System and method for dry powder coating layer of electrochemical cell

Abstract

To provide a system for forming a particle layer on a substrate.SOLUTION: A system 100 for forming a particle layer on a substrate may include at least one sprayer 104 and at least two masks 108A, 108B configured to selectively mask a substrate 101 in a first region and second region of the substrate 101. The at least one sprayer 104 may be configured to spray particles at the substrate 101. The at least two masks 108A, 108B maintain the first region and second region substantially free of the deposited material. A heater may be employed to heat the substrate 101 as the particles are sprayed by the at least one sprayer 104 onto the substrate.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] Related Applications

[0001] This application claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 62 / 848,849, filed May 16, 2019, the disclosure of which is incorporated by reference in its entirety into this specification.

[0002] Field The disclosed embodiments relate to systems and methods for dry powder coating layers of electrochemical cells. [Background technology]

[0003] background

[0003] Lithium ion batteries usually contain two or more electrodes separated by an electrically insulating material that is permeable to the diffusion of lithium ions between the electrodes. In some cases, one electrode contains an anode material coated onto a copper substrate, and the other contains a cathode material coated onto an aluminum substrate. The manufacture of these electrodes is traditionally carried out using a slurry method, in which the electrochemical material (e.g., anode or cathode material) is mixed with a polymeric binder (e.g., typically polyvinylidene fluoride resin, PVDF) dissolved in a suitable solvent (e.g., usually N-methylpyrrolidone). The resulting slurry is coated onto the electrode substrate. The solvent is then evaporated and recycled to form a dry layer of electrochemical material on the electrode surface. To remove all of the solvent from the electrode prior to incorporation into the battery, a huge amount of time and energy is expended during the use of large conveyor ovens and vacuum dryers that serve to dry the deposited slurry. Summary of the Invention [Means for solving the problem]

[0004] overview In some embodiments, a system for forming a particle layer includes at least one sprayer configured to spray particles toward a substrate, the particles including at least one selected from the group consisting of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material. The system also includes a first mask movable to selectively mask the substrate from the particles in a first region of the substrate and a second mask movable to selectively mask the substrate from the particles in a second region of the substrate, the at least one sprayer directing the spray of particles toward a portion of the substrate between the first mask and the second mask. The system also includes a heater configured to heat the substrate.

[0005]

[0005] In some embodiments, a method of depositing a material layer includes masking a first area of ​​a substrate, masking a second area of ​​the substrate, heating the substrate, and spraying first particles toward the heated substrate, the first particles including at least one selected from the group of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material, to form a first layer on the substrate.

[0006]

[0006] In some embodiments, a method of forming an electrode includes masking a first region of a substrate to inhibit material deposition on the substrate in the first region; masking a second region of the substrate to inhibit material deposition in the second region; applying first particles to the substrate to form a first layer, the first particles comprising at least one selected from the group of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material; and applying second particles to the first layer, the second particles comprising at least one selected from the group of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material, to form a second layer disposed on the first layer.

[0007]

[0007] It should be understood that the foregoing concepts and additional concepts discussed below may be arranged in any suitable combination, as the disclosure is not limited in this respect. Furthermore, other advantages and novel features of the present disclosure will become apparent from the following detailed description of various non-limiting embodiments when considered in conjunction with the accompanying drawings.

[0008] BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The accompanying drawings are not intended to be drawn to scale. In the accompanying drawings, each identical or nearly identical part shown in various figures may be represented by a similar reference numeral. For purposes of clarity, every part may not be labeled in every drawing. [Brief description of the drawings]

[0009] [Figure 1] 1 is a side schematic view of one embodiment of a spray deposition system. [Diagram 2]

[0010] 2 is a side schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Diagram 3]

[0011] 2 is a side schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Figure 4]

[0012] 2 is a side schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Diagram 5]

[0013] 2 is a top schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Figure 6]

[0014] 2 is a top schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Figure 7]

[0015] 2 is a top schematic view of the spray deposition system of FIG. 1 during a material deposition process. [Figure 8]

[0016] 2 is a top schematic view of material produced by the spray deposition system of FIG. 1. [Figure 9]

[0017] FIG. 9 is a schematic side view of the material of FIG. 8. [Figure 10]

[0018] FIG. 2 is a side schematic view of another embodiment of a spray deposition system. [Figure 11]

[0019] FIG. 11 is a side schematic view of the spray deposition system of FIG. 10 during a material deposition process. [Figure 12]

[0020] FIG. 11 is a side schematic view of the spray deposition system of FIG. 10 during a material deposition process. [Figure 13]

[0021] FIG. 11 is a side schematic view of the spray deposition system of FIG. 10 during a material deposition process. [Figure 14]

[0022] 11 is a top schematic view of a material produced by the spray deposition system of FIG. 10. [Figure 15]

[0023] FIG. 15 is a schematic side view of the material of FIG. [Figure 16]

[0024] 1 is a top schematic view of one embodiment of a material produced by a spray deposition system. FIG. [Figure 17]

[0025] FIG. 17 is a schematic side view of the material of FIG. 16. [Figure 18]

[0026] 1 is a side schematic view of yet another embodiment of a spray deposition system during a material deposition process. [Figure 19]

[0027] FIG. 19 is a side schematic view of the spray deposition system of FIG. 18 during a material deposition process. [Figure 20]

[0028] FIG. 19 is a side schematic view of the spray deposition system of FIG. 18 during a material deposition process. [Figure 21]

[0029] FIG. 19 is a side schematic view of the spray deposition system of FIG. 18 during a material deposition process. [Figure 22]

[0030] 1 is a top schematic view of yet another embodiment of a spray deposition system during a material deposition process. [Diagram 23]

[0031] 1 is a side schematic view of yet another embodiment of a spray deposition system during a material deposition process. [Figure 24]

[0032] 1 is a side schematic view of yet another embodiment of a spray deposition system during a material deposition process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Detailed Description

[0033] The present inventors have recognized that conventional processes for dry powder manufacturing of electrochemical cells have produced long lengths of coated material. Specifically, these processes are either continuous or semi-continuous, so that uniform coatings without gaps are formed on the substrate using these methods. Thus, creating suitable locations for attaching electrical leads to current collectors during the battery cell manufacturing process may involve removing a portion of the deposited material prior to calendaring. Furthermore, in some cases where these processes have used resistively heated substrates, current enters and exits the substrate through bare portions of the substrate and corresponding coated portions of the substrate, which may increase the overall resistance and therefore the energy consumption of the battery layer formation process.

[0011]

[0034] In view of the above, the inventors have recognized the benefit of a system for forming one or more layers deposited onto a substrate (such as a current collector) of an electrochemical cell, where two or more masks may selectively cover at least one first region and a second region of the substrate while a desired material is sprayed or otherwise applied onto the substrate to form a layer (e.g., an electrode layer, a separator layer, a solid electrolyte layer, etc.) on the substrate on one or either of two opposing sides of the substrate. The two or more masks may prevent the first region and the second region from being covered by the spray material such that the first region and the second region remain as bare regions of the substrate after deposition of one or more layers thereon. Depending on whether a deposited layer is applied to one or two opposing sides of the substrate, these masks and the corresponding masked bare regions of the substrate may be located on one or two opposing sides of the substrate. In some embodiments, bare regions may be used to represent areas where an otherwise continuous roll of substrate may be separated to form individual electrodes. The bare areas may also be used for welding electrical leads to current collectors during the subsequent battery formation process.

[0012]

[0035] The inventors have also recognized the benefit of employing two or more masks in contact with bare areas of the substrate to pass current through the substrate between the masks without passing current through the layers deposited on the substrate. Thus, resistive heat generated within the substrate by such a system may be more stable and efficient when current is passed directly into and out of the underlying substrate without passing through an intervening layer. This may also limit the area of ​​heat generation within the substrate to be within a portion of the substrate that corresponds to the target area where material is sprayed onto the substrate between the masks. The inventors have also recognized that such a configuration may allow multiple layers of various materials to be deposited in sequence while the substrate is resistively heated through the bare portions maintained by the masks.

[0013]

[0036] In some embodiments, a system for forming a particle layer on a substrate includes at least one sprayer configured to charge and spray particles including at least one selected from the group of electrochemical materials, ionically conductive materials, separator materials, conductive materials, binders, combinations of the above, and / or any other suitable materials for forming a layer toward the substrate in an electrochemical cell. Nevertheless, such particles may be used independently or in combination to form an electrode layer (e.g., an anode or cathode), a solid electrolyte layer, a separator layer, or any other desired material layer. The system may also include a first mask movable to selectively mask a first region of the substrate from the particles and a second mask movable to selectively mask a second region of the substrate from the particles. The first mask and the second mask may be clamps, shields, or other suitable movable objects that may cover the first and second regions of the substrate from the particles. The first and second regions may be positioned on opposite sides of the target region of the substrate toward which the at least one sprayer is directed such that corresponding bare regions of the substrate are positioned on opposite sides of the target region of the substrate to be coated by the at least one sprayer. Thus, the deposited material layer can be limited to a defined target area along the length of the substrate.

