Systems and methods for dry powder coating layers on electrochemical cells - Patents.com

Abstract

A system for forming a particle layer on a substrate can include at least one sprayer and at least two masks configured to selectively mask the substrate in first and second regions of the substrate. The at least one sprayer can be configured to spray particles onto the substrate, and the at least two masks maintain the first and second regions substantially free of deposition material. A heater can be employed to heat the substrate as the particles are sprayed onto the substrate by the at least one sprayer.

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 typically 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 the anode material coated onto a copper substrate, and the other contains the 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., the 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. Significant amounts of time and energy are expended to remove all of the solvent from the electrode prior to incorporation into the battery. deposition This is expended in the use of large conveyor ovens and vacuum dryers to help dry the 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] In some embodiments, the layer of material deposition The method includes masking a first area of ​​a substrate, masking a second area of ​​the substrate, heating the substrate, and spraying 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 toward the heated substrate to form a first layer on the substrate.

[0006] In some embodiments, a method of forming an electrode includes masking a first region of a substrate and depositing a material on the substrate in the first region. deposition a second region of the substrate is masked to inhibit the material in the second region; deposition 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 to form a second layer disposed on 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.

[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. [Figure 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, because these processes are performed in either a continuous or semi-continuous manner, uniform coatings without voids are formed on substrates using these methods. Thus, providing suitable locations for attaching electrical leads to current collectors during the battery cell manufacturing process can be accomplished by forming a suitable coating prior to calendaring. deposition Additionally, in some cases where these processes have used resistively heated substrates, current enters and exits the substrate through bare portions of the substrate and correspondingly covered portions of the substrate, which can increase the overall resistance and therefore the energy consumption of the cell layer formation process.

[0011]

[0034] In consideration of the above, the present inventors have deposition In an electrochemical cell substrate, 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 both of the opposing sides of the substrate. The ... the 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 both of the opposing sides of the substrate. deposition The first and second regions may be prevented from being covered with the spray material so that they are subsequently maintained as bare regions of the substrate. depositionDepending on whether the layers are applied to one or two opposing sides of the substrate, these masks and the corresponding masked bare areas of the substrate may be located on one or two opposing sides of the substrate. In some embodiments, the bare areas 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 present inventors also deposition The inventors have 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 maintained by the masks. Thus, resistive heat generated within the substrate by such a system may be more stable and efficient if 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 to be sprayed onto the substrate between the masks. The inventors have also recognized that such an arrangement may be advantageous in that multiple layers of various materials may be sequentially applied while the substrate is resistively heated through the bare portions maintained by the masks. deposition We realized that this could enable the

[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 a 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 a 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, deposition The applied layer of material 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, a layer of a desired material is deposited on a substrate. depositionThe process of applying a coating to a substrate may include the following: First, a first region and a second region spaced apart from one another along the length of the substrate may be masked. Next, the substrate may be heated (e.g., resistively heated). Next, a plurality of particles may be sprayed onto the substrate. In some embodiments, the particles may be sprayed without the use of a solvent. Further, 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. Nonetheless, in an embodiment, the particles may be aerosolized or otherwise converted into a spray of particles that is directed toward the target region of the substrate in any suitable manner. In some examples, the aerosolized particles are sprayed onto the substrate. deposition The substrate and any existing material thereon may be suitably charged before being applied to the substrate. deposition Thanks to the fact that any layer that is applied is heated, deposition The applied material may be adhered to a heated substrate or layer to form the desired layer disposed thereon.

[0016]

