Advanced synergistic magneto-electro active current collectors for electrochemical energy storage devices and methods of making same

Abstract

The present invention relates to a magnetically active current collector comprising: a porous, independent three-dimensional (3D) structure comprising one layer and / or a plurality of stacked layers of a one-dimensional (1D) nanomaterial, a two-dimensional (2D) nanomaterial or a mixture thereof wherein the 1D and / or 2D material is modified with one or more zero-dimensional (0D) magnetically active particles; and at least one current collector tab; wherein the at least one tab is connected to the three-dimensional structure, and wherein the modified nanomaterial of the 3D structure is aligned toward the at least one tab.

Description

TECHNICAL FIELD

[0001] The present invention relates to an advanced magnetically active current collector comprising a free-standing, self-supporting, porous three-dimensional (3D) structure comprising a low-curvature artificial electronic percolation network present within the 3D structure, and an advanced 3D magnetic flux path through the structure, the artificial electronic percolation network exhibiting a non-uniform electrical conductivity towards the direction and / or arrangement of the current collector tabs. More particularly, the present invention relates to a magnetically active current collector comprising a porous, free-standing 3D structure comprising one or more combinations of one-dimensional (1D), two-dimensional (2D) or “1D+2D” nanomaterials, said nanomaterials being decorated with one or more zero-dimensional (0D) magnetically active particles and aligned towards at least one current collector tab connected to the 3D structure. The present invention also relates to a method for manufacturing said magnetically active current collector, to a device such as an electrochemical cell or battery comprising the current collector, and to the use of said current collector. The electronically and magnetically active current collector can in particular provide: enhanced anisotropic electrical conductivity towards the direction of the current collector tabs, improved energy density, enhanced charge / discharge rate capability, higher stability, uniform metal ion flux distribution, improved metal ion (e.g. Li+, Na+, Mg+, Al+, Ca+, K+, etc.) diffusion kinetics, reduced dendrite formation. BACKGROUND

[0002] Over the past decade, there has been extensive research on storage devices such as lithium-based batteries for electrical energy, as they play a key role in energy conversion and in many applications such as mobile phones, laptops or electric vehicles. In particular, there is a growing demand for storage devices with improved power performance, higher energy density, longer lifetime and safety. Such storage devices typically comprise a positive electrode, a negative electrode, a separator and a redox active material. In recent years, the most advanced rechargeable batteries have also been recommended as a potential alternative, not only in replacing fossil fuels, but also in addressing energy and environmental crises.

[0003] Due to several advantageous properties such as high theoretical capacity (1675 mAhg - ¹), high energy density (2600 Whkg -Lithium-sulfur (Li-S) batteries have gained significant attention over the past decade as a potential candidate for next-generation energy storage technology due to their environmental friendliness, high natural abundance, and low cost. Significant progress has been made in developing high-performance Li-S batteries, and a deep understanding has been achieved. However, Li-S batteries have yet to deliver the required energy due to severe capacity decay during cycling. Moreover, the decay in battery performance is more pronounced in the case of high active material / sulfur-loaded electrodes due to significant volume change and poor active material utilization during the charge / discharge process. In addition, due to uneven distribution of active materials, short-circuiting / cell failure is likely to occur, leading to uneven current distribution, triggering parasitic side reactions, such as reactions between the sulfur cathode and Li anode (e.g., exaggerated local Li plating / delamination, Li dendrite formation, etc.). New challenges continue to emerge, redefining the research boundaries, where these limitations include lower ionic conductivity, significant polarization, and premature polysulfide precipitation, leading to sluggish kinetics and rapid consumption of lithium anode.

[0004] Regardless of the battery chemistry, the issues related to uneven current spreading, structural degradation due to associated volume change during lithiation / delithiation, and active material utilization are key factors that limit the commercialization of Li-S technology. Furthermore, the cathode electrolyte interface (CEI) and solid electrolyte interface (SEI) play a decisive role in determining the performance and stability of Li-S batteries. Due to significant volume fluctuations of the lithium metal anode during cycling, the CEI and SEI formed under normal conditions are unstable. For high sulfur-loaded cathodes, the formation and stability of a favorable CEI and SEI with certain additional features are highly desirable and challenging. Significant efforts have been made to overcome the above-mentioned problems, including the use of modified electrolytes, engineered separators, the introduction of artificial interfaces, etc.

[0005] Current collectors are typically made of copper, nickel or aluminum with isotropic electrical conductivity and are attached to the electrodes to extract current from the storage device. In slurry-based electrodes of the tip, the current collector foil also provides mechanical support to the electrode during its movement through subsequent cell manufacturing processes, thus defining the current collector foil as a process substrate. However, for many applications, there is still potential for improvement, especially of the electrical properties such as electrical conductivity as well as physico-chemical and thermal properties. The introduction of 3D porous current collectors made of carbon, aluminum, copper, nickel, etc. has gained wide attention and shown great potential as they are able to accommodate volume changes and suppress dendrite formation, leading to better stability, improved electrical conductivity, superior mechanical stability, and longer cycle life. To further improve battery performance, research is ongoing for different current collectors, including materials, designs, and structures (e.g., etched, carbon-coated, perforated, 3D foam, etc.). For example, lightweight carbon-based current collectors have excellent electrical conductivity and outstanding mechanical flexibility. However, due to the lithium-phobicity (i.e., unfavorable, non-uniform Li deposition) of carbon-based current collectors, various lithiumophilic heteroatoms / species, for example including N, F, O, and phosphides (such as CoP, Cu3P), are introduced to their surface. However, it is found that some of the proposed lithiumophilic species are prone to react with Li, leading to irreversible loss. In addition, manipulating lithium deposition can inevitably lead to the agglomeration of Li, causing the formation of limited lithium dendrites.

[0006] In the absence of an externally applied magnetic field, the dominant driving forces in the electrolyte components are, for example, electromigration, diffusion, and convection - both natural and forced convection. However, in the presence of an external magnetic field, five additional forces arise, namely: magnetic field gradient, paramagnetic gradient, electrokinetics, Lorentz, and magnetic damping in the conductivity, which affect the electrochemical behavior of the electrochemical cell. To introduce such forces, the current collector foil and the cell packaging should be permeable to the external magnetic field, acting as a magnetic core inside the cell itself, i.e., there is a magnetically active species within the cell that can interact with a small external magnetic field (<5 mT) even in a multi-layer cell architecture.

[0007] It is known that magnetic fields can have a positive impact on the chemical / electrochemical reactions during the cycling process of electrochemical cells. There are different ways in which an external magnetic field can influence the chemical / electrochemical performance, including, for example: • changes in electrolyte properties due to the Hall effect and changes in electrical conductivity under applied magnetic fields; • changes in active species transport - the superposition of magnetic fields can be mainly attributed to the interaction of magneto-hydrodynamic (MHD) phenomena with the convection-diffusion layer near the electrodes; • changes in electrode kinetics or electrochemical kinetics under magnetic field influence; ● Changes in the deposition kinetics of active substances—magnetic electrolysis.

[0008] Therefore, the object of this invention is to enhance electrons (e - The conductivity (B) and magnetic flux (C) conductivity are synergistically combined to form a magnetic / electrical conductivity current collector that selectively distributes electrons within an artificially created electron permeation network and improves the kinetics of mass transport based on: i) migration driven by potential electrodes, ii) diffusion driven by concentration gradients, and iii) convection driven by small thermal and density gradients. Regarding electrons (e... - One major effect of conductivity is, for example, to enhance and equalize the current distribution non-uniformity (CDNU) within the electrode, thereby achieving improved electron transport due to the shortest travel path (low tortuosity) and reduced internal resistance, and enabling non-uniform distribution of redox reactions on the electrode, thus obtaining high specific power and active material utilization. Additionally, magnetic flux (B) conductivity affects, for example, the charge (e.g., paramagnetic / diamagnetic free radicals / Li) under magnetic field exposure. + The movement of electrons and / or +cations / -anions in the same direction as the flow of electrons causes the resulting forces to affect the trajectory of metal ion deposition / coating, thereby affecting the overall uniform distribution / deposition of charges (e.g., alkali metal ions) and thus ruling out the possibility of dendrite formation.

[0009] Due to their superior properties, nanomaterials have been proposed for a wide range of applications, including zero-dimensional (0D) materials such as quantum dots (QDs), nanoparticles, and polymeric dots (Pdots); one-dimensional (1D) materials such as nanotubes, nanorods, nanofibers, and nanowires; and two-dimensional (2D) materials such as nanoplatelets and nanosheets. A material is not a nanomaterial if it does not possess any dimension small enough to be considered nanoscale. These nanomaterials are well-known for their use in fabricating macroscopic objects such as freestanding, self-supporting three-dimensional (3D) networks. For example, carbon nanotubes (CNTs) can be formed into 3D networks or sheet / paper-like structures, often referred to as "buckypaper," which consists of tangled components of randomly distributed CNTs. Buckypaper is typically fabricated by vacuum filtering CNT and / or graphene dispersions and / or by sequentially enhancing CNT / graphene layers through a filter membrane. Electrodes based on self-supporting buckypaper have recently gained significant attention and have been found to exhibit excellent performance.

[0010] Methods for aligning 1D / 2D nanomaterials or mixtures thereof, such as CNTs, have been reported, including, for example: (i) mechanical stretching of cross-linked CNT pads as described in U.S. Patent No. 8,246,886 B2; (ii) pushing or “domino push” or pulling of vertically aligned carbon nanotubes (VACNTs) as described by Wang et al. (Nanotechnology, 2008; 19(7), 75609; DOI: 10.1088 / 0957-4484 / 19 / 7 / 075609); (iii) applying a large magnetic field, as disclosed in U.S. Patent Application No. 2002 / 0185770 and U.S. Patent No. 7,803,262 B2; and (iv) applying an electric field, such as that reported by Zhu et al. (J. Appl. Phys. 105, 054319 (2009); https: / / doi.org / 10.1063 / 1.3080243) and reported by Zhang et al. (J. Nanosci. Nanotechnol. 9,2887-2893, 2009; doi:10.1166 / jnn.2009.014).

