Current collector for rechargeable battery

Abstract

The present invention provides foils with fine and uniform functional porosity that can be inexpensively produced in a roll-to-roll configuration, the porosity resulting from corrugating and / or perforating the foil. The enhanced metal foils of the present disclosure are useful in many applications, including, but not limited to, use as current collectors in lithium ion batteries.

Description

[Technical field]

[0001] Related Applications This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 267,543, filed February 3, 2022, the contents of which are incorporated herein by reference in their entirety.

[0002] The present invention, in some embodiments thereof, relates to electrochemical cells, and more particularly, but not exclusively, to current collectors suitable for use in primary and secondary batteries.

[0003] In recent years, a substantial century-old change in power supply from engine to battery has occurred in the automotive and renewable energy industries. Lithium-ion batteries (LIBs) play a central role as a power source, and post-LIBs have attracted great interest as alternatives to LIBs. There is a strong demand for rapid development of LIBs and post-LIBs with high performance parameters such as high charge / discharge cyclability of the cells, high energy density, high rate capability, and high safety. Efforts to meet the need for high-performance LIBs have led to many developments with anodes, cathodes, separators, and semiconducting electrolyte materials that play a major role in improving battery performance. Meanwhile, to improve battery performance, binders for combining anode active material particles and cathode active material particles, conductive additives mixed into anode and cathode layers, additives added to electrolytes, and current collectors (CCs) are also required. Binders, additives, and CCs with improved matching to high-performance anode, cathode, separator, and electrolyte materials can enable the implementation of high-performance anode, cathode, separator, and electrolyte materials.

[0004] CCs play an important role in the charge / discharge process of batteries. CCs support the active material layers for the anode and cathode, and they collect and distribute electrons to / from the supported active layers. To accelerate the electron transfer to / from the active layers, the contact between CCs and the active layers should be maintained during the charge / discharge process for thousands of cycles. The active layers are designed so that the pathways for fast electron transport extend throughout the active layer and Li + The CC should have a structure that allows ions to easily diffuse into the active layer. The CC structure should be designed to maintain the function of the active layer structure. Currently, in commercial LIBs, the CC has a thickness of 10-12 μm and is a flat planar surface. Copper (Cu) foil and aluminum (Al) foil are used as CC for the anode and cathode, respectively. In the anode and cathode, Li + Ions and electrons must be rapidly transported to and from the anode and cathode particle surfaces to charge and discharge the cell, respectively, at high current densities. Thus, in the anode and cathode layers, Li + An effective conductive path for the charge carriers and electrons should be designed on the planar CC. In this LIB preparation process, a slurry consisting of anode or cathode active material particles, binder, conductive additive, and solvent is poured onto the planar CC surface, and then the solvent in the slurry is evaporated to dry the anode and cathode layers formed on the CC. The anode and cathode material particles are filled into the prepared anode and cathode layers. The binder and conductive additive are located in the space between the active material particles to bind the particles and make electrical contact between the active material particles. Li + An electrolyte containing ions permeates this space. + The ions travel through the spaces permeated by the electrolyte solution to the surfaces of the anode and cathode active material particles. +and improved pathways for electrons should be constructed in the anode and cathode layers. In addition, the CC should have high mechanical strength, chemical and electrochemical stability, and adhesion between the active material layer and the CC surface. To realize these requirements, optimization of materials for CC, structural modification of CC, and formation of surface layer on CC have been carried out. Improvements in battery performance such as charge / discharge capacity, energy density, and capacity retention at high current density, as well as their stabilization, can be obtained by contributions from these factors.

[0005] Three-dimensional (3D) current collectors have proven promising by enabling both high energy density and high power density batteries. The utilization of 3D current collectors in Li-based batteries benefits from the electrical conductivity of the interconnected 3D structure that ensures that electrons and Li ions can be rapidly transported / diffused throughout the network, as well as the mechanical strength and chemical stability afforded by the microstructure that prevents exfoliation of the active material and framework collapse or corrosion while maintaining a flexible and large pore volume that can ensure sufficient space to accommodate the volumetric expansion of the active material. Despite the advantages of 3D current collectors, there are still some concerns to be addressed: 1) large surface area usually induces high electrode / electrolyte interfacial area, which causes significant consumption of electrolyte and Li species, and consequently causes low coulombic efficiency; 2) 3D porous current collectors still hold a rather large volume due to their irregular microstructure and low packing density, and their volumetric capacity is not comparable to their densely packed materials; 3) the requirement for high stability of battery systems requires that the structure of 3D current collectors be tightly controlled; 4) due to the complexity of synthesizing 3D current collectors, scaled-up 3D current collectors for practical applications are still economically out of reach; and 5) small or single sheet-like 3D current collectors are not compatible with downstream manufacturing processes, since the industry requires that active materials are coated onto metal foils by roll-to-roll process and the current collectors are welded to metal leads.

[0006] Nakamura, T. et al. ["Electrochemical performance of cathodes prepared on current collector with different surface morphologies", J. Power Sources, 2013, 244, 532-537] report cathode electrodes prepared on aluminum current collectors with different surface morphologies through a conventional doctor blade technique, and their electrochemical performance, especially at high current rates, as influenced by the surface morphology of the current collector.

[0007] Wang, GQ et al., ["Investigation of the hole-formation process during double-sided through-mask electrochemical machining", J. Mat. Processing Technology, 2016, 234, 95-101] report a through-mask electrochemical machining developed to fabricate hole arrays in titanium alloys that are difficult to cut using conventional machining.

[0008] Jeong, CU et al., ["Embossed aluminum as a current collector for high-rate lithium cathode performance", J. Power Sources, 2018, 398, 193-200] report that aluminum foil prepared by an anodization process followed by a chromium phosphate treatment has been evaluated for use as a current collector for cathode powders prepared by conventional electrode coating methods.

[0009] Shan, W. et al., ["Three-dimensional Porous Current Collector for Lithium Storage Enhancement of NiO Electrode", Acta Chim. Sinica, 2019, 77(6), 551-558] report the fabrication of 3D porous metals applied as current collectors to improve the cycling stability and high rate capacity of lithium-ion batteries.

[0010] Loghavi, MM et al. ["Improvement of the cyclability of Li-ion battery cathode using a chemically-modified current collector", J. Electroanal. Chem., 2019, 841, 107-110] report an aluminum current collector that was treated by simply reacting the aluminum foil with a solution containing three acids, and the physical effect of this modification on the surface of the current collector was investigated through scanning electron microscopy (SEM) and contact angle testing.

[0011] Choi H. et al., ["Fabrication of a Porous Copper Current Collector Using a Facile Chemical Etching to Alleviate Degradation of a Silicon-Dominant Li-ion Battery Anode", Corrosion Science and Technology, 2021, 20(5), 249-255] report a facile method to fabricate three-dimensional porous copper current collectors (3D Cu CC) for Si-dominant anodes in Li-ion batteries (LiBs). The 3D Cu CC was prepared from planar copper foil by combining chemical etching and thermal reduction.

[0012] Application Publication No. 2002216775(A) teaches a method of forming a current collector foil for an electrode of a secondary battery having a large number of through holes formed therein, and a non-stretched embossed roll having a large number of protrusions and a flat roll without irregularities are provided.

[0013] WO2010011509(A3) teaches an electrode material comprising a first electrode and a current collector disposed adjacent to and joined to the first electrode, wherein the current collector comprises a plurality of conductive protrusions extending in the z-direction from the current collector to the first electrode.

[0014] WO2010116872A1 teaches a method for manufacturing an electrode for an electricity storage device that prevents electrode particles from breaking and the current collector from curving, and forms a plurality of grooves in one direction on the surface of the current collector.

[0015] WO2013157806(A1) relates to a method for producing an electrode for a secondary battery, comprising the step of performing a surface treatment on a current collector to provide a morphology forming a surface roughness (Ra) of 0.001 μm to 10 μm over the entire surface and improved adhesion between the electrode active material and the current collector, and an electrode for a secondary battery produced using this method.

[0016] US Patent Application Publication No. 2016 / 0197353(A1) provides a perforated plate shaped material having at least one through hole penetrating from a first major surface to an opposite second major surface, and having in its cross-sectional shape a minimum width portion on the hole surface and a first major surface portion, the hole surface terminating on the first major surface and including a first protruding curved portion between the first major surface portion and the minimum width portion, at least a portion of the first protruding curved portion having the surface properties / shape of a non-hole surface on the first major surface.

[0017] CN206250289U is a utility model presenting a type of current collector formed with a thickness-wise surface embossed portion, the embossed portion being distributed in a plurality of embossments, the inside of each periphery being embossed from the surface of the current collector to the current collector along the thickness direction of the current collector, and in the peripheral region, a groove extending along the thickness direction of the current collector is formed. Summary of the Invention

[0018] The present invention provides foils with fine and uniform functional porosity that can be produced inexpensively in a roll-to-roll configuration, with the porosity resulting from corrugating and / or perforating the foil. The enhanced metal foils of the present disclosure are useful in many applications, including but not limited to use as current collectors in lithium-ion batteries. The present invention provides enhanced metal foils that benefit from the advantages of finely produced 3D metal structures, but without the cost, time, and production size limitations associated with state-of-the-art methods for metal processing. The functional porosity of thin metal foils is increased to levels that challenge 3D structures (e.g., metal foams) by the unique corrugating and perforation criteria and methodologies presented below, while maintaining and benefiting from the speed, cost, and roll readiness of thin foil production methods.

[0019] Modern current collector design presents several challenges, including: Reducing the resistance of the current collector to improve the efficiency of the device; this is achieved by the provisions of the present invention which teach the use of materials with low electrical resistance such as copper, aluminum or nickel, and by designing the current collector with a low resistance path for the current to flow.

[0020] Increasing the surface area of ​​the current collector to improve its ability to collect electrical current; this is accomplished by the present invention through the addition of surface features such as through-holes, bulges and / or bumps.

[0021] Minimizing the cost of the current collector; this is accomplished by the present invention through teaching the use of low cost materials and by simplifying the production and design of the current collector to reduce manufacturing costs.

[0022] Ensuring that the current collector is compatible with other materials and techniques commonly used in industrial environments; this is achieved by the provisions of the present invention by teaching a continuous production method that gives a current collector that is not limited by size (length) and thus leads to a roll-to-roll coating process.

[0023] The present invention relates to an object comprising a metal member, the object comprising a seamless repeating pattern of perforated texture elements and a seamless repeating pattern of non-punctured texture elements, (b) a local thickness in the range of 3-100 μm, and (c) a functional porosity (P) of at least 10%. f ), and the metal member is at least 0.1 m wide and at least 0.5 m long. The metal member can be made of a variety of metals including aluminum, copper, nickel, gold, cobalt, iron, titanium, steel, stainless steel, and any alloys and combinations thereof. The object can be used as a current collector in an electrode of a battery. The invention also relates to a roll comprising a cylindrical core and an object wound around the core, the object wound into the roll can have any length up to several thousand meters.

[0024] Thus according to an aspect of some embodiments of the present invention there is provided an object including a metal member, the metal member having a seamless repeating pattern of through hole texture elements and (a) A seamless repeating pattern of non-punctured texture elements; (b) a local thickness in the range of 3 to 100 μm, and (c) a functional porosity (Pf) of at least 10%; The metal member is at least 0.1 m wide (at least 0.1 m wide) and at least 0.5 m long (at least 0.5 m long).

[0025] In some embodiments, the metal member is characterized by (a).

[0026] In some embodiments, the metal member is characterized by (b).

[0027] In some embodiments, the metal member is characterized by (c).

[0028] In some embodiments, the metal member is characterized by (a) and (b).

[0029] In some embodiments, the metal member is characterized by (a) and (c).

[0030] In some embodiments, the metal member is characterized by (b) and (c).

[0031] In some embodiments, the metal member is characterized by (a), (b), and (c).

[0032] In some embodiments, the metallic member comprises or consists of a metal selected from the group consisting of aluminum, copper, nickel, gold, cobalt, iron, titanium, steel, stainless steel, and any alloys and combinations thereof.

[0033] In some embodiments, the local thickness of the object is in the range of 3 to 20 μm.

[0034] In some embodiments, the functional porosity is at least 50%.

[0035] In some embodiments, the through-hole texture elements in a seamless repeating pattern have an average opening size in the range of 10 to 200 μm.

[0036] In some embodiments, the seamless repeating pattern has between 30 and 200 holes / mm 2 The pore density ranges from 0.01 to 0.01.

[0037] In some embodiments, the seamless repeating pattern is characterized by a uniformity of at least 5%.

[0038] In some embodiments, the body is characterized by a tensile strength of at least 20-45 MPa.

[0039] In some embodiments of the articles provided herein, The metal member includes copper, the seamless repeating pattern of through hole texture elements includes motifs of rounded holes having diameters of less than 100 μm and horizontal distances of less than 500 μm; The seamless repeating pattern of non-punctured texture elements includes motifs of rounded depressions and / or rounded bulges each having a diameter of less than 500 μm and a horizontal distance of less than 1000 μm; The local thickness is less than 50 μm; The functional porosity is at least 50%; The width is at least 0.1 to 5 m, and The length of the metal component is at least 50 m.

[0040] In some embodiments of the articles provided herein, The metal member includes aluminum. the seamless repeating pattern of through hole texture elements includes motifs of rounded holes having diameters of less than 120 μm and horizontal distances of less than 1,000 μm; The seamless repeating pattern of non-punctured texture elements includes motifs of rounded depressions and / or rounded bulges each having a diameter of less than 500 μm and a horizontal distance of less than 1000 μm; The local thickness is less than 100 μm; The functional porosity is at least 50%; The metal parts are at least 0.1 to 5 m wide, and The metal member is at least 50 m long.

[0041] According to an aspect of some embodiments of the present invention there is provided a roll comprising a cylindrical core and an object as provided herein wound around the core.

[0042] In some embodiments, the width of the objects in the roll is in the range of at least 0.1 to 5 m.

[0043] In some embodiments, the length of the objects in the roll ranges from at least 0.5 to 10,000 m, up to tens of kilometers.

[0044] According to an aspect of some embodiments of the present invention there is provided a current collector comprising at least one object as provided herein.

[0045] According to another aspect of some embodiments of the present invention there is provided an electrode comprising a current collector as provided herein.

[0046] According to another aspect of some embodiments of the present invention there is provided a battery including at least one electrode as provided herein.

[0047] According to another aspect of some embodiments of the present invention there is provided an electrical device including at least one battery as provided herein.

[0048] In some embodiments, the electric device is selected from the group consisting of an electric vehicle for transportation in the air, on land, underwater and / or in space, a smart phone, a laptop computer, a media player, a power tool, a toy, a heating device, a calling device and a lighting device.

[0049] According to some embodiments of the present invention, an enhanced metal foil is made by electroforming. The foil has a pattern of through holes that repeat seamlessly across the foil. To make this enhanced metal foil, a metallized substrate with small non-conductive gaps (called voids) on its surface is used. A metal foil is then formed on this substrate, with the voids acting as a template for the through holes in the foil, so that the through holes repeat seamlessly across the foil. In some embodiments, this enhanced metal foil further undergoes corrugation enhancement.

[0050] In some embodiments of the present invention, a special type of foil, called an "augmented metal foil," is made to exhibit a pattern of small perforations that repeat seamlessly across the foil. The process of making this foil involves using a mask with openings (called voids) through which to etch the metal foil. The voids act as a template for the perforations, so that the perforations repeat seamlessly across the foil. In some embodiments, this augmented metal foil further undergoes corrugation augmentation.

[0051] As used herein, the term "about" refers to ±10%. For example, "about 100 μm" includes 100 μm, as well as 90 μm, 91 μm, 92 μm, 93 μm, 94 μm, 95 μm, 96 μm, 97 μm, 98 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.

[0052] The terms "comprises," "comprising," "includes," "including," "having" and variations thereof mean "including but not limited to."

[0053] The term "consisting of" means "including and limited to."

[0054] The term "consisting essentially of" means that a composition, method, or structure may include additional components, steps, and / or moieties, but only if the additional components, steps, and / or moieties do not materially alter the basic and novel characteristics of the claimed composition, method, or structure.