[0014]

[0037] In some embodiments, the above-described system may also include a heater configured to heat the substrate. The first mask and the second mask may be configured as first and second electrodes configured to pass a current through the substrate between the first and second masks. According to this embodiment, the heater may be configured to pass a current from the first mask through the substrate to the second mask to resistively heat the substrate internally. However, as detailed below, embodiments are also envisioned in which various heating methods are used by one or more heaters to heat the substrate, such as radiative, conductive, and / or convective heating methods, as the disclosure is not so limited.

[0015]

[0038] In some embodiments, the process of depositing a layer of a desired material onto a substrate may include: First, a first region and a second region spaced apart from one another along the length of the substrate may be masked. Then, the substrate may be heated (e.g., resistively heated). Then, a plurality of particles may be sprayed onto the substrate. In some embodiments, the particles may be sprayed without the use of a solvent. Furthermore, in some embodiments, the particles may be a mixture of a first material and a binder, a material pre-coated with a binder, and / or a material itself that can be bonded to the substrate and / or underlying layers. Nevertheless, in an embodiment, the particles may be aerosolized or otherwise transformed into a spray of particles that is directed toward a target region of the substrate in any suitable manner. In some examples, the aerosolized particles may be appropriately charged before being deposited onto the substrate. By virtue of the heating of the substrate and any layers already deposited thereon, the deposited material may adhere to the heated substrate or layer to form the desired layer disposed thereon.

[0016]

[0039] In some embodiments, it may be desirable to deposit two or more layers of material on a substrate. In such embodiments, first particles including at least one selected from the group of electrochemical materials, ionically conductive materials, conductive materials, and separator materials may be applied to a substrate. In some cases, these first particles may form a first electrode layer, such as an anode or a cathode, on the substrate when applied. For example, the first electrode layer may include both an electrochemical material and a solid electrolyte. Second particles including at least one selected from the group of electrochemical materials, ionically conductive materials, conductive materials, and separator materials different from the first particles may then be applied to the substrate on the first layer. In embodiments where the first layer is an electrode layer, the second particles may be made of a material for forming a separator layer and / or a solid electrolyte layer disposed on the electrode layer. Then, in some applications, a second electrode layer may be deposited on the separator layer and / or the solid electrolyte layer. For example, in one embodiment of a battery electrode manufacturing process, an anode layer, a solid electrode and / or separator layer, and a cathode layer may be sequentially deposited on a substrate using the methods and systems disclosed herein. Of course, the systems and methods described herein can be used to form any suitable number of material layers for any desired application, as the disclosure is not so limited.

[0017]

[0040] It should be understood that the disclosed deposition system may include any suitable heater that may be used to heat the substrate during the material deposition process. For example, in one embodiment, the heater may be configured to resistively heat the substrate by passing an electric current through the substrate to generate internal heat within the substrate. Alternatively, the heater employed with the spray deposition system may transfer heat to the substrate and associated deposition layer in any suitable manner, including convective, conductive, and / or radiative heat transfer. For example, suitable types of heaters may include, but are not limited to: radiant heaters; heated surfaces such as smooth heated glass or roller surfaces over which the substrate passes; heated ovens or other environments over which the substrate passes; hot air blowers; or any other suitable device capable of transferring heat to the substrate. Of course, combinations of the above heaters are also envisioned, as the present disclosure is not limited to any particular configuration of heater for heating the substrate.

[0018]

[0041] In some embodiments, a system for forming a particle layer on a substrate includes one or more pairs of calender rollers configured to compress and optionally heat the substrate and one or more layers of material deposited on the substrate as they pass between the opposing calender rollers to densify the one or more layers of material. In some embodiments, the calender rollers may be positioned following each sprayer along the production line so that the deposited material may be calendered to densify and / or sufficiently adhere to the substrate prior to depositing additional layers of material and / or completing the desired layering process. Alternatively, there may be a pair of calender rollers included in the system positioned following multiple sprayers along the direction in which the substrate moves through the system. The sprayers may sequentially deposit separate layers of material. Such an arrangement may thus allow multiple deposited layers of material to be calendered simultaneously by a single pair of calender rollers. It should therefore be understood that any suitable number of calender rollers may be included in the system at any suitable number of locations, as the present disclosure is not limited to any particular arrangement.

[0019]

[0042] According to some embodiments, the particle layer manufacturing process can be a semi-continuous or continuous process. In a semi-continuous process, the substrate can be intermittently passed through the system by a conveyor constructed to move the substrate through the system relative to various sprayers, heaters, calendar rollers, and / or other components. For example, the conveyor can correspond to a pair of rollers on which the substrate can be unwound from a first roller and wound onto a second roller to advance a preselected length of the substrate through the system between the rollers. At least one sprayer and at least one first and second mask can be disposed between the first and second rollers along the path of the substrate extending between the rollers. The first and second masks can be movable to selectively cover the first and second regions of the substrate, respectively, while the substrate is stationary. The at least one sprayer can then deposit material onto a target area of ​​the substrate between the first and second masked areas. The first and second masks may then be moved out of contact with the substrate to release or otherwise uncover the first and second regions over which the first and second rollers may advance the substrate. This semi-continuous process may be repeated multiple times for the entire substrate. As the material is advanced sequentially, the masks cover various regions of the substrate and the material is deposited onto multiple target regions along the length of the substrate while maintaining regions of the substrate between adjacent target regions free of deposition material. In another embodiment, the process may be continuous, where the first and second masks may move in synchrony with the substrate as the substrate is continuously passed through the system, as may occur as the substrate is continuously unwound from the first roller and wound onto the second roller. Additional masks may cover other regions of the substrate. Additionally, at least one fixed or movable sprayer may deposit material onto the substrate as the substrate passes through the system. Thus, such an arrangement may allow material to be continuously deposited onto the substrate. Of course, systems according to the exemplary embodiments described herein may be used in a continuous, semi-continuous, or discontinuous manner as the disclosure is not so limited.

[0020]

[0043] The system may include any suitable type of conveyor for transporting the substrate through the system to one or more sprayers used to deposit material onto the substrate. For example, the conveyor may move the substrate through the system in a direction from an upstream location to a downstream location. Suitable types of conveyors include, but are not limited to: opposing rollers between which the substrate may stretch so as to unwind from one roller and wrap onto the other roller, as disclosed herein; a movable platform and / or conveyor belt on which the substrate is disposed; and / or any other suitable device or structure capable of moving the substrate through the system for depositing one or more layers thereon.

[0021]

[0044] As used herein, a mask refers to any solid object suitable for substantially covering a desired portion of a substrate to prohibit particles from being sprayed or otherwise deposited on the substrate in the area covered by the mask. In some embodiments, the mask may be configured as a clamp or other selectively movable part that can be moved to and contacted with a desired portion of the substrate. Thus, in some embodiments, the mask may clamp the substrate to further prohibit the sprayed particles from covering the masked portion of the substrate. In other embodiments, the mask may be configured as a shield disposed between the sprayer and the substrate to effectively deflect particles from an area or portion of the substrate without physically contacting the substrate. Thus, the mask may be any suitable structure that prohibits material from being deposited on the substrate such that the portion of the substrate that is under the mask remains bare after the layer of material is deposited on the substrate. Again, any suitable structure capable of masking the substrate may be used, but possible structures may include, but are not limited to, a casing, a covering, a packaging, an envelope, a shield, a sheath, and / or any other suitable structure. Furthermore, these masks may be static and / or movable in and out of contact with the substrate depending on the embodiment.

[0022]

[0045] Depending on the particular application, the particles sprayed onto the substrate described above may correspond to any suitable material used in forming one or more layers in an electrochemical cell, including but not limited to an anode, a cathode, a separator, and / or a solid electrolyte layer. These materials may include ionically conductive materials, electrochemical materials, separator materials, conductive materials, binders, combinations of the above, and / or any other suitable materials. Furthermore, depending on the particular material, the material may be deposited by itself, may be mixed with a binder, and / or may be pre-coated with a binder. Thus, both embodiments are envisioned in which particles comprising a single material are sprayed onto a substrate to form a deposition layer on the substrate, and in which particles comprising a combination of various materials are co-sprayed and / or co-aerosolized to form a deposition layer on the substrate, as the disclosure is not so limited.

