Processing apparatus 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 benefits of U.S. Provisional Patent Application No. 63 / 406,711, filed on 14 September 2022, which is incorporated herein by reference in its entirety for all purposes.

[0002] field

[0002] This disclosure relates to calcination, debinding, and / or sintering processes for ceramics. In some examples, such ceramics are deposited as layers on a metal layer. These two layers form a bilayer body. This bilayer body is heated in a continuous processing apparatus. [Background technology]

[0003] background

[0003] Certain sintering methods for lithium-filled garnet (lithium lanthanum zirconium oxide; LLZO), such as batch sintering of LLZO, are described, for example, in U.S. Patent No. 10,563,918B2 or No. 10,840,544B2. Containerless sintering of certain ceramics is disclosed in U.S. Patent Application Publication 2004 / 0206470A1 and also in International Publication 2014 / 103662A1. [Overview of the project] [Problems that the invention aims to solve]

[0004]

[0004] Despite this background, there is a need for manufacturing processes for thin-film ceramics or bilayer ceramics, such as sintering lithium-filled garnet in the form of a thin film or a bilayer. Furthermore, there is a need for processes that utilize high-throughput continuous sintering processes, such as the roll-to-roll method. [Means for solving the problem]

[0005] overview

[0005] In one embodiment, the Specified herein provides a process for producing 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; producing a debindered bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debindered bilayer through a second heating zone; wherein the debindered bilayer is arched when it advances through the second heating zone; the debindered 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 specification provides a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; and a runway having a surface made of 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 other embodiments, the Specified Reference Instrument provides a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; at least one of the following: namely, baffles within a heating zone; baffles between two heating zones; curtain purge between two heating zones; means for controlling at least two individual pressure zones within at least three heating zones; means for exhausting through the center of at least one furnace; means for exhausting through the center of a runway; means for purging gas between two heating zones; means for isolating gas between two heating zones; means for mechanically separating two heating zones; or at least one of these combinations.

[0008]

[0008] In some other embodiments, the specification shows a processing apparatus comprising: a front roller; at least one furnace having at least three heating zones; and a double-layer body kept under tension, where 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 specification shows a processing apparatus comprising: a front roller; at least one furnace having at least three heating zones; a double layer; and at least two or more rollers, wherein the double layer is wound around one of the at least two or more rollers at a winding angle in the range of 0 to 40°.

[0010]

[0010] In yet another embodiment, this specification provides a process for using a continuous process apparatus, which includes the following operations: (a) heating the green bilayer as it moves through at least one furnace to produce a bilayer with an organic content of less than 1 wt% by weight; and (b) winding the bilayer with an organic content of less than 1 wt% onto a roller.

[0011]

[0011] In certain embodiments, this specification provides a process for using a continuous process apparatus, which includes the following operations: (a) providing or leaving a process apparatus as disclosed herein; (b) producing a bisque-fired bilayer by heating the bilayer as it moves through at least one furnace; and (c) winding up the bisque-fired bilayer.

[0012]

[0012] In some other embodiments, the Specified herein describes a process for using a continuous process apparatus, which includes the following operations: (a) providing or leaving a process apparatus as disclosed herein; and (b) producing a sintered bilayer by heating the bilayer as it moves through at least one furnace. [Brief explanation of the drawing]

[0013] Brief explanation of the drawing [Figure 1]

[0013] An embodiment of a process apparatus having a plurality of heating zones and / or cooling zones and a series of internal rollers, the rollers forming an arch-shaped ramp. [Figure 2]

[0014] A portion of an embodiment of the process apparatus is shown. [Figure 3]

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

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

[0017] A photograph of one embodiment of the process apparatus is shown. [Figure 6]

[0018] An image of the two-layer body produced in Example 8 is shown. [Figure 7]

[0019] The image shows a top view of the bilayer obtained by scanning electron microscopy (SEM), where the lithium-filled garnet layer of the bilayer fabricated in Example 8 is visible. The uppermost layer of lithium-filled garnet has a porosity of less than 1 volume percent. [Figure 8]

[0020] This image shows a cross-sectional view of the sintered oxide layer containing the lithium-filled garnet layer of the two-layer body manufactured in Example 8, obtained by scanning electron microscopy (SEM). The uppermost lithium-filled garnet layer has a porosity of less than 1 volume percent. [Figure 9]

[0021] The diagram shows unglazed two-layer and sintered two-layer bodies being wrapped around a roller. [Figure 10]

[0022] This image shows a Keyence microscope image of the flatness of a two-layer structure as a function of the tension acting on it. The flatness analysis using Keyence microscopy is measured on the surface of the sintered oxide layer of the two-layer structure, not the surface of the metal layer. The flatness is a measured value of the flatness of the surface of the sintered oxide layer. [Figure 11]

[0023] The table shows a quantitative representation of the flatness of different two-layer structures as a function of the tension applied to the two-layer structure during sintering. [Figure 12]

[0024] Embodiments of the processing apparatus described herein are shown. [Figure 13]

[0025] The results of the electrochemical cycling treatment from Example 7 are shown. [Figure 14]

[0026] A table is shown that quantifies the flatness as a function of tension acting on a two-layer body sintered on a curved runway. [Figure 15]

[0027] This shows a height map of a two-layer structure fabricated on a flat runway using Keyence microscopy. [Figure 16]

[0028] This shows a Keyence microscope image height map of a two-layer material fabricated on a curved (i.e., arched) runway. [Figure 17]

[0029] This shows the flatness as a function of the tension acting on the two layers during the heat treatment process. [Figure 18]

[0030] This shows the flatness as a function of the tension acting on the two layers during the heat treatment process. [Figure 19]

[0031] This shows the flatness as a function of the tension acting on the two layers during the heat treatment process. [Figure 20]

[0032] This shows the flatness as a function of the tension acting on the two layers during the heat treatment process. [Modes for carrying out the invention]

[0014] Detailed explanation A. Introduction

[0033] The following description is provided to enable those skilled in the art to create and use the present invention and to incorporate it into the context of a detailed application. Various modifications and diverse uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein are applicable to a wide range of embodiments. Thus, the present invention is not intended to be limited to the embodiments presented, but rather should be given the broadest scope consistent with the principles and novel features disclosed herein.

[0015]

[0034] The following detailed description provides numerous specific details to further enhance the understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention can be practiced without necessarily being limited to these specific details. In other cases, to avoid obscuring the disclosure, well-known structures and mechanisms are shown in block diagrams rather than in detail.

[0016]

[0035] All features disclosed herein (including any attached claims, abstracts, and drawings) can be replaced by alternative features serving the same, equivalent, or similar purpose unless otherwise specified. Thus, unless otherwise specified, each disclosed feature is merely an example of a general set of equivalent or similar features.

