High green density ceramic for battery

Abstract

Presented herein are processes and materials for producing thin ceramic green tapes by casting ceramic raw material powders and precursor reactants, binders, and functional additives into thin, unsintered green tapes in a non-reactive environment.

Description

Technical Field

[0001] Cross - Reference to Related Applications

[0001] This application claims priority and the benefit of U.S. Provisional Patent Application No. 62 / 961,611, filed on January 15, 2020, the entire content of which is hereby incorporated by reference in its entirety for all purposes.

[0002] Field

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

Background Art

[0003] Background

[0003] Solid - state ceramics such as lithium - stuffed garnet materials and lithium borohydride, lithium oxide, lithium sulfide, lithium oxyhalide, and lithium halide have several advantages as materials for ion - conductive electrolyte membranes and separators in various electrochemical devices including fuel cells and rechargeable batteries. When compared to 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 that enable high volumetric and gravimetric energy densities accordingly when these materials are incorporated into electrochemical devices as electrolyte separators. Solid - state ion - conductive ceramics are well - suited for solid - state electrochemical devices due to their high ion - conductive properties in the solid state, their electrical insulation properties, their chemical compatibility with various electrode materials such as lithium metal, and their stability over a wide voltage window.

[0004] [

[0004] ] Solid state ion conductive ceramics have a number of advantageous and beneficial properties, but these materials have various problems associated with the formation of high density green films (i.e., green tapes) and the subsequent sintering of these green tapes. When solid state ion conductive ceramics are typically formulated and sintered as thin films, these films tend to adhere to the substrates on which they are prepared, crack or warp due to processing conditions, or are too brittle after sintering to be handled and manipulated. During the sintering of thin films, these films tend to crack, warp, or otherwise exhibit surface degradation. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] [

[0005] ] Thus, a series of problems exist in related fields associated with, but not limited to, casting ceramic green tapes such as garnet and sintering these green tapes to prepare thin high density garnet films. What is needed in the related art are, for example, improved materials and processes for casting green tapes having high density. MEANS FOR SOLVING THE PROBLEMS

[0006] SUMMARY [

[0006] ] The present disclosure presents such materials and processes, in addition to their manufacture and use, and presents other solutions to problems in related fields.

[0007] [

[0007] ] In one embodiment, a process for manufacturing a 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 specific 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 in each case, selected from 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]

[0009] In some embodiments, the process further includes grinding at least one starting material powder in a non-reactive environment in an anhydrous aprotic solvent. In some embodiments, the non-reactive environment includes 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 includes 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 grinding is selected from the group consisting of dry grinding, friction grinding, ultrasonic grinding, high energy grinding, wet grinding, jet grinding, and cryogenic grinding. In some embodiments, the starting material 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 until it has

[0010] In some embodiments, before step (c) or step (d), the process includes mixing a slurry of the raw material powder modified in a non-reactive environment with a binder 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), polyvinyl pyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers (e.g., polyacrylates, polymethacrylates, and copolymers thereof), binders from Paraloid resins, binders from Butvar resins, binders from Mowital resins, and combinations thereof. In some embodiments, the process includes fish oil, C8 - C 20 fatty acids of a certain degree, C8 - C 20 alcohols of a certain degree, C8 - C 20Degree of alkylamine, phosphate ester, phospholipid, polymer dispersant, for example, poly(vinyl pyridine), poly(ethylene imine), poly(ethylene oxide) and its ether, poly(ethylene glycol) and its ether, polyalkyleneamine, polyacrylate, polymethacrylate, poly(vinyl alcohol), poly(vinyl acetate), polyvinyl butyral, maleic anhydride copolymer, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants, including grinding a slurry of the modified raw material powder together with a dispersant selected from the group consisting of surfactants and dispersants. In some embodiments, C8-C 20 Degree of fatty acid is at least one of dodecanoic acid, oleic acid, stearic acid, linolenic acid, and / or linoleic acid. As used herein, C8-C 20 Degree means that the described organic group contains 8 to 20 carbon atoms. In some embodiments, C8-C 20 Degree of alcohol is at least one of dodecanol, oleyl alcohol, and / or stearyl alcohol. In some embodiments, C8-C 20The alkylamine of a certain degree is at least one of dodecylamine, oleylamine, and / or stearylamine. In some embodiments, the phospholipid is phosphatidylcholine and / or lecithin. In some embodiments, before step (c) or step (d), the process further includes mixing a slurry of feed 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 different masses. In some embodiments, the slurry has a solid loading of 1 wt% to 99 wt%, and the solid loading refers to the amount of the feed powder. In some embodiments, the slurry contains 80% wt / wt of the feed powder when dried. In some embodiments, the slurry contains an organic content of about 10 to 25% wt / wt when dried, and the organic content includes slurry components other than the feed powder. In some embodiments, the green tape has a density greater than 2.9 g / cm 3 when measured by geometric density. In some embodiments, the green tape is sintered.

[0011]

[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 above filtrations, the process includes filtering the slurry in a non-reactive environment.

[0012]

[0012] Some embodiments a. Lithium-filled garnet particles or particles of a precursor of lithium-filled garnet, and b. at least one element selected from binders, plasticizers, dispersants, and surfactants to provide a self-supporting green tape.