[0039] In some embodiments, two or more layers of material are provided on the substrate. deposition In such an embodiment, first particles including at least one selected from the group of electrochemical material, ionically conductive material, conductive material, and separator material may be applied to the substrate. In some cases, these first particles, when applied, may form a first electrode layer, such as an anode or cathode, on the substrate. 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 material, ionically conductive material, conductive material, and separator material different from the first particles may then be applied to the substrate on top of the first layer. In an embodiment 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, the second electrode layer may be applied to the substrate on the separator layer and / or the solid electrolyte layer. depositionFor example, in one embodiment of a battery electrode manufacturing process, an anode layer, a solid electrode and / or separator layer, and a cathode layer can be sequentially deposited onto a substrate using the methods and systems disclosed herein. deposition 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] Disclosed deposition The system is a material deposition It should be understood that the heater may include any suitable heater that may be used to heat the substrate during the process. For example, in one embodiment, the heater may be configured to resistively heat the substrate by passing an electrical current through the substrate to generate internal heat within the substrate. Alternatively, the spray deposition The heaters employed with the system may transfer heat to the substrate and associated devices in any suitable manner, including convective, conductive, and / or radiative heat transfer. deposition Heat may be transferred to the layer. For example, suitable types of heaters may include, but are not limited to: radiant heaters; a heated surface such as a smooth heated glass or roller surface over which the substrate passes; a heated oven or other environment over which the substrate passes; a hot air blower; 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 a substrate and a particle layer on the substrate. deposition The calender rollers may include one or more pairs of calender rollers configured to compress and optionally heat the layer or layers of material applied thereto as they pass between the opposing calender rollers to densify the layer or layers of material. In some embodiments, the calender rollers may include one or more pairs of calender rollers configured to compress and optionally heat the layer or layers of material applied thereto as they pass between the opposing calender rollers to densify the layer or layers of material. deposition and / or prior to completing the desired layering process. deposition To densify the material and / or to bond it well to the substrate depositionA pair of calendar rollers may be placed at a location following each sprayer along the production line so that the material can be calendered. Alternatively, there may be a pair of calendar rollers included in the system that are placed at a location following multiple sprayers along the direction that the substrate moves through the system. The sprayers apply separate layers of material in sequence. deposition Thus, such an arrangement may be deposition It may be possible for the layers of material to be calendered simultaneously by a single pair of calender rollers, and therefore, it should be understood that any suitable number of calender rollers may be included in the system in 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 positioned 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 first and second regions of the substrate, respectively, while the substrate is stationary. The at least one sprayer then applies material to a target area of ​​the substrate between the first and second masked areas. deposition 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 across the substrate. As the material is advanced sequentially, the masks cover various regions of the substrate and the material may cover areas of the substrate between adjacent target regions. deposition onto multiple target areas along the length of the substrate while remaining free of material. depositionIn another embodiment, the process may be continuous, where the first mask and the second mask may move in synchronization with the substrate as it is continuously passed through the system, such as may occur as the substrate is continuously unwound from the first roller and wrapped onto the second roller. Additional masks may cover other areas of the substrate. Additionally, at least one fixed or movable sprayer may spray material onto the substrate as the substrate passes through the system. deposition Such an arrangement therefore allows the material to be deposited continuously on the substrate. deposition 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 deposits the material onto the substrate. deposition The conveyor may include any suitable type of conveyor for transporting the substrate through the system to one or more sprayers used to apply the spray to 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 that it can be unwound from one roller and wrapped onto the other roller, as disclosed herein; a movable platform and / or conveyor belt on which the substrate is disposed; and / or a conveyor belt that can apply one or more layers thereto. deposition The present invention also includes any other suitable apparatus or structure capable of moving a substrate through a system for performing a process on a substrate.

[0021]

[0044] As used herein, a mask refers to a device that allows particles to be sprayed or otherwise applied onto a substrate in areas covered by the mask. depositionA mask refers to any solid object suitable for substantially covering a desired portion of a substrate to prohibit a layer of material from being sprayed onto the substrate. In some embodiments, a mask may be configured as a clamp or other selectively movable part that can be moved into contact with a desired portion of a substrate. Thus, in some embodiments, a mask may clamp the substrate to further prohibit the sprayed particles from covering the masked portion of the substrate. In other embodiments, a mask may be configured as a shield that is 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, a mask prevents a portion of the substrate that is beneath the mask from blocking the spray of a layer of material from being sprayed onto the substrate. deposition The material is then applied to the substrate so that it remains bare after application. deposition The mask may be any suitable structure that prevents the substrate from being exposed to the light. 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 to move 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 itself be deposition The material may be pre-coated with a binder, mixed with a binder, and / or the material may be pre-coated with a binder. deposition In an embodiment, particles containing a single material are sprayed onto a substrate to form a layer; deposition Both embodiments are envisioned in which particles comprising combinations of different materials are co-sprayed and / or co-aerosolized to form layers.

[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 cell. However, while the specific materials and processes described herein are directed primarily to electrochemical cells, and more specifically to lithium ion based chemistries, the present disclosure is not limited to any particular application and / or chemistry, and therefore the methods and apparatus just described may be used to produce and bond any suitable type of particulate material to be mixed with and coated with a binder, and / or to have suitable material properties for adhesion to a desired substrate, including various types of electrochemical cell chemistries. deposition It should be understood that the present invention may be used to

[0024]

[0047] To facilitate the fabrication of the above-mentioned layers of the electrochemical cell, various types of materials can be sequentially fabricated in separate layers that are disposed on top of other layers using the methods described herein. deposition For example, in one embodiment, first particles including a first electrochemical material, such as an electrochemical material, are deposited onto an electrode to form a first active layer corresponding to an anode or cathode of an electrochemical cell. deposition A second material, such as a first ion-conducting material or separator material, may then be applied onto the first active layer to form a separator or solid electrolyte layer on the electrode. deposition 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. deposition Alternatively, the other active layers can be deposited on separate electrodes. deposition The laminate may be laminated together and assembled with other layers either through a stacking or winding process. In some embodiments, high pressure calendering may be used to separate the various layers. depositionbetween and / or on the substrate deposition It may be used to help densify the various layers either simultaneously after being applied.

[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 previously formed, such as an electrode in an electrochemical cell. deposition 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 sprayed. deposition It can be combined with the polymer during the process. For example, premixing polymer particles with ceramic particles or gas-phase mixing and co-mixing with ceramic particles. deposition Polymer particles may be used. Alternatively, ceramic particles may be sprayed. deposition The substrate may be pre-coated with a polymer prior to application.