[0023]

[0046] As noted above, in some embodiments, the materials and processes described may be used to form one or more layers used in the manufacture of electrochemical cells. These layers may include one or more of an anode, a cathode, a separator layer, a solid electrolyte layer, and / or any other suitable layer present in a desired electrochemical cell. Examples of electrochemical cells may include, but are not limited to, batteries (primary and secondary), supercapacitors, fuel cells, and / or any other suitable electrochemical cells. However, while the specific materials and processes described herein are directed primarily to electrochemical cells and more specifically to lithium ion based chemistries, it should be understood that the methods and apparatus just described may be used to manufacture and deposit any suitable type of particulate material that is mixed with and coated with a binder, and / or has suitable material properties for adhering to a desired substrate including various types of electrochemical cell chemistries, as the present disclosure is not limited to any particular application and / or chemistry.

[0024]

[0047] To facilitate the fabrication of the aforementioned layers of an electrochemical cell, it may be desirable to sequentially deposit various types of materials in separate layers disposed on top of other layers using the methods described herein. For example, in one embodiment, a first particle including a first electrochemical material, such as an electrochemical material, may be deposited onto an electrode to form a first active layer corresponding to the anode or cathode of the electrochemical cell. A second material, such as a first ion-conducting material or a separator material, may then be deposited onto the first active layer to form a separator or solid electrolyte layer on the electrode. A third material, such as a second electrochemical material, may then be deposited onto the second layer to form a second active layer corresponding to the other of the anode and cathode of the electrochemical cell. Alternatively, other active layers may be deposited onto separate electrodes and assembled with the other layers via either a stacking or winding process. In some embodiments, high pressure calendering may be used to help densify the various layers, either during deposition of the various layers and / or simultaneously after each of the layers has been deposited onto the substrate.

[0025]

[0048] Possible electrochemical materials that may be used with the disclosed methods and systems may include, but are not limited to, lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium manganese cobalt oxide (LMCO), lithium iron phosphate (LFP), lithium manganese iron phosphate (LMFP), lithium nickel cobalt aluminum oxide (NCA), lithium titanate (LTO), silicon, sulfur, and / or combinations thereof. Although specific types of electrochemical materials are listed above, it should be understood that any suitable electrochemical material may be used as the disclosure is not limited to only these materials.

[0026]

[0049] Possible conductive materials that may be used with the disclosed methods and systems may include, but are not limited to, carbon (e.g., graphite) and / or any other suitable conductive material suitable for use in a particular electrochemical cell. It should be noted that carbon may also be used as an electrochemical material (e.g., a lithium ion anode) in some embodiments.

[0027]

[0050] For purposes of this disclosure, an ionically conductive material may include a material that facilitates both the transport of ions through the bulk of the material and / or the transport of ions along the interface between the material and a layer of binder material disposed on the particle surface. For example, Li2O particles may transport lithium ions through the bulk of the particle. In contrast, TiO2, when compounded with polyethylene oxide (PEO), may exhibit enhanced transport of lithium ions compared to either of these materials, which may be due to enhanced transport of lithium ions along the interface between the TiO2 particles and the PEO binder, without wishing to be bound by theory. Of course, it is envisioned that some particle-binder combinations may exhibit either one or both of these effects. In any case, however, these materials are still considered to be ionically conductive materials for purposes of this application.

[0028]

[0051] In view of the above, possible ionically conductive materials that may be used with the disclosed methods and systems may include one or more ionically conductive ceramics, such as metal oxides that facilitate the transport of ions along the interface with the metal oxide and / or binder (such as Al2O3, SiO2, TiO2, MgO, ZnO, ZrO2, CuO, CdO, and Li2O). Alternatively and / or in combination with the above-mentioned metal oxides, the ionically conductive material may be an ionically conductive glass, such as one or more of Li2S, P2S5, and xLi2S-(1-x)P2S5. Although certain types of ionically conductive materials are listed above, it should be understood that any suitable ionically conductive material may be used as the disclosure is not limited to only these materials.

[0029]

[0052] In some embodiments, the ionically conductive materials described above may be used to form the solid electrolyte layer. Alternatively, these materials may be mixed with one or more other materials (such as electrochemical materials, separator materials, conductive materials, and / or any other suitable materials) to increase the ionic conductivity of the layer.

[0030]

[0053] As noted above, in some embodiments, the separator layer may be formed over a previously deposited layer of material, such as an electrode of an electrochemical cell. In such embodiments, the separator may be formed of any suitable number of materials, including, but not limited to, polyethylene, propylene, or other polymers. In other embodiments, the separator layer may be formed of ceramic particles mixed with a polymer. In such embodiments, the ceramic particles may be compounded with the polymer during the spray deposition process. For example, premixed polymer particles with the ceramic particles or gas phase mixed and co-deposited polymer particles with the ceramic particles may be used. Alternatively, the ceramic particles may be pre-coated with the polymer prior to spray deposition.

[0031]

[0054] Suitable types of binders that may be used with the disclosed methods and systems may include, but are not limited to, any suitable thermoplastic polymer. It should be noted that the deposition of material layers without the use of solvents using the methods and systems described herein may improve the properties of the resulting electrochemical cell, but may allow for the use of binder materials that are not typically used in solvent-based deposition processes. For example, binders that are more ionically and / or electronically conductive than typical binders, but are not readily soluble in typical solvents, may be used to form the pre-coated particles. Thus, suitable polymers may include, but are not limited to, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyethylene oxide (PEO), polyacetylene, polyphenylene, polypyrrole, polythiophene, polyaniline, polyphenylene sulfide, and / or combinations of the above.

[0032]

[0055] Depending on the particular binder used, it may be desirable to increase the ionic conductivity of the binder material used. Thus, in some embodiments, an ionically conductive salt may be dissolved in the binder to improve ionic conductivity. In such embodiments, a lithium salt may be dissolved in the thermoplastic material of the binder. In such embodiments, the thermoplastic binder material may correspond to any of the polymers described herein and may include a lithium salt dissolved therein. Suitable lithium salts include, but are not limited to, LiClO4, LiBF4, LiPF6, LiAsF6, LiTf, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiTDI, LiPDI, LiDCTA, and LiB(CN)4. In one particular embodiment, the lithium salt may be dissolved in PEO to form PEO-LiX. Of course, other types of salts, including non-lithium based salts, may be used depending on the particular chemistry of the electrochemical cell in which the binder is used.

[0033]

[0056] As already mentioned above, in some embodiments, the binder may be applied during spray deposition of the material layer either as a separate powder that is co-sprayed with another material and / or the binder may be pre-coated onto particles of the desired material. In either case, any suitable amount of binder may be included in the material layer to provide the desired electrical conductivity combined with binder material properties for bonding the material layer to a substrate or underlying material layer. Thus, a material layer including a binder may include a percentage of binder that is 1%, 10%, 20% or more, or any other suitable percentage of binder. Accordingly, a material layer may include a percentage of binder that is 40%, 30%, 20%, 10% or less, or any other suitable percentage of binder. Combinations of the above ranges are envisioned, including, for example, material layers having a percentage of binder equal to 1%-40% or 1%-10%, or any other suitable percentage of binder both above and below the above percentages, as the disclosure is not so limited.

[0034]

[0057] The particles used with the spray deposition systems and methods described herein may have any suitable size, including microparticles and / or nanoparticles. For example, the particles may have a maximum transverse dimension (e.g., maximum diameter) that is equal to or greater than 10 nm, 50 nm, 100 nm, 250 nm, 1 μm, 100 μm, or any other suitable size. Similarly, the particles may have a maximum transverse dimension that is equal to or less than 300 μm, 250 μm, 100 μm, 1 μm, 250 nm, or any other suitable size. Combinations of the above ranges are envisioned, including, for example, particles having a maximum transverse dimension between 10 nm and 300 μm. Of course, particles having both dimensions greater than and less than the above-mentioned dimensions are also envisioned, as the disclosure is not so limited.

[0035]

[0058] As used herein, the terms coating, pre-coating, and other similar terms generally refer to a layer of material applied to the outer surface of a particle. In addition, this coating of material can either completely coat an individual particle and / or the coating can be applied to at least a portion of a particle such that the particle is not completely coated or encapsulated. In addition, the coating or encapsulation can be applied to a single particle, or multiple particles can be coated or encapsulated within a single outer shell or coating. For example, multiple particles, such as two or three particles, can be encapsulated or coated to form a single larger particle. Thus, it should be understood that multiple particles, including coated particles, can correspond to embodiments in which each particle is individually coated (e.g., when several particles are coated to form a larger composite particle, a particle that is only partially encapsulated, a particle that is completely encapsulated, and composites of these types of particles).

[0036]

[0059] Turning now to the attached drawings, specific non-limiting embodiments will be described in further detail. It should be understood that the various systems, components, features and methods described for these embodiments can be used either individually and / or in any desired combination, as the disclosure is not limited to only the specific embodiments described herein.

