High-green-density ceramic for battery

Abstract

To provide a process and materials for producing a thin ceramic green tape by casting a ceramic raw material powder, precursor reactants, a binder, and a functional additive into a thin unsintered green tape in a non-reactive environment.SOLUTION: A process for producing a high-density green tape includes the steps of: (a) providing a slurry containing raw material powder; (b) mixing the slurry with a binder solution in a non-reactive environment; (c) casting the slurry in a non-reactive environment to form a green tape; and (d) drying the green tape in a non-reactive environment to achieve a geometric density greater than 2.9 g / ml.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 62 / 961,611, filed January 15, 2020, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Field

[0002] The present disclosure relates to precursors of inorganic green tapes having high density, processes for producing green tapes having high density using these precursors, and processes for producing sintered thin films using green tapes having high density. [Background technology]

[0003] background

[0003] Solid-state ceramics, such as lithium-stuffed garnet materials and lithium borohydrides, lithium oxides, lithium sulfides, lithium oxyhalides, and lithium halides, have several advantages as ion-conducting electrolyte membrane and separator materials in various electrochemical devices, including fuel cells and rechargeable batteries. Compared with their liquid-based counterparts, the above-mentioned solid ceramics have safety and economic advantages, as well as advantages related to the solid state and density of the materials, which enable correspondingly high volumetric and gravimetric energy densities when these materials are incorporated into electrochemical devices as electrolyte separators. Solid-state ion-conducting ceramics are well suited for solid-state electrochemical devices due to their high ionic conductivity in the solid state, their electrical insulating properties, and their chemical compatibility with various electrode materials, such as lithium metal, as well as their stability over a wide voltage window.

[0004]

[0004] While solid-state ion-conducting ceramics have a range of advantageous and beneficial properties, these materials suffer from various problems associated with the formation of dense green films (i.e., green tapes) and the subsequent sintering of these green tapes. When solid-state ion-conducting ceramics are typically formulated as thin films and sintered, these films tend to adhere to the substrates on which they are prepared, crack or warp due to processing conditions, or are too brittle to handle and manipulate after sintering. During sintering of thin films, these films tend to crack, warp, or have other surface degradation. Summary of the Invention [Problem to be solved by the invention]

[0005]

[0005] Thus, a series of problems exist in the related art related to casting green tapes of ceramics, such as, but not limited to, garnet, and sintering these green tapes to prepare thin, high-density garnet films. What is needed in the related art are improved materials and processes for casting green tapes having high densities, for example. [Means for solving the problem]

[0006] overview

[0006] This disclosure describes such materials and processes, as well as their manufacture and uses, and provides other solutions to problems in related fields.

[0007] In one embodiment, a process for producing high density green tape is described, the process comprising: (a) providing a slurry comprising at least one raw material powder; (b) mixing the slurry with a binder solution in a non-reactive environment; (c) casting the slurry in a non-reactive environment to form a green tape; (d) drying the green tape in a non-reactive environment to achieve a density greater than 2.9 g / ml comprising. In certain embodiments, each non-reactive environment is unique with respect to temperature, pressure, or atmospheric composition. In certain embodiments, each non-reactive environment is the same non-reactive environment.

[0008]

[0008] In some embodiments, at least one starting powder is calcined in a non-reactive environment to achieve a density greater than 4.7 g / ml as measured by geometric density. In some embodiments, the amount of at least one starting powder in the green tape is at least 50 wt%, 55 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 85 wt%, or 90 wt%. In some embodiments, at least one starting powder is selected from the group consisting of lithium-filled garnet, a chemical precursor of lithium-filled garnet, and lithium-filled garnet containing an aluminum oxide dopant. In some embodiments, the lithium-filled garnet is Li A La B M’ C M” D Zr E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≦ C ≦ 2, 0 ≦ D ≦ 2; 0 ≦ E < 2.5, 10 < F ≦ 13.5, and M’ and M” are each independently selected from the group consisting of Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, Ga, and Ta) and is a material selected from the group consisting of. In some embodiments, the particle size d 50 is from about 100 nm to 200 nm, about 200 nm to 300 nm, about 300 nm to 400 nm, about 400 nm to 500 nm, about 500 nm to 600 nm, about 600 nm to 700 nm, about 700 nm to 800 nm, about 800 nm to 900 nm, about 900 nm to 1 μm, about 1 μm to 2 μm, or about 2 μm to 3 μm.

[0009] In some embodiments, the process further comprises milling at least one raw material powder in a non-reactive environment in an anhydrous aprotic solvent. In some embodiments, the non-reactive environment comprises nitrogen gas and humidity at a dew point of about −10° C. to −20° C., about −20° C. to −30° C., about −30° C. to −40° C., about −40° C. to −50° C., or about −50° C. to −60° C. In some embodiments, the non-reactive environment comprises argon gas and humidity at a dew point of about −10° C. to −20° C., about −20° C. to −30° C., about −30° C. to −40° C., about −40° C. to −50° C., or about −50° C. to −60° C. In some embodiments, the aprotic solvent is selected from the group consisting of benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane. In some embodiments, the milling is selected from the group consisting of dry milling, attrition milling, ultrasonic milling, high-energy milling, wet milling, jet milling, and cryogenic milling. In some embodiments, the raw powder has a particle size d of about 100 nm to 200 nm, about 200 nm to 300 nm, about 300 nm to 400 nm, about 400 nm to 500 nm, about 500 nm to 600 nm, about 600 nm to 700 nm, or about 700 nm to 750 nm. 50 The mixture is ground until it has a

[0010] In some embodiments, prior to step (c) or step (d), the process comprises adding a slurry of the modified raw material powder in a non-reactive environment to a mixture of polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), other polyolefins such as ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), poly(ethylene-co-1-octene) (PE-co-PO), poly(ethylene-co-methylenecyclopentene) (PE-co-PMCP), stereoblock polypropylene (PTPE), and the like. In some embodiments, the process includes mixing a binder selected from the group consisting of a cellulose ester, ... 20 Fatty acids of the order of C8 to C 20 Alcohol of the order of C8-C 20The method further comprises milling a slurry of the modified raw powder with a dispersant selected from the group consisting of surfactants and dispersants from the following classes: alkylamines, phosphate esters, phospholipids, polymeric dispersants, such as poly(vinylpyridine), poly(ethyleneimine), poly(ethylene oxide) and its ethers, poly(ethylene glycol) and its ethers, polyalkyleneamines, polyacrylates, polymethacrylates, poly(vinyl alcohol), poly(vinyl acetate), polyvinyl butyral, maleic anhydride copolymers, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants. In some embodiments, the method further comprises milling a slurry of the modified raw powder with a dispersant selected from the group consisting of surfactants and dispersants from the following classes: C8 to C6 20 The fatty acids of interest are at least one of dodecanoic acid, oleic acid, stearic acid, linolenic acid, and / or linoleic acid. 20 By approximately, it is meant that the described organic group contains 8 to 20 carbon atoms. In some embodiments, C8 to C 20 The alcohol is at least one of dodecanol, oleyl alcohol, and / or stearyl alcohol. In some embodiments, the C8 to C 20The alkylamine is at least one of dodecylamine, oleylamine, and / or stearylamine. In some embodiments, the phospholipid is phosphatidylcholine and / or lecithin. In some embodiments, the process further comprises, prior to step (c) or step (d), mixing the slurry of raw material powder with a plasticizer selected from dibutyl phthalate, dioctyl phthalate, and benzyl butyl phthalate in a non-reactive environment. In some embodiments, the filtration technique is selected from the group consisting of sieving, centrifugation, and separation of particles of different sizes or masses. In some embodiments, the slurry has a solids loading of 1 wt% to 99 wt%, where solids loading refers to the amount of raw material powder. In some embodiments, the slurry contains 80% wt / wt raw material powder when dried. In some embodiments, the slurry contains about 10 to 25% wt / wt organic content when dried, where the organic content includes slurry components other than the raw material powder. In some embodiments, the green tape has a geometric density of 2.9 g / cm3. 3 In some embodiments, the green tape is sintered.

[0011] In some examples, including any of the above, the filtration technique occurs in a non-reactive environment. In some examples, including any of the filtration described above, the process includes filtering the slurry in a non-reactive environment.