[0011] Accordingly, the present invention aims to provide a magnetically active current collector with excellent physicochemical, thermal, and electrical properties (e.g., synergistically promoting Li deposition and mitigating Li dendrite growth at high rates during fast charge / discharge) for a variety of applications. This current collector can be manufactured in an environmentally friendly manner without compromising the physical state and chemical properties of the 1D / 2D nanomaterials included therein, modified with one or more 0D magnetically active particles. Further objectives will become apparent from the following description and patent claims. Summary of the Invention

[0012] This disclosure provides a magnetically active current collector. In a generally preferred embodiment, the current collector is conductive and includes a porous, freestanding, three-dimensional (3D) structure, such as, for example, a self-supporting 3D network, a paper-like or sheet-like structure. In other words, the magnetically / electrically conductive current collector can take the form of a freestanding 3D network, substrate, or sheet-like structure, having electronic (electro-conductive) properties. -The current collector also includes aligned and / or mixed aligned / stacked one-dimensional (1D) nanomaterials (e.g., one layer and / or multiple stacked layers of one-dimensional (1D) nanomaterials), two-dimensional (2D) nanomaterials, and / or combinations of “1D+2D” nanomaterials, forming an artificial electron-permeable network with customized porosity and conductivity optimized for orientation / position toward one / more current collector tabs. This artificial electron-permeable network thus exhibits significant anisotropy in electrical conductivity dominated by the presence of highly advanced electronic pathways and provides superior electrochemical performance. Examples of 1D nanomaterials include nanotubes, such as carbon nanotubes (CNTs), such as single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), and multi-walled carbon nanotubes (MWCNTs), nanorods, nanofibers, nanowires, or combinations thereof. Examples of 2D nanomaterials include nanosheets, nanoplates, nanoflakes, etc., such as graphene and its derivatives, graphitic carbon nitride (g-C3N4), boron carbon nitride (BCN), MoS2, etc., or combinations thereof. Furthermore, the 1D and / or 2D nanomaterials of the current collector are modified with zero-dimensional (0D) magnetically active particles, such as, for example, ferromagnetic or ferrimagnetic nanoparticles, which may be lithiophilic or lithiophoreic in nature. The current collector can be lithiophilic, lithiophoreic, or have a lithiophore-lithophilic gradient in nature. The isotropic magnetic circuit formed and supported by the current collector including the said modified nanomaterials subsequently participates in the formation of an advanced 3D magnetic flux path, which interacts with paramagnetic / diamagnetic species / ions / radicals (e.g., Li). + Na + Mg + Al + Ca + K + The combination of these factors, for example, can generate a Lorentz force that can affect the kinetics of devices based on alkali metal ions or alkaline earth metal ions (e.g., batteries or electrochemical cell units) due to: (i) electrode potential-driven migration, (ii) concentration gradient-driven diffusion, and (iii) convection flow, which are mostly neglected in general calculations.

[0013] In one aspect, the present invention relates to a magnetically active current collector comprising: a porous, freestanding three-dimensional (3D) structure comprising one-dimensional (1D) nanomaterials, two-dimensional (2D) nanomaterials, or mixtures thereof, wherein the 1D and / or 2D materials are modified with one or more zero-dimensional (0D) magnetically active particles; and at least one current collector tab; wherein the at least one tab is connected to the three-dimensional structure, and wherein the modified nanomaterials of the 3D structure are aligned toward the at least one tab.

[0014] The modified 1D or 2D nanomaterials can be made, for example, from pure carbonaceous materials (such as CNTs or graphene), doped carbonaceous materials (such as nitrogen, oxygen, or fluorine-doped carbon), non-carbonaceous materials (such as metals or metal oxides), or mixtures thereof. In a generally preferred embodiment, the 1D nanomaterial / 2D nanomaterial or mixture thereof is a building block for fabricating 3D structures (e.g., freestanding 3D networks, substrates, paper-like or sheet-like collectors) comprising or consisting of modified 1D nanomaterials / 2D nanomaterials made of or including materials such as graphite, carbon, graphene; transition metals such as aluminum (Al), bismuth (Bi), boron (B), copper (Cu), gallium (Ga), germanium (Ge), indium (In), iron (Fe), gold (Au), molybdenum (Mo), platinum (Pt), and ruthenium (R). The following are considered as nanomaterials: silicon (Si), silver (Ag), selenium (Se), tin (Sn), titanium (Ti), tellurium (Te), tungsten (W), vanadium (V), and zinc (Zn), their alloys and / or oxides; transition metal dichalcogenides, such as MoS2, WS2, VS2, VS4, TiS2, TiS4, etc.; transition metal carbides (also known as MXenes), such as Ti2C, V2C, Mo2C, Ti3AlC2, Mo2TiC2, etc.; transition metal nitrides / carbonitrides, such as g-C3N4, h-BN, BCN; silylene, phosphorene, germanene, or alloys or composite mixtures of any two or more of the foregoing. 1D nanomaterials can be, for example, nanotubes, nanorods, nanofibers, or nanowires made from any of the above materials, including, for example, carbon nanotubes or boron carbonitride nanotubes. 2D nanomaterials can be, for example, nanosheets, nanoplates, or nanosheets made of the aforementioned indicated materials, including, for example, materials such as graphene, graphene oxide, reduced graphene oxide, Mxenes, graphitic carbonitrides, hexagonal boron nitride, silicene, phosphorene, germanene, hexagonal boron nitride nanosheets, or transition metal dichalcogenide nanosheets.

[0015] According to the preferred embodiments generally applicable in this disclosure, the 0D magnetically active particles modified with 1D and / or 2D nanomaterials comprise at least one paramagnetic material, superparamagnetic material, ferromagnetic material, ferrimagnetic material, superconducting magnetic material, antiferromagnetic material, or any mixture of two or more of the foregoing. Further generally preferred is that the 0D magnetically active particles do not contain any material that would react with the electrode material and / or electrolyte components to cause irreversible loss of the electrode material and / or electrolyte components (e.g., for example, Li / Li). +Materials that are lost. Examples of magnetic materials included in 0D ferromagnetic particles include, for example, Co, Ni, Fe, Zn, Cu, Al, Ti, Mn, Samarium, Neodymium Iron Boron, Cerium, Antimony, Chromium, Vanadium, Molybdenum, their oxides or alloys or combinations thereof. In this disclosure, the presence of Ni, Co and / or Fe, including, for example, Ni-Co alloys and Ni-Fe alloys, especially the presence of Fe, is generally preferred. For example, Fe is a complete ferromagnetic material that cannot alloy with lithium. Examples of magnetic materials included in 0D ferrimagnetic particles include, for example, rare earth transition metals, ferrites, gadolinium, terbium, dysprosium and combinations thereof with at least one of Fe and Co. Examples of magnetic materials included in 0D paramagnetic particles include, for example, aluminum, stainless steel, gadolinium, chromium, nickel, copper, iron, manganese, and / or mixtures thereof. Examples of magnetic materials included in 0D superparamagnetic particles include, for example, iron oxides, such as Fe2O3 and Fe3O4. Examples of magnetic materials included in 0D superconducting magnetic materials include, for example, yttrium barium copper oxide, thallium barium calcium copper oxide, bismuth strontium calcium copper oxide, and combinations thereof.

[0016] The number of contacts in the magnetically active current collector according to the embodiments of this disclosure is not particularly limited, including, for example, one, two or more, three or more, four or more, five or more, six or more, or two to ten current collector contacts.

[0017] In another aspect, the present invention relates to devices including the magnetically active current collector described herein, such as electrodes, primary or secondary energy storage devices, or electrochemical battery cells. The device may be, for example, an electrochemical battery cell or battery comprising alkali metal and / or alkaline earth metals (e.g., Li, Na, K, Ca, Mg, etc.), Al, or Zn metals / ions, such as lithium-ion batteries, sodium-ion batteries, aluminum-ion batteries, zinc-ion batteries, potassium-ion batteries, calcium-ion batteries, and magnesium-ion batteries; or alkali metal / alkaline earth metal chalcogenide batteries, such as lithium-sulfur batteries, lithium-selenium batteries, lithium-sulfur-selenium batteries, sodium-sulfur batteries, sodium-selenium batteries, aluminum-sulfur batteries, potassium-sulfur batteries, calcium-sulfur batteries, and magnesium-sulfur batteries; or alkali metal / alkaline earth metal air batteries, such as lithium-air batteries, sodium-air batteries, aluminum-air batteries, and zinc-air batteries. In a generally preferred embodiment, the device including the magnetically active current collector according to embodiments of the present disclosure may be, for example, a lithium-ion battery or a lithium-sulfur battery.

[0018] On the other hand, the present invention relates to a method for preparing a magnetically active current collector, preferably a method for preparing a magnetically active current collector according to a generally preferred embodiment of the present disclosure, such as a method based on dielectric aligning of nanomaterials, layer-by-layer (LbL) assembly of aligned nanomaterial layers, and a method for connecting the assembled layers to current collector contacts by welding, stamping, or pressing. Within the scope of the present disclosure, such a method may, for example, include the following steps: - Provide modified 1D nanomaterials, modified 2D nanomaterials, or mixtures thereof, wherein the 1D and / or 2D materials are modified using one or more 0D magnetically active particles; - Align the modified nanomaterials; - Forming a porous, freestanding 3D structure comprising the aligned modified nanomaterials; - Connect the 3D structure to at least one current collector patch such that the nanomaterials included in the 3D structure are aligned toward the at least one patch.

[0019] For clarity, some definitions of terms used throughout the specification and claims are provided. Unless the context requires a different meaning, the definitions should be used to determine the meaning of the corresponding expressions.

[0020] The terms “a” or “an” do not exclude the plural; that is, the singular forms “a,” “an,” and “the” should be understood to include the plural referent unless the context explicitly indicates otherwise. In other words, all references to the singular features or limitations of this disclosure should include the corresponding plural features or limitations, and vice versa, unless otherwise expressly stated or the context of the reference explicitly implies the opposite. Therefore, unless otherwise defined, the terms “a,” “an,” and “the” have the same meaning as “at least one” or “one or more.” For example, references to “nanomaterials” include mixtures of nanomaterials, etc.

[0021] The terms “comprise,” “comprises,” and “comprising,” and similar expressions, should be interpreted in an open and inclusive sense as “including but not limited to.” In particular, as used herein, “comprising,” “containing,” “characterized by,” and their grammatical equivalents are inclusive or open-ended terms that do not exclude additional, unmentioned elements or methodological steps. However, “comprise,” etc., should also be interpreted to include, respectively, the more restrictive terms “substantially consisting of” and “consisting of.”

[0022] As used herein, “composed of” excludes any element, step or component not specified in the claims.

[0023] When a product name is used in this document, it is intended to independently include the product formula, the characteristics of the product, and each element or ingredient of the product.

[0024] Terms related to attributes or values, such as “substantially,” “approximately,” “approximately,” “substantially,” etc., include exact attributes or precise values, as well as any attributes or values ​​that are typically considered to fall within the normal range or range of variation accepted in the relevant technical field.

[0025] The terms “binder-free” and “surfactant-free” mean that the material does not intentionally contain binders or surfactants, but do not exclude the presence of residual amounts. That is, the term “free” means that the material contains less than the functional amount of the corresponding component, typically less than 1% by weight, preferably less than 0.1% or even less than 0.01%, and includes zero weight percentage of the corresponding component.

[0026] As used herein, the terminology defining the range boundaries, such as, for example, "from 1 to 5," means any positive number from 1 to 5, including any technically reasonable natural number, integer, positive integer, and fraction. In other words, any range defined by two explicitly mentioned numbers (integers) is intended to include and disclose any technically reasonable number that defines the said boundary, as well as any technically reasonable number included within the range.

[0027] For the physical properties described herein, unless the measurement conditions and methods are specifically described, the physical properties are measured according to the measurement conditions and methods commonly used by those skilled in the art.

[0028] Generally, unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, and are consistent with common textbooks and dictionaries. Unless otherwise stated, conventional chemical and nanomaterial synthesis methods, conventional analytical methods for characterizing materials and nanomaterials, and conventional techniques for applying and assembling nanomaterials onto surfaces are used, including solution-based synthesis, vapor deposition techniques, and electrolysis. In this application, unless otherwise stated, “or” and “and” are used to mean “and / or”. Furthermore, the use of the term “including” and other forms such as “include,” “includes,” and “included” is not limiting. Section headings used herein are for organizational purposes only and should not be construed as limiting the described subject matter. Attached Figure Description

[0029] Figure 1This is a schematic diagram of a porous, freestanding, three-dimensional (3D) layer / film structure, in which aligned modified 1D nanomaterials are oriented toward a current collector patch.