[0017]

[0036] The continuous production lines shown in the figures of this specification are shown in a horizontal configuration, but in some embodiments they can also be assembled in a vertical configuration, in which case the green tape or bilayer moves in a direction parallel or antiparallel to the downward force that gravity exerts directly on the Earth's surface. For example, in a vertical configuration, the green tape or bilayer may move vertically, perpendicular (at 90°; i.e., at a right angle) to the floor on which the process is taking place. Furthermore, there may be angles between the various ovens, which will cause the green tape to deviate from a straight line and curve while being processed. The figures of this specification are presented as representative, non-limiting embodiments of the present disclosure. Other configurations and orientations of ovens and sintering lines are intended to be included in the present disclosure. Depending on the configuration, the green tape moves parallel to gravity. For example, the green tape may hang down like a curtain under the weight of gravity. Depending on the configuration, the tape moves perpendicular to gravity; for example, the green tape may move in a direction parallel to the floor.

[0018]

[0037] As used herein, a green film moving through a processing apparatus may be represented by x, y, and z dimensions. 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. When the green film moves through the processing apparatus, i.e., in the machine direction (MD), the film is described as moving along the x dimension or web dimension. The web cross-sectional dimension (i.e., the transverse direction (CD)) represents the y dimension which lies in the same plane as the web. The z dimension is perpendicular to the web and represents the thickness of the web.

[0019]

[0038] This specification describes equipment and processes useful for realizing high-quality ceramic electrolyte films through high-speed processing. This specification describes a high-throughput continuous sintering process for thin-film ceramics. The ceramics include, but are not limited to, lithium aluminum titanium phosphate (LATP) and lithium-filled garnet oxide (e.g., Li7La3Zr2O). 12 and Li7La3Zr2O 12Examples include Al2O3 (also known as LLZO), lithium lanthanum titanate, and lithium aluminum germanium phosphate (LAGP). The process, in certain embodiments, includes a sintering step, where the film being sintered (i.e., the green film or green body on a bilayer undergoing a process to become a sintered film or sintered bilayer) does not come into contact with any surface during sintering. In some embodiments, when a bilayer is used, the metal layer may come into contact with the surface of the apparatus during passage through one or more furnaces, but the green body does not come into contact with the surface. By sintering without contact with other surfaces during sintering, the sintered ceramic films prepared by this process unexpectedly possess advantageous properties, such as low flatness. For lithium-filled garnet, the apparatus unexpectedly possesses advantageous properties, such as the ability to retain the stoichiometric amount of lithium in a given LLZO formula, and an advantageous LLZO microstructure (e.g., high density, small grain size, and combinations thereof). In some embodiments, by not coming into contact with other surfaces, the prepared material is free of surface scratches. In some embodiments, by preventing the green material from contacting the surface, the two-layer bodies prepared herein are free from surface scratches on the ceramic side of the two-layer body. In some embodiments, by preventing contact with other surfaces, the material is prepared without problems such as adhesion to the substrate. In addition, these sintered LLZOs are prepared using a novel high-speed sintering process, which is faster than other LLZO sintered film manufacturing processes in terms of product volume.

[0020]

[0039] This specification describes a process for continuously processing a bilayer, comprising step 1) binder burnout (BBO) performed at room temperature or a moderately high temperature to remove organic material from the bilayer, and step 2) sintering at an extremely high temperature to convert the ceramic powder into a dense solid.

[0021]

[0040] During both stages, as well as during the subsequent cooling to room temperature, the temperature profile and gas environment must be controlled, and the web of the two-layer tape must be handled in a way that ensures the final product is flat and defect-free. The specific requirements for achieving this quality are described below in this document.

[0022]

[0041] Depending on the process, both processing steps (BBO and sintering) are performed with a single tool as described herein. In other embodiments, separate tools are used for each step, i.e., one tool is used for BBO and another for sintering.

[0023] B. Definition

[0042] As used herein, the term “about” refers to a range of values ​​that are approximately the modified number, including, for example, about 15% w / w, and optionally, ±10% of that modified number. For example, about 15% w / w includes 15% w / w as well as 13.5% w / w, 14% w / w, 14.5% w / w, 15.5% w / w, 16% w / w, 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 ~” means a single member from the group, two or more members from the group, or a combination of members from the group. Members selected from the group consisting of A, B, and C include, for example, A only, B only, or C only, as well as A and B, A and C, B and C, and A, B, and C.

[0025]

[0044] As used herein, “roller” means a rotating cylinder or other shape on which something resting on or on is moved, or used to carry, 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 on which a tape or membrane can be passed over or bent around; or a shape on which a tape or membrane can be wound. In some embodiments, a roller has an outer diameter of 6 cm or more. In some embodiments, a roller has a winding tension of 20 g / cm or more. A roller may have a convex or concave profile. A roller has one axis of rotational symmetry.

[0026]

[0045] In this specification, a "two-layer body" includes a ceramic layer deposited on a metal layer. The ceramic layer may be a green body or a sintered body. In some embodiments, the green body is continuous, and in other embodiments, the green body is deposited in a patch-coating manner. After sintering, the two-layer body may have a ceramic layer thickness of 10 to 50 μm and a metal layer thickness of 2 to 20 μm. Alternatively, the two-layer body may have a ceramic layer thickness of 20 to 30 μm and a metal layer thickness of 3 to 10 μm.

[0027]

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

[0028]

[0047] The sintered bilayer body is a green bilayer body that has been processed using the apparatus described herein, and in this case, the sintered bilayer body is composed of a sintered body and a metal layer.

[0029]

[0048] As used herein, the terms “green film” or “green tape” refer to an unsintered tape or unsintered film comprising lithium-filled garnet, a precursor of lithium-filled garnet, or a combination thereof, and at least one of a binder, plasticizer, carbon, dispersant, solvent, or combination thereof. As used herein, “green film tape” refers to a roll, continuous layer, or cut portion thereof of a cast tape of green film, whether dry or not. The term “green body” is used synonymously with green film or green tape. Green tape may also include patches of green body deposited on a metal layer (i.e., a patch coating on a metal layer).

[0030]

[0049] As used herein, “green body” is a material deposited from a slurry, comprising ceramics or a ceramic precursor and at least one member selected from a solvent, binder, dispersant, plasticizer, surfactant, or a combination thereof. A green body is considered green before it is heated for either the removal of organic materials such as solvents, binders, dispersants, plasticizers, surfactants, or combinations thereof, or for the sintering of the ceramic component of the green body, or both. A green body is made by depositing a slurry onto a substrate and optionally drying the deposited slurry.

[0031]

[0050] As used herein, “front roller” refers to a roller located at the beginning of the processing apparatus that unwinds or spreads the roll of an unsintered film, green film, or green bilayer.

[0032]

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

[0033]

[0052] As used herein, “sintered product receiving machine” refers to any mechanism, including, but not limited to, an end roller or a machine for cutting and stacking sintered films. As used herein, an oven or furnace is a partially or fully enclosed compartment in which materials can be heated to a temperature above room temperature. For example, an oven can be heated to a maximum of 1,200°C. A binder burnout oven is typically heated to less than 750°C. A bisque oven is typically heated to 600–900°C. A sintering oven is 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 apparatus is enclosed in an atmospheric enclosure. As used herein, oven and furnace are used synonymously.

