WO2025053982A1 - Extended microstructures and methods of making and using thereof - Google Patents

Abstract

According to one aspect, a method of manufacturing a structure is provided. The method includes the step of obtaining a deposit design, the deposit design comprising an indication of one or more extended microstructure regions. The method includes the step of obtaining a flowable liquid comprising an active material. The method includes the step of generating a plurality of droplets from the flowable liquid. The method includes the step of depositing the plurality of generated droplets on a support based on the deposit design by controlling at least one of a quantity, size, or placement of droplets deposited in the one or more extended microstructure regions.

Description

EXTENDED MICROSTRUCTURES AND METHODS OF MAKING AND USING THEREOF

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63/580,808, filed September 6, 2023, the entire contents of which is fully incorporated herein by reference.

TECHNICAL FIELD

[0002] The subject matter disclosed herein is generally directed to extended microstructures and methods of making and using thereof. In some embodiments, the extended microstructures have structural features in the 1-1000 micrometers range.

BACKGROUND

[0003] Traditional methods of making devices such as secondary electrochemical cells, sensors and catalyst systems employ different methods of depositing the active material onto a support such as slot-die coating, different spraying techniques, or simply dipping a support into a solution containing the active material. The common aim of these methods is to achieve a uniform coating of the active material on the support.

[0004] Many articles of manufacture or their components have various active materials coated on supports that are important for certain functions of the articles. The current methods of coating involve mixing the active materials, typically in particulate-form, along with a binder material and, in some cases, other additives in a fluid to produce a flowable liquid that could then be slot-die coated, sprayed, blade-cast, dip-coated, screen printed, etc., onto a support. The role of the binder is to provide physical integrity to the coated structure and adhesion to the support. A drying process could follow the coating step to drive off the fluid. The resulting coating is homogenous with no ordered structures at the millimeter, micrometer or nanometer scale.

[0005] Alternatively, the active materials could be vaporized, either physically at high temperatures or chemically in a reactive vapor-form, onto a support. These vapor-deposited coatings are typically in the nanometer scale.

[0006] All these coating methods result in homogeneous coatings where the active materials, binders and other additives are distributed uniformly throughout the coating. [0007] Some applications, such as in a battery electrode (e.g., an anode and/or cathode), may have a metal foil, a metallized polymer foil, or any other material capable of conducting electricity as support, on which a layer of a composite material containing one or more active materials and other elements is coated. The battery can be a primary or secondary battery, such as a lithium-ion battery or any other present or future electrochemical formula, having a structure of anode electrode, separator and cathode electrode. Such a battery can use a liquid, gel, solid or any other type of electrolyte responsible for transporting ions between the electrodes.

[0008] Existing techniques for electrode coating produce a homogeneous distribution of the active material and elements with no control at the micrometer or nanometer scale where the particles of the active material, the binding material, or current enhancer are located spatially. Conventional electrodes are made from randomly sized, randomly oriented, and relatively poorly packed active materials, which create long and indirect paths through the electrolyte for the lithium ions to travel. In materials science, these paths are described as "tortuous." [1], As described in [1], these tortuous paths are akin to not having rows of seats in the auditorium, just randomly distributed clusters of seats. Further, conventional electrodes also use an excessive amount of inactive materials, both polymer binders and conductive additives, because it is difficult to distribute those inactive materials to only where they are needed in the electrode, which are the points where particles touch one another.

[0009] Another example is in catalysis where it may be advantageous to have the active catalyst materials placed at or near the surface of the coating to enable chemical reactants to easily reach the active catalytic sites and for products of the chemical reaction to be easily transported away once the chemical reaction is completed. With a homogeneous catalyst coating, the active catalyst sites that are placed deeper in the coating structure are less accessible to the chemical reactants and the products of the chemical reaction will also take longer to be transported away. Therefore, a uniform distribution of active catalyst sites does not always provide the optimum structure for catalysis.

[00010] Yet another example is in controlled release application where a compound, or a drug, is desired to be released in a controlled manner in a transport medium, such as a body fluid. With a homogeneous coating of the active drug material on a support, those active drug material placed at or near the surface of the coating will be released more quickly than those active drug material buried deeper in the coating microstructure leading to a non-uniform release of the active drug material. In this controlled release example, it may be more desirable to purposely place the active drug material deeper in the coating microstructure and not at the surface to effect a more uniform release of the active drug material.

SUMMARY

[00011] U.S. Patent No. 11,476,540, the entire disclosure of which, except for any definitions, disclaimers, disavowals, and inconsistencies, is incorporated herein by reference, discloses that coatings of the active material containing microstructure features are more desirable than simply a uniform coating to enhance the ionic diffusion of the coating.

[00012] Furthermore, improved lithium-ion diffusion kinetics of such structures can be achieved by an increase in active surface area. Laser ablation has been used to design electrode materials with increased surface area. Laser ablation is a technique of selectively removing by evaporating active material with a laser. To design and structure electrode materials using laser ablation, the active materials must first be coated on a support, resulting in a slower, more inefficient manufacturing process. The more complex the electrode design, the longer the process will take. Other inherent drawbacks of laser ablation are heat input to surrounding materials from the laser that may damage the electrode and material loss. It is important to minimize material loss to keep manufacturing costs down. Another potential drawback is that debris from laser ablation could interfere with the designed function.

[00013] Another technique used to design electrode materials with increased surface area is mechanical embossing. Mechanical embossing is a forming process in which a high pressure is applied to a structure to change its surface. This process, like laser ablation, is slow and may result in material loss. It also increases the difficulty of manufacturing unaligned designs from one layer to the next in a structure.