[0055] As used herein, the phrase "selected from the group consisting of" includes all members of the recited group, each member of the recited group, and all possible combinations. For example, selection from the group consisting of A, B, and C includes A only, and B only, and C only, and A and B, and A and C, and B and C, and A, B, and C.

[0056] As used herein, the phrases "substantially devoid" and / or "essentially devoid" in the context of a particular substance refer to a composition that is completely devoid of that substance or that contains less than about 5, 1, 0.5, or 0.1 percent of the substance based on the total weight or volume of the composition. Alternatively, the phrases "substantially devoid" and / or "essentially devoid" in the context of a process, method, property, or characteristic refer to a process, composition, structure, or article that is completely devoid of a particular process / method step, or a particular property or characteristic, a process / method in which a particular process / method step is effected at less than about 5, 1, 0.5, or 0.1 percent compared to a given standard process / method, or a property or characteristic that is characterized by less than about 5, 1, 0.5, or 0.1 percent of a property or characteristic compared to a given standard.

[0057] As used herein, when applied to an original, desired, or imparted property of an object or composition, the term "substantially maintain" means that the property does not change by more than 20%, 10%, or 5% in the treated object or composition.

[0058] The word "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any embodiment described as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments and / or does not exclude the incorporation of features from other embodiments.

[0059] The words "optionally" or "alternatively" are used herein to mean "is provided in some embodiments and is not provided in other embodiments." Any particular embodiment of the invention may include multiple "optional" features, provided such features are not inconsistent.

[0060] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly indicates otherwise. For example, the term "a compound" or "at least one compound" can include a plurality of compounds, including mixtures thereof.

[0061] Throughout this application, various embodiments of the invention may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Thus, the description of a range should be considered to have specifically disclosed all possible subranges and individual numerical values ​​within that range. For example, the description of a range such as 1-6 should be considered to have specifically disclosed subranges such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., as well as individual numerical values ​​within that range such as 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0062] Whenever a numerical range is given herein, it is intended to include any recited numbers (fractional or integer) within the given range. The phrases "ranging / ranges" from a first denoted number to a second denoted number and "ranging / ranges" "from" a first denoted number to a second denoted number are used interchangeably herein and are intended to include the first and second denoted numbers and all fractional and integer numbers therebetween.

[0063] As used herein, the terms "process" and "method" refer to manners, means, techniques, and procedures for accomplishing a given task, including but not limited to manners, means, techniques, and procedures that are either known or readily developed from known manners, means, techniques, and procedures by practitioners in the chemical, materials, mechanical, computer, and digital fields.

[0064] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, exemplary methods and / or materials are described below. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be necessarily limiting. [Brief description of the drawings]

[0065] Some embodiments of the present invention are herein described, by way of example only, with reference to the accompanying drawings. Referring now specifically to the drawings in detail, it is stressed that the details shown are by way of example and are for the purpose of illustrative discussion of embodiments of the invention. In this regard, the description taken in conjunction with the drawings will make apparent to those skilled in the art how embodiments of the present invention may be practiced.

[0066] In the figure, [Figure 1A]Exemplary motifs (tiles) and their corresponding seamless repeat patterns are presented. [Figure 1B] Exemplary motifs (tiles) and their corresponding seamless repeat patterns are presented. [Figure 1C] Exemplary motifs (tiles) and their corresponding seamless repeat patterns are presented. [Figure 1D] Exemplary motifs (tiles) and their corresponding seamless repeat patterns are presented. [Figure 1E] Exemplary motifs (tiles) and their corresponding seamless repeat patterns are presented. [Diagram 2] A simplified illustrative diagram of the concepts of local thickness, minimal bounding box (MBB) thickness, and functional performance is presented. [Diagram 3] A schematic illustration of two tapered through holes in a foil is presented, showing that the diameter of the hole at the top side of the foil (d1) is smaller than the diameter of the hole at its bottom side (d2). [Figure 4A] Various non-limiting examples of members or current collectors according to some embodiments of the present invention are presented, each exhibiting a different type of perforation enhancement in the metal foil. [Figure 4B] Various non-limiting examples of members or current collectors according to some embodiments of the present invention are presented, each exhibiting a different type of perforation enhancement in the metal foil. [Figure 4C] Various non-limiting examples of members or current collectors according to some embodiments of the present invention are presented, each exhibiting a different type of perforation enhancement in the metal foil. [Figure 4D] Various non-limiting examples of members or current collectors according to some embodiments of the present invention are presented, each exhibiting a different type of perforation enhancement in the metal foil. [Figure 4E] Various non-limiting examples of members or current collectors according to some embodiments of the present invention are presented, each exhibiting a different type of perforation enhancement in the metal foil. [Diagram 5]Nine non-limiting examples of seamless repeating patterns provided by corrugation enhancement according to some embodiments of the present invention are presented. [Figure 6] 1A-1C are schematic illustrations of exemplary members exhibiting SRPs of rounded depressions and bulges imparted by corrugation augmentation using spaced non-puncture texture elements in accordance with some embodiments of the present invention, illustrating the local thickness and bounding box thickness of the exemplary members; [Figure 7A] 7A-7C are schematic illustrations of enhanced metal foil coating schemes according to some embodiments of the present invention, where the top cross-sectional illustration (FIG. 7A) shows an electrode with a thickness equal to the total thickness of the corrugated foil member (MBB thickness), as well as the middle illustration (FIG. 7B) showing a perforated and corrugated member, and the bottom illustration (FIG. 7C) shows an electrode with a greater thickness compared to the total thickness of the corrugated member (MBB thickness). [Figure 7B] 7A-7C are schematic illustrations of enhanced metal foil coating schemes according to some embodiments of the present invention, where the top cross-sectional illustration (FIG. 7A) shows an electrode with a thickness equal to the total thickness of the corrugated foil member (MBB thickness), as well as the middle illustration (FIG. 7B) showing a perforated and corrugated member, and the bottom illustration (FIG. 7C) shows an electrode with a greater thickness compared to the total thickness of the corrugated member (MBB thickness). [Figure 7C] 7A-7C are schematic illustrations of enhanced metal foil coating schemes according to some embodiments of the present invention, where the top cross-sectional illustration (FIG. 7A) shows an electrode with a thickness equal to the total thickness of the corrugated foil member (MBB thickness), as well as the middle illustration (FIG. 7B) showing a perforated and corrugated member, and the bottom illustration (FIG. 7C) shows an electrode with a greater thickness compared to the total thickness of the corrugated member (MBB thickness). [Figure 8A]8A and 8B present micrographs obtained using an optical microscope taken of enhanced metal foils made of 12 μm thick copper foil (FIG. 8A) and 60 μm thick aluminum foil (FIG. 8B), each of which underwent corrugation enhancement in the form of hexagonally arranged circular depressions spaced horizontally from each other by approximately 500 μm. [Figure 8B] 8A and 8B present micrographs obtained using an optical microscope taken of enhanced metal foils made of 12 μm thick copper foil (FIG. 8A) and 60 μm thick aluminum foil (FIG. 8B), each of which underwent corrugation enhancement in the form of hexagonally arranged circular depressions spaced horizontally from each other by approximately 500 μm. [Figure 9] Photographs taken using a Leica DVM6 optical microscope are presented, taken on a 60 μm thick aluminum foil that has undergone drilling and corrugation enhancements in the form of circular holes and dimples, respectively, arranged in a hexagonal shape, spaced approximately 500 μm apart from each other in the horizontal direction. [Figure 10] 1 presents a photograph taken using a Leica DVM6 optical microscope and taken of a dried layer of slurry applied onto a corrugated aluminum foil or member according to some embodiments of the present invention after the aluminum has been removed by acid etching, showing five protruding texture elements and four recessed texture elements pointing to opposite sides. [Figure 11] 1 presents a photograph taken using a Leica DVM6 optical microscope and taken of a dried layer of slurry applied onto a perforated component made from aluminum according to some embodiments of the present invention after the aluminum has been removed by acid etching, showing some rounded protrusions made from active material formed within the voids where the holes are in the used component. [Figure 12A]Presenting battery cycling results obtained for lithium-ion cells with corrugated current collectors according to some embodiments of the invention, FIG. 12A presents measurements of the retention capacity of cells constructed using corrugated CC as provided herein (the capacity measure is a percentage of the initial capacity), and FIG. 12B presents measurements of the internal resistance of the cells at various states of charge, comparing the results to those obtained for similar cells with conventional (flat non-porous) current collectors. [Figure 12B] Presenting battery cycling results obtained for lithium-ion cells with corrugated current collectors according to some embodiments of the invention, FIG. 12A presents measurements of the retention capacity of cells constructed using corrugated CC as provided herein (the capacity measure is a percentage of the initial capacity), and FIG. 12B presents measurements of the internal resistance of the cells at various states of charge, comparing the results to those obtained for similar cells with conventional (flat non-porous) current collectors. [Figure 13A] Optical scans of 0.53 cm2 samples of perforated and flat (non-corrugated) enhanced foils produced using one of the continuous manufacturing processes described herein are presented, with FIG. 13A showing an aluminum object with a local thickness of 20 μm and an SRP consisting of rounded through-hole motifs with an average radius of 55.1 μm and a standard deviation of 2.4 μm (SRP uniformity of 4.4% SD) and FIG. 13B showing a copper object with a local thickness of 22 μm and an SRP consisting of rounded through-hole motifs with an average radius of 58.9 μm and a standard deviation of 1.4 μm (SRP uniformity of 2.4% SD). [Figure 13B]Optical scans of 0.53 cm2 samples of perforated and flat (non-corrugated) enhanced foils produced using one of the continuous manufacturing processes described herein are presented, with FIG. 13A showing an aluminum object with a local thickness of 20 μm and an SRP consisting of rounded through-hole motifs with an average radius of 55.1 μm and a standard deviation of 2.4 μm (SRP uniformity of 4.4% SD) and FIG. 13B showing a copper object with a local thickness of 22 μm and an SRP consisting of rounded through-hole motifs with an average radius of 58.9 μm and a standard deviation of 1.4 μm (SRP uniformity of 2.4% SD). [Figure 14A] SEM micrographs of the corrugated and perforated objects are presented, showing for demonstration purposes a top view of a copper current collector with active material coated on one side of it (FIG. 14A) and a cross section of an SRP perforated aluminum current collector (FIG. 14B). [Figure 14B] SEM micrographs of the corrugated and perforated objects are presented, showing for demonstration purposes a top view of a copper current collector with active material coated on one side of it (FIG. 14A) and a cross section of an SRP perforated aluminum current collector (FIG. 14B). [Figure 15] 1 presents a plot of capacity retention versus cycle number at 35 mAh initial capacity at 100%, measured on lithium-ion cells produced with perforated and corrugated CC according to some embodiments of the present invention. [Figure 16] 1 is a comparative plot showing DCIR as a function of cycle life between two configurations, namely, a cell constructed with conventional (raw foil) CC and a cell constructed with enhanced metal foil as provided herein. [Figure 17A]Photographs of an enhanced metal foil (metal member) including aluminum and exhibiting corrugated enhancements according to some embodiments of the present invention are presented, where the local thickness is about 20 μm, the vertical distance (height) of the rounded badges (non-punctured texture elements) is about 72 μm, which is also the thickness of the MBB, and the horizontal distance between the texture elements is about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 17A with a magnified inset, and a microscope image showing the corrugated texture elements is presented in FIG. 17B. [Figure 17B] Photographs of an enhanced metal foil (metal member) including aluminum and exhibiting corrugated enhancements according to some embodiments of the present invention are presented, where the local thickness is about 20 μm, the vertical distance (height) of the rounded badges (non-punctured texture elements) is about 72 μm, which is also the thickness of the MBB, and the horizontal distance between the texture elements is about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 17A with a magnified inset, and a microscope image showing the corrugated texture elements is presented in FIG. 17B. [Figure 18A] Photographs of enhanced copper foil exhibiting corrugation enhancement according to some embodiments of the present invention are presented, with a local thickness of about 12 μm, an MBB thickness of about 100 μm, and a horizontal distance between texture elements of about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 18A, a close-up inset is presented in FIG. 18B, and a microscope image showing the corrugated texture elements is presented in FIG. 18C. [Figure 18B] Photographs of enhanced copper foil exhibiting corrugation enhancement according to some embodiments of the present invention are presented, with a local thickness of about 12 μm, an MBB thickness of about 100 μm, and a horizontal distance between texture elements of about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 18A, a close-up inset is presented in FIG. 18B, and a microscope image showing the corrugated texture elements is presented in FIG. 18C. [Figure 18C]Photographs of enhanced copper foil exhibiting corrugation enhancement according to some embodiments of the present invention are presented, with a local thickness of about 12 μm, an MBB thickness of about 100 μm, and a horizontal distance between texture elements of about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 18A, a close-up inset is presented in FIG. 18B, and a microscope image showing the corrugated texture elements is presented in FIG. 18C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0067] The present invention, in some embodiments thereof, relates to electrochemical cells, and more particularly, but not exclusively, to current collectors suitable for use in primary and secondary batteries.

[0068] Before describing at least one embodiment of the invention in detail, it is to be understood that the invention is not necessarily limited in its application to the details set forth in the following description or illustrated by way of examples. The disclosure is intended to encompass other embodiments or to be practiced or carried out in various ways.

[0069] As discussed above, current collectors serve to electrically contact the anode and cathode in a rechargeable battery so that charge is transferred through the flow of ions, or, specifically, in the case of lithium and lithium-ion batteries, lithium ions Li. + Electrons can flow in and out of a rechargeable battery to balance the flow of Li + When Li enters the cathode, an electron must also enter the cathode for charge balance. + Because the current collectors (CCs) conduct electrons through the electrolyte, which does not conduct electrons, the electrons need another path to get to and from the cathode and anode. Current collectors (CCs) provide this path. An external electrical circuit (the "load", e.g., a light bulb or an electric vehicle) is connected to the rechargeable battery through terminals that are in electrical contact with the CCs.

[0070] Commercially available primary and secondary batteries traditionally use planar flat metal foils, metal fabrics, or meshes attached to the backside of the cathode and anode as their CCs. These CCs are limited in terms of their capacity to support large amounts of active material, and their ability to transport charge uniformly from the active material bulk and extract useful energy from the large amounts of active material packed into them. Lack of uniformity and other spatial inconsistencies are the main causes of battery malfunctions, failures, and even dangerous outcomes, most of which are due to delamination of the active material from the CCs, formation of hot spots, cracking, and swelling.

[0071] While considering the present invention, the inventors envisioned a CC for battery electrodes that can be manufactured, i.e., coated and integrated into a battery manufacturing line according to industrial requirements, standards, practices and machines, and, unlike other 3D CCs, can be manufactured quickly, in any length (rolls of tens, hundreds and thousands of meters long), and at a cost comparable to standard metal foils of similar dimensions / mass. The inventors considered that corrugation can increase the surface area of ​​thin metal foils because the corrugated foil takes on a wavy / bumpy texture with a series of ridges and grooves that increase the total surface area of ​​the foil compared to a flat foil of the same size, since the wavy / bumpy texture creates more surface area for contact with the active material. It was also considered that increasing the surface area is beneficial in structural materials that can increase the bonding surface area between the foil and other materials. The inventors also contemplated perforation to increase the surface area of ​​thin metal foils, provided by creating a series of small holes or openings in the foil. Perforating the foil creates additional surface area by exposing the edges of the holes, which can be beneficial in improving electrical pathways within the current collector and increase the efficiency of the electrochemical processes taking place within the battery electrode. The perforations also allow the top and bottom active material layers applied on the CC to contact through the holes, thereby increasing the bonding strength between the active material and the current collector.

[0072] While reducing the invention to practice, the inventors have demonstrated that an enhanced metal foil with texture elements increases its surface area and the void space of its minimum bounding box (see Functional Porosity below), such that the amount of active material that can be carried thereon is much greater compared to a flat featureless metal foil of similar dimensions / mass. The texture elements of the enhanced metal foil also shorten the electrical paths within the layer of active material deposited thereon, thereby improving the contact and charge transfer parameters of electrodes using this enhanced metal foil as a CC.

[0073] Thus, described herein are enhanced metal foils that can be used as current collectors, and processes for making and using the same, that overcome the above-mentioned shortcomings and address some of the problems in the related art to which this disclosure pertains.