[0012]

[0012] Some embodiments include: a. lithium-filled garnet particles or lithium-filled garnet precursor particles; b. at least one element selected from a binder, a plasticizer, a dispersant, and a surfactant; The present invention provides a free-standing green tape comprising:

[0013] In some embodiments, the free-standing green tape has a viscosity of 2.9 to 5.0 g / cm 3density, thickness of 0.5 to 100 μm, and thickness of 0.5 to 400 cm 2 In some embodiments, the particles have a lateral dimension of about 0.1-0.2 μm, about 0.2-0.3 μm, about 0.3-0.4 μm, about 0.4-0.5 μm, about 0.5-0.6 μm, about 0.6-0.7 μm, about 0.7-0.8 μm, about 0.8-0.9 μm, about 0.9-1.0 μm, or about 1.0-1.1 μm. 50 In some embodiments, the free-standing green tape has a thickness between about 500 nm and about 100 μm. In some embodiments, the area of ​​the green tape is at least 0.5 cm 2 In some embodiments, the thickness of the green tape is 10 cm 2 In some embodiments, the green tape has a ceramic loading of about 50-80 vol%, a thickness of about 0.5-100 μm, and an area of ​​about 0.5-400 cm 2 In some embodiments, the green tape has a ceramic loading of about 55-80 vol%, a thickness of about 0.5-100 μm, and a lateral dimension of about 0.5-400 cm 2 lateral dimension, ceramic loading of about 55 to 75 vol%, thickness of about 0.5 to 100 μm, and thickness of about 0.5 to 400 cm 2 lateral dimension, ceramic loading of about 50 to 75 vol%, thickness of about 0.5 to 100 μm, and thickness of about 0.5 to 400 cm 2 lateral dimension, ceramic loading of about 55 to 70 vol%, thickness of about 0.5 to 100 μm, and thickness of about 0.5 to 400 cm 2 lateral dimension, ceramic loading of about 50 to 65 vol%, thickness of about 0.5 to 100 μm, and thickness of about 0.5 to 400 cm 2 or a ceramic loading of about 55-65 vol%, a thickness of about 0.5-100 μm, and a thickness of about 0.5-400 cm 2 It has a lateral dimension of

[0014] In some embodiments, including any of the above, the green tape has a viscosity of 2.9 to 5.0 g / cm 3density, thickness of 0.5~100um, and 0.5~400cm 2 In some embodiments, the particles have a lateral dimension of about 0.1 to about 0.2 μm. 50 In some embodiments, the particles have a d of 0.2 to about 0.3 μm. 50 In some embodiments, the particles have a d of 0.3 to about 0.4 μm. 50 In some embodiments, the particles have a d of 0.4 to about 0.5 μm. 50 In some embodiments, the particles have a d of 0.5 to about 0.6 μm. 50 In some embodiments, the particles have a d of 0.6 to about 0.7 μm. 50 In some embodiments, the particles have a d of 0.7 to about 0.8 μm. 50 In some embodiments, the particles have a d of 0.8 to about 0.9 μm. 50 In some embodiments, the particles have a d of 0.9 to about 1.0 μm. 50 In some embodiments, the particles have a d of 1.0 to about 1.1 μm. 50 In some embodiments, the free-standing green tape has a thickness between about 500 nm and about 100 μm. In some embodiments, the area of ​​the green tape is at least 0.5 cm 2 In some embodiments, the thickness of the green tape is 10 cm 2 In some embodiments, the green tape has a raw powder solids loading of about 50 to about 80 vol%, a thickness of about 0.5 to about 100 um, and an area variation of about 0.5 to 400 cm. 2 In some embodiments, the green tape has a ceramic loading of about 55 to about 80 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2 In some embodiments, the green tape has a ceramic loading of about 55 to about 75 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2In some embodiments, the green tape has a ceramic loading of about 50 to about 75 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2 In some embodiments, the green tape has a ceramic loading of about 55 to about 70 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2 In some embodiments, the green tape has a ceramic loading of about 50 to about 65 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2 In some embodiments, the green tape has a ceramic loading of about 55 to about 65 vol %, a thickness of about 0.5 to about 100 um, and a lateral dimension of about 0.5 to 400 cm 2 It has a lateral dimension of [Brief explanation of the drawings]

[0015] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] 1 illustrates an example flow chart according to an embodiment of the process described herein. [Figure 2]

[0016] 1 shows a scanning electron microscopy (SEM) image of a green tape produced by the casting process shown in Example 1. The organic portion is labeled 201 and the lithium-filled garnet portion is labeled 202. [Figure 3]

[0017] 1 shows a scanning electron microscopy (SEM) image of the sintered green tape produced in Example 1. The organic portion is labeled 301 and the garnet portion is labeled 302. [Figure 4]

[0018] 4 shows optical microscope images of a disk of the green tape produced in Example 1 before sintering and the resulting disk after sintering. The green tape disk is labeled 401 and the sintered disk is labeled 402. DETAILED DESCRIPTION OF THE INVENTION

[0016]

[0019] The drawings depict various embodiments of the present disclosure for purposes of illustration only. Those skilled in the art will readily recognize from the following discussion that alternative embodiments of the structures and processes described herein may be used without departing from the principles described herein.

[0017] Detailed Description

[0020] The following description is presented to enable one skilled in the art to make and use the disclosed subject matter and to incorporate it into the context of the present application. Various modifications and various uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide range of embodiments. Thus, the present disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0018]

[0021] In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present disclosure. However, it will be apparent to those skilled in the art that the present disclosure may be practiced without necessarily being limited to these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present disclosure.

[0019]

[0022] The disclosure herein describes high-density green tapes prepared in a non-reactive environment, a process for producing these green tapes, and a process for sintering these green tapes. The processes herein result in thin green tapes with higher densities compared to green tapes prepared by previously known processes. Sintered films produced from the green tapes have surfaces suitable for incorporation into electrochemical devices without further processing, such as polishing or lapping. These green tapes shrink less when sintered compared to previously known processes. These green tapes do not warp or crack during sintering compared to previously known processes. These green tapes are suitable for electrochemical device applications.

[0020] A.Definition

[0023] As used herein, "providing" refers to providing, producing, presenting, or delivering what is provided. Providing includes making something available. For example, providing a powder refers to the process of making the powder available or delivering the powder so that it can be used as indicated in the processes described herein. As used herein, providing also means measuring, weighing, transferring, combining, or compounding.

[0021]

[0024] As used herein, "casting" means providing, depositing, or delivering a casting solution or slurry onto a substrate. Casting includes, but is not limited to, slot casting, screen printing, gravure coating, dip coating, and doctor blading.

[0022]

[0025] As used herein, the phrase "slot casting" refers to a deposition process in which a substrate is coated or deposited with a solution, liquid, slurry, etc. by flowing the solution, liquid, slurry, etc. through a slot or mold of fixed dimensions that is positioned adjacent to, in contact with, or above the substrate on which the deposition or coating is to occur. In some examples, slot casting includes a slot opening of about 1-100 μm.

[0023]

[0026] As used herein, the phrases "dip casting" or "dip coating" refer to a deposition process in which a substrate is coated or deposited with a solution, liquid, slurry, etc. by lowering the substrate into or out of the solution, liquid, slurry, etc., often vertically.

[0024]

[0027] As used herein, "casting a slurry" refers to a process in which a slurry is deposited onto or adhered to a substrate. Casting can include, but is not limited to, slot casting and dip casting. As used herein, casting also includes depositing, coating, or spreading a casting solution or casting slurry onto a substrate.

[0025]

[0028] As used herein, "aluminum oxide dopant" refers to a lithium-filled garnet that contains, for example, an amount of Li7Zr2La3O 12 The empirical formula of lithium-filled garnets (e.g., Li7Zr2La3O) is 12 This means that the aluminum or alumina content is such that the aluminum or alumina content can be written as 0.0 ...

[0026]

[0029] As used herein, the phrases "film casting" or "green tape casting" refer to the process of delivering or moving a liquid or slurry into a mold or onto a substrate so that the liquid or slurry forms or is formed into a green tape. Casting can be done by doctor blade, Meyer rod, comma coater, gravure coater, microgravure, reverse comma coater, slot die, slip and / or tape casting, and other processes known to those skilled in the art.

[0027]

[0030] As used herein, the term "laminating" refers to the process of sequentially depositing layers of one precursor species, e.g., a lithium precursor species, onto a deposition substrate, followed by the deposition of an additional layer using a second precursor species, e.g., a transition metal precursor species, on the previously deposited layer. This lamination process can be repeated to build up several layers of deposited vapor phase. As used herein, the term "laminating" also refers to the process in which a layer comprising an electrode, e.g., a layer comprising a positive electrode or cathode active material, is contacted with another material, e.g., a layer comprising a garnet electrolyte. The lamination process may involve the reaction or use of a binder to adhere or physically maintain contact between the laminated layers. Lamination also refers to the process of bonding unsintered, i.e., "green," ceramic films, potentially under pressure, and / or by heating the films to join them.

[0028]

[0031] As used herein, the phrases "green tape" or "green film" refer to an unsintered tape or film that includes at least one member selected from garnet material, precursors of garnet material, binders, plasticizers, carbon, dispersants, or combinations thereof.

[0029]

[0032] As used herein, the phrase "non-reactive environment" refers to an ambient atmosphere (e.g., air or dry air) having a temperature below 30°C and a dew point below -40°C, unless otherwise specified to the contrary, or an argon gas-supplied environment having a temperature below 30°C and a dew point below -40°C. Unless otherwise specified, a "non-reactive environment" refers to an ambient atmosphere (e.g., air or dry air) having a temperature below 30°C, a dew point below -10°C, and a pressure of 1 atmosphere. A "non-reactive environment" may also include an ambient atmosphere having a temperature below 100°C and a dew point below -10°C; or an environment containing argon gas or nitrogen gas, or a combination thereof, having a temperature below 100°C and a dew point below -10°C. A non-reactive environment has a pressure of 1 atmosphere, unless otherwise specified to the contrary. Examples include dry chambers, such as those commercially available from Scientific Climate Systems. Other examples include glove boxes, such as those sold by MBraun.