[00014] Thus, there is a need for a technique of depositing electrode materials having extended microstructure regions while manufacturing occurs, granting greater control over the electrode’s design and resulting in a more efficient manufacturing process. Such processes may also produce electrodes with rate capability retention and extended cycle life.

[00015] These and other aspects, objects, features, and advantages of the example embodiments will become apparent to those having ordinary skill in the art upon consideration of the following detailed description of illustrated example embodiments. [00016] According to one aspect, a method of manufacturing a structure is provided. The method includes the step of obtaining a deposit design, the deposit design comprising an indication of one or more extended microstructure regions. The method includes the step of obtaining a flowable liquid comprising an active material. The method includes the step of generating a plurality of droplets from the flowable liquid. The method includes the step of depositing the plurality of generated droplets on a support based on the deposit design by controlling at least one of a quantity, size, or placement of droplets deposited in the one or more extended microstructure regions.

[00017] According to another aspect, a structure comprising a plurality of stacked planar layers comprising an active material is provided. A first layer of the plurality of stacked planar layers comprises a first set of one or more extended microstructure regions. A second layer of the plurality of stacked planar layers different from the first layer comprises a second set of one or more extended microstructure regions. In some embodiments, at least one of a size, location, density, distribution, or shape, of the first set of one or more extended microstructure regions is different from a size, location, density, distribution, or shape of the second set of one or more extended microstructure regions.

BRIEF DESCRIPTION OF THE DRAWINGS

[00018] The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of embodiments of the invention.

[00019] FIG. 1A is a topographical scanning electron micrograph image of a structure, according to some embodiments.

[00020] FIG. IB is a topographical scanning electron micrograph image of a structure, according to some embodiments.

[00021] FIG. 2A illustrates a deposit design according to some embodiments.

[00022] FIG. 2B illustrates a deposit design according to some embodiments.

[00023] FIG. 2C illustrates a deposit design according to some embodiments.

[00024] FIG. 3 is a graph comparing specific rate capability of equivalent battery cells with and without extended microstructural features under different charging rates. [00025] FIG. 4 is a schematic representation of a structure, according to some embodiments.

[00026] FIG. 5 is a schematic representation of a structure, according to some embodiments.

[00027] FIG. 6 is a schematic representation of a structure, according to some embodiments.

[00028] FIG. 7 is a schematic representation of a structure, according to some embodiments.

[00029] FIG. 8 is a schematic representation of a structure, according to some embodiments.

[00030] FIG. 9 is a schematic representation of a structure, according to some embodiments.

[00031] FIG. 10 is a method of manufacturing a structure, according to some embodiments.

[00032] FIG. 11 is a topographical scanning electron micrograph image of a structure, according to some embodiments.

[00033] FIG. 12 is a topographical scanning electron micrograph image of a structure, according to some embodiments.

DETAILED DESCRIPTION

[00034] The present disclosure provides a structure with microstructure units whose properties may be controlled during the manufacture process using a deposit design. In some embodiments, the present disclosure introduces a unique electrode manufacturing technology to create different microstructure patterns such as shown in the example structures provided herein. Through the engineering of those patterns, which form part of a deposit design, one may modify at will the tradeoff between energy density and power density, also extending the cycle life of the battery.

[00035] In some embodiments, by selectively patterning the surface of an electrode using a deposit design, extended microstructures can have arbitrary shape, density and spatial distribution. That results in controllable performance enhancements. In some embodiments, the extended microstructures disclosed herein provide yet additional performance advantages, including when coupled with the techniques disclosed in U.S. Patent No. 11,476,540 for the creation of microstructural features. As disclosed herein, the extended microstructures may provide enhanced charging and discharging behavior. In some embodiments, the extended microstructures are in the 1-1000 micrometers range.

[00036] The manufacturing process may involve preparing a liquid comprising an active material, a binding material and, in some cases, additives that can be dispensed as droplets onto a support, where such droplets may self-assemble to form microstructure units in a continuous coating. Furthermore, the binding material may self-segregate from the active material so that the active material and/or binding material non-uniformly distribute in each of the microstructure units. The present disclosure further provides a method of manufacturing the structure, with which the non-uniform distribution of the active material and/or the binding material may be controlled to form microstructure units with desired properties according to a deposit design. [00037] In some embodiments, the self-assembly and self-segregation of the active material and the binding material may give rise to a number of phenomena. The self-assembly of droplets, containing the active material and the binding material, may create unique microstructure units in a continuous coating. In some battery applications, the active material may comprise a lithium intercalation or conversion material, or other electrical charge carrying species, to form the cathode and/or the anode electrode. The self-segregation of the binding material that may not impede ion diffusion, may greatly decrease the tortuosity of the diffusion pathways, thereby creating an additional “secondary pore network” [2] to enhance ion mass transport. This secondary pore network may have the effect of increasing the power density and charging speeds of the battery without compromising the energy density of the electrode. The self-segregation of the binding material to or near the edges of the microstructure unit may add structure strength to the microstructural unit, thereby increasing the mechanical integrity of the electrode. Also, the self-segregation of the active material may increase the parti cl e-to-p article contact of the active material, thereby increasing the electrical conductivity of the electrode.

