface of the annular belt conveyor.

43. The method according to any one of claims 31-42, wherein The feeding is achieved by a feed roller; The collection is achieved on the output roller; Or both.

44. The method according to any one of claims 31-43, further comprising rinsing the electro-etched foil prior to the collection.

45. An electrodeposition method, comprising: A conductive starting foil is fed into an electrodeposition unit including a mask and an anode, such that at least one contact segment of the foil is disposed within the electro-etching unit; The contact section of the mask is brought into contact with the contact section of the foil to form a contact area, wherein the contact section of the mask is located between the contact section of the anode and the contact section of the foil; A current, voltage, or both are applied between the anode and the foil while simultaneously advancing the foil through the electro-etching unit, thereby electrodepositing metal on the starting metal foil, wherein the advancement is coordinated with the movement of the mask; and Collect patterned foil, in: The mask has the form of a circumferentially closed strip, the strip having an electrically insulating outer surface; and The contact area is curved.

46. ​​The method of claim 45, further comprising guiding the electrolyte composition substantially tangential to the outer surface of the mask along the entire length of the contact section of the mask.

47. A metal component comprising a base foil and a plurality of raised textured elements located on the surface of the base foil, wherein: The plurality of raised texture elements are arranged in a seamless repeating pattern.

48. The metal component according to claim 47, wherein the width is at least 0.1m and the length is at least 0.5m.

49. The metal component according to any one of claims 47 to 48, which is prepared by the method according to claim 42.

50. A roll comprising a cylindrical core and a metal component according to any one of claims 47-48 wound on the core.

51. A current collector comprising at least one metal component according to any one of claims 47-48.

52. An electrode comprising the current collector according to claim 51.

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