Processing device and method of use

Abstract

1. A process for manufacturing a sintered bilayer, comprising: providing a green bilayer comprising a green body layer and a metal layer under tension of 1 N to 300 N per meter of web width; creating a debound bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debound bilayer through a second heating zone; wherein the debound bilayer is arch-shaped as it advances through the second heating zone; the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the temperature of the second heating zone is 1050°C to 1250°C; and the thickness of the sintered bilayer is less than 100 microns.

Description

[Technical Field]

[0001] cross reference

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 406,711, filed September 14, 2022, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Field This disclosure relates to processes for calcining, debinding, and / or sintering ceramics. In some cases, such ceramics are deposited as a layer on top of a metal layer. These two layers create a bilayer. The bilayer is heated in a continuous processing device. [Background technology]

[0003] background

[0003] Certain sintering methods for lithium-loaded garnet (lithium lanthanum zirconium oxide; LLZO), such as batch sintering of LLZO, are described, for example, in U.S. Patent Nos. 10,563,918 B2 or 10,840,544 B2. Containerless sintering of certain ceramics is disclosed in U.S. Patent Application Publication No. 2004 / 0206470 A1; and also in WO 2014 / 103662 A1. Summary of the Invention [Problem to be solved by the invention]

[0004]

[0004] Despite this background, there is a need for a process for producing thin film ceramics or ceramic bilayers, such as sintering lithium-filled garnets in thin film or bilayer form, and a need for a process that uses a high-throughput continuous sintering process, such as a roll-to-roll process. [Means for solving the problem]

[0005] overview

[0005] In one embodiment, the present specification describes a process for manufacturing a sintered bilayer, comprising: providing a green bilayer comprising a green body layer and a metal layer under a tension of 1 N to 300 N per meter of web width; creating a debound bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debound bilayer through a second heating zone; wherein the debound bilayer is arch-shaped as it advances through the second heating zone; the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the temperature of the second heating zone is 1050°C to 1250°C; and the thickness of the sintered bilayer is less than 100 μm.

[0006]

[0006] In some embodiments, the present specification describes a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; and a runway having a surface comprising a material selected from nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite, alumina (Al2O3), zirconia (ZrO2), boron nitride, silicon carbide, magnesium oxide, or a combination thereof.

[0007]

[0007] In another embodiment, the present specification discloses a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; and at least one of the following: a baffle within a heating zone; a baffle between two heating zones; a curtain purge between two heating zones; a means for controlling at least two separate pressure zones within the at least three heating zones; a means for exhausting through the center of at least one furnace; a means for exhausting through the center of a runway; a means for purging gas between two heating zones; a means for isolating gas between two heating zones; a means for mechanically separating two heating zones; or at least one combination thereof.

[0008]

[0008] In some other embodiments, the present specification describes a processing apparatus comprising: a front roller; at least one oven including at least three heating zones; and a bilayer held under tension, wherein the tension is in the range of 0.1 g / cm to 500 g / cm per web width.

[0009]

[0009] In certain other embodiments, the present specification describes a processing apparatus comprising: a front roller; at least one oven including at least three heating zones; a bilayer; and at least two or more rollers; wherein the bilayer is wrapped around one of the at least two or more rollers at a wrap angle in the range of 0 to 40 degrees.

[0010]

[0010] In yet another embodiment, the present specification describes a process for using continuous process equipment, comprising the following operations: (a) producing a bilayer having an organic content of less than 1 weight percent (wt%) by heating the green bilayer as it passes through at least one furnace, and (b) winding the bilayer having an organic content of less than 1 wt% onto a roller.

[0011]

[0011] In certain embodiments, the present specification discloses a process for using continuous process equipment, the process comprising the following operations: (a) providing, or having provided, process equipment as disclosed herein; (b) producing a bisque bilayer body by heating the bilayer body as it advances through at least one furnace; and (c) winding up the bisque body.

[0012]

[0012] In some other embodiments, the present specification discloses a process for using continuous process equipment, the process comprising the following operations: (a) providing, or having provided, process equipment as disclosed herein; and (b) producing a sintered bilayer by heating the bilayer as it advances through at least one furnace. [Brief explanation of the drawings]

[0013] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1]

[0013] An embodiment of a process apparatus having multiple heating and / or cooling zones and a series of internal rollers, the rollers forming an arcuate ramp, is shown. [Figure 2]

[0014] 1 illustrates a portion of an embodiment of a process apparatus. [Figure 3]

[0015] 1 shows a series of tube furnaces in an embodiment of a process apparatus. [Figure 4]

[0016] 1 shows a series of tube furnaces in an embodiment of a process apparatus. [Figure 5]

[0017] 1 shows a photograph of one embodiment of a process apparatus. [Figure 6]

[0018] 1 shows an image of the bilayer produced in Example 8. [Figure 7]

[0019] A scanning electron microscopy (SEM) top view of the bilayer shows the lithium-filled garnet layer of the bilayer produced in Example 8. The lithium-filled garnet top layer has a porosity of less than 1% by volume. [Figure 8]

[0020] Figure 1 shows a scanning electron microscopy (SEM) cross-sectional image of the sintered oxide layer including the lithium-loaded garnet layer of the bilayer produced in Example 8. The lithium-loaded garnet top layer has a porosity of less than 1% by volume. [Figure 9]

[0021] 1 shows a biscuit and sintered bilayer wrapped around a roller. [Figure 10]

[0022] 1 shows a Keyence microscope image of bilaminate flatness as a function of tension applied to the bilaminate. The Keyence microscope flatness analysis is measured at the surface of the sintered oxide layer of the bilaminate, not the surface of the metal layer of the bilaminate. The flatness is a measure of the flatness of the surface of the sintered oxide layer. [Figure 11]

[0023] 1 shows a table quantifying the flatness of different bilayers as a function of the tension applied to the bilayer during sintering. [Figure 12]

[0024] 1 illustrates an embodiment of a processing device as described herein. [Figure 13]

[0025] 1 shows the electrochemical cycling results from Example 7. [Figure 14]

[0026] 10 shows a table quantifying flatness as a function of tension applied to bilayers sintered on a curved runway. [Figure 15]

[0027] 1 shows a Keyence microscope height map of a bilayer fabricated on a flat runway. [Figure 16]

[0028] 1 shows a Keyence microscope height map of a bilayer fabricated on a curved (i.e., arched) runway. [Figure 17]

[0029] 1 shows the flatness as a function of tension applied to the bilayer during the heat treatment process. [Figure 18]

[0030] 1 shows the flatness as a function of tension applied to the bilayer during the heat treatment process. [Figure 19]

[0031] 1 shows the flatness as a function of tension applied to the bilayer during the heat treatment process. [Figure 20]

[0032] 1 shows the flatness as a function of tension applied to the bilayer during the heat treatment process. DETAILED DESCRIPTION OF THE INVENTION

[0014] Detailed Description A. Introduction

[0033] The following description is presented to enable one skilled in the art to make and use the invention and to place it in the context of a particular application. Various modifications and uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide range of embodiments. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0015]

[0034] In the following detailed description, numerous specific details are set forth to provide a more thorough understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without necessarily being limited to these specific details. In other instances, well-known structures and mechanisms are shown in block diagram form, rather than in detail, in order to avoid obscuring the present disclosure.

[0016]

[0035] All features disclosed in this specification (including any accompanying claims, abstract, and drawings), unless expressly stated otherwise, may be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.

[0017]

[0036] While the continuous production line in the figures herein is shown in a horizontal configuration, in some embodiments, it can be assembled in a vertical configuration, with the green tape or bilayer running parallel or anti-parallel to the downward force of gravity exerted directly on the Earth's surface. For example, a vertical configuration could result in the green tape or bilayer running up and down in a direction perpendicular (at 90°; i.e., perpendicular) to the floor on which the process is occurring. Additionally, there may be angles between the various ovens, causing the green tape to bend out of a straight line as it is processed. The figures herein are presented as exemplary, non-limiting embodiments of the present disclosure. Other configurations and orientations of ovens and sintering lines are contemplated as encompassed by the present disclosure. In some configurations, the green tape runs parallel to gravity. For example, the green tape may hang like a curtain weighted by gravity. In some configurations, the tape runs perpendicular to gravity; for example, the green tape may run in a direction parallel to the floor.

[0018]

[0037] As used herein, a green film progressing through a processing device may be described by an x-dimension, a y-dimension, and a z-dimension. The x- and y-directions of the green film represent the length and width of the green film, while the z-direction represents the thickness of the green film. As the green film progresses through the processing device, i.e., in the machine direction (MD), the film is described as progressing in the x-dimension, or web dimension. The cross-web dimension (i.e., cross direction (CD)) represents the y-dimension, which is in the same plane as the web. The z-dimension is perpendicular to the web and represents the thickness of the web.

[0019]

[0038] Described herein are equipment and processes useful for achieving high quality ceramic electrolyte membranes with high throughput. Described herein is a high-throughput continuous sintering process for thin film ceramics, including but not limited to lithium aluminum titanium phosphate (LATP), lithium-filled garnet oxides (e.g., Li7La3Zr2O 12 and Li7La3Zr2O 12Examples of suitable ceramic materials include Al2O3 (also known as LLZO), lithium lanthanum titanate, and lithium aluminum germanium phosphate (LAGP). The process includes a sintering step in certain embodiments, in which the sintered film (i.e., the green film or green body on a bilayer undergoing processing to become a sintered film or sintered bilayer) does not come into contact with any surfaces during sintering. In some embodiments, when a bilayer is used, the metal layer may come into contact with the surfaces of the processing equipment during its passage through one or more furnaces, but the green body does not come into contact with any surfaces. By sintering without contact with other surfaces during sintering, the sintered ceramic films prepared by this process unexpectedly have advantageous properties, such as low flatness. For lithium-filled garnets, the processing equipment unexpectedly has advantageous properties that allow for the retention of the lithium stoichiometry in a given LLZO formula, as well as an advantageous LLZO microstructure (e.g., high compactness, small grain size, and combinations thereof). In some embodiments, the lack of contact with other surfaces results in the prepared material being free of surface scratches. In some embodiments, the lack of surface contact of the green body allows the bilayers prepared herein to be free of surface scratches on the ceramic side of the bilayer. In some embodiments, the lack of surface contact allows the material to be prepared without issues such as adhesion to the substrate. Additionally, such sintered LLZO is prepared using a novel, high-speed sintering process that is faster per unit volume of product than other LLZO sintered film manufacturing processes.

[0020]

[0039] Presented herein is a process for sequential processing of the bilayer, including step 1) binder burnout (BBO) at room temperature to moderately elevated temperatures to remove organic materials from the bilayer, and step 2) sintering at very high temperatures to convert the ceramic powder into a dense solid.

[0021]

[0040] During both stages, and during the subsequent cooling to room temperature, the temperature profile and gas environment must be controlled, and the web of bi-ply tape must be handled to ensure that the final product is flat and free of defects. The specific requirements for achieving this quality are described later in this document.

[0022]

[0041] In some processes herein, both processing steps (BBO and sintering) are performed in a single tool, while in other embodiments, separate tools are used for each step, i.e., one tool for BBO and one tool for sintering.

[0023] B. Definition

[0042] As used herein, the term "about," when used to modify a number, such as about 15% w / w, refers to a number within a range that is approximately the modified number, including the modified number and, optionally, ±10% of that number. For example, about 15% w / w includes 15% w / w as well as 13.5%, 14%, 14.5%, 15.5%, 16%, or 16.5% w / w. For example, "about 75°C" includes 75°C as well as 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, or 83°C.

[0024]

[0043] As used herein, "selected from the group consisting of" refers to a single member from the group, two or more members from the group, or a combination of members from the group. A member selected from the group consisting of A, B, and C includes, for example, A alone, B alone, or C alone, as well as A and B, A and C, B and C, and A, B, and C.

[0025]

[0044] As used herein, a "roller" refers to a rotating cylinder or other shape on which something is moved or which is used to transport, move, press, shape, spread, or flatten something. A roller does not necessarily have to be a mathematically perfect cylinder. A roller can be any shape over which or around which a tape or film could be rolled; or a shape around which a tape or film could be wound. In some embodiments, a roller has an outer diameter of 6 cm or greater. In some embodiments, a roller has a winding tension of 20 g / cm or greater. A roller can have a convex or concave profile. A roller has a single axis of rotational symmetry.

[0026]

[0045] As used herein, a "bilayer" includes a ceramic layer deposited on a metal layer. The ceramic layer can be a green body or a sintered body. In some embodiments, the green body is continuous, while in other embodiments, the green body is deposited in a patch coating manner. After sintering, the bilayer may have a ceramic layer thickness of 10-50 μm, and the metal layer thickness is 2-20 μm thick. The bilayer may have a ceramic layer thickness of 20-30 μm, and the metal layer thickness is 3-10 μm thick.

[0027]

[0046] A green bilayer, prior to binder burnout and sintering, unless otherwise specified, includes a thin metal foil with a thicker layer of green ceramic material deposited thereon. The green ceramic layer consists of ceramic powder particles embedded in an organic matrix. The green bilayer, as used herein, includes a green body layer and a metal layer.

[0028]

[0047] The sintered bilayer is a green bilayer that has been processed in the processing equipment described herein, where the sintered bilayer is comprised of a sintered body and a metal layer.

[0029]

[0048] As used herein, the phrase "green film" or "green tape" refers to a green tape or film including lithium-filled garnet, a precursor to lithium-filled garnet, or a combination thereof, and at least one of a binder, a plasticizer, carbon, a dispersant, a solvent, or a combination thereof. As used herein, "green film tape" refers to a roll, continuous layer, or cut portion of a cast tape of green film, whether dry or not. Green body is used synonymously with green film or green tape. Green tape can also include a patch of green body deposited on a metal layer (i.e., a patch coating of a metal layer).

[0030]

[0049] As used herein, a "green body" is a material deposited from a slurry, comprising a ceramic or ceramic precursor and at least one member selected from a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof. A green body is considered green before it is heated to either remove organic materials such as a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof; or to sinter the ceramic component of the green body, or both. Green bodies are made by depositing a slurry onto a substrate and, optionally, drying the deposited slurry.

[0031]

[0050] As used herein, "front roller" refers to the roller located at the beginning of the processing equipment that unwinds or unrolls the green film, green film, or green bilayer.

[0032]

[0051] As used herein, "end roller" refers to a roller located at the end of a processing device that winds up or rolls the sintered film, bilayer, or debindered film or bilayer.

[0033]

[0052] As used herein, "sinter receiver" refers to any mechanism, including, but not limited to, end rollers or machines that cut and stack sintered films. As used herein, an oven or furnace is a partially or fully enclosed compartment in which material can be heated to temperatures above room temperature. For example, an oven can be heated up to 1,200°C. Binder burnout ovens are typically heated to less than 750°C. Bisque ovens are typically heated to 600-900°C. Sintering ovens are typically heated to 900-1,450°C. In some embodiments, at least one oven is enclosed in an atmospheric enclosure. In other embodiments, the processing equipment is enclosed in an atmospheric enclosure. The terms oven and furnace are used interchangeably herein.

[0034]

[0053] As used herein, "atmosphere control" refers to a system that controls the moisture content, oxygen content, gas flow rate, gas temperature, one or more gas contents, one or more gas concentrations, total pressure, vacuum level, and combinations thereof within an enclosed or confined space. Atmosphere control can be dynamic, in the sense that the system responds to sensed conditions to modify the atmosphere to more closely adhere to specific, predetermined conditions. In this example, atmosphere refers to the gaseous environment in direct contact with the green tape being heated, calcined, sintered, or cooled; or the gaseous environment in direct contact with the sintered tape being heated, sintered, annealed, or cooled. In some embodiments described herein, atmosphere control includes controlling the flow rate of an inlet gas containing any of oxygen, argon, nitrogen, helium, and / or hydrogen. In some embodiments described herein, atmosphere control includes controlling the amount of water, oxygen, and lithium present in a gaseous state and in direct contact with the green tape being heated, calcined, sintered, or cooled; or the sintered tape being heated, sintered, annealed, or cooled. Atmosphere control can use various gas curtains, gas densities, gas flow rates, gas flow directions, or gas pulses at, around, and near the oven, furnace, and any inlets or outlets and any openings through which material, such as green tape or sintered products, may pass when entering or exiting the oven or furnace. Atmosphere control can refer to a system in which nitrogen gas, argon gas, forming gas, dry air, or humidified air is used in an enclosed or confined space. Atmosphere control can refer to a system in which a partial vacuum can be applied, such as when the pressure is less than atmospheric.

[0035]

[0054] As used herein, a "gas curtain" refers to the gas flow rate at a particular entry or exit point of the oven (e.g., the green tape inlet and the sintered film outlet) where the gas flow rate is determined. For example, the gas flow rate can be 1 to 50 liters / minute at standard temperature and pressure. For example, the gas flow rate can be greater than 50 liters / minute at standard temperature and pressure. The gas curtain can be configured to achieve a specific number of gas changes within the chamber per unit time, e.g., one change per minute for the volume of the chamber. For example, for a chamber with an internal volume that holds 30 liters of gas, the gas curtain can be configured to flow 30 liters / minute at STP to achieve one change per minute. The gas curtain can have a pressure sensor at the outlet. The gas curtain flows across the entry or exit point of the oven to control the gas flow within the oven. The gas curtain can help maintain a constant atmosphere within the oven by partially or completely preventing gas from entering or exiting the oven.

[0036]

[0055] As used herein, the phrase "dry air" refers to air with a reduced moisture content. Dry air may be supplied to a clean room. Dry air is characterized as having a dew point of less than -20°C, less than -30°C, less than -40°C, less than -50°C, less than -60°C, or less than -70°C.

[0037]

[0056] As used herein, the phrase "solid separator" refers to a substantially electronically insulating Li + Refers to ionically conductive materials (e.g., lithium ion conductivity is at least 10 times that of electronic conductivity). 3 times, often 10 6 The electrolyte acts as a physical barrier or spacer between the positive and negative electrodes of an electrochemical cell.

[0038]

[0057] As used herein, the phrase "annealing" refers to heating a material in a controlled atmosphere, such as dry air, nitrogen, or argon, to, for example, 100°C to 1400°C, or to, for example, 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, 1350°C, or 1450°C. For some exemplary annealing methods, see U.S. Pat. No. 9,966,630 B2, which is incorporated herein by reference in its entirety for all purposes.

[0039]

[0058] As used herein, "area-specific resistance" (ASR) is measured by electrochemical cycling using an Arbin, Maccor, or Biologic instrument unless otherwise specified. ASR is calculated by measuring the voltage drop, ΔV, after 30 to 180 seconds in response to a current interrupt measurement, where ASR = ΔV / J, where J is A / cm 2 is the unit current density).

[0040]

[0059] As used herein, ionic conductivity is measured by electrical impedance spectroscopy methods known in the art.

[0041]

[0060] As used herein, the phrase "ambient conditions" refers to room temperature and a natural atmosphere, such as Earth's atmosphere, which contains approximately 78% N2 and 21% O2; and / or moisture is also present. Ambient conditions include standard temperature and pressure with a relative humidity of at least 1%.

[0042]

[0061] As used herein, the term "electrolyte" refers to an ionically conductive and electrically insulating material. An electrolyte is a material that allows the transfer of ions, such as Li, through the electrolyte. + They are useful for electrically insulating the positive and negative electrodes of a rechargeable battery while allowing conduction of current.

[0043]

[0062] As used herein, the phrase "film" or "thin film" refers to a thin membrane less than 0.5 mm thick and greater than 10 nm thick. A thin film also has a lateral dimension greater than 5 mm. A "film" or "thin film" may be fabricated by a continuous process such as tape casting, spray coating, or slip casting. In some embodiments, fabrication may include a batch process. In some embodiments, fabrication may include a screen printing process.

[0044]

[0063] As used herein, the phrase "thickness" refers to the distance between the top and bottom surfaces of a film, layer, or bilayer, or the median of the measured distance. As used herein, the top and bottom surfaces of a bilayer refer to the sides of the bilayer with the largest surface area. As used herein, thickness is measured by cross-sectional scanning electron microscopy unless otherwise specified. Cross-sectional SEM can also be used to determine the thickness of the metal layer of a bilayer and the thickness of the sintered oxide layer of a bilayer. The thickness of the sintered oxide layer is the distance from the side of the sintered oxide layer with the largest surface area to the interface between the metal layer and the sintered oxide layer. The thickness of the metal layer is the distance from the side of the metal layer with the largest surface area to the interface between the metal layer and the sintered oxide layer.

[0045]

[0064] As used herein, "binder" refers to a polymer capable of increasing the adhesiveness and / or cohesion of a material, such as the solids content in a green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene-alpha-olefin copolymers. "Binder" refers to a material that aids in the adhesion of another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders can include polycarbonates. Other binders can include polyacrylates and polymethacrylates. These embodiments of binders are not intended to be limiting with respect to the overall scope of binders contemplated herein, but merely constitute embodiments. Binders useful in the present disclosure include, but are not limited to, polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene-pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-l-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylics, polyvinylacetacetal resin, ethyl methacrylate, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylenes, polypropylene-polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, silicones, and the like.In some embodiments, including any of the foregoing, the binder is selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), poly(butyl methacrylate), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE- The polymer is selected from the group consisting of AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene polymer (EPR), nitrile rubber (NPR), styrene-butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, α-polyolefin, ethylene α-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA).

[0046]

[0065] The solvent used herein can be selected from alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, and other classes of organic solvents such as ethers and aromatic solvents, including, but not limited to, dibutyl ether, diethyl ether, diisopropyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, toluene, xylene, toluene:ethanol, acetone, N-methyl-2-pyrrolidone (NMP) diacetone alcohol, ethyl acetate, acetonitrile, hexane, nonane, dodecane, and methyl ethyl ketone (MEK).

[0047]

[0066] In certain embodiments, the dispersant used is selected from fish oil, Mehaden Blown Fish Oil, mineral oil, phosphate esters, Rhodoline™, Rhodoline 4160, phospholan-131™, BYK™ 22124, BYK-22146™, Hypermer KD1™, Hypermer KD6™, and Hypermer KD7™.

[0048]

[0067] As used herein, the phrase "casting a film" refers to the process by which a liquid or slurry forms or is made into the shape of a film by pouring or transferring the liquid or slurry into a mold or onto a substrate. Casting may be performed by doctor blade methods, Mayer rod methods, comma coater methods, gravure coater methods, microgravure methods, reverse comma coater methods, slot die methods, slip and / or tape casting methods, and other methods.