[0074] Thus, in accordance with some embodiments of the present invention, there are provided articles, referred to herein as enhanced metal foils, which have the following characteristics: Made from a conductive material, preferably a metal; exhibiting a seamless repeating pattern of non-punctured texture elements; exhibiting a seamless repeating pattern of through hole texture elements; exhibiting a local thickness of less than 100 μm or a local thickness in the range of 3 to 100 μm, a functional porosity of at least 10%, or greater than 50%, The enhanced metal foil or object is at least 0.1 m wide and at least 0.5-200 m long, or alternatively at least the width or the length is greater than 0.5 m long.

[0075] Enhanced Metal Foil: As used herein, the terms "enhanced" and "enhanced" refer to an improvement in some property of a foil-like object compared to those properties in an equivalent raw metal foil or non-enhanced foil, with raw foil and enhanced foil each being relevant in the context of an object used as a current collector in an electrode, regardless of the process by which each is obtained. Depending on the embodiment, the term "enhanced" encompasses "expanded," "extended," "inflated," "strengthened," "expanded," "bulged," "enhanced," "amplified," "broadened," "developed," "laterally spread," "bulged," "refined," "extended," "spread," "stretched," "expanded," and "bulged."

[0076] One of the objectives of the present invention is to provide an enhanced metal foil that can be effectively used in an industrial environment, particularly as a current collector to form electrodes for the battery industry. The phrase "enhanced metal foil" is used interchangeably with the terms "component" and "object" and refers to the final product regardless of the process by which it is obtained, i.e., the term "enhanced" is used as a pronoun rather than a verb and does not necessarily imply that the raw foil is a precursor to the final product.

[0077] In the context of embodiments of the present invention, raw metal foils are typically very thin metal sheets made by rolling, hammering and / or electrochemical deposition. The term "raw" is used herein and throughout to refer to unamplified foils, or precursor substrates of the members provided herein, according to some embodiments of the present invention, or steps in the process of making members, according to some embodiments of the present invention. In some embodiments, the term "raw metal foil" refers to non-porous, flat, smooth, planar metal foils, or unamplified metal foils.

[0078] In some embodiments, the enhanced metal foil (object, member) is made of a conductive metal. In some embodiments, the object comprises or consists of aluminum, copper, nickel, magnesium, cobalt, iron, titanium, platinum, tungsten and gold, and any alloys thereof, including steel, stainless steel, carbonized / nitrided steel, bronze, electrum, pewter, brass and pig iron. In some embodiments, the alloy comprises magnesium, manganese, chromium, molybdenum, and vanadium, as well as semi-metallic and / or non-metallic elements.

[0079] As used herein, the term "thickness" refers to the local thickness of the raw foil, or the thickness of the uncorrugated member, or the thickness achieved by foil build-up, according to some embodiments of the present invention.

[0080] In some embodiments, the object (member) is a corrugated foil, and the local thickness refers to the properties of the flat unprocessed foil that undergoes corrugation, not the thickness of the corrugated foil. Unless explicitly specified otherwise, the thickness of the corrugated object is the thickness of the minimum bounding box corresponding to the augmented object, as described below.

[0081] In some embodiments of the invention, the local thickness of the features provided herein is as low as about 3 micrometers (μm), and generally the local thickness of the features is 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. In some embodiments, the local thickness of the feature is about 3 micrometers μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, about 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, about 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, 400 μm, 410 μm, 420 μm, 430 μm, 440 μm, 450 μm, 460 μm, 470 μm, 480 μm, 490 μm, 500 μm, 510 μm, 520 μm, 530 μm, 540 μm, 550 μm, 560 μm, 570 μm, 580 μm, 590 μm, 600 μm, 610 μm, 620 μm, 630 μm, 640 μm, 650 μm, 660 μm, 70 μm, 180 μm, 190 μm, about 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, about 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, or about 400 μm or more in thickness. In some embodiments of the present invention, the thickness of the metal foil is in the range that forms the basis of the member. In some embodiments of the invention, the local thickness of the feature is in the range of 3-100 μm, 4-50 μm, 4-40 μm, 4-30 μm, 4-20 μm, or 4-10 μm, 10-50 μm, 40-100 μm, 90-200 μm, 190-300 μm, or 290-400 μm.

[0082] In some embodiments, the enhanced metal foil is a perforated enhanced metal foil. In some embodiments, the enhanced metal foil is a corrugated enhanced metal foil. In some embodiments, the enhanced metal foil is a metal foil that is both perforated and corrugated enhanced.

[0083] In some embodiments, the metal is aluminum and the local thickness of the object is in the range of about 3-250 μm, 3-100 μm, 3-50 μm, 4-500 μm, 10-50 μm, 50-100 μm, or in the range of about 100-250 μm. According to some embodiments of the invention, the thickness of an aluminum smooth (planar, non-corrugated) member, or the local thickness of an aluminum member that is corrugated with a seamless repeating pattern (SRP) of non-punctured texture elements but not perforated, or the local thickness of an aluminum member that is SRP corrugated and SRP perforated, as defined herein, is less than 100 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 8 μm, or less than 6 μm.

[0084] In some embodiments, the metal is copper and the local thickness of the object is in the range of about 4-250 μm, 4-50 μm, 6-50 μm, or in the range of about 10-100 μm. According to some embodiments of the invention, the thickness of a smooth (flat, non-corrugated) copper member, or the local thickness of an aluminum member that has been SRP corrugated but not drilled, or the local thickness of a copper member that has been SRP corrugated and SRP drilled, as defined herein, is less than 100 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 8 μm, less than 6 μm, or less than 5 μm.

[0085] The members provided herein are enhanced to increase their functional porosity as presented below. The enhanced body can be thicker than its precursor, the raw foil, and thus in some embodiments, including any of the above, the thickness of the member (see below, MBB thickness) is about 10 μm, about 20 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm, about 100 μm, about 150 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or about 1 mm.

[0086] The local thickness of the members or objects provided herein may be measured using microscopic techniques such as scanning electron microscopy (SEM), optical microscopy, micrometer, or other methods, unless otherwise specified.

[0087] In some embodiments, the metal foil is in the form of a long sheet having a fixed width and an unlimited length, constrained only by practical limitations, in some embodiments, the metal foil has a width in the range of 10 cm to 5 meters, and a length of at least 0.5 meters, or at least 1 meter, or at least 2 meters, or at least 5 meters, or at least 10 meters.

[0088] In some embodiments of the present invention, the enhanced metal foils provided herein are produced as single sheets or as continuous rolls using manual or automated processes. The substrates herein can be metal meshes (i.e., perforated materials), dense metal layers, metal foils, etc. The processes used to enhance the metal substrates can be carried out at room temperature or by using heat to assist the deformation process. Processes using heating can be carried out in standard atmosphere or in an atmosphere with vacuum or inert gas.

[0089] After enhancing the metal foil substrate, the enhanced metal foil (member) may be laminated onto other members. In some embodiments, the enhanced metal foil is laminated to form a layered structure, and in some embodiments, the laminated members are bonded together. In some embodiments, the bonding is achieved by diffusion bonding. In yet other embodiments, the bonding is achieved by ultrasonic welding. In other embodiments, the bonding is achieved by welding. In some embodiments, the laminated members are layered to provide a thicker object. In some embodiments, the layers are 1 μm, 5 μm, 10 μm, 25 μm, 50 μm, or 100 μm thick. The assignee's WO2022064483(A1) teaches a method of liquid cold welding (LCW) that includes: (a) engaging two or more porous conductive substrate layers between a perforated non-conductive frame such that the substrate layers contact each other; (b) immersing the substrate layers in an electrolyte solution; and (c) applying a current and / or voltage and / or power to the electrolyte solution. Apparatus suitable for carrying out some embodiments of the method is also disclosed in WO2022064483(A1).

[0090] In some embodiments, the member may be laminated onto another metal substrate that is not augmented. In some embodiments, the non-augmented metal substrates are laminated. In some embodiments, the non-augmented metal substrates are laminated and bonded together. In some embodiments, the bonding is accomplished by diffusion bonding, thermal welding, ultrasonic welding, or electrochemical welding.

[0091] In some embodiments, the member is produced as a single sheet, with or without heat. In some embodiments, the member is produced as a continuous sheet, with or without heat.

[0092] In some embodiments, the metal components provided herein are manufactured by a continuous process as discussed below and wound into a roll, in some embodiments, the components are wound into a cylindrical roll and have a width in the range of 10 cm to 3 meters and a length of at least 10 meters, or at least 100 m long.

[0093] The enhanced metal foils provided herein are typically designed for continuous manufacturing resulting in rolls of the object, and further designed to be used in roll form in an industrial environment. Thus, the objects provided herein are characterized by mechanical properties that make them producible and usable in an industrial environment. One of these properties is tensile strength, which is sufficient to withstand the forces and stresses of pulling, rolling, stretching, and other operations used in the manufacturing process. The tensile strength required for a typical foil used to make a current collector for a battery in a typical industrial environment varies depending on the specific application, as well as the foil, coating material, and battery type. For example, foils used for lithium-ion batteries typically have a tensile strength of about 45 MPa (approximately 4.6 KgF / mm2 in terms of kilograms of force per square millimeter). 2 ) minimum tensile strength. The enhanced metal foils provided herein differ from raw foils in that the enhanced features should also withstand the forces and stresses used in industrial environments, the object should not tear, and its texture elements should be preserved. In the context of some embodiments of the present invention, the objects provided herein are characterized by a tensile strength of at least 20-45 MPa, or at least 60 MPa, at least 55 MPa, at least 50 MPa, at least 45 MPa, at least 40 MPa, at least 35 MPa, at least 30 MPa, at least 25 MPa, or at least 20 MPa.

[0094] Seamless repeat pattern: One of the objectives of the present invention is to provide an enhanced metal foil characterized by high uniformity of texture elements and features essentially over its entire area, and therefore the features of the enhancement are also required to be substantially the same over the entire area of ​​the foil. It should be noted that in this specification, the term "texture elements" refers to the surface quality or feel of a material, such as its roughness, smoothness, or pattern. Texture elements are the visual aspects of a surface that give a sense of depth and dimension. In the context of the present invention, the term "texture elements" encompasses puncture elements (through holes) and non-puncture elements (bulges, depressions).

[0095] The uniform distribution of fine texture elements (through holes and / or non-puncture elements) can enhance the electrical conductivity and reduce the resistance of the enhanced metal foil provided herein. To exhibit uniform enhancement, the enhanced metal foil provided herein is characterized, among other things, by a non-random, purposefully designed seamless repeating pattern (SRP) of texture elements that conceptually spans the entire area of ​​the metal foil without visible boundaries or irregular / arbitrary / random transitions between or within the repeating pattern motifs. In the context of the present invention, the enhanced metal foil is interpreted as an infinite planar area limited only by practical limitations.

[0096] As used herein, the term "patterned" with respect to foils refers, in some embodiments of the present invention, to metal foils that are not random, but are purposefully designed and engineered to have regularly spaced and oriented texture elements on their surface. Features can be, but are not limited to, holes, peaks, valleys, defects, bends, kinks, undulations, pores, or combinations thereof.

[0097] As used herein, the phrase "seamless repeating pattern", herein abbreviated as SRP, refers to a pattern that spans an undefined and unlimited surface without visible transitions or boundaries. An SRP is an infinite repeating pattern of texture elements that consist of repeating elements arranged in a two-dimensional format, such as a geometric shape or decorative design. An SRP continues infinitely in all directions, creating a seamless visual effect. This type of pattern is often used in textiles, wallpaper, flooring, and other decorative materials, as well as graphic design, packaging, and branding. As discussed herein, an SRP can be defined by a repeating pattern unit, but placing multiple such units closely adjacent (juxtaposed) to one another gives the SRP. The repeating unit is referred to herein as a tile or motif.

[0098] A motif is defined by one or more texture elements, each of which blends into neighboring motifs to achieve the SRP. In the context of the present invention, a motif includes texture elements in the form of holes (i.e., perforations, openings, through windows) or protrusions / indentations (i.e., bumps / depressions, bulges / creases, valleys / ridges), but the entire SRP can be defined by the motif. The arrangement of any given texture element in the seamless repeating pattern that characterizes the metal members provided herein is not random, as opposed to the random distribution of similar texture elements over a similar area, as described below, and therefore the SRP that characterizes the metal foils provided herein is by definition non-random.

[0099] The coating of a planar metal foil surface with the aforementioned SRP follows any standard tessellation or tiling approach, using one or more geometric shapes (tiles, motifs) that are essentially free of overlaps and gaps. Note that while some embodiments of the invention are drawn to metal foils, which are essentially two-dimensional entities when thickness is ignored, tessellations can be generalized to higher dimensions and various geometric shapes. In some embodiments, the SRP is given by a periodic tiling, although some embodiments include regular tilings with regular polygonal tiles that all have the same shape, and some embodiments include semi-regular tilings with regular tiles of two or more shapes, with all corners identically positioned.

[0100] The term "motif" or "tile" as used herein refers to the smallest and simplest single texture element or non-repeating group of texture elements, the repetition of which forms and defines the SRP. In the context of the present invention, a motif is closely related to a unit cell in a 3D lattice (crystal / lattice), while an SRP is formed by repeating a motif on a plane in any direction on the plane. There may be one texture element or more than one texture element within a motif. In some embodiments, a motif includes two or more texture elements that are related to each other by symmetric operations in a 2D plane, such as translation, rotation, and reflection transformation operations. In some embodiments, a motif includes two or more texture elements that are asymmetrically arranged with respect to each other, or two or more texture elements that have different sizes / shapes. A flat plane, or an SRP, can be completely tiled (covered) with triangles, rectangles, and hexagons polygons (tiles), each polygon having one or more texture elements arranged within it. Rectangular and hexagonal tiles can be installed using the same tile orientation (translation only, no rotation), while triangular tiles are installed with a 60° rotation (translation and rotation).

[0101] An example of a simple motif is a rounded dot, the manifestation of which is a hole (perforation augmentation) and / or a bulge / dimple (corrugation augmentation), while the SRP may be a circular filling of a square or hexagon, where the circles are evenly spaced and, in the case of through holes, do not touch each other to allow for continuous foil material between them.) More exemplary and non-limiting embodiments of motifs and their corresponding SRPs according to some embodiments of the present invention are presented in Figures 1A-1E.

[0102] 1A-1E present exemplary motifs (tiles) and their corresponding seamless repeating patterns: FIG. 1A presents a square motif (left side) presenting rounded, cornered and rectangular texture elements of various sizes arranged asymmetrically within the tile and the corresponding SRP resulting from repeating the motif infinitely on a plane; FIG. 1B presents three variations of the square motif, two with an asymmetric arrangement of texture elements and one with a symmetric arrangement (bottom left, rotated four times) leading to the same SRP; FIG. 1C presents three variations of the tile shape and the same SRP resulting from repeating the motif infinitely on a plane by translational movements; FIG. 1D presents four variations of the tile and the same SRP resulting from repeating the motif infinitely on a plane by rotational and translational movements; and FIG. 1E presents the tile and its corresponding SRP resulting from repeating the motif infinitely on a plane by reflection, rotational and translational movements.

[0103] It should be noted that the terms "texture element," "motif" / "tile," and "seamless repeating pattern" (SRP) refer to any type of foil augmentation as these terms are discussed below. In other words, the part is required to exhibit a seamless repeating pattern with respect to any of its texture elements, including perforations, depressions / protrusions, and / or creases.

[0104] In fact, in some embodiments, the enhanced metal foil exhibits SRP over its entire area, from edge to edge, and in some embodiments, the SRP extends over the main area of ​​the foil, leaving a narrow margin along its edges due to technical / practical requirements of industrial processing machines. By margin, it is meant that the foil does not exhibit SRP in the area considered as margin, the foil can be raw or have a different pattern than the SRP. In some embodiments, the margin extends on each edge of the metal foil, and in some embodiments, the foil is a long sheet with a length more than 10 times greater than the width, and the margin extends less than 1%, less than 2%, less than 5%, or less than 10% of the total width of the metal foil. In some embodiments, one or more unpatterned strips are present near or in the center along the long axis of the member, designed for practical and industrial purposes, such as cutting the member into narrower strips. In such embodiments, the majority of the member contains SRP, while narrow strips of raw foil separate the wide strips of SRP.