[0030]

[0033] As used herein, the phrases "thickness" or "film thickness" or "green tape thickness" refer to the distance, or measured median distance, between the top and bottom surfaces of the green tape. As used herein, the top and bottom surfaces refer to the sides of the green tape having the largest surface area.

[0031]

[0034] As used herein, "thin," when limiting green tapes, films, etc., means thickness dimensions less than 200 μm, sometimes less than 100 μm, and in some instances between 0.1 and 60 μm.

[0032]

[0035] As used herein, the phrases "garnet precursor chemicals," "chemical precursors of garnet-type electrolytes," or "garnet chemical precursors" refer to chemicals that react to form the lithium-filled garnet materials described herein. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., LiO), lithium carbonate (e.g., LiCO), zirconium oxide (e.g., ZrO), lanthanum oxide (e.g., LaO), aluminum oxide (e.g., AlO), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO), aluminum nitrate nonahydrate, corundum, (oxy)aluminum hydroxide (gibbsite and boehmite), gallium oxide, niobium oxide (e.g., NbO), and tantalum oxide (e.g., TaO).

[0033]

[0036] As used herein, the phrase "the subscripts and molar coefficients in the empirical formula are based on the amounts of raw materials initially batched to make the described example" refers to the amount of the subscript (e.g., Li7La3Zr2O 12 coefficients of 7, 3, 2, 12, and 0.35 for Al2O3) for a given material (e.g., Li7La3Zr2O 12 This term refers to the respective elemental ratios in the chemical precursors (e.g., LiOH, La2O3, ZrO2, Al2O3) used to prepare a 0.35% Al2O3 (0.35% Al2O3). Molar ratios are as batched unless expressly indicated to the contrary.

[0034]

[0037] As used herein, the term "batched" refers to the molar amounts of each of the components initially mixed or provided at the start of the synthesis. For example, a batched molten metal of the formula Li7La3Zr2O 12 is Li7La3Zr2O 12 This means that the ratio of Li to La to Zr to O in the reagents used to make this was 7:3:2:12.

[0035]

[0038] As used herein, the phrase "characterized by the formula" refers to the molar ratio of the constituent atoms as batched or experimentally determined during the process for producing the characterized material.

[0036]

[0039] As used herein, the term "solvent" refers to a liquid suitable for dissolving or solvating the components or materials described herein. For example, solvents include liquids such as toluene that are suitable for dissolving components, such as binders, used in the garnet sintering process.

[0037]

[0040] As used herein, the term "anhydrous" refers to a material that contains less than 20 ppm of water.

[0038]

[0041] As used herein, the term "aprotic solvent" refers to a liquid comprising solvent molecules that do not contain labile or dissociable proton, hydronium, or hydroxyl species. Aprotic solvent molecules do not contain hydroxyl or amine groups.

[0039]

[0042] As used herein, the phrase "solvent removal" refers to a process in which the solvent is extracted or separated from the components or materials described herein. Solvent removal includes, but is not limited to, evaporation of the solvent. Solvent removal includes, but is not limited to, using high temperatures, vacuum, or reduced pressure to drive the solvent from the mixture, e.g., an unsintered green tape. In some examples, the film containing the binder and solvent is heated or, optionally, placed in a vacuum or reduced pressure atmospheric environment to evaporate the solvent, leaving the solvated binder in a thin film after the solvent has been removed.

[0040]

[0043] As used herein, "green film tape" refers to a roll, continuous layer, or cut section thereof of cast, dried or undried tape, which can be sintered.

[0041]

[0044] As used herein, "binder" refers to a material that aids in the adhesion of another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders may include polycarbonates. Other binders may include polyacrylates and polymethacrylates. These examples of binders are not limiting as to the overall scope of binders contemplated herein, but serve merely as examples. Binders useful in the present disclosure include, but are not limited to, polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylics, polyvinyl acetoacetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, silicones, and the like.

[0042]

[0045] As used herein, the phrase "lithium-filled garnet electrolyte" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Lithium-filled garnets have the formula Li A La B M' C M” D Zr E O F , Li A La B M' C M” D Ta E O F , or Li A La B M' C M” D NbE O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≦ C ≦ 2, 0 ≦ D ≦ 2; 0 ≦ E < 2, 10 < F < 13, and M’ and M” are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta in each case), or Li a La b Zr c Al d Me” e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≦ 2.5; 0 ≦ d < 2; 0 ≦ e < 2, 10 < f < 13, and Me” is selected from Nb, Ta, V, W, Mo, Ga, or Sb and is a metal as described herein). The garnets used herein include the above garnets doped with Al2O3. The garnets used herein include the above garnets doped such that Al 3+ replaces Li + . When used herein, lithium-filled garnets and garnets generally contain Li 7.0 La3(Zr t1 +Nb t2 +Ta t3 )O 12 +0.35Al2O3, but are not limited thereto; here, (t1 + t2 + t3 = subscript 2) such that the La:(Zr / Nb / Ta) ratio is 3:2. Also, the garnets used herein include Li x La3Zr2O 12 +yAl2O3 (where x ranges from 5.5 to 9 and y ranges from 0 to 1), but is not limited thereto. In some examples, x is from 6 to 7 and y is 1.0. In some examples, x is 7 and y is 0.35. In some examples, x is from 6 to 7 and y is 0.7. In some examples, x is from 6 to 7 and y is 0.4. Also, the garnets used herein include Li x La3Zr2O 12+yAl2O3. Non-limiting examples of lithium-filled garnet electrolytes can be found, for example, in U.S. Patent Application Publication No. 2015-0200420A1, published July 16, 2015.

[0043]

[0046] As used herein, garnet refers to YAG-garnet (i.e., yttrium aluminum garnet, or YAlO, for example). 12 ) As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon-stone, tsavorite, uvarovite, and andradite, and the solid solutions pyrope-almandine-spessartite and uvarovite-grossular-andradite. Garnet herein does not include nesosilicates having the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn; and Y is Al, Fe, and / or Cr.

[0044]

[0047] As used herein, the phrase "garnet-type electrolyte" refers to an electrolyte that includes the lithium-filled garnet material described herein as an ionic conductor. The advantages of solid-state Li-filled garnet electrolytes are numerous, including as a replacement for the liquid, flammable electrolytes commonly used in rechargeable lithium batteries.

[0045]

[0048] As used herein, "d 50 The phrase "diameter" refers to the median diameter in a size distribution as measured by microscopy or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 50 D includes the characteristic dimension below which 50% of the particles are smaller than the stated size. 50 is calculated here on a volume basis, rather than on a number basis.

[0046]

[0049] As used herein, particle size distribution "PSD" is measured by light scattering using, for example, a Horiba LA-950V2 particle size analyzer, where the solvent used for the analysis includes toluene, IPA, or acetonitrile, and where the analysis includes sonication for 1 minute prior to measurement.

[0047]

[0050] As used herein, "d 90 The phrase "diameter" refers to the 90th percentile size in a size distribution as measured by microscopy or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 90 D includes the characteristic dimension below which 90% of the particles are smaller than the stated size. 90 is calculated here on a volume basis, rather than on a number basis.

[0048]

[0051] As used herein, the term "calcining" refers to a process involving chemical decomposition reactions or chemical reactions between solids (see Ceramic Processing and Sintering, Second Edition, MN Rahaman, 2005). Calcining, as used herein, is a different process from sintering. Sintering involves densification and aims to achieve a stable mechanical object rather than a desired material phase. Sintering requires a high starting density and is usually carried out at a higher temperature, the so-called firing temperature. Calcining involves chemical decomposition reactions or chemical reactions between solids and does not involve a reduction in the surface free energy of agglomerated particles.

[0049]

[0052] As used herein, the phrases "sintering a green tape," "sintering," or "sintering a film" refer to a process in which a thin green tape as described herein is densified (made denser or made less porous) through the use of heat sintering or field-assisted sintering. Sintering involves the process of forming a solid mass of material through heat and / or pressure without melting it to a fully liquefied state. Sintering causes a reduction in the surface free energy of agglomerated particles, which can be achieved by atomic diffusion processes resulting in densification of the object, by transporting material from the interior particles into the pores, by coarsening of the microstructure, or by rearrangement of material between different parts of the pore surface without actually reducing the pore volume (see Rahaman at p. 32).

[0050]

[0053] As used herein, the term "plasticizer" refers to an additive that imparts either flexibility or plasticity to the green tape. It can be a substance or material used to increase the flexibility, workability, or expansion of the binder. Flexibility is the ability to bend without breaking. Plasticity is the ability to be permanently deformed.

[0051]

[0054] As used herein, the phrase "stress relief" refers to a process of removing residual stresses in the cast green tape during drying and associated shrinkage. One process of stress relief involves heating the green tape above the glass transition temperature of the organic components in the green tape to allow structural and stress rearrangement in the cast green tape to remove the residual stresses. Another process of stress relief involves heating the cast green tape to 70°C and holding it at that temperature for a short period of time to allow the cast green tape to relieve stress.