[0030] Figure 2 This is a schematic diagram of a porous, freestanding, three-dimensional layer / film structure, in which aligned modified 1D nanomaterials are oriented toward two current collector tabs.

[0031] Figure 3 It is a schematic diagram of a porous, freestanding, three-dimensional layer / film structure, in which aligned modified 1D nanomaterials are oriented toward three current collector tabs.

[0032] Figure 4A , Figure 4B , Figure 4C , Figure 4D , Figure 4E and Figure 4F Various exemplary embodiments of the magnetically active current collector according to this disclosure are illustrated schematically in cross-section.

[0033] exist Figure 4A The image shows a first example of an embodiment of a magnetically active current collector manufactured according to the present invention, in cross-section. This magnetically active current collector comprises two stacked layers with different thicknesses and density gradients of 0D magnetically active particles. The example magnetically active current collector has a first layer 41 and a second layer 42. The first layer 41 comprises or is composed of a first 1D and / or 2D nanomaterial modified with a first amount of one or more 0D magnetically active particles, and the second layer 42 comprises or is composed of a second 1D and / or 2D nanomaterial modified with a second, higher amount of one or more 0D magnetically active particles.

[0034] exist Figure 4B The image shows a second example of an embodiment of a magnetically active current collector manufactured according to the present invention, in cross-section. This magnetically active current collector comprises three stacked layers with different thicknesses and density gradients of 0D magnetically active particles. The example magnetically active current collector has a first layer 43, a second layer 41, and a third layer 42. The first layer 43 comprises or is composed of a first 1D and / or 2D nanomaterial modified with a first, lower amount of one or more 0D magnetically active particles. The second layer 41 comprises or is composed of a second 1D and / or 2D nanomaterial modified with a second, higher amount of one or more 0D magnetically active particles. The third layer 42 comprises or is composed of a third 1D and / or 2D nanomaterial modified with a third amount of one or more 0D magnetically active particles, the third amount being higher than the first and second amounts.

[0035] exist Figure 4CThe image shows a third example of an embodiment of a magnetically active current collector manufactured according to the present invention, illustrated in cross-section. The magnetically active current collector comprises three stacked layers with different thicknesses and density gradients of OD magnetically active particles, wherein the density of the particles is higher at their center / core. This example of a magnetically active current collector is... Figure 4B In an alternative embodiment of the illustrated embodiment, the magnetically active current collector includes layers 41, 42, and 43 in a different order, such that layer 42, having the highest quantity of one or more OD magnetically active particles, is sandwiched between layers 43 and 41. As a result, the density of OD magnetically active particles at the center / core of the current collector is higher than at the surface of the current collector in this embodiment.

[0036] exist Figure 4D The image shows a fourth example of an embodiment of a magnetically active current collector manufactured according to the present invention, illustrated in cross-section. This magnetically active current collector comprises three stacked layers with different thicknesses and density gradients of OD magnetically active particles, wherein the density of the particles is higher at their center / core. This example of a magnetically active current collector is... Figure 4B and Figure 4C In an alternative embodiment of the illustrated method, the magnetically active current collector comprises only layers 42 and 43 in a different order, such that layer 42, having the highest quantity of one or more OD magnetically active particles, is sandwiched between two layers 43. As a result, the density of OD magnetically active particles at the center / core of the current collector is higher than that at the surface of the current collector in this embodiment.

[0037] exist Figure 4E The image shows a fifth example of an embodiment of a magnetically active current collector manufactured according to the present invention, illustrated in cross-section. This magnetically active current collector comprises three stacked layers with different thicknesses and modifications. This example of a magnetically active current collector is an alternative embodiment comprising a layer 44 sandwiched between two layers 41. Layer 44 comprises or is composed of unmodified 1D and / or 2D nanomaterials, and layer 41 comprises or is composed of 1D and / or 2D nanomaterials modified with a certain amount of one or more 0D magnetically active particles.

[0038] exist Figure 4F The image shows a sixth example of an embodiment of a magnetically active current collector manufactured according to the present invention, illustrated in cross-section. This magnetically active current collector comprises four stacked layers with different thicknesses and density gradients of OD magnetically active particles, wherein the highest density is at the center / core; and an unmodified layer. This example of a magnetically active current collector is another alternative embodiment, comprising layers 44, 41, 42, 41, and 43 in a top-to-bottom order.

[0039] Figure 5A flowchart illustrating an example of a method for manufacturing a magnetically active current collector is shown.

[0040] Figure 6 The charge-discharge characteristics of an asymmetric battery cell with a magnetically active current collector as the working electrode and lithium metal as the counter electrode are shown. Detailed Implementation

[0041] In this disclosure, a magnetically active current collector is provided, comprising: a porous, freestanding three-dimensional (3D) structure comprising one-dimensional (1D) nanomaterials, two-dimensional (2D) nanomaterials, or mixtures thereof, wherein the 1D and / or 2D materials are modified with one or more zero-dimensional (0D) magnetically active particles; and at least one current collector tab; wherein the at least one tab is connected to the three-dimensional structure, and wherein the modified nanomaterials of the 3D structure are aligned toward the at least one tab.

[0042] The inventors have discovered that the claimed magnetically active current collector effectively facilitates the transport of charge carriers (e-) between the current collector / battery electrode and an external source. In particular, the 3D structure is found to act as an artificial electron permeation network exhibiting anisotropic electrical conductivity in response to placement toward one or more current collector tabs. Generally, in the porous, freestanding 3D structure, optimized electrical conductivity and minimal electron curvature in the orientation and arrangement toward the current collector tabs result in reduced impedance while maintaining maximum uniformity of current flowing to or from the electrodes. This ensures reliable, optimized, and safer performance of devices including current collectors (such as electrochemical battery cells or primary or secondary rechargeable batteries containing alkalis and / or alkaline earth elements (e.g., Li, Na, K, Ca, Mg, etc.), Al or Zn metals / ions, or alkali / alkaline earth metal chalcogenides, or alkali / alkaline earth-oxygen, or alkali / alkaline earth air), including, for example, high-energy lithium-ion batteries, lithium-sulfur batteries, or lithium-oxygen batteries. In particular, the presence of an artificially anisotropic electron permeation network within / inside a 3D network can significantly benefit the uniformity of current distribution along / through the electrodes, compared to state-of-the-art systems where current distribution depends on a randomly distributed permeation network driven by physical interactions between active materials, binders, and conductive additives at the particle / aggregate level. In other words, conventional current collectors have randomly distributed and assembled material networks, resulting in less uniform current distribution and a significantly increased path length for electron curvature. It was also found that nanomaterials are distributed in a non-aggregate manner and arranged such that directly adjacent nanomaterials (e.g., modified CNTs) partially overlap along their length in a planar direction, forming chains or nanowires. Thus, the formed nanowires are separated from each other by a customized spacing and are substantially parallel to each other (e.g., see [link to relevant documentation]).Figures 1 to 3 This further improves the transport of charge carriers through the permeation network. This unique arrangement of nanomaterials in the artificial permeation network leads to high specific power and active material utilization, i.e., better performance, due to the electron permeation trajectory from the electrode to the junction being as short as possible (electron curvature).

[0043] Further findings indicate that isotropic magnetic circuits formed and supported by such 3D structures, including 1D / 2D nanomaterials or mixtures thereof modified with 0D magnetic particles (e.g., ferromagnetic and / or ferrimagnetic 0D particles), according to embodiments of this disclosure, subsequently participate in the formation of advanced 3D magnetic flux paths that traverse perpendicularly and / or pass along the surface to accelerate mass transfer of the current collector as needed, for example, to influence Li 0 Coating morphology and / or Li dendrite formation, etc. Generally, the presence of 0D magnetically active particles allows the magnetic field distribution to be (i) perpendicular to the surface of the 3D current collector structure (e.g., foil) and (ii) along its surface, such that the magnetic and electric fields (including ion fields, if applicable) generated in the current collector can synergistically influence properties and / or processes in a defined manner. For example, an applied magnetic field (B) perpendicular to the surface of the 3D current collector structure affects the final morphology of the metal coating (e.g., Li) and mitigates dendrite formation, i.e., the magnetic field (B), metal ions (e.g., Li) + Lithium atoms (Li) 0 and electrons (e - Examples of synergistic effects between fluxes. For instance, if a magnetic field is applied along the surface of a current collector, metal ions (e.g., Li) will... + ) and e - Flux will affect Li + This generates a force that enhances convection by triggering the MHD effect. Unbound by any theory, the MHD effect enhances charge (e.g., paramagnetic / diamagnetic radicals, Li...) + The movement of charges under the influence of an external magnetic field in the same direction as the flow of electrons and / or cations / anions causes the resulting force to affect the trajectory of the charges, thereby influencing, for example, the deposition / stripping of metal ions, such as alkali metal ions (e.g., Li). + Uniform distribution / coating of ) and elimination of the possibility of dendrite formation. Generally, once the 3D magnetic flux is associated with paramagnetic, diamagnetic species / ions (e.g., Li), + The combination of these elements generates Lorentz and / or Kelvin forces, which are determined by (a) migration driven by electrode potential, (b) diffusion driven by concentration gradient, and (c) convection typically neglected in general calculations, to determine the species / ion (e.g., Li). + The dynamics of ) are discussed. This invention benefits most from the MHD effect, which can influence charged species (e.g., Li) under the influence of a magnetic field due to the Lorentz force perpendicular to both the electric and magnetic fields.+ The dynamics of (e.g., enhanced movement). For example, during the charging of a lithium battery, Li + Ions move from the cathode toward the anode, and at the anode, Li + With Li 0 Form coating, correspondingly, in Li + Applying a magnetic field in the direction of ion flow has a significant and favorable effect on the lithium morphology, because "migration" will lead to "spiral" Li. + The trajectory improved Li 0 The morphology of the coating favors the formation of a denser layer and effectively prevents dendrite growth, even at high C rates exceeding 20 mA / cm², such as in Li / Li symmetric cell cells. Typically, the external magnetic field can have a strength >15 mT, while the internal magnetic field may be weaker.

[0044] In this disclosure, the magnetically active current collector can be a current collector foil or a current collector substrate. Typically, the 3D structure of the current collector is not particularly limited and can have any geometry suitable for its intended use. Illustrative examples of such geometries include, for example, hollow (high porosity) or substantially solid (low porosity), circular, square, triangular, rectangular, etc. In a generally preferred embodiment, the 3D structure can be in the form of a porous, rectangular, or hexagonal sheet-like structure. In a generally preferred embodiment, the 3D structure of the current collector is binder-free and / or surfactant-free. In this context, binder-free and / or surfactant-free can be understood as the 3D structure being formed essentially solely of 1D / 2D nanomaterials or mixtures thereof according to embodiments of this disclosure. According to the preferred embodiments generally applicable in this disclosure, the 3D structure of the current collector can be a porous, freestanding, or self-supporting network structure comprising or composed of aligned and modified 1D / 2D nanomaterials or mixtures thereof according to embodiments of this disclosure, for example, in the form of a porous, freestanding, or self-supporting layer, film, paper-like, or sheet-like structure.