[0105] Seamless repeating patterns according to embodiments of the present invention are mathematically defined or constructed, in some embodiments, the SRPs are generated by machine learning.

[0106] roll: The objects provided herein are very thin, have a high surface area to volume ratio, and are highly flexible, meaning that they can be easily bent, folded, and shaped without breaking, and can withstand a variety of stresses and forces. Therefore, due to these properties and the requirements of the manufacturing and utilization industries, one of the optimal formats for handling the objects provided herein is in the form of a roll.

[0107] The long-trip rolls of materials provided herein can be described as cylindrically shaped articles consisting of a thin metal body wound around an axis. The rolls are typically of a fixed width and can be tens, hundreds, or even thousands of meters long. The rolls can be wrapped in protective materials to avoid any damage during transportation and storage.

[0108] Rolls of foil are also characterized by their winding density. The winding density of a roll of foil refers to the compactness of the foil as it is wound onto the roll. It is a measure of how tightly the foil is wound around the core of the roll. Winding density is typically expressed as the ratio of the foil width to the diameter of the roll, and is usually measured in units of width per unit of diameter (e.g., millimeters per millimeter, or inches per inch). Winding density can be affected by various factors such as the foil width, foil thickness, core diameter, and tension applied during the winding process. A higher winding density results in a smaller diameter roll with a higher packing density of the foil, while a lower winding density results in a larger diameter roll with a lower packing density of the foil. Winding density is an important parameter in the manufacture of foil rolls because it affects the amount of foil that can be wound onto the roll and the overall size of the roll. It can also affect the handling and storage of the foil roll, as well as the performance of the foil in its intended application. Since the winding density is related to the thickness of the MBB of the object provided herein, the winding density can be determined for a fixed number of roll layers per thickness of the MBB, where a roll layer corresponds to one complete winding of the foil around the roll. Thus, according to some embodiments of the present invention, the winding density of the roll is in the range of at least 101 times the thickness of the MBB of the object per 100 roll layers to at least 150 times the thickness of the MBB of the object per 100 roll layers.

[0109] The enhanced metal foils provided herein can be wound onto a core tube or hollow cylinder having inner and outer diameters that can be selected to suit the manufacturing and utilization settings.

[0110] Therefore, according to one aspect of the present invention, a roll is provided, comprising a cylindrical core and an enhanced metal foil wound around the core. The roll is typically composed of a central cylindrical support made of cardboard, plastic or metal, and the members provided herein are wound around the core. The core is typically hollow and provides the necessary support for the roll, while the members are materials used, for example, to produce electrodes for batteries. Depending on the specific application, the rolls can be of different sizes and the members can be of different thicknesses.

[0111] In some embodiments, a single continuous member provided in the form of a roll can have any fixed width, for example, 0.1 to 5 meters wide, and any length, for example, at least 0.5 m, 1 m, 10 m, 30 m, 50 m, at least 100 m long, at least 500 m long, at least 1,000 m long, or at least 0.5 to 100 m long, at least 50 to 500 m long, or at least 100 to 1,000 m long, in some embodiments, at least 1 to 5 kilometers long.

[0112] An exemplary roll of corrugated aluminum having local thicknesses of 20 μm and 70 μm MBB includes the following dimensions: width 193 mm, length 350 m±10 m, inner roll diameter 80 mm, and outer roll diameter 180 mm.

[0113] Foil Intensification: The enhanced metal foils (members) provided herein can be viewed as metal foils that have been enhanced to uniformly increase their surface area by being perforated as a mesh and / or corrugated as a checkerboard; these two forms of foil enhancement are referred to herein as perforated enhancement and corrugated enhancement, respectively, and the property that is affected is referred to as "functional porosity," which term is defined below.

[0114] In some embodiments, the member is corrugated, folded, bulged, bent, twisted, wavy, or a combination thereof (corrugation enhancement). In some embodiments, the member is perforated, punctured, cut, perforated, enmeshed, or a combination thereof (perforation enhancement). According to embodiments of the invention, the member exhibits corrugation enhancement, perforation enhancement, or both perforation and corrugation enhancement simultaneously.

[0115] In embodiments where the foil exhibits two or more types of enhancement simultaneously, each enhancement type is required to be essentially uniform over the area of ​​the foil, in some embodiments the uniformity of each enhancement type is required to correspond to the standard deviation for the size of its texture elements, e.g. the size and shape of the texture elements as estimated by the similarity between motifs (tile similarity).

[0116] As used herein, the term "size" refers to a characteristic dimension of an object or texture element. When referring to the size of a plurality of objects, it refers to an average value obtained by measuring the size of a representative group of objects. The size of an object that is circular can refer to the diameter of the object. For objects that are non-circular, the size of the non-circular object can refer to the diameter of a corresponding circular object that exhibits or has a particular set of derivable or measurable properties that are substantially the same as the properties of the non-circular object. Alternatively, or in addition, the size of a non-circular object can refer to the average of the object's various orthogonal dimensions. Thus, for example, the size of an object that is an ellipse can refer to the average of the object's major and minor axes. When referring to a set of objects as having a particular size, it is contemplated that the objects can have a distribution of sizes around the particular size. Thus, as used herein, the size of a set of objects can refer to a typical size of the size distribution, such as an average size, a median size, or a peak size.

[0117] Functional porosity: In the context of the present invention, the enhanced metal foil is said to have a non-zero functional porosity. As used herein, the phrase "functional porosity" refers to a structural property of an object that defines and quantifies the available volume within the object's minimum bounding box (MBB). The minimum bounding box is the smallest bounding rectangular parallelepiped of an object, as this geometric concept is known in the art. In the context of a foil defined as being unlimited in width and length, the concept of MBB refers to any chosen section, segment or piece of the foil, or, for example, to the thickness dimension, as shown in FIG. 6.

[0118] The available volume is considered to be all the volume within the MBB that is not occupied by the material of the object. For solid (non-perforated) foils, the functional porosity (P f ) is calculated as defined in Equation 1: P f =(T b -T l ) / T b Formula 1. In the formula, T l is the thickness or local thickness of the raw (smooth) foil, and T b is the thickness of the corrugated member or the thickness of the MBB.

[0119] With respect to the more general example of a perforated and corrugated member according to an embodiment of the present invention, the functional porosity (P, or P f ) is the volume fraction of the MBB that is not occupied by the component material, as defined in Eq. 2: P f =1-V m / V b formula 2 In the formula, V m is the volume occupied by the material of the member, and V b is the volume of the MBB, including the material and voids of the component. Functional porosity can also be expressed as a percentage of thickness or volume. The volume of the components provided herein can be determined by dividing the mass of the component by the density of the component (m / cm 3). Herein, the density of the foil material is given in units of mass per unit volume. Thus, by recording the density of the material of the component, measuring the mass of the component, and determining the volume of the MBB, the functional porosity of the component is calculated. For example, the functional porosity of a foil that is crimped to exhibit peaks and valleys is higher than the functional porosity of a flat / smooth foil made from the same material. In other words, a wrinkled foil has a higher functional porosity compared to a flat / smooth foil, since a completely flat foil occupies 100% of the MBB and its functional porosity is zero.

[0120] As used herein, functional porosity refers to corrugated members (i.e., protrusions, bumps / depressions, bulges / creases, valleys / ridges) and / or perforated members (i.e., mesh-like through holes). For example, to calculate the functional porosity of a perforated, flat and wrinkle-free foil, or a flat mesh, one should consider that the thickness of the foil is much smaller than its width or length, but the pores "expose" the inner walls that allow access to a larger surface area of ​​the foil, and that in terms of volume, the pores free up space that would otherwise be occupied by the material of the foil. Thus, the functional porosity of a mesh with a finite thickness is higher than that of a raw (non-perforated) foil. It is clear that the density, shape and size of the pores (pore geometry) affect the functional porosity of a perforated member, and the thicker the foil, the greater the effect of the pore geometry on the functional porosity. As with perforation, corrugation also increases the functional porosity of the member.

[0121] FIG. 2 presents a simplified illustrative diagram of the concepts of local thickness, bounding box thickness, and functional prominence, where the straight horizontal thick black bands (top) represent longitudinal cross sections of raw foils with a given local thickness (shown on the right side of the cross section), showing the minimum bounding box (dotted rectangle) of foils with perforation enhancements (left side), the MBB of foils with corrugated enhancements (right side), and the MBB and its thickness for foils with both perforation and corrugated enhancements (bottom).

[0122] As can be seen in FIG. 2, each enhancement increases the free volume within the MBB, the drilling enhancement increases the surface area within the MBB, the corrugation enhancement also increases the volume of the MBB, and as can be further seen, the simultaneous drilling and corrugation enhancement increases the functional porosity to a maximum when considering the foil as the basis of the component.

[0123] In some embodiments, the materials provided herein are characterized by a functional porosity of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, 120%, 125%, 130%, 135%, 140%, 145%, 150%, 155%, 160%, 165%, 170%, 175%, 180%, 185%, 190%, 195%, or at least 200% or more. In some embodiments, the functional porosity of the component ranges from 5 to 100%, or 10 to 100%, or 50 to 150%, or 50 to 200%, or 100 to 150%, or 100 to 200% functional porosity.

[0124] Perforation Enhancement: Metal mesh can be produced in a range of thicknesses depending on the intended application and the manufacturing method used. Generally, metal mesh can be produced very thin, but thinner meshes may be more prone to tearing or breaking and may be less suitable for certain applications. There are several methods that can be used to produce thin metal meshes, including electroforming, electroplating, rolling, weaving, forging, and cutting and drawing. Each of these methods has its own set of advantages and limitations, and the optimal method depends on the specific requirements of the application. It is also possible to produce thin metal meshes by etching or laser cutting sheets of metal, which allows for the production of very fine and precise patterns in the mesh, but these methods are very expensive and time consuming and therefore suitable for relatively small sheets, which are typically not suitable for industrial environments.

[0125] In some embodiments, the texture elements of the perforation enhancement are small pores, i.e. small through holes. The terms "pore", "hole", "through-hole" (TH), "thru-hole (TH)", "clearance hole", and "hole-type texture element" are used interchangeably herein. According to embodiments of the present invention, the holes can take any shape and orientation, including rounded, rectangular, triangular, hexagonal, elliptical, diamond-shaped, or irregular.

[0126] An alternative definition of SRP describes the member as a foil with a patterned surface, where the patterned surface is a porous surface with a designed pore location distribution (PLD). In some embodiments, the pores are positioned at regularly spaced intervals on the member. In some embodiments, the member has different sized pores at different locations on the member. In some embodiments, the member has different types of pores at different locations on the member. In some embodiments, the member has different shaped pores at different locations on the member. In some embodiments, the member has pores aligned in a straight line. In some embodiments, the member has pores aligned in a line that is inclined at an angle to the side of the member.

[0127] As discussed above, the metal foil enhancement follows a seamless repeating pattern, or SRP, where the holes may be defined by tangential tiles or motifs where the texture elements are positioned. The SRP is formed by filling a plane with tiles. A tile may contain a portion of a hole (symmetrical), a single hole or any shape, or two or more holes of the same or different shapes (mix of shapes), and / or portions thereof.

[0128] Metal foils augmented with perforations following a seamless repeating pattern are also referred to herein as SRP perforated members.

[0129] In some embodiments, the through holes may have parallel walls perpendicular to the plane of the foil. In some embodiments, the through holes may have slanted walls, making one opening of the through hole different in size and shape from the opening on the opposite side of the same hole. For example, the space defining a rounded hole may have a tapered shape like a truncated cone, and the space defining a rectangular hole may have a tapered shape like a truncated pyramid.

[0130] FIG. 3 presents a schematic illustration of two tapered holes in a foil with local thickness, showing that the diameter of the hole at the top side of the foil (d1) is smaller than the diameter of the hole at its bottom side (d2).

[0131] In some embodiments, the holes in the member with perforation enhancement are characterized by a tapered opening, or in other words, the holes narrow from one surface side to the other surface of the plane of the foil. It is noted that this through-hole morphology is typical of processes in which the enhanced metal foil is provided by electroforming the foil onto a conductive substrate that has been surface-patterned with non-conductive voids as an SRP template. In some embodiments, the member with perforation enhancement has a bottom side and a top side, and all holes in the member are wider on the bottom side than on the top side of the member, i.e., all holes taper toward the same side of the member (see FIG. 3). According to some embodiments, the tapering of the holes is about 1-100% size reduction, or 1-50%, or 1-30%, or 1-20%, or 1-10% tapering (opening size reduction) in terms of the reduction in the diameter (or estimated size) of the opening from bottom to top. A 50% tapering (opening diameter / size reduction) means that the surface of the bottom opening is 50% larger than the top opening. 100% tapering means that the holes are closed on the top side of the foil and the formation is a non-punctured texture element.

[0132] According to some embodiments, the diameter (opening size) of the pore openings of members having a seamless repeating pattern of through-hole texture elements as provided herein can be as small as 10-200 μm. In some embodiments, the through-hole opening size ranges from 10 μm to 5000 μm, or about 10-2000 μm, or about 10-1000 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 embodiments, the opening size (holes, pores) of the through-hole texture elements is 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.

[0133] In some embodiments, including any of the foregoing, the pores have an opening (aperture, opening size) of about 1-100 μm×about 1-100 μm, or about 40 μm×50 μm, or about 52 μm×52 μm.

[0134] In some embodiments, the horizontal distance between the centers of two adjacent through-hole texture elements is in the range of 1-1000 μm, or about 10-100 μm, or 20-100 μm, 30-100 μm, 40-100 μm, 50-100 μm, 60-100 μm, 70-100 μm, 80-100 μm, or about 90-100 μm. In some embodiments, the horizontal distance between the centers of two through holes (pores) in the perforated augment is about 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 about 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, or about 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, or about 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, about 900 μm, 950 μm, or about 1,000 μm.

[0135] Pore ​​density depends on the size of the holes and the horizontal distance between adjacent holes. In the context of the present invention, the pore density of a perforated member (or foil) relates to the number of through holes per unit area. In some embodiments, the pore density relates to the ratio between the material (metal) area and the void (pore) area per unit area. According to some embodiments, the pore density is 1 mm 2 30 holes / mm~200 holes / mm 2 Non-limiting examples of porosity enhancement are provided in the Examples section below with respect to pore size, density and uniformity.

[0136] The SRP uniformity of the perforation augmentation is determined by any experimental method, such as, for example, taking photographs of different sections of the member, scanning a predefined area within the photographs or within different photographs, identifying and digitizing motifs within the scanned images, measuring the size and horizontal distance of a predefined number of motifs per scanned portion, and calculating the standard deviation of the motifs across the section. In embodiments where the motif / tile encompasses a single hole, the SRP uniformity is related to the standard deviation between individual holes. In embodiments where the motif / tile encompasses two or more holes, the SRP uniformity is related to the standard deviation between the motifs / tiles. In some embodiments, the standard deviation in the motif overlap is in the range of 1-05%. In some embodiments, the standard deviation in the motif overlap is less than 15%, less than 10%, or less than 5%.

[0137] 4A-4E provide various non-limiting examples of members or current collectors according to some embodiments of the present invention, each exhibiting a different type of perforation enhancement in the metal foil.

[0138] According to some embodiments of the present invention, enhanced metal foils containing a seamless, repeating pattern of through-holes are produced by electroforming a metal foil onto a metal deposition substrate having voids on its conductive surface, with the voids acting as a template for the seamless, repeating pattern of through-holes in the deposited metal foil.

[0139] According to some embodiments of the present invention, enhanced metal foils containing a seamless, repeating pattern of through-holes have been produced by electrolytically etching a metal foil through a mask having voids (openings) therein, with the voids acting as templates for the seamless, repeating pattern of through-holes in the etched metal foil.

[0140] Waveform processing enhancement: Corrugated metal foils are used in a variety of applications, including packaging materials, structural materials, and electrical and thermal insulation. Corrugating thin metal foils refers to the process of creating ridges or grooves in the foil to increase its surface adhesion, surface area, strength, and stiffness. This is typically done by subjecting the foil to high pressure, which causes it to deform and take on a wavy or bumpy texture. The resulting corrugated foil is stronger and more resistant to bending and deformation, with a larger surface area than a flat foil of the same initial thickness.

