Powdered solid electrolytes and electroactive materials

Abstract

Powdered solid electrolytes and electroactive materials, as well as related methods of manufacture and use, are disclosed. In one embodiment, the ionically conductive powder comprises a plurality of ionically conductive particles. The ionically conductive particles comprise an ionically conductive salt dissolved in a thermoplastic polymer, to which optional ingredients (e.g., electroactive particles and / or inorganic solid particles) can be dispersed. Related methods for producing these ionically conductive powders are also disclosed. These methods include, but are not limited to, cryogenic milling, spray drying, and aerosol polymerization. Also described are embodiments related to using the resulting ionically conductive powders in spray deposition processes.

Description

[Technical Field]

[0001] (Cross-reference of related applications)

[0001] This application claims the benefit of priority under § 119(e) of U.S. Provisional Patent Application No. 63 / 064,449, filed on 12 August 2020. The disclosure of this Provisional Application is incorporated in its entirety by reference.

[0002]

[0002] The disclosed embodiments relate to powdered solid electrolytes and electroactive materials, as well as related manufacturing and use methods. [Background technology]

[0003]

[0003] Lithium-ion batteries typically contain two or more electrodes, which are separated by an electrically insulating material that is permeable to lithium ion diffusion between the electrodes. In some examples, one electrode contains an anode powder material coated on a copper substrate and the other contains a cathode powder material coated on an aluminum substrate, but other electrode materials and chemicals are also used. These electrodes are conventionally produced using the slurry casting method. In this method, electroactive material (e.g., anode or cathode material) powder is mixed with a polymer binder (e.g., typically polyvinylidene fluoride PVDF) dissolved in a suitable solvent (e.g., typically N-methylpyrrolidone). The resulting slurry is cast onto an electrode substrate. The solvent is then evaporated and recovered to form a dry electrochemical material layer on the electrode surface. Slurry casting is also used to form solid electrolytes using electrolyte slurry. Often, the electrolyte slurry contains a lithium salt solvated in a polymer binder, which is prepared by dissolving it in what is often called a "non-solvent" (e.g., typically N-methylpyrrolidone). After this, the non-solvent is evaporated to form a dry electrolyte material layer between the electrodes. A tremendous amount of time and energy is spent using large conveyor ovens and vacuum dryers to remove all solvent from the electrodes and / or electrolyte after slurry casting, thereby accelerating the drying of the deposited slurry. [Overview of the project]

[0004]

[0004] In a particular embodiment, an ion-conducting powder is provided.

[0005]

[0005] In some embodiments, the ion-conducting powder comprises a plurality of ion-conducting particles. At least one of the plurality of ion-conducting particles comprises a thermoplastic polymer, an ion-conducting salt dissolved in the thermoplastic polymer, and a plurality of inorganic solid and / or electroactive material particles dispersed in the thermoplastic polymer.

[0006]

[0006] In some embodiments, the ion-conducting powder comprises a plurality of ion-conducting particles. At least one of the plurality of ion-conducting particles comprises a thermoplastic polymer and an ion-conducting salt dissolved in the thermoplastic polymer, and at least one of the plurality of ion-conducting particles is substantially free of particulates.

[0007]

[0007] In some embodiments, the ion-conducting powder comprises a plurality of ion-conducting particles. At least one of the plurality of ion-conducting particles comprises a thermoplastic polymer, an ion-conducting salt dissolved in the thermoplastic polymer, and a plurality of inorganic solid particles dispersed in the thermoplastic polymer, wherein the weight percentage of the plurality of inorganic solid particles in the powder is at least 50 wt% of the total weight of the powder.

[0008]

[0008] In a particular embodiment, a method is provided.

[0009]

[0009] In some embodiments, the method includes forming a mixture by combining a molten thermoplastic polymer with an ion-conducting salt, dissolving the ion-conducting salt in the molten thermoplastic polymer, solidifying the mixture, and grinding the solidified mixture to produce a plurality of ion-conducting particles.

[0010]

[0010] In some embodiments, the method includes: combining a thermoplastic polymer, an ion-conducting salt, and a solvent to form a mixture; dissolving the ion-conducting salt and the thermoplastic polymer in a solvent, wherein the mixture is substantially free of fine particles; and spraying the mixture, wherein the solvent evaporates while the mixture is being sprayed to form a plurality of ion-conducting particles.

[0011]

[0011] In some embodiments, the method includes: forming a mixture by combining a photocurable polymer and / or monomer, a photoinitiator, and an ion-conducting salt; dissolving the ion-conducting salt and the photoinitiator in the photocurable polymer and / or monomer; spraying the mixture; and exposing the spray to electromagnetic radiation to cure the photocurable polymer and / or monomer and form a plurality of ion-conducting particles.

[0012]

[0012] In some embodiments, the method includes spraying a plurality of ion-conductive particles, applying an electric charge to the ion-conductive particle spray, heating a substrate, and providing the heated substrate with the charged ion-conductive particle spray to form a film of ion-conductive particles on the substrate.

[0013]

[0013] The concepts described above and the additional concepts discussed below can be made up of any suitable combination, and it will be acknowledged that the disclosure is not limited in this respect. Furthermore, other advantages and novel features of the disclosure will become apparent from the following detailed description of various non-limiting embodiments in conjunction with the accompanying drawings. [Brief explanation of the drawing]

[0014]

[0014] The attached drawings are not intended to be drawn to a specific scale. In the drawings, identical or nearly identical components shown in various drawings may be represented by the same number. For clarity, not all components are numbered in all drawings.

[0015] [Figure 1]

[0015] A schematic diagram of ion-conducting particles according to a specific embodiment is shown. [Figure 2]

[0016] A schematic diagram shows a method for producing ion-conducting particles, including direct dissolution in a molten polymer and low-temperature milling, according to a specific embodiment. [Figure 3]

[0017] A schematic diagram of a method for producing ion-conductive particles including spray drying and / or aerosol polymerization according to a specific embodiment is shown. [Figure 4A]

[0018] A schematic representation of a schematic diagram of a method for creating the ion-conductive particles shown in FIG. 2 according to a specific embodiment is shown, and a schematic diagram related to the direct dissolution of materials in a molten polymer is shown. [Figure 4B]

[0018] A schematic representation of a schematic diagram of a method for creating the ion-conductive particles shown in FIG. 2 according to a specific embodiment is shown, and a schematic diagram related to a low-temperature milling process using a ball mill is shown. [Figure 5]

[0019] A schematic side view of an aerosol photopolymerization system according to a specific embodiment is shown. [Figure 6]

[0020] A schematic side view of a spray drying and photopolymerization system according to a specific embodiment is shown. [Figure 7]

[0021] A schematic side view of a spray deposition system during a material deposition process according to a specific embodiment is shown. [Figure 8A]

[0022] SEM images of a plurality of ion-conductive particles including PVDF-HFP, LiTFSI, and lithium nickel manganese cobalt oxide (NMC) particles generated by spray drying according to a specific embodiment are shown. [Figure 8B]

[0023] SEM-EDS images of the plurality of ion-conductive particles of FIG. 8A according to a specific embodiment are shown, showing a uniform sulfur distribution from LiTFSI in the plurality of ion-conductive particles. [Figure 9A]

[0024] An optical image of a plurality of ion-conductive particles according to a specific embodiment is shown. [Figure 9B]

[0024] An optical image of a plurality of ion-conductive particles according to a specific embodiment is shown. [Figure 9C]

[0024] An optical image of a plurality of ion-conductive particles according to a specific embodiment is shown. [Figure 9D]

[0024] Optical images of multiple ion-conducting particles according to a specific embodiment are shown. [Figure 9E]

[0024] Optical images of multiple ion-conducting particles according to a specific embodiment are shown. [Figure 9F]

[0024] Optical images of multiple ion-conducting particles according to a specific embodiment are shown. [Figure 10A]

[0025] Additional SEM-EDS images of multiple ion-conducting particles according to a specific embodiment are shown, and SEM images of multiple ion-conducting particles are shown. [Figure 10B]

[0025] Additional SEM-EDS images of multiple ion-conducting particles according to a specific embodiment are shown, and SEM-EDS images of the fluorine distribution in the multiple ion-conducting particles are shown. [Figure 10C]

[0025] Additional SEM-EDS images of multiple ion-conducting particles according to a specific embodiment are shown, and SEM-EDS images of the cobalt distribution in the multiple ion-conducting particles are shown. [Figure 10D]

[0025] Additional SEM-EDS images of multiple ion-conducting particles according to a specific embodiment are shown, and SEM-EDS images of the manganese distribution in the multiple ion-conducting particles are shown. [Figure 10E]

[0025] Additional SEM-EDS images of multiple ion-conducting particles according to a specific embodiment are shown, and SEM-EDS images of the nickel distribution in the multiple ion-conducting particles are shown. [Figure 11]

[0026] The graph shows thermogravimetric analysis (TGA) measurements indicating minute amounts of residual acetone and water in multiple ion-conducting particles after spray drying, according to a specific embodiment. [Modes for carrying out the invention]

[0016]

[0027] The inventors recognized that a deposition method in which separate particles and binders are combined during the deposition process before deposition can lead to extra complexity and, in some cases, to heterogeneity of the deposited material. Therefore, the inventors recognized that in some applications, it is desirable to reduce the complexity of the deposition process while increasing the uniformity of the deposited material. Thus, in some embodiments, substantially solvent-free powders can be deposited. Some conventional methods for producing electrode materials dissolve the binder using supercritical carbon dioxide as a solvent, forming a binder coating on electroactive particles. However, when the supercritical carbon dioxide evaporates, the binder forms a thin, uniform layer of individual binder particles deposited on the surface of the core electroactive particles. Furthermore, supercritical carbon dioxide has a low solubility limit for the solvation of certain salts, such as lithium salts, so its use may be limited when producing electrolyte powders containing high concentrations of solvated salts.

[0017]

[0028] Considering the above, the inventors recognized the need for improved electrolyte and electrode powders for use in spray deposition in solid-state battery manufacturing technology. Furthermore, since residual solvents and / or moisture associated with typical manufacturing methods lead to a shortened battery life, such as accelerated degradation of electrochemical cells, the inventors recognized the advantages associated with preparing spray deposition materials with significantly reduced amounts of internal residual solvents and moisture.