[0013]

[0013] In some embodiments, the self-supporting green tape has a density of 2.9 to 5.0 g / cm 3a density, a thickness of 0.5 to 100 μm, and a lateral size of 0.5 to 400 cm 2 have. In some embodiments, the particles are 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, about 1.0 - 1.1 μm in d 50 have. In some embodiments, the self - supporting 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 is. In some embodiments, the change in the thickness of the green tape with respect to the area of 10 cm 2 is less than 5%. In some embodiments, the green tape has a ceramic loading of about 50 - 80 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 have. 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 size of about 0.5 - 400 cm 2 in lateral size, a ceramic loading of about 55 - 75 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 in lateral size, a ceramic loading of about 50 - 75 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 in lateral size, a ceramic loading of about 55 - 70 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 in lateral size, a ceramic loading of about 50 - 65 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 in lateral size, or a ceramic loading of about 55 - 65 vol%, a thickness of about 0.5 - 100 μm, and a lateral size of about 0.5 - 400 cm 2 have.

[0014]

[0014] In some embodiments including any of the above, the green tape has a density of 2.9 - 5.0 g / cm 3a density, a thickness of 0.5 to 100 μm, and a lateral size of 0.5 to 400 cm 2 have. In some embodiments, the particles have a d of about 0.1 to about 0.2 μm 50 have. In some embodiments, the particles have a d of 0.2 to about 0.3 μm 50 have. In some embodiments, the particles have a d of 0.3 to about 0.4 μm 50 have. In some embodiments, the particles have a d of 0.4 to about 0.5 μm 50 have. In some embodiments, the particles have a d of 0.5 to about 0.6 μm 50 have. In some embodiments, the particles have a d of 0.6 to about 0.7 μm 50 have. In some embodiments, the particles have a d of 0.7 to about 0.8 μm 50 have. In some embodiments, the particles have a d of 0.8 to about 0.9 μm 50 have. In some embodiments, the particles have a d of 0.9 to about 1.0 μm 50 have. In some embodiments, the particles have a d of 1.0 to about 1.1 μm 50 have. In some embodiments, the self-supporting 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 is. In some embodiments, the thickness of the green tape changes by less than 5% with respect to the area of 10 cm 2 have. In some embodiments, the green tape has a raw material powder solid loading of about 50 to about 80 vol%, a thickness of about 0.5 to about 100 μm, and a lateral size of about 0.5 to 400 cm 2 have. 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 μm, and a lateral size of about 0.5 to 400 cm 2 have. 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 μm, and a lateral size of about 0.5 to 400 cm 2has a lateral size. In 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 size of about 0.5 to 400 cm 2 has a lateral size. 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 size of about 0.5 to 400 cm 2 has a lateral size. 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 size of about 0.5 to 400 cm 2 has a lateral size. 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 size of about 0.5 to 400 cm 2 has a lateral size.

Brief Description of the Drawings

[0015] Brief Description of the Drawings

Figure 1

[0015] Shows an example of a flowchart according to an embodiment of the process shown in this specification.

Figure 2

[0016] Shows a scanning electron microscopy (SEM) image of a green tape manufactured by the casting process shown in Example 1. The organic part is denoted by 201, and the lithium-filled garnet part is denoted by 202.

Figure 3

[0017] Shows a scanning electron microscopy (SEM) image of a sintered green tape manufactured in Example 1. The organic part is denoted by 301, and the garnet part is denoted by 302.

Figure 4

[0018] Shows optical microscopy images of a green tape disk manufactured in Example 1 before sintering and the resulting disk after sintering. The green tape disk is denoted by 401, and the sintered disk is denoted by 402.

Modes for Carrying Out the Invention

[0016]

[0019] The drawings show various embodiments of the present disclosure for illustrative purposes 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 a person skilled in the art to make and use the disclosed subject matter and to incorporate it in the context of the present application. Various modifications, as well as 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. Accordingly, the present disclosure is not intended to be limited to the embodiments presented, but rather the broadest scope consistent with the principles and novel features disclosed herein should be given.

[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 to avoid obscuring the present disclosure.

[0019]

[0022] The disclosure herein shows high-density green tapes prepared in a non-reactive environment, processes for manufacturing these green tapes, and processes for sintering these green tapes. The processes herein produce thin green tapes with high density as compared to green tapes prepared by conventional known processes. The sintered films manufactured from the green tapes have surfaces suitable for incorporation into electrochemical devices without further processing such as polishing or lapping finishes. These green tapes have less shrinkage when sintered as compared to conventional known processes. These green tapes do not warp or crack during sintering as compared to conventional known processes. These green tapes are suitable for use in electrochemical device applications.

[0020] A. Definitions

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

[0021]

[0024] As used herein, "casting" means providing, depositing, or delivering a cast 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 term "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 fixed-dimension slot or mold that is adjacent to, in contact with, or disposed on the substrate on which the deposition or coating occurs. In some examples, slot casting includes a slot opening of about 1 to 100 μm.

[0023]

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

[0024]

[0027] As used herein, "casting of slurry" refers to the process by which a slurry is deposited on 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 cast solution or cast slurry on a substrate.

[0025]

[0028] As used herein, "aluminum oxide dopant" means an amount of aluminum or alumina such that the lithium-filled garnet can be written with an empirical formula (e.g., Li7Zr2La3O 12 including a certain amount of Al2O3 in addition to a certain amount of Li7Zr2La3O 12 Al2O3).

[0026]

[0029] As used herein, the terms "casting of a film" or "casting of a green tape" refer to the process of delivering or moving a liquid or slurry into a mold or onto a substrate such that the liquid or slurry forms or is formed into a green tape. Casting can be performed 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 continuously depositing a layer of one precursor species, such as a lithium precursor species, onto a deposition substrate, and subsequently depositing an additional layer on top of the already deposited layer using a second precursor species, such as a transition metal precursor species. This lamination process can be repeated to build several layers of the deposited vapor phase. As used herein, the term "laminating" also refers to the process by which a layer containing an electrode, such as a layer containing a positive electrode or cathode active material, is contacted with another material, such as a layer containing a garnet electrolyte. The lamination process can include the reaction or use of a binder that adheres the layers being laminated or physically maintains contact between the layers being laminated. Laminating also refers to the process of potentially bonding "green", i.e., non-sintered, ceramic films under pressure and / or heating the films to join them.