[00038] In some embodiments, the active material may intercalate ions (e.g., lithium ions) or have a conversion reaction in the presence of ions (e.g., lithium ions). For example, the active material may facilitate the chemical reaction in which ions (e.g., lithium ions) are intercalated into a host matrix with essential retention of the crystal structure. In some embodiments, the active materials may comprise transition metals (e.g., nickel, cobalt, manganese, copper, zinc, vanadium, chromium, iron), and their oxides, phosphates, phosphites, sulfides, and silicates, as well as alkalis and alkaline earth metals, aluminum, aluminum oxides, and aluminum phosphates. Examples of active materials include LiCoCh, LiMmCh, LiFePCh, LiNii/3Mm/3Coi/302LiNio.8Coo.i5Alo.o502, LiCe, Li^isOn, LiNiCoAlCh, LiNiCoMnCh, LiNio.5Mm.5O4, Li2TiO3, Li(Nio.5Mm.5)02, Li2S, graphite (artificial or natural), hard carbon, titanate, titania, transition metals in general, halides, and/or chalcogenides, silicon, and other elements in group 14 (e.g., tin, germanium, etc.). In some examples, the active material may comprise LiFePO4. In some embodiments, the active material may be an insulator.

[00039] In some embodiments, the active material may be an active catalyst capable of causing or accelerating a chemical reaction between reactants, and the reactants and/or the products of the chemical reaction may be transported through the microstructure units. In some examples, the catalyst may be an enzyme or a chemical catalyst.

[00040] In some embodiments, the active material may be an active adsorbent capable of selectively binding to an adsorbate, and a medium carrying the adsorbate may be transported through the microstructure units. An active adsorbent may be a material (e.g., solid or semi-solid material) capable of bind to (e.g., selectively bind to) an adsorbate, which may be a gas, or dissolved substance or suspended particle in a solution, or a mixture thereof. In some embodiments, the active adsorbent may give a response when binding to an adsorbate. Such response may be a change in physical, chemical, electrical, optical, or magnetic properties, or any combination thereof of the adsorbent. In some examples, such a response may be a measurable response, e.g., a light, sound, electrical signal.

[00041] In some embodiments, the active material may be an active carrier of a compound, and wherein at least a part of the compound may be released in a controlled manner when contacted with a transport medium, and the transport medium may be transported through the microstructure units. For example, the transport medium may be capable of transporting the compound through the microstructure units. The transport medium may be in a gaseous, liquid or solid state. In one example, the transport medium may be a body fluid (e.g., blood, urine, or saliva).

[00042] In some embodiments, the active material may be an active carrier of a photosensitive compound, and the photo-sensitive compound may give an optical response when excited photonically. Examples of photo-sensitive compounds include fluorescent dyes. [00043] In some embodiments, the active material may be an active carrier of a magnetic- sensitive compound. The magnetic-sensitive compound may give a magnetic response when excited magnetically. In some embodiments, the active material may be an active carrier of a pigment. The pigment may have an optical response (e.g., generating an optical signal) when excited (e.g., with visible, ultraviolet or infrared light).

[00044] The binding material may be any material capable of facilitating the adherence of particles in the active material in the structure. In some examples, the binding material may comprise an organic material. In some examples, the binding material may comprise an inorganic material. In some examples, the binding material may comprise a combination or mixture of an organic material and an inorganic material. In one example, the binding material may be a polymer, e.g., poly vinylidene difluoride (PVDF), carboxyl-methyl cellulose (CMC), styrene-butadiene rubber (SBR), or a mixture or combination thereof.

[00045] The structure may comprise one or more additional components needed for a particular function. In some embodiments, the structure may comprise one or more conductive materials. Examples of conductive materials include carbon (e.g., nanometer-sized carbon) such as carbon black, graphite, ketjen black, a graphitic carbon, a low dimensional carbon (e.g., carbon nanotubes), and/or a carbon fiber.

[00046] In some embodiments, the structure may be coated on an electrode of a battery. The physical properties of the microstructure of the electrode coating may provide higher power density and higher energy density compared to an electrode coated with the same mass of active material but without the microstructure.

[00047] The applications of the method and the structure provided herein are not limited to batteries. For example, the method and the structure may be used in catalyst applications, pharmaceutical products, aerospace technologies, medical devices, and consumer goods, among others. For example, in a catalyst application, deliberate placement of the active catalyst materials near the surface of the microstructure units may allow the chemical reactants easy access to the active catalyst sites while allowing products of the chemical reaction to be transported away quickly from the active catalyst sites.

[00048] In one aspect, the present disclosure provides a method of manufacturing the structure described herein. In general, the method may comprise obtaining a deposit design, the deposit design comprising an indication of one or more extended microstructure regions, obtaining a flowable liquid comprising an active material and a binding material (e.g., a homogenous mixture of an active material and a binding material), generating a plurality of droplets from the flowable liquid, and depositing the plurality of generated droplets on a support based on the design of the deposit. When deposited on the support, the plurality of droplets may self-assemble to form a structure, which comprises a plurality of microstructure units and extended microstructure regions, and the active material and the binding material may selfsegregate to form a non-uniform distribution of the materials in each of the units.

[00049] The self-assembly of the droplets may be driven by the reduction of surface energy. Droplets may tend to coalesce and self-assemble to forms with the lowest surface energy. The self-segregation in a mixture of materials may be driven by surface charge properties. Coulombic repulsion may dominate when the surface charges are similar leading to selfsegregation. On the other hand, if surface charges are dissimilar, coulombic attraction may dominate, leading to self-coalescence. The ways to alter surface charge properties of a material may be to introduce a surfactant to enhance steric hindrance or add a coupling agent such as a silane.

[00050] In some examples, the self-segregated binding material may accumulate at edges of the units. The active material may be distributed within an area in each microstructure unit bounded by the respective unit. In some examples, the active material may be distributed non- uniformly within the area of each unit.

[00051] In some embodiments, the composition for manufacturing the structure may comprise a flowable liquid comprising an active material and a binding material. For example, the flowable liquid may comprise a homogenous mixture of an active material and a binding material.