[0018]

[0029] Another limitation recognized by the inventors in relation to typical manufacturing methods such as slurry casting is the limited choice of compositions from which electrolyte slurries can be produced. For example, typical electrolytes may contain components such as binders, salts, inorganic solids (e.g., ion-conducting ceramics and / or glass, and non-ion-conducting ceramics and / or glass), or other additives such as plasticizers. While the electrolyte slurry is deposited onto the electrode, it must have a composition within a suitable range to ensure the formation of a standing electrolyte film / layer. In some cases, slurry casting methods cannot be used to form a standing film with an inorganic solid content exceeding 50 wt%. Operation outside the compositional range can lead to non-uniform distribution of certain components and manufacturing defects in solid-state batteries. Furthermore, evaporation of the solvent from the electrolyte slurry can make it difficult to maintain the solvation of additives or salts during manufacturing, potentially resulting in poor conductivity of the electrochemical cell. Considering the above problems, the inventors recognized the need for the development of electrolyte and / or electrode powders to be used in powder coating techniques for manufacturing spray deposition bases for electrochemical devices.

[0019]

[0030] Considering the above, the inventors recognized the advantages of ion-conducting powders containing multiple ion-conducting particles that can be used in powder spray coating processes. In some examples, the ion-conducting powder can be an electrolyte powder, such as a powder that can facilitate ion species transport between electrodes, such as anodes and cathodes. In some examples, the ion-conducting powder can be an electrode powder, such as a powder containing an electroactive material that can be used to form electrodes. In some embodiments, at least one, the majority, or substantially all of the multiple ion-conducting particles contain a thermoplastic polymer and an ion-conducting salt dissolved in the thermoplastic polymer. Depending on the embodiment, at least one, the majority, or substantially all of the multiple ion-conducting particles may exhibit a continuous phase structure containing a thermoplastic polymer and an ion-conducting salt solvated and uniformly distributed in the thermoplastic polymer.

[0020]

[0031] In some embodiments, at least one, the majority, or substantially all of the plurality of ion-conducting particles are substantially free of fine particles. As used herein, the term “fine particles” can refer to any component or species that is insoluble or has reached its solubility limit in a given continuous phase. For example, according to one set of embodiments, a plurality of ion-conducting particles comprising one or more salts solvated in one or more thermoplastic polymers may include fine particles dispersed in the ion-conducting particles in amounts of 10 wt% or less, 5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, or any other appropriate weight percent or less.

[0021]

[0032] In another embodiment, at least one, the majority, or substantially all of the multiple ion-conducting particles contained in the powder comprise a thermoplastic polymer and an ion-conducting salt dissolved in the thermoplastic polymer, allowing for the dispersion of multiple inorganic solids (e.g., ceramic or glass particles) and / or electroactive material particles within the thermoplastic polymer. In some such embodiments, the multiple ion-conducting particles may comprise a continuous phase of the thermoplastic polymer containing the dissolved ion-conducting salt and a dispersed phase containing inorganic solids and / or electroactive material particles suspended within the continuous thermoplastic polymer phase. In some examples, the particles suspended in the continuous thermoplastic polymer phase can be uniformly dispersed within the thermoplastic polymer.

[0022]

[0033] In one embodiment, at least one, the majority, or substantially all of the multiple ion-conducting particles contained in the powder comprise a thermoplastic polymer and multiple ion-conducting salts dissolved in the thermoplastic polymer, and may also comprise multiple inorganic solids (e.g., ceramic or glass particles). The inorganic solids may include non-lithiated inorganic solids (i.e., inorganic solids lacking lithium atoms), as detailed below, and / or may be present in relatively large quantities throughout the powder, and / or may be dispersed in the thermoplastic polymer in any of the percentages disclosed herein for these materials.

[0023]

[0034] It will be understood that the ion-conducting powders disclosed herein may also include any suitable additional components. For example, non-limiting examples of additional components that may be included in the ion-conducting powders described herein include, but are not limited to, plasticizers (e.g., succinonitrile (SN), glutaronitrile (GN), ethylene carbonate (EC), etc.) and / or any other suitable materials.

[0024]

[0035] As described above, the various ion-conductive powders disclosed herein may contain ion-conductive particles having compositions of the structure and range described herein in any suitable weight percentage (wt.%) of the total powder weight. For example, at least one, the majority, or substantially all of the multiple ion-conductive particles contained in the powder may represent the materials and range of the disclosed combination compositions. The range of particles representing the disclosed compositions may be present in at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 99 wt.%, 99.9 wt.%, and / or any other suitable weight percentage.

[0025]

[0036] Certain aspects of this disclosure relate to methods for generating multiple ion-conducting particles for use, for example, as an electrolyte and / or electrode powder in the manufacture of solid lithium-ion batteries. While various embodiments described herein are for generating and / or using multiple ion-conducting particles as an electrolyte and / or electrode powder in the manufacture of solid lithium-ion batteries, this disclosure is not limited thereto, and it will be understood that multiple ion-conducting particles in particular embodiments may be generated and / or used as an electrolyte and / or electrode powder in the manufacture of other types of solid batteries, such as sodium-ion batteries.

[0026]

[0037] In one embodiment, a method for producing a plurality of ion-conducting particles, including a cryo-mill, is provided herein. A particular embodiment first involves forming a mixture by combining a molten thermoplastic polymer with an ion-conducting salt. The ion-conducting salt can be dissolved in the molten thermoplastic polymer. Depending on the application, the thermoplastic polymer may be substantially free of fine particles such as, for example, undissolved ion-conducting salt, inorganic solids (e.g., ceramic or glass particles), and electroactive material particles. Alternatively, in some embodiments, the undissolved ion-conducting salt particles, inorganic solids, and / or electroactive material particles can be dispersed in the molten thermoplastic polymer before the mixture is solidified. Other additives (e.g., plasticizers) may be added to the mixture. In any case, the mixture can be cooled and solidified. According to a particular embodiment, the solidified mixture is ground in a mill (e.g., a ball mill, a cryo-mill, a rotor mill, a knife mill, a jet mill, etc.) to produce a plurality of ion-conducting particles as described herein.

[0027]

[0038] In one embodiment, a method for producing a plurality of ion-conducting particles involves spray drying. In some embodiments, a thermoplastic polymer can first be combined with an ion-conducting salt to form a mixture. Certain embodiments involve a co-dissolution process, which involves dissolving both the ion-conducting salt and the thermoplastic polymer in a solvent. As used herein, “solvent” refers to a liquid capable of dissolving more than a trace amount of the ion-conducting salt and / or thermoplastic polymer. For example, in some embodiments, the solvent is present in some amount, and the salt and thermoplastic polymer may have sufficient solubility in the solvent so that a large portion of the salt and thermoplastic polymer (e.g., more than 50 wt%), and in some examples substantially all of the salt and thermoplastic polymer (e.g., more than 90 wt%, more than 95 wt%, more than 99 wt%, or any other arbitrary percentage), can be dissolved in the solvent. Optionally, particulate matter, such as inorganic solid and / or electroactive material particles, may be suspended in the resulting solution. The mixture is then sprayed, and the solvent is evaporated during the spraying process to produce a plurality of ion-conducting particles. The resulting plurality of ion-conducting particles may contain a thermoplastic polymer along with a dissolved ion-conducting salt, and may be substantially particle-free or contain particles dispersed in a continuous phase of the thermoplastic polymer. As with other embodiments described herein, additives (e.g., plasticizers) may be added to the mixture before spraying.

[0028]

[0039] In one embodiment, it may be desirable to combine the spray drying process and aerosol photopolymerization process disclosed herein to produce a plurality of ion-conducting particles. In such embodiments, instead of dissolving the thermoplastic polymer in a solvent when forming the mixture, the photocurable polymer, photoinitiator, and ion-conducting salt may be added to the mixture. In some examples, the ion-conducting salt and photoinitiator may be dissolved in the photocurable polymer, and optionally, a solvent, inorganic solid, electroactive material particles, and / or other additives may be added to the mixture. As in the embodiments described above, the mixture can then be sprayed or aerosolized into droplets, which can then be photopolymerized. For example, by applying electromagnetic radiation to the spray mixture, the photocurable polymer in each spray droplet can be photocrosslinked to produce a plurality of ion-conducting particles. The plurality of ion-conducting particles thus obtained include a continuous phase of the photocrosslinked polymer containing the dissolved salt and optionally inorganic solid, electroactive material particles, and / or other additives.

[0029]

[0040] In processes that use photopolymerization when spraying a mixture, if a solvent is involved, the solvent is evaporated and the spray droplets are exposed to electromagnetic radiation. Depending on the droplet size, process temperature, and other appropriate operating parameters, the evaporation of the solvent may be performed before, simultaneously with, and / or after exposing multiple ion-conducting particles to electromagnetic radiation.

[0030]

[0041] In some embodiments, the plurality of ion-conducting particles described herein may have an average maximum cross-sectional dimension, such as a diameter of 250 μm or less. It should be noted that the average maximum cross-sectional dimension of the plurality of ion-conducting particles can be any average value, such as an average value based on the number of the plurality of ion-conducting particles. For example, the average maximum cross-sectional dimension of the plurality of ion-conducting particles can be at least 1 μm, at least 5 μm, at least 10 μm, at least 20 μm, at least 40 μm, at least 60 μm, at least 80 μm, at least 100 μm, at least 200 μm, at least 300 μm, at least 400 μm, at least 600 μm, or at least 800 μm. In some embodiments, the average maximum cross-sectional dimensions of a plurality of ion-conducting particles are 1 mm or less, 900 μm or less, 700 μm or less, 500 μm or less, 350 μm or less, 250 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 25 μm or less, 15 μm or less, or 5 μm or less. Combinations of the above ranges are also possible (e.g., at least 1 μm and 250 μm or less, or at least 20 μm and 100 μm or less). Other values ​​are also possible. For example, ion-conducting particles can have any suitable size, provided that particles can be used during a powder spray deposition process to form a (e.g., structurally stable) film for fixing electrolytes or electrodes, and the conductivity of the resulting film is not adversely affected.

[0031]

[0042] In some embodiments, the plurality of ion-conducting particles contain a solvent and / or water content of 0.5 wt% or less. As described above, a high residual solvent and / or water content can adversely affect battery life by leading to rapid degradation of the electrochemical cell. In some embodiments, the plurality of ion-conducting particles may favorably contain solvent and / or water content of 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.3 wt% or less, 0.2 wt% or less, 0.1 wt% or less, 0.05 wt% or less, or 0.01 wt% or less. As described herein, residual solvent may refer to the remaining solvent used to solvate any component, such as a thermoplastic polymer and / or an ion-conducting salt, in any of the above methods for producing ion-conducting particles. Residual water may refer to the final amount of water contained in the ion-conducting particles produced using any of the above methods.