[0049]

[0068] As used herein, the phrase "lithium-filled garnet" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Examples of lithium-filled garnets include the formula Li A La B Zr C O F 、Li A La B M’ C M” D Ta E O F 、or Li A La B M’ C M” D Nb 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, and M’ and M” are each, independently for each example, selected from Al, Mo, W, Nb, Ga, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta); or Li a La b Zr c Ald 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 a metal selected from Nb, V, W, Mo, Ta, Ga, and Sb) include compounds having the same. Garnets also include, as used herein, garnets as described above doped with Al or Al2O3. Also, garnets include, as used herein, but are not limited to, Li A La B Zr C O F +yAl2O3 (where x may be 5.8 - 7.0 and y may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0; and where 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2; 10 < F < 13) are also included. Also, garnets include, as used herein, but are not limited to, Li x La3Zr2O 12 +yAl2O3 (where x may be 5.8 - 7.0 and y may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0) are also included. As used herein, garnets do not include YAG - garnet (i.e., yttrium aluminum garnet, or, for example, Y3Al5O 12 ) is not included. As used herein, garnets do not include pyrope, almandine, spessartine, grossular, hessonite, or cinnamon stone, zavoite, uvarovite and andradite such as silicate - based garnets and solid - solution pyrope - almandine - spessarite and uvarovite - grossular - andradite. In this specification, garnets do 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). Lithium - filled garnets include, but are not limited to, the formula Li7La3Zr2O 12 Al2O3; Li6-7 La3Zr2O 12-13 Al2O3; Li7La3Zr2O 12 (0.1 - 1)Al2O3; Li 6-7 La3Zr2O 12-13 (0.1 - 1)Al2O3; Li7La3Zr2O 12 (0.1)Al2O3; Li7La3Zr2O 12 (0.2)Al2O3; Li7La3Zr2O 12 (0.3)Al2O3; Li7La3Zr2O 12 (0.4)Al2O3; Li7La3Zr2O 12 (0.5)Al2O3; Li7La3Zr2O 12 (0.6)Al2O3; Li7La3Zr2O 12 (0.7)Al2O3; Li7La3Zr2O 12 (0.8)Al2O3; Li7La3Zr2O 12 (0.9)Al2O3; Li7La3Zr2O 12 (1.0)Al2O3; Li 6-7 La3Zr2O 12-13 (0.1)Al2O3; Li 6-7 La3Zr2O 12-13 (0.2)Al2O3; Li 6-7 La3Zr2O 12-13 (0.3)Al2O3; Li 6-7 La3Zr2O 12-13 (0.4)Al2O3; Li 6-7 La3Zr2O 12-13 (0.5)Al2O3; Li 6-7 La3Zr2O 12-13 (0.6)Al2O3; Li 6-7 La3Zr2O 12-13 (0.7)Al2O3; Li 6-7 La3Zr2O 12-13 (0.8)Al2O3; Li 6-7 La3Zr2O 12-13 (0.9)Al2O3; Li 6-7 La3Zr2O 12-13 (1.0)Al2O3; or Li 7-3x La3Zr2O 12 Al x(wherein x is 0 to 2). In some examples, lithium-filled garnets include compounds having the formula Li 7-3x La3Zr2O 12 Al x where x is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, or 2.0. In particular examples, lithium-filled garnets include Li 7-3x La3Zr2O 12 Al x (wherein x is 0.25, 0.5, or 0.75).

[0050]

[0069] As used herein, the phrases "garnet precursor chemical" or "chemical precursor of a garnet-type electrolyte" refer to chemicals that react to form the lithium-filled garnet materials described herein. Such chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., LiO), lithium carbonate (e.g., LiCO), zirconium oxide (e.g., ZrO), lanthanum oxide (e.g., LaO), aluminum oxide (e.g., AlO), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO), aluminum nitrate nonahydrate, niobium oxide (e.g., NbO), and tantalum oxide (e.g., TaO).

[0051]

[0070] As used herein, the phrase "d 50 "Diameter" refers to the median diameter of a particle size distribution as measured by microscopy or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 50 "Number D 50 " or "Volume D 50 ", where "number D 50" is the diameter at which 50% of the particles have a smaller diameter, and "volume D 50 " is the diameter at which 50% of the volume of the smallest particle has a smaller diameter. Unless otherwise specified, D 50 is the volume D 50 That is, D 50 includes the characteristic dimension where 50% of the volume of the particle is smaller than the stated size.

[0052]

[0071] As used herein, the phrase "d 90 "Diameter" refers to the particle size on a particle size distribution as measured by microscopy or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 90 includes the characteristic dimension where 90% of the particle volume is smaller than the stated size.

[0053]

[0072] As used herein, the "flatness" of a surface refers to the largest normal distance between the lowest point on the surface and the plane containing the three highest points on the surface, or alternatively, the largest normal distance between the highest point on the surface and the plane containing the three lowest points on the surface. This can be measured using an atomic force microscope (AFM), a high-precision optical microscope, a 3D vision system, or surface height mapping by laser interferometry. The Keyence VR-3000 is an example of an optical microscope capable of measuring flatness using structured light. Unless otherwise specified, the Keyence VR-3000 is used for flatness measurements in this specification.

[0054]

[0073] As used herein, the phrase "speed bump" refers to a surface protuberance on a runway or on a surface of process equipment that the bilayer travels over as it moves through the process equipment. The speed bump aids in applying a normal force to the bilayer by applying a speed bump to the bilayer, where the speed bump contacts a metal layer of a bilayer disclosed herein. Unless otherwise specified, the metal layer of the bilayer is the layer that may contact the speed bump as the bilayer travels over it.

[0055]

[0074] As used herein, the phrase "heating zone" refers to a volume heated by one or more heating elements, which is measured by one or more temperature sensors, with feedback control between the sensors and a set point. In some embodiments, the first heating zone and the second heating zone are both contained within a single furnace or oven. In some other embodiments, the first heating zone and the second heating zone are each individually located within a furnace or oven that is different from the furnace or oven used for the other heating zone.

[0056]

[0075] As used herein, the term "runway" refers to a material that is at least 10 cm long, at least as wide as the tape being treated, and at least 100 μm thick that can make point or line contact with the tape being treated in the heated zone.

[0057]

[0076] As used herein, the term "biscuit bilayer" refers to a bilayer herein in which the ceramic layer has a porosity of at least 10 vol% with an organic content of less than 1 wt%. As used herein, the organic content includes compounds containing carbon.

[0058]

[0077] As used herein, the term "debindered film" refers to a green body having a binder content of less than 1% by weight.

[0059]

[0078] As used herein, the term "web width" refers to the width of the metal layer of the bilayer.

[0060]

[0079] As used herein, the term "green bilayer" refers to a green film or green body, as defined above, having a metal substrate layer attached or adhered to the underlayer of the green film or green body.

[0061]

[0080] As used herein, the term "Invar" is a Ni / Fe material.

[0062]

[0081] As used herein, the phrase "vertical handling" means that the bilayer is oriented in a vertical handling direction as it travels through the CML. Vertical handling means that the bilayer travels parallel or anti-parallel to the Earth's gravity.

[0063]

[0082] As used herein, the phrase "curtaining" means that the bilayer is positioned in a curtaining orientation as it travels through the CML. Curtaining means that the bilayer is folded so that both the metal and green body layers travel parallel to the ground, but the metal layer is not below the green body layer; rather, the metal and green body layers are side-by-side. Curtaining can be useful to prevent debris from falling onto the upper surface of the green body. Curtaining can be useful to prevent sagging of the bilayer.

[0064]

[0083] As used herein, "under tension" means that tension is applied to the bilayer using a physical mechanism, such as, but not limited to, at least one roller, at least one weight, at least one load cell, at least one motor, at least one tension control mechanism, a series of mechanisms, or a combination thereof. In some embodiments, under tension includes the use of a load cell in a feedback loop in conjunction with at least one roller, at least one weight, at least one motor, at least one tension control mechanism, a series of mechanisms, or a combination thereof. A bilayer resting on a flat surface has a natural internal tension that holds the structure of the bilayer together, even when not attached to anything other than the bilayer itself. As used herein, "under tension" means that there is some amount of tension in addition to the natural tension of the material. The tension may be applied externally to the bilayer, for example, to stretch, expand, flatten, or conform to a shape.

[0065]

[0084] As used herein, "a tolerance of 10% or less," when used in connection with a tension controller, means that the tension controller can maintain a tension on the bilayer with a tolerance of 10 percent. For example, if the tension on the bilayer is set to 150 N per meter of web width, a tolerance of 10% or less can mean that the tension controller can maintain a tension on the bilayer between 135 N per meter of web width and 165 N per meter of web width. "Or less" means that the tension controller has an even tighter tolerance range. For example, for a tension controller set to 150 N per meter of web width, a tolerance of 5% or less can mean that the tension controller can maintain a tension on the bilayer between 142.5 N per meter of web width and 157.5 N per meter of web width.

[0066]

[0085] As used herein, "arched shape characterized by a radius of curvature" means that the bilayer bends in a curved manner because the bilayer is held under tension against a runway, at least one speed bump, or at least one roller. The curvature of the bilayer can be mathematically approximated using a radius of curvature for the bend of the bilayer. The radius of curvature includes the radius of a circular arc that best approximates the curvature at that point. For surfaces, the radius of curvature is the radius of a circle that best fits a normal cross section of the contact surface of the bilayer. Unless otherwise specified, the contact surface is the metal layer of the bilayer.

[0067] C. Processing equipment

[0086] FIG. 1 illustrates an embodiment of a process apparatus disclosed herein. The process apparatus 100 includes a front roller 101 around which the green bilayer is wrapped. The process apparatus 100 includes end rollers 102 around which the bisque or sintered bilayer is wrapped. The process apparatus 100 includes multiple zones 103 for heating, cooling, temperature maintenance, or a combination thereof. Five zones 103 are illustrated in FIG. 1 . However, more or fewer zones 103 are contemplated herein. For example, the process apparatus 100 may include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 12 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 11 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 10 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 9 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 8 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 7 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process equipment 100 may include 1 to 6 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process tool 100 may include 1 to 5 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process tool 100 may include 1 to 4 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process tool 100 may include 1 to 3 zones 103 for heating, cooling, temperature maintenance, or a combination thereof.For example, the process tool 100 may include one or two zones 103 for heating, cooling, temperature maintenance, or a combination thereof. In some embodiments, including any of the above, one zone 103 is larger than another zone 103. In certain embodiments, the bilayer advances through the process tool at a constant velocity. In these embodiments, the residence time within a zone 103 will depend on the velocity at which the bilayer advances and the length of the zone 103.

[0068]

[0087] Within zone 103 are rollers 102. The rollers 102 are arranged in a ramp shape. The ramp may have a parabolic shape. The ramp may have an elliptical shape. The ramp may have a circular shape. The ramp may have a catenary shape. In certain examples, the ramp may be symmetrical. In other examples, the ramp may not be symmetrical. The angle that the tape makes as it passes over each roller ranges from 0 to 40 degrees. The height difference between the highest and lowest rollers may range from 0 to 10 meters.

[0069]

[0088] In certain embodiments, the width of the ramp is 120 mm to 800 mm. In certain embodiments including any of the above, the length of each zone is 100 to 1000 mm. In certain embodiments including any of the above, the height of each zone is 10 mm to 1000 mm.

[0070]

[0089] FIG. 2 shows a portion of a process apparatus 200. Heating zone 201 is a furnace or oven capable of burning, vaporizing, or a combination of these, the binder in the green bilayer. In some embodiments, zone 201 is a binder burnout zone. On one side of zone 201 is a curved runway. The curved runway includes a susceptor 204. The curved runway includes a heating element 203. The heating element 203 may be a heat lamp, a heating coil, an induction heater, or any heat source. The curved runway includes rollers 202 spaced apart throughout the curved runway. The rollers 202 may be fixed (stationary), overdriven (the roller edge at the contact point rotates faster than the web speed), underdriven (the roller edge at the contact point rotates slower than the web speed), or driven at the same speed as the web. The rollers 202 may have a cylindrical, convex, or concave profile. The roller surface may comprise metals (including iron, nickel, molybdenum, tungsten, stainless steel) or ceramics (including silicon carbide, alumina, zirconia, spinel, tungsten carbide, magnesium oxide, boron nitride, and similar high temperature ceramics).

[0071]

[0090] As used herein, a susceptor is used to absorb energy, such as heat from a heater, and re-radiate that heat to the film.

[0072]

[0091] FIG. 3 illustrates process apparatus 300. Process apparatus 300 includes at least one tube furnace 305 and at least one tube furnace 306. Additional tube furnaces may be present. In some embodiments, the tube furnaces are heating zones, such as zone 103 in FIG. 1. Process apparatus 300 includes exhaust ports 301, which are located at the entry and exit points of each of tube furnaces 305 and 306. Process apparatus 300 includes rollers 302, which are located before and after tube furnaces 305 and 306. In some embodiments, including any of the above, tension control mechanisms may be used in place of rollers 302. FIG. 3 illustrates tube furnace entry point 303. FIG. 3 also illustrates controller 304, which may be used to control the temperature or atmosphere of the tube furnaces, or a combination thereof. The distance between tube furnaces 305 and 306 may be adjusted by moving the furnaces relative to each other.

[0073]

[0092] FIG. 4 illustrates process apparatus 400. Process apparatus 400 includes at least one tube furnace 405 and at least one tube furnace 406. Additional tube furnaces may be present. In some embodiments, the tube furnaces are heating zones, such as zone 103 in FIG. 1. Process apparatus 400 includes exhaust ports 401, which are located at the entry and exit points of each of tube furnaces 405 and 406. Process apparatus 400 includes rollers 402, which are located before and after tube furnaces 405 and 406. In some embodiments, including any of the above, tension control mechanisms may be used in place of rollers 402. FIG. 4 illustrates tube furnace entry point 403. FIG. 4 also illustrates controller 404, which may be used to control the temperature or atmosphere of the tube furnaces, or a combination thereof. The distance between tube furnaces 405 and 406 may be adjusted by moving the furnaces relative to each other.

[0074]

[0093] In some embodiments, the present specification describes a continuous production line such as that described in International Patent Application No. PCT / US2022 / 019641, filed March 9, 2022, entitled "RAPID CERAMIC PROCESSING TECHNIQUES AND EQUIPMENT," the entire contents of each of which are incorporated herein by reference in their entirety for all purposes.

[0075]

[0094] In some embodiments, described herein is a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; and a runway having a surface comprising a material selected from nickel (Ni), iron (Fe), anodized aluminum, a Ni alloy, an Fe alloy, a Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite; alumina (Al2O3), zirconia (ZrO2), silicon carbide, magnesium oxide, molybdenum, a molybdenum alloy such as titanium-zirconium-molybdenum (TZM) or molybdenum-lanthanum (MoLa), tungsten, a tungsten alloy, or a combination thereof.

[0076]

[0095] In some instances, the runway has a surface comprising aluminum oxide. In particular instances, the runway comprising aluminum oxide contacts the back (metal side) of the bilayer.

[0077]

[0096] In some instances, the runway has a surface comprising magnesium oxide. In particular instances, the magnesium oxide-containing runway contacts the back (metal side) of the bilayer.

[0078]

[0097] In some instances, the runway has a surface comprising boron nitride. In certain instances, a runway comprising magnesium oxide contacts the back (metal side) of the bilayer.

[0079]

[0098] In some examples, the runway has a surface comprising boron nitride. In particular examples, the runway comprising boron nitride contacts the backside (metal side) of the bilayer.

[0080]

[0099] In some instances, the runway has a surface comprising silicon carbide. In particular instances, the silicon carbide-comprising runway does not contact the bilayer, but is located within 0.5 cm to 5 cm of the bilayer.

[0081]

[0100] In some instances, the runway has a surface that includes graphite. In particular instances, the runway that includes graphite does not contact the bilayer, but is located within 0.5 cm to 5 cm of the bilayer.

[0082]

[0101] In some examples, the runway has a surface comprising a carbon fiber composite. In particular examples, the runway comprising the carbon fiber composite does not contact the bilayer but is located within 0.5 cm to 5 cm of the bilayer. In particular examples, the carbon fiber composite is coated with boron nitride.

[0083]

[0102] In some instances, the runway has a surface comprising molybdenum (Mo). In some instances, the runway has a surface comprising tungsten (W). In particular instances, the Mo or W-containing runway does not contact the bilayer, but is located within 0.5 cm to 5 cm of the bilayer.

[0084]

[0103] In some embodiments, there is a runway in the binder burnout zone.

[0085]

[0104] In some embodiments, there is a runway in the bisque zone.

[0086]

[0105] In some embodiments, the sintering zone has a runway. In some of these embodiments, the runway has an alumina-containing surface. In some of these embodiments, the runway has a refractory material-containing surface.

[0087]

[0106] In some embodiments, there are runways in the bisque zone and the sinter zone.

[0088]

[0107] In some embodiments, there are runways in the binder burnout zone and the bisque zone.

[0089]

[0108] In some embodiments, there are runways in the binder burnout zone and the sintering zone.

[0090]

[0109] In some embodiments, there are runways in the binder burnout zone, the bisque zone, and the sintering zone.

[0091]

[0110] In some embodiments, the cooling zone includes a runway. In some of these embodiments, the runway has a carbon-containing surface.

[0092]

[0111] In some embodiments, including any of the above, the runway comprises rollers.

[0093]

[0112] In certain embodiments, the roller is configured to contact only the metal layer of the bilayer disclosed herein.

[0094]

[0113] In certain embodiments, the roller is configured to contact only the metal layer of the bilayer disclosed herein. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 30°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 60°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 90°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 150°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 200°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer has a temperature greater than 250°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 300°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 400°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 500°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 600°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 700°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 800°C. In some embodiments, the roller does not contact the ceramic layer of a bilayer disclosed herein while the bilayer has a temperature greater than 900°C. In some embodiments, the rollers do not contact the ceramic layer of the bilayer disclosed herein until after the sintering zone of the processing equipment.

[0095]

[0114] In some embodiments, the present specification provides a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; and at least one of the following: a baffle within a heating zone; a baffle between two heating zones; a curtain purge between two heating zones; a means for controlling at least two separate pressure zones within the at least three heating zones; a means for exhausting through the center of at least one furnace; a means for exhausting through the center of a runway; a means for purging gas between two heating zones; a means for isolating gas between two heating zones; a means for mechanically separating two heating zones; or at least one combination thereof.

[0096]

[0115] In some embodiments, including any of the above, the runway includes an exhaust system. In certain examples, the exhaust system is located in the center of the runway. In certain examples, the exhaust system is located at multiple points along the binder burnout path. In certain embodiments, the gas flow is configured to flow in a cross-web direction. In certain embodiments, the exhaust is heated from a furnace to a cold trap.

[0097]

[0116] In some embodiments, the present disclosure describes a processing apparatus comprising a front roller; at least one oven including at least three heating zones; and a bilayer held under tension, where the tension ranges from 0.1 g / cm to 500 g / cm. Figure 10 shows, on the left, a bilayer film made under high tension of 30 to 100 g / cm web width. Figure 10 shows, on the right, a bilayer film made under low tension of 1 to 15 g / cm web width. In some embodiments, the present disclosure describes a processing apparatus comprising a front roller; at least one oven including at least three heating zones; and a bilayer held under tension, where the tension ranges from 1 to 15 g / cm web width. The tension is measured using a load cell herein when the bilayer is unwound from the roll and before heating the bilayer for binder burnout. In some examples, the tension ranges from 1 to 14 g / cm web width. In some cases, the tension is in the range of 1 to 13 g / cm of web width. In some cases, the tension is in the range of 1 to 12 g / cm of web width. In some cases, the tension is in the range of 1 to 11 g / cm of web width. In some cases, the tension is in the range of 1 to 10 g / cm of web width. In some cases, the tension is in the range of 1 to 9 g / cm of web width. In some cases, the tension is in the range of 1 to 8 g / cm of web width. In some cases, the tension is in the range of 1 to 7 g / cm of web width. In some cases, the tension is in the range of 1 to 6 g / cm of web width. In some cases, the tension is in the range of 1 to 5 g / cm of web width. In some cases, the tension is in the range of 1 to 4 g / cm of web width. In some cases, the tension is in the range of 1 to 3 g / cm of web width. In some cases, the tension is in the range of 1 to 2 g / cm of web width. In some cases, the tension is in the range of 1 to 15 g / cm of web width. In some cases, the tension is in the range of 2 to 15 g / cm of web width. In some cases, the tension is in the range of 3 to 15 g / cm of web width. In some cases, the tension is in the range of 4 to 15 g / cm of web width. In some cases, the tension is in the range of 5 to 15 g / cm of web width. In some cases, the tension is in the range of 6 to 15 g / cm of web width. In some cases, the tension is in the range of 7 to 15 g / cm of web width.In some cases, the tension is in the range of 8 to 15 g / cm of web width. In some cases, the tension is in the range of 9 to 15 g / cm of web width. In some cases, the tension is in the range of 10 to 15 g / cm of web width. In some cases, the tension is in the range of 11 to 15 g / cm of web width. In some cases, the tension is in the range of 12 to 15 g / cm of web width. In some cases, the tension is in the range of 13 to 15 g / cm of web width. In some cases, the tension is in the range of 14 to 15 g / cm of web width.

[0098]

[0117] In certain embodiments, the bilayer is held under tension at a tension equivalent to 30 g for a 100 mm wide web containing a 10 μm thick Ni foil layer in the bilayer. 2 In certain embodiments, the bilayer is held under tension in the range of 0.01 g / cm to 10 g / cm of web width.

[0099]

[0118] In certain embodiments, the bilaminate is held under tension in the range of 0.01 g / cm to 100 g / cm for a bisque bilaminate.

[0100]

[0119] In certain embodiments, the bilaminate is held under tension in the range of 0.01 g / cm to 500 g / cm for the green bilaminate.

[0101]

[0120] In some embodiments, the tension in different areas of the processing equipment is not the same. For example, the unwind and unwind areas may have a higher tension than the hot area. In some embodiments, the tension is isolated using nip rollers, vacuum rollers, and / or rollers with wrap angles configured to increase or decrease tension across the rollers. In some embodiments, the tension in the winding and / or unwinding areas is 5 kg / cm of web cross-sectional area. 2 Over 10kg / cm 2 Over 15kg / cm 2 Over 20kg / cm 2 Over 25kg / cm 2In some embodiments, the tension in the winding region is greater than 5 kg / cm 2 Over 10kg / cm 2 Over 15kg / cm 2 Over 20kg / cm 2 Over 25kg / cm 2 In some embodiments, the tension in the unwinding region is greater than 5 kg / cm of cross-sectional area of ​​the web. 2 Over 10kg / cm 2 Over 15kg / cm 2 Over 20kg / cm 2 Over 25kg / cm 2 In some embodiments, in at least one zone where the temperature exceeds 800° C., the tension is 6 kg / cm 2 of cross-sectional area of ​​the web. 2 Less than or 5kg / cm 2 Less than or 4kg / cm 2 Less than or 3kg / cm 2 Less than or 2kg / cm 2 Less than or 1kg / cm 2 Less than or 0.5kg / cm 2 is less than.

[0102]

[0121] In some embodiments, the present specification provides a processing apparatus comprising: a front roller; at least one oven including at least three heating zones; a bilayer; and at least two or more rollers; wherein the bilayer is wrapped around one of the at least two or more rollers at a wrap angle ranging from 0 to 40 degrees.

[0103]

[0122] In some embodiments, including any of the above, the two aligned rollers are parallel to one another. The wrap angle refers to the angle between the incoming and outgoing bilayers relative to the rollers. In some examples, the bilayer is wrapped around one of at least two or more rollers at a wrap angle ranging from 5° to 10°. In some examples, rollers used for web handling are aligned with respect to one another with a maximum deviation of 0.0005 to 0.005 degrees. In some examples, the rollers are rounded to within a tolerance of 0.001 inches, or within a tolerance of 0.002 inches, or within a tolerance of 0.003 inches, or within a tolerance of 0.004 inches, or within a tolerance of 0.005 inches. In some examples, at least one of the rollers has a diameter of at least 7 cm. In some examples, at least one of the rollers has a diameter of at least 8 cm. In some examples, at least one of the rollers has a diameter of at least 9 cm. In some examples, at least one of the rollers has a diameter of at least 10 cm. In some cases, at least one of the rollers has a diameter of at least 15 cm.

[0104]

[0123] In some embodiments, including any of the above, the bilayer is wrapped around one of at least two or more rollers at a wrap angle of 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 22°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39°, or 40°.

[0105]

[0124] In some embodiments, including any of the above, the process device comprises a bilayer.

[0106]

[0125] In some embodiments, including any of the above, the three different heating zones include: (a) a binder burnout section; (b) a bisque section; and (c) a sintering section.