[0037]

[0060] FIG. 1 is a side schematic view of one embodiment of a spray deposition system 100 for forming a layer on a substrate. In particular, the spray deposition of FIG. 1 can be configured to form a battery electrode, including an anode or cathode material. As shown in FIG. 1, the spray deposition system includes a conveyor for moving a substrate 101, such as a metal foil, through the system. For example, in the depicted embodiment, the conveyor can include a first roller 102A and a second roller 102B between which the substrate is suspended. The first and second rollers are configured to move the substrate from one roller to the other (e.g., from the first roller to the second roller or from the second roller to the first roller). In either case, the substrate is unwound from one roller and wrapped onto the other roller so that the material can be deposited in a continuous or semi-continuous process as desired. However, embodiments in which the substrate is passed through the spray deposition system without the use of rollers are also envisioned, as the disclosure is not so limited. The spray deposition system also includes at least one sprayer 104 that is directed toward the substrate to deposit material thereon. For example, in some embodiments where it is desirable to deposit material on both sides of a substrate simultaneously, two sprayers 104 may be positioned on opposite sides of the substrate for depositing material onto the two sides of the substrate in a single process. In either case, the sprayers may be configured as spray guns or any other suitable device capable of aerosolizing, and in some embodiments suitably charging, a powder that is then sprayed onto the side of the substrate for a powder coating process.

[0038]

[0061] In the above embodiment, the sprayers are each connected to a reservoir 106 containing powder material for deposition on the substrate. In some embodiments, the reservoir may correspond to a fluidized bed, a venture atomizer, a Wright duster, or other suitable device capable of aerosolizing and / or otherwise transporting dry powder to the sprayer. As will be further discussed with reference to FIG. 2, the sprayer may charge the particles emitted from the spray gun, which may facilitate the particles being uniformly dispersed and deposited on an area of ​​the substrate targeted by the sprayer.

[0039]

[0062] As previously discussed, the powder materials may include any suitable material used in forming one or more layers in an electrochemical cell, including but not limited to an anode, a cathode, a separator, and / or a solid electrolyte layer. These materials may include ionically conductive materials, electrochemical materials, separator materials, conductive materials, binders, combinations of the above, and / or any other suitable materials. Furthermore, depending on the particular material, the material may be deposited by itself, mixed with a binder, and / or the material may be pre-coated with a binder.

[0040]

[0063] As shown in the embodiment of FIG. 1, the spray deposition system also includes a first mask 108A and a second mask 108B coupled to a first mask actuator 110A and a second mask actuator 110B, respectively. According to the embodiment of FIG. 1, the first mask and the second mask are configured as clamps that grip the upper and lower surfaces of the substrate 101 to selectively grip and cover some areas of the substrate to keep them bare during the spray deposition process. However, embodiments are also envisioned in which the first and second masks are applied to only one side of the substrate. The positions of the first and second masks are controlled by actuators such that the masks are movable between a first position in contact with the substrate and a second position not in contact with the substrate. For example, the first and second mask actuators can move the first and second masks closer to the substrate or further away from it. The first and second mask actuators can be electromechanical actuators (e.g., linear actuators, servo motors, DC motors, brushless motors, etc.), pneumatic actuators, hydraulic actuators, and / or any other suitable actuators suitable for moving the masks relative to the substrate. The first and second mask actuators are controlled by a first mask actuator controller 112A and a second mask actuator controller 112B that control the supply of electrical, pneumatic, and / or hydraulic fluids employed by the mask actuators to move the mask into and out of contact with the substrate. Of course, in other embodiments, the spray deposition system may employ a single mask actuator controller or any other suitable number of mask actuator controllers to control any suitable number of mask actuators, as the disclosure is not so limited. Additionally, these controllers may include at least one hardware processor and at least one associated non-transitory computer-readable storage medium that stores processor-executable instructions that control the actuators and other components of the system to perform the methods described herein when executed by the at least one hardware processor.

[0041]

[0064] According to the embodiment of FIG. 1, the first and second masks 108A, 108B are configured to pass an electric current provided by an associated power source through the substrate 101 between the first and second masks to resistively heat the substrate between the masks in the area where the one or more sprayers 104 are directed. That is, the passage of electric current through the substrate in combination with the substrate's internal electrical resistance generates internal heat within the substrate in that area of ​​the substrate between the first and second masks. For example, the first and second masks may be configured to function as electrodes in electrical contact with the substrate when the masks contact the substrate to mask bare areas of the substrate from the sprayed particles. Depending on the particular embodiment, the first and second masks may be constructed of any suitable conductive material or may include one or more conductive portions such that an electric current may be passed through the substrate through the first and second masks. It should be noted that the electric current may be passed through the substrate in any suitable direction. That is, in some embodiments, current may be passed from the first mask 108A to the second mask 108B, and in other embodiments, current may be passed from the second mask to the first mask, as the disclosure is not limited in this manner. Additionally, the conductive portions of the first and second masks that contact the substrate may be suitably sized to avoid hot spots from forming on the substrate via current crowding, and to further promote resistive heating. For example, in one embodiment, the conductive portions of the first and second masks may span the entire width of the substrate to mitigate potential hot spot formation, although smaller electrical contact sizes are also envisioned. In some embodiments, the mask actuator controllers 112A, 112B may also selectively pass current to the first and second masks 108A, 108B, so that the number of various controllers may be reduced. Of course, current may be passed to the masks using any suitable number of independent or combined controllers, as the disclosure is not so limited.

[0042]

[0065] It should be noted that while the embodiment of FIG. 1 uses the first and second masks as electrodes for passing current through the substrate, any suitable arrangement of electrodes may be employed for passing current through the substrate. For example, conductive rollers or conductive brushes at various locations may pass current through the substrate. For example, in some embodiments, the conductive rollers or brushes may pass current through the substrate and one or more layers of material deposited by the sprayer. That is, current may be passed into or out of the underlying substrate through a conductive roller or brush that is in electrical contact with a layer of material disposed on the substrate. In such an embodiment, a calendar roller may be used to pass or draw current through the layer of material to the substrate. In this embodiment, another roller or brush may be used to pass or draw current directly from the substrate at a location of the substrate that has not yet received a spray deposition. Of course, any suitable resistive heating arrangement may be employed as the disclosure is not so limited.

[0043]

[0066] As shown in FIG. 1, the spray deposition system 100 may also include a pair of calender rollers 114 that may be used to densify the deposited material layer. The calender rollers may be heated and may apply a sufficiently high pressure to the substrate and any layer of material that may be disposed on the substrate to densify and bond the layer to a desired thickness as the substrate passes between the pair of calender rollers. Thus, after the deposited material layer is passed through the calender rollers, the material layer may have a uniform density and thickness in addition to being denser than an uncalendered layer. In some embodiments, the calender rollers may be used to densify multiple material layers simultaneously.

[0044]

[0067] FIG. 2 is a schematic side view of the spray deposition system 100 of FIG. 1 during a material deposition process. As shown in FIG. 2, a first mask 108A and a second mask 108B are moved into contact with the substrate 101 to mask (i.e., cover) the bare areas of the substrate on both sides of the substrate so that the material to be deposited does not accumulate on the bare mask areas. However, again, embodiments are envisioned in which a material layer is deposited on one side of the substrate and a single pair of masks is used. While the masks are in the clamped position, the first and second rollers 102A, 102B, which control the motion of the substrate 101 extending therebetween, are held stationary. As previously discussed, the first and second masks may be configured as electrodes and may be in electrical communication with each other through the substrate in the clamped state shown in FIG. 2. When properly positioned, an electric current is passed through the first and second masks to resistively heat the substrate between the first and second masks. As shown in FIG. 2, two sprayers 104 located on opposite sides of the target area of ​​the substrate between the masks charge and aerosolize first particles 200, then spray the first particles toward the opposite exposed surface of the substrate. The first particles are supplied to the sprayers from a reservoir 106. The spray deposition process can be continued until a suitable amount of the first particles is deposited on the substrate between the first and second masks. The thickness of the deposited layer can be controlled by the deposition rate of the material emitted from the spray gun, the time of deposition, and / or other suitable control parameters. In some embodiments, the potential applied to the substrate through the first and second masks can be selected such that the charged particles are attracted toward the substrate. For example, the charged particles can be charged with a large negative or positive potential, and the potential applied by the first and second masks can be lower and / or opposite to the potential of the charged particles such that the charged particles are attracted to and stick to the substrate when sprayed. In one embodiment, one of the first mask and the second mask can be grounded such that at least a portion of the substrate adjacent the grounded mask is grounded.

[0045]

[0068] As previously noted above, various types of structures can be formed using the described processes, depending on what type of material is sprayed onto the substrate to form the deposition layer. For example, the disclosed systems can be used to deposit electrode layers, separator layers, solid electrolyte layers, conductive layers, and / or other suitable material layers. Thus, while several possible embodiments have been described above, it should be understood that the materials and processes of the present disclosure should not be limited to only these types of applications and structures.