[0141] In some embodiments, including any of the foregoing, raw or perforated metal foils are provided with non-planar patterned features (non-smooth embossed textures, where the non-planar patterned features protrude from the general plane of the foil), i.e., the foil is corrugated, folded, protruding, bent, twisted, wavy, or combinations thereof, collectively referred to herein as non-planar patterned or corrugated foils. As used herein, the term "non-planar" refers to a substrate that is not flat, smooth, planar, does not lie in or cannot be confined to a single plane, has a three-dimensional quality, or has some angles on its surface that are less than or greater than 180°.

[0142] As used herein, the term "corrugation" refers to both multiple embossed and debossed texture elements that provide a patterned texture, regular surface roughness, and / or regular surface relief. As used herein, the term "corrugation" combines and encompasses both embossing and debossing, and "dual level embossing" and / or "dual level debossing" refer to creating both raised and recessed texture elements in the same design on a material. In some embodiments, the corrugated texture elements are regular in size, shape, spacing, and relative orientation. According to an embodiment of the present invention, corrugation is defined as multiple non-punctured texture elements arranged in a seamless repeating pattern (SRP), and the term "non-punctured" refers to identifiable texture features on the surface of the foil that are not holes and do not disrupt the surface to allow material to pass through.

[0143] Metal foils that have been augmented by corrugation according to a seamless repeating pattern are also referred to herein as SRP corrugated members.

[0144] Unlike through holes, non-punctured texture elements such as folds can span any length relative to the size of the member, i.e., folds can extend from edge to edge while forming part of the SRP of the parallel folds. Furthermore, unlike through holes, non-punctured texture elements can disrupt the surface on one side thereof, which can be a bulge (e.g., a peak) or a depression (e.g., a valley), depending on the definition of the "top side" and "bottom side" of the member. Thus, non-punctured texture elements can be divided into groups of spaced apart elements that can form a single localized bulge, and groups of extended elements that can form a ridge across the foil that terminates at the edge of the foil.

[0145] Non-limiting examples of non-punctured texture elements include bulges, bumps, folds, depressions, peaks, protrusions, ridges, and valleys. The shape of a non-punctured spaced texture element can be defined by the "footprint" of the element on the surface of the foil, for example, as viewed from above. The shape of a non-punctured extended texture element can be defined by a cross-section of the foil perpendicular to the general direction of the element. For example, a simple rounded bulge / depression is an example of a spaced non-punctured texture element having a rounded (circular) shape, while wavy parallel ridges / valleys, or parallel waves in a sinusoidal (sine wave) shape are examples of extended non-punctured texture elements. An extended non-punctured texture element can span the width of the member perpendicular to the longitudinal axis of the member, or at any angle to the longitudinal axis and parallel to the longitudinal axis of the member.

[0146] FIG. 5 presents nine non-limiting examples of seamless repeating patterns provided by corrugation enhancement, according to some embodiments of the present invention.

[0147] FIG. 6 provides a schematic illustration of an exemplary member exhibiting SRP of rounded shaped depressions and bulges imparted by corrugation enhancement using spaced non-puncture texture elements in accordance with some embodiments of the present invention, showing the local thickness and bounding box thickness of the exemplary member.

[0148] Compared with the perforated augmentation of the metal foil provided herein, the texture elements of the corrugated augmentation can be smaller, similar, or larger, and can be defined by height and planar size and shape. The height of the corrugated texture element refers to the vertical distance from the lower side to the upper side of the member, or in other words, the thickness of the MBB. For example, a valley refers to a depression in a surface, and a peak refers to the midpoint of two adjacent valleys that extend above a portion of the surface. The vertical distance from peak to valley or the distance from peak to valley is the distance between the top of the peak and the bottom of the adjacent valley, and is also the thickness of the MBB.

[0149] The horizontal distance ("horizontal pitch") between texture elements (non-punctured or through holes) is essentially the distance between the centers of two adjacent texture elements (see Figures 4 and 5). In some embodiments, the horizontal distance between the centers of two adjacent spaced apart or extended non-punctured texture elements in a corrugated augmentation is in the range of 1-1000 μm, or about 10-100 μm, or 20-100 μm, 30-100 μm, 40-100 μm, 50-100 μm, 60-100 μm, 70-100 μm, 80-100 μm, or about 90-100 μm. In some embodiments, the horizontal distance between the centers of two non-puncture texture elements is 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. In some embodiments, the horizontal distance between the centers of two non-puncture texture elements is at least about 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or at least about 1,000 μm.

[0150] It is noted herein that in some corrugation processes where a thin foil is pressed against a flat or rounded corrugated template (or vice versa) to imprint the SRP of the template onto the foil, the thickness of the foil may vary depending on the type of corrugation used. In some embodiments, the corrugation is effected by mechanically expanding a perforated member. For example, if a perforated member is characterized by a functional porosity of 55% (45% of the volume occupied by metal) and is 20 μm thick, and the perforated member (mesh) is pressed to exhibit a corrugated texture element while being stretched to a local thickness of 100 μm (stretched 5 times), this reduces the metal portion in the member by 5 times, from 45% to 9%. This also increases the functional porosity, from 55% to 91%. In some embodiments, the stretching is achieved using an embossing technique. In one particular example, the stretched member is long and rolled up for use in a factory assembly line.

[0151] The above can be illustrated numerically as follows: P0 is the functional porosity of the raw foil or flat perforated member; P1 is the functional porosity after corrugation (stretching), M (0) is the fraction occupied by metal in the raw foil or flat perforated part, M1 is the fraction of the augmented metal component occupied by metal; T0 is the local thickness of the blank foil or flat perforated part; T1 is the local thickness after corrugation (stretching), Therefore, M (0) =1-P (0) It is.

[0152] Since no material is added or removed during corrugation: M (1) =M (0) ·(T (0) / T (1) ), and P(1) =1-M (1) .

[0153] Therefore, starting from a P of 50%, stretching by 4 times results in P (1) =1-M (1) =1-50% / 4=87 / 5%. P (0) Starting from =80%, P (1) =95%.

[0154] In some embodiments, stretching (local thinning) occurs primarily where the angles of the texture elements are the sharpest or where there is a dramatic change in planarity. Such thinning or stretching of the foil may cause tears in the foil, which can be intentionally designed, thereby forming through holes, which should otherwise be avoided in the foil. Thus, the size of the corrugated texture elements also depends on the foil thickness and, in some embodiments, on the perforations in the foil, which affect the tendency to tear under corrugation stretching.

[0155] In some embodiments, the ratio of the thickness of the MBB to the local thickness (thickness of the raw foil) is at least 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.4:1, at least 1.5:1, at least 1.6:1, at least 1.7:1, at least 1.8:1, at least 1.9:1, at least 2:1, at least 2.2:1, at least 2.3:1, at least 2.4:1, at least 2.5:1, at least 2.6:1, at least 2.7:1, at least 2.8:1, at least 2.9:1, or at least 3:1. In some embodiments, the ratio of the thickness of the MBB to the local thickness is in the range of 1.1:1 to 2:1, or 1.1:1 to 3:1, or 1.1:1 to 4:1, or 1.1:1 to 5:1. In some embodiments, the thickness of the MBB is 5 to 10 times greater than the local thickness. The ratio of MBB thickness to local thickness is also an indication of functional porosity on non-perforated members with corrugation-enhanced SRP, i.e., a ratio of 1.1:1 corresponds to a functional porosity of 10% and a ratio of 3:1 corresponds to a functional porosity of 200%.

[0156] In some embodiments, the thickness of the MBB of the member having the corrugated enhancement ranges from 6 μm to 5000 μm. In some embodiments, the thickness, or alternatively the vertical distance, of the MBB of the member having the corrugated enhancement is 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. In some embodiments, the MBB thickness of a member having corrugation enhancements is at least about 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, about 100 μm, 150 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1,000 μm, 1200 μm, 1400 μm, or at least about 1500 μm (about 1.5 mm).

[0157] In some embodiments, the size of the spaced apart non-punctured texture elements (diameter, footprint, or widest horizontal span at the base of the texture element) ranges from 10 μm to 5000 μm. In some embodiments, the size of the spaced apart non-punctured texture elements is less than about 400 μm, less than 350 μm, less than 300 μm, less than 250 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 90 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.

[0158] In some embodiments, the corrugated SRP is a long continuous sheet and includes extended texture elements, such as creases or undulations, that run perpendicular to the longitudinal axis of the member, hi some embodiments, the extended texture elements intersect the longitudinal axis at an angle.

[0159] In some embodiments, the corrugated SRP comprises spaced apart texture elements, such as bulges (protrusions) and depressions (depressions), protruding on one size of the member (bulges only), or protruding on both sides of the member (bulges and depressions). In some embodiments, the spaced apart texture elements are aligned in a straight line. In some embodiments, the spaced apart texture elements are aligned in a slanted line that is inclined relative to the longitudinal axis of the member or one of its edges. In some embodiments, the spaced apart texture elements are arranged in tiles / motifs, as presented above and illustrated in FIG. 5.

[0160] In some embodiments, the texture elements of the perforated augmentation are much smaller and more densely spaced (10-100 times smaller) than the texture elements of the corrugated augmentation. As a non-limiting example, the rounded through holes of a mesh-type foil that has undergone perforation augmentation are 10-100 times smaller than the bulges / dimples of the same foil that has undergone corrugation augmentation, such that the member has the appearance of a rough fine mesh / screen.

[0161] In some embodiments, the texture elements of the perforated augmentation are substantially similar in size, and in some embodiments similarly positioned, as compared to the texture elements of the corrugated augmentation, hi some embodiments, the SRPs of the perforated augmentation are aligned with the SRPs of the corrugated augmentation, in which case the two SRPs are said to share a frequency.

[0162] The post-production uniformity of the SRP of the corrugated augmentations can be determined by any empirical or statistical method similar or different to that used for the perforated augmentations, in some embodiments, the standard deviation in the overlap of the corrugated motifs is less than 15%, less than 10%, or less than 5%.

[0163] Continuous manufacturing process: The methods of making the members provided herein result in the production of a continuous SRP on or in a continuous metal foil, also referred to herein as a metal substrate, and include continuous additive manufacturing methods, continuous subtractive manufacturing methods, bonding methods, and in some embodiments further include a continuous post-manufacturing enhancement step. The present invention provides a means to inexpensively and quickly produce long lengths of enhanced metal foil with high uniform porosity, with the enhancement of the functional porosity of the thin foil such that these enhanced foils offer the advantages of 3D structures (e.g., metal foams) while maintaining the advantages of uniformity (non-random SRP), production speed, production cost, and roll readiness obtained from thin foil manufacturing methods.

[0164] The present invention provides for the formation of very thin, highly perforated foils in a single additive manufacturing step, i.e., the metal members provided herein can be provided in any length (up to kilometers long) in a single process step and already exhibit some of the properties that define the objects provided herein, such as local thickness and perforation enhancement under SRP conditions and uniformity requirements. In some embodiments, the additive manufacturing technique is electroforming, where metal is deposited on a surface that serves as a substrate for metal deposition and foil formation, and simultaneously serves to provide perforation enhancement under SRP conditions, as discussed below. For example, copper can be deposited on a cylindrical surface with a well-ordered arrangement of voids or small gaps that are uniformly spaced on the surface and made of a non-conductive material. In the context of the present invention, this well-ordered arrangement is a template for SRP, and a cylinder with a conductive surface and small non-conductive voids can be used to form a thin metal perforated foil with micropores by an electroforming process. The voids serve as a template for forming holes in the metal member. The non-conductive material prevents metal deposition in those areas, creating holes in the metal mesh that are approximately the same size and shape as the voids. This results in a seamless repeating pattern of fine through holes in the metal member that mirrors the arrangement of the voids on the surface. According to some embodiments of the present invention, the perforated metal member can also undergo intensified corrugation to further increase its functional porosity as presented herein, with intensified corrugation being provided by continuous roll-to-roll setting or as a step in the manufacture of other products that use the metal member, such as electrodes.

[0165] The present invention provides for the enhancement of preformed thin metal foils to exhibit perforation enhancement in a single subtractive manufacturing step, i.e., the metal members provided herein can be provided in any length (up to a kilometer long) by introducing perforations into a foil that already exhibits some of the properties that define the objects provided herein, such as local thickness. The perforation enhancement step is performed under SRP conditions and uniformity requirements. In some embodiments, the subtractive manufacturing technique is electroetching, where the metal is subjected to metal etching conditions through a mask exhibiting openings arranged under SRP conditions, causing selective removal of the metal through the openings, as discussed below (through mask or masked electroetching). For example, a thin aluminum foil can be subjected to masked electroetching through a mask with a well-ordered arrangement of voids or small gaps uniformly spaced within the mask. In the context of the present invention, this well-ordered arrangement is the template for SRP, and the voids serve as a template for the formation of holes in the metal member. This step results in a seamless repeating pattern of fine perforations in the metal member that mirrors the arrangement of the voids in the mask. According to some embodiments of the present invention, the perforated metal member can also undergo corrugation intensification to further increase its functional porosity as presented herein, with the corrugation intensification being provided by continuous roll-to-roll setting or as a step in the manufacture of other products that use the metal member, such as electrodes.

[0166] In some embodiments, including any of the foregoing, enhancing the metal foil, substrate, or surface includes increasing the available volume relative to the total bounding box volume, or in other words, increasing its functional porosity.

[0167] In some additive manufacturing embodiments, the metal foil is electroformed. In some embodiments, the metal foil is electroformed onto a mandrel, which can be flat or have other shapes, such as a cylindrical drum (cylinder). The terms "drum," "cylinder," and "mandrel" are used interchangeably herein to refer to a curved surface on which the metal foil can be formed, processed, and / or enhanced as described herein. In some embodiments, the metal foil is electroformed onto a mold, and the dielectric material completely or partially fills a portion of the mold. In some embodiments, such a mold allows for the creation of a non-planar material. In some embodiments, such a non-planar material can be dense / flat or have functional porosity (dense refers to the absence of pores).

[0168] In some subtractive manufacturing embodiments, the metal substrate is chemically etched. In some embodiments, the metal substrate is electroetched. In some examples, the metal substrate is electroetched on a cylindrical drum or any other non-planar shape.

[0169] In some embodiments, the metal substrate is bonded to another metal substrate via diffusion bonding, ultrasonic welding, arc welding, electrochemical welding. In some embodiments, the metal substrate is deformed. In some examples, the substrate is a metal foil. In some examples, the substrate is a metal mesh.

[0170] In some embodiments, the metal substrates are rolled to further reduce their thickness. In some embodiments, after the metal substrate is either electroformed or etched (chemically or electrolytically), the metal substrate further undergoes corrugation enhancement to increase its functional porosity.

[0171] In some embodiments, described herein is a process for making a part that includes electroforming a metal structure onto a mandrel, which can be flat or can have other shapes, such as a cylindrical drum.

[0172] In some embodiments, including any of the foregoing, the process includes using a mandrel on which electroforming of the structure is performed, hi some embodiments, the mandrel has a flat surface or a patterned surface.

[0173] In some embodiments, patterning the surface of the mandrel is accomplished by machining, such as machining, etching, milling, laser machining, or any combination thereof.

[0174] In some embodiments, the process includes using forward and reverse current / voltage / power pulses and modifying the pulse amplitude, shape, duration, and rate / frequency of the pulses by modifying the pulse supply during the electroforming process to control the lateral growth of the metal and create the structure. In some embodiments, the process includes using direct current during the electroforming process.

[0175] In some embodiments, the pulse shape is not symmetrical, hi some embodiments, the pulse shape, amplitude or duration can be varied during the electroforming process to specifically control lateral growth at any stage of metal deposition.

[0176] In some embodiments, including any of the foregoing, the process includes creating a perforated member via electroforming in which some portions of the working electrode are exposed and some portions of the working electrode are covered by a dielectric material, while the dielectric material is non-conductive and the working electrode is a conductive surface onto which metal electrodeposition (plating) occurs. The portions on the surface of the working electrode that are non-conductive are also referred to herein as voids. The dielectric material can include various types of plastics, polymers, adhesives, epoxies, and other non-conductive materials.