[0107]

[0126] In some embodiments, including any of the above, the process device comprises an end roller.

[0108]

[0127] In some embodiments, including any of the above, the front roller is mechanically coupled to at least one furnace.

[0109]

[0128] In some embodiments, including any of the above, the front roller has a motor that is sealed from the at least one furnace.

[0110]

[0129] In some embodiments, including any of the above, the process equipment comprises a runway comprising a material selected from nickel (Ni), iron (Fe), a Ni alloy, an Fe alloy, a Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber, graphite; alumina (Al2O3), zirconia (ZrO2), or a combination thereof. In some embodiments, including any of the above, the runway may be coated with a material selected from nickel (Ni), iron (Fe), a Ni alloy, an Fe alloy, a Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber, graphite; alumina (Al2O3), zirconia (ZrO2), or a combination thereof. In some embodiments, the runway comprises nickel, carbon, or carbon fiber. In some embodiments, the runway is coated with at least a layer of iron, a Ni-Fe alloy, silicon carbide, or boron nitride.

[0111]

[0130] In some embodiments, including any of the above, the runway is internal to at least one furnace.

[0112]

[0131] In some embodiments, including any of the above, the runway is internal to the sintering section.

[0113]

[0132] In some embodiments, including any of the above, the runway comprises an exhaust vent.

[0114]

[0133] In some embodiments, including any of the above, the runway comprises speed bumps.

[0115]

[0134] In some embodiments, including any of the above, the top runway is centerless.

[0116]

[0135] In some embodiments, including any of the above, the runway comprises holes in its upper surface.

[0117]

[0136] In some embodiments, including any of the above, at least one furnace is sealed.

[0118]

[0137] In some embodiments, including any of the above, the process device includes a cooling section.

[0119]

[0138] In some embodiments, including any of the above, the process apparatus includes at least one atmosphere controller that controls at least one condition within the furnace selected from the group consisting of gas flow rate, flow direction, gas composition, pressure, and combinations thereof.

[0120]

[0139] In some embodiments, including any of the above, the bi-layer is wrapped around a front roller.

[0121]

[0140] In some embodiments, including any of the above, the bilayer includes a metal layer and a green body layer.

[0122]

[0141] In some embodiments, including any of the above, at least one furnace comprises a multi-zone tunnel kiln (MZTK).

[0123]

[0142] In some embodiments, including any of the above, the roller comprises a material selected from silicon carbide, Ni, stainless steel, or combinations thereof.

[0124]

[0143] In some embodiments, including any of the above, the rollers are mechanically alignable to within 0.005 inches. In some embodiments, including any of the above, the rollers are mechanically alignable to within 0.001 inches.

[0125]

[0144] In some embodiments, including any of the above, the rollers are mechanically positionable in three dimensions.

[0126]

[0145] In some embodiments, including any of the above, the process equipment includes nip rollers. As used herein, nip rollers are two rollers that contact the bilayer at the same point, top and bottom. Nip rollers are used to isolate tension zones—the tension can be different on either side of the nip roller.

[0127]

[0146] In some embodiments, including any of the above, the process equipment includes at least two nip rollers. In some examples, one nip roller is located after the unwind section. In some examples, one nip roller is located before the unwind section. In some examples, the nip rollers isolate tensions so that higher tensions (greater than 6 g / cm) can be applied in the unwind and rewind sections, while lower tensions (less than 6 g / cm) can be applied in the hot zone.

[0128]

[0147] In some embodiments, including any of the above, at least one oven comprises a hot roller.

[0129]

[0148] In some embodiments, including any of the above, at least one furnace includes rollers configured to form a ramp.

[0130]

[0149] In some embodiments, including any of the above, the MZTK has rollers configured to form an arch within the MZTK. In some examples, the arch is as shown in FIG. 1.

[0131]

[0150] In some embodiments, including any of the above, the MZTK includes 1 to 20 rollers configured to form a ramp.

[0132]

[0151] In some embodiments, including any of the above, the MZTK is hermetically sealed.

[0133]

[0152] In some embodiments, including any of the above, the MZTK is sealed under vacuum.

[0134]

[0153] In some embodiments, including any of the above, the front roller has a motor that is sealed from the MZTK under vacuum.

[0135]

[0154] In some embodiments, including any of the above, the process equipment includes baffles between each heating zone.

[0136]

[0155] In some embodiments, including any of the above, the wrap angle about the roller ranges from 0° to 40°.

[0137]

[0156] In some embodiments, including any of the above, the wrap angle on the roller ranges from 0° to 40° in the binder burnout section.

[0138]

[0157] In some embodiments, including any of the above, the wrap angle for the rollers ranges from 0° to 40° in the sintering section.

[0139]

[0158] In some embodiments, including any of the above, the process equipment comprises nip rollers, where the upper roller makes contact with each edge of the web for less than 10 cm, or less than 8 cm, or less than 6 cm, or less than 5 cm, or less than 4 cm, or less than 3 cm, or less than 2 cm, or less than 1 cm, of the web. In some embodiments, including any of the above, the process equipment comprises nip rollers, where the upper roller contacts the top of the web. In some embodiments, including any of the above, the process equipment comprises speed bumps, air bearings, or a combination thereof.

[0140]

[0159] In some embodiments, including any of the above, the bilayer is suspended in the MZTK. In some embodiments, including any of the above, the bilayer moves vertically in at least one zone heated to greater than 600°C.

[0141]

[0160] In some embodiments, including any of the above, the at least one furnace comprises: (a) a binder burnout section; (b) a bisque section; and (c) a sintering section.

[0142]

[0161] In some embodiments, including any of the above, at least one furnace is sealed, and at least one atmosphere controller controls gas flow into and out of the at least one furnace. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 100 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 90 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 80 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 70 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 60 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 50 ppm by weight when the furnace is purged with flowing N2. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 40 ppm by weight when the furnace is purged with flowing N2. In some examples, the closed furnace maintains an oxygen partial pressure of less than 30 ppm by weight when the furnace is purged with a flow of N2.

[0143]

[0162] In some embodiments, including any of the above, the process equipment includes a pressurized gas line between the bisque section and the sinter section, which pumps gas into the bisque section and into the sinter section.

[0144]

[0163] In some embodiments, including any of the above, at least one furnace is enclosed within a sealed container.

[0145]

[0164] In some embodiments, including any of the above, the sealed container contains an atmosphere of Ar, N2, H2O, H2, or combinations thereof.

[0146]

[0165] In some embodiments, including any of the above, the atmosphere controller maintains a reducing atmosphere in the sintering section.

[0147]

[0166] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere in the sintering section that includes argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof. In some embodiments, including any of the above, the gas flow is configured to capture moisture in a temperature zone below 800°C. In some embodiments, including any of the above, the gas flow is configured to separate gas from a temperature zone below 800°C from an environment in a temperature zone above 900°C.

[0148]

[0167] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 500 ppm O in the bisque section, the sintering section, or both the bisque and sintering sections.

[0149]

[0168] In some embodiments, including any of the above, H2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0150]

[0169] In some embodiments, including any of the above, the green body layer is a green tape.

[0151]

[0170] In some embodiments, including any of the above, the green body layer is a patch-coated green tape.In some embodiments, including any of the above, the green body layer is a lane-coated green tape.

[0152]

[0171] In some embodiments, including any of the above, the bilayer is oriented for curtain processing as it travels through the process equipment.

[0153]

[0172] In some embodiments, including any of the above, the bilayer is positioned in a vertical processing orientation as it travels through the process equipment.

[0154]

[0173] In some embodiments, including any of the foregoing, the metal layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium, tungsten, molybdenum, alloys thereof, or combinations thereof.

[0155]

[0174] In some embodiments, including any of the above, the metal layer is an alloy of Fe and Ni.

[0156]

[0175] In some embodiments including any of the above, the metal layer is an alloy of Fe and Ni, with the amount of Fe being 1% to 25% (w / w) and the remainder being Ni.In some embodiments including any of the above, the metal layer is a bilayer of Fe and Ni, with the amount of Fe being 1% to 25% (w / w) and the remainder being Ni.

[0157]

[0176] In some embodiments including any of the above, the thickness of the metal layer is 1 μm to 20 μm. In some embodiments including any of the above, the thickness of the metal layer is 4 μm to 10 μm. In some embodiments including any of the above, the thickness of the metal layer is 6 μm to 10 μm. In some embodiments including any of the above, the thickness of the metal layer is 8 μm to 10 μm.

[0158]

[0177] In some embodiments, including any of the foregoing, the bilayer is suspended as it travels through the sintering zone.

[0159]

[0178] In some embodiments, including any of the above, the process equipment includes a sintered bilayer wrapped around at least one end roller.

[0160]

[0179] In some embodiments, including any of the above, the sintered bilayer comprises a sintered lithium-filled garnet.

[0161]

[0180] In some embodiments, including any of the above, the process equipment is configured to advance the bilayer through at least one furnace at a rate of at least 2 inches per minute.

[0162]

[0181] In some embodiments, including any of the above, the process equipment has a production capacity of at least 200,000 sintered bilayers per week. In some embodiments, including any of the above, the process equipment has a production capacity of at least 1,000 m per week. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce sintered bilayers of at least 1 m per hour. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce a sintered bilayer of at least 2 m per hour. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce a sintered bilayer of at least 3 m per hour. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce a sintered bilayer of at least 4 m / hr. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce a sintered bilayer of at least 5 m / hour. 2 In some embodiments, including any of the above, the process equipment has a capacity to produce a sintered bilayer of at least 6 m / hr. 2 It has the capacity to produce sintered bilayer bodies.

[0163]

[0182] In some embodiments, including any of the above, the process equipment produces bilayers cut to dimensions of 73 mm x 90 mm.

[0164]

[0183] In some embodiments, including any of the above, the minimum web speed required for the process equipment to achieve this throughput is 1.0 meters per minute, and this will be the assumed web speed in the following sections.

[0165]

[0184] In some embodiments, including any of the above, the process equipment produces bilayers having lengths of 400 m to 1500 m, corresponding to maximum incoming coil diameters (using 6-inch cores) of 295 mm to 485 mm and maximum coil weights of 50 to 180 kg.

[0166]

[0185] In some embodiments, including any of the above, the process equipment produces bilayers with a maximum exit coil diameter (using a 12-inch core) of 360-450 mm and a maximum coil weight of 40-140 kg.

[0167]

[0186] In some embodiments, including any of the above, the binder burnout zone and the sintering zone are positioned parallel to one another.

[0168]

[0187] In some embodiments, including any of the above, the binder burnout zone is located above the sintering zone.

[0169]

[0188] In some embodiments, including any of the above, the process equipment includes a second binder burnout zone.

[0170]

[0189] In some embodiments, including any of the above, the entire process apparatus is under vacuum.

[0171]

[0190] In some embodiments, including any of the above, at least one furnace comprises a single furnace including a cooling section, a binder burnout section, a bisque section, and a sintering section, followed by another cooling section. In some embodiments, the additional cooling section is between the binder burnout section and the bisque section or between the bisque section and the sintering section.

[0172]

[0191] In some embodiments, including any of the above, the sintering section is not directly exposed to the Earth's atmosphere. This means that the sintering section has the only atmosphere in contact with the portion of the sintering film or bilayer inside the sintering section, and that only atmosphere is not the Earth's atmosphere (e.g., 78% N, 21% O). Instead, in the sintering section, the gas in contact with the sintering film or bilayer is an inert or reducing gas, such as Ar, N, H, or a combination thereof. This can be achieved by sealing (partially or completely sealing) the sintering section in a manner that isolates it from the Earth's atmosphere. This can be achieved by directing gas flow into and out of the sintering section in a manner that isolates it from the Earth's atmosphere. This can be achieved by placing the sintering section in a chamber filled with an inert or reducing gas.

[0173]

[0192] In some embodiments, including any of the above, at least one furnace is not directly exposed to the Earth's atmosphere. This means that the at least one furnace has only one atmosphere in contact with the portion of the sintering film or bilayer inside the at least one furnace, and that only atmosphere is not the Earth's atmosphere (e.g., 78% N, 21% O). Instead, in the at least one furnace, the gas in contact with the sintering film or bilayer is an inert or reducing gas, such as Ar, N, H, or a combination thereof. This may be achieved by sealing the at least one furnace in a manner that isolates it from the Earth's atmosphere. This may be achieved by directing gas flow into and out of the at least one furnace in a manner that isolates it from the Earth's atmosphere. This may be achieved by placing the at least one furnace in a chamber filled with an inert or reducing gas.

[0174]

[0193] In some embodiments, including any of the above, the at least one furnace is sealed and at least one atmosphere controller controls gas flow into and out of the at least one furnace.

[0175]

[0194] In some embodiments, including any of the above, the flow rate in the binder burnout section is higher than the flow rate in the bisque section, higher than the flow rate in the sintering section, or both higher than the flow rate in the bisque section and higher than the flow rate in the sintering section.

[0176]

[0195] In some embodiments, including any of the above, the atmospheric controller maintains consistent atmospheric conditions inside the at least one furnace.

[0177]

[0196] In some embodiments, including any of the above, the atmospheric controller maintains consistent atmospheric conditions within the binder burnout section.

[0178]

[0197] In some embodiments, including any of the above, the atmosphere controller maintains consistent atmospheric conditions within the bisque section.

[0179]

[0198] In some embodiments, including any of the above, the atmosphere controller maintains consistent atmospheric conditions within the sintering section.

[0180]

[0199] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere in the bisque section that includes argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof.

[0181]

[0200] In some embodiments, including any of the above, the atmosphere controller maintains a reducing atmosphere in the sintering section.

[0182]

[0201] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere in the sintering section that includes argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof.

[0183]

[0202] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 500 ppm O in the bisque section, the sintering section, or both the bisque and sintering sections.

[0184]

[0203] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 400 ppm O2 in the bisque section, the sintering section, or both the bisque and sintering sections.

[0185]

[0204] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 300 ppm O2 in the bisque section, the sintering section, or both the bisque and sintering sections.

[0186]

[0205] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 200 ppm O2 in the bisque section, the sintering section, or both the bisque and sintering sections.

[0187]

[0206] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 100 ppm O2 in the bisque section, the sintering section, or both the bisque and sintering sections.

[0188]

[0207] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 10 ppm O in the bisque section, the sintering section, or both the bisque and sintering sections.

[0189]

[0208] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere in the binder burnout section that includes less than 5% v / v HO.

[0190]

[0209] In some embodiments, including any of the above, H2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0191]

[0210] In some embodiments, including any of the above, H2 gas is present at about 2.9% v / v.

[0192]

[0211] In some embodiments, including any of the above, H2 gas is present at about 5% v / v.

[0193]

[0212] In some embodiments, including any of the above, at least one furnace, or a portion thereof, is under vacuum at a pressure less than 1 atmosphere (atm).

[0194]

[0213] In some embodiments, including any of the above, at least one furnace, or a portion thereof, is under vacuum at a pressure of less than 100 Torr.

[0195]

[0214] In some uses herein, at least one furnace is pumped to a rough vacuum to evacuate the air inside the at least one furnace, and then the at least one furnace is refilled with an inert or reducing gas. For example, the at least one furnace may be refilled with N. For example, the at least one furnace may be refilled with Ar / H. For example, the at least one furnace may be refilled with Ar.

[0196]

[0215] In some embodiments, including any of the above, the atmosphere in the binder burnout section is different from the atmosphere in the bisque section.

[0197]

[0216] In some embodiments, including any of the above, the atmosphere in the binder burnout section is different from the atmosphere in the sintering section.

[0198]

[0217] In some embodiments, including any of the foregoing, the atmosphere in the bisque section is different from the atmosphere in the sinter section.

[0199]

[0218] In some embodiments, including any of the above, the amount of O2 in the binder burnout section is less than 0.2% by volume.

[0200]

[0219] In some embodiments, including any of the above, the amount of CO2 in the binder burnout section is less than 0.2% by volume.

[0201]

[0220] In some embodiments, including any of the above, the amount of carbon from CO2 in the sintered section is less than 100 parts per million (ppm).

[0202]

[0221] In some embodiments, including any of the above, the amount of carbon from CO2 in the sintered section is about 50 ppm to 100 ppm.

[0203]

[0222] In some embodiments, including any of the above, the bilayer shrinks primarily in the z-direction as it progresses through the sintering section. As used herein, the z-direction is directly perpendicular to the bilayer surface. As used herein, the x-direction is the direction in which the bilayer progresses through the processing equipment. The y-direction is perpendicular to the x-direction and is in the same plane as the bilayer. The z-direction is perpendicular to both the x- and y-directions.

[0204]

[0223] In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a rate greater than 2.5° C. / min.

[0205]

[0224] In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a rate greater than 5°C / min, 10°C / min, 15°C / min, 20°C / min, 25°C / min, 30°C / min, 35°C / min, 40°C / min, 45°C / min, 50°C / min, 55°C / min, 60°C / min, 65°C / min, 70°C / min, 75°C / min, 80°C / min, 85°C / min, 90°C / min, 100°C / min, 200°C / min, or 300°C / min.

[0206]

[0225] In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a rate of about 5° C. / min to about 50° C. / min.

[0207]

[0226] In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 0.5°C / cm to about 50°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 1°C / cm to about 5°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 0.5°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 1°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 2°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 3°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 4°C / cm. In some embodiments, including any of the above, the processing equipment is configured to heat the bilayer at a space velocity of about 5°C / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 6° C. / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 7° C. / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 8° C. / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 9° C. / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 10° C. / cm. In some embodiments, including any of the above, the processing device is configured to heat the bilayer at a space velocity of about 11° C. / cm.

[0208]

[0227] In some embodiments, including any of the above, the processing device includes an infrared heater, which is used to heat the bilayer.

[0209]

[0228] In some embodiments, including any of the above, the processing equipment includes an induction carbon plate heater. In certain embodiments, the carbon plate does not contact the green body. In certain embodiments, the carbon plate does not contact the bilayer body.

[0210]

[0229] In some embodiments, including any of the above, the processing equipment heats the bilayer using a carbon plate / induction heating.

[0211]

[0230] In some embodiments, including any of the above, the processing apparatus includes heating with an illumination lamp to heat the bilayer. In some embodiments including heating with an illumination lamp, the processing apparatus further includes a susceptor configured to absorb at least 20% of the radiation emitted by the illumination lamp.

[0212]

[0231] In some embodiments, including any of the above, the processing equipment includes heating by an oven.

[0213]

[0232] Depending on the embodiment, the heating element used herein may be a carbon plate or carbon paper. In some embodiments, the carbon plate or carbon paper comprises inductive carbon. Depending on the embodiment, the heating element may be a molybdenum plate or molybdenum paper. In some embodiments, the molybdenum plate or molybdenum paper may comprise inductive molybdenum. By applying an electric current, the inductive carbon plate or inductive carbon paper element may be heated at an appropriate rate to a temperature that facilitates sintering within the temperature ranges described herein.

[0214]

[0233] In some embodiments, the maximum heating temperature may be in the range of 900°C to 2000°C. In some embodiments, the heating temperature may be in the range of 900°C to 1900°C. In some embodiments, the heating temperature may be in the range of 900°C to 1800°C. In some embodiments, the heating temperature may be in the range of 900°C to 1800°C. In some embodiments, the heating temperature may be in the range of 900°C to 1700°C. In some embodiments, the heating temperature may be in the range of 900°C to 1600°C. In some embodiments, the heating temperature may be in the range of 900°C to 1500°C. In some embodiments, the heating temperature may be in the range of 900°C to 1400°C. In some embodiments, the heating temperature may be in the range of 900°C to 1300°C. In some embodiments, the heating temperature may be in the range of 900°C to 1200°C.

[0215]

[0234] In some embodiments, the time in the highest temperature heating zone may range from 5 seconds to 30 minutes. In some embodiments, the heating time may range from 5 seconds to 25 minutes. In some embodiments, the heating time may range from 5 seconds to 20 minutes. In some embodiments, the heating time may range from 5 seconds to 15 minutes. In some embodiments, the heating time may range from 5 seconds to 10 minutes. In some embodiments, the heating time may range from 5 seconds to 5 minutes. In some embodiments, the heating time may range from 5 seconds to 4 minutes. In some embodiments, the heating time may range from 5 seconds to 3 minutes. In some embodiments, the heating time may range from 5 seconds to 4 minutes. In some embodiments, the heating time may range from 5 seconds to 1 minute.

[0216]

[0235] In some embodiments, the heating element may have the same area as the material under heat. In some embodiments, the heating element may be longer than and as wide as the material under heat. In some embodiments, the heating element may be the same length as and wider than the material under heat. In some embodiments, the heating element may be shorter than the material under heat. In embodiments with a single heating element, the heating element may have any of the area relationships just described relative to the material under heat.

[0217]

[0236] In some embodiments, including any of the above, the processing equipment has a cooling zone after the sintering section. For example, a 60-inch furnace may have a 20-inch warming zone before the hot zone, a 20-inch hot zone, and a 20-inch cooling zone after the hot zone.

[0218]

[0237] In some cases, at least one furnace has a 1 mm gap above the green bodies. In some cases, at least one furnace has a 2 mm gap above the green bodies. In some cases, at least one furnace has a 3 mm gap above the green bodies. In some cases, at least one furnace has a 4 mm gap above the green bodies. In some cases, at least one furnace has a 5 mm gap above the green bodies. This gap prevents lithium from leaking out of the green bodies.

[0219]

[0238] In some embodiments, including any of the above, the processing device is configured to apply an appropriate amount of tension to reduce or eliminate cross-web wrinkles. For example, the tension may be kept relatively low to avoid plastic deformation of the metal foil substrate at high temperatures. In a specific example, the tension applied to the metal foil during sintering is between 0.4 N and 4 N.

[0220]

[0239] In some embodiments, including any of the above, when a separate tool is used for binder burnout or when splitting the tension between the sintering section and the binder burnout section, the tension on the metal foil during binder burnout can be 1.2 N to 12 N.

[0221]

[0240] In some embodiments, including any of the above, the processing device is configured to reduce or eliminate cross-web wrinkles by using rollers at the entry or exit point of at least one oven. Slip rollers, drive rollers, bottom drive rollers, top drive rollers, or other rollers may be used.

[0222]

[0241] In some embodiments, including any of the above, the processing equipment is configured to provide a residence time in the sintering section of 2 minutes or less.

[0223]

[0242] In some embodiments, including any of the above, the processing equipment is configured so that the residence time in the sintering section is 1 minute 30 seconds or less.

[0224]

[0243] In some embodiments, including any of the above, the processing equipment is configured to provide a residence time in the sintering section of 1 minute or less.

[0225]

[0244] In some embodiments, including any of the above, the processing equipment is configured so that the residence time in the sintering section is about 30 seconds or less.

[0226]

[0245] In some embodiments, including any of the above, the processing equipment is configured such that the residence time in the sintering section is about 30 seconds.

[0227]

[0246] In some embodiments, including any of the above, the processing equipment is configured such that the residence time in the binder burnout section is about 10 times the residence time in the sintering section.

[0228]

[0247] In some embodiments, including any of the above, the processing device includes at least one tension adjuster.

[0229]

[0248] In some embodiments, including any of the above, the tension in the bi-layer after the front roller is about 270 g.

[0230]

[0249] In some embodiments, including any of the above, the tension in the bilayer before the end rollers is about 500 g.

[0231]

[0250] In some embodiments, including any of the above, the width of the bilayer is 8 cm.

[0232]

[0251] In some embodiments, including any of the above, the tension applied to the bilayer is about 34 g / cm.

[0233]

[0252] In some embodiments, including any of the above, the tension applied to the bilaminate is about 0.1 N per μm of thickness.