[0046]

[0069] Although a reel-to-reel spray deposition system 100 is shown in Figures 1-2, it should be noted that alternative spray deposition systems may be employed that do not include the first roller 102A and the second roller 102B. In one such embodiment, the first mask 108A and the second mask 108B may be configured to hold the substrate stationary during spray deposition by the sprayer 104. That is, the first mask and the second mask may be used to selectively grip individual substrates disposed between and held in place by the masks such that the spray deposition process may be performed non-continuously.

[0047]

[0070] FIG. 3 is a schematic side view of the spray deposition system 100 of FIG. 1 during a material deposition process after a first material layer 202 has been deposited on the substrate 101. As shown in FIG. 3, a material layer of a desired thickness has been deposited from the sprayer 104 onto the substrate. The first mask 108A and the second mask 108A have been moved to a release position away from the surface of the substrate so that the substrate can be moved laterally through the system between the masks. That is, in the embodiment of FIG. 3, the first mask actuator 110A and the second mask actuator 110B move the first mask 102A and the second mask 102B, respectively, away from the substrate and out of contact with the substrate. As represented by the arrow adjacent to the second roller 102B, the first roller 102A and the second roller 102B can rotate (or another suitable conveyor structure can be actuated) to move the substrate through the system once the first mask 102A and the second mask 102B are no longer in contact with the substrate. The mask may be appropriately spaced from the substrate in an open configuration to avoid contacting the deposited layer as the substrate is moved. In the depicted embodiment, the first and second rollers rotate clockwise relative to the page to unwind the substrate from the first roller and wrap it onto the second roller, although the disclosure is not limited to this direction and / or method of substrate movement through the system. Thus, the first and second rollers move the deposited layer of material toward the calender roller 114 to calender it.

[0048]

[0071] FIG. 4 is a schematic side view of the spray deposition system 100 of FIG. 1 during a material deposition process subsequent to the state shown in FIG. 3. As shown in FIG. 4, the first deposition material layer is passed through the calender rollers 114 such that the first material is densified to form a calendered material layer 204. In some embodiments, the calender rollers can be heated to facilitate densification of the deposition material layer and adhesion of the deposition material layer to the substrate. As shown in FIG. 4, once the first deposition material layer is moved past the second mask 108B, the first and second rollers 102A, 102B can stop the substrate so that another first material layer is deposited on the substrate. That is, once the bare areas initially covered by the first mask 108A are aligned with the second mask 108B, the substrate can be stopped and the first and second masks moved to grip the substrate. The first mask actuator 110A and the second mask actuator 110B can move the first mask and the second mask toward and into contact with the substrate so that the bare areas of the substrate are covered. As shown in Figure 4, the sprayer 104 may deposit charged first particles 200 from a reservoir 106 onto both sides of the substrate while first and second masks shield the bare areas from particle deposition and pass a current through the substrate to resistively heat the substrate. Thus, the spray deposition system of Figures 1-4 sequentially deposits layers of material onto the substrate separated by masked bare areas. As previously mentioned, the bare areas may help ensure consistent resistive heating of the substrate within the target area of ​​the sprayer while also providing some areas of bare substrate that facilitate cutting of the substrate and / or attachment of electrical leads to the substrate during subsequent formation steps.

[0049]

[0072] It should be understood that the calender rollers 114 depicted in the above embodiment may be positioned at any suitable location in the system along the length of the substrate passing through the system. For example, the calender rollers may be positioned as depicted in the accompanying figures, or the calender rollers may be positioned over bare areas of the substrate to avoid applying heat and / or pressure to a portion of the deposited material layer during extended periods while a new target area of ​​the substrate is positioned between the masks. Thus, the calender rollers are not limited to only the depicted locations.

[0050]

[0073] FIG. 5 is a top schematic view of the spray deposition system 100 of FIG. 1 during a material deposition process. The state shown in FIG. 5 corresponds to a state subsequent to that shown in FIG. 4, where a plurality of first material layers 202 have been deposited and passed through the calender rollers 114 to form a plurality of calendered first material layers 204. Each of the calendered first material layers is separated from an adjacent calendered first material layer by a bare area 118 of the substrate corresponding to the area covered by the first mask 108A and the second mask 108B. The next target area 116 of the substrate is aligned between the first mask 108A and the second mask 108B for material deposition, and the previously deposited first material layer has been partially and / or completely calendered depending on the position of the calender rollers along the length of the substrate. Furthermore, in this particular configuration, the portion of the substrate already shielded by the first mask is now aligned with and shielded by the second mask.

[0051]

[0074] FIG. 6 is a top schematic view of the spray deposition system 100 of FIG. 1 following the state shown in FIG. 5. As shown in FIG. 6, the sprayer 104 sprays first particles toward a target area of ​​the substrate to form another first material layer 202 while a bare area adjacent to the target area is covered by a first mask 108A and a second mask 108B. The first mask and the second mask may contact the underlying substrate during the spraying process to effectively cover the underlying area of ​​the substrate and inhibit the sprayed particles from being deposited on the bare area. As shown in FIG. 6, the first mask and the second mask cover the entire width of the substrate, although embodiments are envisioned in which the masks extend partially across the width of the substrate and / or exhibit various configurations and / or shapes. In either case, when the masks are placed in contact with the substrate, an electric current may be passed between the first and second masks through the substrate to resistively heat the target area of ​​the substrate while the first particles are deposited from the sprayer 104.

[0052]

[0075] FIG. 7 shows a continuation of the process of FIG. 6. From the state shown in FIG. 6 where an additional first material layer 202 is deposited in the target area of ​​the substrate, the first mask 108A and the second mask 108B are moved out of contact with the substrate by an appropriate distance so as not to interfere with the substrate or the deposited material layer as the substrate is moved. The first roller 102A and the second roller 102B (or other suitable substrate handling system) are then actuated to move the substrate towards the calendar roller 114. Once the next target area 116 is aligned between the first and second masks, the first and second rollers are stopped. From this state, the first and second masks may be retracted and again contact the substrate at the bare area so that an additional material layer may be deposited. This process may be repeated as many times as desired to produce a series of sequentially arranged deposited material layers and bare areas along the length of the substrate.

[0053]

[0076] 8-9 are top and side schematic views, respectively, of materials produced by the spray deposition system of FIGS. 1-7. As previously mentioned, the final material produced by the spray deposition system of FIGS. 1-7 may be a substrate 101 having alternating regions of deposited material layers 204 and bare regions 118 located along the length of the substrate. Furthermore, in some embodiments, the material layers are calendered material layers, and each of the deposited calendered material layers may be at least partially separated from the other calendered material layers by a bare region. Thus, several sections of the substrate may be easily separated (i.e., cut) along the bare regions to produce various electrodes that may have electrical leads welded, soldered, or otherwise coupled to the substrate in the bare regions during a later formation process. Such materials may greatly simplify the manufacture of batteries or other electrochemical cells, since they eliminate additional processing steps that remove material from the substrate prior to calendering and / or attachment of electrical leads.

[0054]

[0077] 10-13 are side schematic views of another embodiment of a spray deposition system 300 in which multiple materials are sequentially deposited on a substrate. Similar to the embodiment of FIGS. 1-7, the deposition system shown in FIG. 10 may include a first roller 302A and a second roller 302B that allow the substrate 101 to be continuously unwound from one roller and wound onto the other roller. As shown in FIG. 10, the spray deposition system includes two separate stations in which various layers of materials are sequentially deposited. The first station of the spray deposition system includes a first sprayer 304A coupled to a first reservoir 306A to deposit first particles on the substrate. A first mask 308A and a second mask 308B also form part of the first station. The first mask 308A and the second mask 308B are configured to selectively contact the substrate to cover bare areas and define a first target area of ​​the substrate therebetween for material deposition. As in the embodiment of Figures 1-7, the first mask and the second mask are controlled by a first mask actuator 310A and a second mask actuator 310B, respectively. The first mask actuator and the second mask actuator are controlled by a first mask actuator controller 312A and a second mask actuator controller 312B. Finally, the first station may include a first set of calendar rollers 314A downstream of the first work station, which may be configured to densify the first material layer as it is deposited by the first sprayer 304A. The second station of the spray deposition system includes similar components to the first station. The second station includes a second sprayer 304B coupled to a second reservoir 306B. The second station also includes a third mask 308C and a fourth mask 308D defining a second target area therebetween for depositing material onto the substrate. The third and fourth masks may be coupled to a third mask actuator 310C and a fourth mask actuator, respectively, controlled by a third mask actuator controller 312C and a fourth mask actuator controller 312D. Finally, the second station may also include a second calender roller 314 downstream of the second station, configured to densify the second material layer deposited by the second sprayer.10-13 are configured to sequentially deposit and calendar two separate layers of material onto a substrate. Of course, although two stations for depositing two layers are described above, it should be understood that the system may include any number of deposition stations for sequentially depositing any number of different layers of material, as the present disclosure is not limited to the number of deposition stations included in the system.