[0045] In a generally preferred embodiment of the magnetically active current collector disclosed herein, the 3D structure may have a layered structure. Typically, such a layered structure may comprise two or more stacked layers. More generally preferred is that each layer in the layered structure may independently comprise or be formed of modified 1D or 2D nanomaterials according to a generally preferred embodiment of the modified 1D and / or 2D nanomaterials described in this disclosure, or any mixture of two or more thereof. In any case, generally within the scope of this disclosure, each layer of the 3D structure may comprise the same or at least one different modified nanomaterial. Similarly, it is also generally preferred that each layer in the layered structure, independently of each other, may have its own thickness and may individually comprise its own amount and / or type of 0D magnetically active particles. In any case, generally within the scope of this disclosure, the 0D magnetically active particles modified on the nanomaterials may be the same or different from each other. Within the scope of this disclosure, the 3D structure may, for example, comprise only a single 0D magnetically active particle made of a single ferromagnetic material. In alternative, generally preferred embodiments, the 3D structure may, for example, comprise 0D magnetically active particles made of various ferromagnetic materials, such as particles made of, for example, Fe, Zn, and Ni-Co alloys. The 3D structure may, for example, comprise a first layer and a second layer stacked on the first layer, the first layer comprising or formed of 1D nanomaterials such as CNTs modified with 0D Fe particles, and the second layer comprising or formed of 2D nanomaterials such as graphene, or mixtures of 2D nanomaterials such as molybdenum disulfide / graphene nanosheets (MoS2 / GNSs), modified with 0D particles made of both Fe and Ni-Co alloys. Within the scope of this disclosure, it is also preferred that the 3D structure may (but only as an additional material) comprise 1D and / or 2D nanomaterials not modified with 0D magnetically active particles, or mixtures of two or more thereof, comprising one or more layers comprising or composed of said 1D / 2D nanomaterials not modified with 0D magnetically active particles.

[0046] According to the preferred embodiment generally applicable in the context of this disclosure, the stacked layers in the three-dimensional structure are bonded by interlayer van der Waals bonds. Within the scope of this disclosure, it is also generally preferred that the stacked layers are bonded solely by interlayer van der Waals bonds, i.e., without the aid of any adhesives, glues, base agents, etc. The stacking of layers can, for example, be carried out in the vertical direction, which allows for combinations of layers with variable vertical compositions. In a generally preferred embodiment, the 3D structure may include at least one layer made of modified 1D nanomaterials, which comprise 0D magnetically active particles made of or composed of ferromagnetic materials. An exemplary embodiment of the modified 1D nanomaterials may be, for example, CNTs modified with 0D Fe particles.

[0047] The current collector may include two or more, three or more, four or more, five or more, six or more, or 2 to 10 current collector contacts.

[0048] According to another generally preferred embodiment, the 3D structure of the current collector disclosed herein may include a total of 2 to 5000 stacked layers, 3 to 2000 stacked layers, 4 to 1000 stacked layers, 4 or 5 to 500 stacked layers, 6 to 200 stacked layers, 7 to 100 stacked layers, 8 to 50 stacked layers, 9 to 20 stacked layers, such as 10, 50, 100, 200, 250, 500, or 1000 stacked layers. In one generally preferred embodiment, these layers may be stacked one on top of another along the z-axis or x-axis. In an alternative generally preferred embodiment, the 3D structure may include portions in which layers are stacked one on top of another along the z-axis, and portions in which layers are stacked one on top of another along the x-axis. Within the scope of this disclosure, it is generally preferred that the portions in which the layers are arranged along the z-axis or x-axis can be arranged in any order, such as, for example, in a 3D structure comprising three layers arranged along the z-axis (one on top of the other), 12 layers arranged along the x-axis (side by side and perpendicular to the three layers arranged along the z-axis), and 20 layers arranged along the z-axis above the side-by-side layers. According to preferred embodiments generally applicable in the context of this disclosure, the stacked layers of a porous, freestanding 3D structure may include a combination of (i) and (ii): (i) more than one layer comprising modified 1D nanomaterials; and (ii) at least one layer formed of modified 2D nanomaterials. This combination has been found to provide an increased active surface area, thereby improving electrical conductivity. In the context of this disclosure, the individual layers made of 1D nanomaterials can be rotated against each other. For example, if the individual layers of the porous, freestanding 3D structure are square, they can be rotated against each other by 90°; if they are hexagonal, they can be rotated against each other by 120°. Typically, the 3D structure of the current collector disclosed herein can have a total thickness of 0.1 µm to 50 µm, 0.25 µm to 40 µm, 0.5 µm to 30 µm, 0.75 µm to 20 µm, or 1 µm to 10 µm.

[0049] In another generally preferred embodiment, the porosity of the 3D structure can be at least 1% V / V based on the total volume of the three-dimensional structure. For example, the porosity of the 3D structure can be 5% V / V or more, 10% V / V or more, 15% V / V or more, 20% V / V or more, 50% V / V or more, 80% V / V or more, or 90% V / V or more. Porosity can be determined using a helium specific gravity bottle, where the sample is sealed in a closed container of a fixed volume under a fixed pressure. By this technique, porosity is defined as the volume displacement between the empty container and the container containing the sample. The morphology of the porous network can be determined, for example, by physical gas adsorption or computed microtomography. It has been found that the 3D structure has ordered porosity due to alignment, which not only contributes to anisotropic electrical conductivity optimized towards one or more current collector tabs, but also generally allows for enhanced charge (such as electrons and / or ions, e.g., Li) + It not only facilitates the movement of 3D structures, but also improves their mechanical properties.

[0050] In another generally preferred embodiment, the 3D structure of the current collector can be lithiophilic, lithiophore-repellent, or have a lithiophore-lithophilic gradient, meaning the 3D structure can also include one or more lithiophilic and / or lithiophore-repellent materials. Lithophilic materials have a strong attraction to lithium ions, while lithiophore-repellent materials repel them. Examples of lithiophilic materials include certain carbon-based materials such as graphene and carbon nanotubes, Cu, Al, Co, Ag, Au, TiO2, SnO2, and ZnO. Examples of lithiophore-repellent materials include stainless steel, titanium, and some nickel-based alloys. In this disclosure, lithiophilic current collectors are generally preferred because they facilitate the formation of a stable solid electrolyte interface (SEI) layer on the collector surface. The SEI layer is a thin film of lithium-containing compounds formed on the current collector surface during the first charging of a lithium battery. This layer acts as a barrier, preventing further electrolyte decomposition and providing a stable platform for the deposition and dissolution of lithium ions during battery cycling. On the other hand, poor lithiophilicity leads to uneven Li deposition, resulting in an unstable SEI layer and inevitably leading to dendrite growth. Lithophilic materials tend to form a passivating oxide layer on their surface, which can interfere with the transport of lithium ions into and out of the battery active material. In this disclosure, it is generally preferred that the OD magnetic active particles are lithiumophilic or lithiumphophilic, so that the lithiumophilicity can be controlled or adjusted as needed to synergistically promote Li deposition and mitigate Li dendrite growth at high rates, such as during battery fast charging / discharging processes.

[0051] According to another generally applicable preferred embodiment of this disclosure, the 3D structure of the current collector may also include a density gradient of OD magnetically active particles, i.e., spatial variation in the amount of particles present within the 3D structure. Within the scope of this disclosure, the density may vary between different portions of the 3D structure, for example, between different layers. In a generally preferred embodiment, the density of the OD magnetically active particles contained in the 3D structure may be higher at the center or core of the 3D structure than at the surface.

[0052] In this disclosure, it is generally preferred that the 3D structure of the current collector has at least one substantially flat surface. In one generally preferred embodiment, the flat surface may comprise a conductive material. In another generally preferred embodiment, the flat surface may be modified with OD magnetically active particles. In yet another generally preferred embodiment, the 3D structure may further comprise semiconductor and / or insulating materials. In yet another generally preferred embodiment, the 3D structure may further comprise a metal. Illustrative examples of metals in this disclosure include transition metals such as Al, Cu, Ti, Zr, W, Ni, Fe, Co, Zn, or Cd, noble metals such as Ag, Au, Pt, Ir, Ru, Rh, Os, Ir, dysprosium, gadolinium, samarium cobalt, or combinations thereof. Additionally, the 3D structure may comprise a mixture of two or more metals, a mixture of metals and nonmetallic or non-carbonaceous materials, or combinations thereof.

[0053] According to the preferred embodiments generally applicable in this disclosure, at least one side of the current collector described herein may be in direct contact with an electrode or a redox-active material. In a generally preferred embodiment, one side of the current collector may be in direct contact with an electrode, while the other side may be in direct or indirect contact with a redox-active material.

[0054] According to another generally preferred embodiment, the 3D structure of the current collector described herein may further include additional, separate, and distinct current collectors, particularly as adhesive interlayers serving as binders for electrodes or redox active materials. Typically, such optional additional current collectors may be metallic and / or non-metallic current collectors. Illustrative examples of metallic current collectors in this disclosure include collectors comprising or composed of Li, Na, K, Ca, Mg, Cu, Al, Zn, Ni, stainless steel, etc. In this disclosure, a separate optional current collector may, for example, be attached to a 3D structure comprising OD magnetically active particles, such that the OD magnetically active particles of the 3D structure are in electrical contact with the optional current collector. In a generally preferred embodiment, the optional additional current collector may comprise a conductive foil, sheet, or mesh made of carbon, non-carbon, metal, non-metal, and / or alloys or composite mixtures thereof. According to a preferred embodiment generally applicable in this disclosure, the optional additional current collector may be substantially inactive, i.e., it does not participate in electrochemical reactions and does not contribute to battery capacity. In this disclosure, illustrative examples of substantially inactive current collectors include collectors comprising, for example, carbonaceous or non-carbonaceous sheet-like structures, foils, or foams made of aluminum (Al), copper, stainless steel, nickel, and / or alloys thereof, such as collectors comprising, for example, Al foil, Cu foil, carbon / graphene-coated Al foil, carbon / graphene-coated Cu foil, etc. Within the scope of this disclosure, current collectors according to embodiments described herein are ionically and electronically conductive, chemically bonded to and inseparable from the active material of the electrodes (e.g., cathodes or anodes), and may not contain any optional current collectors, which may also be preferred.

[0055] According to another generally preferred embodiment, the inner and / or outer surfaces of the 3D structure may be additionally modified with seed crystals due to the presence of defect sites therein / on them. For example, according to a generally preferred embodiment of this disclosure, the 3D structure itself, including modified 1D / 2D nanomaterials or mixtures thereof, can serve as a substrate (e.g., a host or active template) for the nucleation and growth of individual nano or micron crystals other than 0D magnetically active particles. For example, the porous 3D structure of a current collector according to embodiments described herein can serve as a template or host for the nucleation and growth of individual nano / micron crystals that interact with surrounding crystals during further growth and form polycrystalline 3D bodies through crystal twinning, branching, and hyperbranching, such as by growing a monolithic wafer-shaped sulfur electrode (e.g., a cathode) using a direct crystal imprinting (DCi) process as described in WO 2021 / 233965 A1. The growth of such a monolithic sulfur wafer benefits from the synergistic effect between numerous individual 1D / 2D nanostructures carrying defect sites on their surfaces, through which polycrystalline 3D bodies / electrodes are formed by controlled crystallization. By using this unique and innovative manufacturing method, highly efficient electrodes can be produced. It can be demonstrated that the electrodes prepared according to WO 2021 / 233965 A1 exhibit excellent performance, high efficiency, and stability.