[0234]

[0253] In some embodiments, including any of the above, the bilaminate is subjected to a tension of less than 50% of its yield strength.

[0235]

[0254] In some embodiments, including any of the above, the tension applied to the bilayer is less than 50% of the yield strength of the metal layer.

[0236]

[0255] In some embodiments, including any of the above, the tension applied to the bilayer is about 25% to 50% of its yield strength.

[0237]

[0256] In some embodiments, including any of the above, the tensile strength of the bilayer is about 25% to 50% of the yield strength of the metal layer.

[0238]

[0257] In some embodiments, including any of the above, the green body is a green tape.

[0239]

[0258] In some embodiments, including any of the above, the green body is a patch-coated green tape. Patch-coated means that the green body is not continuously deposited on the metal layer. Patch-coated means that the green body is deposited on the metal layer with gaps. The metal layer may be gapped or partially cut between patches. The metal between the patches may be used as tabs for battery cells.

[0240]

[0259] In some embodiments, including any of the above, the binder burnout section is a binder burnout furnace.

[0241]

[0260] In some embodiments, including any of the foregoing, the binder burnout furnace is a furnace heated to a temperature sufficient to volatilize, pyrolyze, combust, or decompose the binder present in the green bodies.

[0242]

[0261] In some embodiments, including any of the above, the temperature of the binder burnout furnace is between 80°C and 500°C.

[0243]

[0262] In some embodiments, including any of the above, the temperature of the binder burnout furnace is between 100°C and 500°C.

[0244]

[0263] In some embodiments, including any of the above, the temperature of the binder burnout furnace is between 80°C and 800°C.

[0245]

[0264] In some embodiments, including any of the above, the binder burnout furnace contains oxygen. In certain of these embodiments, the sintering furnace does not contain oxygen.

[0246]

[0265] In some embodiments, including any of the above, the biscuit section is a biscuit furnace.

[0247]

[0266] In some embodiments, including any of the above, the bisque furnace is a furnace that is heated to a temperature sufficient to bisque-fire the green body after binder removal.

[0248]

[0267] In some embodiments, including any of the above, the temperature of the bisque furnace is between 100°C and 800°C.

[0249]

[0268] In some embodiments, including any of the above, the sintering section is a sintering furnace.

[0250]

[0269] In some embodiments, including any of the foregoing, the sintering furnace is a furnace that is heated to a temperature sufficient to sinter the green body.

[0251]

[0270] In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature sufficient to sinter lithium-filled garnet. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature sufficient to sinter lithium aluminum titanium phosphate. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature sufficient to sinter lithium aluminum germanium phosphate. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature of 800-900°C. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature of 900-1000°C. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature of 1000-1100°C. In some embodiments, including any of the above, the sintering furnace is a furnace heated to a temperature of 1100-1200°C.

[0252]

[0271] In some embodiments, including any of the above, the temperature of the sintering furnace is between 500°C and 1300°C.

[0253]

[0272] In some embodiments, including any of the above, the temperature of the sintering furnace is between 1000°C and 1300°C.

[0254]

[0273] In some embodiments, including any of the above, the temperature of the sintering furnace is between 1100°C and 1300°C.

[0255]

[0274] In some embodiments, including any of the above, the binder burnout furnace is hermetically coupled to the bisque furnace, and the bisque furnace is hermetically sealed to the sintering furnace.

[0256]

[0275] In some embodiments, including any of the above, the at least one oven is a single oven. In some embodiments, including any of the above, at least one end roller has a roller diameter greater than 4 cm. In some embodiments, including any of the above, at least one end roller has a roller diameter greater than 5 cm. In some embodiments, including any of the above, at least one end roller has a roller diameter greater than 6 cm. In some embodiments, including any of the above, at least one end roller has a roller diameter greater than 7 cm. In some embodiments, including any of the above, at least one end roller has a roller diameter greater than 8 cm. In some embodiments, including any of the above, at least one end roller has a winding tension greater than 20 g per linear cm of web width.

[0257]

[0276] In some embodiments, including any of the above, the cavities above and below the bilayer are configured to maintain a lithium-rich atmosphere in contact with the film during sintering.

[0258]

[0277] In some embodiments, including any of the above, the voids above and below the bilayer are configured such that the bilayer contains at least 95% more lithium by weight after processing than before processing in the processing device.

[0259]

[0278] In some embodiments, including any of the above, the processing device includes at least two end rollers.

[0260]

[0279] In some embodiments, including any of the foregoing, the green body comprises an unsintered lithium-filled garnet or a chemical precursor to a lithium-filled garnet.

[0261]

[0280] In some embodiments, including any of the above, the processing apparatus includes a sintered bilayer wrapped around at least one end roller.

[0262]

[0281] In some embodiments, including any of the above, the sintered bi-laminate comprises a lithium-filled garnet body. In some embodiments, including any of the above, the sintered bi-laminate comprises a lithium aluminum germanium phosphate body. In some embodiments, including any of the above, the sintered bi-laminate comprises a lithium aluminum titanium phosphate body.

[0263]

[0282] In some embodiments, including any of the above, the green body includes a binder.

[0264]

[0283] In some embodiments, including any of the above, the green body includes a dispersant.In some embodiments, including any of the above, the green body includes a plasticizer.

[0265]

[0284] In some embodiments, including any of the above, the green body includes a solvent or combination of solvents.

[0266]

[0285] In some embodiments, including any of the above, the processing device is configured to advance the bilayer through at least one furnace at a rate of at least 2 inches per minute.

[0267]

[0286] In some embodiments, including any of the above, the processing equipment is configured to advance the bilayer through the sintering section at a rate of at least 2 inches per minute.

[0268]

[0287] In some embodiments, including any of the above, the processing equipment comprises a curved ramp before at least one furnace. In some embodiments, including any of the above, the processing equipment comprises a curved ramp before the binder burnout section. In some embodiments, including any of the above, the processing equipment comprises a curved ramp before the bisque section. In some embodiments, including any of the above, the processing equipment comprises a curved ramp before the sintering section. In some embodiments, including any of the above, the processing equipment comprises a curved ramp inside at least one furnace. In some embodiments, including any of the above, the processing equipment comprises a curved ramp inside the binder burnout section. In some embodiments, including any of the above, the processing equipment comprises a curved ramp inside the bisque section. In some embodiments, including any of the above, the processing equipment comprises a curved ramp inside the sintering section. In some embodiments, including any of the above, the curved ramp is coated.

[0269]

[0288] In some embodiments, including any of the above, the coating is a lithium aluminate coating. In some embodiments, including any of the above, the coating is an alumina coating. In some embodiments, including any of the above, the coating is a silicon carbide coating.

[0270]

[0289] In some embodiments, including any of the above, the coating is a boron nitride coating.

[0271]

[0290] In some embodiments, including any of the above, the upper surface of the curved ramp is made of ceramic.

[0272]

[0291] In some embodiments, including any of the above, the ceramic is silicon carbide, boron nitride, alumina, zirconia, or lithium aluminate.

[0273]

[0292] In some embodiments, including any of the above, the ramp is made of SS 430, SS 304, Kovar, Invar, Haynes 214, greater than 99.5% (w / w) alumina, carbon composite, boron nitride, or combinations thereof. In some embodiments, speed bumps are placed on the runway. In some embodiments, speed bumps are placed on flat runways. In some embodiments, speed bumps are placed on curved runways. These bumps relieve stress on the metal layer that is in constant contact with the runway. These bumps create "air gaps" as the membrane rides over and passes over the "speed bumps." In some embodiments, there are speed bumps on the runway that are spaced about 1 inch apart from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced about 2 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced about 3 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 4 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 5 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 6 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 7 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 8 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 9 inches from the next speed bump. In some embodiments, there are speed bumps on the runway that are spaced approximately 10 inches from the next speed bump.

[0274]

[0293] By unique atmosphere, in this case, it is meant that the gaseous or steam environment in one furnace is substantially different from the gaseous or steam environment in another furnace. For example, a substantial difference in one oven compared to another oven can include, but is not limited to, a 5% or greater difference in total pressure, a 5% or greater difference in partial pressure, a two-fold difference in the concentration or amount of a given gas (e.g., O, H, N, Ar, Xe, or H0), or a 50% difference in the flow rate of a gas or gases (e.g., a gas mixture) in one oven compared to another oven. For example, one oven may contain sufficient amounts of H0 and / or O2 so that organic materials can burn if heated to their ignition temperature. This may be a condition of a binder burnout section. In such an example, if another oven had a low concentration of O2, combustion may not be sustained even at combustion temperatures, demonstrating a substantial difference in one oven compared to another oven. For example, a sintering oven may have a lower oxygen concentration than a binder burnout oven. In another example, one furnace may contain water vapor at a concentration greater than 1,000 parts per million (ppm); another oven may contain water vapor at a concentration less than 100 ppm. This difference in HO partial pressure may also demonstrate a substantial difference in one oven compared to another. In another example, one oven may be under vacuum while another oven may be at 1 atmosphere, and this difference may be a substantial difference in one oven compared to another. In another example, two ovens may have similar gas mixtures, but one oven may have a total pressure that is 5% or more lower than the other, and this difference may be a substantial difference in one oven compared to another.

[0275]

[0294] In certain embodiments, the binder burnout oven may include an oxidizer mixed into the gas or atmosphere that contacts the green tape. Such oxidizers may include HO, O, or clean, dry air. In certain embodiments, the sintering oven does not include an oxidizer mixed into the gas or atmosphere that contacts the sintering film.

[0276]

[0295] In some embodiments, the pressurized enclosure contains argon (Ar) gas.

[0277]

[0296] In some embodiments, the pressurized enclosure contains nitrogen (N2) gas.

[0278]

[0297] In some embodiments, the pressurized enclosure further comprises hydrogen (H2) gas.

[0279]

[0298] In some embodiments, H2 gas is present at about 5% v / v.

[0280]

[0299] In some embodiments, the pressurized enclosure further comprises aqueous (H2O) gas.

[0281]

[0300] In some embodiments, the pressurized enclosure further comprises an inert gas such as, but not limited to, N2, H2, Ar, and mixtures thereof, e.g., N2 and H2. In some embodiments, the mixture is 2.9% H2 and 97.1% N2. In some embodiments, the mixture is 0% H2 and 100% N2. In some embodiments, the mixture is 1% H2 and 99% N2. In some embodiments, the mixture is 2% H2 and 98% N2. In some embodiments, the mixture is 3% H2 and 97% N2. In some embodiments, the mixture is 4% H2 and 98% N2. In some embodiments, the mixture is 5% H2 and 96% N2. In some embodiments, the mixture is 6% H2 and 94% N2. In some embodiments, the mixture is 7% H2 and 93% N2. In some embodiments, the mixture is 8% H2 and 92% N2. In some embodiments, the mixture is 9% H2 and 91% N2. In some embodiments, the mixture is 10% H2 and 90% N2. In some embodiments, the mixture is 0-10% H2 and 90-100% N2. In some embodiments, the mixture is 0-5% H2 and 95-100% N2. In some embodiments, including any of the above, O2 is present at less than 10 parts per million (ppm). In some embodiments, including any of the above, O2 is present at 5-10 ppm.

[0282]

[0301] In some embodiments, including any of the above, O2 is present in the binder burnout oven at less than 10 ppm.

[0283]

[0302] In some embodiments, including any of the above, O2 is present in the sintering oven at less than 10 ppm. In some embodiments, including any of the above, O2 is present in the cooling section after the sintering oven at less than 100 ppm. In some embodiments, including any of the above, O2 is present in the cooling section after the sintering oven at less than 70 ppm. In some embodiments, including any of the above, O2 is present in the cooling section after the sintering oven at less than 50 ppm.

[0284]

[0303] In some embodiments, including any of the above, O2 is present in the binder burnout oven at 5-10 ppm.

[0285]

[0304] In some embodiments, including any of the above, O2 is present in the sintering oven at 5-10 ppm.

[0286]

[0305] In some embodiments, including any of the above, O is added to the sintering oven at 10 -16 ~10 -20 Present in Pa.

[0287]

[0306] In some embodiments, the oven contains 1-500 ppm H2O.

[0288]

[0307] In some embodiments, the oven contains 1-1000 ppm H2O.

[0289]

[0308] In certain embodiments, rapid sintering occurs within the confined space. The confined space can have an atmosphere that reduces lithium loss during LLZO sintering and helps maintain the stoichiometric amount of lithium in a given LLZO formula. The confined space can be a portion of an oven through which the sintering film moves as it sinters. Certain processes described herein include suspending the film under tension without contact with a surface. The tension may be applied by weights, roller motors, load cells, or other methods for applying tension. Certain processes described herein include suspending the film under tension without contact with a surface while the film moves through the confined space. Herein, the suspended portion of the film is not in contact with a surface, but the mechanism used to apply the tension is in contact with the rest of the film. In some embodiments, only the suspended portion of the film is sintered, while the film is not touching any other surface. Certain processes described herein involve contacting only one surface during sintering (e.g., the bottom surface of the tape or film may be in contact with a roller, tensioning mechanism, or substrate). Certain processes described herein involve suspending the film without surface contact using tension, gas flow, or a combination of both tension and gas flow. As used herein, "without surface contact" specifically refers to the sintering film as it travels through the oven. During the sintering stage, the portion of the green tape undergoing sintering does not come into contact with any surface that could impart sintering defects to the surface of the green tape. As the green tape exits the oven, it may encounter rollers, rewinders, pins, posts, tensioning mechanisms, etc., which come into contact with the surface of the green tape. Similarly, as the sintering film exits the oven, the sintered film may come into contact with rollers, rewinders, pins, posts, etc., which come into contact with the sintered film. In this case, the contact occurs after the film is sintered, not during sintering. The particular process illustrated herein involves continuously peeling the green tape from the Mylar substrate on which it is placed.This may be done at the beginning of the sintering process, where the green tape is unwound from the roller and the peeled green tape is introduced into a binder burnout oven. Certain processes described herein include applying tension to the green film while it is being sintered. Certain processes described herein include avoiding reaction with water / oxygen in the ambient environment during processing of the green tape from the green tape to a sintered LLZO film. In some embodiments, a metal foil is used instead of a Mylar substrate. In some embodiments, the metal foil is iron foil, copper foil, nickel foil, alloys thereof, or combinations thereof. In some embodiments, the metal foil is a combination of iron and nickel. In certain embodiments, the combination of iron and nickel is greater than 1% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 2% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 3% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 4% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 5% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 6% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 7% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 8% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 9% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 10% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 11% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 12% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 13% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 14% iron, with the remainder being nickel.In certain embodiments, the combination of iron and nickel is greater than 15% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 16% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 17% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 18% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 19% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 20% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 11% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 12% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 13% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 14% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 15% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 16% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 17% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 18% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 19% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 20% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 11% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 12% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 13% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 14% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 15% iron, with the remainder being nickel.In certain embodiments, the combination of iron and nickel is greater than 16% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 17% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 18% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 19% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 20% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 21% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 22% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 23% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 24% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 25% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 26% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 27% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 28% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 29% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 30% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 31% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 32% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 33% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 34% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 35% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 36% iron, the remainder being nickel.In certain embodiments, the combination of iron and nickel is greater than 37% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 38% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 39% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 40% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 41% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 42% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 43% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 44% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 45% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 46% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 47% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 48% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 49% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 50% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 51% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 52% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 53% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 54% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 55% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 56% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 57% iron, the remainder nickel.In certain embodiments, the combination of iron and nickel is greater than 58% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 59% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 60% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 61% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 62% iron. and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 63% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 64% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 65% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 66% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 67% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 68% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 69% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 70% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 71% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 72% iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is greater than 73% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 74% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 75% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 76% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 77% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 78% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 79% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 80% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 81% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 82% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 83% iron, the remainder nickel.In certain embodiments, the combination of iron and nickel is greater than 84% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 85% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 86% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 87% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 88% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 89% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 90% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 91% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 92% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 93% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 94% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 95% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 96% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 97% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 98% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel is greater than 99% iron, with the remainder being nickel.

[0290]

[0309] In some embodiments, the binder burnout chimney is replaced with a Watlow heater cartridge embedded in a plate that is perforated to allow gas diffusion through it. The plate may incorporate a gas diffuser, gas manifold, channel, or other means for directing gas flow across one or more product surfaces. The unit includes an exhaust port for removing the debinding products.

[0291]

[0310] In some embodiments, a 6-inch diameter Lindbergh biscuit tube furnace is used. In some embodiments, the furnace is at 650°C. The furnace can be between 200 and 900°C. The furnace may incorporate multiple temperature zones. The furnace can include members to support the moving product; the members may be made of Inconel, Hastelloy, Haynes alloy 214, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, alumina, or another ceramic or metal. The support members can include a coating of Haynes alloy, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, alumina, or another ceramic or metal.

[0292] D. Use Process

[0311] In some embodiments, the present specification describes a process for using a continuous process apparatus, the process comprising the following operations: (a) producing a bi-layer having an organic content of less than 1% by heating the green bi-layer as it passes through at least one furnace; and (b) winding the bi-layer having an organic content of less than 1% onto a roller.

[0293]

[0312] In some embodiments, the present specification provides a process for using continuous process equipment, the process comprising: (a) providing or having provided the process equipment disclosed herein; (b) producing a bisque bilayer by heating the bilayer as it advances through at least one furnace; and (c) winding the bisque body.

[0294]

[0313] In some embodiments, including any of the foregoing, the process includes step (d) unrolling the bisque fired bilayer.

[0295]

[0314] In some embodiments, including any of the foregoing, the process includes step (e) sintering the bilayer.

[0296]

[0315] In some embodiments, including any of the above, the process includes winding the sintered bilayer onto end rollers.

[0297]

[0316] In some embodiments including any of the above, the sintered bilayer as cut strips.

[0298]

[0317] In some embodiments, including any of the foregoing, the bisque bilayer after step (c) is wound up on a roller until it is subsequently sintered.

[0299]

[0318] In some embodiments, provided herein is a process for using a continuous process apparatus, the process comprising: (a) providing, or having provided, a process apparatus as disclosed herein; and (b) producing a sintered bilayer by heating the bilayer as it travels through at least one furnace.

[0300]

[0319] During this process, various embodiments are possible depending on the specific conditions and the article being produced. In some examples, a leader tape will be used. This leader tape will be attached to the green tape by high-temperature ceramic (e.g., zirconia) epoxy, metal welding, or a mechanical bond such as staples. During the binder burnout process, the green tape is suspended in certain embodiments so that it does not come into contact with a surface (e.g., a setter). During the sintering process, the green tape is suspended in certain embodiments so that it does not come into contact with a surface (e.g., a setter). This suspension can be achieved by various means. For example, the green tape can be suspended using tension, air bearings, or other mechanisms. In some embodiments, surfaces of rollers, for example, that the green tape may come into contact with before or after sintering, may be coated with nickel or a nickel-containing inert coating. During sintering, in some embodiments, the sintering tape passes through a narrow gap made by a nickel-plated metal plate. In some embodiments, the metal plate is a stainless steel metal plate. In some embodiments, the gap will be less than 5 mm thick, where thickness is the maximum distance between the nickel-plated metal plates perpendicular to one surface of the metal plates. In some embodiments, the gap will be less than 4.5 mm. In some embodiments, the gap will be less than 4 mm. In some embodiments, the gap will be less than 3.5 mm. In some embodiments, the gap will be less than 3 mm. In some embodiments, the gap will be less than 2.5 mm. In some embodiments, the gap will be less than 2 mm. In some embodiments, the gap will be less than 1.5 mm. In some embodiments, the gap will be less than 1 mm. In some embodiments, the gap will be less than 0.5 mm. In some embodiments, the gap will be less than 500 μm. In some embodiments, the gap will be less than 400 μm.In some embodiments, the gap will be less than 300 μm. In some embodiments, the gap will be less than 200 μm. In some embodiments, the gap will be less than 100 μm. In some embodiments, the narrow gap helps prevent lithium loss from the sintered article during the sintering process.

[0301]

[0320] In some embodiments, the flatness of the green tape will be controlled by applying tension to the green tape. In some embodiments, the flatness of the green tape will be controlled by precise tape slitting to minimize stress on the edges of the sintered article. In some embodiments, the flatness of the green tape will be controlled by laser cutting the edges of the article before or after sintering. In some embodiments, the flatness of the green tape will be controlled by tailoring the lateral heating profile, for example, by heating the center of the film first. In some embodiments, the flatness will be controlled by precise alignment of the tensioning roller and other rollers in the processing equipment.

[0302]

[0321] In some embodiments, the sintered microstructure (high density, small grain size) of the produced sintered article will be controlled by rapid sintering. In some embodiments, the sintered microstructure (high density, small grain size) of the produced sintered article will be controlled by temperature ramp rate control, tape speed, multiple heating zones, or a combination thereof.

[0303]

[0322] In some embodiments, the process will use atmospheric control. This may include, for example, controlling the amount of O in the sintering oven to less than 100 ppm or even lower. In some embodiments, atmospheric control includes using N, Ar, or other inert gases to form a gas curtain around the periphery of the oven (e.g., around the oven inlet and outlet). In some embodiments, atmospheric control includes using vortex flow around the oven inlet and outlet. In some embodiments, atmospheric control includes using narrow openings around the oven inlet and outlet. In some embodiments, atmospheric control includes using gas injection near the center of the oven. This gas injection may result in laminar flow from the center to both ends of the oven. In some embodiments, atmospheric control includes passive or active overpressure inside the oven by using high gas flow rates and small opening diameters around the oven inlet and outlet.

[0304]

[0323] In some embodiments, atmospheric control includes using an enclosure to provide an enclosed environment with atmospheric control around or near the oven. For example, the enclosure is filled with nitrogen and some areas are exposed to a reducing environment. The reducing environment may be achieved by providing a partial pressure of H or CO.

[0305]

[0324] In some embodiments, the green tape is rapidly sintered. The time that any given portion of the film remains above room temperature can be between 15 seconds and 20 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 10 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 5 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 2 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 90 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 75 minutes. In other embodiments, the time that any given portion of the film remains above room temperature can be between 1 minute and 60 minutes.

[0306]

[0325] To avoid surface contamination of the sintered or pre-sintered article as it progresses through processing equipment, the film may be cooled to below 40°C. In some embodiments, the sintered film is maintained in an atmosphere with a low HO content. For example, the HO content may be less than 10 ppm. In some embodiments, the sintered film is maintained in an atmosphere that is mostly argon gas. In some embodiments, the sintered film is maintained in an atmosphere that is mostly nitrogen gas. In some embodiments, the sintered film is maintained in clean dry air (CDA).

[0307]

[0326] Because the mechanical properties of the green tape bilayer cause it to shrink as it is processed through the processing equipment, different tape speeds (e.g., different roller rotation speeds) may be used for the green tape stage compared to the binder burnout stage or the sintering stage. Different tape speeds may also be used for different parts of the line. Such varying speeds may be achieved in some embodiments by independent tension control (e.g., dancer after bisque, tension control after sintering).

[0308]

[0327] Because the bilayer may shrink laterally during sintering, the length of the sintering zone (along the tape direction) may be increased compared to the lateral shrinkage distance, which results in a smaller tape edge angle.

[0309]

[0328] Green tape strength can change as it is processed through the processing equipment. To accommodate this, tape tension can be variable throughout the processing equipment. For example, in the binder burnout oven, the tape can be under one tension setting, in the bisque oven, the tape can be under a different tension setting, and yet in the sintering oven, the tape can be under yet another different tension. The bilayer can be under higher tension in the take-up and unwinding section than in the burnout oven or bisque oven or sintering oven.

[0310]

[0329] In some embodiments, the green tape is peeled from the Mylar substrate before proceeding through a continuous production line, which may be accomplished using a sharp knife edge (e.g., a 180° angle at the knife edge), tension control, and other mechanisms.