[0177] In some embodiments, pockets are machined either mechanically, by laser, by a controlled chemical process, or by any other means, and then such pockets are filled with a dielectric material, resulting in electrochemical deposition (electroforming) of metal on the conductive mandrel surfaces but not on the non-conductive dielectric material, where holes are formed, typically having a tapered void shape that narrows from the bottom to the top of the formed foil (see FIG. 3).

[0178] In some embodiments, pockets are machined either mechanically, by laser, by controlled chemical processes, or by any other means, and then such pockets are partially filled with dielectric material. This results in electrochemical deposition (electroforming) occurring on the mandrel surfaces not covered by the dielectric material, including on the exposed portions of the inner walls of the pockets, resulting in edged holes with tapered cavity shapes as seen in FIG. 3, and edges around the wider openings elevated above the surface of the foil. In this and similar embodiments of the invention, a continuous electroforming process is used to create texture elements that simultaneously pierce the surface and protrude from the surface, in other words, simultaneous drilling and corrugation enhancements with the same texture elements.

[0179] In some embodiments, described herein are processes for making the members provided herein, the processes including providing a metal foil having a patterned surface and enhancing the metal foil (corrugation enhancement) such that the metal is non-planar and has a functional porosity of 5-98%.

[0180] In some embodiments, including any of the foregoing, the process includes providing a metal foil having a patterned surface, where the metal is initially a planar surface, but is transformed into a non-planar metal by corrugation augmentation. The transformation may be accomplished using electrical, mechanical, magnetic, or other forces, or a combination thereof.

[0181] In some embodiments, including any of the foregoing, the process includes providing a substrate in the form of a metal foil, a perforated metal foil (mesh), or a member having perforation enhancements as provided herein, and includes applying a localized mechanical force to the substrate. In other embodiments, the corrugation enhancement includes using a metal tool (flat or drum) to press against the metal foil, thereby forming non-punctured texture elements in the metal foil. In certain other embodiments, the process includes using a metal structure, such as a template or substrate, to press against the metal foil, thereby creating non-planar, non-punctured texture elements in the metal foil.

[0182] In some other embodiments, the metal foil is modified using a drawing process. In some other embodiments, the metal foil is modified using a forging process. In some other embodiments, the metal foil is modified using a twisting process. In some other embodiments, the metal foil is modified using a corrugating process. In some other embodiments, the metal foil is modified using a bending process. In some other embodiments, the metal foil is modified at room temperature. In some other embodiments, the metal foil is modified at an elevated temperature.

[0183] In some embodiments, including any of the above, the process includes modifying a metal substrate to provide the member provided herein. In some embodiments, including any of the above, the process includes enhancing a metal foil, and includes applying a mechanical force to the metal substrate, such as a raw thin metal foil or a perforated thin metal foil (SRP perforated member). In some embodiments, the process includes enhancing the metal by stretching the metal substrate. As used herein, modifying includes modifying the shape of the metal substrate, modifying the porosity of the metal substrate, modifying the pore size of a porous metal substrate, modifying the pore shape of a porous metal substrate, or a combination of two or more of the above. As used herein, enhancing a substrate includes increasing any physical dimension of the metal surface, such as its thickness and / or functional porosity. For example, enhancing a substrate can include increasing the size of the pores in the porous metal surface. For example, enhancing a substrate can include increasing the surface area of ​​the metal surface. Enhancement can include increasing the length or width of the metal surface. In yet other embodiments, strengthening the substrate includes stretching the metal so that it is longer or wider, but also thinner.

[0184] According to some embodiments of the invention, the members provided herein may be manufactured by continuous electroforming (additive manufacturing) of a member having perforation enhancements (e.g., mesh). In some embodiments, including any of the foregoing, the continuous process includes providing a raw metal foil by electroforming and further enhancing the foil to include corrugation enhancements as described herein. In some embodiments, including any of the foregoing, the process includes providing a perforated member by electroforming onto a patterned drum / mandrel and further enhancing the perforated member to include corrugation enhancements as described herein, thereby providing a perforated and corrugated member as described herein.

[0185] As used herein, electroforming includes the process of forming a mesh or solid using electricity (specifically, current, voltage, or power). Electroforming includes electrodeposition, where metal ions are reduced to a metal, which has the shape of a mesh or foil, thereby forming a mesh or foil. Electroforming can include the use of a template on which the reduced metal is formed, which may or may not be patterned. In some embodiments, the template is flat. In some embodiments, the template is curved, such as a drum / mandrel.

[0186] In some embodiments, the process for electroforming a mesh or foil includes electroforming a mesh or foil that includes or consists of copper, nickel, or zinc.

[0187] In some embodiments, the process for etching (chemically or electrochemically) a mesh or foil includes etching a mesh that includes or is made of copper, aluminum, titanium, or steel / stainless steel, and generally any metal that is conductive to etching.

[0188] Electroforming of copper on a drum is a standard production method used by providers of copper foils such as those used for current collectors in batteries. In some embodiments, including any of the above, the equipment used to electroform the metal foil is similar to the equipment used to make screens for silk screen printing, screens for electric shavers, and nickel mesh as filters, which are primarily used by the sugar industry. In some embodiments, the tools or mandrels used for electroforming of the components provided herein are reusable, leading to continuous additive manufacturing of components. In certain other instances, the tools or mandrels used for electroforming are not reusable.

[0189] In some embodiments, including any of the foregoing, the process further includes stretching the solid foil or mesh, where the stretching also increases the pore size of the mesh. In other instances, this type of enhancement increases the length or width of the mesh. In yet other instances, this type of enhancement increases the length or width of the mesh and also decreases the thickness of the mesh. In some embodiments, a combination of the foregoing types of enhancement steps is accomplished.

[0190] In some embodiments, the processes herein include a first step of fabricating a metal mesh or a member having perforation enhancements by either continuous additive manufacturing or continuous subtractive manufacturing, as presented above.

[0191] In some embodiments, the processes herein include a second step of increasing the functional porosity of the metal mesh or member by corrugation enhancement. In some embodiments, a metal foil or perforated member formed by a continuous electroforming and / or continuous etching process is subjected to a mechanical force that introduces non-punctured (corrugated) texture elements into the foil or mesh in a continuous manner.

[0192] In some embodiments, including any of the foregoing, the process includes enhancing a metal surface including etching a pattern onto the metal surface. In some embodiments, the etching is accomplished using a neutral, acidic, or alkaline etching solution. In some embodiments, the etching is accomplished using electricity to oxidize the metal surface. In some embodiments, the etching is a combination of electricity and chemical etching. In some embodiments, the etched pattern includes punctured (pores) and non-punctured (pits) texture elements.

[0193] For electrochemical etching of aluminum, an aqueous solution can be used having 0.5-3 M NaCl and a pH range of 0 to 5. A constant or pulsed positive voltage in the range of 3-20 V on Al can then be applied to the aluminum substrate for 5-600 seconds.

[0194] In some embodiments, etching a pattern onto a metal surface includes using a mask such that the pattern is etched through openings in the mask. The openings in the mask are also referred to herein as voids. In some embodiments, the mask is coated onto the substrate to be etched. In some embodiments, the mask is inserted between two electrodes, one of which is a foil, but does not contact either electrode. In some embodiments, the mask is inserted between two electrodes, but does not contact the substrate to be etched. In some embodiments, the mask is attached to a counter electrode. In some embodiments, the etching is a chemical etch. In some embodiments, the etching is an electrochemical etch.

[0195] In some embodiments, including any of the foregoing, fabricating the metal substrate includes electroforming or electroetching on a drum. In some of these embodiments, the drum is made from Al, Ni, Cu, Mg, Ti, steel, stainless steel, steel coated with chromium or other suitable metals, and in some embodiments, the drum is made from a dielectric material.

[0196] In some embodiments, the diameter of the drum / cylinder / mandrel used to electroform metal foils or features according to some embodiments of the present invention, or the diameter of the drum used for electrolytic etching, are each independently about 100 mm, 200 mm, 300 mm, 400 mm, 500 mm, 600 mm, 700 mm, 800 mm, 900 mm, 1,000 mm, 200 cm, 300 cm, 400 cm, 500 cm, 600 cm, 700 cm, 800 cm, 900 cm, or about 1-4 m, about 2 m, 3 m, 4 m, or about 5 m in diameter.

[0197] In some embodiments, including any of the foregoing, the drum / cylinder / mandrel has a patterned texture on its curved surface arranged with SRP around its circumference, and the elements of the patterned texture on the curved surface can be any shape and size according to a designed motif. In some embodiments, the elements of the patterned texture on the curved surface are approximately circular and have a diameter in the range of 1-500 μm. In some embodiments, the elements of the patterned texture on the curved surface are approximately 1 μm in diameter, or approximately 1-10 μm, 10-20 μm, 20-30 μm, 30-40 μm, 40-50 μm, 50-60 μm, 60-70 μm, 70-80 μm, 80-90 μm, 90-100 μm, 100-110 μm, 110-120 μm, 120-130 μm, 130-140 μm, 1 The diameter is 40 to 150 μm, 150 to 160 μm, 160 to 170 μm, 170 to 180 μm, 180 to 190 μm, 190 to 200 μm, 200 to 220 μm, 220 to 240 μm, 240 to 260 μm, 260 to 280 μm, 280 to 300 μm, 300 to 220 μm, 300 to 350 μm, 350 to 400 μm, 400 to 450 μm, or about 450 to 500 μm.

[0198] In some embodiments, including any of the foregoing, the elements of the patterned texture are in the form of holes in the curved surface of the drum / cylinder / mandrel and are at least 10-100 μm deep, at least 20-100 μm deep, at least 30-100 μm deep, at least 40-100 μm deep, or at least 50-100 μm deep. In some embodiments, including any of the foregoing, the holes in the drum / cylinder / mandrel are at least 10 μm deep, or at least 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or at least 100 μm deep, at least 110 μm deep, or at least 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, or at least 200 μm deep, or at least 210 μm deep, at least 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, or at least 300 μm deep.

[0199] Currently known subtractive manufacturing methods for perforating metal foils less than 100 μm thick, such as aluminum foil, are unable to provide fine texture elements as currently provided by the present invention, i.e., the state of the art cannot consistently and efficiently form uniform holes less than 50 μm in thin aluminum foils less than 100 μm thick in a roll-to-roll mode. At best, the state of the art provides finite size metal foil sheets (not unlimited length rolls) perforated with relatively large holes greater than 150 μm that are not uniform (hole size variation greater than 30%) and have jagged edges.

[0200] State of the art includes chemical etching through a photoresist mask applied to one or both sides of the foil, with etching occurring on one or both sides of the foil, respectively. State of the art also includes metal foil drilling with electron beam radiation or lasers. These and other subtractive manufacturing approaches to foil drilling do not produce highly uniform patterns and / or are at best slow and expensive, limited to the production of relatively small sheets, and therefore not conducive to unlimited length roll-to-roll mode production and use.

[0201] The perforated metal foils provided herein were achieved by electrochemical etching, using an electric current under certain chemical conditions to dissolve certain locations in the metal foil, atom by atom, from one side of the foil, using a mask. By choosing to perforate the metal foil with electrochemical rather than chemical etching, the inventors achieved control over the process parameters and therefore a uniform perforation pattern was achieved.

[0202] Briefly, electrochemical etching is provided by, inter alia, clamping a metal foil over at least a portion of the circumference of a curved surface of a conductive cylinder, which acts as an anode in the electroetching process to form a conductive contact between the foil and the cylinder. In some embodiments, the anode is a flat surface, and in other embodiments, the anode is a curved conductive surface. A mask is placed on the exposed surface of the foil essentially over the area of ​​the foil in contact with the anode, and a cathode, curved to match the curvature of the anode, is brought into close proximity (about 0.1-10 mm) from the mask, preferably 3 mm according to some embodiments, thereby forming a closed working space. Once the working space is sealed to act as a flow cell, electrolyte is continuously flowed therein and electric current is continuously applied between the anode and cathode, thereby continuously etching the foil through the holes in the mask while the foil is continuously advanced through the flow cell.

[0203] The challenge of seamless and infinitely repeatable patterning was achieved by using a mask configured for a continuous production mode based on a roll-to-roll architecture. This architecture and the use of an SRP conductive mask allowed the production of "infinite" perforated foils, overcoming the limitations of the state of the art. In some embodiments, the mask is in the form of a closed band and is tensioned directly onto a narrow rolled section of aluminum foil. In some other embodiments, a temporary mask is produced directly on the surface of the metal foil, for example by continuous printing of an SRP conductive mask onto a narrow rolled section of the foil.

[0204] Current Collector: Current collectors (CCs) have a common role in battery systems: (i) CCs support the electrode layers since a typical electrode is fabricated by injecting a slurry (a mixture of active materials, polymer binder, and carbon additive) onto the CCs, and (ii) CCs provide an electrical path to deliver electrons between the electrode materials and the external circuit. By controlling the properties of CCs, the following effects can be obtained: (i) lower thickness and higher strength allow more active materials to be stacked in a confined space, resulting in higher volumetric energy density, and (ii) additional electronic paths can be achieved by strengthening the connection between active materials and CCs with a large contact area, thus reducing the internal resistance of the cell. Generally, Cu and Al are applied as CCs for anodes (0-1.5 V vs. Li / Li+) and cathodes (3-4.7 V vs. Li / Li+), respectively, due to their electrochemical stability and active material compatibility in each reaction potential range.

[0205] The present invention provides an enhanced metal foil that exhibits high functional porosity and uniformity, thereby allowing a greater amount of active material slurry to be loaded thereon, increases the contact surface area between the active material and the CC, and exhibits uniformity throughout the area of ​​the CC, thereby reducing active material delamination, cracking, swelling, detrimental formation of "hot spots," and other mechanical failures that lead to battery malfunction.

[0206] Current collectors with large surface area and low density (low weight) may have several advantages in lithium-ion battery electrodes compared to solid, flat and smooth foil current collectors. Increased active material utilization: A larger surface area allows more active material, such as lithium ions, to be deposited on the current collector, leading to an increase in the overall energy density of the electrode. Improved electrical conductivity: A high surface area current collector can have greater electrical conductivity, which can improve the overall performance of the battery. Reduced weight: A low weight current collector can reduce the overall weight of the battery, making the battery more portable and convenient to use in applications such as electric vehicles and portable electronic devices. Better mechanical stability: A high surface area current collector can have greater mechanical stability, which can improve the overall durability and lifespan of the battery. Better rate capability: A high surface area current collector can have greater rate capability, which means that the battery can be charged and discharged faster without its performance being degraded. Overall, current collectors with large surface area and low density can improve the overall performance and efficiency of lithium-ion batteries.

[0207] In some embodiments of the present invention, enhanced metal foils acting as current collectors with high surface area and low density (high functional porosity) provide the following advantages: (i) Lower thickness and higher strength allow more active material to be stacked in a confined space, resulting in higher volumetric energy density; (ii) By strengthening the connection between the active material and the CC with a large contact area, additional shorter electron paths can be achieved, thus reducing the internal resistance of the cell; (iii) Low cost and rapid continuous manufacturing and provision in industrial size rolls, leading to machinery and processes used in the modern and advanced electrode and battery industries.

[0208] Therefore, according to one aspect of some embodiments of the present invention, a current collector in the sense of a part of the electrode that collects electrons from the electrode material and transports them to an external circuit is provided, the CC consisting of or comprising the enhanced metal foil (member) provided herein.

[0209] As used herein, the term "current collector" refers to a substrate that conducts electrons in a manner sufficient to be used in a battery or electrochemical cell to complete an electric circuit in the cathode and anode. 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 context of a secondary battery, CCs in the cathode conduct electrons to the cathode during discharge and from the cathode during charging, while in the anode, CCs conduct electrons to the anode during charging and from the anode during discharging.

[0210] A current collector may further include contacts and contact leads, terminators, and other features commonly and / or required as part of a current collector or required for its assembly and mounting in an electrical device, and these additional features, all or any selection of them, are encompassed within the definition of a current collector as used herein.

[0211] In some embodiments, the current collector comprises or consists of a member (eg, a mesh) that has undergone perforation enhancement, as defined and exemplified herein.

[0212] In some embodiments, the current collector comprises or consists of a member that has undergone corrugation intensification, as defined and exemplified herein.