[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. The methods and systems described herein may be used to form layers of material without the use of solvents. deposition Solvent-based electrochemical cells can improve the performance of the resulting electrochemical cells. deposition It should be noted that the process may allow for the use of binder materials not normally used. 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 is sprayed onto the material layer as a separate powder that is co-sprayed with another material. deposition Either the binder may be applied into the material layer 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 within 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 percentages of binder equal to 1%-40% or 1%-10%, or any other suitable percentages of binder both above and below the above percentages, as the disclosure is not so limited.

[0034]

[0057] The spraying described herein depositionThe particles used by the systems and methods 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 or 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 shows a spray pattern for forming a layer on a substrate. deposition FIG. 1 is a schematic side view of one embodiment of the system 100. deposition The spray can be configured to form a battery electrode including an anode or cathode material. deposition The 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 conveyed through the conveyor such that the material is conveyed in a continuous or semi-continuous process as desired. deposition The substrate may be unwound from one roller and wrapped onto the other roller so that the substrate can be sprayed without the use of rollers, however, as the disclosure is not so limited. deposition Embodiments in which the system is passed through are also envisioned. deposition The system also applies material to it. deposition The at least one sprayer 104 can be directed toward the substrate to spray material onto both sides of the substrate simultaneously. deposition In some embodiments, it may be desirable to deposit the material onto both sides of the substrate in a single process. deposition Two sprayers 104 may be positioned on opposite sides of the substrate for spraying the powder onto the surface of the substrate. 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, the powder that is then sprayed onto the surface of the substrate for the powder coating process.

[0038]

[0061] In the above embodiment, each of the atomizers is provided on the substrate. depositionThe spray gun is connected to a reservoir 106 containing powder material for spraying. 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 distributed 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. Additionally, depending on the particular material, the material may itself be a material that is suitable for use 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. deposition The material may be pre-coated with a binder, may be mixed with a binder, and / or the material may be pre-coated with a binder.

[0040]

[0063] As shown in the embodiment of FIG. deposition The 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 arranged to spray certain areas of the substrate. depositionThe masks are configured as clamps that grip the top and bottom surfaces of the substrate 101 to selectively grip and cover to keep it bare during the process. However, embodiments are envisaged 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 may move the first and second masks closer to the substrate or further away from it. The first and second mask actuators may 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 fluid employed by the mask actuators to move the masks into and out of contact with the substrate. Of course, in other embodiments, the first and second mask actuators may be configured to move the masks closer to the substrate or further away from the substrate. deposition The system may employ a single mask actuator controller or any other suitable number of mask actuator controllers controlling any suitable number of mask actuators, as the disclosure is not so limited. Further, these controllers may include at least one hardware processor and at least one associated non-transitory computer-readable storage medium storing processor-executable instructions that, when executed by the at least one hardware processor, control the actuators and other components of the system to perform the methods described herein.

[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 although the embodiment of FIG. 1 uses first and second masks as electrodes for passing a current through the substrate, any suitable arrangement of electrodes may be employed for passing a current through the substrate. For example, conductive rollers or conductive brushes at various locations may pass a current through the substrate. For example, in some embodiments, a conductive roller or brush may be in contact with the substrate and the sprayer. deposition Electric current may be passed through the sprayed layer or layers of material. That is, electric current may be passed into or out of the underlying substrate via a conductive roller or brush that is in electrical contact with the layer of material disposed on the substrate. In such an embodiment, the calendar roller may be used to pass or draw electric current through the layer of material to the substrate. In this embodiment, a separate roller or brush may be used to apply the electric current to the sprayed layer or layers of material. deposition This may be used to pass or draw current directly from the substrate at locations on the substrate that have not yet received a resistive heating circuit. Of course, any suitable resistive heating arrangement may be employed as the disclosure is not so limited.

[0043]

[0066] As shown in Figure 1, spray deposition The system 100 also includes: deposition It may include a pair of calender rollers 114 that may be used to densify the layer of material. 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 the layer to a desired thickness and bond it to the substrate as the substrate passes between the pair of calender rollers. Thus, deposition After the material layer is passed through the calender rollers, the material layer may have a uniform density and thickness in addition to being denser than a non-calendered layer, hi some embodiments, the calender rollers may be used to densify multiple material layers simultaneously.

[0044]

[0067] Figure 2 shows the material deposition Figure 1 Spraying in process deposition 2 is a schematic side view of the system 100. As shown in FIG. 2, the first mask 108A and the second mask 108B are depositionThe mask layer was then 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 being applied would not accumulate on the bare mask areas. However, once again, a layer of material was applied to one side of the substrate. deposition An embodiment is also envisaged in which the masks are clamped 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 stretched therebetween, are held stationary. As already 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 the first particles 200, and then spray the first particles toward the opposite exposed surfaces of the substrate. The first particles are supplied to the sprayers from a reservoir 106. Spraying deposition The process includes depositing a suitable amount of first particles onto a substrate between a first and a second mask. deposition This can continue until deposition The thickness of the layer is determined by the amount of material ejected from the spray gun. deposition speed, deposition The time of spraying may be controlled by, and / or other suitable control parameters. In some embodiments, the potentials applied to the substrate through the first mask and the second mask may be selected such that the charged particles are attracted towards the substrate. For example, the charged particles may be charged with a large negative or positive potential, and the potentials applied by the first and second masks may 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 may be grounded such that at least a portion of the substrate adjacent to the grounded mask is grounded.