[0311]

[0330] In some embodiments, the method includes (a) loading a roll of green film onto a front roller, (b) unrolling the roll of green film, (c) sintering the green film to form a sintered film, and (d) rolling the sintered film into a roll onto end rollers, where these operations are performed in a controlled atmosphere. The rollers may be used to hold the green or sintered film in a desired position.

[0312]

[0331] In some embodiments, the green tape advances through the processing equipment at a rate of about 2 to 25 inches per minute. In some embodiments, the green tape advances through the processing equipment at a rate of about 3 to 6 inches per minute. In some embodiments, the green tape advances through the processing equipment at a rate of about 1 to 5 inches per minute. In some embodiments, the green tape advances through the processing equipment at a rate of about 5 to 10 inches per minute.

[0313]

[0332] In some embodiments, the tape advances through the processing device at a speed of about 2 to 25 inches per minute. In some embodiments, the tape advances through the processing device at a speed of about 3 to 6 inches per minute.

[0314]

[0333] In some embodiments, including any of the above, the speed at which the tape advances through the processing equipment refers to the distance traveled and the time taken to advance through the sintering oven.

[0315]

[0334] FIG. 12 shows one embodiment of a processing device in a vertical processing orientation. Bilayer 1101 unwinds as bilayer 1109 as it travels through first heating zone 1102, second heating zone 1104, third heating zone 1106, and fourth heating zone 1107. Heating zone 1107 may also be a cooling zone. Rollers 1103 and 1105 help guide the bilayer and maintain proper tension on the bilayer. The final product is shown as sintered roll 1108, which could also be bisque roll 1108 if no sintering occurs in the heating zones. Bilayer 1109 travels vertically upward, away from the ground, as it travels through zone 1102. Bilayer 1109 travels downward, toward the ground, as it travels through zone 1106. Bilayer 1109 travels parallel to the ground as it travels through zone 1104.

[0316] E. Materials Formed by the Processes Disclosed Herein

[0335] In some embodiments, provided herein are biscuits prepared by the processes herein.

[0317]

[0336] In some embodiments, provided herein are sintered articles prepared by the processes herein.

[0318]

[0337] In some embodiments, provided herein is a biscuit bilayer comprising a lithium-filled garnet, where the biscuit bilayer is wrapped around a roller and the bilayer is less than 100 μm thick.

[0319]

[0338] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 μm to 30 μm and the metal foil layer has a thickness of 2 to 10 μm.

[0320]

[0339] In some embodiments, including any of the above, the grain size of the ceramic sintered layer of the bilayer body is d 90 The sintered ceramic layer has a porosity of <10 vol%, <8 vol%, <6 vol%, <5 vol%, <4 vol%, <3 vol%, <2 vol%, <1 vol%, or <0.5 vol%. The interfacial porosity (porosity within 5 um closest to the bilayer interface) is <2 vol%, <1.5 vol%, <1 vol%, or <0.5 vol%. These variables can be controlled by the sintering atmosphere used to produce the sintered bilayer. These characteristics can be achieved by controlling the gas atmosphere, ramp rate, and sintering hold time. The slurry contains pores with a density of <1 μm, <0.5 μm, <0.25 μm, or <0.1 μm. 50 The ceramic particles may have a particle size of

[0321]

[0340] In some embodiments, provided herein is a sintered bilayer comprising a lithium-filled garnet, where the bilayer is wrapped around a roller and the bilayer is less than 100 μm thick.

[0322]

[0341] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 to 30 μm and the metal foil layer has a thickness of 2 to 10 μm.

[0323]

[0342] In some embodiments, including any of the foregoing, the metal foil layer comprises nickel, iron, or a combination thereof.

[0324]

[0343] In some embodiments, provided herein are sintered bilayers prepared by the processes herein.

[0325]

[0344] In some embodiments, including any of the above, the sintered bilayer includes a lithium-filled garnet.

[0326]

[0345] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 to 30 μm and the metal foil layer has a thickness of 2 to 10 μm.

[0327]

[0346] In some embodiments, including any of the foregoing, the metal foil layer comprises nickel, iron, or a combination thereof.

[0328]

[0347] In some embodiments, including any of the foregoing, the green body layer comprises unsintered lithium-filled garnet.

[0329]

[0348] In some embodiments, including any of the above, the green body layer includes a chemical precursor of a lithium-filled garnet.

[0330]

[0349] In some embodiments, including any of the foregoing, the metal layer of the bilayer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.

[0331]

[0350] In some embodiments, including any of the above, the metal layer of the bilayer is an alloy of Fe and Ni.

[0332]

[0351] In some embodiments, including any of the above, the metal layer of the bilayer is an alloy of Fe and Ni, with the amount of Fe being 1% to 25% (w / w) and the remainder being Ni.

[0333]

[0352] In some embodiments, including any of the above, the thickness of the metal layer of the bilayer is between 1 μm and 20 μm.

[0334]

[0353] In some embodiments, including any of the above, the metal layer of the bilayer has a thickness of 1 μm to 10 μm.

[0335]

[0354] In some embodiments, including any of the above, the processing device includes a green tape wound around at least one front roller.

[0336]

[0355] In some embodiments, sintering of the LLZO film is performed without contacting the portion of the LLZO film being sintered with other surfaces, such as the surface of a processing device, during sintering. The lack of contact of the portion of the film being sintered can unexpectedly result in advantageous properties, such as low flatness, retention of the stoichiometric amount of lithium in a given LLZO formula, and advantageous microstructure (e.g., high density, small grain size, and combinations thereof). The lack of contact on the upper surface of the film results in fewer surface defects, such as scratches or tears.

[0337]

[0356] In some embodiments, including any of the foregoing, the sintered article comprises a bi-layer. In embodiments, the bi-layer comprises a metal foil and a ceramic membrane. In some embodiments, the sintered article comprises a tri-layer, where two ceramic layers sandwich a metal layer. In some embodiments, the metal is Ni. In some embodiments, the Ni is 1 μm thick. In some embodiments, the Ni is 2 μm thick. In some embodiments, the Ni is 3 μm thick. In some embodiments, the Ni is 4 μm thick. In some embodiments, the Ni is 5 μm thick. In some embodiments, the Ni is 6 μm thick. In some embodiments, the Ni is 7 μm thick. In some embodiments, the Ni is 8 μm thick. In some embodiments, the Ni is 9 μm thick. In some embodiments, the Ni is 10 μm thick. In some embodiments, the Ni is 11 μm thick. In some embodiments, the Ni is 12 μm thick. In some embodiments, the Ni is 13 μm thick. In some embodiments, the Ni is 14 μm thick. In some embodiments, the Ni is 15 μm thick. In some embodiments, the Ni is 16 μm thick. In some embodiments, the Ni is 17 μm thick. In some embodiments, the Ni is 18 μm thick. In some embodiments, the Ni is 19 μm thick. In some embodiments, the Ni is 20 μm thick.

[0338]

[0357] In some embodiments, the slurry may be deposited onto a piece of foil to form a green tape with a foil backing. In some embodiments, the foil is Mylar foil. The green tape with the foil backing may be wound into a roll to form a roll of green film with a foil backing. The roll of green film with a foil backing may be loaded into a processing apparatus as described herein. In some embodiments, a method of using the processing apparatus may include (a) loading the roll of green film with a foil backing onto a front roller, (b) unrolling the roll of green film, (c) sintering the green film to form a sintered film with a foil backing, and (d) rolling the sintered film with a foil backing onto an end roller, wherein these operations are performed in a controlled atmosphere. In some embodiments, the backing foil may comprise nickel metal or nickel foil.

[0339]

[0358] In some embodiments, the green films sintered using the processing equipment are bilayer or trilayer.

[0340]

[0359] In some embodiments, various layer configurations are contemplated and can be sintered according to the sintering methods set forth herein: A) freestanding lithium-filled garnet material; B) freestanding lithium-filled garnet material optionally comprising an active material, a binder, a solvent, and / or carbon; C) a bilayer having one lithium-filled garnet layer and one metal powder, foil, or sheet layer; D) a bilayer having one lithium-filled garnet layer and one metal powder, foil, or sheet layer; E) a lithium-filled garnet material layer optionally comprising an active material, a binder, a solvent, and / or carbon and one metal powder, foil, or sheet layer; F) a tri-layer body having two lithium-filled garnet layers and a metal powder, foil, or sheet layer between and in contact with the garnet layers; G) a tri-layer body having two lithium-filled garnet layers and a metal powder, foil, or sheet layer between and in contact with the garnet layers; and H) a tri-layer body having two lithium-filled garnet material layers, each garnet layer optionally containing an active material, a binder, a solvent, and / or carbon, and a metal powder, foil, or sheet layer between and in contact with the garnet layers.

[0341]

[0360] In some cases, bilayer bodies may be sintered using the processing equipment described herein. In some cases, trilayer bodies may be sintered using the processing equipment described herein.

[0342]

[0361] The tri-layer may include a lithium-filled garnet layer, a metal layer, and a second lithium-filled garnet layer opposite the metal layer. The bi-layer may be passed through a processing device with the lithium-filled garnet layer facing up and the second lithium-filled garnet layer facing down.

[0343]

[0362] The bilayer may include a lithium-filled garnet layer and a metal foil layer. In some embodiments, the metal layer includes Ni, Fe, Cu, Al, Sn, In, Ag, Au, steel, an alloy, or a combination thereof. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 90% Ni and 10% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 91% Ni and 9% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 92% Ni and 8% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 93% Ni and 7% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 94% Ni and 6% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 95% Ni and 5% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 96% Ni and 4% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 97% Ni and 3% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 98% Ni and 2% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 99% Ni and 1% Fe. In some embodiments, the metal layer is sheet metal. In some embodiments, the metal layer is sheet aluminum. In some embodiments, the metal layer is sheet nickel. In some embodiments, the metal layer may be malleable. In some embodiments, the metal layer is 1 μm thick. In some embodiments, the metal layer is 2 μm thick. In some embodiments, the metal layer is 3 μm thick. In some embodiments, the metal layer is 4 μm thick. In some embodiments, the metal layer is 5 μm thick. In some embodiments, the metal layer is 6 μm thick. In some embodiments, the metal layer is 7 μm thick. In some embodiments, the metal layer is 8 μm thick. In some embodiments, the metal layer is 9 μm thick. In some embodiments, the metal layer is 10 μm thick. In some embodiments, the metal layer is 11 μm thick. In some embodiments, the metal layer is 12 μm thick. In some embodiments, the metal layer is 13 μm thick.In some embodiments, the metal layer is 14 μm thick. In some embodiments, the metal layer is 15 μm thick. In some embodiments, the metal layer is 16 μm thick. In some embodiments, the metal layer is 17 μm thick. In some embodiments, the metal layer is 18 μm thick. In some embodiments, the metal layer is 19 μm thick. In some embodiments, the metal layer is 20 μm thick.

[0344]

[0363] In some embodiments, the lithium-filled garnet-metal sintered films herein are 1 μm to 100 μm thick. In certain embodiments, such films are co-sintered with mixed amounts of lithium-filled garnet and metal. The metal may be selected from the group consisting of Ni, Mg, Li, Fe, Al, Cu, Au, Ag, Pd, Pt, Ti, steel, alloys thereof, and combinations thereof. The lithium-filled garnet and metal are mixed as powders and then co-sintered to form the film. In some embodiments, the film comprises a uniform mixture of lithium-filled garnet and metal. The relative amounts of lithium-filled garnet and metal can vary, by volume, from 1% lithium-filled garnet and the remainder metal to up to 99% lithium-filled garnet and the remainder metal.

[0345]

[0364] In some embodiments, including any of the above, the lithium-filled garnet is sintered onto the ceramic-metal film.

[0346]

[0365] The processing equipment systems and processes described herein are useful for the production of a variety of materials, including, but not limited to, lithium-filled garnet films, including, but not limited to, bilayers of a lithium-filled garnet film on a metal layer, or trilayers of a metal layer between two lithium-filled garnet films.The processing equipment systems and processes described herein may be used in conjunction with other applications including, but not limited to, PCT / US2016 / 043428, filed July 21, 2016, and published as WO 2017015511A1, entitled "PROCESSES AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS"; PCT / US2019 / 056584, filed October 16, 2019, and published as WO 2020081718A1, entitled "SINTERING LARGE AREA CERAMIC FILMS"; and PCT / US2016 / 15209, filed January 27, 2016, and published as WO 2017131676A1, entitled "ANNEALED GARNET ELECTROLYTE SEPARATORS"; PCT / US2017 / 039069, filed January 23, 2017, published as WO 2018236394A1, entitled "LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS"; PCT / US2019 / 54117, filed October 1, 2019, published as WO 2020072524A1, entitled "METHODS OF MAKING AND USING AN ELECTROCHEMICAL CELL COMPRISING AN and 10,103,405 (each of which is incorporated herein by reference in its entirety for all purposes).

[0347]

[0366] In some embodiments, including any of the above, the ceramic-metal film can be an oxide-metal film. In some embodiments, the film has one layer that is ceramic and one layer that is metal. In other embodiments, the film is a homogeneous mixture of ceramic and metal. In some embodiments, the ceramic-metal film comprises ceramic and metal. In some embodiments, the volume percentage of ceramic is 10% and the volume percentage of metal is 90%. In some embodiments, the volume percentage of ceramic is 20% and the volume percentage of metal is 80%. In some embodiments, the volume percentage of ceramic is 30% and the volume percentage of metal is 70%. In some embodiments, the volume percentage of ceramic is 40% and the volume percentage of metal is 60%. In some embodiments, the volume percentage of ceramic is 50% and the volume percentage of metal is 50%. In some embodiments, the volume percentage of ceramic is 60% and the volume percentage of metal is 40%. In some embodiments, the volume percentage of ceramic is 70% and the volume percentage of metal is 30%. In some embodiments, the volume percentage of ceramic is 80% and the volume percentage of metal is 20%. In some embodiments, the volume percentage of ceramic is 90% and the volume percentage of metal is 10%. In some embodiments, the volume percentage of ceramic is 5% and the volume percentage of metal is 95%. In some embodiments, the volume percentage of ceramic is 15% and the volume percentage of metal is 85%. In some embodiments, the volume percentage of ceramic is 25% and the volume percentage of metal is 75%. In some embodiments, the volume percentage of ceramic is 35% and the volume percentage of metal is 65%. In some embodiments, the volume percentage of ceramic is 45% and the volume percentage of metal is 55%. In some embodiments, the volume percentage of ceramic is 55% and the volume percentage of metal is 45%. In some embodiments, the volume percentage of ceramic is 65% and the volume percentage of metal is 32%. In some embodiments, the volume percentage of ceramic is 75% and the volume percentage of metal is 25%.In some embodiments, the volume percentage of ceramic is 85% and the volume percentage of metal is 15%. In some embodiments, the volume percentage of ceramic is 95% and the volume percentage of metal is 5%.

[0348]

[0367] In some embodiments, including any of the above, the ceramic-metal film comprises an oxide and a metal. In some embodiments, the volume percentage of the oxide is 10% and the volume percentage of the metal is 90%. In some embodiments, the volume percentage of the oxide is 20% and the volume percentage of the metal is 80%. In some embodiments, the volume percentage of the oxide is 30% and the volume percentage of the metal is 70%. In some embodiments, the volume percentage of the oxide is 40% and the volume percentage of the metal is 60%. In some embodiments, the volume percentage of the oxide is 50% and the volume percentage of the metal is 50%. In some embodiments, the volume percentage of the oxide is 60% and the volume percentage of the metal is 40%. In some embodiments, the volume percentage of the oxide is 70% and the volume percentage of the metal is 30%. In some embodiments, the volume percentage of the oxide is 80% and the volume percentage of the metal is 20%. In some embodiments, the volume percentage of the oxide is 90% and the volume percentage of the metal is 10%. In some embodiments, the volume percentage of oxide is 5% and the volume percentage of metal is 95%. In some embodiments, the volume percentage of oxide is 15% and the volume percentage of metal is 85%. In some embodiments, the volume percentage of oxide is 25% and the volume percentage of metal is 75%. In some embodiments, the volume percentage of oxide is 35% and the volume percentage of metal is 65%. In some embodiments, the volume percentage of oxide is 45% and the volume percentage of metal is 55%. In some embodiments, the volume percentage of oxide is 55% and the volume percentage of metal is 45%. In some embodiments, the volume percentage of oxide is 65% and the volume percentage of metal is 32%. In some embodiments, the volume percentage of oxide is 75% and the volume percentage of metal is 25%. In some embodiments, the volume percentage of oxide is 85% and the volume percentage of metal is 15%. In some embodiments, the volume percentage of oxide is 95% and the volume percentage of metal is 5%.

[0349]

[0368] In some embodiments, including any of the above, the ceramic-metal film can be an oxide-metal film. In some embodiments, the ceramic-metal film comprises a ceramic and a metal. In some embodiments, the weight percentage of the ceramic is 10% and the weight percentage of the metal is 90%. In some embodiments, the weight percentage of the ceramic is 20% and the weight percentage of the metal is 80%. In some embodiments, the weight percentage of the ceramic is 30% and the weight percentage of the metal is 70%. In some embodiments, the weight percentage of the ceramic is 40% and the weight percentage of the metal is 60%. In some embodiments, the weight percentage of the ceramic is 50% and the weight percentage of the metal is 50%. In some embodiments, the weight percentage of the ceramic is 60% and the weight percentage of the metal is 40%. In some embodiments, the weight percentage of the ceramic is 70% and the weight percentage of the metal is 30%. In some embodiments, the weight percentage of the ceramic is 80% and the weight percentage of the metal is 20%. In some embodiments, the weight percentage of ceramic is 90% and the weight percentage of metal is 10%. In some embodiments, the weight percentage of ceramic is 5% and the weight percentage of metal is 95%. In some embodiments, the weight percentage of ceramic is 15% and the weight percentage of metal is 85%. In some embodiments, the weight percentage of ceramic is 25% and the weight percentage of metal is 75%. In some embodiments, the weight percentage of ceramic is 35% and the weight percentage of metal is 65%. In some embodiments, the weight percentage of ceramic is 45% and the weight percentage of metal is 55%. In some embodiments, the weight percentage of ceramic is 55% and the weight percentage of metal is 45%. In some embodiments, the weight percentage of ceramic is 65% and the weight percentage of metal is 32%. In some embodiments, the weight percentage of ceramic is 75% and the weight percentage of metal is 25%. In some embodiments, the weight percentage of ceramic is 85% and the weight percentage of metal is 15%. In some embodiments, the weight percentage of ceramic is 95% and the weight percentage of metal is 5%.

[0350]

[0369] In some embodiments, including any of the above, the ceramic of the ceramic-metal film can be selected from alumina, silica, titania, lithium-filled garnet, lithium aluminate, aluminum hydroxide, aluminosilicate, lithium zirconate, lanthanum aluminate, lanthanum zirconate, lanthanum oxide, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate, lithium lanthanum titanate, lithium lanthanum oxide, zirconia, LiZrO, xLiO-(1-x)SiO (where x = 0.01 to 0.99), aLiO-bBO-cSiO (where a + b + c = 1), LiLaO, LiAlO, LiO, LiPO, or a combination thereof.

[0351]

[0370] In embodiments, the tri-layer body includes a metal foil and a green ceramic film on both sides of the metal foil. The metal foil of the bi-layer or tri-layer body can have a thickness of 0.5 μm to 50 μm. The metal foil of the bi-layer or tri-layer body can have a thickness of 3 μm to 30 μm. In some embodiments, the metal foil of the bi-layer or tri-layer body can have a thickness of 5 μm to 20 μm. In other embodiments, the metal foil of the bi-layer or tri-layer body can have a thickness of 5 μm to 15 μm.

[0352]

[0371] In some embodiments, including any of the above, the sintered article comprises LLZO.

[0353]

[0372] In some embodiments, the sintered ceramic membrane has a D of less than 5 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 4 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 3 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 2 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 1 μm. 50In some embodiments, the sintered ceramic membrane has a grain size of less than 0.9 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.8 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.7 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.6 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.5 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.4 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.3 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.2 μm. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.1 microns. 50 In some embodiments, the sintered ceramic membrane has a grain size of less than 5 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 4 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 3 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 2 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 1 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.9 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.8 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.7 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.6 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.5 μm. 90In some embodiments, the sintered ceramic membrane has a grain size of less than 0.4 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.3 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.2 μm. 90 In some embodiments, the sintered ceramic membrane has a grain size of less than 0.1 microns. 90 In some embodiments, the sintered ceramic membrane has a porosity of less than 5 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 4 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 3 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 2 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 1 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 0.5 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 0.4 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 0.3 vol%. In some embodiments, the sintered ceramic membrane has a porosity of less than 0.2 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 95 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 96 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 97 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 98 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99.5 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99.6 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99.7 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99.8 vol%. In some embodiments, the sintered ceramic membrane has a density greater than 99.9 vol%.

[0354]

[0373] In some embodiments, the roll of sintered membrane may further include additional padding material sandwiched between the layers of the roll.

[0355]

[0374] In some embodiments, including any of the above, the sintered ceramic membrane has a D of less than 5 microns (μm). 50 It has a grain size.

[0356]

[0375] In some embodiments, including any of the above, the sintered ceramic membrane has a D of less than 5 μm. 90 It has a grain size.

[0357]

[0376] In some embodiments, including any of the above, the sintered ceramic membrane has a porosity of less than 5% by volume.

[0358]

[0377] In some embodiments, including any of the above, the sintered membrane has an aspect ratio (height / diameter) greater than 1 and a circumference of 1000 μm. 2 The surface has a surface defect density of less than 100 protrusions per square centimeter that are greater than 2 microns in height relative to the median height of the surface.

[0359]

[0378] In some embodiments, including any of the above, the sintered membrane has an aspect ratio (height / diameter) greater than 1 and a circumference of 1000 μm. 2 and a surface defect density of less than 100 valleys per square centimeter that are greater than 2 microns deep from the surface relative to the median height of the surface area.

[0360]

[0379] In some embodiments, including any of the foregoing, the sintered film has a surface defect density of less than 100 protrusions per square centimeter at the interface between the lithium-filled garnet film and the metal layer with an aspect ratio (height / diameter) greater than 1.

[0361]

[0380] In some embodiments, including any of the foregoing, the sintered film has a surface defect density of less than 100 valleys per square centimeter at the interface between the lithium-filled garnet film and the metal layer, where the valleys have an aspect ratio (height / diameter) greater than 1.

[0362]

[0381] In some embodiments including any of the above, D 50 The grain size is at least 10 nm.

[0363]

[0382] In some embodiments including any of the above, D 50 The grain size is at least 50 nm.

[0364]

[0383] In some embodiments including any of the above, D 50 The grain size is at least 0.5 μm.

[0365] F. Lithium-loaded garnet sintered on metal foil

[0384] The processing equipment disclosed herein may be used to sinter lithium-filled garnets onto metal foils. In some embodiments, the metal foil is a densified metal layer. In certain embodiments, the metal foil is a densified metal layer that also includes a ceramic. In some of these embodiments, the ceramic is a lithium-filled garnet.

[0366]

[0385] In some embodiments, the metal foil or metal layer is nickel, steel, stainless steel, copper, aluminum, Kovar, Invar, ceramics, Haynes 216, or combinations thereof. In some embodiments, the metal foil is produced at least in part by roll annealing. In some embodiments, the metal foil is produced at least in part by electrodeposition.