[0032]

[0043] In some embodiments, the plurality of ion-conducting particles are substantially uniform in at least one of their size, shape, or mass. In some embodiments, the plurality of ion-conducting particles are substantially uniform in size. For example, the plurality of ion-conducting particles may have a polydispersity index (PDI) of 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.1 or less, 0.05 or less, 0.02 or less, or any other suitable index including both larger and smaller indices. The polydispersity index is generally described as the square of the standard deviation of particle diameter divided by the mean particle diameter. Advantageously, the plurality of ion-conducting particles can be substantially homogeneous, for example, with relatively low polydispersity in size, shape, or mass, thereby allowing the particles to be configured to form a substantially homogeneous and uniform electrode and / or electrolyte layer.

[0033]

[0044] As described above, the plurality of ion-conducting particles may comprise a plurality of solvated and / or dispersed components in a continuous phase comprising a thermoplastic polymer. In some such embodiments, the solvated components comprise one or more dissolved ion-conducting salts and / or one or more dissolved additives, and the dispersed components comprise inorganic solids, electroactive material particles, or fine particles such as particulate additives. In a particular set of embodiments, the ion-conducting powder is an electrolyte powder comprising a plurality of ion-conducting particles, comprising ion-conducting salts dissolved in a thermoplastic polymer, and optionally also comprising inorganic solids and / or additives (e.g., plasticizers) dispersed in the thermoplastic polymer. In some embodiments, the ion-conducting powder is an electrode powder comprising a plurality of ion-conducting particles, comprising electroactive material particles dispersed in a thermoplastic polymer, and optionally also comprising inorganic solids and / or additives (e.g., plasticizers) dispersed in the thermoplastic polymer.

[0034]

[0045] Suitable thermoplastic polymers that can be used to form the plurality of ion-conducting particles described herein include, but are not limited to, any suitable thermoplastic polymer. Furthermore, it should be noted that by depositing a material layer without the use of solvents using the plurality of ion-conducting particles described herein, the properties of the resulting electrochemical cell can be improved, and thermoplastic polymers not typically used in solvent-based slurry casting processes can be used. For example, ion-conducting particles can be formed using thermoplastic polymers that have higher ion and / or electronic conductivity than typical thermoplastic polymers but do not readily dissolve in typical solvents. According to certain embodiments, suitable polymers may include, but are not limited to, polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), polyethylene glycol (PEG), polyvinyl acetate (PVA), polytetrafluoroethylene (PTFE), styrene-butadiene (SBR), polyethylene oxide (PEO), polyacetylene, polyphenylene, polypyrrole, polythiophene, polyaniline, polyphenylene sulfide, poly(vinyl alcohol) (PVOH or PVA); polyethyleneimine (PEI); poly(vinylpyrrolidone) (PVP), carbonate polymers (e.g., poly(ethylene carbonate) (PEC), poly(propylene carbonate) (PPC), etc.), and / or combinations thereof. In some examples, at least two or more polymers can be combined to form a polymer blend. In some cases, at least two or more polymers may comprise one of the thermoplastic polymers described herein. In one set of embodiments, the polymer blend may comprise one or more carbonate polymers.

[0035]

[0046] Additionally or alternatively, the thermoplastic polymers in some examples may include, but are not limited to, any suitable copolymers, such as PVDE-HFP, poly(acrylonitrile-butadiene-styrene) (ABS), poly(ethylene-vinyl acetate copolymer (PEVAc), poly(ethylene oxide-epichlorohydrin copolymer) (PEO-EPI), poly(styrene-ethylene oxide copolymer) (PS-EO), etc. In some examples, the copolymer may consist of a mixture of polymers having similar chemical properties but different molecular weights (e.g., a mixture of PEG 4,000 g / mol and PEG 3 5,000 g / mol).

[0036]

[0047] Any suitable amount of thermoplastic polymer can be used to form the plurality of ion-conducting particles described herein. The specific amount depends on the type and amount of dissolved or dispersed components present in the ion-conducting particles, such that the thermoplastic polymer provides the remaining weight percentage of the ion-conducting particles after the weight percentage of other components has been provided. For this reason, in some embodiments, the weight percentage (wt%) of the thermoplastic polymer in the ion-conducting particles can be 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, and / or any other suitable weight percentage or less. Accordingly, the weight percentage of thermoplastic polymer in ion-conducting particles can be 10 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, 80 wt% or more, 90 wt% or more, and / or any other suitable weight percentage or more. The aforementioned combinations of values ​​are envisioned, including weight percentages of thermoplastic polymer between 40 wt% and 95 wt%. However, the disclosure is not limited in this way, and weight percentages of thermoplastic polymer in multiple ion-conducting particles can be both larger and smaller than those described above. Any suitable type and amount of ion-conducting salt can be used to form multiple ion-conducting particles. Depending on the specific thermoplastic polymer used, it may be desirable to increase the ion conductivity of the thermoplastic polymer used. Therefore, an ion-conducting salt can be dissolved in the thermoplastic polymer. In one such embodiment, a lithium salt may be dissolved in the thermoplastic polymer. In such an embodiment, the thermoplastic polymer corresponds to any of the polymers described herein and may contain the dissolved lithium salt. Suitable lithium salts include, but are not limited to, LiNO3, LiCl, LiI, LiClO4, LiBF4, LiPF6, LiAsF6, LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiDFOB, LiTDI, LiPDI, LiDCTA, and LiB(CN)4.In one particular embodiment, a lithium salt (LiX) can be dissolved in PEO to form PEOLiX. In another particular embodiment, a lithium salt (e.g., LiFTSI) can be dissolved in PVDF-HFP. Of course, depending on the specific chemical substances of the electrochemical cell and the materials used to form it, other types of salts and non-lithium salts may be used. For example, in some embodiments, sodium-based salts (e.g., NaI) can be used.

[0037]

[0048] In some embodiments, ion-conducting salts having a relatively small molecular weight and / or containing a relatively small anion can be used. Compared to ion-conducting salts having a relatively large molecular weight and / or a relatively large anion, such ion-conducting salts have improved material compatibility with thermoplastic polymers, making it possible to form powders with increased chemical and structural stability. While we do not wish to be bound by theory, such lithium salts can improve the stability of thermoplastic polymers (e.g., carbonate polymers) in powders because their anionic components and / or molecular weights are smaller than those of larger components, thus interacting well with thermoplastic polymers. In some embodiments, such ion-conducting salts may have a relatively small molecular weight, such as 150 g / mol or less, 125 g / mol or less, 100 g / mol or less, 80 g / mol or less, 70 g / mol or less, 60 g / mol or less, 50 g / mol or less, 40 g / mol or less, 30 g / mol or less, and / or any other suitable molecular weight. In some embodiments, ion-conducting salts having a relatively small molecular weight may have a molecular weight of 20 g / mol or more, 30 g / mol or more, 40 g / mol or more, 50 g / mol or more, 60 g / mol or more, 70 g / mol or more, 80 g / mol or more, 90 g / mol or more, 100 g / mol or more, 125 g / mol or more, and / or any other suitable molecular weight or more. Combinations of the above ranges are also possible (e.g., 20 mol / g or more and 150 mol / g or less). Examples of ion-conducting salts having a relatively small molecular weight include, but are not limited to, LiNO3, LiI, LiCl, LiClO4, LiBF4, etc.

[0038]

[0049] According to certain embodiments, the ion-conducting salt may be present in an amount of at least 5 wt% of the total weight of the ion-conducting powder. However, any suitable amount of the ion-conducting salt may be present in any suitable form. For example, the weight percentage of the salt may be selected so that the ion-conducting salt is supersaturated in the thermoplastic polymer, so that it is completely dissolved in the thermoplastic polymer, and / or so that the particles of the ion-conducting salt are uniformly dispersed in the thermoplastic polymer and the polymer is sufficiently saturated. In any case, the amount of the ion-conducting salt can be adjusted for the desired application based on its solubility in the solvent. For example, the ion-conducting salt may be present in an amount of at least 1 wt%, at least 2 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, or at least 70 wt% of the total weight of the powder. In some embodiments, the ion-conducting salt is present in amounts of 75 wt% or less, 65 wt% or less, 55 wt% or less, 45 wt% or less, 35 wt% or less, 25 wt% or less, 15 wt% or less, 5 wt% or less, 3 wt% or less, 1.5 wt% or less, 0.5 wt% or less, or 0.1 wt% or less of the total weight of the powder. Combinations of the above ranges are also possible (for example, at least 5 wt% and 50 wt% or less, or at least 50 wt% and 75 wt% or less). Other values ​​including both larger and smaller ranges than those above are also possible.

[0039]

[0050] In some embodiments, ion-conducting salts may be present in relatively large amounts in the thermoplastic polymer. In some embodiments, the ion-conducting salt may be present in amounts of 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, or 80 wt% or more relative to the total weight of the thermoplastic polymer. In some embodiments, the ion-conducting salt may be present in amounts of 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, or 50 wt% or less relative to the total weight of the thermoplastic polymer. Combinations of the above ranges are also possible (e.g., 50 wt% or more and 80 wt% or less). Other ranges are also possible.

[0040]

[0051] As described above, according to certain embodiments, the plurality of ion-conducting particles may also include a plurality of inorganic solids (e.g., ceramics or glass) and / or electroactive material particles dispersed in a continuous phase of a thermoplastic polymer forming the individual ion-conducting particles. According to some such embodiments, the plurality of inorganic solids and / or electroactive material particles are uniformly dispersed in the thermoplastic polymer such that, for example, there is little or no particle aggregation. In some such examples, the number of particles (e.g., inorganic solids and / or electroactive material particles) per unit volume of ion-conducting particles can be substantially the same. During the production of ion-conducting particles, mechanical forces such as stirring and / or mixing can be applied to uniformly disperse the plurality of inorganic solids and / or electroactive material particles in the thermoplastic polymer.