[0028]

[0031] As used herein, the terms "green tape" or "green film" refer to a non-sintered tape or film that includes at least one member selected from a garnet material, a precursor of a garnet material, a binder, a plasticizer, carbon, a dispersant, or a combination thereof.

[0029]

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

[0030]

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

[0031]

[0034] As used herein, "thin" means a thickness dimension of less than 200 μm, sometimes less than 100 μm, and in some examples between 0.1 and 60 μm when restricting green tapes, films, etc.

[0032]

[0035] As used herein, the terms "garnet precursor chemical", "chemical precursor of garnet-type electrolyte", or "garnet chemical precursor" 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., Li2O), lithium carbonate (e.g., Li2CO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), aluminum oxide (e.g., Al2O3), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO3), aluminum nitrate nonahydrate, corundum, aluminum hydroxide (oxy) (gibbsite and boehmite), gallium oxide, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., Ta2O5).

[0033]

[0036] As used herein, the phrase "the subscripts and molar coefficients in the empirical formula are based on the amounts of raw materials first batch processed to make the described examples" means that the subscripts (e.g., 7, 3, 2, 12 in Li7La3Zr2O 12 and the coefficient 0.35 in 0.35Al2O3) refer to the respective elemental ratios in the chemical precursors (e.g., LiOH, La2O3, ZrO2, Al2O3) used to prepare a given material (e.g., Li7La3Zr2O 12 ·0.35Al2O3). The molar ratios are as batch processed unless explicitly indicated to the contrary.

[0034]

[0037] As used herein, the phrase "batch processed" refers to the respective molar amounts of the components first mixed or provided at the start of the synthesis. For example, batch processed formula Li7La3Zr2O 12 means that the ratio of Li to La to Zr to O in the reagents used to make Li7La3Zr2O 12 was 7 to 3 to 2 to 12.

[0035]

[0038] As used herein, the phrase "characterized by a formula" refers to a molar ratio of component atoms that is batch processed or determined experimentally during the process for manufacturing 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 suitable for dissolving components used in the garnet sintering process, such as binders, for example, toluene.

[0037]

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

[0038]

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

[0039]

[0042] As used herein, the phrase "removal of solvent" refers to the process by which the solvent is extracted or separated from the components or materials shown herein. Removal of solvent includes, but is not limited to, evaporation of the solvent. Removal of solvent includes, but is not limited to, using high temperature, vacuum, or reduced pressure to drive the solvent out of a mixture, such as a non-sintered green tape. In some examples, the film containing the binder and solvent is heated, or optionally, placed in a vacuum or reduced pressure ambient environment, to evaporate the solvent and leave 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 portions of a cast dried or non-dried tape that can be sintered.

[0041]

[0044] As used herein, "binder" refers to a material that aids in the adhesion of other materials. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders may include polycarbonate. Other binders may include polyacrylates and polymethacrylates. Examples of these binders are not intended to be limiting with respect to the entire scope of binders contemplated herein, but rather serve as examples only. 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), polyolefin, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylene cyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylic, polyvinyl acetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, and the like.

[0042]

[0045] As used herein, the phrase "lithium-filled garnet electrolyte" refers to an oxide characterized by a crystal structure associated with a 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 those in which Al 3+ is doped to replace Li + in the above garnets. When used herein, lithium-filled garnets and garnets generally include 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 are 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 is included, but not limited to these. Non-limiting examples of lithium-filled garnet electrolytes can be found, for example, in US Patent Application Publication No. 2015-0200420A1, published on July 16, 2015.

[0043]

[0046] As used herein, garnet does not include YAG-garnet (i.e., yttrium aluminum garnet, or, for example, Y3Al5O 12 ). As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon-stone, tschermigite, uvarovite and andradite, and solid solution 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 materials described herein as ion conductors. There are many advantages to solid-state Li-filled garnet electrolytes, including advantages as a substitute for the liquid flammable electrolytes commonly used in rechargeable lithium batteries.

[0045]

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

[0046]

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

[0047]

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

[0048]

[0051] As used herein, the term "calcining" refers to a process that includes chemical decomposition reactions or chemical reactions between solids (see Ceramic Processing and Sintering, Second Edition, M.N. 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 the desired material phase. Sintering requires a high starting density and is usually carried out at a higher temperature, the so-called firing temperature. Calcining includes chemical decomposition reactions or chemical reactions between solids and does not include a reduction in the surface free energy of the aggregated particles.

[0049]

[0052] As used herein, the phrases "sintering the green tape", "sintering", or "sintering the film" refer to the process by which a thin green tape as described herein is densified (made more dense or with reduced porosity) by the use of heat sintering or field assisted sintering. Sintering includes the process of forming a solid mass of material by heat and / or pressure without melting it to complete liquefaction. Sintering causes a reduction in the surface free energy of the aggregated particles, which can be achieved by atomic diffusion processes that result in densification of the object, by transporting material from internal particles into pores, by coarsening of the microstructure, or by rearrangement of material between different parts of the pore surface without actually resulting in a reduction of the pore volume (see page 32 of Rahaman).

[0050]

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

[0051]

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

[0052]

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

[0053]

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

[0054]

[0057] As used herein, a green tape is considered to have a high density if its density is higher 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 down-sized garnet powder is considered to have a high density if its density is higher than 4 g / ml.