[00052] In some embodiments, the flowable liquid may comprise a liquid carrier. For example, the binding material may comprise the liquid carrier. When the composition is deposited on a support, the liquid carrier may be allowed to evaporate to facilitate the formulation of the structure. In some examples, the liquid carrier may comprise an organic composition. For example, the liquid carrier may be an organic solvent, e.g., N- Methylpyrrolidone. In some examples, the liquid carrier may comprise an inorganic composition. In some examples, the liquid carrier may comprise a mixture or a combination of an organic composition and an inorganic composition. [00053] In some embodiments, the flowable liquid may comprise a material configured to change the surface charge of the active material and/or the binding material. In some examples, the material may be configured to change the surface charge of the active material. In some examples, the material may be configured to change the surface charge of the binding material. In some examples, the material may comprise a coupling agent (e.g., an agent capable of enhancing adhesion or bonding between two materials). For example, the coupling agent may be silane (e.g., binary silicon -hydrogen compounds and compounds with four substituents on silicon, including organosilicon compounds). Examples of silanes include trichlorosilane (SiHCE), tetramethylsilane (Si(CHs)4), and tetraethoxysilane (Si(OC2Hs)4)).

[00054] In some embodiments, the flowable liquid may comprise a material configured to change the zeta potential of the active material. In some examples, such a material may comprise a surfactant (e.g., a substance or compound comprising a hydrophobic tail and a hydrophilic head). Examples of surfactants include sodium stearate, 4-(5-dodecyl) benzenesulfonate, docusate (dioctyl sodium sulfosuccinate), alkyl ether phosphates, benzalkonium chloride (BAC), perfluorooctanesulfonate (PFOS), (2,[4,4-trimethylpentan-2-yl)phenoxy]ethanol, Octyl phenol ethoxylate, and hexadecyltrimethylammonium bromide (CTAB). In some examples, such a material may comprise a dispersant (e.g., a substance or compound, when added to a suspension of particles, capable of improving the separation of the particles and preventing their settling or clumping). Examples of dispersants include sodium pyrophosphate, ammonium citrate, sodium citrate, sodium tartrate, sodium succinate, glyceryl trioleate, phosphate ester, random copolymers, comb polymers, poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), ammonium polyacrylate, sodium polyacrylate, sodium polysulfonate, and polyethylene imine). In some examples, the dispersants may act sterically not only changing zeta potential. The surfactants may disperse and change/adjust surface tension.

[00055] In some embodiments, in the flowable liquid, a mass ratio between the active material and the binding material may be from 0.000001 to 1000000, e.g., from 0.000001 to 0.000005, from 0.000005 to 0.00001, from 0.00001 to 0.00005, from 0.00005 to 0.0001, from 0.0001 to 0.0005, from 0.0005 to 0.001, from 0.001 to 0.005, from 0.005 to 0.01, from 0.01 to 0.05, from 0.05 to 0.1, from 0.1 to 0.5, from 0.5 to 1, from 1 to 5, from 5 to 10, from 10 to 50, from 50 to 100, from 100 to 500, from 500 to 1000, from 1000 to 5000, from 5000 to 10000, from 10000 to 50000, from 50000 to 100000, from 100000 to 500000, or from 500000 to 1000000.

[00056] In some embodiments, the flowable liquid may have a viscosity from 1 to 2000 centipoise, e.g., from 3 to 1500, from 3 to 50, from 50 to 100, from 100 to 200, from 200 to 300, from 300 to 400, from 400 to 500, from 500 to 600, from 600 to 700, from 700 to 800, from 800 to 900, from 900 to 1000, from 1000 to 1100, from 1100 to 1200, from 1200 to 1300, from 1300 to 1400, or from 1400 to 1500 centipoise.

[00057] FIG. 1A is a topographical scanning electron micrograph image of a structure

IOOA, according to some embodiments. FIG. 1A shows an example structure 100A built according to the techniques described herein. The structure 100A comprises a plurality of microstructure units 104A, e.g., microstructure units in the shape of honeycombs, and two extended microstructure regions 102a-b.

[00058] FIG. IB is a topographical scanning electron micrograph image of a structure

IOOB, according to some embodiments. FIG. IB shows an example structure comprising microstructure units 104B, e.g., microstructure units in the shape of honeycombs, and six extended microstructure regions 102c-h.

[00059] In some embodiments a structure comprises a plurality of microstructure units. The structure may comprise an active material and a binding material. The active material and the binding material may self-segregate when being deposited on a surface or support when forming the structure. When segregated from the active material, the binding material may accumulate at certain areas of the units. Similarly, when segregated from the binding material, the active material may accumulate at certain areas of the units, which may be the same or different from the areas where the binding material accumulates. Such self-segregation of the active material and the binding material may cause non-uniform distribution of the materials in the structure, which form a microstructure comprising a plurality of units. The non-uniform distribution may be controlled by the manufacturing process so that the microstructure units have desired properties, e g., a desired physical, thermal, chemical, catalytic, electrochemical, electrical, magnetic, radioactive, photonic, or biological property, or any combination thereof. Each of the microstructure units may comprise an active material and a binding material. In some embodiments, each of the units may comprise more than one active material and/or more than one binding material. [00060] The microstructure units may be three-dimensional open-ended cells. In some embodiments, some or all of the microstructure units may comprise an area bounded by at least 3 sides, e.g., by 3, 4, 5, 6, 7, 8, 9, 10 or more sides. In some examples, the lengths of the sides may be substantially the same. In one example, a subset or all of the microstructure units (e.g., a majority of the microstructure units in the structure such as at least 50%, 60%, 70%, 80%, 90%, 95%, or 99% of the microstructure units in the structure) may comprise an area bounded by 6 sides. Such units may be bound by 6 sides with substantially the same length, e.g., in the shape of honeycomb cells.