[0041]

[0052] It should be noted that the inorganic solids disclosed herein may include one or more selected from the group of ion-conducting or non-ion-conducting ceramics and / or glasses. In some examples, the inorganic solids may include ion-conducting materials that can favorably facilitate ion transport between electrodes in an electrochemical cell. For example, the use of ion-conducting ceramics or glasses in ion-conducting powders (e.g., electrolytes and electrode powders) described herein can facilitate ion transport in the resulting electrolyte or electrode layer. In consideration of the foregoing, the ion-conducting materials that can be used may include one or more ion-conducting metal oxides and / or ceramics such as metal oxides that facilitate ion transport through the inorganic solid and / or along the interface with the surrounding thermoplastic polymer matrix. These materials include, but are not limited to, Al2O3, SiO2, TiO2, MgO, ZnO, ZrO2, CuO, CdO, Li7La3Zr2O 12The material may include at least one of (LLZO) and Li2O. Instead of and / or in combination with the above metal oxides, the ion-conducting material may also include ion-conducting glasses such as one or more of Li2S, P2S5, and xLi2S-(1-x)P2S5. Although certain types of ion-conducting materials have been listed above, it will be understood that the disclosure is not limited to these materials and any suitable ion-conducting material may be used. In some embodiments, the inorganic solids may include non-ion-conducting ceramics or glasses. In some such embodiments, non-ion-conducting inorganic solids (e.g., ceramics and / or glasses) can be used to provide structural integrity to the layers, which may be advantageous in applications such as solid electrolyte layers and / or separator layers in electrochemical cells. Of course, it will be understood that ion-conducting and non-ion-conducting inorganic solids are not limited to use in any particular application.

[0042]

[0053] In some embodiments, the plurality of inorganic solids disclosed herein, which may include a plurality of inorganic solid particles, include lithium-ion conductive additives. For example, the lithium-ion conductive additive may include one or more selected from the group of non-lithified inorganic solids (e.g., non-lithified ceramics and / or non-lithified glasses). In some such embodiments, a non-lithified inorganic solid refers to an inorganic solid that lacks lithium atoms. Advantageously, the presence of such a non-lithified inorganic solid can form an ion-conductive powder with increased lithium-ion conductivity. In some embodiments, the non-lithified inorganic solid includes ion-conductive non-lithified ceramics (e.g., metal oxides) and / or ion-conductive non-lithified glasses. Examples of such non-lithified inorganic solids include, but are not limited to, Al2O3, SiO2, TiO2, MgO, ZnO, ZrO2, CuO, CdO, P2S5, or combinations thereof. While various embodiments described herein relate to lithium-ion conductive additives including non-lithified inorganic solids, this disclosure is not limited thereto, and it will be understood that lithium-ion conductive additives in particular embodiments may include lithified inorganic solids (e.g., lithified ceramics and / or lithified glass). For example, in some cases the lithified inorganic solid may be Li7La3Zr2O 12 Includes ceramics such as (LLZO).

[0043]

[0054] According to certain embodiments, the ion-conducting powder contains a substantial amount of a plurality of inorganic solids described herein (e.g., Li-ion conductive and / or non-lithium-containing ceramics and / or glass). Any suitable amount of any of the inorganic solids may be present in the powder so that the powder has a particular desired ion conductivity or other desired properties. For example, the weight percentage (wt%) of the plurality of inorganic solids in the powder can be at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt% of the total weight of the powder. In some embodiments, the weight percentage (wt%) of the plurality of inorganic solids in the powder can be 75 wt% or less, 65 wt% or less, 55 wt% or less, 45 wt% or less, 35 wt% or less, 25 wt% or less, 15 wt% or less, 5 wt% or less, or 1 wt% or less of the total weight of the powder. Combinations of the above ranges are also possible (e.g., at least 50 wt% and 70 wt% or less, or at least 10 wt% and 75 wt% or less). Other values, including both larger and smaller values ​​than those above, are also possible. Furthermore, it should be noted that weight percentages of inorganic solids greater than about 50 wt% that can be achieved using the methods and materials described herein may be difficult or impossible to achieve using typical manufacturing methods such as slurry casting. It should also be noted that the presence of a relatively large amount (e.g., at least 50 wt%) of ion-conducting inorganic solids can favorably form powders with increased lithium ion conductivity (e.g., solid electrolyte powders).

[0044]

[0055] It should be noted that the weight percentages mentioned above refer to the weight percentage in the final powder containing the ion-conducting particles. Therefore, different weight percentages may be present in the mixture during manufacturing if a solvent is used. For example, in some cases, multiple inorganic solids are present in amounts of 60 wt% or more of the mixture used to form an ion-conducting powder containing multiple ion-conducting particles. It should be noted that any amount of inorganic solid may be present in the mixture, as long as the amount (wt%) of inorganic solid in the resulting ion-conducting powder falls within the range described above. It should be noted that the same applies to all other components in the mixture, such as ion-conducting salts, thermoplastic polymers, electroactive material particles, and additives. These components may be present in the mixture in any amount (wt%), as long as the wt% of each component in the resulting ion-conducting powder falls within the range described elsewhere in this specification.

[0045]

[0056] In some embodiments, the multiple inorganic solids described herein are provided as multiple particles, and these particles may have any suitable particle size. For example, the average maximum cross-sectional dimension of the multiple inorganic solids may be 100 μm or less, 80 μm or less, 60 μm or less, 40 μm or less, 20 μm or less, 10 μm or less, or 5 μm or less. Accordingly, the average maximum cross-sectional dimension of the multiple inorganic solids may be 1 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, 40 μm or more, 60 μm or more, 80 μm or more, and / or any other suitable range. For example, combinations of the above values ​​are envisioned, including the average maximum cross-sectional dimension of the multiple inorganic solids between 1 μm and 100 μm. Other values ​​including both larger and smaller dimensions than those mentioned above are also possible.

[0046]

[0057] As described above, according to certain embodiments, the plurality of ion-conducting particles may include a plurality of electroactive material particles dispersed in a thermoplastic polymer. In certain embodiments, the average maximum cross-sectional dimension of the plurality of electroactive material particles is 30 μm or less. However, the electroactive material particles may have any suitable particle size. For example, the average maximum cross-sectional dimension of the plurality of electroactive material particles can be less than 100 μm, 100 μm or less, 70 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less. Accordingly, the average maximum cross-sectional dimension of the electroactive material particles can be 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, and / or any other suitable range. For example, the above combinations of values ​​are conceivable, including the average maximum cross-sectional dimension of electroactive material particles between 10 μm and 100 μm. Other values ​​are also possible.

[0047]

[0058] In certain embodiments, electroactive material particles comprise one or more electroactive materials. For example, the electroactive materials that may be used are, 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 iron manganese phosphate (LMFP), lithium nickel cobalt aluminum oxide (NCA), lithium titanate (LTO), lithium manganese oxide (LMO), lithium manganese nickel oxide (LMNO), graphite, silicon, sulfur, and Prussian blue (i.e., PB or A). x Fe[Fe(CN)6], where A is an alkali metal), Prussian blue analogs (i.e., PBA or A x MA y [MB(CN)6]z·nH2O, where MA and MB are transition metals typically selected from the group Mn, FeCo, Ni, Cu, and Zn, and A is typically selected from the group Li, Na, or K), Prussian white (i.e., PW or Na2CoFe(CN)6), and / or combinations thereof. While specific types of electroactive materials have been listed, it should be understood that this disclosure is not limited to these materials, and any suitable electroactive material may be used.

[0048]

[0059] In some embodiments, the electroactive material particles may include one or more of the above electroactive materials that may be particularly advantageous for use as electrolytes and / or electrode powders in solid sodium ion batteries. In some such embodiments, the electroactive material particles may include a sodium-based electroactive material (e.g., a material containing sodium atoms). In embodiments where the battery is a sodium ion battery, the electroactive material particles (e.g., cathode powder) may include one or more of the electroactive materials (e.g., cathode electroactive materials) selected from the group consisting of Prussian blue, Prussian blue analogs, and Prussian white. In some embodiments, one or more of the electroactive materials selected from the group consisting of Prussian blue, Prussian blue analogs, and Prussian white contain sodium (e.g., A represents Na such as A x Fe[Fe(CN)6], A x MA y [MB(CN)6] z ·nH2O, etc.).

[0049]

[0060] In some embodiments, at least one of the multiple ion-conducting particles contains one or more additives. In some embodiments, one or more additives are dissolved or dispersed in a thermoplastic polymer. In some such embodiments, one or more additives contain plasticizers. Non-limiting examples of plasticizers include, but are not limited to, succinonitrile (SN), glutaronitrile (GN), etc. Additives such as plasticizers can be introduced into a thermoplastic polymer to increase its plasticity or reduce its viscosity, for example, to facilitate handling during manufacturing. Any suitable amount of additives may be present in the multiple ion-conducting particles. For example, the additive may be present in an amount of at least 10 wt%, at least 20 wt%, or at least 30 wt% of the total weight of the powder. In some embodiments, the additive may be present in an amount of 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, or 5 wt% or less of the total weight of the powder. Of course, weight percentages of additives including both larger and smaller values ​​than those mentioned above are also conceivable.

[0050]

[0061] As described above, certain embodiments involve dissolving an ion-conducting salt and a thermoplastic polymer in a solvent by a co-dissolution process. It will be understood that any suitable type of solvent can be used to dissolve the thermoplastic polymer and the ion-conducting salt. For example, depending on the specific salt and polymer used, non-limiting examples of solvents may include, but are not limited to, acetone, DMSO, DMF, acetonitrile, ethanol, methanol, deionized water, etc. In some embodiments, the solvent must be capable of dissolving the polymer and salt to the required concentration and evaporating at the required rate to prevent recrystallization of the ion-conducting salt. For example, a solvent (e.g., N,N-DMF) is more favorable than another solvent (e.g., acetone) for co-dissolving a salt (e.g., LiBOB) and a thermoplastic polymer, and can achieve a suitable evaporation rate during drying to prevent recrystallization of the salt. In some examples, favorable solvent selection can achieve a suitable solvent evaporation rate (e.g., not too fast or too slow) to prevent salt crystallization and allow for uniform distribution of the salt throughout the ion-conducting particles during spray drying. In one particular embodiment, LiTFSI and PVDF-co-HFP can be co-dissolved in acetone. Considering the above, it will be understood that in some embodiments, the solvent used in the various embodiments described herein may be a liquid solvent.