[0057]

[0060] As used herein, a down-sized 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 term "sintering aid" refers to an additive that is used to lower the melting point of the liquid phase or enables sintering to occur more rapidly than might otherwise be possible without the sintering aid. Sintering aids assist in the diffusion / mobility of the atoms being sintered. For example, Li3BO3 can be used as an additive in sintering to provide faster or more complete densification of garnet during sintering.

[0059]

[0062] As used herein, the term "starting powder" refers to the inorganic materials used in the slurries shown herein. In some examples, the starting powder is a lithium-filled garnet. For example, the starting powder can include a powder of Li7La3Zr2O 12 ·0.5Al2O3.

[0060]

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

[0061]

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

[0062]

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

[0063] B. Green Tape

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

[0064]

[0067] In one embodiment, the present disclosure shows 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 at least one of the calcined powders 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 shows a slurry for casting a green tape, where the slurry includes 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 shows a slurry for preparing a green tape, where the slurry includes a solvent, a raw material powder, at least one aprotic anhydrous solvent selected from the group consisting of 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), polyvinyl pyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers (such as polyacrylates, polymethacrylates, and copolymers thereof), binders from Paraloid resins, binders from Butvar resins, binders from Mowital resins;Fish oil, fatty acids of about C8 - C20 (for example, dodecanoic acid, oleic acid, stearic acid, linolenic acid, linoleic acid), alcohols of about C8 - C20 (for example, dodecanol, oleyl alcohol, stearyl alcohol), alkylamines of about C8 - C20 (for example, dodecylamine, oleylamine, stearylamine), phosphate esters, phospholipids (for example, 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, Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, Span surfactants; a plasticizer selected from the group consisting of dibutyl phthalate, dioctyl phthalate, or benzyl butyl phthalate; a raw material powder selected from lithium-filled garnet; or a combination thereof; comprises.

[0067]

[0070] In a fourth embodiment, the present disclosure shows a green tape comprising a 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 embodiments shown herein, the green tapes cast by the processes shown herein have a high density. These green tapes are cast from slurries made of downsized ceramic materials. They may contain refractories and / or ceramic materials formulated as ceramic particles intimately mixed with a binder. The purpose of this binder is, among other things, to assist in sintering the ceramic particles to result in a uniform and thin film or layer of refractory or ceramic after sintering. During the sintering process, the binder is removed from the green tape by a binder removal step. In some examples, this binder removal occurs at a temperature of less than 700°C, less than 450°C, less than 400°C, less than 350°C, less than 300°C, less than 250°C, or in some examples less than 200°C, or in some examples less than 150°C, or in some examples less than 100°C. During the binder removal process, the partial pressures of oxygen and water can be controlled. The binder removal process can include multiple steps.

[0069] C. Manufacturing Process of Green Tape

[0072] The green tapes shown herein can be manufactured by various processes. In some processes, a slurry containing calcined raw material powder is prepared in a non-reactive environment using an anhydrous aprotic solvent; this slurry is cast onto a substrate or setter plate and then the slurry is dried and sintered to prepare a dried and sintered solid ion conductive ceramic. In certain examples, the substrate can include, for example, Mylar, silicone-coated Mylar, a surface coated with a polymer, a surface-modified polymer, or a surface-organized 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, the first step 100 includes mixing, grinding, drying, and calcining a garnet precursor. The next step 101 involves placing raw material powders such as a solvent, a dispersant, and garnet into a container in a non-reactive environment. A grinding medium is also added. In step 102, the combined contents are ground for 1 hour to 3 days. In the fourth step 103, a binder solution is added to the ground mixture and mixed in a non-reactive environment, and the resulting slurry is then degassed by a degassing process in a non-reactive environment to remove gas. In the fifth step 104, the slurry is cast onto a substrate (e.g., silicone-coated Mylar) by a doctor blade casting process and dried in a non-reactive environment. In the sixth step 105, the cast green tape is sintered. Variations of this process are also contemplated. In one example, the slurry is filtered before casting. In one example, casting is performed by a slot die, screen printing, gravure printing, or other casting process.

[0071]

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

[0072]

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

[0073]

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

[0074]

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

[0075]

[0078] In some embodiments, the ceramic loading of the green tape (i.e., the amount of solid ceramic or raw material powder present in the green tape) is greater than a specific 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 examples, 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. Grinding

[0080] In some embodiments, the processes herein include process steps related to mixing and / or process steps related to grinding. Grinding includes ball mill grinding. Grinding also includes a grinding process using a non-aqueous solvent 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 grinding is ball mill grinding. In some examples, the grinding is horizontal grinding. In some examples, the grinding is attritor grinding. In some examples, the grinding is immersion grinding. In some examples, the grinding is jet grinding. In some examples, the grinding is steam jet grinding. In some examples, the grinding is high energy grinding.

[0079]

[0082] In some examples, the high energy grinding process results in a grinding particle size distribution where d 50 is about 100 nm as measured by light scattering. In some examples, the high energy grinding process is used to achieve a particle size distribution where d 50 is about 750 nm as measured by light scattering. In some examples, the high energy grinding process is used to achieve a particle size distribution where d 50 is about 150 nm as measured by light scattering. In some examples, the high energy grinding process is used to achieve a particle size distribution where d 50 is about 200 nm as measured by light scattering. In some examples, the high energy grinding process is used to achieve a particle size distribution where d 50 is about 250 nm as measured by light scattering. In some examples, the high energy grinding process is used to achieve a particle size distribution where d 50achieve a particle size distribution with a d of about 300 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 350 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 400 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 450 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 500 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 550 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 600 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 650 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 700 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 800 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 850 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 900 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 950 nm. In some examples, a high energy milling process is used to achieve a particle size distribution where d, when measured by light scattering, is 50 achieve a particle size distribution with a d of about 1000 nm.