[0056] In a generally preferred embodiment of this disclosure, the 1D nanomaterials modified with one or more 0D magnetically active particles may be nanotubes, nanorods, nanofibers, nanowires, or mixtures thereof. Within the scope of this disclosure, it should be understood that if the 3D structure does not include any other alternative components according to the current collector embodiments disclosed herein, the 1D nanomaterials included in the 3D structure of the current collector described herein are modified with one or more 0D magnetically active particles. In the context of this disclosure, carbon nanotubes may be single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), or multi-walled carbon nanotubes (MWCNTs). Typically, 1D nanomaterials comprise carbonaceous materials, non-carbonaceous materials, or mixtures thereof, or are made from carbonaceous materials, non-carbonaceous materials, or mixtures thereof. In this context, there are no particular limitations on the size, shape, porosity, and chemical composition of the 1D nanomaterials. For example, 1D nanomaterials include or can be made of carbon, including materials such as graphite and porous carbon; metals such as aluminum (Al), bismuth (Bi), boron (B), copper (Cu), gallium (Ga), germanium (Ge), indium (In), iron (Fe), gold (Au), molybdenum (Mo), platinum (Pt), ruthenium (Ru), silicon (Si), silver (Ag), selenium (Se), tin (Sn), titanium (Ti), tellurium (Te), tungsten (W), vanadium (V), zinc (Zn), their oxides such as CuO, ZnO, TiO2, MoO2, WO2, and their alloys; and transition metal dichalcogenides such as MoS2, WS2, VS2, VS4, TiS2, and TiS4, or composite mixtures of any of the above elements. 1D nanomaterials can be doped and / or functionalized with one or more functional groups. Examples of doped 1D nanomaterials can be 1D nanomaterials doped with heteroatoms such as fluorine, nitrogen, oxygen, or combinations thereof, such as carbon materials including nitrogen doping. Examples of functional groups include -O, -OH, -COOH, -F, -COO, -NO3, -NO2, -R, -Cl, and -NH. In the context of this disclosure, 1D nanomaterials can be, for example, carbon nanotubes or boron carbonitride nanotubes. According to a generally preferred embodiment, the 1D nanomaterial (which may be modified or unmodified, depending on the case) can be in the form of porous, freestanding, or self-supporting layers, films, paper-like, or sheet-like structures that can form a 3D structure of a current collector or be part of it. The electrical conductivity of layers comprising or made of aligned modified 1D nanomaterials can, for example, be from 10² S / cm to 10⁻⁶ along the alignment direction. 6 Within the range of S / cm. In a generally preferred embodiment, the 1D nanomaterial may be carbon nanotubes. In a generally preferred embodiment, the 1D nanomaterial included in the 3D structure of the current collector described herein may, for example, consist of modified carbonaceous materials, modified non-carbonaceous materials, or mixtures thereof.

[0057] In a generally preferred embodiment of this disclosure, the 2D nanomaterials modified with one or more 0D magnetically active particles may be nanosheets, nanoflakes, or nanoplates, or mixtures thereof. Within the scope of this disclosure, it should be understood that if the 3D structure does not include any other alternative components according to the current collector embodiments disclosed herein, the 2D nanomaterials included in the 3D structure of the current collector described herein are modified with one or more 0D magnetically active particles. Typically, the 2D nanomaterials include carbonaceous materials, non-carbonaceous materials, or mixtures thereof, or are made of carbonaceous materials, non-carbonaceous materials, or mixtures thereof. In this context, there are no particular limitations on the size, shape, porosity, and chemical composition of the 2D nanomaterials. For example, 2D nanomaterials include or can be made of carbon, including materials such as graphite, porous carbon, graphene, and fullerenes; metals such as aluminum (Al), bismuth (Bi), boron (B), copper (Cu), gallium (Ga), germanium (Ge), indium (In), iron (Fe), gold (Au), molybdenum (Mo), platinum (Pt), ruthenium (Ru), silicon (Si), silver (Ag), selenium (Se), tin (Sn), titanium (Ti), tellurium (Te), tungsten (W), vanadium (V), and zinc (Zn), and their oxides such as CuO, ZnO, TiO2, and Mo. O2 and WO2, and their alloys; transition metal dichalcogenides, such as MoS2, WS2, VS2, VS4, TiS2, and TiS4; transition metal carbides (MXenes), such as Ti2C, V2C, Mo2C, Ti3AlC2, and Mo2TiC2; transition metal nitrides / carbonitrides, such as graphitic carbon nitride (g-C3N4), hexagonal boron nitride (h-BN), silylene, phosphorene, germanene, boron carbonitride (BCN), aluminum nitride, molybdenum nitride, titanium nitride, and their alloys; or composite mixtures of any of the foregoing. 2D nanomaterials may be doped and / or functionalized with one or more functional groups. Examples of doped 2D nanomaterials may be 2D nanomaterials doped with heteroatoms such as fluorine, nitrogen, oxygen, or combinations thereof, for example, carbon materials including nitrogen doping. Examples of functional groups include -O, -OH, -COOH, -F, -COO, -NO3, -NO2, -R, -Cl, and -NH. Commonly preferred examples of 2D nanomaterials include, for example, graphene nanosheets, graphene oxide, reduced graphene oxide, MXene, g-C3N4, h-BN, silicene, phosphorene, germanene, BCN, transition metal dichalcogenides, or mixtures thereof. According to a generally preferred embodiment, the 2D nanomaterials (which may be modified or unmodified, depending on the case) can form a 3D structure of a current collector or a portion thereof. The electrical conductivity of a layer comprising or made of aligned modified 2D nanomaterials can, for example, be from 10² S / cm to 10 4Within the range of S / cm. Within the range of a generally preferred embodiment, the 2D nanomaterial can be graphene nanosheets, graphene / graphene oxide, or MoS2. In a generally preferred embodiment, the 2D nanomaterials included in the 3D structure of the current collector described herein can, for example, consist of modified carbonaceous materials, modified non-carbonaceous materials, or mixtures thereof.

[0058] According to the preferred embodiments generally applicable in this disclosure, 0D magnetically active particles modified with 1D and / or 2D nanomaterials may, for example, comprise at least one magnetically active metal, transition metal, metal oxide, transition metal oxide, alloy of the foregoing, or a composite mixture thereof. In a generally preferred embodiment, the 0D magnetically active particles may comprise at least one paramagnetic material, superparamagnetic material, ferromagnetic material, ferrimagnetic material, superconducting magnetic material, antiferromagnetic material, or any two or more of the foregoing. Further generally preferred is that the 0D magnetically active particles do not contain any material that would react with the electrode material and / or electrolyte components, thereby causing irreversible loss of the electrode material and / or electrolyte components (e.g., Li / Li). +Materials that are lost. Examples of magnetic materials included in 0D ferromagnetic particles include, for example, Co, Ni, Fe, Zn, Cu, Al, Ti, Mn, Samarium, Neodymium Iron Boron, or combinations thereof. In this disclosure, the presence of Ni, Co, and / or Fe, including, for example, Ni-Co alloys and Ni-Fe alloys, especially the presence of Fe, is generally preferred. For example, Fe is a complete ferromagnetic material that cannot alloy with lithium. Examples of magnetic materials included in 0D ferrimagnetic particles include, for example, rare earth transition metals, ferrites, gadolinium, terbium, dysprosium, and combinations thereof with at least one of Fe and Co. Examples of magnetic materials included in 0D paramagnetic particles include, for example, aluminum, stainless steel, gadolinium, chromium, nickel, copper, iron, manganese, and / or mixtures thereof. Examples of magnetic materials included in 0D superparamagnetic particles include, for example, iron oxides, such as Fe2O3 and Fe3O4. Examples of magnetic materials included in 0D superconducting magnetic materials include, for example, yttrium barium copper oxide, thallium barium calcium copper oxide, bismuth strontium calcium copper oxide, and combinations thereof. 0D magnetically active particles can be lithiophilic or lithiophore-resistant. In a generally preferred embodiment, the 0D magnetically active particles can be lithiophilic. In another generally preferred embodiment, the 0D magnetically active particles can be lithiophilic and ferromagnetic or ferrimagnetic. Further generally preferred is that the 0D magnetically active particles comprise at least one material selected from the group consisting of iron, nickel, cobalt, zinc, dysprosium, gadolinium, samarium, iron oxide, alloys of the foregoing, or composite mixtures thereof. Typically, 0D magnetically active particles can have sizes of 1 nm to 50 nm, 2 nm to 40 nm, 3 nm to 30 nm, 4 nm to 20 nm, or 5 nm to 15 nm, for example, 5 nm or 10 nm. According to the preferred method generally applicable in this disclosure, the amount of 0D magnetically active particles in the 3D structure as a percentage of the total weight of the 3D structure can be from 0.05 wt% to 10 wt%, 1.5 wt% to 9 wt%, 2.5 wt% to 7.5 wt%, or 4.5 wt% to 5.5 wt%, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, or 6 wt%.

[0059] Within the scope of this disclosure, current collectors may include two or more, three or more, four or more, five or more, six or more, or two to ten current collector tabs. As previously mentioned, current distribution nonuniformity has a significant impact on energy density. Therefore, the number of tabs and their placement can be key factors affecting performance. In general, it has been found that increasing the number of tabs can improve the overall performance of the current collector. Furthermore, tab configuration and overall performance are directly related. Due to advanced anisotropic conductivity with customized electron curvature optimized toward one or more tabs, the tab configuration disclosed herein ensures low current distribution nonuniformity factors and reduces Joule heating and its associated adverse effects, such as irreversible electrochemical side reactions and reduced energy density. In other words, the tab configuration provided herein improves the uniformity of current distribution and overall performance, including improved power output, cycling behavior, and safety.

[0060] Examples of embodiments of a current collector according to this disclosure, including modified 1D nanomaterials aligned toward the direction of the current collector contacts, are provided. Figures 1 to 3 It is shown schematically in the diagram.

[0061] This disclosure also includes an electrode comprising a current collector as described herein. According to another aspect, this disclosure provides a primary or secondary energy storage device, or an electrochemical battery cell, comprising the current collector and / or electrode disclosed herein. Illustrative examples of energy storage devices include, for example, batteries, fuel cell units, supercapacitors, such as, for example, metal-ion batteries or metal-sulfur batteries, such as, for example, lithium-ion batteries or Li-S batteries as described in WO 2021 / 233965 A1.

[0062] According to other generally preferred embodiments, the current harvester described herein may also be included in systems such as energy harvesting devices, transparent conductive electrodes, filter membranes, capacitive deionization nanoelectrodes for seawater desalination, diaphragms, flat panel displays, etc.

[0063] Within the scope of this disclosure, it is also preferred that the electrode (e.g., cathode) including the current collector described herein may be included in a primary or secondary rechargeable battery, supercapacitor, or fuel cell unit containing alkali metal / alkaline earth metals (e.g., Li, Na, K, Ca, Mg, etc.) or Al metal / ions, as it is expected to provide sufficient ionic and electronic conduction and high utilization of the electrode active material during cycling. For example, the electrode may be included in an electrochemical energy storage device containing alkali metal / alkaline earth metal / ions (e.g., Li, Na, K, Ca, Mg, etc.), Zn, or Al, such as, for example, intercalated, inserted, and / or alloyed lithium-ion batteries or multi-step redox conversion Li-S batteries. In a generally preferred embodiment, the energy storage device may include an embodiment of an electrode (e.g., cathode) comprising an embodiment of a current collector including additional optional metals (e.g., made of or including Li, Na, K, Ca, Mg, Cu, Al, Zn, Ni, stainless steel, etc.) and / or non-metallic current collectors as described above.