[0034]

[0053] As used herein, “atmosphere control” refers to a system that controls the water content, oxygen content, gas flow rate, gas temperature, the content of one or more gases, the concentration of one or more gases, total pressure, vacuum level, and combinations thereof within an enclosed or closed space. Atmosphere control can be dynamic in the sense that the system changes the atmosphere in response to detected conditions, thereby making the atmosphere more strictly faithful to a predetermined specific condition. In this example, the atmosphere refers to a gaseous environment in direct contact with the green tape being heated, calcined, sintered, or cooled; or a 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 oxygen, argon, nitrogen, helium, and / or hydrogen. In some embodiments described herein, atmosphere control includes controlling the amounts 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 in direct contact with the sintered tape being heated, sintered, annealed, or cooled. Atmosphere control may involve the use of various gas curtains, gas densities, gas velocities, gas flow directions, or gas pulses around and near ovens, furnaces, and any inlets or outlets, as well as any openings through which materials such as green tape or sintered products may pass when entering or leaving the oven or furnace. Atmosphere control may refer to systems in which nitrogen gas, argon gas, foaming gas, dry air, or humidified air is used in enclosed or closed spaces. Atmosphere control may refer to systems in which a partial vacuum can be applied, for example, when the pressure is below atmospheric pressure.

[0035]

[0054] As used herein, “gas curtain” refers to the gas flow velocity at a specific entry or exit point of the oven (e.g., a green tape inlet and a sintered film outlet) where the gas flow velocity is determined. For example, the gas flow velocity may be between 1 and 50 liters / minute at standard temperature and pressure. For example, the gas flow velocity may be between 50 liters / minute and greater at standard temperature and pressure. The gas curtain may be configured so that a specific number of gas exchanges in the chamber per unit time is achieved, for example, so that a fraction of the chamber's volume is exchanged once per minute. For example, in the case of a chamber with an internal volume that holds 30 liters of gas, the gas curtain may be configured so that an exchange of 1 per minute is achieved by a flow of 30 liters / minute at STP. The gas curtain may have a pressure sensor at the outlet. The gas flow in the oven is controlled by the gas curtain flowing across the entry or exit point of the oven. The gas curtain may help maintain a constant atmosphere inside the oven by partially or completely preventing gas from entering or leaving the oven.

[0036]

[0055] As used herein, the term “dry air” refers to air with reduced moisture content. Dry air may be supplied to a cleanroom. Dry air is characterized by having a dew point below -20°C, below -30°C, below -40°C, below -50°C, below -60°C, or below -70°C.

[0037]

[0056] As used herein, the term “solid separator” refers to a substantially electronically insulating Li + This refers to ion-conducting materials (for example, lithium-ion conductivity is at least 10 times that of electronic conductivity). 3 Twice, often 10 6 It acts as a physical barrier or spacer between the positive and negative electrodes of an electrochemical cell (it is twice as large).

[0038]

[0057] As used herein, the term “annealing” means 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, refer to U.S. Patent No. 9,966,630B2, which is incorporated herein by reference in its entirety for any purpose.

[0039]

[0058] When used herein, "Specific Area Resistivity" (ASR) is measured by electrochemical cycling using Arbin, Maccor, or Biologic instruments unless otherwise specified. ASR is calculated by measuring the voltage drop ΔV after 30 to 180 seconds according to the current interruption measurement method, and the formula is ASR = ΔV / J (where J is A / cm²). 2 (This is the current density per unit area.)

[0040]

[0059] When used herein, ionic conductivity is measured by electrical impedance spectroscopy, a method known in the art.

[0041]

[0060] As used herein, the term “ambient conditions” refers to the natural atmosphere, such as the Earth’s atmosphere, which includes room temperature and approximately 78% N2 and 21% O2; and / or moisture. 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 ionic conductive and electrically insulating material. An electrolyte is an ionic conductive and electrically insulating material. + It is useful for electrically isolating the positive and negative electrodes of a rechargeable battery while enabling conductivity.

[0043]

[0062] As used herein, the terms “film” or “thin film” refer to thin membranes with a thickness of less than 0.5 mm and a thickness of more than 10 nm. Thin films also have a lateral dimension greater than 5 mm. “Film” or “thin film” may be manufactured by a continuous process such as tape casting, spray coating, or slip casting. In some embodiments, the manufacturing process may include a batch process. In some embodiments, the manufacturing process may include screen printing.

[0044]

[0063] As used herein, the term "thickness" refers to the distance between the top and bottom surfaces of a film, layer, or bilayer, or the median of the measured distances. As used herein, the top and bottom surfaces of a bilayer refer to the sides with the largest surface area within the bilayer. As used herein, thickness is measured by cross-sectional scanning electron microscopy unless otherwise specified. Using cross-sectional SEM, the thickness of the metal layer and the sintered oxide layer of a bilayer can also be determined. The thickness of the sintered oxide layer is the distance from the surface with the largest surface area within the sintered oxide layer to the interface between the metal layer and the sintered oxide layer. The thickness of the metal layer is the distance from the surface with the largest surface area within the metal layer 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 adhesion and / or tackiness of a material, such as the solids in green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene-α-olefin copolymers. “Binder” refers to a material that helps to bond another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for bonding garnet materials. Other binders include polycarbonates. Other binders include polyacrylates and polymethacrylates. These embodiments of binders are not limiting to the entire range of binders contemplated herein, but merely constitute embodiments. Useful binders in this 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 copolymer, and silicones.In some embodiments that include any of the above, the binder is polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), poly(butyl methacrylate), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(arylglycidyl ether)PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(arylglycidyl ether) (PEO-MEEGE- The polymer is selected from the group consisting of AGE, polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), ethylene propylene (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 ethyl polyacrylate (PEA).

[0046]

[0065] The solvents used herein may be selected from other classes of organic solvents, including but not limited to alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, and hexanol, as well as alcohols such as 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), as well as ethers and aromatic solvents.

[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 membrane" refers to a process in which a liquid or slurry is poured or transferred into a mold or onto a substrate, such that the liquid or slurry forms a membrane or is formed into the shape of a membrane. Casting may be performed by doctor blade method, Meyer rod method, comma coater method, gravure coater method, microgravure method, reverse comma coater method, slot die method, slip and / or tape casting method, 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. 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 (wherein 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, in each instance independently, 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 (wherein 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). As used herein, garnet also includes garnets as described above doped with Al or Al₂O₃. Also, as used herein, garnet includes, but is not limited to, Li A La B Zr C O F +yAl₂O₃ (wherein x may be 5.8 to 7.0, 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 in the formula, 4<A<8.5, 1.5<B<4, 0<C≦2, 0<D<2; 10<F<13). Also, as used herein, garnet includes, but is not limited to, Li x La₃Zr₂O 12 +yAl₂O₃ (wherein x may be 5.8 to 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). As used herein, garnet does not include YAG-garnet (i.e., yttrium aluminum garnet, or, for example, Y₃Al₅O 12 ). As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or cinnamon-stone, tsavorite, uvarovite and andradite, and solid solutions pyrope-almandine-spessarite and uvarovite-grossular-andradite. As used herein, garnet does not include nesosilicates having the general formula X₃Y₂(SiO₄)₃ wherein X is Ca, Mg, Fe, and / or Mn; and Y is Al, Fe, and / or Cr. Lithium-filled garnet includes, but is not limited to, lithium-filled garnet of 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 xExamples of compounds having the formula (where x is between 0 and 2) include Li 7-3x La3Zr2O 12 Al x Examples include (wherein 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 a specific example, lithium-filled garnet is Li 7-3x La3Zr2O 12 Al x Examples include (where x is 0.25, 0.5, or 0.75).