[0045]

[0068] As mentioned above, depositionDepending on what type of material is sprayed onto the substrate to form the layers, various types of structures can be formed using the described processes. 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. deposition 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] Reel-to-reel spraying deposition An alternative spray system 100 may be used as shown in FIGS. 1-2 but does not include the first roller 102A and the second roller 102B. deposition It should be noted that the system may be employed in one such embodiment. In one such embodiment, the first mask 108A and the second mask 108B are sprayed by the sprayer 104. deposition The first mask and the second mask may be configured to hold the substrate stationary during spraying. deposition It can be used to selectively grip individual substrates disposed between and held in place by the masks so that the process can be performed non-sequentially.

[0047]

[0070] FIG. 3 shows a first material layer 202 on a substrate 101. deposition Material after it has been cut deposition Figure 1 Spraying in process deposition 3 is a schematic side view of the system 100. As shown in FIG. 3, a layer of material of a desired thickness is sprayed from a sprayer 104 onto a substrate. depositionThe first mask 108A and the second mask 108B have been moved to a release position such that they are spaced from the surface of the substrate so that the substrate may 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 108A and the second mask 108B, respectively, away from and out of contact with the substrate. Once the first mask 108A and the second mask 108B are 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 may rotate (or another suitable conveyor structure may be activated) to move the substrate through the system. The masks rotate as the substrate is moved. deposition The substrate may be appropriately spaced from the substrate in an open configuration to avoid contact with the layer. In the depicted embodiment, the first roller and the second roller rotate clockwise relative to the page to unwind the substrate from the first roller and wrap it onto the second roller, however, the disclosure is not limited to this direction and / or method of substrate movement through the system. Thus, the first and second rollers may be deposition The layer of finished material is moved towards calender rollers 114 for calendering.

[0048]

[0071] FIG. 4 shows the material following the state shown in FIG. deposition Figure 1 Spraying in process deposition FIG. 4 is a schematic side view of the system 100. deposition The layer of material is passed through calender rollers 114 such that the first material is densified to form a calendered layer of material 204. In some embodiments, the calender rollers deposition Densification of the material layer and attachment to the substrate deposition Heat may be applied to facilitate adhesion of the layers of material. As shown in FIG. deposition As the layer of material is moved past the second mask 108B, the first and second rollers 102A, 102B deposit another layer of the first material onto the substrate. depositionThat is, once the bare areas initially covered by the first mask 108A are aligned with the second mask 108B, the substrate may be stopped and the first and second masks moved to grip the substrate. The first mask actuator 110A and the second mask actuator 110B may move the first mask and the second mask towards and into contact with the substrate such that the bare areas of the substrate are coated. As shown in FIG. 4, the sprayer 104 sprays the first and second masks with particles to coat the bare areas. deposition The charged first particles 200 are then pumped from the reservoir 106 to both sides of the substrate while the substrate is shielded from the outside and a current is passed through the substrate to resistively heat it. deposition Therefore, the sprays in Figs. deposition The system deposits layers of material sequentially onto the substrate separated by bare areas blocked by a mask. deposition As previously mentioned, the bare regions 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 located 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 apply heat and / or pressure for an extended period of time while a new target area of ​​the substrate is positioned between the masks. deposition The calender rollers may be positioned over bare areas of the substrate to avoid applying to portions of the material layer, and thus are not limited to only the depicted locations.

[0050]

[0073] Figure 5 shows the material deposition Figure 1 Spraying in process deposition 5 is a top schematic view of the system 100. The state shown in FIG. 5 corresponds to a state subsequent to that shown in FIG. 4, in which a plurality of first layers of material 202 are calendered to form a plurality of calendered first layers of material 204. depositionThe calendered first layers of material are then passed through calender rollers 114. Each calendered first layer of material is separated from an adjacent calendered first layer of material by a bare area 118 of the substrate corresponding to the area covered by the first mask 108A and the second mask 108B. A next target area 116 of the substrate is then applied to the calendered first layer of material. deposition For this reason, the first mask 108A and the second mask 108B are aligned with each other, as previously described. deposition The applied first layer of material is partially and / or fully calendered depending on the position of the calender rollers along the length of the substrate, and further, in this particular configuration, portions of the substrate that were already masked by the first mask are now aligned with and masked by the second mask.

[0051]

[0074] FIG. 6 shows the spray of FIG. 1 following the state shown in FIG. deposition 6 is a top schematic view of the system 100. 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 and second masks effectively cover underlying areas of the substrate such that the sprayed particles are deposited on the bare area. deposition 6, the first and second masks 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, a current is applied to the first particles from the sprayer 104. deposition The substrate may be passed between first and second masks to resistively heat a target area of ​​the substrate while it is being heated.