[0055]

[0078] In the state shown in Figure 10, the spray deposition system is in a starting state where no layer of material has been deposited. Such a state may exist when a roll of substrate 101 is initially connected to the first roller 302A and the second roller 302B. As shown in Figure 10, each of the first, second, third, and fourth masks 308A-D are spaced apart from the substrate in this starting state.

[0056]

[0079] FIG. 11 depicts the spray deposition system of FIG. 11 during deposition of the first material layer 202. As shown in FIG. 11, the first mask 308A and the second mask 308B have been moved into contact with the substrate. Thus, bare areas of the substrate disposed under the first and second masks are shielded to remain bare and uncoated as the first particles 200 are dispensed from the first reservoir 306A and sprayed from the first sprayer 304A toward the substrate to form the first material layer 202 on the opposing sides of the substrate. Similar to the embodiment of FIGS. 1-7, the first sprayer 304A may charge the first particles 200 such that the first particles 200 are attracted to the substrate and uniformly distributed between the first mask and the second mask. According to the embodiment of FIGS. 10-13, the substrate may be configured to be resistively heated. As shown in Figure 11, the first mask 308A may function as a negative, ground, or low potential electrode, and the second mask 308B may function as a positive or high potential electrode, such that current is passed from the second mask to the first mask through the substrate to heat the substrate. Thus, both the first mask and the second mask shield bare areas from material deposition and function as heaters for the substrate. Of course, while the embodiment of Figure 11 is configured to pass current from the second mask to the first mask, the direction of current may be reversed in some other embodiments (i.e., by the first mask having a positive or high potential and the second mask having a negative, ground, or low potential), as the disclosure is not so limited.

[0057]

[0080] Once a sufficient amount of the first particles 200 have been deposited into the first material layer 202, the spray deposition system proceeds to the state shown in FIG. 12. As shown in FIG. 12, the first mask 308A and the second mask 308B have been moved to a spaced, non-contact position relative to the substrate by the first mask actuator 310A and the second mask actuator 310B. As the first roller 302A and the second roller 302B translate the first material layer and the substrate toward the second deposition station via the first calendar roller 314A, the second mask 308B can be spaced from the substrate by a sufficient dimension for the second mask to clear the first material layer 202. The first and second rollers move the substrate until the desired portion of the substrate is located between the third mask 308C and the fourth mask 308D (which can be positioned separated from each other by a distance equal to the separation distance between the first mask and the second mask). Thus, the third mask and the fourth mask may be aligned with corresponding bare areas of the substrate already covered by the first mask and the second mask when the spray deposition system advances to the state shown in FIG.

[0058]

[0081] As shown in Fig. 13, the previously deposited first material layer 202 was moved to be aligned between the third mask 308C and the fourth mask 308D. The rollers then stop the substrate so that an additional material layer can be deposited and the masks can be moved to contact the substrate in the bare portion of the substrate aligned with the masks. As shown in Fig. 13, the third mask 308C and the fourth mask 308D were moved by the third mask actuator 310C and the fourth mask actuator 310D, respectively, into contact with the substrate 101 such that the substrate is gripped by the third and fourth masks. Similarly, the first mask 308A and the second mask 308B were also moved by the first mask actuator 310A and the second mask actuator 310B into contact with another portion of the substrate. Thus, each of the first, second, third and fourth masks directly contacts and shields a corresponding portion of the substrate while particles are deposited onto the substrate from the first sprayer 304A and the second sprayer 304B. As shown in FIG. 13, the first sprayer deposits particles 200 onto the opposite side of the substrate to form an additional first material layer on the substrate. Meanwhile, the second sprayer 304B deposits second particles 206 from the second reservoir 306B onto the opposite calendered first material layer 204 to form a second material layer 208 on the opposite side of the substrate. As the layer is then translated through the system towards the second roller 302B, the first and second layers as well as the substrate may pass through the second calender roller 314B before being wrapped onto the second roller.

[0059]

[0082] As shown in FIG. 13, multiple layers of material may be deposited simultaneously in separate stations. As already mentioned, the substrate may be resistively heated in the target area as particles are deposited on the substrate. According to the embodiment of FIGS. 10-13, the third mask 308C and the fourth mask 308D may be configured as electrodes that pass current to the substrate at the second station of the spray deposition system. However, to avoid resistive heating of the substrate between adjacent deposition systems (e.g., between the second and third masks), the third mask and the fourth mask pass current in the opposite direction to the first mask 308A and the second mask 308B. That is, as shown in FIG. 13, the second mask 308B and the third mask 308C may be configured as positive or high potential electrodes, while the first mask 308A and the fourth mask 308D may be configured as negative, ground, or low potential electrodes. Thus, the current flows in the opposite direction from the second mask or the third mask outward toward either the first mask or the fourth mask. Thus, the masks adjacent to each other between the first and second stations may have equal potential so that no current is passed from the third mask to the second mask. Thus, this arrangement of masks may allow current to be passed exclusively to the substrate in the target area exposed to particle deposition (as opposed to heating the entire substrate). Such a configuration may reduce energy consumption or otherwise improve the efficiency of the spray deposition process. In addition to the above, in an embodiment where rollers are not used between sequentially arranged deposition stations (where material is sprayed onto two or more adjacent target areas of the substrate), a single mask may be placed between the adjacent target areas and may function as an electrode to heat both target areas due to the use of alternating high and low potential masks along the length of the substrate.

[0060]

[0083] In view of the above, it should be noted that a mask having any suitable positive, negative, relative, or ground potential may be positioned to isolate the passage of electrical current within a target area of ​​the substrate. Furthermore, in other embodiments, additional stations may be added to the spray deposition system, with the masks in adjacent stations sharing equal or similar electrical potentials to inhibit electrical current transmission through the substrate between stations. However, in some embodiments, electrical current may not be isolated to a particular station, and any desired portion (e.g., any length) of such a substrate, and potentially the entire substrate, may be resistively heated, as the present disclosure is not limited to embodiments in which resistive heating of the substrate is limited to within one or more deposition stations of the system.

[0061]

[0084] This process may continue to perform deposition cycles and periodically move the substrate through the system shown in FIG. 13 until the supply of substrate is exhausted. That is, the first, second, third, and fourth masks 308A-D may be moved out of contact with the substrate, and the first roller 302A and the second roller 302B may provide the first material layer 202 through the first calendar roller 314A and the second material layer 208 through the second calendar roller 314B. Thus, after being calendared, the second material layer may be wound onto the second roller 302B. The first and second rollers may stop the substrate when the next uncoated first material layer 202 is aligned between the third and fourth masks such that the state of FIG. 14 may be repeated. Thus, the spray deposition system may perform a semi-continuous process by advancing the substrate, stopping, depositing a material layer, and advancing the substrate again. The formed material may have a series of regions having a first material layer 202 and a second material layer 208 disposed on the first material layer separated by bare regions of the substrate.

[0062]

[0085] Although the embodiments of FIGS. 10-13 are shown having multiple stations that sequentially deposit layers of material after moving the substrate 101 between the multiple stations, in other embodiments, multiple stations may be combined into a single station where multiple layers of material are deposited without moving the substrate. For example, in some embodiments, multiple reservoirs of material may be coupled to one or more sprayers such that a first layer of material may be deposited and then a second layer of material may be deposited later without moving the substrate or any mask contacting the substrate. In another embodiment, multiple sprayers coupled to separate reservoirs may be in close proximity to each other such that both effectively target the same area of ​​the substrate. In this embodiment, a first sprayer may deposit a first layer of material and a second sprayer may deposit a second layer of material on top of the first layer of material without moving the substrate. Of course, the spray deposition system may use any suitable number of stations, sprayers, reservoirs, and masks as the disclosure is not so limited.

[0063]

[0086] Figures 14-15 are schematic top and side views, respectively, of material produced by the spray deposition system of Figures 10-13. As shown in Figures 14-15, a calendered second layer of material 208 is disposed over a calendered first layer of material 204, which is disposed on the opposite side of a substrate 101. Each cross section of the calendered first and second layers of material is separated from adjacent cross sections of the deposited layers of material by a bare region 118 of the substrate. As previously mentioned, such an arrangement improves manufacturing processes where it is desirable to easily separate some sections of a layer of material and / or to couple (e.g., by welding or soldering) the substrate to another structure, such as an electrical lead.

[0064]

[0087] In some embodiments, the materials of Figures 14-15 may be used to form a plurality of separate electrodes. In this embodiment, the calendered material layer 204 may be formed using an electrochemical material (i.e., an anode or cathode material). In such an embodiment, the calendered second material layer 210 may be a separator and / or a solid electrolyte layer. In some other embodiments, the first calendered material layer may also include a binder and / or a solid electrolyte. Of course, any suitable material or mixture of materials may be used to form the calendered first and second material layers as the disclosure is not so limited.