[0050]

[0069] As used herein, the terms “garnet precursor chemical” or “chemical precursor of garnet-type electrolyte” refer to chemical substances 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., Li2O), lithium carbonate (e.g., Li2CO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), aluminum oxide (e.g., Al2O3), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO3), aluminum nitrate notahydrate, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., Ta2O5).

[0051]

[0070] When used in this specification, the phrase "d 50 "Diameter" refers to the median diameter on the particle size distribution measured by microscopy or other particle size analysis techniques, including but not limited to scanning electron microscopy or dynamic light scattering. 50 "Math D" 50 " or "Volume D 50 It can also be characterized as "Math D" 50" is the diameter when 50% of the particles have a smaller diameter, and "volume D 50 " is the diameter when 50% of the volume of all particles has a smaller diameter. Unless otherwise specified, in the present specification, D 50 refers to volume D 50 , that is, D 50 includes the characteristic dimension when 50% of the volume of the particles is smaller than the stated size.

[0052]

[0071] As used herein, the phrase "particle diame 90 ter" refers to a particle diameter on a particle size distribution measured by microscopy or other particle size analysis techniques, including but not limited to scanning electron microscopy or dynamic light scattering. D 90 includes the characteristic dimension when 90% of the volume of the particles is smaller than the stated size.

[0053]

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

[0054]

[0073] As used herein, the term “speed bump” refers to a surface ridge on a runway or on the surface of a process apparatus over which a bilayer body moves as it moves through the process apparatus. The speed bump helps to apply a force normal to the bilayer body by making contact with the metal layer of the bilayer body disclosed herein. Unless otherwise specified, the metal layer of the bilayer body is the layer that may come into contact with the speed bump as the bilayer body moves over the speed bump.

[0055]

[0074] As used herein, the term “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 setpoint. In some embodiments, both the first and second heating zones are contained within a single furnace or oven. In some other embodiments, the first and second heating zones are each located separately within a different furnace or oven than the one 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 processed, and at least 100 μm thick, and that can make point or line contact with the tape being processed in a heated zone.

[0057]

[0076] As used herein, the term “earthenware bilayer” refers to a bilayer in which the ceramic layer has a porosity of at least 10 vol% and an organic content of less than 1% by weight. In this specification, the organic content includes carbon-containing compounds.

[0058]

[0077] As used herein, the term “debindered membrane” refers to a green material 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 in a two-layer structure.

[0060]

[0079] As used herein, the term “green bilayer” refers to a green film or green body as defined above, wherein a metal substrate layer is attached to or bonded to the underlying layer of the green film or green body.

[0061]

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

[0062]

[0081] As used herein, the term “vertical processing” means that when a bilayer travels through the CML, it is positioned in a vertical processing orientation. Vertical processing means that a bilayer travels parallel or counter-parallel to Earth’s gravity.

[0063]

[0082] As used herein, the term “curtain treatment” means that when a bilayer body moves through the CML, it is positioned in a curtain treatment orientation. Curtain treatment means that the bilayer body is folded back so that both the metal layer and the green layer move parallel to the ground, but the metal layer is not beneath the green layer; rather, the metal layer and the green layer are side by side. Curtain treatment may be beneficial in preventing debris from falling onto the upper surface of the green body. Curtain treatment may be beneficial in preventing sagging of the bilayer body.

[0064]

[0083] As used herein, “under tension” means that tension is applied to the bilayer using a physical mechanism, including, 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 set of mechanisms, or a combination thereof. In some embodiments, “under tension” includes the use of a load cell in a feedback loop in combination with at least one roller, at least one weight, at least one motor, at least one tension control mechanism, a set of mechanisms, or a combination thereof. A bilayer placed on a flat surface has a natural internal tension that holds the structure of the bilayer together, even if it is not attached to anything else except the bilayer itself. As used herein, “under tension” means that there is tension of some magnitude in addition to the natural tension of the material. Tension is applied to the bilayer from the outside, for example, to stretch, widen, flatten, or conform the dimensions of the bilayer.

[0065]

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

[0066]

[0085] As used herein, “arch shape characterized by radius of curvature” means that the two layers bend in a curved manner because they are held under tension relative to a runway, at least one speed bump, or at least one roller. The curvature of the two layers can be mathematically approximated using the radius of curvature. The radius of curvature includes the radius of the arc that best approximates the curvature at the point in question. For surfaces, the radius of curvature is the radius of the circle that best fits the normal cross-section of the contact surface of the two layers. Unless otherwise specified, the contact surface is the metal layer of the two layers.

[0067] C. Processing Unit

[0086] Figure 1 shows an embodiment of the process apparatus disclosed herein. The process apparatus 100 comprises a front roller 101 around which a green bilayer is wound. The process apparatus 100 comprises an end roller 102 around which a porcelain bilayer or sintered bilayer is wound. The process apparatus 100 comprises a plurality of zones 103 for heating, cooling, temperature maintenance, or a combination thereof. Five zones 103 are illustrated in Figure 1. However, more or fewer zones 103 are also intended herein. For example, the process apparatus 100 may comprise 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 apparatus 100 may have 1 to 12 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 11 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 10 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 9 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 8 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 7 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 6 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 5 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 4 zones 103 for heating, cooling, temperature maintenance, or a combination thereof. For example, the process apparatus 100 may have 1 to 3 zones 103 for heating, cooling, temperature maintenance, or a combination thereof.For example, the process apparatus 100 may have one or two zones 103 for heating, cooling, temperature maintenance, or a combination thereof. In some embodiments, which include any of the above, one zone 103 is larger than another zone 103. In certain embodiments, the two layers move through the process apparatus at a certain speed. In these embodiments, the residence time within the zone 103 will depend on the speed at which the two layers pass through and the length of the zone 103.

[0068]

[0087] Inside zone 103 are rollers 102. The rollers 102 are arranged in a ramp. The ramp may be parabolic, elliptical, circular, or catenary. In certain examples, the ramp may be symmetrical. In other examples, the ramp may not be symmetrical. The angle the tape makes as it passes over each roller is in the range of 0 to 40°. The height difference between the highest and lowest rollers may be in the range of 0 to 10m.