[0052]

[0075] Figure 7 shows a continuation of the process of Figure 6. An additional layer of first material 202 is deposited in the target area of ​​the substrate. deposition From the state shown in FIG. 6, the first mask 108A and the second mask 108B are moved to the substrate or depositionThe first and second rollers 102A and 102B (or other suitable substrate handling system) are then actuated to move the substrate toward the calender 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 are moved out of contact with the substrate by an appropriate distance so as not to interfere with the layer of material. deposition The process can be repeated in a series of sequentially positioned electrodes along the length of the substrate. deposition This may be repeated as many times as desired to create material layers and bare areas.

[0053]

[0076] Figures 8-9 show the sprays in Figures 1-7. deposition 1-7 are schematic top and side views, respectively, of the material produced by the system. deposition The final material produced by the system is located along the length of the substrate. deposition The material layer may be a substrate 101 having alternating areas of calendered material layer 204 and bare areas 118. Further, in some embodiments, the material layer is a calendered material layer; deposition Each of the calendered layers of material may be at least partially separated from the other calendered layers of material by a bare area. Thus, several sections of the substrate may be easily separated (i.e., cut) along the bare areas to produce various electrodes that may have electrical leads welded, soldered, or otherwise coupled to the substrate in the bare areas during a later forming process. Such materials may greatly simplify the manufacture of batteries or other electrochemical cells, by eliminating additional processing steps that remove material from the substrate prior to calendering and / or attachment of electrical leads.

[0054]

[0077] Figures 10 to 13 show how multiple materials are sequentially applied to a substrate. deposition Spraying to be done deposition FIG. 10 is a schematic side view of another embodiment of a system 300. depositionThe system 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. deposition The system is designed so that various layers of material are deposition It includes two separate stations where spraying is performed. deposition The first station of the system is coupled to a first reservoir 306A and deposits first particles onto a substrate. deposition The first station includes a first sprayer 304A for spraying the material over the bare areas. 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 cover the bare areas and spray the material over the bare areas. deposition 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 includes a first sprayer 304A downstream of the first work station. deposition The spray may include a first set of calender rollers 314A that may be configured to densify the first layer of material upon spraying. deposition The second station of the system includes similar components as the first station. The second station includes a second sprayer 304B coupled to a second reservoir 306B. The second station also sprays material onto the substrate. deposition The second station includes a third mask 308C and a fourth mask 308D defining a second target area therebetween for spraying the second target area. The third and fourth masks may be coupled to a third mask actuator 310C and a fourth mask actuator controlled by a third mask actuator controller 312C and a fourth mask actuator controller 312D, respectively. Finally, the second station also includes a third mask actuator 310C and a fourth mask actuator controlled by a third mask actuator controller 312C and a fourth mask actuator controller 312D, respectively, downstream of the second station. depositionThe sprayed second layer of material may include a second calender roller 314 configured to densify the sprayed second layer of material. deposition The system deposits two separate layers of material sequentially onto the substrate. deposition Naturally, the two layers are deposition Although two stations for performing the above-described process are described above, the system may be modified in accordance with the present disclosure. deposition Any number of different material layers can be applied sequentially, without being limited by the number of stations deposition Any number of deposition It should be understood that the term may include a station.

[0055]

[0078] In the state shown in FIG. deposition The system can deposition 10, the first, second, third and fourth masks 308A-D are in an unattached starting state, which may exist when the roll of substrate 101 is initially connected to the first roller 302A and the second roller 302B. As shown in FIG. 10, each of the first, second, third and fourth masks 308A-D are spaced from the substrate in this starting state.

[0056]

[0079] FIG. 11 shows the first material layer 202 deposition Spray in Figure 11 deposition11 depicts a system. As shown in FIG. 11, the first mask 308A and the second mask 308B are moved into contact with the substrate. Thus, the bare areas of the substrate located under the first and second masks are shielded to remain bare and uncoated when 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 opposite side 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. 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 a 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 may cover the bare areas with material. deposition 11 is configured to pass current from the second mask to the first mask, the direction of the 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] A sufficient amount of the first particles 200 is introduced into the first material layer 202. deposition When this happens, the spray deposition The system proceeds to the state shown in Figure 12. As shown in Figure 12, the first mask 308A and the second mask 308B are moved to a non-contact position spaced apart from the substrate by the first mask actuator 310A and the second mask actuator 310B. The first roller 302A and the second roller 302B press the first material layer and the substrate against the second calender roller 314A. depositionWhen translated toward the station, the second mask 308B may be spaced from the substrate by a distance sufficient for the second mask to clear the first layer of material 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 may be positioned separated from each other by a distance equal to the separation distance between the first and second masks). Thus, the third and fourth masks may be spaced apart from the substrate by a distance equal to the separation distance between the first and second masks. deposition When the system proceeds to the state shown in FIG. 13, it can be aligned with corresponding bare areas of the substrate that have already been covered by the first and second masks.