[0367] In certain embodiments, the LLZO is sintered onto a metal foil. In some of these embodiments, the metal foil is pure Ni. In some of these embodiments, the metal foil is a combination of Ni and Fe. In some of these embodiments, the metal foil comprises 5-20% Fe and 80-95% Ni. In some of these embodiments, the metal foil comprises 10-20% Fe and 80-90% Ni.

[0368]

[0386] In certain embodiments, the LLZO is sintered onto a metal foil. In some of these embodiments, the metal foil is pure Cu. In some of these embodiments, the metal foil comprises 5-20% Cu and 80-95% Ni. In some of these embodiments, the metal foil comprises 10-20% Cu and 80-90% Ni. In some of these embodiments, the metal foil is a combination of Cu and Fe.

[0369]

[0387] In some embodiments, the green tape described above as being deposited on Mylar foil is instead deposited on a metal layer. The metal can be nickel, steel, stainless steel, copper, aluminum, Kovar, Invar, ceramics, Haynes 216, or a combination thereof. In this example, the green tape does not need to be peeled from the Mylar, but can instead be sintered directly onto the metal. The green tape and metal may be rolled together before advancing the green tape through processing equipment. In some embodiments, a backing layer is added to the metal, which is rolled onto the metal along with the green tape. In some embodiments, when the metal is rolled with the green tape on the metal, an interleaf layer is used. The interleaf provides padding between the rolled layers.

[0370]

[0388] In some embodiments, the processing equipment is used to sinter lithium-filled garnets without an underlying substrate.

[0371]

[0389] In some embodiments, the processing equipment is used to sinter a green lithium-filled garnet layer adjacent to a green oxide / metal mixed layer. The green oxide / metal mixed layer can include 0.0001-25 wt% Ni powder, 1-25 wt% Fe powder, or a combination thereof. In some cases, the green oxide / metal mixed layer includes 1-20 wt% Ni and 1-10 wt% Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal mixed layer includes 5-15 wt% Ni and 1-5 wt% Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal mixed layer includes 10-15 wt% Ni and 3-5 wt% Fe, with the remainder being lithium-filled garnet.

[0372]

[0390] Other configurations are contemplated herein. For example, the bare film configuration can be as follows: a sintered LLZO film without other metal-containing layers.

[0373]

[0391] For example, a co-sintered configuration can include a bilayer of green LLZO and a green metal-ceramic layer, the latter being metal and ceramic powder while in the green state.

[0374]

[0392] For example, a configuration on a metal foil can be as follows: This involves casting green LLZO onto a metal layer / metal foil. The metal layer is a dense layer, not a powder. The metal foil in this case has no ceramics in it and can be purchased, typically made by a process other than sintering (e.g., electrodeposition or roll-annealing). The metal layer can additionally contain less than 10 vol% ceramic inclusions.

[0375] G. Bilayers and Additional Embodiments

[0393] In some embodiments, including any of the above, the width of the bilayer to be processed is about 700 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 600 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 500 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 400 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 300 mm.

[0376]

[0394] In some embodiments, including any of the above, the width of the bilayer to be processed is about 250 mm.

[0377]

[0395] In some embodiments, including any of the above, the width of the bilayer to be processed is about 200 mm.

[0378]

[0396] In some embodiments, including any of the above, the width of the bilayer to be processed is about 150 mm.

[0379]

[0397] In some embodiments, including any of the above, the width of the bilayer to be processed is about 100 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 90 mm. In some embodiments, including any of the above, the width of the bilayer to be processed is about 80 mm.

[0380]

[0398] In some embodiments, including any of the above, the width of the bilayer to be processed is about 50 mm.

[0381]

[0399] In some embodiments, including any of the above, the metal foil in the bilayer tape is an alloy of nickel, consists essentially of Ni, consists essentially of pure Ni, or consists solely of pure Ni.

[0382]

[0400] In some embodiments, including any of the above, the average thickness of the metal foil will be in the range of 4.5 μm to 10.5 μm. In particular examples, the average thickness is 4, 5, 6, 7, 8, 9, 10, or 11 μm. In particular examples, the average thickness is 4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, or 11.5 μm. Thickness is measured by scanning electron microscopy (SEM) unless otherwise specified.

[0383]

[0401] In some embodiments, including any of the above, the thickness of the metal foil can vary by up to ±1.25 μm across its width and length.

[0384]

[0402] In some embodiments, including any of the above, the ceramic layer covers most of the width of the metal foil, but there may be areas on both edges of the metal foil that are free of any ceramic layer; such areas may be up to 15 mm wide. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 3 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 4 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 5 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 6 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 7 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 8 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges that are about 9 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges of about 10 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges of about 11 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges of about 12 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges of about 13 mm. In some embodiments, including any of the above, the metal foil has one or two uncoated edges of about 14 mm.

[0385]

[0403] In some embodiments, including any of the above, the average thickness of the sintered dense ceramic layer will range from 18 μm to 42 μm in the central region of the ceramic layer, and the thickness may vary locally across the width and length of the web by up to ±1.5 μm.

[0386]

[0404] In some embodiments, including any of the above, the thickness of the ceramic layer before processing will be up to 2.25 times greater than the thickness after sintering, and thus the average thickness of the ceramic layer in the central region before sintering will be up to 95 μm, which can vary across width and length by up to ±3.4 μm.

[0387]

[0405] In some embodiments, including any of the above, the incoming bi-layer will be in the form of a roll wound on a core having a diameter of 3 inches to 6 inches.

[0388]

[0406] At the end of the process, in some embodiments including any of the above, the sintered tape is rewound into a roll with a minimum core diameter of 6 to 12 inches.

[0389]

[0407] In some embodiments, including any of the above, where BBO and sintering are performed by separate means, the tape is wound up after the BBO process onto a roll with a minimum core diameter of 6 to 12 inches, allowing it to be transported in roll form to the sintering means.

[0390]

[0408] In some embodiments, including any of the above, the maximum diameter of the exiting coil (when using a 12-inch winding core) is 360 to 450 mm, and the maximum coil weight is 40 to 140 kg.

[0391] H. Gases and atmospheres I. Configuration

[0409] In some examples, each heating zone has its own individually controllable gas outlet and exhaust ports, thus allowing each zone to flow different gases, different total flow rates, and different exhaust openings. Gas flow within each zone is, in these examples, perpendicular to the web movement (i.e., machine) direction. This means that either cross-web flow or cross-web flow is allowed, but not machine-direction flow.

[0392] II. Available Gas

[0410] The systems and devices herein are intended to allow the flow of the following gases, or mixtures thereof: nitrogen (N2), forming gas (N2 + H2, where H2 < 5%), wet nitrogen, wet forming gas.

[0393] III. Atmosphere Requirements

[0411] In some embodiments, O levels are maintained below 10 ppm to 50 ppm throughout the tool (e.g., furnace) as measured by sampling gas from each zone individually using an O analyzer while flowing only N gas through all zones.

[0394]

[0412] In some embodiments, the HO level requirements are different for different sections of the temperature profile as measured by sampling gas from each zone individually using a dew point analyzer while the tool is in its typical gas flow configuration (which may include flowing forming gas and wet nitrogen and wet forming gas).

[0395] IV. Gas Flow

[0413] In some embodiments, during the BBO stage, the maximum refresh rate is 1-3 exchanges per minute. One exchange per minute means that the gas flow rate, in volume per minute, is equal to the internal volume available for the gas. Two exchanges per minute means that the gas flow rate, in volume per minute (at STP), is twice the internal volume available for the gas. In some embodiments, during the sintering stage, the maximum refresh rate is 0.3-3 exchanges per minute.

[0396] V. Waste Management

[0414] Organic vapors from binder removal tend to condense and leave residue on cooler surfaces. Any condensation on the interior surfaces of the tool must be avoided by heating the interior surfaces where the binder waste enters; this heating should be continuous without cold spots until it reaches the building's exhaust system or cold trap.

[0397] VI. Atmosphere Control

[0415] Atmospheric control may be provided by enclosing the processing equipment as a complete system, or various components of the processing equipment (eg, ovens) in an enclosure.

[0398]

[0416] Atmospheric control may be provided by using different gas curtains in the processing equipment as a complete system or in different components of the processing equipment (eg, ovens).

[0399]

[0417] In some embodiments, atmospheric control includes using a narrow oven opening.

[0400]

[0418] In some embodiments, atmospheric control includes using vortex flow at the oven inlet and outlet. In some embodiments, atmospheric control includes using N2 or Ar filled glove boxes around various components such as rollers. In some embodiments, atmospheric control includes using overpressure inside the oven. In some embodiments, the pressure inside the oven is at least 0.1 inches of water column above ambient pressure. In some embodiments, the pressure inside the oven is at least 0.3 inches of water column above ambient pressure. In some embodiments, the pressure inside the oven is at least 0.5 inches of water column above ambient pressure. In some embodiments, the pressure inside the oven is at least 0.7 inches of water column above ambient pressure. In some embodiments, the pressure inside the oven is at least 0.9 inches of water column above ambient pressure. In some embodiments, the pressure inside the oven is at least 1 inch of water column above ambient pressure.

[0401]

[0419] In some embodiments, the atmosphere control includes controlling the amount of H2O in the oven. In some embodiments, the atmosphere control includes controlling the amount of O2 in the oven. In some embodiments, the atmosphere control includes controlling the amount of O2 in the oven to a level less than 100 ppm. In some embodiments, the atmosphere control includes controlling the amount of O2 in the oven to a level less than 10 ppm. In some embodiments, the atmosphere control includes controlling the amount of O2 in the oven to a level less than 1 ppm. In some embodiments, the atmosphere control includes controlling the amount of H2 in the oven. In some embodiments, the atmosphere control includes controlling the amount of N2 in the oven.

[0402]

[0420] In some embodiments, the gas curtain is a N2 curtain.

[0403]

[0421] In some embodiments, an airbox (tunnel shaped) is used in conjunction with the exhaust outlet.

[0404]

[0422] In some embodiments, an air box with a feedback loop is used to form the gas supply line. In some embodiments, the oven also includes one or more O2 sensors.

[0405]

[0423] In some embodiments, the process will use atmospheric control. This may include, for example, controlling the amount of O in the sintering oven to less than 100 ppm or even lower. In some embodiments, atmospheric control includes using N, Ar, or other inert gases to form a gas curtain around the periphery of the oven (e.g., around the oven inlet and outlet). In some embodiments, atmospheric control includes using vortex flow around the oven inlet and outlet. In some embodiments, atmospheric control includes using narrow openings around the oven inlet and outlet. In some embodiments, atmospheric control includes using gas injection near the center of the oven. This gas injection may result in laminar flow from the center to both ends of the oven. In some embodiments, atmospheric control includes passive or active overpressure inside the oven by using high gas flow rates and small opening diameters around the oven inlet and outlet.

[0406]

[0424] In some embodiments, atmospheric control includes using an enclosure to provide an enclosed environment with atmospheric control around or near the oven. For example, the enclosure is filled with nitrogen and some areas are exposed to a reducing environment. The reducing environment may be achieved by providing a partial pressure of H or CO.

[0407]

[0425] In some embodiments, parts of a production line are enclosed in a container or room with atmospheric control. For example, a production line may be completely enclosed in a clean room. The inlets and / or outlets of processing equipment may be enclosed in a clean room. In certain of these embodiments, gases are introduced into particle-free enclosed containers or rooms (e.g., clean rooms). CDA refers to clean dry air, which is air or gas that has been filtered to remove particles based on particle size. Gases can include N2, Ar, forming gas (Ar / H2; or N2 / H2), or combinations thereof.

[0408]

[0426] The pressure is measured by one or more pressure gauges and the gas flow is controlled by a mass flow controller.

[0409]

[0427] In some embodiments, the present disclosure provides: With front roller; at least one furnace including at least three heating zones; It's a runway, Nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite, alumina (Al2O3), zirconia (ZrO2), boron nitride, silicon carbide, magnesium oxide, or combinations thereof a runway having a surface comprising a material selected from the group consisting of: A processing device is shown comprising:

[0410]

[0428] In some embodiments, the present disclosure provides: a front roller; and at least one furnace including at least three heating zones; baffles located within the heating zone; a baffle between the two heating zones; Curtain purge between two heating zones; means for controlling at least two separate pressure zones within the at least three heating zones; At least one means of exhausting the furnace; means for purging gas between the two heating zones; Means for isolating the gas between the two heating zones; a means for mechanically separating the two heating zones; or A combination of these and at least one of:

[0411]

[0429] In some embodiments, the present disclosure provides: With front roller; at least one furnace including at least three heating zones; A bilayer body maintained under tension, the tension being in the range of 0.1 g / cm to 500 g / cm per web width. A processing device is shown comprising:

[0412]

[0430] In some embodiments, the present disclosure provides: With front roller; at least one furnace including at least three heating zones; with two layers; At least two rollers A processing device comprising: A processing device is shown in which the bilayer is wrapped around one of at least two or more rollers at a wrap angle in the range of 0 to 40°.

[0413]

[0431] In some embodiments, including any of the above, the processing device comprises a bilayer.

[0414]

[0432] In some embodiments, including any of the above, the bilayer is a metal-ceramic bilayer.

[0415]

[0433] In some embodiments, including any of the above, the three different heating zones comprise: (a) a binder burnout section; (b) a bisque section; and (c) a sintering section.

[0416]

[0434] In some embodiments, including any of the above, the processing device includes end rollers.

[0417]

[0435] In some embodiments, including any of the above, the front roller is mechanically coupled to at least one furnace.

[0418]

[0436] In some embodiments, including any of the above, the front roller has a motor that is sealed from the at least one furnace.

[0419]

[0437] In some embodiments, including any of the above, the runway is inside at least one furnace. In some embodiments, including any of the above, the runway is inside the sintering section. In some embodiments, including any of the above, the runway comprises an exhaust vent. In some embodiments, including any of the above, the runway comprises a speed bump. In some embodiments, including any of the above, the top runway is centerless. In some embodiments, including any of the above, the runway comprises holes in its upper surface. In some embodiments, including any of the above, at least one furnace is sealed.

[0420]

[0438] In some embodiments, including any of the above, the processing device includes a cooling section.

[0421]

[0439] In some embodiments, including any of the above, the processing equipment includes at least one atmosphere controller that controls at least one condition within the furnace selected from the group consisting of gas flow rate, flow direction, gas composition, pressure, and combinations thereof.

[0422]

[0440] In some embodiments, including any of the above, the bi-layer is wrapped around a front roller.

[0423]

[0441] In some embodiments, including any of the above, the bilayer includes a metal layer and a ceramic layer.

[0424]

[0442] In some embodiments, including any of the above, the ceramic layer is green, bisque fired, or sintered.

[0425]

[0443] In some embodiments, including any of the above, at least one furnace comprises a multi-zone tunnel kiln (MZTK).

[0426]

[0444] In some embodiments, including any of the above, the roller comprises a material selected from silicon carbide, Ni, stainless steel, or combinations thereof.

[0427]

[0445] In some embodiments, including any of the above, the processing device comprises rollers that are mechanically positionable to within 0.005 inches. In some embodiments, including any of the above, the processing device comprises rollers that are mechanically positionable to within 0.001 inches. In some embodiments, including any of the above, the processing device comprises rollers that are mechanically positionable in three dimensions.

[0428]

[0446] In some embodiments, including any of the above, the processing equipment comprises a nip roller.In some embodiments, including any of the above, the at least one oven comprises a hot roller.

[0429]

[0447] In some embodiments, including any of the above, at least one furnace includes rollers configured to form a ramp. In some embodiments, including any of the above, the MZTK has rollers configured to form an arch inside the MZTK. In some embodiments, including any of the above, the processing equipment includes 1 to 30 rollers configured to form a ramp. In some embodiments, including any of the above, the processing equipment includes 1 to 20 rollers configured to form a ramp.

[0430]

[0448] In some embodiments, including any of the above, the MZTK is hermetically sealed.

[0431]

[0449] In some embodiments, including any of the above, the MZTK is sealed under vacuum.

[0432]

[0450] In some embodiments, including any of the above, the front roller has a motor that is sealed from the MZTK under vacuum.

[0433]

[0451] In some embodiments, including any of the above, the process equipment includes baffles between each heating zone.

[0434]

[0452] In some embodiments, including any of the above, the wrap angle about the roller ranges from 0° to 40°. In some embodiments, including any of the above, the wrap angle about the roller ranges from 0° to 40° in the binder burnout section. In some embodiments, including any of the above, the wrap angle about the roller ranges from 0° to 40° in the sintering section. In some embodiments, including any of the above, the processing equipment comprises nip rollers on the edges, speed bumps, air bearings, or combinations thereof.

[0435]

[0453] In some embodiments, including any of the above, the bilayer is suspended in the process equipment.

[0436]

[0454] In some embodiments, including any of the above, the at least one furnace comprises: (a) a binder burnout section; (b) a bisque section; and (c) a sintering section.

[0437]

[0455] In some embodiments, including any of the above, at least one furnace is sealed and at least one atmosphere controller controls gas flow into and out of the at least one furnace.

[0438]

[0456] In some embodiments, including any of the above, the processing equipment includes a pressurized gas line between the bisque section and the sinter section, which pumps gas into the bisque section and into the sinter section.

[0439]

[0457] In some embodiments, including any of the above, at least one furnace is enclosed within a sealed container.

[0440]

[0458] In some embodiments, including any of the above, the sealed container contains an atmosphere of Ar, N2, H2, or combinations thereof.

[0441]

[0459] In some embodiments, including any of the above, the atmosphere controller maintains a reducing atmosphere in the sintering section.

[0442]

[0460] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere in the sintering section that includes argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof.

[0443]

[0461] In some embodiments, including any of the above, the atmosphere controller maintains an atmosphere containing less than 500 ppm O2 in the bisque section, the sintering section, or both the bisque and sintering sections.

[0444]

[0462] In some embodiments, including any of the above, H2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0445]

[0463] In some embodiments, including any of the above, the ceramic layer is green and is a green tape.

[0446]

[0464] In some embodiments, including any of the above, the ceramic layer is green and is a patch coated green tape.

[0447]

[0465] In some embodiments, including any of the above, the bilayer is oriented for curtain processing as it travels through the process equipment.

[0448]

[0466] In some embodiments, including any of the above, the bilayer is positioned in a vertical processing orientation as it travels through the process equipment.

[0449]

[0467] In some embodiments, including any of the foregoing, the metal layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium, tungsten, molybdenum, alloys thereof, or combinations thereof.

[0450]

[0468] In some embodiments, including any of the above, the metal layer is an alloy of Fe and Ni.

[0451]

[0469] In some embodiments, including any of the above, the metal layer is an alloy of Fe and Ni, with the amount of Fe being 1% to 25% (w / w) and the remainder being Ni.

[0452]

[0470] In some embodiments, including any of the above, the metal layer has a thickness of 1 μm to 20 μm. In some embodiments, including any of the above, the bilayer is suspended as it advances through the sintering zone. In some embodiments, including any of the above, the processing equipment includes a sintered bilayer wrapped around at least one end roller. In some embodiments, including any of the above, the sintered bilayer includes a metal layer and a sintered oxide layer. In some embodiments, including any of the above, the sintered bilayer includes a metal layer and a lithium-loaded garnet sintered body layer. In some embodiments, including any of the above, the process equipment is configured to advance the bilayer through at least one furnace at a speed of at least 2 inches per minute. In some embodiments, including any of the above, the binder burnout zone and the sintering zone are positioned parallel to one another.

[0453]

[0471] In some embodiments, including any of the above, the binder burnout zone is located above the sintering zone.

[0454]

[0472] In some embodiments, including any of the above, the processing apparatus further comprises a second binder burnout zone.

[0455]

[0473] In some embodiments, including any of the above, the entire process apparatus is under vacuum.

[0456]

[0474] In some embodiments, described herein is a process for using a continuous process apparatus to perform the following operations: (a) producing a bilayer having an organic content of less than 1% by heating the green bilayer as it passes through at least one furnace; and (b) Winding a bilayer having an organic content of less than 1% onto a roller. A process including: In some embodiments, the present specification provides a process for using a continuous process apparatus to perform the following operations: (a) providing or having provided a process apparatus as described herein; (b) producing a bisque-fired bilayer by heating the bilayer as it advances through at least one furnace; and (c) Winding up the biscuit body A process including: In some embodiments including any of the above, the process further includes (d) unrolling the bisque fired bilayer. In some embodiments including any of the above, the process further includes (e) sintering the bilayer.

[0457]

[0475] In some embodiments, including any of the above, the process further includes winding the sintered bilayer onto end rollers.

[0458]

[0476] In some embodiments including any of the above, the sintered bilayer as cut strips.

[0459]

[0477] In some embodiments including any of the above, the bisque fired bilayer after step (c).

[0460]

[0478] In some embodiments, provided herein are biscuits prepared by the processes provided herein.

[0461]

[0479] In some embodiments, provided herein are sintered articles prepared by the processes provided herein.

[0462]

[0480] In some embodiments, provided herein is a biscuit bilayer comprising a lithium-loaded garnet, where the biscuit bilayer is wrapped around a roller and the bilayer is less than 100 μm thick.

[0463]

[0481] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 μm to 30 μm and the metal foil layer has a thickness of 2 μm to 10 μm.

[0464]

[0482] In some embodiments, provided herein is a sintered bilayer comprising a lithium-filled garnet, where the bilayer is wrapped around a roller and the bilayer is less than 100 μm thick.

[0465]

[0483] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 μm to 30 μm and the metal foil layer has a thickness of 2 μm to 10 μm.

[0466]

[0484] In some embodiments, including any of the foregoing, the metal foil layer comprises nickel, iron, or a combination thereof.

[0467]

[0485] In some embodiments, provided herein is a process for using a continuous process apparatus, the process comprising the following operations: (a) providing, or having provided, a process apparatus as described herein; and (b) producing a sintered bilayer by heating the bilayer as it advances through at least one furnace.

[0468]

[0486] In some embodiments, provided herein are sintered bilayers prepared by the above processes.

[0469]

[0487] In some embodiments, including any of the above, the process includes lithium-filled garnets.

[0470]

[0488] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet layer and a metal foil layer, where the lithium-filled garnet layer has a thickness of 10 μm to 30 μm and the metal foil layer has a thickness of 2 to 10 μm.

[0471]

[0489] In some embodiments, including any of the foregoing, the metal foil layer comprises nickel, iron, or a combination thereof.

[0472] I. Additional Embodiments

[0490] In at least one embodiment, provided herein is a process for making a sintered bilayer, the process comprising: providing a green bilayer comprising a green body layer and a metal layer under tension of 1 N to 300 N per meter of web width; creating a debound bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debound bilayer through a second heating zone; the debound bilayer is arch-shaped as it advances through the second heating zone; the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the temperature of the second heating zone is 1050°C to 1250°C; and the thickness of the sintered bilayer is less than 100 μm.

[0473]

[0491] In some embodiments, including any of the above, the tension is between 10 N and 200 N per meter of web width.

[0474]

[0492] In some embodiments, including any of the above, the tension is between 40N and 200N per meter of web width.

[0475]

[0493] In some embodiments, including any of the above, the tension is between 80N and 150N per meter of web width.

[0476]

[0494] In some embodiments, including any of the above, the tension is between 125N and 200N per meter of web width.

[0477]

[0495] In some embodiments, including any of the above, the green bilayer is under the described tension in the first heating zone.

[0478]

[0496] In some embodiments, including any of the foregoing, the debound bilayer is under the described tension in the second heating zone.

[0479]

[0497] In some embodiments, including any of the above, the tension in the first heating zone is different from the tension in the second heating zone.

[0480]

[0498] In some embodiments, including any of the above, the tension in the first heating zone is lower than the tension in the second heating zone.

[0481]

[0499] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 10N to 200N per meter of web width in the second heating zone.