[00061] In some embodiments a structure comprises a plurality of extended microstructure regions. The extended microstructure regions are those areas where the deposit design designates an unalike dispersion of droplets compared to the whole of the structure. In some embodiments, the deposit design may designate extended microstructure regions that comprise less material, more material, or no material. In some embodiments, the extended microstructure regions may comprise varying shapes and sizes. In some embodiments, the structure may comprise a plurality of extended microstructure regions. In some embodiments, the deposit design comprises an indication of one or more extended microstructure regions.

[00062] FIG. 2A illustrates a deposit design 206A. The deposit design 206A shown in FIG. 2A is a digital design fde with no extended microstructure regions. FIG. 2B illustrates a deposit design 206B according to some embodiments. The deposit design 206B is a hexagonal close packed distribution. The deposit design 206B indicates one or more extended microstructure regions as empty areas in the deposit design. FIG. 2C illustrates a deposit design 206C according to some embodiments. The deposit design 206C is a square packed distribution. The deposit design 206C indicates one or more extended microstructure regions as empty areas in the deposit design. In some embodiments, the one or more extended microstructure regions comprise an area of a structure in which a quantity of droplets should be controlled as part of a manufacturing process. In some embodiments, no droplets should be deposited in the one or more extended microstructure regions indicated in deposit design 206B or 206C. FIG. IB is an electrode made using the deposit design 206A shown in FIG. 2B.

[00063] In some embodiments, the volume and position of the droplets deposited on the surface may be controlled by a digitally controlled tool and a deposit design 206A-C. In some examples, the droplets may be generated and deposited by technologies that include but are not limited to: a printing technology (e.g., a 3D printing technology, drop-on-demand industrial inkjet printing technology, digital printing technology, or computer-controlled aerosol printing technology), digital fabrication technology, or digital deposition technology. Examples of printing technologies include those described in Hebner, T R et al., (1998) Appl. Phys. Lett., 72, 519-521(1998), Blazdell, P F et al., Mater. Process. Technol., 99, 94-102 (2000), Jacobs, HO, Science, 291, 1763-1766 (2001), Zhao, Y et al., Electrochim. Acta, 51, 2639-2645 (2006), and Xu, F et al., Chem. Phys. Lett., 375, 247-251 (2003), which are incorporated by reference herein in their entireties. In some examples, the methods and compositions described herein may allow a synthesis control of electrodes at the micro scale level, and obtaining 3D structures which improve the battery performance. In some examples, the digital deposition technology deposits the generated droplets according to the deposit design.

[00064] In some embodiments, the method may further comprise polymerizing the binding material. For example, the binding material may be polymerized by heat or irradiation. In some examples, the polymerization may be performed after the binding material and the active material self-segregate to fix the position or distribution pattern of the binding material and/or the active material.

[00065] FIG. 3 illustrates a graph comparing specific discharge capacity of battery cells with and without extended microstructure regions under different charging rates, referred to as C-rates. FIG.3 illustrates that a cell with extended microstructure regions has a better capacity retention at charging rates higher than 5C when compared to the cell without extended microstructures.

[00066] In some embodiments, the structure may comprise a continuous layer (e.g., a continuously planar layer). The layer may be along a planar surface of a support. In some embodiments, the structure may comprise a plurality of stacked layers (e.g., stacked planar layers).

[00067] In some embodiments, the structure comprises a layer comprising a plurality of the units along a planar surface of the support. In some embodiments, the structure comprises a plurality of stacked layers along a planar surface of the support and each stacked layer comprises a plurality of the units. In some embodiments, an average diameter in a first layer of the plurality of stacked layers is different from the average diameter of the microstructure units in a second layer of the plurality of stacked layers. In some embodiments, a first layer of the plurality of stacked layers comprises one or more of: a material that is different than one or more materials in a second layer of the plurality of stacked layers, or an active material that is the same as an active material in the second layer of the plurality of stacked layers, and the active material in the first layer has having a different physical, electrical, chemical, electrochemical or combinations thereof characteristic than the same active material in the second layer of the plurality of stacked layers.

[00068] In some embodiments, the structure may comprise at least 2, 5, 10, 50, 100, 150, 200, 250, 300, 350 stacked layers (e.g., stacked planar layers). In some examples, the first layer of the stacked layers may comprise an active material that is the same as an active material of a second layer of the stacked layers, and the first layer has different particle size characteristics than the second layer of the plurality of stacked layers. In some examples, the average diameters of the units on at least two layers may be different. In some examples, the average diameters of the units on at least two layers may be the same. In some examples, a first layer of the plurality of stacked layers may comprise a material that is different than one or more materials in a second layer of the plurality of stacked layers, or the same active material having a different physical, electrical, chemical, electrochemical or combinations thereof, characteristic in a second layer of the plurality of stacked layers.

[00069] In some embodiments, the structure comprises a plurality of stacked planar layers comprising an active material, wherein a first layer of the plurality of stacked planar layers comprises a first set of one or more extended microstructure regions, wherein a second layer of the plurality of stacked planar layers different than the first layer comprises a second set of one or more extended microstructure regions, and wherein at least one of a size, location, density, distribution, or shape, of the first set of one or more extended microstructure regions is different than a size, location, density, distribution, or shape of the second set of one or more extended microstructure regions. In some embodiments, a first planar layer is unaligned from the second planar layer.

[00070] FIGS. 4-9 are schematic representations of structures, according to some embodiments.

[00071] FIG. 4 is a schematic representation of a structure 400 comprising a plurality of planar layers 408 on a support 410, wherein the plurality of planar layers comprise a plurality of extended microstructure regions 402. FIG. 4 further illustrates that the extended microstructure regions 402 may be different sizes but also that the extended microstructure regions 402 may not be aligned between the plurality of planar layers 408.