[0069]

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

[0070]

[0089] Figure 2 shows a portion of the process apparatus 200. A heating zone 201 is a furnace or oven capable of burning, evaporating, or a combination thereof, 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 heating lamp, a heating coil, an induction heater, or any heat source. The curved runway includes rollers 202 spaced apart along the entire curved runway. The rollers 202 may be fixed (stationary), accelerated (the rotation of the roller edge at the contact point is faster than the web speed), decelerated (the rotation of the roller edge at the contact point is slower than the web speed), or driven at the same speed as the web. The rollers 202 may have a cylindrical, convex, or concave shape. The roller surface may contain metals (including iron, nickel, molybdenum, tungsten, and stainless steel) or ceramics (including silicon carbide, alumina, zirconia, spinel, tungsten carbide, magnesium oxide, boron nitride, and similar high-temperature ceramics).

[0071]

[0090] In this specification, a susceptor is used to absorb energy, such as heat from a heater, and re-radiate that heat to a membrane.

[0072]

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

[0073]

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

[0074]

[0093] In some embodiments, this specification shows a continuous production line as described in international patent application PCT / US2022 / 019641, filed on March 9, 2022, entitled “RAPID CERAMIC PROCESSING TECHNIQUES AND EQUIPMENT” (all of which are incorporated herein by reference in whole for all purposes).

[0075]

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

[0076]

[0095] In some cases, the runway has a surface containing aluminum oxide. In certain cases, the aluminum oxide-containing runway is in contact with the back (metal side) of the bilayer.

[0077]

[0096] In some cases, the runway has a surface containing magnesium oxide. In certain cases, the runway containing magnesium oxide is in contact with the back (metal side) of the bilayer.

[0078]

[0097] In some cases, the runway has a surface containing boron nitride. In certain cases, the runway containing magnesium oxide is in contact with the back (metal side) of the bilayer.

[0079]

[0098] In some cases, the runway has a surface containing boron nitride. In certain cases, the boron nitride-containing runway is in contact with the back (metal side) of the bilayer.

[0080]

[0099] In some cases, the runway has a surface containing silicon carbide. In certain cases, the silicon carbide-containing runway does not touch the bilayer but is located within 0.5 cm to 5 cm of the bilayer.

[0081]

[0100] In some cases, the runway has a surface containing graphite. In certain cases, the graphite-containing runway does not touch 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 containing carbon fiber composite material. In certain examples, the runway containing carbon fiber composite material does not touch the bilayer but is located within 0.5 cm to 5 cm of the bilayer. In certain examples, the carbon fiber composite material is coated with boron nitride.

[0083]

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

[0084]

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

[0085]

[0104] In some embodiments, there is a runway in the unglazed pottery 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 heat-resistant material-containing surface.

[0087]

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

[0088]

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

[0091]

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

[0092]

[0111] In some embodiments that include any of the above, the runway is equipped with rollers.

[0093]

[0112] In certain embodiments, the roller is configured to contact only the metal layer of the two-layer structure 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 is at a temperature higher than 30°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 60°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 90°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 150°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 200°C. In some embodiments, the roller does not contact the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 250°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 300°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 400°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 500°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 600°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 700°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 800°C. In some embodiments, the roller does not come into contact with the ceramic layer of the bilayer disclosed herein while the bilayer is at a temperature higher than 900°C. In some embodiments, the roller does not come into contact with the bilayer ceramic layer disclosed herein until after the sintering zone of the processing apparatus.

[0095]

[0114] In some embodiments, the Specified Information 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: namely, baffles within a heating zone; baffles between two heating zones; curtain purge between two heating zones; means for controlling at least two individual pressure zones within at least three heating zones; means for exhausting through the center of at least one furnace; means for exhausting through the center of a runway; means for purging gas between two heating zones; means for isolating gas between two heating zones; means for mechanically separating two heating zones; or at least one combination thereof.

[0096]

[0115] In some embodiments, including all 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 transversely across the web. In certain embodiments, the exhaust is heated from the furnace to a cooling trap.

[0097]

[0116] In some embodiments, this specification describes a processing apparatus comprising a front roller and; at least one furnace including at least three heating zones and; and a bilayer body kept 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 / web width 1 cm. Figure 10 shows, on the right, a bilayer film made under low tension of 1 to 15 g / web width 1 cm. In some embodiments, this specification describes a processing apparatus comprising a front roller and; at least one furnace including at least three heating zones and; and a bilayer body kept under tension, where the tension ranges from 1 to 15 g / web width 1 cm. The tension is measured using a load cell when unwinding the bilayer body from the roll and before heating the bilayer body for binder burnout. In some examples, the tension ranges from 1 to 14 g / web width 1 cm. In some cases, the tension is in the range of 1-13g / 1cm web width. In some cases, the tension is in the range of 1-12g / 1cm web width. In some cases, the tension is in the range of 1-11g / 1cm web width. In some cases, the tension is in the range of 1-10g / 1cm web width. In some cases, the tension is in the range of 1-9g / 1cm web width. In some cases, the tension is in the range of 1-8g / 1cm web width. In some cases, the tension is in the range of 1-7g / 1cm web width. In some cases, the tension is in the range of 1-6g / 1cm web width. In some cases, the tension is in the range of 1-5g / 1cm web width. In some cases, the tension is in the range of 1-4g / 1cm web width. In some cases, the tension is in the range of 1-3g / 1cm web width. In some cases, the tension is in the range of 1-2g / 1cm web width. In some cases, the tension is in the range of 1-15g / 1cm web width. In some cases, the tension is in the range of 2-15g / 1cm web width. In some cases, the tension is in the range of 3-15g / 1cm web width. In some cases, the tension is in the range of 4-15g / 1cm web width. In some cases, the tension is in the range of 5-15g / 1cm web width. In some cases, the tension is in the range of 6-15g / 1cm web width. In some cases, the tension is in the range of 7-15g / 1cm web width.In some examples, the tension is in the range of 8 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 9 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 10 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 11 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 12 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 13 to 15 g per 1 cm of web width. In some examples, the tension is in the range of 14 to 15 g per 1 cm of web width.

[0098]

[0117] In a specific embodiment, the two-layer body is maintained under tension equivalent to 30 g for a 100 mm-wide web including a 10 μm-thick Ni foil layer in the two-layer body. In some examples, the tension is 1 cm 2 per 3 kg (cross-sectional area). In a specific embodiment, the two-layer body is maintained under tension in the range of 0.01 g / cm to 10 g per 1 cm of web width.

[0099]

[0118] In a specific embodiment, the two-layer body is maintained under tension in the range of 0.01 g / cm to 100 g / cm for the unfired two-layer body.

[0100]

[0119] In a specific embodiment, the two-layer body is maintained under tension in the range of 0.01 g / cm to 500 g / cm for the green two-layer body.