[0213] In some embodiments, the current collector comprises or consists of a member that has undergone perforation and corrugation processing as defined and exemplified herein.

[0214] In some embodiments, including any of the foregoing, the current collector, as that term is defined above, is provided in the form of a roll.

[0215] In some embodiments, the current collector provided herein comprises a distinct metal layer(s). A distinct layer is defined herein as a plurality of metal layers that are distinguishable from one another under microscopic imaging conditions. If the layers are melted, joined, welded, soldered, or diffused together or to one another such that the boundaries between them are not observable under microscopic imaging, the layers are not distinguishable. However, if the layers are joined together such that the boundaries between them are distinguishable under microscopic imaging, the layers are said to be distinct.

[0216] In the context of the present invention, particularly in the context of multi-layer current collectors, the layers comprise or consist of enhanced metal foils as provided herein. For example, a CC may be 100 μm thick in total, including five distinct layers, each 20 μm thick, while these five layers, when stacked on top of each other, add up to a layer thickness of 100 μm. In some embodiments, the metal layers may be porous or non-porous, and each may be independently corrugated, perforated, or both perforated and corrugated.

[0217] In some embodiments, including any of the foregoing, the CC comprises separate layers, each of which is independently characterized by a total thickness (MBB thickness) in a range of about 4-20 μm, or 5-20 μm, or about 10-50 μm.

[0218] In some embodiments of the present invention, a CC is prepared by laminating individual components as layers of metal as provided herein and is further characterized by indistinguishable layers (the layers are not distinct from one another).

[0219] In some embodiments, including any of the above, the SRP of the CC comprises pores with a diameter of 20-200 μm. In some embodiments, the SRP of the CC comprises pores with a diameter of 15-500 μm. In some embodiments, including any of the above, the SRP of the CC comprises circular pores with a diameter of 50 μm, a functional porosity of 90%, and the CC is 100 μm thick (the thickness of the MBB).

[0220] In some embodiments, including any of the above, the pores have rectangular or polygonal shaped openings. In some embodiments, the pores have opening dimensions of about 40 μm×50 μm. In some embodiments, the pores have opening dimensions of about 52 μm×52 μm. In some embodiments, including any of the above, the CC comprises 50 μm×50 μm square pores, 90% functional porosity, and the CC is 100 μm thick.

[0221] According to one aspect of some embodiments of the present invention, there is provided a current collector suitable for use in an electrode, such as in a battery, comprising at least one enhanced metal foil as presented herein, the enhanced metal foil being produced by a continuous manufacturing process such that it can be produced in a width of at least 0.1 m and in an unlimited length of at least 0.5 m, and having the following properties: Seamless repeating pattern of non-punctured texture elements, A seamless repeating pattern of perforated texture elements; a local thickness in the range of 4 to 100 μm, and Characterized by at least some of the functional porosity being at least 10%.

[0222] Corrugated current collector: According to one aspect of some embodiments of the present invention, there is provided a current collector suitable for use in an electrode, e.g., in a battery, comprising at least one enhanced metal foil as presented herein, the enhanced metal foil being produced by a continuous corrugation process such that it can be produced in a width of at least 0.1 m and in an unlimited length of at least 0.5 m; Seamless repeating pattern of non-punctured texture elements (scalloped SRP), a local thickness in the range of 4 to 100 μm, and A functional porosity of at least 10%.

[0223] In some embodiments, the current collector comprises or consists of an enhanced metal foil (member) produced by any continuous manufacturing technique known in the art, including a continuous corrugation step that imparts a corrugation enhancement to the member, as these terms and characteristics are explained above.

[0224] Unless expressly stated otherwise, the member is corrugated but not perforated, i.e., not a mesh. In such embodiments, the corrugated SRP may include spaced apart non-perforated texture elements and / or extended non-perforated texture elements, as defined above, that provide a functional porosity of the corrugated member, as provided herein, of greater than 10%.

[0225] In some embodiments, the size (diameter, maximum width at base) of spaced apart non-punctured texture elements in the SRP of the corrugated member ranges from 10 μm to 5000 μm, or 10 to 500 μm. In some embodiments, the horizontal distance between non-punctured texture elements in the SRP of the corrugated member ranges from 100 to 5000 μm, or 100 to 500 μm.

[0226] In some embodiments, the horizontal distance between two adjacent non-punctured texture elements within a corrugated augmentation ranges from 1 to 2000 μm, or from about 10 to 100 μm.

[0227] In such embodiments, the height of the corrugated texture elements characterizing the member can be expressed in terms of the ratio between the local thickness and the thickness of the MBB, where the MBB of an uncorrugated foil is equal to the local thickness of its initial thickness before corrugation. In such embodiments, the ratio of the MBB thickness to the local thickness (thickness of the raw foil) is at least 1.1:1 to 2:1. In some embodiments, the ratio of the MBB thickness to the local thickness is at least 3:1, 4:1, 5:1, 10:1, or at least 20:1. For example, a raw foil having a local thickness of 10 μm can be augmented by corrugation to exhibit a thickness of the MBB of 200 μm.

[0228] In some embodiments, the thickness of the MBB of the member having the corrugation enhancement ranges from 6 μm to 5000 μm.

[0229] In some embodiments, including any of the foregoing, the enhanced metal foil produced by the continuous corrugating process is provided in the form of a roll of foil, with the foil width or roll width being at least 0.1 m, at least 0.5 m, at least 1 m, at least 2 m, at least 3 m, at least 4 m, or at least 5 m wide and having a length of at least 0.5 m, 1 m, 10 m, 100 m, 200 m, 300 m, or 400 m long.

[0230] Perforated Current Collector: In some embodiments, the current collector comprises or consists of an enhanced metal foil characterized by perforation enhancement produced by a continuous electroforming process. In some embodiments, the CC produced by the continuous electroforming process comprises or consists of copper. In some embodiments, the enhanced metal foil produced by the continuous electroforming process is perforated by electroforming it onto the curved surface of a conductive cylinder with the SRP of a non-conductive material engraved or placed on the surface of the cylinder. In some embodiments, the enhanced metal foil is produced by the continuous electroforming process to exhibit the SRP of perforated texture elements as presented herein, and is optionally corrugated to exhibit the SRP of corrugated texture elements as presented herein.

[0231] In some embodiments, the current collector produced by the continuous electroetching process comprises or consists of aluminum. In some embodiments, the current collector produced by the continuous electroetching process comprises or consists of copper. In some embodiments, the enhanced metal foil produced by the continuous electroetching process is perforated by electroetching the enhanced metal foil using a mask having an SRP. In some embodiments, the enhanced metal foil produced by the continuous electroetching process is further corrugated to exhibit the SRP of the corrugated texture elements as presented herein.

[0232] In some embodiments, the perforated member that forms part of or comprises the current collector is also corrugated.

[0233] In some embodiments, including any of the foregoing, the enhanced metal foil produced by a continuous electrolytic etching or continuous electroforming process and exhibiting only perforation enhancement or exhibiting perforation as well as corrugation enhancement, as described above, is provided in the form of a roll of object, where the width of the object, or the width of the roll, is at least 0.1 m, at least 0.5 m, at least 1 m, at least 2 m, at least 3 m, at least 4 m, or at least 5 m wide, and has a length of at least 0.5 m, at least 1 m, at least 10 m, at least 100 m, at least 1000 m, or at least 10,000 m long.

[0234] electrode: As discussed above, advantages provided by the enhanced metal foils provided herein include reducing the mass of the electrode, increasing the amount of active material that can be loaded per unit area, increasing the surface area in contact with the active material, improving the electrical pathway within the active material, and all of the above, while maintaining low production costs and compatibility with mass production machinery and processes, as compared to currently used raw solid (non-porous) and flat (flat, smooth) metal foils.

[0235] The members and CCs provided herein contribute to a significant reduction in local current density by expanding the surface area of ​​the CCs. Since reducing the current density at the electrode can delay the onset of dendritic growth and slow down the growth rate, the CCs provided herein effectively reduce dendritic growth. In addition, since the CCs act as hosts for Li metal, the CCs provided in the present invention block randomly generated Li metal-electrolyte interphase and internal pressure changes caused by the volume change of Li metal during cycling.

[0236] Compared to other 3D porous metal sheets proposed and demonstrated in the art, the present invention provides a solution to the very high costs, long manufacturing times, and most profoundly, the very limited production capacity of all other 3D porous structures, which cannot be mass-produced in rolls of tens and hundreds of meters long, as required by modern electrode coating production in mass production factory facilities. The members provided herein, as well as current collectors comprising or consisting of them, can be implemented in electrode production in the form of a continuous roll of feed foil that is fed to an active material coating device and then cut into individual electrodes.

[0237] Thus, according to some embodiments of the present invention, an electrode is provided, for example in connection with a battery or capacitor, comprising at least one current collector and an active electrode material (also known as a coating material) disposed on the CC, the current collector comprising or consisting of at least one of the enhanced metal foils (members) provided herein. Throughout this specification, the term "electrode" refers to both anodes and cathodes, unless expressly stated otherwise.

[0238] Electrode coating is an important part of the battery manufacturing process and contributes greatly to the final microstructure and therefore the function of the resulting electrode. According to embodiments of the present invention, the enhanced metal foil coating provided herein can be carried out through various routes, while the coater device can be a drawdown coater, which is commonly used in laboratories to produce small coatings, or a roll-to-roll (also known as R2R or reel-to-reel) coater, for which the members of the present disclosure are most suitable for larger industrial applications. In a roll-to-roll setting, the coater geometry used to coat members according to some embodiments of the present invention can be a doctor blade (a fine blade set at a fixed gap from the CC), a comma bar (a comma-shaped geometry with a curved leading edge), a slot die (where the coating material is extruded from the slot onto the CC), a "knife over roll" (where the coating material is dispensed onto the CC and then passes through a knife and a roller), a "reverse roll", a "Mayer rod" (where the roller applies the coating material onto the CC and then the Mayer bar meters out the exact amount), and these methods and devices are known in the art. The coating can be applied while the CC is supported by a roller, or it can be applied to an unsupported CC under tension, which is known as tensioned web coating. Other electrode coating processes known in the art can be used to coat the current collectors described herein.

[0239] The coating material is directly introduced onto the CC without additional morphological modification of the CC, and can be introduced on one or both sides of the member depending on the battery design requirements. For example, the corrugated member as provided herein has been used in an industrial electrode coating machine to successfully produce electrodes for LiBs, demonstrating the feasibility of large-scale production and applicability to practical industry. This simple manufacturing process can also be associated with its cost-effective nature.

[0240] Thus, according to some embodiments of the present invention, electrodes are produced by any known R2R process using rolls of the enhanced metal foils provided herein.

[0241] In some embodiments, the thickness of the electrode including the coating material is greater than the total thickness of the current collector (MBB thickness) due to an additional layer of coating material disposed thereon. In some embodiments, the thickness of the electrode including the coating material is similar to the total thickness of the current collector (MBB thickness) including an additional layer of coating material disposed thereon.

[0242] 7A-7C provide schematic illustrations of enhanced metal foil coating schemes according to some embodiments of the present invention, with the top cross-sectional illustration (FIG. 7A) showing an electrode with a thickness equal to the total thickness of the corrugated foil member (MBB thickness) as well as the middle illustration (FIG. 7B) showing a perforated and corrugated member, and the bottom illustration (FIG. 7C) showing an electrode with a greater thickness compared to the total thickness of the corrugated member (MBB thickness).

[0243] In some non-limiting embodiments where the electrode thickness is similar to the current collector thickness, the CC thickness is 9-12 μm, or up to 100 μm. In some non-limiting embodiments where the electrode thickness is greater than the current collector thickness, the current collector has 50 μm holes on its surface and the porosity is greater than 90% imparted by corrugation and / or perforation.

[0244] As discussed herein, the current collector can include two or more metal layers, where at least one of the layers is an enhanced metal foil as provided herein, or all are enhanced metal foils.

[0245] Coating Material: Because the enhanced metal foils provided herein are designed to be suitable for modern industrial electrode production, all known and commonly used processes, methodologies, and techniques for producing and applying active coating materials onto current collectors are applicable and useful for use with the enhanced metal foils.

[0246] In some embodiments, the process involves coating the current collector with a wet or fluid active material composition in the form of a slurry, paste, liquid, etc. In some embodiments, the coating is applied by dry (solventless) coating, in which the active material is deposited on the current collector with little or no solvent to carry the active material.

[0247] Electrodes with corrugated current collectors: According to some embodiments of the present invention, an electrode is provided that includes at least one current collector and an active electrode material disposed on a CC, the current collector including or consisting of at least one of the enhanced metal foils (members) in the form of corrugated metal foils as presented above. In some embodiments, the member is not perforated.

[0248] An electrode comprising a perforated and optionally corrugated current collector: According to some embodiments of the present invention, an electrode is provided, comprising at least one current collector and an active electrode material disposed on a CC, the current collector comprising at least one of the enhanced metal foils (members) in the form of a perforated metal foil as presented above, or consisting of the enhanced metal foil (member). In some embodiments, the perforated member is also corrugated as described above.

[0249] Batteries and Electrical Devices In view of the above, there is provided a cell or battery comprising at least one electrode, the electrode comprising at least one enhanced metal foil as provided herein, or the electrode comprising at least one enhanced metal foil (component, object) as provided herein, or comprising a current collector made of an enhanced metal foil (component, object). Note that, as used herein, a cell is a single unit of a device that converts chemical energy into electrical energy, and a battery is a collection of cells that convert chemical energy into electrical energy, although the terms "cell" and "battery" are used interchangeably herein.

[0250] Correspondingly, there is provided an electrical device including a cell, an array of cells, a battery, or an array of batteries, as provided herein.

[0251] In some embodiments, the cell or battery includes at least one electrode including at least one current collector, and the CC is a corrugated metal foil or a corrugated enhanced metal foil as described herein.

[0252] In some embodiments, the cell or battery includes at least one electrode including at least one current collector, and the CC is a perforated enhanced metal foil or a perforated enhanced metal foil as described herein.

[0253] In some embodiments, the cell or battery includes at least one electrode including at least one current collector, and the CC is a metal foil that is perforated and corrugated, or a metal foil enhanced by both perforation and corrugation, as described herein.

[0254] Electrical devices contemplated within the scope of the present invention include any electrical device that can use cells or batteries as a primary, auxiliary, or secondary energy source, or alternatively, an electrical device that includes at least one battery and uses electricity stored within the device battery as a power source.

[0255] Examples of electric devices include, but are not limited to, electric vehicles for transportation in the air, on land, underwater, and / or in space, smart phones, laptop computers, portable media players, power tools, toys, heating devices, calling devices, lighting articles (e.g., flashlights), and the like.

[0256] In some embodiments, the electric device is a device that requires a battery with high power density, such as a vehicle (e.g., an electric vehicle). In the context of a battery, power density refers to the amount of power that can be stored or delivered by a battery per unit volume or unit mass. High power density means that the battery has the ability to store or deliver a relatively large amount of power in a relatively small space or weight. This is one of the characteristics of the battery using the enhanced metal foil provided herein, which is designed for use in portable electronic devices and electric vehicles, where size and weight are important factors. A high power density battery can also have a higher energy density, which means that it can store more energy per unit weight or unit volume.

[0257] It is expected that many related enhanced metal foils will be developed during the life of any patent following this application, and the scope of the phrase "enhanced metal foil" is intended to include a priori all such new technologies.

[0258] It is understood that certain features of the invention that are described in the context of separate embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features of the invention are described in the context of a single embodiment for brevity, but may also be provided separately or in any suitable subcombination or combination in other described embodiments of the invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment cannot function without those elements.

[0259] Various embodiments and aspects of the present invention as delineated hereinabove and as claimed in the claims section below are found to be experimentally supported in the following examples. EXAMPLES

[0260] Reference is now made to the following examples, which together with the above descriptions illustrate some embodiments of the invention in a non-limiting fashion.

[0261] Example 1 Waveform processing enhancement Copper and aluminum foils having local thicknesses of 12 μm and 60 μm, respectively, and lengths of at least 125 m were subjected to the roll-to-roll corrugation augmentation process described herein. The SRP of the non-punctured texture elements consisted of rounded dimples spaced by a horizontal distance of about 500 μm and arranged in a hexagonal array, resulting in a total post-corrugation thickness (MBB thickness) of 60 μm for copper and 190 μm for aluminum.