[0058]

[0081] As shown in Figure 13, deposition The first layer of material 202 was then moved to be aligned between the third mask 308C and the fourth mask 308D. The roller was then moved to align the additional layer of material 202 between the third mask 308C and the fourth mask 308D. deposition 13, the third mask 308C and the fourth mask 308D are 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 are 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 are adapted to spray particles from the first sprayer 304A and the second sprayer 304B onto the substrate. deposition As shown in FIG. 13, the first sprayer sprays particles 200 onto the opposite side of the substrate to form an additional layer of the first material on the substrate. deposition Meanwhile, a second sprayer 304B sprays second particles 206 from a second reservoir 306B onto the opposing calendered first material layer 204 to form a second material layer 208 on the opposing side of the substrate. depositionAs the layer is then translated through the system toward the second roller 302B, the first and second layers as well as the substrate may pass over a second calender roller 314B before being wrapped onto the second roller.

[0059]

[0082] As shown in FIG. 13, multiple layers of material can be simultaneously deposited at separate stations. deposition As already mentioned, the substrate may be a substrate on which particles are deposition According to the embodiment of Figures 10-13, the third mask 308C and the fourth mask 308D are arranged to spray the electric current. deposition The electrode may be configured to pass through the substrate at the second station of the system. deposition To avoid resistive heating of the substrate between the systems (e.g., between the second and third masks), the third and fourth masks pass current in the opposite direction to the first and second masks 308A and 308B. That is, as shown in FIG. 13, the second and third masks 308B and 308C may be configured as positive or high potential electrodes, while the first and fourth masks 308A and 308D may be configured as negative, ground, or low potential electrodes. Thus, current flows in the opposite direction from the second or third mask outward to either the first or fourth mask. Thus, masks adjacent to each other between the first and second stations may have equal potentials such that no current is passed from the third mask to the second mask. This arrangement of the masks therefore prevents the particles from being heated. deposition This may allow current to be passed exclusively to the substrate in the target area exposed to the plasma (as opposed to heating the entire substrate). Such a configuration may reduce energy consumption or otherwise reduce the amount of spraying. deposition In addition to the above, the efficiency of the process can be improved. depositionIn embodiments where rollers are not used between stations (where material is sprayed onto two or more adjacent target areas of a substrate), a single mask may be placed between the adjacent target areas and may act as an electrode for heating 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 insulate the passage of electrical current within a target area of ​​a substrate. deposition In some embodiments, however, the present disclosure provides that resistive heating of the substrate may be applied to one or more of the systems. deposition Without being limited to embodiments that are restricted to being within a station, the 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.

[0061]

[0084] This process continues through the system shown in FIG. 13 until the supply of substrates is exhausted. deposition The cycle may continue to periodically move the substrate. 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 deliver 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 so that the state of FIG. 14 may be repeated. Thus, the spraying may be performed. deposition The system advances the substrate, stops, and deposits layers of material. depositionA semi-continuous process may be performed by stepping down the substrate and then stepping 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] The substrate 101 is moved between multiple stations and then the layers of material are sequentially deposition Although the embodiment of FIGS. 10-13 is shown having multiple stations for forming a multi-layer structure, in other embodiments, multiple stations may be used to form multiple layers of material without moving the substrate. deposition For example, in some embodiments, multiple reservoirs of material may be combined into a single station where a first layer of material is deposited without moving the substrate or having any mask in contact with the substrate. deposition and then a second layer of material can be applied later. deposition In another embodiment, multiple atomizers coupled to separate reservoirs may be in close proximity to each other such that they effectively target the same area of ​​the substrate. In this embodiment, a first atomizer sprays a first layer of material. deposition and a second sprayer may be configured to spray a second layer of material onto the first layer of material without moving the substrate. deposition Of course, spraying deposition The system may use any suitable number of stations, sprayers, reservoirs, and masks as the disclosure is not so limited.

[0063]

[0086] Figures 14 and 15 show the sprays in Figures 10 to 13, respectively. deposition 14-15, a calendered second layer of material 208 is disposed on top of a calendered first layer of material 204 that is disposed on the opposite side of a substrate 101. Each cross-section of the calendered first and second layers of material is separated by a bare area 118 of the substrate. depositionAs previously mentioned, such an arrangement improves manufacturing processes where it is desirable to easily separate some sections of the material layer 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] Figures 16-17 show spray deposition 16-17 are top and side schematic views of one embodiment of a material produced by the system. The material in 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., anode or cathode). Accordingly, the second material layer 210 may be an ion-conducting 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 formed in any desired order and in any number of layers as the disclosure is not so limited. deposition It can be done.

[0066]

[0089] Figures 18 to 21 show the materials deposition Spraying during process deposition FIG. 4 is a schematic side view of yet another embodiment of a system 400. In contrast to the previous embodiments that implemented a discontinuous or semi-continuous process, the atomization of FIGS. deposition The system is configured to form a layer of material on the substrate 101 in a continuous process as the substrate is constantly unwound from the first roller 402A and wrapped onto the second roller 402B. deposition The 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. deposition The 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 control the first and second particles. deposition The mask actuators are operably coupled to tracks 412 configured to allow the mask to move synchronously with the substrate while maintaining contact with the substrate to mask bare areas of the substrate when the mask actuators are moved from a first roller to a second roller, in some embodiments, the track 412 may be continuous such that the substrate is repeatedly recirculated within the system to mask the substrate as it is moved from a first roller to a second roller. deposition The masks may be connected via chains, belts, or other suitable structures that maintain a predetermined distance between each of the masks so that they are aligned. 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, the third mask 408C and the third mask actuator 410C follow the first mask and the second mask along a track.