[0051]

[0062] In embodiments using photocuring of ion-conducting particles, a photocurable polymer can be selected based on its solubility in a given photoinitiator and / or ion-conducting salt. Any suitable photocurable polymer and / or monomer may be used. For example, non-limiting examples of photocurable monomers include, but are not limited to, acrylic acid, acrylonitrile, vinyl acetate, methacrylate, methacrylic acid, ethylene oxide, ethylene glycol, N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, 4-vinylpyridine, 2-hydroxyethyl acrylate (HEA), N,N-dimethylaminoethyl methacrylate, quaternary ammonium compounds, and their derivatives. Quaternary ammonium compounds are cationic compounds having a protonated basic nitrogen atom or containing a quaternary nitrogen atom. Exemplary quaternary ammonium compounds include N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, allylamine, vinylamine, L-lysine, ornithine, L-arginine, and D-glucosamine.Non-limiting examples of photocurable polymers include, but are not limited to, polyimides, poly(ethylene glycol) diacrylate (PEGDA), and poly(ethylene glycol) diacrylamide (PEGDAA); polysaccharides such as cellulose, alginates, chitosan, hyaluronic acid, glucosaminoglycans, dimethylaminoethyl (DEAE)-cellulose, and DEAE-dextran; hydrophilic poly(amino acids) such as poly-L-glutamic acid, gamma-polyglutamic acid, poly-L-aspartic acid, poly-L-serine, polyornithine, poly-L-arginine, and poly-L-lysine; poly(oxyethylated polyols); poly(olefin alcohols) such as poly(vinyl alcohol) and aminoacetalized poly(vinyl alcohol); poly(N-vinylpyrrolidone); poly(amideamine); poly(acrylic This includes acrylic or acrylate polymers such as acids, poly(acrylate), poly(methacrylic acid), poly(methacrylate), poly(hydroxyethyl acrylate), and alkacrylic or alkacrylate polymers; poly(N,N-dimethylaminoethyl methacrylate), poly(N,N-dimethylaminoethyl acrylate), poly(hydroxyalkyl methacrylate), e.g., poly(hydroxyethyl methacrylate); acrylamide polymers such as poly(acrylamide), poly(N,N-dimethylacrylamide), poly(hydroxyalkyl methacrylamide), e.g., poly(hydroxyethyl methacrylamide); poly(ethyleneimine); poly(allylamine); poly(bilylamine); poly(4-vinylpyridine); and copolymers thereof.

[0052]

[0063] It should be noted that the photocurable polymer can be selected to have any appropriate average molecular weight, depending on the desired properties of the crosslinked polymer matrix in the resulting ion-conducting particles. For example, if a rigid crosslinked polymer network with a small mesh size is desired, a low molecular weight photocurable polymer can be selected. Conversely, if a relatively flexible crosslinked polymer network with a large mesh size is desired, a high molecular weight photocurable polymer may be selected.

[0053]

[0064] Any suitable photoinitiator can be used to photoinitiate the polymerization of photocurable polymers and / or monomers. In some examples, the photoinitiator may be selected on a hydrophobic basis so that an effective amount for initiating the polymerization reaction can be dissolved in the photocurable polymer. Suitable initiators and activators for polymerization and crosslinking polymerizable monomers or macromas are known in the art. These include, but are not limited to, free radical initiators, atom transfer radical polymerization (ATRP) initiators, nitroxide-mediated polymerization (NMP) initiators, ionic polymerization initiators, amine photochemical co-initiators, and organic photoinitiators. Examples of photoinitiators include, but are not limited to, methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, and the like. Any suitable amount of photoinitiator may be present in the mixtures described herein. For example, the photoinitiator may be present in an amount of at least 1 wt%, at least 5 wt%, at least 10 wt%, at least 20 wt%, or at least 30 wt% of the total weight of the mixture. In some embodiments, the additive may be present in the mixture in amounts of 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, or 1 wt% or less. Of course, the disclosure is not so limited, and both larger and smaller weight percentages of the photoinitiator present in the mixture may also be used.

[0054]

[0065] It will be understood that a photocurable polymer may possess the properties of a thermoplastic polymer once it has been photocured. For example, polyethylene glycol diacrylate (PEGDA) of a specific molecular weight (e.g., 575 g / mol, 700 g / mol, etc., Mn) can be used and photopolymerized to form a crosslinked network containing polyethylene glycol (PEG), i.e., a thermoplastic polymer. Therefore, the disclosed photocured polymer may be any of the thermoplastic polymers discussed herein. Furthermore, when both a photocurable polymer and a thermoplastic polymer are present in the spray mixture, the resulting ion-conductive particles may include a continuous phase containing a thermoplastic polymer uniformly mixed within the crosslinked polymer network formed by the photocured polymer.

[0055]

[0066] Certain aspects of this disclosure relate to a method of using a plurality of ion-conductive particles disclosed herein by spray deposition to form, for example, a solid electrolyte layer and / or a solid electrode layer in an electrochemical cell. According to some embodiments, the plurality of ion-conductive particles used herein can be formed according to any one of the aforementioned methods, such as low-temperature milling, spray drying, or aerosol polymerization. In some embodiments, a system for forming particle layers on a substrate includes at least one sprayer configured to charge and spray the disclosed ion-conductive particles toward the substrate to form one or more layers of ion-conductive particles arranged on the substrate. These layers may correspond to one or more selected from the group of electrode layers (e.g., anode or cathode), solid electrolyte layers, separator layers, or any other desired material layers. Depending on the particular application, the substrate may be heated before, during, and / or after spray deposition of the ion-conductive powder to improve the adhesion of the sprayed particle layer to the substrate. Heating of the substrate can be performed using any suitable method. This method includes, but is not limited to, radiant heating of the substrate, conductive heating of the substrate, convective heating of the substrate, and / or resistive heating of the substrate when an electric current is passed through the portion of the substrate corresponding to the location on which ion-conductive particles are sprayed onto the substrate. The material is sprayed onto the heated substrate and any layers already deposited on the substrate. The deposited material can adhere to the heated substrate or layers, forming a desired layer thereon (e.g., an electrolyte layer and / or an electrode layer).

[0056]

[0067] In some embodiments, it may be desirable to deposit two or more material layers on a substrate. In such embodiments, a first set of ion-conductive particles, such as electrode powder, can be provided to the substrate to form a first electrode layer, such as an anode or cathode, on the provided substrate. In embodiments where the first layer is an electrode layer, a second set of ion-conductive particles may be made from a material for forming a solid electrolyte layer to be placed on top of the electrode layer. For example, an electrolyte layer can be formed by providing a second set of ion-conductive particles, such as electrolyte powder, on the first electrode layer of the substrate. The disclosure is not limited thereto, and any number of suitable material layers can be formed for any desired application using the systems and methods described herein. For example, additional material layers (e.g., additional electrode layers, separator layers, solid electrolytes, etc.) can be deposited as needed for the application.

[0057]

[0068] Using ion-conducting powders in spray deposition can easily access a wide range of compositional parameters that were previously unavailable with slurry casting methods. For example, ion-conducting powders can hold high concentrations of inorganic solids (e.g., at least 60 wt%) and / or high concentrations of ion-conducting salts (e.g., at least 50 wt%). Furthermore, a wide variety of components (e.g., salts, electroactive materials, ceramic powders, plasticizers, thermoplastic polymers, and other additives) can be simultaneously incorporated into the ion-conducting particles. For example, as mentioned above, the complexity of production can be reduced by combining these components into a mixture in a one-step process during powder manufacturing.

[0058]

[0069] Different types of ion-conducting powders can be formed simply by adjusting the components in a combined mixture. For example, the method described herein allows for easy switching between the production of different types of powders (e.g., electrolyte powder, electrode powder). Advantageously, by using these powders in combination, solid-state batteries can be constructed containing a desired number and type of structures (e.g., electrode layers, electrolyte layers).

[0059]

[0070] When the ion-conducting powders described herein are used in the manufacture of electrochemical cells, electrochemical cells with improved conductivity and extended battery life can be obtained. For example, uniform solvation of ion-conducting salts and / or uniform dispersion of electroactive materials and / or ceramic powders in multiple ion-conducting powders makes it possible to form electrode / electrolyte layers with improved conductivity. Furthermore, because the moisture content and residual solvent content associated with the powders are low, degradation of the electrochemical cell is reduced, thereby extending its operating life.

[0060]

[0071] Moving on to the drawings, certain non-limiting embodiments will be described in more detail. Since this disclosure is not limited to the specific embodiments described herein, it will be understood that various systems, components, features, and methods relating to these embodiments may be used individually and / or in any desired combination.

[0061]

[0072] Figure 1 shows a schematic diagram of ion-conducting particles according to a particular embodiment. A non-limiting cross-section of the ion-conducting particle 10 is shown. The particle comprises a continuous phase 15, which comprises an ion-conducting salt dissolved in a thermoplastic polymer, and optionally also comprises a plurality of inorganic solid particles (e.g., ceramic and / or glass particles) 20 and / or electroactive material particles 25 dispersed in the continuous phase. As shown, the plurality of inorganic solid particles 20 and / or electroactive material particles 25 can be uniformly dispersed in the thermoplastic polymer. However, examples are also conceivable in which two or more particles form aggregates within the continuous thermoplastic phase. In some cases, at least one or more of the plurality of dispersed inorganic solid particles and / or electroactive material particles can be embedded at least partially within the ion-conducting polymer. For example, as shown in Figure 1, the majority of the electroactive material particles 25 are completely embedded within the internal volume of the ion-conducting particle 10, while the electroactive material particles 25A are only partially embedded, as indicated by, for example, the partial protrusion of particles 25A outside the thermoplastic polymer 15.

[0062]

[0073] It should be noted that other combinations of components and arrangements may be possible within the ion-conducting particles. For example, in one specific set of embodiments, the ion-conducting particles comprise an ion-conducting salt, inorganic solid particles, a thermoplastic polymer, and an optional additive such as a plasticizer. In another specific set of embodiments, the ion-conducting particles comprise electroactive material particles, inorganic solid particles (e.g., ceramic and / or glass particles), a thermoplastic polymer, a plasticizer, and an optional ion-conducting salt. Furthermore, embodiments in which the ion-conducting particles substantially do not contain fine particles are also conceivable. In some examples, it is also possible to incorporate other components, such as photocurable polymers, into the ion-conducting particles, as disclosed elsewhere in this specification.