[0482]

[0500] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 40N to 200N per meter of web width in the second heating zone.

[0483]

[0501] In some embodiments, including any of the above, the tension is 3N to 35N per meter of web width in the first heating zone; and 3N to 35N per meter of web width in the second heating zone. In certain examples, the tension is applied using a flat runway.

[0484]

[0502] In some embodiments, including any of the above, the tension is 125 N to 250 N per meter of web width in the first heating zone; and 40 N to 190 N per meter of web width in the second heating zone. In certain examples, the tension is applied using an arch-shaped runway. In certain examples, the arch shape has a radius of curvature of 3 to 5 meters.

[0485]

[0503] In some embodiments, including any of the above, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0486]

[0504] The process of any preceding embodiment, further comprising cooling the sintered bilayer. In certain examples, the process comprises cooling the sintered bilayer to room temperature.

[0487]

[0505] In some embodiments, including any of the above, the green body layer includes ceramic powder and a binder.

[0488]

[0506] In some embodiments, including any of the foregoing, the sintered bilayer includes a sintered oxide layer.

[0489]

[0507] In some embodiments, including any of the foregoing, the sintered bilayer includes a lithium-filled garnet sintered body.

[0490]

[0508] In some embodiments, including any of the above, the metal layer comprises nickel, iron, or an alloy thereof.

[0491]

[0509] In some embodiments, including any of the above, the metal layer has a thickness of 1 μm to 10 μm.

[0492]

[0510] In some embodiments, including any of the above, the sintered oxide layer has a thickness of 5 μm to 40 μm.

[0493]

[0511] In some embodiments, including any of the above, the width of the sintered bilayer is 300 mm or less.

[0494]

[0512] In some embodiments, including any of the above, the width of the sintered bilaminate is at least 0.5 μm.

[0495]

[0513] In some embodiments, including any of the above, the sintered bilaminate has a length of at least 1 meter.

[0496]

[0514] In some embodiments, including any of the above, the length of the sintered bilayer is less than 500 meters.

[0497]

[0515] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 1 cm / min and 200 cm / min.

[0498]

[0516] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 5 cm / min and 100 cm / min through the second heated zone.

[0499]

[0517] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 8 cm / min and 80 cm / min.

[0500]

[0518] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 20 cm / min and 80 cm / min.

[0501]

[0519] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 80 cm / min.

[0502]

[0520] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of between 0.5 meters and 4.0 meters.

[0503]

[0521] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0504]

[0522] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0505]

[0523] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0506]

[0524] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0507]

[0525] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 4.0 meters.

[0508]

[0526] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0509]

[0527] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0510]

[0528] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0511]

[0529] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0512]

[0530] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of 5.0 meters.

[0513]

[0531] In some embodiments, including any of the above, at least one runway provides an arch shape, meaning that the runway is used with tension to bend the bilayer into an arch shape.

[0514]

[0532] In some embodiments, including any of the above, at least one roller provides an arched shape, meaning that at least one or more rollers are used with tension to bend the bilayer into an arched shape.

[0515]

[0533] In some embodiments, including any of the above, at least one speed bump provides an arched shape, meaning that at least one or more speed bumps are used with tension that causes the bilayer to bend into an arched shape.

[0516]

[0534] In some embodiments, including any of the above, the first heating zone is 60 inches long.

[0517]

[0535] In some embodiments, including any of the above, the second heating zone is 60 inches long.

[0518]

[0536] In some embodiments, including any of the above, the debinding bilayer is in the second heating zone for about 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds.

[0519]

[0537] In some embodiments, including any of the above, the green bilayer advances horizontally through the first heating zone.

[0520]

[0538] In some embodiments, including any of the above, the green bilayer travels vertically through the first heating zone.

[0521]

[0539] In yet another embodiment, provided herein is a process for making a sintered bilayer, comprising: providing a green bilayer comprising a green body layer and a metal layer; creating a debound bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debound bilayer through a second heating zone; wherein the debound bilayer is arch-shaped as it advances through the second heating zone; the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the temperature of the second heating zone is 1050°C to 1250°C; and the thickness of the sintered bilayer is less than 100 μm.

[0522]

[0540] In some embodiments, including any of the above, the tension is between 10 N and 200 N per meter of web width.

[0523]

[0541] In some embodiments, including any of the above, the tension is between 40N and 200N per meter of web width.

[0524]

[0542] In some embodiments, including any of the above, the tension is between 80N and 150N per meter of web width.

[0525]

[0543] In some embodiments, including any of the above, the tension is between 125N and 200N per meter of web width.

[0526]

[0544] In some embodiments, including any of the above, the tension is between 150N and 200N per meter of web width.

[0527]

[0545] In some embodiments, including any of the above, the tension is between 180N and 200N per meter of web width.

[0528]

[0546] In some embodiments, including any of the above, the green bilayer is under the described tension in the first heating zone.

[0529]

[0547] In some embodiments, including any of the foregoing, the debound bilayer is under the described tension in the second heating zone.

[0530]

[0548] In some embodiments, including any of the above, the tension in the first heating zone is different from the tension in the second heating zone.

[0531]

[0549] In some embodiments, including any of the above, the tension in the first heating zone is lower than the tension in the second heating zone.

[0532]

[0550] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 10N to 200N per meter of web width in the second heating zone.

[0533]

[0551] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 40N to 200N per meter of web width in the second heating zone.

[0534]

[0552] In some embodiments, including any of the above, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0535]

[0553] The process of any preceding embodiment, further comprising cooling the sintered bilayer. In certain instances, the process comprises cooling the sintered bilayer to room temperature.

[0536]

[0554] In some embodiments, including any of the above, the green body layer includes ceramic powder and a binder.

[0537]

[0555] In some embodiments, including any of the foregoing, the sintered bilayer includes a sintered oxide layer.

[0538]

[0556] In some embodiments, including any of the foregoing, the sintered bilayer includes a lithium-filled garnet sintered body.

[0539]

[0557] In some embodiments, including any of the above, the metal layer comprises nickel, iron, or an alloy thereof.

[0540]

[0558] In some embodiments, including any of the above, the metal layer has a thickness of 1 μm to 10 μm.

[0541]

[0559] In some embodiments, including any of the above, the sintered oxide layer has a thickness of 5 μm to 40 μm.

[0542]

[0560] In some embodiments, including any of the above, the width of the sintered bilayer is 300 mm or less.

[0543]

[0561] In some embodiments, including any of the above, the width of the sintered bilaminate is at least 0.5 μm.

[0544]

[0562] In some embodiments, including any of the above, the sintered bilaminate has a length of at least 1 meter.

[0545]

[0563] In some embodiments, including any of the above, the length of the sintered bilayer is less than 500 meters.

[0546]

[0564] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 1 cm / min and 200 cm / min.

[0547]

[0565] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 5 cm / min and 100 cm / min through the second heated zone.

[0548]

[0566] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 8 cm / min and 80 cm / min.

[0549]

[0567] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 20 cm / min and 80 cm / min.

[0550]

[0568] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 80 cm / min.

[0551]

[0569] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of between 0.5 meters and 4.0 meters.

[0552]

[0570] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0553]

[0571] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0554]

[0572] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0555]

[0573] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0556]

[0574] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 4.0 meters.

[0557]

[0575] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0558]

[0576] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0559]

[0577] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0560]

[0578] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0561]

[0579] In some embodiments, including any of the above, at least one runway provides an arch shape.

[0562]

[0580] In some embodiments, including any of the above, at least one roller provides an arched shape.

[0563]

[0581] In some embodiments, including any of the above, at least one speed bump provides an arched shape.

[0564]

[0582] In some embodiments, including any of the above, the first heating zone is 60 inches long.

[0565]

[0583] In some embodiments, including any of the above, the second heating zone is 60 inches long.

[0566]

[0584] In some embodiments, including any of the above, the debinding bilayer may be dehydrated in about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 61 seconds, 62 seconds, 63 seconds, 64 seconds, 65 seconds, 66 seconds, 67 seconds, 68 seconds, 69 seconds, 70 seconds, 71 seconds, 72 seconds, 73 seconds, 74 seconds, 75 seconds, 76 seconds, 77 seconds, 78 seconds, 79 seconds, 80 seconds, 81 seconds, 82 seconds, 83 seconds, 84 seconds, 85 seconds, 86 seconds, 87 seconds, 88 seconds, 89 seconds, 90 seconds, 91 seconds, 92 seconds, 93 seconds, 94 seconds, 95 seconds, 96 seconds, 97 seconds, 98 seconds, 99 seconds, 10 In the second heating zone for 1 second, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds.

[0567]

[0585] In some embodiments, including any of the above, the green bilayer advances horizontally through the first heating zone.

[0568]

[0586] In some embodiments, including any of the above, the green bilayer travels vertically through the first heating zone.

[0569]

[0587] In yet another embodiment, provided herein is a process for making a sintered bilayer, comprising: providing a green bilayer comprising a green body layer and a metal layer under tension of 1 N to 300 N per meter of web width; advancing the green bilayer through a first heating zone to create a debound bilayer; and advancing the debound bilayer through a second heating zone to prepare a sintered bilayer; wherein the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the temperature of the second heating zone is 1050°C to 1250°C; and the thickness of the sintered bilayer is less than 100 μm.

[0570]

[0588] In some embodiments, including any of the above, the debound bilayer is arch-shaped as it travels through the second heating zone.

[0571]

[0589] In some embodiments, including any of the foregoing, the debound bilayer is in a flat shape as it passes through the second heating zone.

[0572]

[0590] In some embodiments, including any of the above, the tension is between 3N and 100N per meter of web width.

[0573]

[0591] In some embodiments, including any of the above, the tension is between 3N and 80N per meter of web width.

[0574]

[0592] In some embodiments, including any of the above, the tension is between 3N and 50N per meter of web width.

[0575]

[0593] In some embodiments, including any of the above, the tension is between 3N and 35N per meter of web width.

[0576]

[0594] In some embodiments, including any of the above, the tension is between 3N and 30N per meter of web width.

[0577]

[0595] In some embodiments, including any of the above, the tension is between 10N and 20N per meter of web width.

[0578]

[0596] In some embodiments, including any of the above, the green bilayer is under the described tension in the first heating zone.

[0579]

[0597] In some embodiments, including any of the foregoing, the debound bilayer is under the described tension in the second heating zone.

[0580]

[0598] In some embodiments, including any of the above, the tension in the first heating zone is different from the tension in the second heating zone.

[0581]

[0599] In some embodiments, including any of the above, the tension in the first heating zone is lower than the tension in the second heating zone.

[0582]

[0600] In some embodiments, including any of the above, the tension is 3N to 50N per meter of web width in the first heating zone; and 3N to 50N per meter of web width in the second heating zone.

[0583]

[0601] In some embodiments, including any of the above, the tension is 3N to 35N per meter of web width in the first heating zone; and 3N to 35N per meter of web width in the second heating zone.

[0584]

[0602] In some embodiments, including any of the above, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0585]

[0603] The process of any preceding embodiment, further comprising cooling the sintered bilayer. In certain instances, the process comprises cooling the sintered bilayer to room temperature.

[0586]

[0604] In some embodiments, including any of the above, the green body layer includes ceramic powder and a binder.

[0587]

[0605] In some embodiments, including any of the foregoing, the sintered bilayer includes a sintered oxide layer.

[0588]

[0606] In some embodiments, including any of the foregoing, the sintered bilayer includes a lithium-filled garnet sintered body.

[0589]

[0607] In some embodiments, including any of the above, the metal layer comprises nickel, iron, or an alloy thereof.

[0590]

[0608] In some embodiments, including any of the above, the metal layer has a thickness of 1 μm to 10 μm.

[0591]

[0609] In some embodiments, including any of the above, the sintered oxide layer has a thickness of 5 μm to 40 μm.

[0592]

[0610] In some embodiments, including any of the above, the width of the sintered bilayer is 300 mm or less.

[0593]

[0611] In some embodiments, including any of the above, the width of the sintered bilaminate is at least 0.5 μm.

[0594]

[0612] In some embodiments, including any of the above, the sintered bilaminate has a length of at least 1 meter.

[0595]

[0613] In some embodiments, including any of the above, the length of the sintered bilayer is less than 500 meters.

[0596]

[0614] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 1 cm / min and 200 cm / min.

[0597]

[0615] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 5 cm / min and 100 cm / min through the second heated zone.

[0598]

[0616] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 8 cm / min and 80 cm / min.

[0599]

[0617] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 20 cm / min and 80 cm / min.

[0600]

[0618] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 80 cm / min.

[0601]

[0619] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of between 0.5 meters and 4.0 meters.

[0602]

[0620] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0603]

[0621] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, 4.0 meters, or 5.0 meters.

[0604]

[0622] In some embodiments, including any of the above, the debinding bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0605]

[0623] In some embodiments, including any of the above, the debinding bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0606]

[0624] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 6.0 meters.

[0607]

[0625] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 4.0 meters.

[0608]

[0626] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0609]

[0627] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, 4.0 meters, or 5.0 meters.

[0610]

[0628] In some embodiments, including any of the above, the green bilayer is an arch shape characterized by a radius of curvature of 1 meter.

[0611]

[0629] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0612]

[0630] In some embodiments, including any of the above, the green bilayer is arch-shaped characterized by a radius of curvature of 5.0 meters.

[0613]

[0631] In some embodiments, including any of the above, at least one runway provides an arch shape.

[0614]

[0632] In some embodiments, including any of the above, at least one roller provides an arched shape.

[0615]

[0633] In some embodiments, including any of the above, at least one speed bump provides an arched shape.

[0616]

[0634] In some embodiments, including any of the above, the first heating zone is 60 inches long.

[0617]

[0635] In some embodiments, including any of the above, the second heating zone is 60 inches long.

[0618]

[0636] In some embodiments, including any of the above, the debinding bilayer may be dehydrated in about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 61 seconds, 62 seconds, 63 seconds, 64 seconds, 65 seconds, 66 seconds, 67 seconds, 68 seconds, 69 seconds, 70 seconds, 71 seconds, 72 seconds, 73 seconds, 74 seconds, 75 seconds, 76 seconds, 77 seconds, 78 seconds, 79 seconds, 80 seconds, 81 seconds, 82 seconds, 83 seconds, 84 seconds, 85 seconds, 86 seconds, 87 seconds, 88 seconds, 89 seconds, 90 seconds, 91 seconds, 92 seconds, 93 seconds, 94 seconds, 95 seconds, 96 seconds, 97 seconds, 98 seconds, 99 seconds, 10 In the second heating zone for 1 second, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds.

[0619]

[0637] In some embodiments, including any of the above, the green bilayer advances horizontally through the first heating zone.

[0620]

[0638] In some embodiments, including any of the above, the green bilayer travels vertically through the first heating zone.

[0621]

[0639] In another embodiment, the present specification provides a process for sintering a bilayer body, comprising: providing a bilayer body under a tension of 1 N to 300 N; the bilayer body having a thickness of 1 μm to 100 μm; the bilayer body comprising a ceramic-containing layer disposed on a metal layer; and sintering the bilayer body at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0622]

[0640] In some embodiments, including any of the above, the ceramic layer comprises ceramic powder.

[0623]

[0641] In some embodiments, including any of the above, the ceramic layer comprises a sintered ceramic.

[0624]

[0642] In some embodiments, including any of the above, the ceramic layer comprises a lithium-filled garnet.

[0625]

[0643] In some embodiments, including any of the above, the metal layer is nickel foil.

[0626]

[0644] In some embodiments, including any of the above, the thickness of the bilaminate is between 1 μm and 50 μm.

[0627]

[0645] In some embodiments, including any of the above, the ceramic layer has a thickness of less than 25 μm.

[0628]

[0646] In some embodiments, including any of the above, the metal layer has a thickness of less than 25 μm.

[0629]

[0647] In some embodiments, including any of the above, the width of the bilayer is 300 mm or less.

[0630]

[0648] In some embodiments, including any of the above, the length of the bilayer is at least 1 meter long.

[0631]

[0649] In some embodiments, including any of the above, the bilaminate is sintered at about 1100°C to about 1200°C.

[0632]

[0650] In some embodiments, including any of the above, the bilayer travels at a speed of about 5 cm / min to about 100 cm / min.

[0633]

[0651] In some embodiments, including any of the above, the bilayer is placed on a flat runway.

[0634]

[0652] In some embodiments, including any of the above, the bilayer is positioned on a curved runway.

[0635]

[0653] In some embodiments, including any of the above, the tension is between 10 N and 200 N per meter of web width.

[0636]

[0654] In some embodiments, including any of the above, the tension is between 40N and 200N per meter of web width.

[0637]

[0655] In some embodiments, including any of the above, the tension is between 80N and 150N per meter of web width.

[0638]

[0656] In some embodiments, including any of the above, the tension is between 125N and 200N per meter of web width.

[0639]

[0657] In some embodiments, including any of the foregoing, the bilayer is under the described tension as it travels through the first heating zone.

[0640]

[0658] In some embodiments, including any of the foregoing, the bilayer is under the described tension as it passes through the second heated zone.

[0641]

[0659] In some embodiments, including any of the above, the tension in the first heating zone is different from the tension in the second heating zone.

[0642]

[0660] In some embodiments, including any of the above, the tension in the first heating zone is lower than the tension in the second heating zone.

[0643]

[0661] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 10N to 200N per meter of web width in the second heating zone.

[0644]

[0662] In some embodiments, including any of the above, the tension is 125N to 250N per meter of web width in the first heating zone; and 40N to 200N per meter of web width in the second heating zone.

[0645]

[0663] In some embodiments, including any of the above, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0646]

[0664] The process of any preceding embodiment, further comprising cooling the bilayer. In certain instances, the process comprises cooling the bilayer to room temperature.

[0647]

[0665] In some embodiments, including any of the foregoing, the bi-layer body includes a green body layer that includes ceramic powder and a binder.

[0648]

[0666] In some embodiments, including any of the above, the bilayer includes a sintered oxide layer.

[0649]

[0667] In some embodiments, including any of the above, the bilayer comprises a lithium-filled garnet sintered body.

[0650]

[0668] In some embodiments, including any of the above, the metal layer comprises nickel, iron, or an alloy thereof.

[0651]

[0669] In some embodiments, including any of the above, the metal layer has a thickness of 1 μm to 10 μm.

[0652]

[0670] In some embodiments, including any of the above, the sintered oxide layer has a thickness of 5 μm to 40 μm.

[0653]

[0671] In some embodiments, including any of the above, the width of the sintered bilayer is 300 mm or less.

[0654]

[0672] In some embodiments, including any of the above, the width of the sintered bilaminate is at least 0.5 μm.

[0655]

[0673] In some embodiments, including any of the foregoing, the sintered bilaminate has a length of at least 1 meter. In some cases, the sintered bilaminate has a length of at least 2 meters. In some cases, the sintered bilaminate has a length of at least 3 meters. In some cases, the sintered bilaminate has a length of at least 4 meters. In some cases, the sintered bilaminate has a length of at least 5 meters. In some cases, the sintered bilaminate has a length of at least 6 meters. In some cases, the sintered bilaminate has a length of at least 7 meters. In some cases, the sintered bilaminate has a length of at least 8 meters. In some cases, the sintered bilaminate has a length of at least 9 meters. In some cases, the sintered bilaminate has a length of at least 10 meters. In some cases, the sintered bilaminate has a length of at least 20 meters. In some cases, the sintered bilaminate has a length of at least 30 meters. In some cases, the sintered bilaminate has a length of at least 40 meters. In some cases, the sintered bilaminate has a length of at least 50 meters. In some cases, the sintered bilaminate has a length of at least 60 meters. In some cases, the length of the sintered bilaminate is at least 70 meters. In some cases, the length of the sintered bilaminate is at least 80 meters. In some cases, the length of the sintered bilaminate is at least 90 meters. In some cases, the length of the sintered bilaminate is at least 100 meters.

[0656]

[0674] In some embodiments, including any of the above, the length of the sintered bilayer is less than 500 meters.

[0657]

[0675] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 1 cm / min and 200 cm / min.

[0658]

[0676] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of between 5 cm / min and 100 cm / min through the second heated zone.

[0659]

[0677] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 8 cm / min and 80 cm / min.

[0660]

[0678] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of between 20 cm / min and 80 cm / min.

[0661]

[0679] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 10 cm / min.

[0662]

[0680] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 20 cm / min.

[0663]

[0681] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 30 cm / min.

[0664]

[0682] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 40 cm / min.

[0665]

[0683] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 50 cm / min.

[0666]

[0684] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 60 cm / min.

[0667]

[0685] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 70 cm / min.

[0668]

[0686] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 80 cm / min.

[0669]

[0687] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 90 cm / min.

[0670]

[0688] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 100 cm / min.

[0671]

[0689] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 110 cm / min.

[0672]

[0690] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 120 cm / min.

[0673]

[0691] In some embodiments, including any of the above, the bilayer advances through the second heating zone at a speed of about 130 cm / min.

[0674]

[0692] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 140 cm / min.

[0675]

[0693] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 150 cm / min.

[0676]

[0694] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 160 cm / min.

[0677]

[0695] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 170 cm / min.

[0678]

[0696] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 180 cm / min.

[0679]

[0697] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a speed of about 190 cm / min.

[0680]

[0698] In some embodiments, including any of the above, the bilayer advances through the second heated zone at a rate of about 200 cm / min.

[0681]

[0699] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 6.0 meters.

[0682]

[0700] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature between 0.5 meters and 4.0 meters.

[0683]

[0701] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature of between 2.0 meters and 4.0 meters.

[0684]

[0702] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature between 2.0 meters and 6.0 meters.

[0685]

[0703] In some embodiments, including any of the above, the bilayer is arched in shape characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, 4.0 meters, or 5.0 meters.

[0686]

[0704] In some embodiments, including any of the above, the bilayer is arched in shape characterized by a radius of curvature of 1 meter.

[0687]

[0705] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature of 3.8 meters.

[0688]

[0706] In some embodiments, including any of the above, the bilayer is arch-shaped characterized by a radius of curvature of 5.0 meters.

[0689]

[0707] In some embodiments, including any of the above, at least one runway provides an arch shape.

[0690]

[0708] In some embodiments, including any of the above, at least one roller provides an arched shape.

[0691]

[0709] In some embodiments, including any of the above, at least one speed bump provides an arched shape.

[0692]

[0710] In some embodiments, including any of the above, the first heating zone is 60 inches long.

[0693]

[0711] In some embodiments, including any of the above, the second heating zone is 60 inches long.

[0694]

[0712] In some embodiments, including any of the above, the bilayer may be heated for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, In the second heating zone for 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds.

[0695]

[0713] In some embodiments, including any of the above, the bilayer travels horizontally through the first heating zone.

[0696]

[0714] In some embodiments, including any of the above, the bilayer travels vertically through the first heating zone.

[0697]

[0715] In a further embodiment, the present specification provides a sintering process for a bilayer body, comprising: providing a bilayer body under a tension of 5N to 100N; the bilayer body having a thickness of 1 μm to 100 μm; the bilayer body comprising a layer comprising a ceramic disposed on a metal layer; and sintering the bilayer body into an arch shape at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0698]

[0716] In another embodiment, the present specification provides a sintering process for a bilayer body, the process including providing a bilayer body; the bilayer body having a thickness of 1 μm to 100 μm; the bilayer body including a layer including a ceramic disposed on a metal layer; and sintering the bilayer body into an arch shape at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0699]

[0717] In some embodiments, including any of the above, the bilayer is under tension of 5N to 100N.

[0700]

[0718] In some embodiments, including any of the above, the radius of curvature of the bilayer is between 2 meters and 4 meters.

[0701]

[0719] In some embodiments, including any of the above, the radius of curvature of the bilayer is between 2 meters and 6 meters.