[0067]

[0090] 18, the first mask 408A and the second mask 408B grip the substrate 101 to effectively mask the bare areas of the substrate that are covered by the masks. The first mask and the second mask cover the target areas of the substrate between them (where the material layer is deposition As shown in FIG. 18, when the target area between the first mask and the second mask passes the first sprayer 404A, the first sprayer sprays the first particles 200 onto the substrate to form a first material layer. deposition While flowing from the first reservoir 406A, the first particles may 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 may move at a constant speed from the first roller to the second roller. According to this embodiment, the thickness of the first material layer may be determined by the amount of material discharged from the first sprayer 404A. deposition The heating may be controlled by the speed of the first mask, 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 may be resistively heated by a current passed through the first and second masks. According to some embodiments, and as shown in FIG. 18, the masks may be placed 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 and second sprayers 404A and 404B. More specifically, the first mask has a positive or otherwise high potential, and the second and third masks 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 shows the spray from the state shown in FIG. deposition The process continues as shown in FIG. depositionand the first sprayer 404A ceases spraying. The substrate 101, the first mask 408A, the second mask 408B and the third mask 408C are moved further towards the second roller 402B. Once the third mask 408C is suitably adjacent to the substrate, the third mask actuator 410C may move the third mask into contact with the substrate to grip the substrate and define another target area of ​​the substrate between the first and third masks. As previously 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 along certain portions of the track closer to the substrate and move the mask further away from the substrate along other portions of the track to control the relative motion of the mask with respect to the substrate. These track portions can thus be configured to move the mask closer to the substrate and further away from the substrate, respectively. deposition It may be positioned to passively come in and out of contact with areas of the substrate that are to be masked during processing. In some embodiments, the mask actuators may be combined with various track geometries to move the mask in any desired direction relative to the substrate as the disclosure is not so limited.

[0070]

[0093] FIG. 20 shows the spray shown in FIG. deposition Material from the state of the system 400 deposition20, the substrate 101, the first mask 408A, the second mask 408B and the third mask 408C continued 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 areas where the substrate was contacted by the mask. In the state of FIG. 20, the target areas of the substrate defined by the first and second masks were accordingly transferred from the second reservoir 406B onto the first material layer 202 to form the second material layer 208. deposition Meanwhile, a target area of ​​the substrate defined by the first and third masks is adjacent to a second sprayer 404B which sprays the first particles 200 into a first material layer disposed directly on the substrate. deposition Each of these layers is positioned adjacent to a first sprayer. deposition During this process, 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 shows the material following the state shown in FIG. deposition 21, the substrate 101, the first mask 408A, the second mask 208B, the third mask 408C, and the fourth mask 408D are further moved toward the second roller 402B. depositionOnce the second mask has released the substrate, the fourth mask 408D is moved by the fourth mask actuator 410D into contact with the substrate. Thus, the third mask 408C and the fourth mask 408D are no longer in contact with the substrate. The released portion of the substrate, including the second layer of material 208 and the first layer of material 202, is fed into a calender roller 414 which simultaneously densifies the first and second layers of material prior to wrapping the substrate onto the second roller 402B. Once the second mask has released the substrate, the fourth mask 408D is moved by the fourth mask actuator 410D into contact with the substrate. Thus, the third mask 408C and the fourth mask 408D are no longer in contact with the substrate. deposition Further target regions therebetween for may be defined.

[0072]

[0095] The embodiment shown in Figures 18-21 is a method for distributing the material in a burst (i.e., discontinuous manner). deposition Although the timing of the first and second sprayers 404A, 404B is depicted as being such that the first and second sprayers spray material continuously, in other embodiments, the first and second sprayers spray material continuously. deposition That is, the first particles and the second particles may be successively ejected from the first sprayer and the second sprayer as the substrate and mask move from the first roller 402A toward the second roller 402B. According to this embodiment, the sprayer may spray particles directly onto the substrate once the mask and substrate pass under the sprayer 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] Figure 22 shows a continuous material deposition Spraying during process deposition FIG. 22 is a top schematic view of yet another embodiment of the system 500. deposition The system sequentially deposits three layers of material at various stations. deposition 18-21 except that 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 ... deposition The system includes a first sprayer 504A, a second sprayer 504B, and a third sprayer 504C that spray the substrate with the material. The system also includes a plurality of masks 508 and mask actuators 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 discussed with reference to the embodiment of Figures 18-21, the masks are arranged to mask the material such that each target area is separated from adjacent target areas by bare areas of the substrate that are masked by the mask. deposition According to the embodiment of FIG. 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 define a target area therebetween for the material to be sprayed by each of the sprayers. deposition The second and fourth electrodes are then 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.