[0063]

[0074] Figure 2 shows a schematic diagram of a method for producing ion-conducting particles according to a particular embodiment, which involves directly dissolving an ion-conducting salt in a molten polymer and then performing a low-temperature mill. According to a particular embodiment, moisture is removed from the individual components of the mixture before mixing. This may include drying the thermoplastic polymer, the ion-conducting salt, and any optional components (e.g., additives, electroactive materials, inorganic solids (e.g., ceramic and / or glass powders), etc.) by heating, vacuum treatment, exposure to a low-moisture atmosphere, a combination thereof, and / or any other suitable drying method before forming the mixture (e.g., 30 in Figure 2). In some examples, moisture is removed before forming the mixture so that the moisture content of all components is 2 wt%, 1 wt%, 0.5 wt%, 0.2 wt%, 0.1 wt%, or any other suitable weight percent. As shown in Figure 2, the thermoplastic polymer can then be melted and combined with the ion-conducting salt to form the mixture (e.g., 35 and 40 in Figure 2). Optionally, other components such as electroactive material particles, inorganic solid particles, and additives (e.g., plasticizers) may be incorporated into the mixture. According to certain embodiments, the mixture is then stirred to dissolve the ion-conducting salt and, optionally, to uniformly disperse the additional components (e.g., electroactive material particles, inorganic solid particles, additives, etc.) into the molten thermoplastic polymer (e.g., 45 in Figure 2). It should be noted that the thermoplastic polymer can be stirred at a temperature relatively close to its melting point without significant aeration. This is because excessively high temperatures (e.g., close to the decomposition temperature) or strong aeration can lead to undesirable degradation of the thermoplastic polymer. Depending on the type of additive, it should be noted that the additive may be dissolved or dispersed into the thermoplastic polymer. Any suitable stirring method and stirring time can be used, as will be discussed below.

[0064]

[0075] After mixing, the mixture obtained by 45 may be cooled and solidified at a temperature higher or lower than the glass transition temperature of the thermoplastic polymer, as described above (e.g., 50 in Figure 2). The solidified mixture obtained by 50 may be ground to form particles, such as the ion-conducting particles described herein. As described above, any type of milling apparatus (e.g., ball mill, knife mill, etc.) may be used. The particles may be ground until a target particle size is reached (e.g., 55 in Figure 2). The final particle size may be controlled by several operating parameters, including milling time and frequency, but is not limited to these. In some examples, the ground particles may be optionally passed through one or more sieves containing meshes of a specific size, for example, to remove larger particles and / or to reduce the polydispersity of the size of the ground particles.

[0065]

[0076] As described above, in certain embodiments, the ion-conducting salt can dissolve in the molten thermoplastic polymer at a temperature above the melting point of the thermoplastic polymer. For example, the ion-conducting salt can dissolve in the molten thermoplastic polymer at temperatures of 350°C or below, 300°C or below, 250°C or below, 175°C or below, 150°C or below, 125°C or below, 100°C or below, 80°C or below, 60°C or below, 40°C or below, and 20°C or below. In some embodiments, the ion-conducting salt can dissolve in the molten thermoplastic polymer at temperatures of at least 20°C, at least 40°C, at least 60°C, at least 80°C, at least 100°C, at least 140°C, at least 180°C, at least 220°C or at least 260°C. Combinations of the above ranges are also possible (e.g., at least 60°C and 175°C or below). Other values ​​are also possible depending on the specific salt and polymer used. For example, the ion-conducting salt can dissolve in some thermoplastic polymers (e.g., copolymer blends) at room temperature.

[0066]

[0077] It will be understood that any suitable method can be used to stir the mixture to uniformly dissolve the ion-conducting salt in the molten polymer and / or uniformly disperse the particles in the mixture. For example, the mixture may be heated to a temperature such that the thermoplastic polymer has a desired viscosity so that multiple inorganic solid particles and / or electroactive material particles can be efficiently mixed and dispersed in the thermoplastic polymer. In certain embodiments, depending on the viscosity of the thermoplastic polymer, the mixture may be stirred for an appropriate amount of time (e.g., at least 0.25 days, at least 0.5 days, at least 1 day, at least 2 days, etc.) until uniform dispersion is achieved. Any suitable stirring method can be used, such as mechanical stirring (e.g., a mixer) or ultrasonic stirring (e.g., an ultrasonic crushing device).

[0067]

[0078] As described above, after stirring the mixture, the resulting mixture can be solidified by cooling it to a temperature higher or lower than the glass transition point of the thermoplastic polymer, depending on the specific materials used. In some embodiments, the powder can be ground at temperatures below 100°C, below 80°C, below 60°C, below 40°C, below 20°C, below 0°C, below -20°C, below -40°C, or below -60°C. Other temperatures may also be possible if the solidified mixture can be effectively ground.

[0068]

[0079] Figure 3 shows a schematic diagram of a method for producing ion-conducting particles, including spray drying and / or aerosol polymerization, according to a specific embodiment. First, before forming the mixture, water can be removed from the individual components of the mixture, which includes a thermoplastic polymer, an ion-conducting salt, and optional components (e.g., additives, electroactive material particles, inorganic solid particles, etc.) (e.g., 30 in Figure 3). It should be noted that this water removal step may be the same as in the embodiment described with respect to Figure 2. For example, before forming the mixture, water can be removed so that the water content of all components is 0.5 wt% or less.

[0069]

[0080] As shown in Figure 3 at 60, a thermoplastic polymer can be combined with an ion-conducting salt and a solvent to form a mixture. Optionally, other components such as electroactive material particles, inorganic solid particles, and additives (e.g., plasticizers) may be incorporated into the mixture. According to certain embodiments, the mixture can be stirred to dissolve both the salt and the polymer in the solvent through a co-dissolution process, while optionally containing materials (e.g., electroactive material particles, ceramic powder, etc.) in the solvent (e.g., at 65 in Figure 3). Any of the aforementioned ion-conducting salts, thermoplastic polymers, and solvents may be used. Any stirring means can be used, provided that proper solvation of the salt and polymer, as well as dispersion of components in the mixture (e.g., electroactive material, ceramic powder), can be achieved. For example, a mechanical mixer, an ultrasonic device, and / or any other suitable mixing method may be used to stir the mixture so that multiple inorganic solid particles and / or electroactive material particles are uniformly dispersed in the thermoplastic polymer.

[0070]

[0081] As shown in Figure 3, 70, the mixture can then be sprayed, or aerosolized, to form a plurality of droplets having a desired range of sizes. In some examples, the solvent can be evaporated from the aerosolized mixture (droplets) to form a plurality of ion-conducting particles (e.g., Figure 3, 75). In some such examples, the resulting plurality of ion-conducting particles are substantially solvent-free. For example, according to certain embodiments, the plurality of ion-conducting particles contain a solvent and / or water content of 0.5 wt% or less, or any other solvent / water content disclosed elsewhere in this specification. In some cases, as described elsewhere in this specification, if a photocurable polymer is present in the mixture (e.g., Figure 3, 30), a polymerization reaction may occur in the droplets during the spraying or aerosol polymerization process in which the photocurable polymer and initiator present in the droplets are exposed to electromagnetic radiation to photocur the ion-conducting particles (e.g., Figure 3, 75). Such processes are further described in relation to Figures 5 to 6.

[0071]

[0082] Figures 4A and 4B show schematic diagrams of a method for creating the ion-conducting particles shown in Figures 2(40 and 45) according to a particular embodiment. Figure 4A shows schematic diagram 100 related to the direct dissolution of the material in the molten polymer. As shown, the mixture placed in the container 125 may contain an ion-conducting salt 115 combined with a molten thermoplastic polymer 15. The mixture may contain one or more optional components, including additives 105, electroactive material particles 25, and inorganic solid particles 20. The mixture can be stirred at a high temperature for an appropriate amount of time using a mixing blade 120 to dissolve the ion-conducting salt and uniformly disperse the optional components, although other methods described above for mixing the mixture may also be used.

[0072]

[0083] After the mixture has cooled and solidified (e.g., 50 in Figure 2), the solidified mixture can be ground. Figure 4B shows a schematic diagram relating to a low-temperature milling system 200 using a ball mill. As shown, the ball mill includes an inlet 230, a rotating cylinder 210 partially filled with balls 205, and an outlet 235. During operation, the raw material for the solidified mixture 220 can be supplied into the rotating cylinder 210 through the inlet 230. As the rotating cylinder 210 rotates around its central axis, the balls 205 roll and collide with the solidified mixture 220, grinding the solidified mixture 220 into particles of a specific average size. The ground particles can exit through the outlet 235. In some examples, the resulting particle size and polydispersity may be influenced by the operating time and power input of the ball mill, in addition to parameters such as the size and material of the balls. The solidified mixture can finally be ground to an ion-conductive powder 215 containing multiple ion-conductive particles. As shown in the figures, the resulting ion-conducting particles may include structures and materials as described in relation to the various embodiments disclosed herein.

[0073]

[0084] Figure 5 shows a schematic side view of an aerosol photopolymerization system according to a specific embodiment. As shown, the aerosol photopolymerization system 300 can be used to aerosolize a mixture into aerosolized droplets and then photopolymerize the aerosolized droplets to form a plurality of ion-conducting particles (for example, as shown in 75 of Figure 3). In some examples, the aerosol photopolymerization system 300 includes a spray nozzle 320 filled with a mixture 340, a light source 310 (e.g., a UV lamp), and a gas-filled chamber 315 housed in a container 305. As shown in Figure 5, the mixture 340 may include an ion-conducting salt, a photoinitiator, a photocurable polymer, and optionally a solvent. Depending on whether separate particles are arranged within the formed ion-conducting particles, one or more optional components (e.g., additive 105, inorganic solid particles 20, and electroactive material particles 25) may also be present in the mixture.

[0074]

[0085] As shown in Figure 5, the mixture 340 can be sprayed from the spray nozzle 320 into the internal gas-filled chamber 315, and the sprayed mixture is aerosolized by the spray nozzle 320 into droplets. Depending on the materials used, the gas-filled chamber may contain any suitable atmosphere, including but not limited to argon, nitrogen, and / or any other suitable gas, which is relatively unreactive with the material of the ion-conducting particles. It should be noted that this gas should be sufficiently dry, i.e., free of moisture, to avoid significant reactions with electroactive materials if present, and to further promote the evaporation of the solvent (including moisture) from the droplets. In some examples, it may also be desirable to control the temperature of the gas contained in the container to a desired operating temperature to facilitate the evaporation of the solvent from the droplets. Furthermore, the aerosolized droplets may be exposed to electromagnetic radiation from the in-flight light source 310. When exposed to light, the photocurable polymer in the aerosolized droplets can photopolymerize to form a powder 325 containing multiple curable ion-conducting particles 330. However, as mentioned above, examples in which a light source and photocurable polymer are not used are also conceivable. Therefore, in examples in which a photocurable polymer is used, the curable ion-conducting particles 330 may contain multiple dispersed components (e.g., electroactive material particles 25, inorganic solid particles 20, etc.) uniformly dispersed in the crosslinked polymer network 335, and may have the structure and composition described elsewhere in this specification.