[0080]

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

[0081]

[0084] In some examples, the grinding includes a high-energy wet grinding process using 0.3 mm yttria-stabilized zirconium oxide grinding media beads. In some examples, ball mill grinding, horizontal grinding, attritor grinding, or immersion grinding can be used. In some examples, using a high-energy grinding process results in a particle size distribution of d 50 of approximately about 100 nm to 5000 nm.

[0082]

[0085] In some examples, the grinding can include a classification step such as sieving, centrifugation, or other known laboratory means of separating particles of different sizes and / or masses.

[0083] E. Slurry

[0086] In some examples, the aprotic anhydrous 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 dispersants, optionally with one or more binders, and optionally with one or more plasticizers. In some examples, the solvent comprises about 0-35% w / w anhydrous toluene. In some examples, the solvent comprises about 0-35% w / w benzene. In some examples, the solvent comprises about 0-35% xylene. In some examples, the solvent comprises about 0-35% dioxane. In some examples, the solvent comprises 0-35% w / w tetrahydrofuran. In some examples, the solvent comprises about 0-35% w / w 1,2-dimethoxyethane. In some examples, the dispersant 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 examples, a dispersant is used during the grinding 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-C 20 alcohols of a certain degree (e.g., dodecanol, oleyl alcohol, stearyl alcohol), C8-C 20Alkylamines of a certain degree (e.g., dodecylamine, oleylamine, stearylamine), phosphate esters, phospholipids (e.g., phosphatidylcholine, lecithin), polymeric dispersants such as poly(vinyl pyridine), poly(ethylene imine), poly(ethylene oxide) and its ethers, poly(ethylene glycol) and its ethers, polyalkylene amines, 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 dodecylbenzene sulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, Brij surfactants, Triton surfactants, and dispersants selected from the group consisting of Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants are included, but not limited to these. The dispersants may be combined.

[0085]

[0088] In some examples, binders suitable for use with the slurries described herein include binders used to facilitate adhesion between Li-filled garnet particles, including 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), polyvinyl pyrrolidinone (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymers (e.g., polyacrylates, polymethacrylates, and copolymers thereof), binders from Paraloid resins, binders from Butvar resins, binders from Mowital resins, but are not limited thereto. 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 be combined.

[0087] F. Casting

[0090] In some of the processes shown herein, the process includes 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] Some tape casting processes are known in the relevant art, and the entire contents of Mistler, R. E. and Twiname, E. R, Tape Casting: Theory and Practice, 1 st Edition Wiley - American Ceramic Society; 1 edition (December 1, 2000) are incorporated herein by reference in their entirety for all purposes. Other casting processes and materials are as shown in U.S. Patent No. 5,256,609 (Dolhert, L. E.) entitled "Clean Combustion 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 D. J. Shanefield Organic Additives and Ceramic Processing, Springer Science & Business Media, (Mar 9, 2013), which is incorporated herein by reference.

[0089] G. Drying of the tape after casting

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

[0090] H. Sintering Plate

[0093] In some examples, the green tape prepared by the processes in this specification and the processes incorporated by reference is sintered between sintering plates. In some examples, the green tape prepared by the processes in this specification and the processes incorporated by reference is sintered on at least one sintering plate. In some examples, these sintering plates are composed of metals, oxides, nitrides, or metals, oxides, or nitrides having an organic or silicone laminate layer thereon. In a specific example, the sintering plate is a platinum (Pt) sintering plate, a palladium (Pd) sintering plate, a gold (Au) sintering plate, a copper (Cu) sintering plate, a nickel sintering plate, an aluminum (Al) sintering plate, an alumina sintering plate, a porous alumina sintering plate, a steel sintering plate, a zirconium (Zr) sintering plate, a zirconia sintering plate, a porous zirconia sintering plate, a lithium oxide sintering plate, a porous lithium oxide sintering plate, a lanthanum oxide sintering plate, a porous lanthanum oxide sintering plate, a garnet sintering plate, a porous garnet sintering plate, a lithium-filled garnet sintering plate, a porous lithium-filled garnet sintering plate, and combinations thereof. In some examples, the sintering plate is a garnet sintering plate or a porous garnet sintering plate. In some examples, the sintering plate has an oxide material with a lithium concentration exceeding 5 mmol / cm 3 and contains.

[0091]

[0094] In some examples of the processes described herein, the setter plate of lithium-filled garnet for the production of solid electrolytes shown in US Patent Application Publication No. 20170062873A1, titled "Setter Plate of Lithium-Filled Garnet for the Production of Solid Electrolytes", and the setter plate and sintering process shown in PCT Patent Application International Publication No. 2016168723A1, titled "Setter Plate for the Production of Solid Electrolytes and Process for Its Use for Preparing a High-Density Solid Electrolyte", filed on October 20, 2016, are hereby incorporated by reference in their entirety into this specification.