[0074]

[0097] As shown in the embodiment of FIG. deposition The system produces three distinct layers of material that are simultaneously calendered before being wrapped onto the second roller 502B. deposition That is, as the substrate passes the first sprayer 504A, a first material layer 202 is formed on the substrate. As the substrate continues and is positioned adjacent to the second sprayer 504B, the second sprayer sprays a second material layer 208 onto the first material layer. deposition Continuing, the substrate is then formed with a third material layer 212 on top of the second material layer. deposition The third layer of material is moved adjacent to the third sprayer 504C. depositionAfter the mask is calendered, 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, they are simultaneously densified to produce a calendered three-layer composite that is wrapped onto the second roller 502B. As previously stated, the three layers may include 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 has been shown and described with reference to the embodiment of FIG. 22, it should be understood that the tracks may have any suitable shape and any number of tracks may be used to address the masks in the system as the disclosure is not limited to any particular number and / or arrangement of tracks in the system. Further, in some embodiments, the spray deposition The 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, it may move out of contact with the substrate and travel in a direction opposite to the direction of travel 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 disclosure is not so limited.

[0076]

[0099] Figure 23 shows the material deposition Spraying during process deposition 23 is a schematic side view of yet another embodiment of the system 100. The embodiment of FIG. 23 uses spraying instead of resistive heating of the substrate. deposition 1-7, except that the system heats the substrate by using a plurality of radiant heaters 120. As shown in FIG. 23, the radiant heaters 120 heat the first particles 200 from the atomizer 104 onto the substrate. deposition The heat sources 104 may be disposed on one or both sides of the substrate 101 so as to radiate heat towards the substrate so that the substrate is efficiently heated when the heat sources 104 are ....

[0077]

[0100] Figure 24 shows the material deposition Spraying during process deposition 24 is a schematic side view of yet another embodiment of the system 100. As with the embodiment of FIG. deposition The system comprises: a first particle 200 on a substrate; deposition 23, the radiative heater 202 radiates heat to the substrate 101 when the substrate 101 is heated. In contrast to the embodiment of FIG. 23, the radiative heat is directed to the 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. deposition Such an arrangement may promote even more consistent heating of the substrate within the target area as compared to heaters that heat 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. deposition The system applies a single layer or layers of material to one or two opposing sides of a substrate. deposition In addition, the disclosed spray deposition The system deposits a layer of material onto a substrate as part of a discontinuous, semi-continuous, or continuous process. deposition The disclosed spray deposition The system may also employ actuators to move individual masks into and out of contact with the substrate, or combination actuators to move multiple masks simultaneously. deposition The system may be adapted to process multiple layers of material at different times in a single station and / or in separate physically separated stations, as the disclosure is not so limited. deposition In the system, deposition possible.

[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, the first mask being a clamp actuated by an actuator, the clamp configured to selectively grip the substrate; a second mask movable to selectively mask the substrate from particles in a second region of the substrate; and a heater configured to heat the substrate; The at least one sprayer directs the spray of particles toward a portion of the substrate between the first mask and the second mask.

2. The system of claim 1 , wherein the actuator is a pneumatic, hydraulic, or electrical actuator.

3. 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.

4. 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.

5. 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.

6. 6. The system of claim 5, 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.

7. 6. The system of claim 5, 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.

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

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

10. 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.

11. 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 spraying first particles toward the heated substrate, 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, to form a first layer on the substrate; A method, wherein masking the first area of ​​the substrate includes gripping the substrate with a first clamp.

12. 12. The method of claim 11 , 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.

13. 12. The method of claim 11, 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.

14. The method of claim 11 , wherein masking the second area of ​​the substrate comprises clamping the substrate with a second clamp.

15. The method of claim 14 , further comprising moving the substrate relative to the first and second clamps.

16. The method of claim 15 , further comprising moving the heated substrate while the first particles are sprayed toward the substrate.

17. The method of claim 11 further comprising calendering the first layer.

18. The method of claim 11 , wherein the first particles further comprise a binder.

19. The method of claim 11 , further comprising spraying second particles onto the first layer to form a second layer disposed on the first layer.

20. 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; spraying and depositing first particles onto the substrate, 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 to form a first layer; and spraying and depositing second particles onto the first layer, the second particles including at least one selected from the group consisting 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; A method, wherein masking the first region of the substrate includes gripping the first region of the substrate with a first clamp.

21. 21. The method of claim 20, wherein spraying and depositing the first particles and the second particles comprises spraying the first particles toward the substrate and spraying the second particles toward the first layer.

22. 21. The method of claim 20, wherein the first particles comprise the electrochemical material and the second particles comprise the separator material and / or the ionically conductive material.

23. 21. The method of claim 20, further comprising sequentially calendering the first layer and the second layer.

24. 21. The method of claim 20, further comprising simultaneously calendering the first layer and the second layer.

25. The method of claim 20 further comprising heating the substrate.

26. 26. The method of claim 25, 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.

27. 21. The method of claim 20, wherein masking the second region of the substrate comprises gripping the second region of the substrate with a second clamp.

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