[0052]

[0055] As used herein, "geometric density" is calculated by dividing the mass of a green tape by its volume. The volume of a green tape is obtained from the thickness and diameter measurements of the tape; or the thickness, width, and length measurements. A micrometer may be used to measure the thickness, while the diameter is obtained using optical microscopy. Density herein is geometric density unless expressly stated otherwise or to the contrary.

[0053]

[0056] As used herein, "pycnometric density" is measured using a Micromeritics AccuPycII 1340 Calibrate instrument. With this instrument, a controlled amount of powder sample is placed in a cup and its mass is measured. The instrument is then used to measure the volume and calculate density by mass / volume.

[0054]

[0057] As used herein, a green tape is considered to have a high density if its density is greater than 2.9 g / ml.

[0055]

[0058] As used herein, a green tape is considered to have a low density if its density is 2.6 g / ml or less.

[0056]

[0059] As used herein, a downsized garnet powder is considered to have a high density if its density is greater than 4 g / ml.

[0057]

[0060] As used herein, a downsized garnet powder is considered to have a low density if its density is 3.6 g / ml or less.

[0058]

[0061] As used herein, the phrase "sintering aid" refers to an additive used to lower the melting point of the liquid phase or allow faster sintering than would otherwise be possible without the sintering aid. Sintering aids aid the diffusion / kinetics of the atoms being sintered. For example, Li3BO3 may be used as an additive in sintering to provide faster or more complete densification of the garnet during sintering.

[0059]

[0062] As used herein, the phrase "raw material powder" refers to the inorganic material used in the slurries described herein. In some examples, the raw material powder is a lithium-loaded garnet. For example, the raw material powder may be Li7La3Zr2O 12 · May contain 0.5Al2O3 powder.

[0060]

[0063] As used herein, the term "DBP" refers to a compound of formula C having a molecular weight of 278.35 g / mol. 16 H 22 It refers to the chemical dibutyl phthalate, which has the O4 group.

[0061]

[0064] As used herein, the term "BBP" refers to benzyl butyl phthalate C4 having a molecular weight of 312.37 g / mol. 19 H 20 Refers to O4.

[0062]

[0065] As used herein, the term "PEG" refers to polyethylene glycol. Unless otherwise specified, PEG has a molecular weight of 400-6000 g / mol.

[0063] B. Green tape

[0066] In some embodiments, the present disclosure provides improved materials and processes for casting green tapes with high density in a dry environment that prevents the formation of low density phases, such as lithium carbonate, prior to the sintering step, which can contribute to low ceramic density, sticking and warping during sintering, and poor lithium ion conductivity of the material.

[0064]

[0067] In one embodiment, the present disclosure provides a process for casting a green tape, where the process generally includes providing at least one raw material powder, calcining the powder in a non-reactive environment, milling the at least one calcined powder with an aprotic solvent and a dispersant in a non-reactive environment to prepare a slurry, mixing the slurry with a binder solution in a non-reactive environment, casting the slurry in a non-reactive environment to form a green tape, drying the green tape in a non-reactive environment to achieve a high density green tape, and sintering the green tape to form a thin sintered film. In some embodiments, the process further includes filtering the slurry in a non-reactive environment.

[0065]

[0068] In a second embodiment, the present disclosure provides a slurry for casting a green tape, wherein the slurry comprises a raw material powder, optionally a precursor of the raw material powder, and at least one component selected from a binder, a dispersant, and a solvent.

[0066]

[0069] In a third embodiment, the present disclosure provides a slurry for preparing a green tape, wherein the slurry comprises a solvent, a raw material powder, and an anhydrous aprotic solvent selected from the group consisting of at least: benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; Binders selected from the group consisting of polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), other polyolefins such as ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), poly(ethylene-co-1-octene) (PE-co-PO), poly(ethylene-co-methylenecyclopentene) (PE-co-PMCP), stereoblock polypropylene, polypropylene polymethylpentene, polyethylene oxide (PEO), PEO block copolymers, silicone polymers and copolymers, polyvinyl butyral (PVB), poly(vinyl acetate) (PVAc), polyvinylpyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers (such as polyacrylates, polymethacrylates, and copolymers thereof), binders from the Paraloid resins, binders from the Butvar resins, binders from the Mowital resins;Fish oil, C8 to C20 fatty acids (e.g., dodecanoic acid, oleic acid, stearic acid, linolenic acid, linoleic acid), C8 to C20 alcohols (e.g., dodecanol, oleyl alcohol, stearyl alcohol), C8 to C20 alkylamines (e.g., dodecylamine, oleylamine, stearylamine), phosphate esters, phospholipids (e.g., phosphatidylcholine, lecithin), polymer dispersants, for example, poly(vinylpyridine), poly(ethyleneimine), poly(ethylene oxide) and its ethers, poly(ethylene glycol) and its ethers, polyalkyleneamines, polyacrylates, polymethacrylates, poly(vinyl alcohol), poly(acetic acid), vinyl), polyvinyl butyral, maleic anhydride copolymer, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, a dispersant selected from the group consisting of surfactants and dispersants from Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants; a plasticizer selected from the group consisting of dibutyl phthalate, dioctyl phthalate, or benzyl butyl phthalate; a raw powder selected from lithium-filled garnet; or a combination thereof; Includes.

[0067]

[0070] In a fourth embodiment, the present disclosure provides a green tape comprising: raw garnet powder; a plasticizer; a binder; and a dispersant, wherein the green tape has a geometric density greater than 2.9 g / ml.

[0068]

[0071] In some examples described herein, the green tapes cast by the processes described herein are dense. These green tapes are cast from a slurry made with downsized ceramic material. They may contain refractory and / or ceramic materials formulated as ceramic particles intimately mixed with a binder. The purpose of the binder is, in part, to aid in the sintering of the ceramic particles, resulting in a uniform, thin film or layer of refractory or ceramic after sintering. During the sintering process, a debindering step removes the binder from the green tape. In some examples, this debindering occurs at temperatures below 700°C, below 450°C, below 400°C, below 350°C, below 300°C, below 250°C, or in some examples, below 200°C, or in some examples, below 150°C, or in some examples, below 100°C. During the debindering process, the partial pressures of oxygen and water may be controlled. The debindering process may include multiple stages.

[0069] C. Green Tape Manufacturing Process

[0072] The green tapes described herein can be manufactured by a variety of processes. In some processes, a slurry containing calcined raw material powders is prepared in a non-reactive environment using an anhydrous aprotic solvent; the slurry is cast onto a substrate or setter plate, and the slurry is then dried and sintered to prepare a dried and sintered solid ionically conductive ceramic. In certain examples, the substrate can include, for example, Mylar, silicone-coated Mylar, a polymer-coated surface, a surface-modified polymer, or a surface-assembled monolayer adhered, attached, or bonded to the surface.

[0070]

[0073] In one example, the process described herein is substantially as shown in FIG. 1. In this process, a first step 100 involves mixing, grinding, drying, and calcining a garnet precursor. A next step 101 involves placing raw powders, such as a solvent, dispersant, and garnet, into a container in a non-reactive environment. Grinding media is also added. In step 102, the combined contents are ground for one hour to three days. In a fourth step 103, a binder solution is added to the ground mixture in a non-reactive environment and mixed. The resulting slurry is then degassed in a non-reactive environment using a degassing process. In a fifth step 104, the slurry is cast onto a substrate (e.g., silicone-coated Mylar) using a doctor blade casting process and dried in a non-reactive environment. In a sixth step 105, the cast green tape is sintered. Variations on this process are also contemplated. In one example, the slurry is filtered prior to casting. In one example, casting is done by slot die, screen printing, gravure printing, or other casting process.

[0071]

[0074] In some instances, the green tape density, as measured by the Archimedes method, is 2.5 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 2.6 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 2.7 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 2.8 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 2.9 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 3.0 g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is greater than 3.1 g / cm 3In some instances, the green density, as measured by geometric process, is greater than 2.5 g / cm 3 is greater than.

[0072]

[0075] In some examples, the geometric density of the green tape is 2.3 g / cm 3 In some examples, the geometric density of the green tape is greater than 2.4 g / cm 3 In some instances, the geometric density of the green tape is greater than 2.5 g / cm 3 In some examples, the geometric density of the green tape is greater than 2.6 g / cm 3 In some examples, the geometric density of the green tape is greater than 2.7 g / cm 3 In some examples, the geometric density of the green tape is greater than 2.8 g / cm 3 In some instances, the density of the green tape as measured by the geometric process is greater than 2.9 g / cm 3 In some instances, the geometric density of the green tape is greater than 3.0 g / cm 3 In some examples, the geometric density of the green tape is greater than 3.1 g / cm 3 is greater than.

[0073]

[0076] In some instances, the green tape density, as measured by the Archimedes method, is 2.5 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 2.6 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 2.7 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 2.8 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 2.9 g / cm3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 3.0 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density, as measured by the Archimedes method, is between 3.1 g / cm 3 ~3.2g / cm 3 It is between.