[00072] FIG. 5 is a schematic representation of a structure 500 comprising a plurality of planar layers 508 on a support 510, wherein the plurality of planar layers 508 comprise a plurality of extended microstructure regions 502. FIG. 5 further illustrates that the extended microstructure regions 502 may be different sizes and shapes and that the extended microstructure regions 502 may not be aligned between the plurality of planar layers 508.

[00073] FIG. 6 is a schematic representation of a structure 600 comprising a plurality of planar layers 608 on a support 610, wherein the plurality of planar layers 608 comprise a plurality of extended microstructure regions 602. FIG. 6 further illustrates that the plurality of planar layers 608 may have different densities of extended microstructure regions 602 and that the extended microstructure regions 602 may not align between the plurality of planar layers 608

[00074] FIG. 7 is a schematic representation of a structure 700 comprising a plurality of planar layers 708 on a support 710, wherein the plurality of planar layers 708 comprise a plurality of extended microstructure regions 702. FIG. 7 further illustrates that the plurality of planar layers 708 may have different distributions of extended microstructure regions 702 and that the extended microstructure regions 702 may not align between the plurality of planar layers 808

[00075] FIG. 8 is a schematic representation of a structure 800 comprising a plurality of planar layers 808 on a support 810, wherein the plurality of planar layers 808 comprise a plurality of extended microstructure regions 802. FIG. 8 further illustrates that the extended microstructure regions 802 may be the same size and shape but also that the extended microstructure regions 802 may not be aligned between the plurality of planar layers 808.

[00076] FIG. 9 is a schematic representation of a structure 900 comprising a plurality of planar layers 908 on a support 910, wherein the plurality of planar layers 908 comprise a plurality of extended microstructure regions 902. FIG. 9 further illustrates that the extended microstructure regions 902 may be the same size and shape and that the extended microstructure regions 902 may be aligned between the plurality of planar layers 908.

[00077] FIG. 10 shows a flowchart of a method 1000 of manufacturing a structure, according to some embodiments. The method 1000 comprises Steps 1001, 1003, 1005, and 1007. Step 1001 comprises obtaining a deposit design, the deposit design comprising an indication of one or more extended microstructure regions. In some embodiments, the deposit design may be in a digital format. Step 1003 comprises obtaining a flowable liquid comprising an active material. Step 1005 comprises generating a plurality of droplets from the flowable liquid. Step 1007 comprises depositing the plurality of generated droplets on a support based on the deposit design by controlling at least one of a quantity, size, or placement of droplets deposited in the one or more extended microstructure regions. In some embodiments, the structure may comprise a plurality of microstructure units, and the active material and the binding material self-segregate to form a non-uniform distribution of the active material and the binding material in each of the units.

[00078] The method may further comprise controlling the sizes of the generated droplets. In some embodiments, the sizes of the droplets may be controlled by applying force to the flowable liquid. For example, the force may be mechanical pressure, collision with another liquid or fluid, ultrasonic waves, electrical charge, or a combination thereof. In some examples, the sizes of the droplets may be controlled by forcing the flowable homogenous liquid through orifices or openings of different sizes.

[00079] FIG. 11 is a topographical scanning electron micrograph image of a structure, according to some embodiments. FIG. 11 illustrates a micrograph of a structure 1100 with extended microstructure regions 1102 and microstructure units 1104. The structure 1100 is an electrode before calendering, and includes extended microstructure regions in the approximately 150 - 350 micrometers range. FIG. 12 is a topographical scanning electron micrograph image of a structure, according to some embodiments. FIG. 12 illustrates a micrograph of a structure 1200 with extended microstructure regions 1202 and microstructure units 1204. The structure 1200 is the electrode shown in FIG. 11 after calendering.

[00080] In another aspect, the present disclosure provides an article comprising the structure described herein. In some examples, the article may comprise a support coated with the structure. Such support may comprise a metallic fdm, a metallized plastic fdm, metallized polymer film, glass film, ceramic film, polymer film, or paper. In one example, the support may be a metallic film. In another example, the support may be a metallized film. In another example, the support may be a plastic film. In another example, the support may be a glass film. In another example, the support may be a ceramic film. In another example, the support may be a polymer film. In another example, the support may be paper. In some examples, the article may comprise a component filled with a material with the structure described herein.

[00081] In some embodiments, the article may be an electrochemical cell. The electrochemical cell may comprise one or more electrodes comprising (e.g., coated with) the structure described herein. In some examples, the electrode may comprise the structure with microstructure units, each of which is bounded by 6 sides, e.g., in a honeycomb shape. The electrode may comprise multiple layers of the structure. In some examples, at least two of the layers may be offset.

[00082] In some embodiments, the structure may be used to coat electrodes to improve the performance of batteries. In some examples, the techniques disclosed in U.S. Patent No.

11,476,540 may be used to control the placement of the active material and the binding material on a substrate, thereby allowing precision control of the electrode microstructure. In some examples, the structure coating the electrode may have a microstructure in the form of a honeycomb, e.g., with the binding material forming a honeycomb shape and the area within the honeycomb units filled with the active material. Such a structure may be layered in various ways to optimize electrochemical cell performance for different applications. In some examples, the electrode may comprise a single or a plurality of layers of printed honeycomb structures. [00083] The microstructure units in the structure on the electrode may have certain physical properties such as material densities, porosities, and binding material placement. In some embodiments, such properties may enhance the mass transport of ions (e.g., lithium ions) through the electrode, which may result in a higher power density when compared to electrodes using the same material but without the microstructure units. In some embodiments, the structure with the microstructure units may be stronger than the amorphous structure, leading to stronger battery electrodes with reduced or no electrode cracking. Since electrode cracking is one of the issues affecting battery life, the electrode with the structure described herein may create longer battery cycle life, when compared to electrodes with the same material but without the microstructure features.