[0064] In another generally preferred embodiment, the device including a current collector or electrode according to an embodiment of this disclosure may be, for example, a battery as described above, such as a lithium-ion battery or a lithium-sulfur battery, especially a lithium-sulfur battery including at least one current collector according to an embodiment of this disclosure (e.g., WO 2021 / 233965 A1). According to another generally preferred embodiment, a primary or secondary energy storage device, electrochemical cell, or electrode including a current collector according to the foregoing embodiments may also include a magnetic field source adapted to generate a magnetic field in at least a portion of the current collector or electrode. Examples of magnetic field sources include, for example, permanent magnets, temporary magnets, electromagnets, or systems including one or more of the foregoing. It goes without saying that the advantages described with respect to the current collector can also be achieved by the device. For example, devices such as energy storage devices or electrochemical cell units according to this disclosure have particularly improved electrical and thermal properties due to the presence of an artificial permeation network toward the current collector contacts, superior cycling behavior due to effective control, for example, Li deposition (including the formation of a stable solid electrolyte interface (SEI) layer and prevention of Li dendrite growth), and enhanced safety.

[0065] The charge carriers can be alkali metal ions, alkaline earth metal ions, aluminum ions, zinc ions, fluorine ions, and more preferably, the counter electrode is a chalcogenide.

[0066] Another object of this disclosure is to provide a method for manufacturing a magnetically active current collector, particularly a method for manufacturing a magnetically active current collector according to the above embodiments. Typically, the method for manufacturing a magnetically active current collector includes the following steps: - Provide modified 1D nanomaterials, modified 2D nanomaterials, or mixtures thereof, wherein the 1D and / or 2D materials are modified with one or more 0D magnetically active particles; - Align the modified nanomaterials; - Forming a porous (e.g., mesh-like) independent 3D structure comprising the aligned modified nanomaterials; - Connect the 3D structure to (e.g., simultaneously form a further patch region for connection) at least one current collector patch, such that the nanomaterials included in the 3D structure are aligned toward the at least one patch.

[0067] The preparation of 1D nanomaterials, 2D nanomaterials, or mixtures thereof, such as in the form of nanotubes, nanorods, nanofibers, nanowires, nanosheets, nanoplates, or nanoflakes, is generally known to those skilled in the art. As described above, 1D and 2D nanomaterials include or are made of carbonaceous materials, non-carbonaceous materials, or mixtures thereof, and these materials are generally known in the art. Similarly, the preparation of 0D magnetically active particles and the chemical functionalization (including surface modification) of nanomaterials are common knowledge in the art. In one embodiment, the step of providing modified nanomaterials may further include using suitable cations adsorbed on the surface of 1D nanomaterials, 2D nanomaterials, or mixtures thereof to form modified 1D nanomaterials, 2D nanomaterials, or mixtures thereof, and subsequently reducing the modified 1D nanomaterials, the modified 2D nanomaterials, or mixtures thereof to 0D magnetically active nanoparticles via an electrochemical or chemical reduction pathway. The step of providing modified nanomaterials may further include coupling 0D magnetically active particles to 1D nanomaterials, 2D nanomaterials, or mixtures thereof to form modified 1D nanomaterials, 2D nanomaterials, or mixtures thereof. The coupling / deposition of such 0D magnetically active particles can be carried out, for example, according to the attachment technique disclosed in WO 2011 / 120643.

[0068] Figure 5 An example of a method for manufacturing a magnetically active current collector according to the principles described herein is illustrated in the form of a flowchart. According to the method (500) for manufacturing a magnetically active current collector, the step of forming a porous, independent layer made of aligned nanomaterials may include the following steps (501A1 and 501A2 or 501B1 and 501B2): providing a dispersion / suspension of nanomaterials, (502) applying an external field to align the dispersed / floating nanomaterials and form a layer, and (503) recovering the layer.

[0069] In a generally preferred embodiment of the method, a dispersion / suspension of the nanomaterial is prepared by adding the modified nanomaterial to a liquid medium via (501A1 and 501A2) followed by chemical and / or mechanical treatment. In an alternative preferred embodiment of the method, a dispersion / suspension of the nanomaterial is prepared by directly spreading a randomly oriented dry solid powder of the modified nanomaterial onto the surface of the liquid medium / processing liquid via (501B1 and 501B2), optionally followed by mechanical treatment. In this context, a dispersion or suspension refers to nanomaterials, such as modified CNTs and / or graphene, dispersed or suspended in the liquid medium in a single form. In some embodiments, the dispersion / suspension is prepared at room temperature. In some embodiments, the dispersed / suspended nanomaterial floats on the surface of the processing liquid / liquid medium. Suitable liquid media include water, ethanol, methanol, acetone, isopropanol (IPA), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and dimethyl sulfoxide (DMSO), or mixtures thereof. In some embodiments, the liquid medium may be water, a mixture of water and ethanol, or acetone. In a generally preferred embodiment, the liquid medium or processing liquid may be surfactant-free. In other generally preferred embodiments, the liquid medium may include one or more surfactants. According to the preferred embodiments generally applicable in this disclosure, the liquid medium or processing liquid is binder-free, but the liquid medium or processing liquid may include surfactants for inducing surface charges (i.e., positive, negative, or neutral charges).

[0070] Chemical treatment may include, for example, functionalization and / or treatment with strong acids and / or surfactants. Suitable strong acids include, for example, nitric acid (HNO3) and sulfuric acid (H2SO4) and mixtures thereof. Examples of functionalization include introducing one or more functional groups selected from -O, -OH, -COOH, -F, -COO, -NO3, -NO2, -R, -Cl, and -NH2.

[0071] Suitable surfactants include, for example, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), hexadecyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), polyoxyethylene octylphenyl ether (Triton X-100), and mixtures thereof. Surfactants help prevent or avoid the formation of aggregates. Suitable mechanical treatments include, for example, ultrasonication, probe-based ultrasonication, centrifugation, calendering, ball milling, and combinations thereof. In some embodiments, the nanomaterial (501A2) is ultrasonicated to ensure a uniform dispersion / suspension. In some embodiments, the nanomaterial (501B2) undergoes an electrostatic dispersion process under an applied direct current (DC). In some embodiments, the DC may be high-voltage (HV) DC to ensure a uniform dispersion / suspension.

[0072] In a generally preferred embodiment of this method, modified nanomaterials can be aligned and formed into 3D structures (e.g., layers, sheets, or membranes) by applying an external force to dispersed / suspended nanomaterials. When the modified (1D) nanomaterials are aligned, their longitudinal axis is perpendicular to the substrate surface. The substrate surface can be, for example, the bottom of a container containing a dispersion / suspension of modified nanomaterials or the surface of a filter membrane. Generally, in this disclosure, the alignment of modified or unmodified 1D / 2D nanostructures can be achieved along the surface of a liquid in which the nanostructures (e.g., modified and / or unmodified CNTs) are dispersed / suspended.

[0073] Suitable external forces include, for example, electrostatic fields, electric fields, magnetic fields, electromagnetic fields, or any combination thereof. In one embodiment, the dispersion is subjected to an electrostatic field. In another embodiment, the dispersion is subjected to an (502) electric field. In yet another embodiment, the dispersion is subjected to a magnetic field. In yet another embodiment, the dispersion is subjected to an electromagnetic field. In a generally preferred embodiment, an alternating current (AC) electric field can be applied to the liquid dispersion / suspension to align the nanomaterials and form a layer. For example, the AC can be an HVAC, such as an HVAC operating at a power of 1 kV to 300 kV and a frequency in the range of 3 kHz to 1.2 MHz. Due to the application of the external force, the nanomaterials align in the direction of the applied external force, thereby forming a layer. Alternatively, the external force can generate internal forces in situ within the nanomaterials, such as an electric field induced by the charge flowing through the alignment / chain lines (right-hand rule) and an external magnetic field preferably generated by a Helmholtz coil. Such internal forces can be used to control and / or customize the inter-distance between aligned nanomaterials and the porosity within the layered structure. In some implementations, aligned 1D nanomaterials can form nanowires, such as Figures 1 to 3As shown. For example, the inter-line spacing formed by aligned nanomaterials (e.g., modified CNTs) can be adjusted by the amount of current flowing through them due to an in-situ generated magnetic field, which has a repulsive effect on adjacent lines (nanowires) formed by the aligned nanomaterials. The stronger the current, the stronger the magnetic field, and therefore the inter-line spacing between the individual nanowires increases; or vice versa, the weaker the current, the lower the repulsive effect, resulting in a more tightly packed nanowires. Naturally, this also applies to porosity; the more tightly the nanowires are packed, the lower the porosity within the resulting layer. In this context, it is generally preferred to apply an electric field (AC and / or DC) to align the modified nanomaterials in an aqueous liquid dispersion / suspension.

[0074] In a generally preferred embodiment of the method, the step of forming a porous, freestanding 3D structure (e.g., a layer, sheet, or membrane) may further include the following steps: optionally providing a processing liquid; optionally spreading / spraying / dispersing 0D-modified 1D and / or 2D nanomaterials on the processing liquid; optionally aligning the 0D-modified 1D and / or 2D nanomaterials; optionally repeating the foregoing steps until a desired number of stacked layers are obtained; optionally lifting the formed 3D porous structure, removing the liquid medium or processing liquid without interfering with or altering the alignment of the modified nanomaterials, thereby forming a porous, freestanding 3D structure, layer, sheet, or membrane comprising the modified nanomaterials, or forming a porous, freestanding 3D structure, layer, sheet, or membrane composed of modified nanomaterials; separating the 3D layer or membrane; and optionally curing, washing, and / or drying the 3D layer or membrane. For example, aligned layers of modified nanomaterials formed from a liquid dispersion of nanomaterials can be recovered by vacuum filtration (503) using a filter membrane. It has been found that vacuum-assisted filtration using a suitable membrane allows for the acquisition of aligned layers of modified nanomaterials without disrupting or altering the alignment, i.e., the orientation of the formed nanowires and the distance between them. The filter membrane can have nanopores, nanochannels, micropores, macropores, macrochannels, or combinations thereof. Additionally, the filter membrane can be hydrophilic or have a hydrophilic coating. In some embodiments, the filter membrane can be porous, having a variable pore size ranging from 20 nm to 50 micrometers. In generally preferred embodiments, vacuum filtration can be performed at low speeds, particularly as slow as possible. Slower filtration speeds have been found to be particularly helpful in maintaining alignment and allowing the aligned nanomaterial layers to float on the surface of the liquid medium, making it easy to pick up / lift the aligned nanomaterial layers from the liquid medium without disrupting the alignment. Filtration speeds can, for example, range from 10 ml / min to 100 ml / min.

[0075] After filtration, the layer comprising aligned modified nanomaterials can be separated from the filter membrane, or the layer composed of aligned modified nanomaterials can be separated from the filter membrane, and optionally cured, washed, and / or dried. In a generally preferred embodiment, residual solvents and / or surfactants can be removed by washing with deionized water, isopropanol, methanol, or mixtures thereof, by calcination, or any combination thereof. Typically, the presence of solvents or surfactants can negatively affect the physical and / or electrical properties of the aligned nanomaterial layer.