[0075]

[0086] It should be noted that in some examples, the resulting powder (e.g., 325 in Figure 5) can be collected by any method, including, but not limited to, gravity sedimentation, inertial impaction, cyclone separation, and filtering.

[0076]

[0087] It should be noted that the average particle size of the resulting powder 325 can be controlled by adjusting several operating parameters, including, but not limited to, the viscosity of the mixture 340, the feeding rate of the mixture 340, the spray pressure of the nozzle 320, the temperature of the gas-filled chamber 315, and / or any other suitable operating parameters. The resulting multiple ion-conducting particles may have any of the average particle size and size polydispersity disclosed elsewhere in this specification.

[0077]

[0088] Figure 6 shows a schematic side view of a spray drying and aerosol photopolymerization system according to a particular embodiment. Figure 6 includes a dual spray drying and aerosol photopolymerization system 400 that has improved drying capabilities in addition to a previously disclosed spray polymerization system (e.g., 300 in Figure 5). For example, the spray drying and polymerization system 400 includes the same system components as the spray polymerization system described with respect to Figure 5, including a spray nozzle 320 filled with a mixture 340, a light source 310 (e.g., a UV lamp), and a gas-filled chamber 315 housed in a container 305. As described above, the mixture 340 includes an ionic conductive salt, a photoinitiator, a photocurable polymer, an optional solvent, and optional components (e.g., additive 105, inorganic solid particles 20, and electroactive material particles 25). Furthermore, according to a particular embodiment, the mixture 340 may include a thermoplastic polymer dissolved in the solvent.

[0078]

[0089] As shown in Figure 6, according to a particular embodiment, when the mixture 340 is sprayed from the spray nozzle 320 into the internal gas-filled chamber 315, the sprayed mixture is aerosolized by the spray nozzle 320 into droplets. Thus, the aerosolized droplets receive heat from both a heater 410, which can be a convection heater and / or a radiant heater positioned on both sides of the container toward the particle path, and may also be exposed to electromagnetic radiation from the light source 310 in the air. In such embodiments, by increasing solvent evaporation during photocuring, a powder 325 can be formed containing a plurality of substantially solvent-free cured ion-conducting particles 330. Similar to the embodiments described above, the cured ion-conducting particles 330 may contain a plurality of dispersed components (e.g., electroactive material particles 25, inorganic solid particles 20) uniformly dispersed in the crosslinked polymer network 420, and may have a structure and properties similar to those disclosed elsewhere in this specification and / or the ion-conducting particles 10 in Figure 1.

[0079]

[0090] While embodiments of the photocurable spraying system have been described above, it will be understood that similar spraying systems for forming the materials described herein may be used without a light source when evaporating a solvent from droplets that do not contain a photocurable polymer.

[0080]

[0091] Figure 7 is a schematic side view of one embodiment of a spray deposition system 500 for forming layers on a substrate. Specifically, the spray deposition system of Figure 7 may be configured to form battery electrodes and / or solid electrolytes, including anode or cathode material. As shown in Figure 7, the spray deposition system includes an open-reel manufacturing system for moving a substrate 501, such as metal foil, through the system, although a static manufacturing mechanism is also conceivable. For example, in the illustrated embodiment, the system includes a first roller 502A and a second roller 502B, on which the substrate can be suspended. The first and second rollers are configured to move the substrate from one roller to the other (e.g., from the first roller to the second roller, or from the second roller to the first roller). In either case, the substrate is unwound from one roller and wound onto the other roller, allowing the material to be deposited in a continuous or semi-continuous process as needed. The spray deposition system also includes at least one sprayer 504 directed toward the substrate for depositing material onto the substrate. For example, according to a particular embodiment, a sprayer 504 can spray a plurality of ion-conducting particles 10 onto the deposition location on the substrate. The ion-conducting particles 10 can be the same particles as those described with respect to Figure 1 and may have any suitable properties of ion-conducting particles as described elsewhere in this specification.

[0081]

[0092] In embodiments where it is desirable to deposit material on both sides of the substrate simultaneously, two sprayers 504 can be positioned on either side of the substrate to deposit material on both surfaces of the substrate in a single process. In either case, the sprayers may be configured as spray guns or as any other suitable device capable of aerosolizing powder and, in some embodiments, appropriately charging it. This powder is then sprayed onto the surface of the substrate in a powder coating process. In the embodiments described above, each sprayer is connected to a storage unit 506 containing powdered material (e.g., a plurality of ion-conducting particles 550) for deposition on the substrate. In some embodiments, the storage unit may correspond to a fluidized bed, a Venturi sprayer, a Wright dust feeder, or any other suitable device capable of aerosolizing dry powder and / or transferring it to the sprayer in other ways. As will be further discussed with reference to Figure 7, the sprayers can charge the particles ejected from the spray gun, thereby facilitating the uniform distribution of particles onto the target substrate area of ​​the sprayer and adhering the particles to this area.

[0082]

[0093] As described above, the powdered material may contain any suitable material components used to form one or more layers within the electrochemical cell. These layers may include, but are not limited to, an anode layer, a cathode layer, a separator layer, and / or a solid electrolyte layer. These materials may include ion-conducting salts, thermoplastic polymers, ion-conducting inorganic materials (e.g., ion-conducting ceramics and / or glass powders), additives, electroactive materials, non-ion-conducting inorganic materials (e.g., non-ion-conducting ceramics or glass powders), conductive materials, combinations thereof, and / or any other suitable materials.

[0083]

[0094] As shown in the embodiment of Figure 7, the spray deposition system may also include one or more masks for defining the deposition area to which the sprayer is directed. For example, a first mask 508A and a second mask 508B can be used, coupled to a first mask actuator 510A and a second mask actuator 510B, respectively. According to the embodiment of Figure 7, the first and second masks are configured as clamps that close the top and bottom surfaces of the substrate 501 to selectively hold and cover areas of the substrate, keeping those areas bare during the spray deposition process. The first and second mask actuators are controlled by a first mask actuator controller 512A and a second mask actuator controller 512B. These controllers 512A and 512B can control the supply of electricity, air, and / or hydraulic fluid used by the mask actuators to move the masks to or from contact with the substrate. Of course, the disclosure is not limited thereto, and spray deposition systems in other embodiments may use a single mask actuator controller, or any other suitable number of mask actuator controllers controlling any suitable number of mask actuators. Furthermore, these controllers may include at least one hardware processor and at least one associated non-temporary computer-readable storage medium storing processor-executable instructions. These processor-executable instructions, when executed by at least one hardware processor, control the actuators and other components of the system to perform the methods described herein.

[0084]

[0095] According to certain embodiments, a charged particle spray can be applied to a heated substrate to form a film of ion-conductive particles on the substrate. In some examples, the first and second masks 508A, 508B are configured to resistively heat the substrate region between the masks by passing a current supplied by an associated power source through the substrate 501 between the first and second masks, so that one or more sprayers 504 can resistively heat the substrate region between the masks. That is, the combination of passing a current through the substrate and the substrate's internal electrical resistance generates internal heat in the substrate region between the first and second masks. For example, if the first and second masks are in contact with the substrate to mask exposed areas of the substrate from spray particles, these masks may be configured to function as electrodes that generate electrical contacts with the substrate. The spray deposition system 500 may also include a pair of calender rollers 514 that can be used to densify the deposited material layer. As the substrate passes between a pair of calender rollers, the calender rollers are heated, applying sufficiently high pressure to the substrate and any material layer that may be deposited on it, thereby densifying the layer to the desired thickness and bonding it to the substrate. Consequently, after the deposited material layer passes through the calender rollers, it can have a higher density and uniform thickness than an uncalendered layer.

[0085]

[0096] While a specific spray deposition system has been described in relation to Figure 7, this disclosure is not limited thereto, and it should be understood that any suitable spray deposition system capable of depositing the materials described herein may be used.

[0086]

[0097] Example 1

[0098] This example illustrates an experiment performed to produce an ion-conducting powder containing multiple ion-conducting particles according to a specific embodiment.

[0087]

[0099] Specifically, multiple ion-conducting particles were produced using a method including spray drying (shown, for example, in Figure 3). First, water was removed from the individual components, including the PVDF-HFP polymer, lithium manganese cobalt oxide (NMC) electroactive particles (average particle size approximately 20 μm), and LiTFSI salt. PVDF-HFP (Sigma-Aldrich purity 99.9%) was mixed with LiTFSI (Sigma-Aldrich purity 99.9%) in a weight ratio of 60:40. The resulting powder mixture was solvated in 0.03 g / mL acetone. To solvate or disperse the individual components in acetone, the mixture was stirred at 300-600 rpm at room temperature until LiTFSI and PVDF-HFP were sufficiently dissolved in the acetone, and until the NMC particles were uniformly dispersed in the acetone. Approximately 50 mL of the mixture was packed into a spray-drying solution column and aerosolized. The resulting mixture was sprayed in a chamber at 30-60°C. The supply pressure was approximately 75 psi. Multiple ion-conducting particles were generated by evaporating acetone during aerosolization. The resulting ion-conducting particle size was optimized by adjusting the input pressure and supply rate of the mixture, the mixture composition (e.g., the amount of PVDF-HFP and / or LiTFSI), and the gas pressure in the atomizer chamber. Particles containing LiTFSI dissolved in PVDF-HFP but without NMC were also generated.