[0074]

[0077] In some instances, the green density as measured by the geometric process is 2.5 g / cm 3 ~3.2g / cm 3 In some examples, the geometric density of the green tape is between 2.6 g / cm 3 ~3.2g / cm 3 In some examples, the geometric density of the green tape is between 2.7 g / cm 3 ~3.2g / cm 3 In some examples, the geometric density of the green tape is between 2.8 g / cm 3 ~3.2g / cm 3 In some instances, the green tape density as measured by geometric process is between 2.9 g / cm 3 ~3.2g / cm 3 In some examples, the geometric density of the green tape is between 3.0 g / cm 3 ~3.2g / cm 3 In some examples, the geometric density of the green tape is between 3.1 g / cm 3 ~3.2g / cm 3 It is between.

[0075]

[0078] In some embodiments, the ceramic loading of the green tape (i.e., the amount of solid ceramic or raw powder present in the green tape) is greater than a particular volume percentage after drying. In some examples, the ceramic loading of the green tape is greater than 40 vol%. In some examples, the ceramic loading of the green tape is greater than 50 vol%. In some examples, the ceramic loading of the green tape is greater than 55 vol%. In some examples, the ceramic loading of the green tape is greater than 60 vol%. In some examples, the ceramic loading of the green tape is greater than 61 vol%. In some examples, the ceramic loading of the green tape is greater than 62 vol%. In some examples, the ceramic loading of the green tape is greater than 63 vol%. In some examples, the ceramic loading of the green tape is greater than 64 vol%. In some examples, the ceramic loading of the green tape is greater than 65 vol%. In some examples, the ceramic loading of the green tape is greater than 66 vol%. In some examples, the ceramic loading of the green tape is greater than 67 vol%. In some examples, the ceramic loading of the green tape is greater than 68 vol%. In some examples, the ceramic loading of the green tape is greater than 69 vol%. In some examples, the ceramic loading of the green tape is greater than 70 vol%. In some examples, the ceramic loading of the green tape is greater than 71 vol%. In some examples, the ceramic loading of the green tape is greater than 72 vol%. In some examples, the ceramic loading of the green tape is greater than 73 vol%. In some examples, the ceramic loading of the green tape is greater than 74 vol%. In some examples, the ceramic loading of the green tape is greater than 75 vol%. In some examples, the ceramic loading of the green tape is greater than 76 vol%. In some examples, the ceramic loading of the green tape is greater than 77 vol%. In some examples, the ceramic loading of the green tape is greater than 78 vol%. In some examples, the ceramic loading of the green tape is greater than 79 vol%.In some instances, the ceramic loading of the green tape is greater than 80 vol%.

[0076]

[0079] In some examples, the ceramic loading of the green tape is between 50 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 55 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 60 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 61 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 62 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 63 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 64 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 65 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 66 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 67 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 68 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 69 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 70 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 71 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 72 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 73 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 74 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 75 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 76 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 77 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 78 vol% and 80 vol%. In some examples, the ceramic loading of the green tape is between 79 vol% and 80 vol%.In some examples, the ceramic loading of the green tape is between 80 vol% and 81 vol%.

[0077] D. Crushing

[0080] In some embodiments, the processes herein include process steps involving mixing and / or milling. Milling includes ball milling. Milling also includes milling processes using anhydrous solvents under non-reactive conditions, such as, but not limited to, benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, or combinations thereof.

[0078]

[0081] In some examples, the milling is ball milling. In some examples, the milling is horizontal milling. In some examples, the milling is attritor milling. In some examples, the milling is immersion milling. In some examples, the milling is jet milling. In some examples, the milling is steam jet milling. In some examples, the milling is high energy milling.

[0079]

[0082] In some instances, high-energy milling processes have shown that d 50 In some instances, high energy milling processes are used to produce milled particle size distributions where d is approximately 100 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 750 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 150 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 200 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 250 nm, as measured by light scattering. 50In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 300 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 350 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 400 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 450 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 500 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 550 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 600 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 650 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 700 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 800 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve a particle size distribution where d is approximately 850 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 900 nm, as measured by light scattering. 50 In some instances, high energy milling processes are used to achieve particle size distributions where d is approximately 950 nm, as measured by light scattering. 50 to achieve a particle size distribution where the mean particle size is about 1000 nm.

[0080]

[0083] In some examples, the aprotic solvent is tetrahydrofuran. In other examples, the aprotic solvent is 1,2-dimethoxyethane. In other examples, the solvent is toluene. In other examples, the solvent is benzene. In other examples, the solvent is xylene. In other examples, the solvent is dioxane. In still other examples, the solvent is dimethyl sulfoxide. In other examples, the solvent is methylene chloride. In other examples, the solvent is benzene. In other examples, the solvent is N-methyl-2-pyrrolidone. In other examples, the solvent is dimethylformamide.

[0081]

[0084] In some examples, milling involves a high-energy wet milling process using 0.3 mm yttria-stabilized zirconium oxide milling media beads. In some examples, ball milling, horizontal milling, attritor milling, or immersion milling can be used. In some examples, a high-energy milling process can be used to obtain a d 50 The particle size distribution is approximately 100 nm to 5000 nm.

[0082]

[0085] In some examples, comminution may include a classification step such as sieving, centrifugation, or other known laboratory steps to separate particles of different sizes and / or masses.

[0083] E. Slurry

[0086] In some examples, anhydrous aprotic solvents for use with the slurries described herein include one or more solvents selected from benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, or combinations thereof, optionally with one or more dispersing agents, optionally with one or more binders, and optionally with one or more plasticizers. In some examples, the solvent includes about 0-35% w / w anhydrous toluene. In some examples, the solvent includes about 0-35% w / w benzene. In some examples, the solvent includes about 0-35% w / w xylene. In some examples, the solvent includes about 0-35% w / w dioxane. In some examples, the solvent includes 0-35% w / w tetrahydrofuran. In some examples, the solvent includes about 0-35% w / w 1,2-dimethoxyethane. In some examples, the dispersing agent is 0-5% w / w. In some examples, the binder is about 0-10% w / w. In some examples, the plasticizer is 0-10% w / w. In these examples, the garnet or calcined precursor material represents the remaining % w / w (e.g., 40, 50, 60%, 70%, or 75% w / w).

[0084]

[0087] In some instances, dispersants are used during the milling process. Examples of dispersants include fish oil, C8-C 20 Fatty acids of a certain degree (e.g., dodecanoic acid, oleic acid, stearic acid, linolenic acid, linoleic acid), C8 to C 20 Alcohols of the order of C8 to C9 (e.g., dodecanol, oleyl alcohol, stearyl alcohol), 20Examples of suitable dispersants include, but are not limited to, alkylamines (e.g., dodecylamine, oleylamine, stearylamine), phosphate esters, phospholipids (e.g., phosphatidylcholine, lecithin), polymeric dispersants such as poly(vinylpyridine), poly(ethyleneimine), poly(ethylene oxide) and its ethers, poly(ethylene glycol) and its ethers, polyalkyleneamines, polyacrylates, polymethacrylates, poly(vinyl alcohol), poly(vinyl acetate), polyvinyl butyral, maleic anhydride copolymers, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, and surfactants and dispersants from Brij surfactants, Triton surfactants, and Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants. Dispersants may also be combined.

[0085]

[0088] In some examples, binders suitable for use with the slurries described herein include binders used to facilitate adhesion between Li-loaded garnet particles, such as polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), other polyolefins, such as ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), poly(ethylene-co-1-octene) (PE-co-PO), poly(ethylene-co-methylenecyclopentene) (PE-co- Examples of binders include, but are not limited to, polypropylene (PMCP), stereoblock polypropylene, polypropylene polymethylpentene, polyethylene oxide (PEO), PEO block copolymers, silicone polymers and copolymers, polyvinyl butyral (PVB), poly(vinyl acetate) (PVAc), polyvinylpyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers (e.g., polyacrylates, polymethacrylates, and copolymers thereof), binders from the Paraloid resins, binders from the Butvar resins, and binders from the Mowital resins. Binders may be combined.

[0086]

[0089] In some examples, the slurry may also include a plasticizer. A non-limiting list of plasticizers includes dibutyl phthalate, dioctyl phthalate, and benzyl butyl phthalate. Plasticizers may also be combined.

[0087] F.Casting

[0090] In some processes described herein, the process involves casting a tape of ceramic raw material powder onto a substrate (e.g., porous or non-porous alumina, zirconia, garnet, alumina-zirconia, lanthanum alumina-zirconia). In some examples, the tape is prepared on a substrate such as a silicone-coated substrate (e.g., silicone-coated Mylar, or silicone-coated Mylar on alumina).