[0076] The thickness of a 3D structure or layer comprising aligned modified nanomaterials, or a 3D structure or layer composed of aligned modified nanomaterials, can be controlled by the amount and / or concentration of nanomaterials contained in the liquid dispersion. According to preferred embodiments generally applicable in this disclosure, a 3D structure comprising aligned modified nanomaterials (e.g., a layer, sheet structure, or membrane), a layer composed of aligned modified nanomaterials, or a membrane composed of aligned modified nanomaterials can have a thickness, for example, in the range of about 50 nm to 1000 nm, 100 nm to 750 nm, 200 nm to 600 nm, 250 nm to 500 nm, or 300 nm to 350 nm.

[0077] In a generally preferred embodiment, the porous, freestanding 3D structure, layer, sheet structure, or membrane comprising modified aligned nanomaterials, or a porous, freestanding 3D structure, layer, sheet structure, or membrane composed of modified aligned nanomaterials, may have at least one flat surface. In another generally preferred embodiment, the flat surface may be electrically conductive and / or electrochemically active. In this disclosure, the surface area of ​​the flat surface may range from a few mm² to several m², for example, from 10 cm² to 100 cm².

[0078] In a generally preferred embodiment of the method, porous, freestanding 3D structures can be provided by a layer-by-layer (LbL) assembly method (504A), wherein individual layers, sheet structures, or membranes comprising or composed of aligned nanomaterials obtained from the dispersion and vacuum filtration steps described above are stacked one on top of another. In this disclosure, the stacking of modified or unmodified 1D / 2D nanostructures can include aligned 3D structures lifted perpendicular to the liquid surface and floating on the liquid surface. In some embodiments, these layers may be stacked vertically one on top of another. In other words, the step of providing porous, freestanding three-dimensional structures can be performed by preparing one or more individual layers of aligned nanomaterials as described above and assembling them by stacking the desired number and type (i.e., the nanomaterial components used to form the layers) of layers one on top of another along the z-axis. In a generally preferred embodiment, the step of forming a porous, freestanding 3D structure may, for example, include stacking two or more 3D structures (e.g., layers, sheets, or films) comprising or composed of modified nanomaterials by a layer-by-layer (LbL) deposition method, thereby forming a porous, freestanding 3D structure comprising 2 to 1000 individual layers or films comprising or composed of modified nanomaterials. According to a preferred embodiment generally applicable in this disclosure, when performing the (504B) layer-by-layer (LbL) assembly method, the individual layers composed of 1D nanomaterials can be rotated against each other. For example, if the individual layers of the porous, freestanding 3D structure are square, they can be rotated against each other by 90°; if they are hexagonal, they can be rotated against each other by 120°. According to a preferred embodiment, by performing a layer-by-layer (LbL) assembly method, a total of 2 to 5000, 3 to 2000, 4 to 1000, 5 to 500, 6 to 200, 7 to 100, 8 to 50, 9 to 20, or 10 or more layers of aligned nanomaterials can be stacked together. Typically, the three-dimensional structure obtained by assembling the individual layers of aligned nanomaterials via LbL assembly can have a total thickness of 0.1 µm to 50 µm, 0.25 µm to 40 µm, 0.5 µm to 30 µm, 0.75 µm to 20 µm, or 1 µm to 10 µm.

[0079] According to the preferred methods generally applicable in this disclosure, the 3D structure described herein can be obtained by repeating cycles of alignment, mechanical lifting / rotation, and stacking. Within the scope of this disclosure, it is generally preferred that the 3D structure comprises at least two layers, sheet structures, or films containing or composed of aligned nanomaterials. In a generally preferred embodiment, the stacked layers of the 3D structure obtained by the above-described (LbL) assembly method may include a combination of (i) and (ii): (i) more than one layer comprising or formed of (modified) 1D nanomaterials; and (ii) at least one layer comprising or formed of (modified) 2D nanomaterials. For example, the 3D structure may include a first layer and a second layer stacked on top of the first layer, the first layer comprising or composed of modified aligned 1D nanomaterials (e.g., CNTs modified with ODFe particles), and the second layer composed of 2D nanomaterials (e.g., graphene). In alternative examples, 3D structures can be assembled by LbL of combinations of layers in various sequences, such as, for example, in the following order: three layers comprising or composed of modified aligned 1D nanomaterials, two layers comprising or composed of unmodified aligned 1D nanomaterials, one layer of modified 2D nanomaterials, and two layers comprising or composed of modified aligned 1D nanomaterials. Such combinations of layers in various sequences are preferred in this disclosure. Without being bound by any particular theory, combinations of layers in various sequences increase the number of active surfaces within the 3D structure due to the different shapes, morphologies, and / or surface areas of such mixed structures, thus potentially driving the distribution / gradient density of electrodes comprising such 3D structures. In a generally preferred embodiment, porous, freestanding 3D structures can be formed solely by assembling layers comprising aligned modified 1D nanomaterials or layers composed of aligned modified 1D nanomaterials and optionally additional unmodified 1D or 2D nanomaterials.

[0080] Within the scope of this disclosure, alternative preferred embodiments of the steps for forming porous, freestanding 3D structures may further include seeding the 3D structure with a redox-active material or growing a redox-active material on the 3D structure.

[0081] The method further includes the step of attaching or interlacing at least one current collector tab to a porous, freestanding 3D structure comprising at least one layer of aligned nanomaterials, such that the nanomaterials included in the 3D structure are aligned toward the at least one tab. In a generally preferred embodiment of the method, the current collector tab may (506) be attached or interlaced with a porous, freestanding 3D structure obtained by the LbL process described above to form a current collector foil or current collector substrate as disclosed herein. In this context, it is crucial that the attachment causes the aligned nanomaterials to align toward the current collector tab. The alignment of the nanomaterials and the current collector tab described herein is essential for achieving anisotropic electrical conductivity and a highly advanced, low-bending electronic path from the electrode to the tab through an artificial electron permeation network formed by a porous, freestanding 3D structure. In some embodiments, the current collector tab may be attached to the porous, freestanding 3D structure by ultrasonic welding, resistance welding, laser welding, stamping, or press-fitting, such that the nanomaterials included in the 3D structure are aligned toward the tab.

[0082] Another object of this disclosure is to provide applications and uses of magnetically active current collectors, electrodes, or energy storage devices according to embodiments of this disclosure. For example, the current collector can be used as a substrate housing the active material of a cathode or anode and / or its subsequent growth. For example, such a cathode or anode can be grown by controlled crystallization at defect sites located within / on a 3D structure, such that the 3D structure of the current collector becomes part of the active material or supports it when it serves as a framework. Electrodes (e.g., cathodes or anodes) thus prepared can be used, for example, in electrochemical energy storage devices containing alkali metal / alkaline earth metal / ions (e.g., Li, Na, K, Ca, Mg, etc.), Zn, or Al, such as, for example, intercalated, inserted, and / or alloyed Li-ion batteries or multi-step redox conversion Li-S batteries.

[0083] According to the preferred embodiments generally applicable in this disclosure, a method is provided to enhance the performance of a primary or secondary energy storage device or electrochemical battery cell having a (e.g., magnetically active) current collector according to embodiments described herein, wherein the magnetically active current collector may be part of an externally induced magnetic circuit, and / or the method may optionally include exposing the collector to a magnetic field. In a generally preferred embodiment, the magnetic field may be a varying magnetic field, such as, for example, a varying magnetic field having a component perpendicular to the current flow path. Examples of varying magnetic fields include rotating magnetic fields, oscillating magnetic fields, and pulsed magnetic fields. In a generally preferred embodiment of the method, the magnetic field rotates about an axis parallel to the current flow path, the device being a positive ion battery, and the current flow path being the direction of travel of positive ions. The direction of the magnetic field and the direction of the active charge carrier ions may be orthogonal to each other. The direction of the magnetic field and the direction of the active charge carrier ions may also be parallel to each other. Typically, the magnetic field may be provided by one or more permanent magnets, temporary magnets, or electromagnets. Without being bound by any particular theory, the magnetic field can facilitate ion transport, thereby improving the performance of the device. One characteristic of a battery cell that can be enhanced using the methods described above is its charging speed. Ion transport within a battery cell is typically a rate-determining process during charging, so aiding ion transport accelerates the charging speed. Another characteristic that can be improved using this method is capacity. This can be achieved by performing the method during device formation or operation. For example, methods for enhancing the rate capability, kinetics, capacity, and / or cycle life of a primary or secondary energy storage device or electrochemical battery cell may include the steps of charging or discharging the primary or secondary energy storage device or electrochemical battery cell while exposing the device or battery cell to a magnetic field.

[0084] According to another generally applicable preferred embodiment of this disclosure, a method is provided for altering the rate of chemical and / or electrochemical reactions and / or the distribution of products generated by chemical and / or electrochemical reactions in a primary or secondary energy storage device or electrochemical battery cell having a (e.g., magnetically active) current collector according to this disclosure. The method includes exposing a battery containing the magnetically active current collector to an externally applied magnetic field, for example, exposing the collector to a magnetic field of sufficient strength to generate a magnetic field within OD magnetically active particles sufficient to alter the rate of chemical or electrochemical reactions occurring near one or more of the OD magnetically active particles and / or the distribution of products thereby generated. In other words, the OD magnetically active particles may be able to generate a magnetic field of sufficient strength to alter the rate and / or distribution of intermediate or final products generated by chemical or electrochemical reactions. The OD magnetically active particles themselves may not participate in chemical / electrochemical or redox reactions. Typically, the magnetic field can be provided by a permanent magnet, a temporary magnet, or an electromagnet. In a generally preferred embodiment, the chemical and / or electrochemical reactions involve reactions that alter mass transport kinetics and charged species, such as Li. + Na + Al³ + Zn² + Ca² + F - and / or Mg² + According to the preferred embodiments generally applicable in this disclosure, the primary or secondary energy storage device or electrochemical battery unit used in this method can be a Li-S battery, a Na-S battery, an Al-S battery, or a Mg-S battery.

[0085] According to another generally applicable preferred embodiment of this disclosure, a method is provided for internally heating a primary or secondary energy storage device or electrochemical cell having one or more (e.g., magnetically active) current collectors as disclosed above. The method of exposing the cell may include exposing such magnetically active current collectors to an external alternating magnetic field to provide inductive heating. The method may optionally include inducing or exposing the collectors to a varying magnetic field of sufficient intensity to provide inductive heating. This method can find application, for example, when the current collectors are used as internal heating elements to reduce the heating time required for operation of the electrochemical cell or in methods for manufacturing the electrochemical cell.

[0086] Figure 6 The charge-discharge characteristics of an asymmetric battery cell using a magnetically active current collector as the working electrode and lithium metal as the counter electrode are shown. Here, lithium is deposited (charged) onto a magnetically active current collector foil in the presence of an applied magnetic field of 10 mT, wherein the direction of the magnetic field is parallel to the Li. +The direction of ion transport. Similarly, stripping (discharge) from the magnetically active current collector foil is performed in the presence of an applied magnetic field of 10 mT, wherein the direction of the magnetic field is parallel to Li. + The direction of ion transport is from the current collector foil to the lithium metal electrode.

[0087] Example Constant current charge and discharge cycles were performed within the coin cell. The counter and reference electrodes were 13 mm diameter, 200 μm thick lithium metal anodes. A 100 μm thick magnetically active 3D current collector foil was used as the counter electrode. The cell was assembled using a 70 μL solution of 1 M LiTFSI and 0.2 M LiNO3 in DOL / DME (1:1) as the electrolyte. The cell was assembled at 5 MPa pressure. An externally applied magnetic field was generated using a Helmholtz coil (HHS 5201-98 - Circular HelmholtzCoils, Schwarzbeck). The coin cell was inserted into the cavity of the Helmholtz coil and aligned parallel to and along the Li... + A magnetic field of 10 mT is applied in the direction of transmission.