[0092]

[0095] In some examples, the green tape prepared by the processes described herein and the processes shown 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) has metal powder disposed between the setter plates and the green tape and is sintered between the setter plates. In certain examples, the setter plates are selected from the group consisting of a platinum (Pt) setter plate, a palladium (Pd) setter plate, a gold (Au) setter plate, a copper (Cu) setter plate, a nickel setter plate, an aluminum (Al) setter plate, an alumina setter plate, a porous alumina setter plate, a steel setter plate, a zirconium (Zr) setter, a zirconia setter plate, a porous zirconia setter plate, a lithium oxide setter plate, a porous lithium oxide setter plate, a lanthanum oxide setter plate, a lithium zirconium oxide (Li2ZrO3) setter plate, a lithium aluminum oxide (LiAlO2) setter plate, a porous lanthanum oxide setter plate, a lithium zirconium oxide (Li2ZrO3) setter plate, a lithium aluminum oxide (LiAlO2) setter plate, a garnet setter plate, a porous garnet setter plate, a lithium-filled garnet setter plate, and a porous lithium-filled garnet setter plate, and combinations of the foregoing. In some examples, the setter plate comprises an oxide material having a lithium concentration greater than 5 mmol / cm 3 In these specific examples, the metal powder is selected from Ni powder, Cu powder, Au powder, Fe powder, or combinations thereof. The metal powder may additionally include a ceramic material.

[0093]

[0096] In some examples, the green tape prepared by the processes in this specification and the processes incorporated by reference is sintered between setter plates with a metal layer or film disposed between the setter plate and the green tape. In some examples, these setter plates are composed of metals, oxides, nitrides, or metals, oxides or nitrides having an organic or silicone laminate layer thereon. In certain examples, the setter plate is selected from the group consisting of a platinum (Pt) setter plate, a palladium (Pd) setter plate, a gold (Au) setter plate, a copper (Cu) setter plate, a nickel setter plate, an aluminum (Al) setter plate, an alumina setter plate, a porous alumina setter plate, a steel setter plate, zirconium (Zr), a zirconia setter plate, a porous zirconia setter plate, a lithium oxide setter plate, a porous lithium oxide setter plate, a lanthanum oxide setter plate, a porous lanthanum oxide setter plate, a garnet setter plate, a porous garnet setter plate, a lithium-filled garnet setter plate, a porous lithium-filled garnet setter plate, a magnesia setter plate, a porous magnesia setter plate. In some examples, the setter plate contains an oxide material having a lithium concentration exceeding 5 mmol / cm 3 . In these specific examples, the metal powder is selected from Ni powder, Cu powder, Mg powder, Mn powder, Au powder, Fe powder, or combinations 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 a portion of it sinters, and if not controlled, can result in cracks or other mechanical defects in the film. In some of these examples, the layer of particles forms a uniform layer of particles. In some other of these examples, the layer of particles includes a uniform layer of particles that is inert or non-reactive with the green tape. Under 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 position of the inert particles between the green tape and the setter plate is disposed between the contact surface of the green tape and the sintered portion of the green tape. In some continuous sintering processes, the setter plate, and / or the particles, layer, or sheet disposed between the setter plate and the green tape, can be moved or repositioned during the sintering process such that a continuous roll of the sintered film is prepared in a continuous process. In these continuous processes, the setter plate and the particles, layer, or sheet are coordinated with the movement of the green tape such that a portion of the sintered green tape contacts the particles, layer, or sheet that also contacts the setter plate. In some examples, the layer or sheet is prepared with a specific weight to prevent warping and surface degradation of the tape.

[0095]

[0098] In some of the examples described herein, a layer or sheet of inert and / or uniform particles (or powder) assists 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, decreases in volume, and increases in density. By reducing the frictional force, the green tape can shrink with minimal stress during the sintering process. This provides an improved sintered film that does not adhere 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 can be used, for example, in combination with the lithium-filled garnet setter plates described herein, as long as the other setter plates 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, lithium-filled garnet, or combinations thereof. Further, these other setter plates should not induce a chemical potential within the sintered film that would result in Li diffusion from the sintered film to the setter plate. Additional materials include lanthanum aluminum oxide, pyrochlore, and materials having a lithium concentration greater than 0.01 mol / cm 3 In some examples, the setter plate can include materials having a lithium concentration greater than 0.02 mol / cm 3 In some examples, the setter plate can include materials having a lithium concentration greater than 0.03 mol / cm 3 In some examples, the setter plate can include materials having a lithium concentration greater than 0.04 mol / cm 3 In some examples, the setter plate can include materials having a lithium concentration greater than 0.05 mol / cm 3 In some examples, the setter plate can include materials having a lithium concentration between 10 and 15 mmol / cm 3 In some examples, the setter material can be provided as a powder or in a non-planar shape.

[0097] I. Sintering

[0100] The green tape shown in this specification can be sintered by the sintering process shown in International Patent Application Publication No. WO 2015 / 076944, which is the published version of International Patent Application No. PCT / US2014 / 059578, filed on October 7, 2014, under the title "Garnet Materials for Li Secondary Batteries and Methods of Manufacturing and Using Garnet Materials", which is incorporated herein by reference in its entirety for all purposes.

[0098]

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

[0099]

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

[0100]

[0103] In any of the processes shown herein, heat sintering may include heating the green tape in the 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 shown herein, heat sintering can include heating the green tape in the 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 shown herein, 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 shown herein, 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 shown herein, heat sintering can include heating the green tape to 700°C. In any of the processes shown herein, heat sintering can include heating the green tape to 750°C. In any of the processes shown herein, heat sintering can include heating the green tape to 850°C. In any of the processes shown herein, heat sintering can include heating the green tape to 900°C. In any of the processes shown herein, heat sintering can include heating the green tape to 950°C. In any of the processes shown herein, heat sintering can include heating the green tape to 1000°C. In any of the processes shown herein, heat sintering can include heating the green tape to 1050°C. In any of the processes shown herein, heat sintering can include heating the green tape to 1100°C.In any of the processes shown in this specification, heat sintering can include heating the green tape to 1125 °C. In any of the processes shown in this specification, heat sintering can include heating the green tape to 1150 °C. In any of the processes shown in this specification, heat sintering can include heating the green tape to 1200 °C.