[0065]

[0088] 16-17 are top and side schematic views of one embodiment of a material produced by a spray deposition system. The material of FIGS. 16-17 is similar to FIGS. 14-15 with first and second material layers 204, 210 that are calendered. In addition, a calendered third material layer 214 may be disposed on the second material layer located on the opposite side of the substrate. In one embodiment, the first material layer 204 may include an electrochemical material for forming a first electrode layer (e.g., an anode or cathode). Accordingly, the second material layer 210 may be an ionically conductive material for forming a solid electrolyte or a separator material for forming a separator layer. The third material layer may be a second electrode layer that includes an electrochemical material different from the first electrode layer. Such an arrangement may be useful for forming multiple battery electrodes on a single substrate prior to use in a subsequent battery formation process. Of course, while specific material layers are discussed above, any material or material mixture may be deposited in any desired order and in any number of layers as the disclosure is not so limited.

[0066]

[0089] 18-21 are side schematic views of yet another embodiment of a spray deposition system 400 during a material deposition process. In contrast to the previous embodiments that performed a discontinuous or semi-continuous process, the spray deposition system of FIGS. 18-21 is configured to form a layer of material on a substrate 101 in a continuous process in which the substrate is constantly unwound from a first roller 402A and wrapped onto a second roller 402B. As shown in FIG. 18, the spray deposition system includes a first sprayer 402A coupled to a first reservoir 406A that directs a spray of material toward the opposing surface of the substrate in a first target area, and a second sprayer 404B coupled to a second reservoir 406B that directs a spray of material toward the opposing surface of the substrate in a second target area. The first and second sprayers deliver first and second particles, respectively. The spray deposition system also includes a first mask 408A and a second mask 408B controlled by a first mask actuator 410A and a second mask actuator 410B. The first mask actuator and the second mask actuator are operably coupled to a track 412 configured to allow the masks to move synchronously with the substrate while maintaining contact with the substrate to mask bare areas of the substrate as the first and second particles are deposited. In some embodiments, the track 412 may be continuous such that the track 412 is repeatedly recirculated within the system to mask the substrate as it is moved from the first roller to the second roller. The mask actuators may be coupled via a chain, belt, or other suitable structure that maintains a predetermined distance between each of the masks such that the material layers are deposited in equal length sections. Of course, the masks may be separated by any suitable equal, unequal, and / or variable distances as the disclosure is not so limited. As shown in FIG. 18, a third mask 408C and a third mask actuator 410C follow the first mask and the second mask along the track.

[0067]

[0090] According to the state shown in FIG. 18, the first mask 408A and the second mask 408B gripped the substrate 101 to effectively mask the bare area of ​​the substrate blocked by the mask. The first mask and the second mask define a target area of ​​the substrate between them, where a material layer is deposited. As shown in FIG. 18, when the target area between the first mask and the second mask crosses the first sprayer 404A, the first sprayer deposits the first particles 200 onto the substrate to form a first material layer. While flowing from the first reservoir 406A, the first particles can be charged by the first sprayer 404A and sprayed onto the substrate to form a first material layer. The substrate, the first mask and the second mask can move at a constant speed from the first roller to the second roller. According to this embodiment, the thickness of the first material layer can be controlled by the deposition rate of the material emitted from the first sprayer 404A, the speed of the substrate 101, and / or other suitable control parameters. While the first particles 200 are being ejected from the first sprayer, the substrate can be resistively heated by a current passed through the first mask and the second mask. According to some embodiments, and as shown in FIG. 18, the masks can be arranged with alternating potentials to ensure that a current is passed through each target area to heat the target area when passing under one of the first sprayer 404A and the second sprayer 404B. More specifically, the first mask has a positive or otherwise high potential, and the second mask and the third mask have a negative, ground, or low potential such that the current flows from the first mask to the second mask and / or the third mask. That is, in the state shown in FIG. 18, the current is passed from the first mask to the second mask and from the third mask to the first mask.

[0068]

[0091] FIG. 19 depicts the continuation of the spray deposition process from the state shown in FIG. 18. As shown in FIG. 19, the first material layer 202 has been deposited and the first sprayer 404A has stopped spraying. The substrate 101, the first mask 408A, the second mask 408B and the third mask 408C have been moved further toward the second roller 402B. When the third mask 408C is suitably adjacent to the substrate, the third mask actuator 410C can move the third mask into contact with the substrate to grip the substrate and define another target area of ​​the substrate between the first mask and the third mask. As already mentioned, each of the masks defines a bare area that is covered or shielded from the material sprayed by the first sprayer 404A and the second sprayer 404B.

[0069]

[0092] It should be noted that although a mask actuator is employed in the embodiments of Figures 18-21, the mask can be moved into or out of contact with the substrate by using a track. For example, in some embodiments, the track can move the mask closer to the substrate along certain portions of the track and further away from the substrate along other portions of the track to control the relative motion of the mask with respect to the substrate. Thus, these track portions can be positioned such that the mask is passively brought into and out of contact with areas of the substrate that are to be masked during the deposition process. In some embodiments, the mask actuator can be combined with various track shapes to move the mask in any desired direction relative to the substrate as the disclosure is not so limited.

[0070]

[0093] FIG. 20 is a continuation of the material deposition process from the state of the spray deposition system 400 shown in FIG. 19. As shown in FIG. 20, the substrate 101, the first mask 408A, the second mask 408B and the third mask 408C continue to move synchronously with each other toward the second roller 402B. Each of the first mask, the second mask and the third mask maintained contact with the underlying substrate and maintained the bare area where the substrate was contacted by the mask. In the state of FIG. 20, the target area of ​​the substrate defined by the first and second masks is adjacent to the second sprayer 404B which accordingly deposits the second particles 206 from the second reservoir 406B onto the first material layer 202 to form the second material layer 208. Meanwhile, the target area of ​​the substrate defined by the first and third masks is positioned adjacent to the first sprayer which deposits the first particles 200 into the first material layer directly disposed on the substrate. During the deposition of each of these layers, the substrate may be resistively heated by current passed from the first mask 408A to both the second mask 408B and the third mask 408C. Of course, in other embodiments, the direction of current passing may be reversed and current passed from the third mask and the second mask to the first mask as the disclosure is not so limited. As shown in FIG. 20, the fourth mask 408D and the fourth mask actuator 410D follow the third mask along the track 412 to define yet another target area between the third and fourth masks.

[0071]

[0094] FIG. 21 depicts the material deposition process following the state shown in FIG. 20. As shown in FIG. 21, the substrate 101, the first mask 408A, the second mask 208B, the third mask 408C, and the fourth mask 408D have been moved further towards the second roller 402B. The deposition of the second material layer 208 between the first and second masks is completed and the second mask has been moved by the second mask actuator 410B out of contact with the substrate. The released portion of the substrate including the second material layer 208 and the first material layer 202 is fed into the calender roller 414 which simultaneously densifies the first and second material layers prior to wrapping the substrate onto the second roller 402B. Once the second mask has released the substrate, the fourth mask 408D has been moved by the fourth mask actuator 410D into contact with the substrate. Thus, the third mask 408C and the fourth mask 408D may define further target areas therebetween for material deposition.

[0072]

[0095] Although the embodiment shown in Figures 18-21 depicts the timing of the first and second sprayers 404A, 404B such that the material is deposited in bursts (i.e., non-continuously), in other embodiments, the first and second sprayers may continuously deposit the material. That is, the first and second particles may be continuously ejected from the first and second sprayers as the substrate and mask move from the first roller 402A toward the second roller 402B. According to this embodiment, the sprayers may spray particles directly onto the substrate once the mask and substrate pass under the sprayers and are within a desired range. However, bare areas of the substrate may still be maintained under the mask in such an arrangement because the mask shields the underlying substrate.

[0073]

[0096] FIG. 22 is a top schematic view of yet another embodiment of a spray deposition system 500 during a continuous material deposition process. According to the embodiment of FIG. 22, the spray deposition system is similar to that of FIGS. 18-21, except that the system sequentially deposits three layers of material at various stations. As shown in FIG. 22, the system includes a first roller 502A and a second roller 502B that translate the substrate 101 by unwinding the substrate from the first roller and winding the substrate onto the second roller in a reel-to-reel process. The system includes a first sprayer 504A, a second sprayer 504B, and a third sprayer 504C, each of which sequentially deposits various materials or material mixtures onto the substrate. The system also includes a plurality of masks 508 and a mask actuator 510 arranged on a continuous track 512 that allows the substrate to be moved in a continuous motion into and out of contact with the substrate. For clarity, the masks and mask actuators in contact with the substrate are labeled as first mask 508A, first mask actuator 510A, second mask 508B, second mask actuator 510B, third mask 508C, third mask actuator 510C, fourth mask 508D and fourth mask actuator 510D. As already described with reference to the embodiment of Figures 18-21, the masks define target areas between them for material deposition such that each target area is separated from an adjacent target area by a bare area of ​​the substrate blocked by the mask. According to the embodiment of Figure 22, the first mask 508A and the third mask 508C are configured as negative, ground or otherwise low potential electrodes. In contrast, the second mask 508B and the fourth mask 508D are configured as positive or otherwise high potential electrodes such that current flows from the second and fourth electrodes to the first and third electrodes, respectively, to resistively heat the substrate as material is deposited by each of the sprayers.