[0088]

[0091] Several tape casting processes are known in the relevant art and are described in Mistler, R. E. and Twiname, E. R., Tape Casting: Theory and Practice, 1999, the entire contents of which are incorporated herein by reference in their entirety for all purposes. st Edition Wiley-American Ceramic Society; 1 edition (December 1, 2000). Other casting processes and materials are as set forth in U.S. Patent No. 5,256,609 (Dolhert, LE), entitled "Clean-Burning Green Tape Casting System Using Atactic Polypropylene Binder," the entire contents of which are incorporated herein by reference in their entirety for all purposes. Other casting processes include those described in DJ Shanefield's Organic Additives and Ceramic Processing, Springer Science & Business Media, (Mar 9, 2013), which is incorporated herein by reference.

[0089] G. Tape drying after casting

[0092] In some examples, the processes described herein include drying. In some processes, drying includes controlling the temperature of the green tape, for example, by using a heated bed to position or deposit the cast film, infrared (IR) heating of the cast tape, or convection heating. In some processes, drying can include managing or controlling the amount of solvent in the drying atmosphere using environmental controls, such as, but not limited to, stagnant and / or flowing environments (e.g., atmospheric air, dry air, inert gas, nitrogen gas, argon gas). In these processes, drying is used to control the rate of solvent removal and ensure that the cast film dries from substrate to surface, rather than surface to substrate.

[0090] H. Setter plate

[0093] In some examples, the green tape prepared by the processes herein and those incorporated by reference is sintered between setter plates. In some examples, the green tape prepared by the processes herein and those incorporated by reference is sintered onto at least one setter plate. In some examples, the setter plates are composed of a metal, oxide, nitride, or a metal, oxide, or nitride having an organic or silicone laminate layer thereon. In certain examples, the setter plate is selected from the group consisting of platinum (Pt) setter plates, palladium (Pd) setter plates, gold (Au) setter plates, copper (Cu) setter plates, nickel setter plates, aluminum (Al) setter plates, alumina setter plates, porous alumina setter plates, steel setter plates, zirconium (Zr) setter plates, zirconia setter plates, porous zirconia setter plates, lithium oxide setter plates, porous lithium oxide setter plates, lanthanum oxide setter plates, porous lanthanum oxide setter plates, garnet setter plates, porous garnet setter plates, lithium-filled garnet setter plates, porous lithium-filled garnet setter plates, and combinations thereof. In some examples, the setter plate is a garnet setter plate or a porous garnet setter plate. In some examples, the setter plate has a densitometry of 5 mmol / cm 3 The oxide material includes an oxide material having a lithium concentration greater than

[0091]

[0094] In some examples of the processes described herein, the setter plates and sintering processes set forth in U.S. Patent Application Publication No. 20170062873A1, entitled "Lithium-Filled Garnet Setter Plates for the Production of Solid Electrolytes," and PCT Patent Application Publication No. WO2016168723A1, filed October 20, 2016, entitled "Setter Plates for the Production of Solid Electrolytes and Process for Using the Same to Prepare High-Density Solid Electrolytes," are incorporated herein by reference in their entireties.

[0092]

[0095] In some examples, green tapes prepared by the processes herein and those set forth in International Publication No. WO 2016 / 168691; International Publication No. WO 2016 / 168723; U.S. Patent Application Publication No. 2017 / 0062873; U.S. Patent Application Publication No. 2017 / 0153060; and U.S. Patent Application Publication No. 2018-0045465A1 (each of which is incorporated by reference in its entirety) are sintered between setter plates with a metal powder disposed between the setter plates and the green tape. In certain examples, the setter plate is selected from the group consisting of platinum (Pt) setter plates, palladium (Pd) setter plates, gold (Au) setter plates, copper (Cu) setter plates, nickel setter plates, aluminum (Al) setter plates, alumina setter plates, porous alumina setter plates, steel setter plates, zirconium (Zr) setter plates, zirconia setter plates, porous zirconia setter plates, lithium oxide setter plates, porous lithium oxide setter plates, lanthanum oxide setter plates, lithium zirconium oxide (LiZrO) setter plates, lithium aluminum oxide (LiAlO) setter plates, porous lanthanum oxide setter plates, lithium zirconium oxide (LiZrO) setter plates, lithium aluminum oxide (LiAlO) setter plates, garnet setter plates, porous garnet setter plates, lithium-filled garnet setter plates, and porous lithium-filled garnet setter plates, and combinations of the foregoing. In some examples, the setter plate has a concentration of 5 mmol / cm 3 In these particular examples, the metal powder is selected from Ni powder, Cu powder, Au powder, Fe powder, or a combination thereof. The metal powder may additionally include a ceramic material.

[0093]

[0096] In some examples, green tapes prepared by the processes herein and those incorporated by reference are sintered between setter plates with a metal layer or film disposed between the setter plates and the green tape. In some examples, these setter plates are composed of a metal, oxide, nitride, or a metal, oxide, or nitride having an organic or silicone laminate layer thereon. In particular examples, the setter plate is selected from the group consisting of platinum (Pt) setter plates, palladium (Pd) setter plates, gold (Au) setter plates, copper (Cu) setter plates, nickel setter plates, aluminum (Al) setter plates, alumina setter plates, porous alumina setter plates, steel setter plates, zirconium (Zr), zirconia setter plates, porous zirconia setter plates, lithium oxide setter plates, porous lithium oxide setter plates, lanthanum oxide setter plates, porous lanthanum oxide setter plates, garnet setter plates, porous garnet setter plates, lithium-filled garnet setter plates, porous lithium-filled garnet setter plates, magnesia setter plates, and porous magnesia setter plates. In some examples, the setter plate has a concentration of 5 mmol / cm 3 In certain of these examples, the metal powder is selected from Ni powder, Cu powder, Mg powder, Mn powder, Au powder, Fe powder, or a combination thereof. The metal powder may additionally include a ceramic material.

[0094]

[0097] During certain sintering conditions, a layer of particles (e.g., a setter sheet) or powder may be placed between the green tape and the setter plate to assist in sintering the green tape. The green tape tends to shrink and densify as portions of it sinter, which, if uncontrolled, can result in cracks or other mechanical defects in the film. In some of these examples, the layer of particles forms a uniform particle layer. In other of these examples, the layer of particles includes a uniform particle layer that is inert or unreactive with the green tape. In some sintering conditions, the layer of particles is provided as a sheet of particles. In some examples, the thickness of the sheet or layer or particles is approximately equal to the size of the particles within the sheet or layer. In other examples, the location of the inert particles between the green tape and the setter plate is between the contact surface of the green tape and the portion of the green tape being sintered. In some continuous sintering processes, the setter plate and / or particles, layers, or sheets placed between the setter plate and the green tape can be moved or repositioned during the sintering process so that a continuous roll of sintered film is prepared in a continuous process. In these continuous processes, the setter plate and particles, layers, or sheets are coordinated with the movement of the green tape so that the portion of the green tape being sintered contacts the particles, layers, or sheets that are also in contact with the setter plate. In some instances, the layers or sheets are prepared with a specific weight to prevent warping and surface degradation of the tape.

[0095]

[0098] In some of the examples described herein, the layer or sheet of inert and / or uniform particles (or powder) aids in the sintering process by providing a minimal amount of friction between the green tape and the setter plate so that the green tape does not distort as it sinters, reduces in volume, and increases in density. By reducing frictional forces, the green tape can shrink with minimal stress during the sintering process. This provides an improved sintered film that does not stick to the setter plate, does not deform during the sintering process, and does not crack during or after the sintering process.

[0096]

[0099] In some examples described herein, other setter plates may be used, for example, in combination with the lithium-loaded garnet setter plates described herein, so long as they have a high melting point, high lithium activity, and stability in a reducing environment. Some examples of these other materials include those selected from Li2ZrO3, xLi2O-(1-x)SiO2 (where x = 0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a + b + C = 1), LiLaO2, LiAlO2, Li2O, Li3PO4, Li-loaded garnet, or combinations thereof. Furthermore, these other setter plates should not induce a chemical potential within the sintered film that would result in Li diffusion from the sintered film into the setter plate. Additional materials include lanthanum aluminum oxide, pyrochlore, and 0.01 mol / cm3 LiAlO. 3 In some examples, the setter plate includes a material having a lithium concentration greater than 0.02 mol / cm 3 In some examples, the setter plate may include a material having a lithium concentration greater than 0.03 mol / cm 3 In some examples, the setter plate may include a material having a lithium concentration greater than 0.04 mol / cm 3 In some examples, the setter plate may include a material having a lithium concentration greater than 5 mmol / cm 3 In some examples, the setter plate may include a material having a lithium concentration greater than 10-15 mmol / cm 3 In some examples, the setter material may be provided as a powder or in a non-planar shape.

[0097] I. Sintering

[0100] The green tapes described herein may be sintered by the sintering process described in International Patent Application Publication No. WO 2015 / 076944, which is a published version of International Patent Application No. PCT / US2014 / 059578, filed October 7, 2014, entitled "Garnet Materials for Li Secondary Batteries and Methods of Making and Using Garnet Materials," which is incorporated herein by reference in its entirety for all purposes.