[00084] In some embodiments, more than one component of the electrochemical cell may comprise the structure described herein. For example, cathode(s), anode(s), separator(s), solid or semi-solid electrolyte(s), other battery chemistries or electrical device(s), or any combination thereof, may comprise the structure (e.g., coated by the structure) for desired functions. For example, cathode(s), anode(s), separator(s), solid or semi-solid electrolyte(s), other battery chemistries or electrical device(s), or any combination thereof, may comprise the structure may be used as the support when making the structure.

[00085] As used herein, the singular forms “a,” “an,” and “the” include both singular and plural referents unless the context clearly dictates otherwise.

[00086] The term “optional” or “optionally” means that the subsequent described event, circumstance or substituent may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[00087] The recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within the respective ranges, as well as the recited endpoints.

[00088] The term “about” in relation to a reference numerical value and its grammatical equivalents as used herein can include the numerical value itself and a range of values plus or minus 10% from that numerical value. For example, the amount “about 10” includes 10 and any amount from 9 to 11.

[00089] The term “substantially the same” or “essentially the same” refers to a sufficiently high degree of similarity between two or more numeric values, compositions or characteristics that one of skill in the art would consider the difference between these values, compositions or characteristics to be of little or no statistical significance within the context of the property being measured. The difference between two substantially the same numeric values may, for example, be less than 10%.

[00090] The term “exemplary” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete fashion.

[00091] The following are certain enumerated embodiments further illustrating various aspects of the disclosed subject matter.

[00092] 1. A method of manufacturing a structure, the method comprising: obtaining a deposit design, the deposit design comprising an indication of one or more extended microstructure regions; obtaining a flowable liquid comprising an active material; generating a plurality of droplets from the flowable liquid; and depositing the plurality of generated droplets on a support based on the deposit design by controlling at least one of a quantity, size, or placement of droplets deposited in the one or more extended microstructure regions.

[00093] 2. The method of embodiment 1, wherein the flowable liquid comprises a homogenous mixture comprising an active material and a binding material.

[00094] 3. The method of embodiments 1 or 2, wherein the active material intercalates lithium ions or has a conversion reaction in the presence of lithium ions.

[00095] 4. The method of any one of embodiments 1-3, wherein the support is comprised in a cathode, anode, separator, solid electrolyte, semi-solid electrolyte, or insulator. [00096] 5. The method of embodiment 2, wherein the binding material is an organic material, inorganic material, or combinations thereof or wherein the binding material comprises a liquid carrier comprising an inorganic composition or organic composition.

[00097] 6. The method of embodiment 2, wherein the plurality of droplets selfassemble to form a continuous structure, wherein the continuous structure comprises a plurality of microstructure units, and wherein the active material and the binding material self-segregate to form a non-uniform distribution of the active material in each of the units.

[00098] 7. The method of embodiment 6, wherein the continuous structure forms around the one or more extended microstructure regions.

[00099] 8. The method of embodiment 6, wherein the active material imparts a physical, thermal, chemical, catalytic, electrical, magnetic, radioactive, photonic, biological, or combinations thereof property, or a combination thereof to the continuous structure.

[000100] 9. The method of any one of embodiments 1-8, wherein the deposit design comprises a plurality of extended microstructure regions, and wherein the plurality of extended microstructure regions are of different or the same sizes or shapes.

[000101] 10. The method of any one of embodiments 1-9, wherein the structure comprises a planar layer.

[000102] 11. The method of any one of embodiments 1-10, wherein the structure comprises a plurality of stacked planar layers, wherein the deposit design comprises a deposit design for each respective planar layer.

[000103] 12. The method of embodiment 11, wherein each deposit design for each planar layer has one or more extended microstructure regions. [000104] 13. The method of embodiment 12, wherein the one or more extended microstructure regions of a first deposit design for a first planar layer have a different shape or size than the one or more extended microstructure regions of a second deposit design for a second planar layer.

[000105] 14. The method of embodiment 12, wherein the one or more extended microstructure regions of a first deposit design for a first planar layer have the same shape or size as the one or more extended microstructure regions of a second deposit design for a second planar layer.

[000106] 15. The method of any one of embodiments 13 or 14, wherein the first deposit design has a different distribution, density, or alignment of extended microstructure regions than the second deposit design.

[000107] 16. The method of any one of embodiments 13 or 14, wherein the first deposit design has a distribution, density, or alignment of extended microstructure regions that is the same as the second deposit design.

[000108] 17. The method of any one of embodiments 1-16, wherein each of the one or more extended microstructure regions is 1-1000 micrometers.

[000109] 18 A structure comprising a plurality of stacked planar layers comprising an active material, wherein a first layer of the plurality of stacked planar layers comprises a first set of one or more extended microstructure regions, wherein a second layer of the plurality of stacked planar layers different than the first layer comprises a second set of one or more extended microstructure regions, and wherein at least one of a size, location, density, distribution, or shape, of the first set of one or more extended microstructure regions is different than a size, location, density, distribution, or shape of the second set of one or more extended microstructure regions.

[000110] Various embodiments are described herein. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s). Reference throughout this specification to “one embodiment,” “an embodiment,” “an example embodiment,” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” or “an example embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments. Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention.

[000111] All publications, published patent documents, and patent applications cited herein are hereby incorporated by reference to the same extent as though each individual publication, published patent document, or patent application was specifically and individually indicated as being incorporated by reference.