[0101]

[0120] In some embodiments, the tension in different regions of the processing apparatus is not the same. For example, the unwinding and rewinding regions may have a higher tension than the high-temperature region. In some embodiments, the tension is isolated using nip rollers, vacuum rollers, and / or winding angle rollers configured to increase or decrease the tension across the rollers. In some embodiments, the tension in the winding and / or unwinding region is 5 kg per 1 cm of web cross-sectional area 2 or more, or 10 kg / cm 2 or more, or 15 kg / cm 2 or more, or 20 kg / cm 2 or more, or 25 kg / cm 2It is extremely high. In some embodiments, the tension in the winding area is 5 kg / cm 2 Over, or 10 kg / cm 2 Over, or 15 kg / cm 2 Over, or 20 kg / cm 2 Over 25 kg / cm 2 It is extremely high. In some embodiments, the tension in the unwinding area is 5 kg / web cross-sectional area 1 cm 2 Over, or 10 kg / cm 2 Over, or 15 kg / cm 2 Over, or 20 kg / cm 2 Over 25 kg / cm 2 It is excessive. In some embodiments, in at least one zone where the temperature exceeds 800°C, the tension is 6 kg / web cross-sectional area 1 cm². 2 Less than 5 kg / cm³ 2 Less than 4 kg / cm³ 2 Less than 3 kg / cm³ 2 Less than 2 kg / cm³ 2 Less than 1 kg / cm³ 2 Less than 0.5 kg / cm³ 2 It is less than.

[0102]

[0121] In some embodiments, the specification shows a processing apparatus comprising: a front roller; at least one furnace including at least three heating zones; a double layer; and at least two or more rollers, wherein the double layer is wound around one of the at least two or more rollers at a winding angle in the range of 0 to 40°.

[0103]

[0122] In some embodiments, including all of the above, the two aligned rollers are parallel to each other. The winding angle refers to the angle created between the incoming and outgoing bilayers relative to the roller. In some examples, the bilayers are wound around one of at least two rollers at a winding angle ranging from 5° to 10°. In some examples, the rollers used for web handling are aligned with a maximum deviation of 0.0005 to 0.005 degrees relative to each other. In some examples, the rollers are rounded to a tolerance of 0.001 inches, or 0.002 inches, or 0.003 inches, or 0.004 inches, or 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 examples, at least one of the rollers has a diameter of at least 15 cm.

[0104]

[0123] In some embodiments, including all of the above, the two layers are wound around one of at least two rollers at a winding 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 that include any of the above, the process apparatus comprises a two-layer structure.

[0106]

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

[0107]

[0126] In some embodiments that include any of the above, the process apparatus includes an end roller.

[0108]

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

[0109]

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

[0110]

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

[0111]

[0130] In some embodiments, including all of the above, the runway is located inside at least one furnace.

[0112]

[0131] In some embodiments, including all of the above, the runway is located inside the sintered section.

[0113]

[0132] In some embodiments that include any of the above, the runway is equipped with an exhaust port.

[0114]

[0133] In some embodiments that include any of the above, the runway is equipped with speed bumps.

[0115]

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

[0116]

[0135] In some embodiments, including all of the above, the runway has holes on its upper surface.

[0117]

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

[0118]

[0137] In some embodiments that include any of the above, the process apparatus 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 inside the furnace, selected from the group consisting of gas velocity, flow direction, gas composition, pressure, and combinations thereof.

[0120]

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

[0121]

[0140] In some embodiments, including all of the above, the two layers include a metal layer and a green layer.

[0122]

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

[0123]

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

[0124]

[0143] In some embodiments that include any of the above, the roller is mechanically alignable to within 0.005 inches. In some embodiments that include any of the above, the roller is mechanically alignable to within 0.001 inches.

[0125]

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

[0126]

[0145] In some embodiments, including all of the above, the process apparatus includes nip rollers. In this specification, nip rollers are two rollers that contact a two-layer body at the same points, upper and lower. The nip rollers are used to isolate tension zones—the tension may differ on either side of the nip rollers.

[0127]

[0146] In some embodiments, including all of the above, the process apparatus comprises at least two nip rollers. In some examples, one nip roller is located after the unwinding section. In some examples, one nip roller is located before the unwinding section. In some examples, the nip rollers isolate tension so that higher tension (greater than 6 g / cm) may be applied in the unwinding and unwinding sections, while lower tension (less than 6 g / cm) may be applied in the hot zone.

[0128]

[0147] In some embodiments, including all of the above, at least one furnace is equipped with a hot roller.

[0129]

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

[0130]

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

[0131]

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

[0132]

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

[0133]

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

[0134]

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

[0135]

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

[0136]

[0155] In some embodiments, including all of the above, the winding angle relative to the roller is in the range of 0° to 40°.

[0137]

[0156] In some embodiments, including all of the above, the winding angle relative to the roller is in the range of 0° to 40° in the binder burnout section.

[0138]

[0157] In some embodiments, including all of the above, the winding angle relative to the roller is in the range of 0° to 40° in the sintered section.

[0139]

[0158] In some embodiments including any of the above, the process apparatus includes a nip roller, 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. In some embodiments including any of the above, the process apparatus includes a nip roller, where the upper roller makes contact with the top of the web. In some embodiments including any of the above, the process apparatus includes a speed bump, an air bearing, or a combination thereof.

[0140]

[0159] In some embodiments, including all of the above, the two-layer body is suspended in the MZTK. In some embodiments, including all of the above, the two-layer body moves vertically in at least one zone that is heated to above 600°C.

[0141]

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

[0142]

[0161] In some embodiments, including all of the above, at least one furnace is sealed, and the inflow and outflow of the gas flow to that at least one furnace is controlled by at least one atmosphere controller. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 100 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 90 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 80 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 70 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 60 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 50 ppm by weight when the furnace is purged with an N2 flow. In some examples, the sealed furnace maintains an oxygen partial pressure of less than 40 ppm by weight when the furnace is purged with an N2 flow. In some cases, a sealed furnace maintains an oxygen partial pressure of less than 30 ppm by weight when the furnace is purged with N2 flow.

[0143]

[0162] In some embodiments, including all of the above, the process apparatus includes a pressurized gas line between the bisque section and the sintering section, which pressurizes and delivers gas into the bisque section and the sintering section.

[0144]

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

[0145]

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

[0146]

[0165] In some embodiments, including all 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 sintered section containing argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof. In some embodiments, including any of the above, the gas stream is configured to take in moisture in the temperature zone below 800°C. In some embodiments, including any of the above, the gas stream is configured to separate the gas from the temperature zone below 800°C from the environment in the temperature zone above 900°C.

[0148]

[0167] In some embodiments, including all of the above, the atmosphere controller maintains an atmosphere containing less than 500 ppm of O2 in the bisque section, the sintered section, or both the bisque section and the sintered section.

[0149]

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

[0150]

[0169] In some embodiments that include all of the above, the green body layer is green tape.

[0151]

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

[0152]

[0171] In some embodiments, including all of the above, the two-layer body is positioned in a curtain-processing orientation as it moves through the process apparatus.

[0153]

[0172] In some embodiments, including all of the above, the two-layer body is positioned in a vertical processing orientation as it moves through the process apparatus.

[0154]

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

[0155]

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

[0156]

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

[0157]

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

[0158]

[0177] In some embodiments, including all of the above, the two layers are suspended as they move through the sintering zone.