[0098]

[0101] The green tapes described herein can be sintered in an oven exposed to a non-reactive environment. In some examples, the green tapes are sintered in an O2-rich atmosphere with a dew point below -40°C. In other examples, the green tapes are sintered in an argon-rich atmosphere with a dew point below -40°C. In still other examples, the green tapes are sintered in an Ar / H2 atmosphere with a dew point below -40°C. In other examples, the green tapes are sintered in a nitrogen-rich atmosphere with a dew point below -40°C. In still other examples, the green tapes are sintered in an N2 / H2 atmosphere with a dew point below -40°C. In other examples, the green tapes are sintered in an argon / H2O atmosphere. In some examples, the atmosphere used to sinter the green tapes is not the same as the atmosphere used to cool the films after they are sintered.

[0099]

[0102] In some examples, the process includes sintering the green tape, where the sintering includes heat sintering. In some of these examples, the heat sintering includes heating the green tape to a temperature in the range of about 700°C to about 1200°C for about 1 to about 600 minutes in an atmosphere having an oxygen partial pressure in the range of 1e-1 atmosphere to 1e-15 atmosphere.

[0100]

[0103] In any of the processes set forth herein, the heat sintering can include heating the green tape in a range of about 700°C to about 1250°C, or about 800°C to about 1200°C, or about 900°C to about 1200°C, or about 1000°C to about 1200°C, or about 1100°C to about 1200°C. In any of the processes set forth herein, the heat sintering can include heating the green tape in a range of about 700°C to about 1100°C, or about 700°C to about 1000°C, or about 700°C to about 900°C, or about 700°C to about 800°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to about 700°C, about 750°C, about 850°C, about 800°C, about 900°C, about 950°C, about 1000°C, about 1050°C, about 1100°C, about 1150°C, or about 1200°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 700°C, 750°C, 850°C, 800°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, or 1200°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 700°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 750°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 850°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 900°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 950°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 1000°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 1050°C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 1100°C.In any of the processes set forth herein, the heat sintering can include heating the green tape to 1125° C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 1150° C. In any of the processes set forth herein, the heat sintering can include heating the green tape to 1200° C.

[0101]

[0104] In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 20 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 30 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 40 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 50 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 60 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 70 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 80 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 90 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 100 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 120 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 140 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 160 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 180 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 200 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 300 to about 600 minutes.In any of the processes set forth herein, the process may include heating the green tape for about 350 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 400 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 450 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 500 to about 600 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 500 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 400 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 300 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 200 minutes. In any of the processes set forth herein, the process may include heating the green tape for about 1 to about 100 minutes. In any of the processes set forth herein, the process can include heating the green tape for about 1 to about 50 minutes.

[0102]

[0105] In some examples, the sintering process may involve sintering in a closed but not sealed furnace (i.e., oven, heating chamber). In some of these examples, the green tape is placed between setter plates, optionally with a setter sheet or layer therebetween, and the green tape for sintering is placed adjacent to or in close proximity to a sacrificial Li source. This sacrificial Li source helps prevent Li loss by evaporation from the sintered garnet. In some examples, the closed system includes argon gas, a mixture of argon gas and either hydrogen gas or water, air, purified air, or nitrogen. In some of these examples, the sacrificial Li source has a surface area greater than the surface area of ​​the green tape to be sintered. In some examples, the Li source and the sintered green tape have the same type of lithium-loaded garnet.

[0103]

[0106] In some examples, the porosity of the fired green tape is less than 10 vol%. In some examples, the porosity of the fired green tape is less than 9 vol%. In some examples, the porosity of the fired green tape is less than 8 vol%. In some examples, the porosity of the fired green tape is less than 7 vol%. In some examples, the porosity of the fired green tape is less than 6 vol%. In some examples, the porosity of the fired green tape is less than 5 vol%. In some examples, the porosity of the fired green tape is less than 4 vol%. In some examples, the porosity of the fired green tape is less than 3 vol%. In some examples, the porosity of the fired green tape is less than 2 vol%. In some examples, the porosity of the fired green tape is less than 1 vol%. In some examples, the porosity of the fired green tape is determined by image analysis of cross-sectional FIB images.

[0104]

[0107] In some embodiments, the sintering equipment used includes a 1e -1 ~1e -20 A 3-inch laboratory tube furnace with a controlled atmosphere in the oxygen partial pressure range of atmosphere was included.

[0105] J. Sintering with Other Device Components

[0108] In certain examples, the green tape is sintered while in contact with other components with which the sintered green tape may be combined when used in an electrochemical device. For example, in some examples, the green tape is layered or laminated to a positive electrode composition so that the sintered green tape adheres to the positive electrode after sintering the green tape. In another example, the green tape is sintered while in contact with a metal powder (e.g., nickel (Ni) powder). As the green tape sinters and the metal powder densifies into a solid metal foil, the sintered green tape bonds to the metal foil. An advantage of these sintering conditions is that two or more components of an electrochemical device can be prepared in a single step, thus saving manufacturing time and resources.

[0106] K. Measurement

[0109] In some embodiments, SEM electron microscopy was performed on a Helios 600i or FEI Quanta for measurements. In some embodiments, surface roughness was measured with an optical microscope such as a Keyence VR, which can measure height and calculate roughness values. In some embodiments, powder density was measured using a pycnometer. In some embodiments, green tape density was measured using a geometric process or by using the Archimedes method. In some embodiments, thickness variation of green tape was measured using a beta-gauge, micrometer, or cross-sectional imaging. [Example]

[0107] L. Example Example 1 - Manufacturing process for calcined lithium-loaded garnet powder

[0110] Calcined lithium-filled garnet powder was prepared by the following sequence of steps: First, lithium hydroxide (LiOH), aluminum nitrate [Al(NO3)39H2O], zirconia (ZrO2), and lanthanum oxide (La2O3) were measured (i.e., weighed) to obtain a composition with a molar ratio of Li 7.1 Zr2La3O12 +0.5Al2O3. Using wet milling techniques and ZrO2 milling media, the combination was milled to obtain a d of 100 nm to 5 μm. 50 This combination was mixed and milled to a particle size of 0.015 mm. A dispersant was also included with the milling media. In some cases, a solvent was also included. 50 After grinding to particle size, the ground reactant combination was separated from the grinding media. The separated ground reactants were then placed in an alumina crucible and calcined in an oven at approximately 800-900 degrees Celsius (900°C) in a non-reactive environment for approximately 2-6 hours, bringing a controlled oxidizing atmosphere into contact with the calcined reactants. The calcination process incinerated and / or combusted residual solvents and dispersants, as well as surfactants. Calcination reacted the inorganic reactants to form lithium-loaded garnet. After cooling to room temperature in a non-reactive environment, the calcined product was removed from the alumina crucible. The product was characterized by various analytical techniques, including X-ray powder diffraction (XRD) and scanning electron microscopy. This product, referred to as calcined lithium-loaded garnet, contained approximately Li. 7.1 Zr2La3O 12 It has an empirical formula of +0.5Al2O3.

[0108] Example 2 - High Density Green Tape Manufacturing and Drying Process

[0111] In a milling vessel inside an argon glovebox, 1000-1500 g of calcined lithium-loaded garnet powder from Example 1 was added to 400-700 g of anhydrous aprotic solvent such as hexane, THF, or methylene chloride along with 20-45 g of oleic acid. The mixture was milled for 2-6 hours in a Hockmeyer mill with zirconium oxide media until a median particle size of less than 750 nm was measured using a Horiba Model LA-950V2 with a refractive index of 2.13.

[0109]

[0112] 200-600 g of the ground garnet slurry from the above step was mixed in a non-reactive environment. The non-reactive environment was a drying chamber at 1 atmosphere pressure. The ambient atmosphere was dry air. The dry air had a dew point below 10°C. A mixture of 20-45 g of Paraloid B-72 resin and 10-30 g of benzyl butyl phthalate dissolved in the same solvent used for milling was added to the ground garnet slurry in a non-reactive environment to obtain a final slurry solids content of approximately 45-60% w / w. The slurry was mixed in a FlackTek SpeedMixer in a non-reactive environment for 10-30 minutes. Next, a green tape was prepared by casting the mixed slurry onto a substrate with a doctor blade in a non-reactive environment. The cast mixed slurry was dried at room temperature in a non-reactive environment for 2-6 hours to form a green tape. The geometric density of the dried green tape was then 2.9 g / cm. 3 was measured to exceed .

[0110]

[0113] The same procedure was completed in ambient air; the geometric density of the dry green tape was 2.5 g / cm 3 It was measured to be.

[0111] Example 3 - Preparation of another high density green tape

[0114] This example demonstrates the manufacturing process for another high-density green tape produced using a different dispersant. In a milling vessel within an argon glovebox, 1000-1500 g of calcined lithium-loaded garnet powder from Example 1 was added to 400-700 g of anhydrous aprotic solvent, such as hexane, THF, or methylene chloride, and 20-35 g of Solsperse M387 dispersant. The mixture was milled for 2-6 hours in a Hockmeyer mill with zirconium oxide media, using a Horiba Model LA-950V2 mill with a refractive index of 2.13, until a median particle size of less than 750 nm was measured.