[0074]

[0097] As shown in the embodiment of FIG. 22, the spray deposition system deposits three distinct layers of material that are simultaneously calendered before being wrapped onto the second roller 502B. That is, as the substrate passes through the first sprayer 504A, a first layer of material 202 is formed on the substrate. The substrate continues and is positioned adjacent to the second sprayer 504B, which deposits a second layer of material 208 on the first layer of material. Continuing, the substrate moves adjacent to the third sprayer 504C, which deposits a third layer of material 212 on the second layer of material. After the third layer of material is deposited, the mask closest to the calender roller 514 (which in the state shown in FIG. 22 is the fourth mask 508D) is moved out of contact with the substrate, and the substrate including the three layers is passed through the calender roller 514. As the three layers are calendered, the three layers are simultaneously densified to produce a calendered three-ply composite that is wrapped onto the second roller 502B. As previously stated, the three layers may comprise any desired material or mixture of materials as the disclosure is not so limited.

[0075]

[0098] It should be noted that although an elliptical track is shown and described with reference to the embodiment of FIG. 22, it should be understood that the track may have any suitable shape and any number of tracks may be used to handle the masks of the system, as the present disclosure is not limited to any particular number and / or arrangement of tracks in the system. Furthermore, in some embodiments, the spray deposition system may include multiple short tracks associated with multiple sprayers. In this embodiment, the mask may move to a start position of the track, contact the substrate, and move simultaneously with the substrate to the end of the track. When the mask reaches the end of the track, the mask may move out of contact with the substrate and travel in a direction opposite to the travel direction of the substrate to return to the start position of the track. Thus, the disclosed system may include any suitable track type and / or any suitable number of tracks, as the present disclosure is not so limited.

[0076]

[0099] Figure 23 is a side schematic view of yet another embodiment of the spray deposition system 100 during a material deposition process. The embodiment of Figure 23 is similar to that of Figures 1-7, except that instead of resistively heating the substrate, the spray deposition system heats the substrate by using a plurality of radiative heaters 120. As shown in Figure 23, the radiative heaters may be positioned on one or both sides of the substrate 101 to radiate heat towards the substrate such that the substrate is effectively heated as the first particles 200 are deposited from the sprayer 104 onto the substrate.

[0077]

[0100] Figure 24 is a side schematic view of yet another embodiment of the spray deposition system 100 during a material deposition process. Like the embodiment of Figure 23, the spray deposition system of Figure 24 employs a radiative heater that radiates heat to the substrate 101 as the first particles 200 are deposited on the substrate. In contrast to the embodiment of Figure 23, the radiative heat is directed to a first side of the substrate and the first particles are deposited in the first material layer 202 on a second side opposite the first side. Such an arrangement may facilitate even more consistent heating of the substrate within the target area compared to a heater that heats the substrate prior to being moved within the target area.

[0078]

[0101] It should be understood that aspects of the various embodiments described herein may be combined or substituted. Furthermore, the exemplary embodiment spray deposition systems disclosed herein may deposit a single layer or material layer onto one side or two opposing sides of a substrate. In addition, the disclosed spray deposition systems may deposit material layers onto a substrate as part of a discontinuous, semi-continuous, or continuous process. The disclosed spray deposition systems may also employ actuators that move individual masks into or out of contact with the substrate or combination actuators that move multiple masks simultaneously. Finally, the disclosed spray deposition systems may sequentially deposit multiple material layers at different times either in a single station and / or in separate physically separated deposition systems, as the disclosure is not so limited.

[0079]

[0102] While the present teachings have been described in conjunction with various embodiments and examples, it is not intended that the present teachings be limited to such embodiments or examples. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those skilled in the art. Accordingly, the foregoing description and drawings are by way of example only.

Claims

1. A system for forming a particle layer, at least one sprayer configured to spray particles including at least one selected from the group consisting of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material toward the substrate; a first mask movable to selectively mask the substrate from particles in a first region of the substrate; a second mask movable to selectively mask the substrate from particles in a second region of the substrate, the at least one sprayer directing the spray of particles toward a portion of the substrate between the first mask and the second mask; and The system includes a heater configured to heat the substrate.

2. The system of claim 1 , wherein the first mask is an actuator-actuated clamp, the clamp configured to selectively grip the substrate.

3. The system of claim 2 , wherein the actuator is a pneumatic, hydraulic, or electrical actuator.

4. 2. The system of claim 1, wherein the at least one sprayer includes a first sprayer configured to spray particles toward a first side of the substrate and a second sprayer configured to spray particles toward a second side of the substrate opposite the first side of the substrate.

5. 2. The system of claim 1, wherein the first mask is a first electrode configured to electrically contact the substrate, the second mask is a second electrode configured to electrically contact the substrate, and the heater is configured to pass a current from the first mask to the second mask through the substrate to resistively heat the substrate.

6. The system of claim 1 , further comprising a conveyor configured to move at least a portion of the substrate relative to the at least one sprayer.

7. 7. The system of claim 6, wherein the conveyor includes a first roller and a second roller configured to move the substrate such that at least a portion of the substrate moves from the first roller toward the second roller, and the substrate is unwound from the first roller and wrapped onto the second roller.

8. 7. The system of claim 6, wherein the conveyor is configured to move the substrate relative to the at least one sprayer while the particles are sprayed toward the substrate, and the first mask and the second mask move synchronously with the substrate.

9. The system of claim 1 further comprising the substrate being a metal foil.

10. The system of claim 1 , wherein the particles further comprise a binder.

11. 2. The system of claim 1, wherein the at least one sprayer comprises a first sprayer and a second sprayer, the first sprayer configured to spray first particles toward the substrate to form a first layer disposed on the substrate, and the second sprayer configured to spray second particles toward the substrate to form a second layer disposed on the first layer.

12. 1. A method for spray depositing a layer of material, comprising: Masking a first area of ​​a substrate; masking a second area of ​​the substrate; heating the substrate; and 1. A method comprising: spraying first particles toward the heated substrate, the first particles comprising at least one selected from the group consisting of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material, to form a first layer on the substrate.

13. 13. The method of claim 12, wherein spraying the first particles toward the heated substrate comprises spraying the first particles toward a first side of the substrate and a second side of the substrate opposite the first side.

14. 13. The method of claim 12, wherein heating the substrate comprises passing a current through the substrate through a first mask in contact with the substrate and a second mask in contact with the substrate to resistively heat the substrate.

15. 13. The method of claim 12, wherein masking the first area of ​​the substrate comprises gripping the substrate with a first clamp and masking the second area of ​​the substrate comprises gripping the substrate with a second clamp.

16. The method of claim 15 , further comprising moving the substrate relative to the first and second clamps.

17. The method of claim 16 , further comprising moving the heated substrate while the first particles are sprayed toward the substrate.

18. The method of claim 12 further comprising calendering the first layer.

19. The method of claim 12 , wherein the first particles further comprise a binder.

20. The method of claim 12 further comprising spraying second particles onto the first layer to form a second layer disposed on the first layer.

21. 1. A method of forming an electrode, comprising the steps of: masking a first region of a substrate to inhibit deposition of material on the substrate in the first region; masking a second region of the substrate to inhibit material deposition in the second region; applying first particles to the substrate to form a first layer, the first particles including at least one selected from the group consisting of an electrochemical material, an ionically conductive material, an electrically conductive material, and a separator material; and applying second particles to the first layer, the second particles comprising at least one selected from the group of the electrochemical material, the ionically conductive material, the electrically conductive material, and the separator material to form a second layer disposed on the first layer.

22. 22. The method of claim 21 , wherein applying the first particles and the second particles comprises spraying the first particles toward the substrate and spraying the second particles toward the first layer.

23. 22. The method of claim 21, wherein the first particles comprise the electrochemical material and the second particles comprise the separator material and / or the ionically conductive material.

24. 22. The method of claim 21 further comprising sequentially calendering the first layer and the second layer.

25. 22. The method of claim 21 further comprising simultaneously calendering the first layer and the second layer.

26. The method of claim 21 , further comprising heating the substrate.

27. 27. The method of claim 26, wherein heating the substrate comprises passing a current through the substrate through a first mask in contact with the substrate and a second mask in contact with the substrate to resistively heat the substrate.

28. 22. The method of claim 21 , wherein masking the first region of the substrate comprises gripping the first region of the substrate with a first clamp, and masking the second region of the substrate comprises gripping the second region of the substrate with a second clamp.

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