[0159]

[0178] In some embodiments, including all of the above, the process apparatus comprises a sintered bilayer body wound around at least one end roller.

[0160]

[0179] In some embodiments that include any of the above, the sintered bilayer body comprises sintered lithium-filled garnet.

[0161]

[0180] In some embodiments, including any of the above, the process apparatus is configured to advance the two-layer body through at least one furnace at a speed of at least 2 inches per minute.

[0162]

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

[0163]

[0182] In some embodiments, including all of the above, the process apparatus produces a two-layer body cut to dimensions of 73 mm x 90 mm.

[0164]

[0183] In some embodiments that include all of the above, the minimum web speed required to achieve this processing capability of the process apparatus is 1.0 meter per minute, and this will be referred to as the assumed web speed in the following sections.

[0165]

[0184] In some embodiments, including all of the above, the process apparatus produces a two-layer body having a length of 400m to 1500m. This corresponds to a maximum incoming coil diameter (when using a 6-inch core) of 295mm to 485mm and a maximum coil weight of 50 to 180kg.

[0166]

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

[0167]

[0186] In some embodiments that include any of the above, the binder burnout zone and the sintering zone are located parallel to each other.

[0168]

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

[0169]

[0188] In some embodiments that include any of the above, the process apparatus includes a second binder burnout zone.

[0170]

[0189] In some embodiments that include all 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 firing section, and a sintering section, followed by another cooling section. In some embodiments, the additional cooling section is located between the binder burnout section and the bisque firing section or between the bisque firing section and the sintering section.

[0172]

[0191] In some embodiments, including all of the above, the sintered section is not directly exposed to the Earth's atmosphere. This means that the sintered section has only one atmosphere in contact with a portion of the sintered film or bilayer inside the sintered section, and that only atmosphere is not the Earth's atmosphere (e.g., 78% N2, 21% O2). Instead, in the sintered section, the gas in contact with the sintered film or bilayer is an inert or reducing gas, such as Ar, N2, H2, or a combination thereof. This can be achieved by sealing (partially or completely sealing) the sintered section in such a way that it is isolated from the Earth's atmosphere. This can be achieved by allowing a gas flow into and out of the sintered section in such a way that it is isolated from the Earth's atmosphere. This can be achieved by placing the sintered section in a chamber filled with an inert or reducing gas.

[0173]

[0192] In some embodiments, including all of the above, at least one furnace is not directly exposed to the Earth's atmosphere. This means that at least one furnace has a single atmosphere in contact with a portion of the sintering film or bilayer inside the at least one furnace, and that single atmosphere is not the Earth's atmosphere (e.g., 78% N2, 21% O2). Instead, in at least one furnace, the gas in contact with the sintering film or bilayer is an inert or reducing gas, such as Ar, N2, H2, or a combination thereof. This can be achieved by sealing at least one furnace in such a way that it is isolated from the Earth's atmosphere. This can be achieved by allowing a gas flow into and out of at least one furnace in such a way that it is isolated from the Earth's atmosphere. This can be achieved by placing at least one furnace in a chamber filled with an inert or reducing gas.

[0174]

[0193] In some embodiments, including all of the above, at least one furnace is sealed, and the inflow and outflow of gases into at least one furnace is controlled by at least one atmosphere controller.

[0175]

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

[0176]

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

[0177]

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

[0178]

[0197] In some embodiments, including all of the above, the atmosphere controller maintains consistent atmospheric conditions inside the unglazed section.

[0179]

[0198] In some embodiments, including all of the above, the atmosphere controller maintains consistent atmospheric conditions inside the sintered section.

[0180]

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

[0181]

[0200] In some embodiments, including all 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 sintered section containing argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof.

[0183]

[0202] In some embodiments, including all of the above, the atmosphere controller maintains an atmosphere containing less than 500 ppm of O2 in the bisque section, the sintered section, or both the bisque section and the sintered section.

[0184]

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

[0185]

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

[0186]

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

[0187]

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

[0188]

[0207] In some embodiments, including all of the above, the atmosphere controller maintains an atmosphere containing less than 10 ppm of O2 in the bisque section, the sintered section, or both the bisque section and the sintered section.

[0189]

[0208] In some embodiments, including all of the above, the atmosphere controller maintains an atmosphere in the binder burnout section containing less than 5% v / v H2O.

[0190]

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

[0191]

[0210] In some embodiments that include all of the above, H2 gas is present at approximately 2.9% v / v.

[0192]

[0211] In some embodiments that include all of the above, H2 gas is present at approximately 5% v / v.

[0193]

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

[0194]

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

[0195]

[0214] In some uses herein, at least one furnace is pumped to a low vacuum to remove air from inside at least one furnace, and then at least one furnace is refilled with an inert or reducing gas. For example, at least one furnace may be refilled with N2. For example, at least one furnace may be refilled with Ar / H2. For example, at least one furnace may be refilled with Ar.

[0196]

[0215] In some embodiments, including all of the above, the atmosphere of the binder burnout section differs from that of the unglazed section.

[0197]

[0216] In some embodiments, including all of the above, the atmosphere of the binder burnout section differs from that of the sintered section.

[0198]

[0217] In some embodiments, including all of the above, the atmosphere of the unglazed section is different from the atmosphere of the sintered section.

[0199]

[0218] In some embodiments that include 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 that include all of the above, the amount of CO2 in the binder burnout section is less than 0.2 volume%.

[0201]

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

[0202]

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

[0203]

[0222] In some embodiments, including all of the above, the bilayer body shrinks primarily in the z direction as it progresses through the sintering section. In this specification, the z direction is directly perpendicular to the surface of the bilayer body. In this specification, the x direction is the direction in which the bilayer body progresses through the processing apparatus. The y direction is perpendicular to the x direction and lies in the same plane as the bilayer body. The z direction is perpendicular to both the x and y directions.

[0204]

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

[0205]

[0224] In some embodiments, including all of the above, the apparatus is configured to heat the two layers at a rate faster 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 all of the above, the processing apparatus is configured to heat the two layers at a rate of approximately 5°C / min to approximately 50°C / min.

[0207]

[0226] In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 0.5°C / cm to about 50°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 1°C / cm to about 5°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 0.5°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 1°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 2°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 3°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 4°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 5°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 6°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 7°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 8°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 9°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 10°C / cm. In some embodiments including all of the above, the apparatus is configured to heat the two-layer body at a space velocity of about 11°C / cm.

[0208]

[0227] In some embodiments including any of the foregoing, the processing apparatus comprises an infrared heater, which is used for heating the two-layer body.

[0209]

[0228] In some embodiments including any of the foregoing, the processing apparatus comprises 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 two-layer body.

[0210]

[0229] In some embodiments including any of the foregoing, the processing apparatus heats the two-layer body using carbon plate / induction heating.

[0211]

[0230] In some embodiments including any of the foregoing, the processing apparatus comprises heating by an illumination lamp for heating the two-layer body. In some embodiments including heating by an illumination lamp, the processing apparatus further comprises a susceptor configured to absorb at least 20% of radiation emitted by the illumination lamp.