[0112]

[0115] 200-600 g of the ground garnet slurry from the above step was mixed in a non-reactive environment. A mixture of 20-45 g of Paraloid B-72 resin and 10-30 g of benzyl butyl phthalate dissolved in the same solvent used for grinding was added to the ground garnet slurry in a non-reactive environment to obtain a final slurry solids content of approximately 45-60% w / w. The slurry was mixed in a FlackTek SpeedMixer in a non-reactive environment for 10-30 minutes. Green tapes were then prepared by casting the mixed slurry onto a substrate with a doctor blade in a non-reactive environment. The cast mixed slurry was dried at room temperature in a non-reactive environment for 2-6 hours to form green tapes.

[0113]

[0116] The same procedure was completed in ambient air; the geometric density of the dry green tape was 2.5 g / cm 3 It was measured to be.

[0114]

[0117] Figure 2 shows a scanning electron microscopy (SEM) image of the green tape produced by the casting process shown in this Example 3. The tape contained 81 wt% garnet, 19 wt% organic content, and had a density of 3.0 g / cm 3 had a geometric density of .

[0115]

[0118] Figure 3 shows a scanning electron microscopy (SEM) image of the sintered tape produced by sintering the green tape produced in Example 2. The density of the sintered green tape was determined by Archimedes' method to be 4.7 g / cm 3 was measured to exceed .

[0116]

[0119] Figure 4 shows optical microscope images of a disk of the green tape produced in Example 1 before sintering and the resulting disk after sintering. Shrinkage during sintering was measured to be 20% based on the reduction in disk diameter. The shrinkage of the green tape prepared in ambient air was 26%.

[0117] Example 4: Sintering of green tape

[0120] In this example, green tapes were prepared as in Examples 1 or 2. In one example, multiple green tapes were stacked and laminated together. The laminated green tape was sintered by placing it between two porous garnet setter plates and then removed from the setter plates. In one example, the green tape was sintered at 1100°C for 1-5 hours. In another example, the tape was sintered at 1125°C for 1-5 hours. In another example, the tape was sintered at 1150°C for 1-5 hours. Prior to sintering, binder removal was performed in Ar gas. In one example, a mixture of Ar gas and water was used for binder removal. In another example, a mixture of Ar gas and purified air was used for binder removal. During sintering, the atmosphere surrounding the sintered green tape was maintained at a temperature of 0.5-10°C. -20 atm range.

[0118]

[0121] The foregoing description of embodiments of the present disclosure has been presented for purposes of illustration; it is not intended to be exhaustive or to limit the scope of the claims to the precise form disclosed. Those skilled in the relevant art will recognize, in light of the above disclosure, that numerous equivalents, modifications, and variations are possible using no more than routine experimentation.

Claims

1. 1. A process for producing high density green tape, comprising: (a) providing a slurry including a raw material powder; (b) mixing the slurry with a binder solution in a non-reactive environment; (c) casting the slurry in a non-reactive environment to form a green tape; (d) drying the green tape in a non-reactive environment to achieve a geometric density greater than 2.9 g / ml; A process involving:

2. 10. The process of claim 1, wherein the raw material powder is calcined in a non-reactive environment to achieve a geometric density greater than 4.7 g / ml.

3. 10. The process of claim 1, wherein the amount of the raw material powder in the green tape is at least 50 wt%, 55 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%.

4. 4. The process of claim 1, wherein the at least one raw material powder is selected from the group consisting of lithium-filled garnets, chemical precursors of lithium-filled garnets, and lithium-filled garnets with aluminum oxide dopants.

5. The lithium-filled garnet is Ａ La Ｂ M' Ｃ M” Ｄ Zr Ｅ O Ｆ 5. The process of claim 4, wherein 4<A<8.5, 1.5<B<4, 0≦C≦2, 0≦D≦2; 0≦E<2.5, 10<F≦13.5, and M′ and M″ are each, independently in each occurrence, selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, Ga, and Ta.

6. At least one of the ingredients has a particle size distribution d of about 100 nm to about 200 nm, about 200 nm to about 300 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, about 900 nm to about 1 μm, about 1 μm to about 2 μm, or about 2 μm to about 3 μm. ５０ The process according to any one of claims 1 to 5, comprising:

7. 7. The process of any one of claims 1 to 6, wherein the process further comprises milling at least one raw material powder in a non-reactive environment in an anhydrous aprotic solvent.

8. 8. The process of any one of claims 1 to 7, wherein the non-reactive environment comprises nitrogen gas or argon gas, or a combination thereof, and humidity at a dew point of about -10°C to -20°C, about -20°C to -30°C, about -30°C to -40°C, about -40°C to -50°C, or about -50°C to -60°C.

9. 9. The process of claim 7 or 8, wherein the aprotic solvent is selected from the group consisting of benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane.

10. 10. The process of any one of claims 1 to 9, wherein the milling is selected from the group consisting of dry milling, attrition milling, ultrasonic milling, high energy milling, wet milling, jet milling, and cryogenic milling.

11. The raw material powder has a particle size distribution d of about 100 nm to 200 nm, about 200 nm to 300 nm, about 300 nm to 400 nm, about 400 nm to 500 nm, about 500 nm to 600 nm, about 600 nm to 700 nm, or about 700 nm to 750 nm. ５０ 11. The process of claim 10, further comprising milling the raw powder until it has:

12. Before step (c) or step (d), a slurry of the raw material powder modified in a non-reactive environment is mixed with a polymerizable copolymer of polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), poly(ethylene-co-1-octene) (PE-co-PO), poly(ethylene-co-methylenecyclopentene) (PE-co-PMCP), stereoblock polypropylene, polypropylene polypropylene, 12. The process of any one of claims 1 to 11, further comprising mixing with a binder selected from the group consisting of methylpentene, polyethylene oxide (PEO), PEO block copolymers, silicone polymers and copolymers, polyvinyl butyral (PVB), poly(vinyl acetate) (PVAc), polyvinylpyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers, binders from the Paraloid resins, binders from the Butvar resins, binders from the Mowital resins, and combinations thereof.

13. In step (b), fish oil, C ８ ~C ２０ Fatty acids of the order of C ８ ~C ２０ degree of alcohol, C ８ ~C ２０ 13. The process of any one of claims 1 to 12, further comprising milling a slurry of the modified raw powder with a dispersant selected from the group consisting of surfactants and dispersants from Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants, including alkylamines, phosphate esters, phospholipids, polymeric dispersants such as poly(vinylpyridine), poly(ethyleneimine), poly(ethylene oxide) and its ethers, poly(ethylene glycol) and its ethers, polyalkyleneamines, polyacrylates, polymethacrylates, poly(vinyl alcohol), poly(vinyl acetate), polyvinyl butyral, maleic anhydride copolymers, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants.

14. Said C ８ ~C ２０ 14. The process of claim 13, wherein the fatty acids are selected from dodecanoic acid, oleic acid, stearic acid, linolenic acid, and / or linoleic acid.

15. Said C ８ ~C ２０ 14. The process of claim 13, wherein the alcohol is selected from dodecanol, oleyl alcohol, stearyl alcohol, and combinations thereof.

16. Said C ８ ~C ２０ 14. The process of claim 13, wherein the alkylamine is selected from dodecylamine, oleylamine, stearylamine, and combinations thereof.

17. 14. The process of claim 13, wherein the phospholipid is selected from phosphatidylcholine, lecithin, and combinations thereof.

18. 18. The process of any one of claims 1 to 17, further comprising, prior to step (c) or step (d), mixing the slurry of raw material powder with a plasticizer selected from dibutyl phthalate, dioctyl phthalate, and benzyl butyl phthalate in a non-reactive environment.

19. The process according to any one of claims 1 to 18, wherein the filtration technique is selected from the group consisting of sieving, centrifugation and separation of particles of different sizes or different masses.

20. 20. The process of any one of claims 1 to 19, wherein the slurry has a solids loading of 1 wt% to 99 wt%, the solids loading referring to the amount of the raw material powder.

21. 21. The process of any one of claims 1 to 20, wherein the slurry when dried contains 80% wt / wt of the feedstock powder.

22. 22. The process of any one of claims 1 to 21, wherein the slurry when dried comprises an organic content of about 10-25% wt / wt, the organic content including slurry components other than the feedstock powder.

23. The process of any one of claims 1 to 22, wherein the green tape comprises particles of lithium-loaded garnet.

24. The green tape has a geometric density of 2.9 g / cm ３ The process of any one of claims 1 to 23, wherein the .alpha.-methyl-.beta.-methyl-.beta.

25. The process of any one of claims 1 to 24, further comprising sintering the green tape.

26. 8. The process of any one of claims 1 to 7, wherein the non-reactive environment comprises an atmosphere of humidity at a dew point of about -10°C to -20°C, about -20°C to -30°C, about -30°C to -40°C, about -40°C to -50°C, or about -50°C to -60°C.

27. 27. The process of any one of claims 1 to 26, wherein the non-reactive environment is the same non-reactive environment in each step.

28. 27. The process of any one of claims 1 to 26, wherein the non-reactive environments are different non-reactive environments in at least one step.

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