[0088] It should be noted that the description and drawings are illustrative in nature only and are not intended to limit the scope of the invention, which is defined by the appended claims.

Claims

1. A magnetically active current collector, comprising: Porous, freestanding three-dimensional (3D) structures comprising one layer and / or multiple stacked layers of one-dimensional (1D) nanomaterials, two-dimensional (2D) nanomaterials, or mixtures thereof, wherein the 1D and / or 2D materials are modified with one or more zero-dimensional (0D) magnetically active particles; and At least one current collector terminal; The at least one tab is connected to the three-dimensional structure, and the modified nanomaterial of the 3D structure is aligned with the at least one tab.

2. The current collector according to claim 1, wherein, The stacked layers are bonded together by van der Waals forces.

3. The current collector according to claims 1 and 2, wherein, The current collector includes two or more, three or more, four or more, five or more, six or more, or two to ten current collector contacts.

4. The current collector according to claims 1 to 3, wherein, The 3D structure comprises a total of 2 to 5000 stacked layers, 3 to 2000 stacked layers, 4 to 1000 stacked layers, 4 to 500 stacked layers, 6 to 200 stacked layers, 7 to 100 stacked layers, 8 to 50 stacked layers, 9 to 20 stacked layers, such as 10, 50, 100, 200, 250, 500, or 1000 stacked layers.

5. The current collector according to any one of claims 1 to 4, wherein, Each layer comprises the same or at least one different modified nanomaterial, said modified nanomaterial comprising lithium-philic or lithium-phobic OD magnetically active particles, i.e., metals, transition metals, metal oxides, transition metal oxides, alloys of the foregoing or composite mixtures thereof.

6. The current collector according to any one of the preceding claims, wherein, The 0D magnetically active particles include at least one paramagnetic material, superparamagnetic material, ferromagnetic material, subferromagnetic material, superconducting material, antiferromagnetic material, or any mixture of two or more of the foregoing.

7. The current collector according to any one of the preceding claims, wherein, The 0D magnetically active particles modified on the nanomaterial may be the same as or different from each other.

8. The current collector according to any one of the preceding claims, wherein, The 3D structure has a total thickness of 0.1 µm to 50 µm, 0.25 µm to 40 µm, 0.5 µm to 30 µm, 0.75 µm to 20 µm, or 1 µm to 10 µm.

9. The current collector according to any one of the preceding claims, wherein, The 3D structure has a density gradient of the 0D magnetically active particles. For example, the density and concentration gradient of the particles at the center or core of the 3D structure is higher than the gradient at the surface of the 3D structure.

10. The current collector according to any one of the preceding claims, wherein, The 0D magnetically active particles include at least one material selected from the following: iron, nickel, cobalt, zinc, dysprosium, gadolinium, samarium, cerium, antimony, chromium, vanadium, molybdenum, oxides of the foregoing substances, alloys of the foregoing substances, or composite mixtures thereof.

11. The current collector according to any one of the preceding claims, wherein, The OD magnetically active particles have a size of 1 nm to 100 nm, 2 nm to 80 nm, 3 nm to 60 nm, 4 nm to 50 nm, or 5 nm to 15 nm. For example, the OD magnetically active particles have a size of 5 nm or 10 nm.

12. The current collector according to any one of the preceding claims, wherein, The 0D magnetically active particles in the 3D structure account for 0.05 wt% to 20 wt%, 1.5 wt% to 9 wt%, 2.5 wt% to 7.5 wt%, or 4.5 wt% to 5.5 wt% of the total weight of the 3D structure. For example, the 0D magnetically active particles in the 3D structure account for 5 wt% of the total weight of the 3D structure.

13. The current collector according to any one of the preceding claims, wherein, Based on the total volume of the three-dimensional structure, the porosity of the 3D structure is at least 1% V / V, for example, the porosity of the 3D structure is 5% V / V or more, 10% V / V or more, 15% V / V or more, 20% V / V or more, 50% V / V or more, 80% V / V or more, or 90% V / V or more.

14. The current collector according to any one of the preceding claims, wherein, The current collector further includes at least one electrically conductive material having a preferred electron conduction path oriented toward one or more current collector contacts.

15. The current collector according to any one of the preceding claims, wherein, The 1D nanomaterials included in the 3D structure include nanotubes, nanorods, nanofibers, nanowires, or mixtures thereof.

16. The current collector according to any one of the preceding claims, wherein, The 2D nanomaterials included in the 3D structure include nanosheets, nanoplatelets, nanoplates, or mixtures thereof.

17. The current collector according to any one of the preceding claims, wherein, The 3D structure includes 1D nanomaterials or 2D nanomaterials composed of modified carbonaceous materials, modified non-carbonaceous materials, or mixtures thereof.

18. The current collector according to any one of the preceding claims, wherein, At least one side of the current collector is in direct contact with an electrode or a redox-active material.

19. The current collector according to any one of the preceding claims, wherein, The current collector also includes an additional adhesive intermediate layer, which serves as a binder for the electrode or redox active material.

20. A primary or secondary energy storage device or an electrochemical cell unit, including a current collector according to any one of the preceding claims.

21. The storage device according to claim 20, wherein, The charge carriers are alkali metal ions, alkaline earth metal ions, aluminum ions, zinc ions, fluorine ions, and more preferably, the counter electrode is a chalcogenide.

22. A method for manufacturing a magnetically active current collector, comprising the following steps: - Provides modified 1D nanomaterials, modified 2D nanomaterials, or mixtures thereof, wherein, 1D and / or 2D materials are modified with one or more 0D magnetically active particles; - Align the modified nanomaterials; - Forming independent 3D structures comprising the aligned modified nanomaterials in a porous, mesh-like shape; - Simultaneously forming a patch region, the patch region also serving to connect the 3D structure to at least one current collector patch, such that the nanomaterials included in the 3D structure are aligned toward the at least one patch.

23. The method for manufacturing a magnetically active current collector according to claim 22, wherein, The step of providing modified nanomaterials further includes using suitable cations adsorbed on the surface of 1D nanomaterials, 2D nanomaterials or mixtures thereof to form modified 1D nanomaterials, modified 2D nanomaterials or mixtures thereof, and then reducing the modified 1D nanomaterials, the modified 2D nanomaterials or mixtures thereof to 0D magnetically active nanoparticles by electrochemical or chemical reduction pathways.

24. The method according to claim 22 or 23, wherein, The step of providing modified nanomaterials further includes providing a dispersion or suspension of the modified 1D nanomaterials, modified 2D nanomaterials, or mixtures thereof in a liquid medium.

25. The method according to claim 23 or 24, wherein, The step of providing modified nanomaterials further includes providing a dry solid powder of randomly oriented modified 1D nanomaterials, modified 2D nanomaterials, or mixtures thereof, and spreading the dry solid powder on the surface of the processing liquid.

26. The method according to claim 24 or 25, wherein, The liquid medium or processing liquid is selected from the following: water, ethanol, methanol, acetone, isopropanol (IPA), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO) or any two or more mixtures thereof.

27. The method according to any one of claims 23 to 26, wherein, The liquid medium or processing liquid is binder-free, but the liquid medium or processing liquid may contain surfactants for inducing surface charges, i.e., positive, negative, or neutral charges.

28. The method according to any one of the preceding claims, wherein, The step of aligning the modified nanomaterials is performed by applying an external field selected from: electrostatic field, electric field, magnetic field, electromagnetic field, or any combination of two or more of the foregoing.

29. The method according to any one of the preceding claims, wherein, The steps to form porous, freestanding 3D structures also include the following: - Provide processing fluids; - Spread / spray / disperse 0D modified 1D nanomaterials and / or 2D nanomaterials on the processing liquid; - Align the 0D-modified 1D and / or 2D nanomaterials; - Repeat the above steps until the desired number of stacked layers is obtained; - The resulting 3D porous structure is lifted; - Remove the liquid medium or process the liquid without interfering with or altering the alignment of the modified nanomaterials, thereby forming a porous, independent 3D layer or membrane comprising the modified nanomaterials or forming a porous, independent 3D layer or membrane composed of the modified nanomaterials. - Separate the 3D layer or film, and optionally cure, wash and / or dry the 3D layer or film.

30. The method according to any one of the preceding claims, wherein, The 3D structure comprising the aligned modified nanomaterials, the layer comprising the aligned modified nanomaterials, or the film comprising the aligned modified nanomaterials having a thickness in the range of approximately 50 nm to 1000 nm, 100 nm to 750 nm, 200 nm to 600 nm, 250 nm to 500 nm, or 300 nm to 350 nm.

31. The method according to any one of the preceding claims, wherein, The steps of forming porous, independent 3D structures also include stacking two or more 3D layers or films comprising or composed of modified nanomaterials by a layer-by-layer (LbL) deposition method, thereby forming porous, independent 3D structures comprising 2 to 1000 individual layers or films comprising or composed of modified nanomaterials.

32. The method according to claim 31, wherein, The LbL deposition also includes rotating and / or interleaving the individual layers against each other.

33. The method according to any one of the preceding claims, wherein, The steps of forming a porous, independent 3D structure also include seeding the 3D structure with a redox-active material or growing a redox-active material on the 3D structure.

34. A primary or secondary energy storage device or electrochemical cell unit, comprising a current collector and / or electrode according to any one of the preceding claims; and a magnetic field source adapted to generate a magnetic field in at least a portion of the current collector or electrode.

35. A method for enhancing the performance of a primary or secondary energy storage device or electrochemical battery cell, said primary or secondary energy storage device or electrochemical battery cell having a magnetically active current collector according to the preceding claim, wherein, The magnetically active current collector is part of an externally induced magnetic circuit.

36. The method according to claim 35, wherein, The direction of the magnetic field is orthogonal to the direction of the active charge carrier ions.

37. The method according to claim 36, wherein, The direction of the magnetic field is parallel to the direction of the active charge carrier ions.

38. The method according to claim 36 or 37, wherein, The magnetic field is provided by a permanent magnet or an electromagnet.

39. A method for enhancing the rate capability, kinetics, capacity, and / or cycle life of a primary or secondary energy storage device or electrochemical battery cell, comprising the steps of charging and / or discharging the primary or secondary energy storage device or electrochemical battery cell while performing the method according to any one of claims 37 to 38.

40. A method for altering the rate of chemical and / or electrochemical reactions and / or the distribution of products obtained from chemical and / or electrochemical reactions in a primary or secondary energy storage device or electrochemical battery cell, said primary or secondary energy storage device or electrochemical battery cell having a magnetically active current collector according to the preceding claim, said method comprising exposing the battery including the magnetically active current collector to an externally applied magnetic field.

41. The method according to claim 40, wherein, The chemical and / or electrochemical reactions involve reactions that alter mass transport kinetics and charged species, for example, the charged species being Li. + Na + Al³ + Zn² + Ca² + F - and / or Mg² + .

42. The method according to any one of claims 40 to 41, wherein, The primary or secondary energy storage device or electrochemical battery unit is a Li-S battery, Na-S battery, Al-S battery, or Mg-S battery.

43. A method for internally heating a primary or secondary energy storage device or electrochemical battery cell having a plurality of magnetically active current collectors as described in the preceding claims, the method comprising exposing a battery containing such magnetically active current collectors to an external alternating magnetic field to provide induction heating.

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