[0101]

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

[0102]

[0105] In some examples, the sintering process can include sintering in a closed but unsealed furnace (i.e., an oven, a heating chamber). In some of these examples, the green tape is placed between setter plates and optionally has a setter sheet or layer therebetween, and the green tape for sintering is placed adjacent to, or very close to, a sacrificial Li source. This sacrificial Li source helps prevent Li loss due to 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 larger than the surface area of the green tape being sintered. In some examples, the Li source and the sintered green tape have the same type of lithium-filled garnet.

[0103]

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

[0104]

[0107] In some embodiments, the sintering equipment used includes a custom temperature and gas flow control system with a 3-inch laboratory tubular furnace having a controlled atmosphere in the oxygen partial pressure range of 1e -1 ~1e -20 atmospheres.

[0105] J. Sintering with Other Device Components

[0108] In certain examples, the green tape is sintered while in contact with other components that the sintered green tape can be combined with when used in an electrochemical device. For example, in some examples, the green tape is layered or laminated onto a cathode composition such that the sintered green tape adheres to the cathode after sintering of the green tape. In another example, the green tape is sintered while in contact with a metal powder (e.g., nickel (Ni) powder). When the green tape is sintered and the metal powder is densified into a solid metal foil, the sintered green tape binds to the metal foil. The advantage of these sintering conditions is that two or more components of the electrochemical device are prepared in one step, thus manufacturing time and resources can be saved.

[0106] K. Measurements

[0109] In some embodiments, for measurements, SEM electron microscopy was performed on a Helios 600i or FEI Quanta. In some embodiments, surface roughness was measured by an optical microscope such as a Keyence VR that can measure height to calculate a roughness value. In some embodiments, powder density was measured using a pycnometer. In some embodiments, green tape density was measured using a geometric process or by use of the Archimedes method. In some embodiments, changes in the thickness of the green tape were measured using a beta-gauge, a micrometer, or a cross-sectional image.

Examples

[0107] L. Examples Example 1 - Production Process of Calcined Lithium-Filled Garnet Powder

[0110] Calcined lithium-filled garnet powder was made in the following series of steps. First, lithium hydroxide (LiOH), aluminum nitrate [Al(NO3)3·9H2O], zirconia (ZrO2), and lanthanum oxide (La2O3) were weighed (i.e., measured by weighing), such that the molar ratio of the constituent elements was Li 7.1 Zr2La3O12 It was mixed with a combination that is +0.5Al2O3. Using wet grinding technology and ZrO2 grinding media, the combination was mixed and ground until the combination had a d 50 particle size in the range of 100 nm to 5 μm. A dispersant was also included with the grinding media. In some examples, a solvent was also included. After grinding to the d 50 particle size, the ground combination of reactants was separated from the grinding media. Next, the separated ground reactants were placed in an alumina crucible and calcined in a non-reactive environment in an oven at about 800 to 900 degrees Celsius (900 °C) for about 2 to 6 hours, and a controlled oxidizing atmosphere was brought into contact with the calcined reactants. The calcination process incinerated and / or combusted the residual solvent and dispersant, as well as the surfactant. By calcination, the inorganic reactants reacted to form a lithium-filled 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 is called a calcined lithium-filled garnet and has an empirical formula of approximately Li 7.1 Zr2La3O 12 +0.5Al2O3.

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

[0111] In a grinding container within an argon glove box, 1000 to 1500 g of the calcined lithium-filled garnet powder from Example 1 was added to 400 to 700 g of an anhydrous aprotic solvent such as hexane, THF, or methylene chloride, along with 20 to 45 g of oleic acid. The mixture was ground for 2 to 6 hours in a Hockmeyer mill containing 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 atmospheric pressure. The ambient atmosphere was dry air. The dry air had a dew point of less than 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 grinding was added to the ground garnet slurry in the non-reactive environment to obtain a final slurry solids content of about 45 - 60% w / w. The slurry was mixed in a FlackTek SpeedMixer for 10 - 30 minutes in the non-reactive environment. Next, the mixed slurry was cast onto a substrate with a doctor blade in the non-reactive environment to prepare a green tape. The cast mixed slurry was dried at room temperature for 2 - 6 hours in the non-reactive environment to form a green tape. Subsequently, the geometric density of the dried green tape was measured to be greater than 2.9 g / cm 3 3.

[0110]

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

[0111] Example 3 - Preparation of Another High-Density Green Tape

[0114] This example shows the manufacturing process of another high-density green tape produced using a different dispersant. In a grinding container within an argon glove box, 1000 - 1500 g of the calcined lithium-filled garnet powder from Example 1 was added to 400 - 700 g of an anhydrous aprotic solvent such as hexane, THF, or methylene chloride and 20 - 35 g of Solsperse M387 dispersant. The mixture was ground in a Hockmeyer mill containing a zirconium oxide media for 2 - 6 hours 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.

[0112]

[0115] 200 - 600 g of the ground garnet slurry from the above steps 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 about 45 - 60% w / w. The slurry was mixed in a FlackTek SpeedMixer for 10 - 30 minutes in a non - reactive environment. Next, the mixed slurry was cast onto a substrate by a doctor blade in a non - reactive environment to prepare a green tape. The cast mixed slurry was dried at room temperature for 2 - 6 hours in a non - reactive environment to form a green tape.