[000112] Various modifications and variations of the described methods, compositions, and kits of the invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been described in connection with specific embodiments, it will be understood that it is capable of further modifications and that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention that are obvious to those skilled in the art are intended to be within the scope of the invention. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure come within known customary practice within the art to which the invention pertains and may be applied to the essential features herein before set forth.

[000113] References

[000114] [1] Gene Berdichevsky, Gleb Yushin, “The Future of Energy Storage, Towards a

Perfect Battery with Global Scale” (Sila Nanotechnologies, Inc., Sep. 2, 2020).

[000115] [2] Usseglio-Viretta, F. L. E., Mai, W., Colclasure, A. M., Doeff, M., Yi, E., &

Smith, K. (2020). Enabling fast charging of lithium-ion batteries through secondary -/dual -pore network: Part I-Analytical diffusion model. Electrochimica Acta, 342, 136034. [0001 16] [3] J.-H. Rakebrandt, P. Smyrek, Y. Zheng, H.J. Seifert, W. Pfleging, Laser processing of thick Li(NiMnCo) 02 electrodes for lithium-ion batteries, in: Proceedings of SPIE, 2017, p. 100920M.

[000117] [4] J. Park, S. Hyeon, S. Jeonga, H.-J. Kim, Performance enhancement of Li-ion battery by laser structuring of thick electrode with low porosity, J. Ind. Eng. Chem. 70 (2019) 178.

[000118] [5] J.B. Habedank, L. Kraft, A. Rheinfeld, C. Krezdorn, A. Jossen, M.F. Zaeh,

Increasing the discharge rate capability of lithium-ion cells with laser-structured graphite anodes: modeling and simulation, J. Electrochem. Soc. 165 (7) (2018) A1563.

[000119] Abbreviations

[000120] C-Rate: C-rate is a measure of the rate at which a battery is charged or discharged relative to its capacity. It is the charge or discharge current in Amps divided by the cell capacity in Ampere-hours. A 1C rate means that the discharge current will discharge the entire battery in 1 hour. A C/5 rate means that the discharge current will discharge in the entire battery in 5 hours.

Claims

1. A method (1000) of manufacturing a structure (100A-B, 400, 500, 600, 700, 800, 900, 1100, 1200) the method comprising: obtaining (1001) a deposit design (206B-C), the deposit design comprising an indication of one or more extended microstructure regions (102a-h, 402, 502, 602, 702, 802, 902, 1102, 1202) obtaining (1003) a flowable liquid comprising an active material; generating (1005) a plurality of droplets from the flowable liquid; and depositing (1007) the plurality of generated droplets on a support based on the deposit design by controlling at least one of a quantity, size, or placement of droplets deposited in the one or more extended microstructure regions.

2. The method of claim 1, wherein the flowable liquid comprises a homogenous mixture comprising an active material and a binding material.

3. The method of claim 1 or 2, wherein the active material intercalates lithium ions or has a conversion reaction in the presence of lithium ions.

4. The method of any one of claims 1-3, wherein the support is comprised in a cathode, anode, separator, solid electrolyte, semi-solid electrolyte, or insulator.

5. The method of claim 2, wherein the binding material is an organic material, inorganic material, or combinations thereof or wherein the binding material comprises a liquid carrier comprising an inorganic composition or organic composition.

6. The method of claim 2, wherein the plurality of droplets self-assemble to form a continuous structure, wherein the continuous structure comprises a plurality of microstructure units (104A-B, 1104, 1204), and wherein the active material and the binding material selfsegregate to form a non-uniform distribution of the active material in each of the units.

7. The method of claim 6, wherein the continuous structure forms around the one or more extended microstructure regions.

8. The method of claim 6, wherein the active material imparts at least one of a physical, chemical, electrochemical, or electrical property to the continuous structure.

9. The method of any one of claims 1-8, wherein the deposit design comprises a plurality of extended microstructure regions, and wherein the plurality of extended microstructure regions are of different or the same sizes or shapes.

10. The method of any one of claims 1-9, wherein the structure comprises a planar layer (408, 508, 608, 708, 808, 908).

11. The method of any one of claims 1-10, wherein the structure comprises a plurality of stacked planar layers (408, 508, 608, 708, 808, 908), wherein the deposit design comprises a deposit design for each respective planar layer.

12. The method of claim 11, wherein each deposit design for each planar layer has one or more extended microstructure regions.

13. The method of claim 12, wherein the one or more extended microstructure regions of a first deposit design for a first planar layer have a different shape or size than the one or more extended microstructure regions of a second deposit design for a second planar layer.

14. The method of claim 12, wherein the one or more extended microstructure regions of a first deposit design for a first planar layer have the same shape or size as the one or more extended microstructure regions of a second deposit design for a second planar layer.

15. The method of claim 13 or 14, wherein the first deposit design has a different distribution, density, or alignment of extended microstructure regions than the second deposit design.

16. The method of claim 13 or 14, wherein the first deposit design has a distribution, density, or alignment of extended microstructure regions that is the same as the second deposit design.

17. The method of any one of claims 1-16, wherein each of the one or more extended microstructure regions is 1-1000 micrometers.

18 A structure comprising a plurality of stacked planar layers comprising an active material, wherein a first layer of the plurality of stacked planar layers comprises a first set of one or more extended microstructure regions, and wherein a second layer of the plurality of stacked planar layers different than the first layer comprises a second set of one or more extended microstructure regions.

19. The structure of claim 18, wherein at least one of a size, location, density, distribution, or shape, of the first set of one or more extended microstructure regions is different than a size, location, density, distribution, or shape of the second set of one or more extended microstructure regions.