[0088]

[0100] The resulting ion-conducting particles contained a continuous phase comprising PVDF-HFP, uniformly distributed LiTFSI after solvation, and uniformly dispersed NMC. Figure 8A shows images of multiple ion-conducting particles, including PVDF-HFP, LiTFSI, and lithium nickel manganese cobalt oxide (NMC) particles, produced by spray drying. Figures 9A to 9F show additional optical images of multiple ion-conducting particles. Figure 8B shows SEM-EDS images of multiple ion-conducting particles from Figure 8A, showing a uniform sulfur distribution from LiTFSI in multiple spray-dried ion-conducting particles. Figures 10A to 10E show EDS images of other elements (e.g., F, Co, Mn, Ni). For example, Figure 10A shows an SEM image of multiple ion-conducting particles, and Figures 10B to 10E show the corresponding SEM-EDS images of fluorine-containing particles (Figure 10B), cobalt-containing particles (Figure 10C), manganese-containing particles (Figure 10D), and nickel-containing particles (Figure 10E) in the multiple ion-conducting particles. As shown, multiple NMC electroactive particles (Figures 10C to 10E) consisting of Ni, Mn, and Co were at least partially or completely encapsulated in polymers and characterized by fluorine-containing particles (Figure 10B).

[0089]

[0101] Thermogravimetric analysis (TGA) was performed on the spray-dried ion-conducting particles obtained in this way to determine the amount of residual acetone and water in the particles. As shown in Figure 11, the TGA results confirmed that very small amounts of residual acetone and water, on the order of less than 0.5 wt%, were present in multiple ion-conducting particles measured after spray drying.

[0090]

[0102] While this instruction has been described in relation to various embodiments and examples, it is not intended to limit this instruction to such embodiments or examples. On the contrary, this instruction includes various substitutes, modifications, or equivalents, as will be recognized by those skilled in the art. Accordingly, the foregoing description and drawings are for illustrative purposes only.

Claims

1. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is The continuous phase of the crosslinked thermoplastic polymer matrix, The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer matrix, A plurality of inorganic solid particles and / or electroactive material particles dispersed and suspended in the crosslinked thermoplastic polymer matrix, Ion-conducting powder containing [a specific substance].

2. The powder according to claim 1, wherein the weight percentage (wt%) of the plurality of inorganic solid particles in the powder is at least 60 wt% of the total weight of the powder.

3. The powder according to any one of claims 1 to 2, wherein the plurality of inorganic solid particles include ceramic and / or glass particles.

4. The powder according to any one of claims 1 to 3, wherein the crosslinked thermoplastic polymer matrix comprises at least one selected from the group consisting of polyvinylidene fluoride, polyethylene glycol, polyvinyl acetate, poly(vinylidene fluoride-hexafluoropropylene copolymer), polytetrafluoroethylene, styrene butadiene, polyethylene oxide, polyacetylene, polyphenylene, polypyrrole, polythiophene, polyaniline, polyphenylene sulfide, poly(vinyl alcohol), polyethyleneimine, poly(vinylpyrrolidone), poly(ethylene carbonate), and poly(propylene carbonate).

5. The powder according to any one of claims 1 to 4, wherein the crosslinked thermoplastic polymer matrix comprises poly(vinylidene fluoride-hexafluoropropylene copolymer) (PVDF-HFP).

6. The powder according to any one of claims 1 to 5, wherein the average maximum cross-sectional dimension of the plurality of electroactive material particles is 30 μm or less.

7. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is Crosslinked thermoplastic polymers and The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer, A plurality of inorganic solid particles and / or electroactive material particles dispersed in the crosslinked thermoplastic polymer, Includes, The ion-conducting powder is characterized in that the ion-conducting salt is present in an amount of at least 5 wt% of the total weight of the powder.

8. The powder according to any one of claims 1 to 7, wherein the average maximum cross-sectional dimension of the plurality of ion-conducting particles is 250 μm or less.

9. The powder according to any one of claims 1 to 8, wherein at least one of the plurality of ion-conducting particles further comprises a plasticizer.

10. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is Crosslinked thermoplastic polymers and The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer, A plurality of inorganic solid particles and / or electroactive material particles dispersed in the crosslinked thermoplastic polymer, Includes, An ion-conducting powder in which the plurality of inorganic solid particles and / or electroactive material particles are uniformly dispersed in the crosslinked thermoplastic polymer.

11. The powder according to any one of claims 1 to 10, wherein the electroactive material particles include at least one selected from the group consisting of lithium cobalt oxide, lithium nickel manganese cobalt oxide, lithium manganese cobalt oxide, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel cobalt aluminum oxide, lithium titanate, lithium manganese oxide, lithium manganese nickel oxide, graphite, silicon, and sulfur.

12. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is Crosslinked thermoplastic polymers and The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer, A plurality of inorganic solid particles and / or electroactive material particles dispersed in the crosslinked thermoplastic polymer, Includes, The electroactive material particles are an ion-conducting powder comprising at least one selected from the group consisting of Prussian blue, Prussian blue analogs, and Prussian white.

13. The ionic conductive salt is LiClO ４ LiBF ４ LiPF ６ LiAsF ６ , LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiDFOB, LiTDI, LiPDI, LiDCTA, LiNO ３ LiCl, LiI, and LiB(CN) ４ The powder according to any one of claims 1 to 12, comprising at least one selected from the group.

14. The inorganic solid particles are Al ２ O ３ , SiO ２ , TiO ２ , MgO, ZnO, ZrO ２ , CuO, CdO, Li ７ La ３ Zr ２ O １２ , and at least one selected from the group consisting of Li ２ O, and the powder according to any one of claims 1 to 13, which contains an ion-conductive metal oxide selected from at least one selected from the group.

15. The powder according to any one of claims 1 to 14, wherein the plurality of ion-conducting particles contain 0.5 wt% or less of a solvent.

16. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is Crosslinked thermoplastic polymers and The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer, A plurality of inorganic solid particles and / or electroactive material particles dispersed in the crosslinked thermoplastic polymer, Includes, The ion-conducting salt is present in an amount of 50 wt% or more relative to the total weight of the crosslinked thermoplastic polymer, and is an ion-conducting powder.

17. The powder according to any one of claims 1 to 16, wherein the plurality of inorganic solid particles include a lithium ion conductive additive selected from the group of non-lithiumized ceramics and / or non-lithiumized glass.

18. An ion-conducting powder comprising a plurality of ion-conducting particles, wherein at least one of the plurality of ion-conducting particles is Crosslinked thermoplastic polymers and The ion-conducting salt dissolved in the aforementioned crosslinked thermoplastic polymer, A plurality of inorganic solid particles dispersed in the crosslinked thermoplastic polymer, An ion-conducting powder comprising the plurality of inorganic solid particles in the powder, wherein the weight percentage of the plurality of inorganic solid particles in the powder is at least 50 wt% of the total weight of the powder.

19. The powder according to claim 18, wherein the weight percentage (wt%) of the plurality of inorganic solid particles in the powder is at least 60 wt% of the total weight of the powder.

20. The powder according to any one of claims 18 to 19, wherein the plurality of inorganic solid particles include a lithium ion conductive additive selected from the group of non-lithiumized ceramics and / or non-lithiumized glass.

21. The plurality of inorganic solid particles are Al ２ O ３ SiO ２ , TiO ２ , MgO, ZnO, ZrO ２ , CuO, CdO, and Li ７ La ３ Zr ２ O １２ The powder according to any one of claims 18 to 20, comprising one or more ion-conducting metal oxides selected from the group.

22. The powder according to any one of claims 18 to 21, wherein the ion-conducting salt is present in an amount of 50 wt% or more relative to the total weight of the crosslinked thermoplastic polymer.

23. The powder according to any one of claims 18 to 22, wherein the crosslinked thermoplastic polymer comprises at least one selected from the group consisting of polyvinylidene fluoride, polyethylene glycol, polyvinyl acetate, poly(vinylidene fluoride-hexafluoropropylene copolymer), polytetrafluoroethylene, styrene butadiene, polyethylene oxide, polyacetylene, polyphenylene, polypyrrole, polythiophene, polyaniline, polyphenylene sulfide, poly(vinyl alcohol), polyethyleneimine, poly(vinylpyrrolidone), poly(ethylene carbonate), and poly(propylene carbonate).

24. The powder according to any one of claims 18 to 23, wherein the crosslinked thermoplastic polymer comprises poly(vinylidene fluoride-hexafluoropropylene copolymer) (PVDF-HFP).

25. The powder according to any one of claims 18 to 24, wherein the ion-conducting salt is present in an amount of at least 5 wt% of the total weight of the powder.

26. The powder according to any one of claims 18 to 25, wherein the average maximum cross-sectional dimension of the plurality of ion-conducting particles is 250 μm or less.

27. The powder according to any one of claims 18 to 26, wherein at least one of the plurality of ion-conducting particles further comprises a plasticizer.

28. The powder according to any one of claims 18 to 27, wherein the plurality of inorganic solid particles are uniformly dispersed in the crosslinked thermoplastic polymer.

29. The ionic conductive salt is LiClO ４ LiBF ４ LiPF ６ LiAsF ６ , LiFSI, LiTFSI, LiBETI, LiCTFSI, LiBOB, LiDFOB, LiTDI, LiPDI, LiDCTA, LiNO ３ LiCl, LiI, and LiB(CN) ４ The powder according to any one of claims 18 to 28, comprising at least one selected from the group.

30. The powder according to any one of claims 18 to 29, wherein the plurality of ion-conducting particles contain a solvent and / or water content of 0.5 wt% or less.

31. The powder according to any one of claims 1 to 30, wherein the plurality of ion-conducting particles contain a water content of 0.5 wt% or less.

32. The powder according to any one of claims 1 to 31, wherein the plurality of inorganic solid particles and / or electroactive material particles are mixed within the matrix of the crosslinked thermoplastic polymer.

33. The powder according to any one of claims 1 to 32, further comprising a conductive material dispersed in the crosslinked thermoplastic polymer.

34. The powder according to any one of claims 1 to 33, wherein the electroactive material particles include at least one selected from the group consisting of lithium cobalt oxide, lithium nickel manganese cobalt oxide, lithium manganese cobalt oxide, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel cobalt aluminum oxide, lithium titanate, lithium manganese oxide, lithium manganese nickel oxide, graphite, silicon, and sulfur.

35. A plurality of ion-conducting particles as described in any one of claims 1 to 34, Applying an electric charge to the aforementioned ion-conducting particle spray, Heating the substrate and To provide an ion-conducting particle spray to which the charge has been applied to the heated substrate, thereby forming a film of the ion-conducting particles on the substrate, A method that includes this.

36. The method according to claim 35, wherein the substrate is heated using resistive heating, conductive heating, convective heating, and / or radiant heating of the substrate.

Images