[0702]

[0720] In some embodiments, including any of the above, the ceramic layer comprises ceramic powder and a binder.

[0703]

[0721] In some embodiments, including any of the above, the ceramic layer comprises a sintered ceramic.

[0704]

[0722] In some embodiments, including any of the above, the ceramic layer is a lithium-filled garnet sintered body.

[0705]

[0723] In some embodiments, including any of the above, the metal layer is nickel foil.

[0706]

[0724] In some embodiments, including any of the above, the thickness of the bilaminate is between 1 μm and 50 μm.

[0707]

[0725] In some embodiments, including any of the above, the ceramic layer has a thickness of less than 25 μm.

[0708]

[0726] In some embodiments, including any of the above, the metal layer has a thickness of less than 10 μm.

[0709]

[0727] In some embodiments, including any of the above, the width of the bilayer is 300 mm or less.

[0710]

[0728] In some embodiments, including any of the above, the length of the bilayer is at least 1 meter long.

[0711]

[0729] In some embodiments, including any of the above, the bilaminate is sintered at about 1100°C to about 1200°C.

[0712]

[0730] In some embodiments, including any of the above, the bilayer travels at a speed of between about 5 cm / min and 80 cm / min.

[0713]

[0731] In some embodiments, including any of the above, the bilayer is positioned on a curved runway. [Example]

[0714] J. Working Example

[0732] The solvents used herein, unless otherwise specified, are selected from alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, and other classes of organic solvents such as ethers and aromatic solvents, including but not limited to dibutyl ether, diethyl ether, diisopropyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, toluene, xylene, toluene:ethanol, acetone, N-methyl-2-pyrrolidone (NMP) diacetone alcohol, ethyl acetate, acetonitrile, hexane, nonane, dodecane, and methyl ethyl ketone (MEK).

[0715]

[0733] Reagents, chemicals, and materials were purchased commercially unless otherwise specified.

[0716]

[0734] The pouch cell container was purchased from Showa Denko.

[0717]

[0735] The electrochemical potentiostat used was an Arbin potentiostat.

[0718]

[0736] Electrical impedance spectroscopy (EIS) was performed on a Biologic VMP3, VSP, VSP-300, SP-150, or SP-200.

[0719]

[0737] Electron microscopy was performed on an FEI Quanta SEM, Apreo SEM, Helios 600i, or Helios 660 FIB-SEM.

[0720]

[0738] Powder X-ray diffraction (XRD) was performed on a Bruker D8 Advance A25 using Cu K-α radiation at room temperature (e.g., 21°C to 23°C). The radiation source was Cu-Ka, wavelength 1.54 Å. The X-rays were 40 kV and 25 mA. The detector was a LYNXEYE_XE with a PSD aperture of 2.843. The divergence slit was fixed at 0.6 mm and the anti-scatter filter was fixed at 5.0 mm.

[0721]

[0739] Milling was performed using a Retsch PM 400 planetary ball mill. Mixing was performed using a Fischer Scientific vortex mixer, a Flaktek speed mixer, or a Primix filmix homogenizer unless otherwise specified.

[0722]

[0740] Casting was performed on a TQC drawdown table. Calendering was performed on an IMC calender unless otherwise specified.

[0723]

[0741] The light scattering method was carried out using a Horiba, Model: Partica, Model Number: LA-950V2, generic name: laser scattering particle size distribution analyzer.

[0724]

[0742] The lithium nickel cobalt manganese oxide (NMC) used in this example was LiNi 0.85 Co 0.1 Mn 0.05 It was O2.

[0725] Example 1 - Preparation of Sintered Rolls - Hypothetical Example

[0743] In this example, a slurry may be prepared by mixing the lithium-loaded garnet, solvent, binder, and plasticizer. The following slurry composition may be used:

[0726]

[0744] Slurry 1: LLZO powder may be dispersed in ethanol containing 2 wt% polyacrylic acid using an ultrasonic horn. Large particles may be allowed to settle. The supernatant may be decanted, and the collected powder may be air-dried. The collected powder, polyvinyl butyral, benzyl butyl phthalate, acetone, and ethanol may be added to a vial in a weight ratio of 37:3:3:29:29 and milled in a ball mill with 2.0 mm diameter ZrO2 beads for 10 to 24 hours. The slurry may be cast onto a metal substrate using a doctor blade; the film thickness may be controlled by adjusting the blade height. This green film may be dried and wound onto a core of at least 8 cm diameter.

[0727]

[0745] Slurry 2: LLZO powder may be dispersed in ethanol with 3 weight percent (wt%) polyacrylic acid. A second solution of polyvinyl butyral, benzyl butyl phthalate, and acetone may be mixed in a 1:1:10 weight ratio. The second solution may be mixed with the first solution in equal volume parts. The resulting slurry may be milled with ZrO2 beads for 8 to 16 hours. A doctor blade may be used to cast the slurry onto a metal substrate with a thickness controlled by the doctor blade height. The green film may be dried and wound onto a core with a diameter of at least 8 cm.

[0728]

[0746] Slurry 3: An aqueous polymer solution may be prepared by dissolving methylcellulose, polyethylene glycol, and glycerol in water. The weight ratio of the components may be water:methylcellulose:polyethylene glycol:glycerol=100:1:4:4. LLZO (lithium-loaded garnet) powder may be added to the polymer solution in an amount equal to the weight of the solution. The slurry may be mixed with ZrO2 beads for 5 to 60 minutes. The slurry may be cast onto a metal foil with a doctor blade; the thickness may be controlled by the gap of the doctor blade. The green film may be dried and wound onto a core of at least 8 cm diameter.

[0729]

[0747] Slurry 4: LLZO was ball-milled in a mixture of equal parts ethanol, xylene, and toluene. 2-5 wt% menhaden oil relative to LLZO may be added dropwise over 30 minutes. 6-10 wt% polyvinyl butyral relative to LLZO, 2-4 wt% polyethylene glycol relative to LLZO, and 3-7 wt% benzyl butyl phthalate relative to LLZO may be added and mixed. A tape may be cast onto a metal substrate with a doctor blade. After drying at 45°C for 1-6 hours, the tape may be wound onto a core of at least 8 cm diameter.

[0730]

[0748] Slurry 5: A slurry may be prepared by mixing 100 g of LLZO powder, 2-4 g of glyceryl trioleate, 100-200 g of n-propyl propionate, and 15-25 g of elvacite E-2046, followed by ball milling. The slurry may be cast onto a metal foil substrate with a doctor blade, dried, and wound up.

[0731]

[0749] Slurry 6: A slurry can be prepared by mixing 20 g of LLZO powder, 25-40 g of a solvent mixture (ethanol:butanol:propylene glycol in a volume percentage range of 70-80:15-25:0-5), 1-3 g of dibutyl phthalate, 1-4 g of PVB, and 0.1-1 g of a dispersant in a mill. The dispersant can be a dispersant such as Anti-terra-202 from BYK. After mixing, the slurry can be filtered, degassed, and cast onto a metal substrate by comma coating. The green tape can be dried and wound up.

[0732]

[0750] Slurry 7: A slurry can be produced by mixing water (30 parts by weight), LLZO powder (12-18 parts by weight), and binder solution (8 parts by weight of WB4101, WB40B-44, and WB40B-53 from Polymer Innovations) in a mill for at least 1 hour. After mixing, the slurry can be filtered, degassed, and cast onto a metal substrate by slot die coating. The green tape can be dried and wound up.

[0733]

[0751] Slurry 8: LLZO powder may be milled in a solvent mixture of toluene and isopropanol plus fish oil. This mixture may be mixed for 1-5 hours to prepare a slurry. Toluene and isopropanol may be mixed with a binder solution of polyvinyl butyral and butyl benzyl phthalate. This binder solution may be added to the slurry and mixed. The mixture may be degassed, filtered, and cast onto a metal support. The green tape may be dried and wound up.

[0734]

[0752] Slurry 9: A slurry of calcined LLZO may be prepared by mixing 80 g of calcined LLZO powder with 50 ml of a 33% w / w solution of polyvinyl butyral in toluene and 4 g of the plasticizer dibutyl phthalate. A polyacrylic acid binder may be included at 3 weight percent of the solution. This slurry may be tape-cast onto a metal substrate using a doctor blade. The cast mixed slurry may be allowed to dry at room temperature for 2 to 6 hours to form a green film. The dried green film may be wound onto a core of at least 8 cm diameter.

[0735]

[0753] After drying, the dried slurry on the nickel foil can be placed on a continuous processing device.

[0736]

[0754] The first step may involve heating the green bilayer to burn off the binder, producing a de-bindered bilayer.

[0737]

[0755] In a second step, the green tape may be heated in a biscuit oven to produce a biscuit bilayer.

[0738]

[0756] In a third step, the green tape may be sintered at about 1100° C. to form a sintered bilayer.

[0739]

[0757] The sintered bilaminate film can be rolled onto end rollers, or the sintered bilaminate can be cut into sheets.

[0740]

[0758] In the second processing equipment, the green bilayer body may be moved back and forth between a biscuit oven and a binder burnout oven. These ovens may be switched on and off to selectively heat the film in either the biscuit oven or the binder burnout oven. Sintering may involve increasing the temperature of the biscuit oven to the sintering temperature.

[0741] Example 2 - Preparation of Sintered Rolls - Hypothetical Example

[0759] In this example, a slurry may be produced by mixing the lithium-loaded garnet, solvent, binder, and plasticizer.

[0742]

[0760] Specifically, the lithium-loaded garnet may be mixed with an acrylic binder and benzyl butyl phthalate in an aprotic solvent to form a slurry. The slurry may be cast onto a Ni foil to form a bilayer. The slurry may be dried and then rolled into a roll.

[0743]

[0761] After drying, the dried slurry on the nickel foil can be placed on a continuous production line. Once the slurry dries on the nickel foil, a green bilayer can be formed. This tape can then be run through an apparatus.

[0744]

[0762] The bilaminate may be advanced through the processing equipment at 5 cm / min and held at about 1100° C. for about 10 minutes in the sintering section.

[0745] Example 3 - Preparation of Controlled Grain and Particle Size Debinding Roll

[0763] Lithium-loaded garnet powder (d 50Slurries were prepared by dispersing 1000 μm (<1 μm) of 1000 μm-sized ceramic powder with a solvent, binder, and plasticizer (where the binder and plasticizer content was 8–20 wt% of the solids). Xylene was added to control the viscosity in the range of 50–1000 cP at a shear rate of 20 Hz. The slurries were cast onto nickel foil 60–150 mm wide using a comma coater with a fixed gap distance of 200–400 μm. The bilayers were dried and rolled around cores with a diameter of approximately 9 cm. The thickness of the green ceramic layer was 50–80 μm; the thickness of the metal layer was 5–15 μm. The rolls were transferred to a processing unit, unwound, and fed at a rate of 5–20 cm / min through temperature zones configured for debinding (i.e., removal of the binder therefrom). The temperature zone was set at 600-900°C, where the atmosphere was configured to remove burnout organic by-products and reduce lithium loss. After debinding, the product was rolled into a roll. The rolls of debound bilayer material were stored for later sintering, testing, and analysis.

[0746] Example 4 - Preparation of controlled grain and particle size clay rolls

[0764] Lithium-loaded garnet powder (d 50 Slurries were prepared by dispersing the green ceramic (<1 μm) with solvent, binder, and plasticizer (where the binder and plasticizer contents were 8 wt% to 20 wt% of the solids). Solvent was added to control the viscosity in the range of 50 to 1000 cP at a shear rate of 20 Hz. The slurry was cast onto metal foil with a width of 60 mm to 150 mm using a comma coater with a fixed gap distance of 200 μm to 400 μm. The bilayer was dried and rolled around a core with a diameter of approximately 9 cm. The thickness of the green ceramic layer was 50 μm to 80 μm; the thickness of the metal layer was 5 μm to 15 μm. The rolls were transferred to a processing device, unwound, and fed at a rate of 5 cm / min to 20 cm / min through temperature zones configured for debinding of the bilayer. The temperature zone was set at 600-900°C, where the atmosphere was configured to remove burnout organic products and reduce lithium loss.

[0747] Example 5 - Preparation of controlled grain and particle size sintered rolls

[0765] Lithium-loaded garnet powder (d 50 Slurries were prepared by dispersing granular particles (<1 μm) with solvent, binder, and plasticizer (where the binder and plasticizer contents were 8–20 wt% of the solids). Solvent was added to control the viscosity in the range of 50–1000 cP at a shear rate of 20 Hz. The slurries were cast onto metal foils 60–150 mm wide using a comma coater with a fixed gap distance of 200–400 μm. The bilayers were dried and rolled around cores approximately 9 cm in diameter. The thickness of the green ceramic layer was 50–80 μm; the thickness of the metal layer was 5–15 μm. The rolls were transferred to a processing apparatus, unwound, and fed at a rate of 5–20 cm / min through temperature zones configured for debinding, bisque firing, and sintering the bilayers. The temperature zone was set at 600-1300°C, where the atmosphere was configured to remove burnout organic products and reduce lithium loss. After sintering, the product was rolled into a roll. The roll of sintered bilayer material was stored for later testing and analysis.

[0748] Example 6 - Testing of sintered rolls

[0766] Sintered films were produced as in Example 5. The area-specific resistance (ASR) was measured by current interruption measurement.

[0749]

[0767] Separator cut from a roll of sintered membrane and 3mAh / cm 2 Load capacity of NMC(Li(Ni 1-x-y Mn x Co y )O2) A battery cell was fabricated from a cathode of the active material. 0.33 mA / cm 2The battery was charged and discharged at 30°C using intermittent current pulses with a constant current density of 1000 kJ / s and an operating voltage range of 3 V to 4.2 V. The current pulses were applied for 30 minutes, the current was stopped, and the system was allowed to relax in an open-circuit state for 3 minutes. This intermittent pulse was repeated until the cell voltage reached 4.2 V during charging and 3 V during discharging. The area-specific resistance (ASR) of the battery cell was determined by reading the voltage drop during the relaxation step during charging. The ASR was 15 to 25 Ω cm at 30°C. 2 was measured.

[0750] Example 7 - Preparation and testing of sintered bilayers

[0768] Sintered bilayer films were prepared as in Example 5. Specifically, lithium-loaded garnet was mixed with an acrylic binder and benzyl butyl phthalate in an aprotic solvent to form a slurry. This slurry was cast onto Ni foil to form a bilayer.

[0751]

[0769] The bilayer (referred to as web) web was advanced through the CML at 5 cm / min and held at about 1100° C. for about 10 minutes in the sintering section.

[0752]

[0770] 30 x 30 mm bilayer separator cut from sintered roll and 3.1 mAh / cm 2 A battery was assembled with a cathode of NMC active material at a load capacity. The cathode was infiltrated with a catholyte or cathode gel containing a lithium salt and a solvent to dissolve the salt. The cell was cycled at 30°C and 50 pounds per square inch (PSI) (approximately 3.4 atm) at a 1C charge / 1C discharge rate. The cell retained more than 90% of its initial capacity after 800 cycles at 100% depth of discharge. See Figure 13.

[0753] Example 8 - Preparation of the material of Figures 6, 7 and 8

[0771] In this specification, D 90 refers to sintered grains unless otherwise stated.

[0754]

[0772] Slurries were prepared by dispersing lithium-loaded garnet powder with solvent, binder, and plasticizer (where the binder and plasticizer contents were 8–20 wt% of the solids). Solvent was added to control the viscosity in the range of 50–1000 cP at a shear rate of 20 Hz. The slurry was cast onto metal foil (60–150 mm wide) using a comma coater with a fixed gap distance of 200–400 μm, dried, and rolled into rolls. The thickness of the green ceramic layer was 50–80 μm; the thickness of the metal layer was 5–15 μm. The rolls were transferred to a processing apparatus and unwound, fed at a rate of 5–20 cm / min through temperature zones configured for layer debinding, bisque firing, and sintering. The binder burnout temperature zone contained an atmosphere configured to remove organic burnout. The sintering temperature zone was set at 900–1250 °C to promote densification. After sintering, the product was rolled into a roll. The roll of sintered material was transferred to a cutting machine where it was cut into smaller sizes of 11 mm discs, 30 x 30 mm squares, and 70 x 85 mm rectangles for testing and analysis. The products are imaged in Figures 6 and 7.

[0755]

[0773] Scanning electron microscopy (SEM) was used to image a cross section of the bilayer produced herein. The lithium-loaded garnet top layer is approximately 32 μm thick. Grain size D 90 The thickness is 1.3-1.9 μm. FIG. 6 shows an optical image of the lithium-filled garnet side of the bilayer. FIG. 7 shows a scanning electron microscopy (SEM) image of the top view of the lithium-filled garnet side of the bilayer. FIG. 8 shows a scanning electron microscopy (SEM) image of a cross section of a bilayer produced by the process apparatus herein. The lithium-filled garnet top layer has a porosity of less than 1% by volume.

[0756]

[0774] Porosity is a percentage by volume and is calculated by image segmentation. A deep learning model is used to identify regions in the image that are porous; the model is trained on manually segmented images and classifies dark regions as porous.

[0757] Example 10 - Sintering of a bilayer using a flat runway

[0775] Lithium-loaded garnet powder (d 50 Slurries were prepared by dispersing 1000-10000 cP (<1 μm) ceramic powder in xylene, acrylic binder, plasticizer, and acrylate dispersant (where the binder, plasticizer, and dispersant contents were 10-20 wt% of the solids). Solvent was added to control the viscosity in the range of 50-1000 cP at a shear rate of 20 Hz. The slurry was cast onto metal foils 60 mm-150 mm wide using a comma coater with a fixed gap distance of 100 μm-200 μm. The thickness of the green ceramic layer was 20 μm-50 μm; the thickness of the metal layer was 5 μm-10 μm. The roll was transferred to a processing device, unwound, and fed through a first heating zone at a speed of 5 cm / min-80 cm / min to prepare debindered bilayers. The temperature of the first heating zone was 700°C-900°C.

[0758]

[0776] The roll was then fed through a second heating zone at a speed of 40 cm / min to 200 cm / min to prepare a sintered bilayer. The temperature of the second heating zone was 1050°C to 1250°C. The second heating zone was a tube furnace approximately 60 inches long. A flat runway extended from the opening of the second heating zone to the exit point. The debound bilayer was subjected to a tension of 3 to 35 N per meter of web width to conform to the shape of the runway.

[0759]

[0777] After sintering, the product was cut into sheets and stored for later testing and analysis.

[0760] Example 11 - Sintering of a two-layer body using an arched runway

[0778] Lithium-loaded garnet powder (d 50Slurries were prepared by dispersing 1000-10000 cP (<1 μm) ceramic powder in xylene, acrylic binder, plasticizer, and acrylate dispersant (where the binder, plasticizer, and dispersant contents were 10-20 wt% of the solids). Solvent was added to control the viscosity in the range of 50-1000 cP at a shear rate of 20 Hz. The slurry was cast onto 60-150 mm wide metal foil using a comma coater with a fixed gap distance of 100-200 μm. The bilayer was dried and rolled around a core with a diameter of approximately 9 cm. The thickness of the green ceramic layer was 20-50 μm; the thickness of the metal layer was 5-10 μm. The roll was transferred to the processing equipment, unwound, and fed through the first heating zone at a speed of 20-200 cm / min to prepare a debindered bilayer. The temperature of the first heating zone was 700°C to 900°C.

[0761]

[0779] The roll was then fed through a second heating zone at a speed of 10 cm / min, 20 cm / min, 40 cm / min, or 101 cm / min to prepare a sintered bilayer. The temperature of the second heating zone was 1050°C to 1250°C. The second heating zone was a tube furnace approximately 60 inches long. The bilayer passed through the second heating zone for a time period ranging from 90 seconds to 5 minutes. An arched runway with a radius of curvature of 5.0 meters extended from the opening of the second heating zone to the exit point. The debound bilayer was subjected to a tension of 40 to 187.5 N per meter of web width to conform to the shape of the runway.

[0762]

[0780] After sintering, the bilayer body was cut into small pieces.

[0763]

[0781] FIG. 16 shows the height map of the resulting bilayer produced in this Example 11.

[0764]

[0782] Figures 17-20 show the flatness of bilayers produced using different heat treatment processes with different tensions in N per meter of web width as listed.

[0765]

[0783] Figure 17 had a web speed of 10 cm / min; Figure 18 had a web speed of 20 cm / min; Figure 19 had a web speed of 40.5 cm / min; and Figure 20 had a web speed of 101 cm / min. The speeds listed in Figures 17-20 are in inches / min.

[0766]

[0784] Table 1 shows the average roughness of the data from Figures 17-20 as measured using a Keyence microscope.

[0767] [Table 1]

[0768]

[0785] The embodiments and examples described above are intended to be illustrative and non-limiting. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific compounds, materials, and procedures. All such equivalents are considered to be within the scope of, and are encompassed by, the appended claims.

Claims

1. providing a green bilayer body comprising a green body layer and a metal layer under a tension of 1N to 300N per meter of web width; forming a debound bilayer by advancing the green bilayer through a first heating zone; preparing a sintered bilayer by advancing the debindered bilayer through a second heated zone. A method for producing a sintered bilayer body, comprising: the debindered bilayer is arch-shaped as it advances through the second heating zone; the debound bilayer is in the second heating zone for about 1 second to about 3 minutes; the tension is 30 N to 200 N per meter of web width in the second heating zone; the temperature of the second heating zone is between 1050°C and 1250°C; and The method wherein the thickness of the sintered bilayer is less than 100 μm.

2. The method of claim 1 , wherein the green bilaminate is under tension of 1N to 300N in the first heating zone.

3. The method of claim 1 , wherein the tension in the first heating zone is different from the tension in the second heating zone.

4. The method of claim 1 , wherein the tension in the first heating zone is lower than the tension in the second heating zone.

5. The method of claim 1, wherein the tension is between 3N and 35N per meter of web width in the first heating zone.

6. The method of claim 1, wherein the tension is between 3N and 30N per meter of web width in the first heating zone.

7. The method of claim 1, wherein the tension is 10 to 20 N per meter of web width in the first heating zone.

8. The method of claim 1 , wherein the sintered bilayer comprises a sintered lithium-filled garnet.

9. The method of claim 1 , wherein the metal layer comprises nickel, iron, or an alloy thereof.

10. The method of claim 1, wherein the metal layer has a thickness of 1 μm to 10 μm.

11. 9. The method of claim 8, wherein the sintered lithium-filled garnet layer has a thickness of 5 μm to 40 μm.

12. 10. The method of claim 1, wherein the sintered bilayer is at least 1 meter in length.

13. 10. The method of claim 1, wherein the debinding bilayer is an arch shape characterized by a radius of curvature of 0.5 meters to 6.0 meters.

14. The method of claim 1 , wherein at least one runway provides the arch shape.

15. The method of claim 1 , wherein at least one roller provides the arched shape.

16. The method of claim 1 , wherein at least one speed bump provides the arch shape.

17. 10. The method of claim 1, wherein the debound bilayer is heated at a rate greater than 300[deg.] C. / min.

18. The method of claim 1, wherein the tension is 31.1 to 200 N per meter of web width in the second heating zone.

19. The method of claim 1, wherein the tension is 31.1 to 187.5 N per meter of web width in the second heating zone.

20. 10. A sintered bilayer having an average roughness of less than 15 as measured by a Keyence microscope, the sintered bilayer being produced by the method of claim 1.

21. 10. The method of claim 1, wherein the debound bilayer advances through the second heated zone at a rate of from 10 cm / min to 80 cm / min.

22. 22. The method of claim 21, wherein the speed is between 20 cm / min and 80 cm / min.

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