[0113]

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

[0114]

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

[0115]

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

[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. The shrinkage during sintering was measured to be 20% based on the decrease 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, a green tape was prepared as in Example 1 or 2. In one example, a plurality of 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 to 5 hours. In another example, the tape was sintered at 1125 °C for 1 to 5 hours. In another example, the tape was sintered at 1150 °C for 1 to 5 hours. Before sintering, binder removal was carried out 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 around the sintered green tape had a PO2 in the range of 0.5 to 10 -20 atm.

[0118]

[0121] The foregoing description of the embodiments of the present disclosure has been presented for purposes of illustration; it is not intended to be exhaustive or to limit the claims to the precise forms disclosed. Those skilled in the relevant art fields will recognize, based on the above disclosure, that numerous equivalents, modifications, and variations are possible using only routine experimentation.

Claims

Claim 1 A process for manufacturing a high-density green tape, comprising: (a) providing a slurry containing raw material powder; (b) mixing the slurry with a binder solution; (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. At least one of the raw material powders 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; wherein at least one of the raw material powders 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; At least one of the raw materials has a particle size distribution d of 100 nm to 200 nm, 200 nm to 300 nm, 300 nm to 400 nm, 400 nm to 500 nm, 500 nm to 600 nm, 600 nm to 700 nm, 700 nm to 800 nm, 800 nm to 900 nm, 900 nm to 1 μm, 1 μm to 2 μm, or 2 μm to 3 μm ５０ and the non-reactive environment includes nitrogen gas or argon gas, or a combination thereof, and a dew point of -10°C to -20°C, -20°C to -30°C, -30°C to -40°C, -40°C to -50°C, or -50°C to -60°C; the process further includes grinding at least one raw material powder in an anhydrous aprotic solvent; the aprotic solvent is selected from the group consisting of benzene, toluene, xylene, ethyl acetate, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; Furthermore, the process includes grinding the raw material powder until the raw material powder has a particle size distribution d of 100 nm to 200 nm, 200 nm to 300 nm, 300 nm to 400 nm, 400 nm to 500 nm, 500 nm to 600 nm, 600 nm to 700 nm, or 700 nm to 750 nm. ５０ ​ Claim 2 The process according to 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. Claim 3 The process according to claim 1 or 2, 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%. Claim 4 wherein 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 in each case, 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 the process according to any one of claims 1 to 3. Claim 5 The process according to any one of claims 1 to 4, wherein the grinding is selected from the group consisting of dry grinding, friction grinding, ultrasonic grinding, high-energy grinding, wet grinding, jet grinding, and cryogenic grinding. Claim 6 Before the said step (c) or the said step (d), in the said step (b), the slurry of the raw material powder is mixed with a binder selected from the group consisting 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 polymethylpentene, polyethylene oxide (PEO), PEO block copolymer, silicone polymer and copolymer, polyvinyl butyral (PVB), poly(vinyl acetate) (PVAc), polyvinyl pyrrolidine (PVP), poly(ethyl methacrylate) (PEMA), acrylic polymer, binder from Paraloid resins, binder from Butvar resins, binder from Mowital resins, and combinations thereof. The process according to any one of claims 1 to 5.

7. In the step (b), fish oil, C ８ to C ２０ fatty acids of a certain degree, C ８ to C ２０ alcohols of a certain degree, C ８ to C ２０ alkylamines of a certain degree, phosphate esters, phospholipids, polymeric 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(vinyl acetate), polyvinyl butyral, maleic anhydride copolymers, glycolic acid ethoxylate lauryl ether, glycolic acid ethoxylate oleyl ether, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, cetyltrimethylammonium bromide, cetylpyridinium chloride, Brij surfactants, Triton surfactants, Solsperse dispersants, SMA dispersants, Tween surfactants, and Span surfactants, further comprising grinding a slurry of the modified raw material powder together with a dispersant selected from the group consisting of surfactants and dispersants, the process according to any one of claims 1 to 6.

8. The above C ８ -C ２０ Degree fatty acids are selected from dodecanoic acid, oleic acid, stearic acid, linolenic acid, and / or linoleic acid, Or, the C ８ -C ２０ level of alcohol is selected from dodecanol, oleyl alcohol, stearyl alcohol, and combinations thereof, Or, the C ８ to C ２０ alkylamine of such a degree is selected from dodecylamine, oleylamine, stearylamine, and combinations thereof, Or, the phospholipid is selected from phosphatidylcholine, lecithin, and combinations thereof. The process according to claim 7.

9. Before the said step (c) or the said step (d), the slurry of the raw material powder is further mixed with a plasticizer selected from dibutyl phthalate, dioctyl phthalate, and benzyl butyl phthalate. The process according to any one of claims 1 to 8.

10. The said process further includes filtering the raw material powder. The said filtration technique is selected from the group consisting of sieving, centrifugation, and separation of particles of different sizes or different masses. The process according to any one of claims 1 to 9.

11. The said slurry has a solid loading of 1 wt% to 99 wt%, and the said solid loading refers to the amount of the raw material powder. The process according to any one of claims 1 to 10.

12. The said slurry contains 80% wt / wt of the said raw material powder when dried. The process according to any one of claims 1 to 11.

13. The said slurry contains an organic content of 10 to 25 wt% when dried. The process according to any one of claims 1 to 12, wherein the organic content comprises slurry components other than the raw material powder.

14. The process according to any one of claims 1 to 13, wherein the green tape comprises particles of lithium-filled garnet.

15. The process according to any one of claims 1 to 14, wherein the green tape has a density greater than 2.9 g / cm3 when measured by geometric density.

16. The process according to any one of claims 1 to 15, further comprising sintering the green tape.

17. The process according to any one of claims 1 to 16, wherein the mixing step and the grinding step are carried out in a non-reactive environment.

Images