[0262] 8A-8B present micrographs obtained using a Nikon eclipse LV100ND optical microscope taken of enhanced metal foils made from 12 μm thick copper foil (FIG. 8A) and 60 μm thick aluminum foil (FIG. 8B), each of which underwent corrugation enhancement in the form of hexagonally arranged circular dimples spaced horizontally apart by approximately 500 μm from each other.

[0263] Example 2 The effect of drilling and corrugating on functional porosity. To demonstrate the effect of both perforating and corrugating a raw metal foil, the same aluminum foil used in Example 1 was subjected to perforation and corrugation augmentation by electrolytic etching as described therein. The perforations were performed in the form of a hexagonal array of rounded through-holes, each positioned centrally between four adjacent depressions, thereby constituting a rounded through-hole SRP.

[0264] FIG. 9 presents photographs taken on a 60 μm thick aluminum foil, obtained using a Leica DVM6 optical microscope, that have undergone drilling and corrugation enhancements in the form of circular holes and dimples, respectively, arranged in a hexagonal shape, spaced about 500 μm apart from each other in the horizontal direction.

[0265] The resulting layer thickness (MBB) of the enhanced metal foil was increased from 60 to 100 μm and the resulting functional porosity was greater than 90% according to bounding box calculations.

[0266] Example 3 Active Material Coating To demonstrate the enhanced metal foil ability to carry electrode active material provided herein, the corrugated aluminum foil presented in Example 1 above was used as a current collector and coated with 95 wt. % NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O2), 3 wt. % poly(vinylidene fluoride) (PVDF), C65 (nano carbon black conductive additive, 2 wt. %), and suspended in NMP (N-methyl-2-pyrrolidone slurry carrier).

[0267] The slurry was applied onto an aluminum current collector member using a drawdown coater and allowed to dry, thereby forming an exemplary cathode according to some embodiments of the present invention. The aluminum was then chemically etched from the cathode to provide a residual layer of dried active material having the morphology shown in FIG.

[0268] FIG. 10 presents a photograph taken using a Leica DVM6 optical microscope and taken of a dried layer of slurry applied onto a corrugated aluminum foil or member according to some embodiments of the present invention after the aluminum has been removed by acid etching, showing five protruding bumps and four dimples pointing to the opposite side.

[0269] A similar experiment was carried out with a different slurry containing LiFePO4, which was coated onto a similar corrugated aluminum foil and allowed to dry.

[0270] FIG. 11 presents a photograph obtained using a Leica DVM6 optical microscope and taken of a dried layer of slurry applied onto a perforated component made from aluminum according to some embodiments of the present invention after the aluminum has been removed by acid etching, showing some rounded protrusions made from active material formed within the voids where the holes are in the used component.

[0271] As can be seen in FIG. 11, columnar structures are formed due to SRP of the holes in the drilled aluminum component.

[0272] Example 4 Lithium-ion cells containing corrugated current collectors Multi-layer lithium ion pouch cells with a capacity range of 1-1.5 Ah were prepared using corrugated copper and aluminum foils as current collectors according to some embodiments of the present invention, the anode was prepared using corrugated copper foil and the cathode was prepared using corrugated aluminum foil according to some embodiments of the present invention.

[0273] The cell contained a graphite anode and a nickel-manganese-cobalt (NMC622) cathode, known in the art, with a cathode active material composition of 94 wt.% NMC622, 2 wt.% PVDF, 2 wt.% C65 (carbon black conductive additive), and the slurry carrier was N-methyl pyrrolidone (NMP) with 1M LiPF6, EC / DEC 1:1 standard electrolyte. The active material was coated onto a current collector using a standard roll-to-roll machine, and the cell was otherwise assembled using standard cell assembly practices.

[0274] The copper current collector used for the anode had a local thickness of 12 μm, an MBB thickness of 43.5 μm, and a hexagonal array of rounded dimples spaced a horizontal distance of 500 μm apart. The aluminum current collector used for the cathode had a local thickness of 20 μm, an MBB thickness of 63.2 μm, and a hexagonal array of rounded dimples spaced a horizontal distance of 500 μm apart.

[0275] The cathode active area is 6 × 10 cm 2 The pouch cells were first subjected to a formation step at a C-rate of C / 20 prior to cycling. After formation, the cells were subjected to charge-discharge cycling at 1C (with periodic capacity checks at C / 3) at room temperature.

[0276] The cycling results are presented in Figure 12A, where the capacity retention of the cell is plotted versus cycle number with an initial capacity of 1.1 Ah at 100%. The cell could be cycled at a high 1C rate for over 450 cycles, with 85% of the initial capacity remaining.

[0277] To compare the direct current internal resistance (DCIR) of pouch cells with corrugated current collectors to those with conventional electrodes, the GITT method was used as in the previous examples. The internal resistance of the cells was measured at three different SOCs during cell discharge. Figure 12B shows a comparison of DCIR as a function of SOC between the two configurations.

[0278] 12A-12B present battery cycling results obtained for a lithium-ion cell with a corrugated current collector according to some embodiments of the present invention, where FIG. 12A presents measurements of the retention capacity of a cell constructed using a corrugated CC as provided herein (the capacity measure is a percentage of the initial capacity) and FIG. 12B presents measurements of the internal resistance of the cell at various states of charge and compares the results with those obtained for a similar cell with a conventional (flat non-porous) current collector.

[0279] Lowering the internal resistance of a battery cell has a significant impact on overall battery performance, as it allows for faster charging and discharging, resulting in less loss to overall capacity retention. As can be seen in Figures 12A-B, the performance of cells constructed according to some embodiments of the present invention is superior to that of cells using convective foils for CC. As can be seen, cells with corrugated CC in the electrodes exhibited lower DCIR (over 2x) when compared to cells with conventional electrodes.

[0280] Example 5 Perforation Augmentation 13A-13B show 0.53 cm sections of perforated and flat (non-corrugated) augmented foils produced using one of the continuous manufacturing processes described herein. 2 13A shows an aluminum object with a local thickness of 20 μm and a SRP consisting of rounded through-hole motifs with a mean radius of 55.1 μm and a standard deviation of 2.4 μm (SRP uniformity of 4.4% SD), and FIG. 13B shows a copper object with a local thickness of 22 μm and a SRP consisting of rounded through-hole motifs with a mean radius of 58.9 μm and a standard deviation of 1.4 μm (SRP uniformity of 2.4% SD). In the copper object, the number of holes found within the area of ​​the sample was 930, which accounted for 35% of the total area of ​​the sample.

[0281] The perforated copper metal components exhibited a tensile strength of about 50 MPa, and the perforated aluminum metal components exhibited a tensile strength of about 45 MPa.

[0282] Dimensional analysis of the objects was performed using an Epson Perfection V850 Pro Scanner and Image Expert software to calculate key metrics related to SRP.

[0283] Table 1 represents the data collected to measure the uniformity of the SRP, where area average refers to the average area of ​​the samples, radius average refers to the average value of the hole radius, and circularity refers to the average measure of the circularity of the holes.

[0284] [Table 1]

[0285] Example 6 Lithium-ion battery containing porous and corrugated current collectors A single-layer pouch cell with an anode and a cathode produced according to some embodiments of the present invention was prepared. The copper CC used for the anode had a local thickness of 18 μm, the MBB had a thickness of 100 μm, and the SRP motif was one square through-hole with a size of 50 μm (see FIG. 17A). The aluminum CC used for the cathode had a local thickness of 100 μm, the MBB had a thickness of 200 μm, and the SRP motif was a rounded through-hole with a radius of 90 μm (see FIG. 17B).

[0286] 14A-B present SEM micrographs of the corrugated and perforated objects, showing a top view of a copper current collector with active material coated on one side of it (FIG. 14A) and a cross section of an aluminum current collector (FIG. 14B) for demonstration purposes.

[0287] The cell contained a graphite anode and a LiFePO4 (LFP) cathode with a cathode active material composition of 90 wt% LFP, 5 wt% PVDF, 5 wt% C45 (carbon black conductive additive), and the slurry carrier was N-methylpyrrolidone (NMP). The cathode active area was 4 × 4 cm 2 The pouch cell formation step included a first cycle of charge and discharge. A standard electrolyte of 1M LiPF6, EC / DEC 1:1 was used.

[0288] The pouch cells first underwent a formation step at a C-rate of C / 30 prior to cycling. After formation, the cells were subjected to over 50 charge-discharge cycles at C / 3 at room temperature (with periodic capacity checks at C / 10). The cycling results are presented in Figure 15.

[0289] FIG. 15 presents a plot of capacity retention versus cycle number at 35 mAh initial capacity at 100%, measured in lithium-ion cells produced with perforated and corrugated CC according to some embodiments of the present invention.

[0290] To compare the direct current internal resistance (DCIR) of pouch cells with perforated and corrugated CCs with pouch cells constructed using conventional (plain foil) current collectors, the Galvanostatic Intermittent Titration Technique (GITT) method was utilized.

[0291] GITT is a common procedure for measuring battery internal resistance using current pulses. Briefly, GITT involves stepwise discharging (or charging) a battery at a known state of charge (SOC), applying a current pulse, and estimating the cell resistance based on the difference between the initial voltage (before the pulse) and the voltage measured at the end of the pulse for the applied current.

[0292] The cell internal resistance was measured at four different SOCs during cell discharge, and the average of these measurements was taken as the cell DC internal resistance, and the results are presented in FIG.

[0293] FIG. 16 is a comparative plot showing DCIR as a function of cycle life between two configurations, namely, a cell constructed with conventional (raw foil) CC and a cell constructed with enhanced metal foil as provided herein.

[0294] As seen in FIG. 16, the cell with perforated and corrugated CC in the electrode maintained a lower DCIR (more than 4 times) over all cycles compared to the performance of the conventional CC.

[0295] In addition to exhibiting reduced internal resistance compared to cells with conventional foils, cells with perforated and corrugated CCs exhibited improved capacity retention during cycling of the cells. When compared to cells with conventional current collectors, the degradation rate (capacity loss over cycling) of cells with perforated and corrugated current collectors was significantly lower, as indicated by the higher capacity retention, as summarized in Table 2.

[0296] [Table 2]

[0297] As can be seen in Table 2, cells constructed with CCs designed and obtained according to some embodiments of the present invention exhibited higher capacity retention compared to cells constructed with CCs of raw foil. Having higher capacity retention after cycling of the cells indicates an improvement in overall cycle life by reducing the rate of degradation. Such an improvement can enable the battery to last longer and perform better.

[0298] Example 7 Example Texture Elements and Corresponding SRPs Table 3 presents the combination of various SRP parameters for perforation augmentation.

[0299] [Table 3]

[0300] Table 4 presents various SRP parameter combinations for corrugation enhancement.

[0301] [Table 4]

[0302] Example 8 Reinforced metal foil roll 17A-17B present photographs of an enhanced metal foil (metal member) including aluminum and exhibiting corrugated enhancements according to some embodiments of the present invention, where the local thickness is about 20 μm, the vertical distance (height) of the rounded badges (non-punctured texture elements) is about 72 μm, which is also the thickness of the MBB, and the horizontal distance between the texture elements is about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 17A with a magnified inset, and a microscope image showing the corrugated texture elements is presented in FIG. 17B.

[0303] 18A-18C present photographs of enhanced copper foil exhibiting corrugation enhancement according to some embodiments of the present invention, with a local thickness of about 12 μm, an MBB thickness of about 100 μm, and a horizontal distance between texture elements of about 500 μm; the entire roll of enhanced metal foil is presented in FIG. 18A, a magnified inset is presented in FIG. 18B, and a microscope image showing the corrugated texture elements is presented in FIG. 18C.

[0304] While the present invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.

[0305] All publications, patents, and patent applications mentioned in this specification are incorporated herein by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated herein by reference. Furthermore, citation or identification of any reference in this application should not be construed as an admission that such reference is available as prior art to the present invention. To the extent section headings are used, they should not be construed as necessarily limiting.

[0306] Any priority documents to this application are hereby incorporated by reference in their entirety.

Claims

1. 1. An object comprising a metal member, the metal member comprising: a seamless repeating pattern of through-hole texture elements; (a) a seamless repeating pattern of non-punctured texture elements; (b) a local thickness in the range of 3 to 100 μm; and (c) at least 10% functional porosity (P ｆ ), and an object characterized by at least one of.

2. The object of claim 1 , wherein the metal member is characterized by (a).

3. 10. The object of claim 1, wherein the metal member is at least 0.1 m wide and at least 0.5 m long.

4. The object of claim 1 , wherein the metal member is characterized by (a) and (b).

5. The object of claim 1 , wherein the metal member is characterized by (a) and (c).

6. The object of claim 1 , wherein the metal member is characterized by (a), (b), and (c).

7. 7. The object of any one of claims 1 to 6, wherein the metal member comprises a metal selected from the group consisting of aluminum, copper, nickel, gold, cobalt, iron, titanium, steel, stainless steel, and any alloys and combinations thereof.

8. The object according to any one of claims 1 to 6, wherein the local thickness is in the range of 3 to 20 μm.

9. The object of any one of claims 1 to 6, wherein the functional porosity is at least 50%.

10. The object of any one of claims 1 to 6, wherein the through-hole texture elements in the seamless repeating pattern have opening sizes in the range of 10 to 200 μm.

11. The seamless repeating pattern has 30 to 200 holes / mm ２ 7. The body of claim 1, having a pore density in the range of

12. The object of any one of claims 1 to 6, wherein the seamless repeating pattern is characterized by a uniformity of at least 5%.

13. The object according to any one of claims 1 to 6, characterized by a tensile strength of at least 20 to 45 MPa.

14. An object described in any one of claims 1 to 6, wherein the metal member includes spaced non-puncture texture elements including protruding bulges and depressions on either side of the metal member.

15. The object described in claim 14, wherein the spaced non-puncture texture elements are aligned in an inclined line.

16. An object described in any one of claims 1 to 6, wherein the seamless repeating pattern of the perforation texture elements comprises a hexagonal array of rounded perforations.

17. the metal member includes copper, the seamless repeating pattern of through-hole texture elements comprises motifs of rounded holes having diameters of less than 250 μm and horizontal distances of less than 500 μm; the seamless repeating pattern of non-puncture texture elements comprises motifs of rounded depressions and / or rounded bulges each having a diameter of less than 500 μm and a horizontal distance of less than 1000 μm; the local thickness is less than 50 μm; The functional porosity (P ｆ ) is at least 50%; An object according to any one of claims 1 to 6.

18. the metal member includes aluminum, the seamless repeating pattern of through-hole texture elements comprises motifs of rounded holes having diameters of less than 250 μm and horizontal distances of less than 1,000 μm; the seamless repeating pattern of non-puncture texture elements comprises motifs of rounded depressions and rounded bulges each having a diameter of less than 500 μm and a horizontal distance of less than 1000 μm; the local thickness is less than 100 μm; The functional porosity (P ｆ ) is at least 50%; An object according to any one of claims 1 to 6.

19. A roll comprising a cylindrical core and the article according to any one of claims 1 to 6 wound around said core.

20. 20. The roll of claim 19, wherein the object has a width in the range of at least 0.1 to 5 m.

21. 20. The roll of claim 19, wherein the length of the objects in the roll is in the range of at least 0.5 to 10,000 m.

22. A current collector comprising at least one object according to any one of claims 1 to 16.

23. An electrode comprising a current collector obtained by cutting at least one object according to any one of claims 1 to 6.

24. A battery comprising at least one electrode according to claim 23.

25. The battery, comprising at least one electrode comprising nickel manganese cobalt oxide or LiFePO 4 (LFP); the metal member comprises aluminum, the at least one electrode comprises graphite, and the metal member comprises copper; 25. The battery of claim 24.

26. 25. An electrical device comprising at least one battery according to claim 24.

27. 27. The electric device of claim 26, selected from the group consisting of an electric vehicle for transportation in air, land, water and / or space, a smartphone, a laptop computer, a media player, a power tool, a toy, a heating device, a calling device, and a lighting device.

Images