[0212]

[0231] In some embodiments including any of the foregoing, the processing apparatus comprises heating by an oven.

[0213]

[0232] According to embodiments, the heating element used herein may be a carbon plate or carbon paper. In some embodiments, the carbon plate or carbon paper comprises induction carbon. According to embodiments, the heating element may be a molybdenum plate or molybdenum paper. In some embodiments, the molybdenum plate or molybdenum paper may comprise induction molybdenum. By applying an electric current, the induction carbon plate or induction carbon paper element can be heated at a suitable rate to a temperature that facilitates sintering within the temperature range described herein.

[0214]

[0233] In one embodiment, the maximum heating temperature may range from 900°C to 2000°C. In one embodiment, the heating temperature may range from 900°C to 1900°C. In one embodiment, the heating temperature may range from 900°C to 1800°C. In one embodiment, the heating temperature may range from 900°C to 1800°C. In one embodiment, the heating temperature may range from 900°C to 1700°C. In one embodiment, the heating temperature may range from 900°C to 1600°C. In one embodiment, the heating temperature may range from 900°C to 1500°C. In one embodiment, the heating temperature may range from 900°C to 1400°C. In one embodiment, the heating temperature may range from 900°C to 1300°C. In one embodiment, the heating temperature may range from 900°C to 1200°C.

[0215]

[0234] In one embodiment, the duration of staying in the maximum temperature heating zone may range from 5 seconds to 30 minutes. In one embodiment, the heating time may range from 5 seconds to 25 minutes. In one embodiment, the heating time may range from 5 seconds to 20 minutes. In one embodiment, the heating time may range from 5 seconds to 15 minutes. In one embodiment, the heating time may range from 5 seconds to 10 minutes. In one embodiment, the heating time may range from 5 seconds to 5 minutes. In one embodiment, the heating time may range from 5 seconds to 4 minutes. In one embodiment, the heating time may range from 5 seconds to 3 minutes. In one embodiment, the heating time may range from 5 seconds to 4 minutes. In one embodiment, 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 heating. In some embodiments, the heating element may be longer than the material under heating and have the same width as the material under heating. In some embodiments, the heating element may have the same length as the material under heating and be wider than the material under heating. In some embodiments, the heating element may be shorter than the material under heating. In an embodiment where there is a single heating element, the heating element may have any of the area relationships described above relative to the material under heating.

[0217]

[0236] In some embodiments, including all of the above, the processing apparatus has a cooling zone after the sintering section. For example, in a 60-inch furnace, there may be a 20-inch heating 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 body. In some cases, at least one furnace has a 2 mm gap above the green body. In some cases, at least one furnace has a 3 mm gap above the green body. In some cases, at least one furnace has a 4 mm gap above the green body. In some cases, at least one furnace has a 5 mm gap above the green body. This gap prevents lithium from leaking out of the green body.

[0219]

[0238] In some embodiments, including all of the above, the processing apparatus is configured to reduce or eliminate wrinkles in the transverse direction of the web by applying a tension of an appropriate magnitude. For example, the tension may be kept relatively low to avoid plastic deformation of the metal foil substrate at high temperatures. In certain examples, the tension applied to the metal foil during sintering is 0.4N to 4N.

[0220]

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

[0221]

[0240] In some embodiments, including all of the above, the processing apparatus is configured to reduce or eliminate web transverse wrinkles by using a roller at at least one furnace entry or exit point. A slip roller, drive roller, lower drive roller, upper drive roller, or other roller may be used.

[0222]

[0241] In some embodiments, including all of the above, the processing apparatus is configured such that the residence time in the sintering section is 2 minutes or less.

[0223]

[0242] In some embodiments that include all of the above, the processing apparatus is configured such that the residence time in the sintering section is 1 minute and 30 seconds or less.

[0224]

[0243] In some embodiments that include any of the above, the processing apparatus is configured such that the residence time in the sintering section is 1 minute or less.

[0225]

[0244] In some embodiments, including all of the above, the processing apparatus is configured such that the residence time in the sintering section is approximately 30 seconds or less.

[0226]

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

[0227]

[0246] In some embodiments that include all of the above, the processing apparatus is configured such that the residence time in the binder burnout section is approximately 10 times the residence time in the sintering section.

[0228]

[0247] In some embodiments, including all of the above, the processing apparatus comprises at least one tension regulator.

[0229]

[0248] In some embodiments that include all of the above, the tension of the two layers after the front roller is approximately 270g.

[0230]

[0249] In some embodiments that include all of the above, the tension of the two layers before the end roller is approximately 500g.

[0231]

[0250] In some embodiments including any of the foregoing, the width of the two-layer body is 8 cm.

[0232]

[0251] In some embodiments including any of the foregoing, the tension applied to the two-layer body is about 34 g / cm.

[0233]

[0252] In some embodiments including any of the foregoing, the tension applied to the two-layer body is about 0.1 N per 1 μm of thickness.

[0234]

[0253] In some embodiments including any of the foregoing, the tension applied to the two-layer body is less than 50% of its yield strength.

[0235]

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

[0236]

[0255] In some embodiments including any of the foregoing, the tension applied to the two-layer body is about 25% to 50% of its yield strength.

[0237]

[0256] In some embodiments including any of the foregoing, the tension of the two-layer body is about 25% to 50% of the yield strength of the metal layer.

[0238]

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

[0239]

[0258] In some embodiments including any of the foregoing, the green body is a patch-coated green tape. Patch-coating means that the green body is not continuously deposited on the metal layer. Patch-coating means that the green body is deposited on the metal layer at intervals. The metal layer may have slits between patches or may be partially cut. The metal between patches can be used as a tab of a battery cell.

[0240]

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

[0241]

[0260] In some embodiments, including all of the above, the binder burnout furnace is a furnace heated to a temperature sufficient to cause volatilization, thermal decomposition, combustion, or decomposition of the binder present in the green material.

[0242]

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

[0243]

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

[0244]

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

[0245]

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

[0246]

[0265] In some embodiments that include all of the above, the firing section is a firing furnace.

[0247]

[0266] In some embodiments, including all of the above, the firing furnace is a furnace that is heated to a temperature sufficient to fire the green body after the binder has been removed.

[0248]

[0267] In some embodiments that include all of the above, the temperature of the firing furnace is between 100°C and 800°C.

[0249]

[0268] In some embodiments that include all of the above, the sintering section is a sintering furnace.

[0250]

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

[0251]

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

[0252]

[0271] In some embodiments that include all of the above, the temperature of the sintering furnace is 500°C to 1300°C.

[0253]

[0272] In some embodiments that include all of the above, the temperature of the sintering furnace is 1000°C to 1300°C.

[0254]

[0273] In some embodiments that include all of the above, the temperature of the sintering furnace is 1100°C to 1300°C.

[0255]

[0274] In some embodiments, including all 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 all of the above, at least one furnace is a single furnace. In some embodiments including all of the above, at least one end roller has a roller diameter greater than 4 cm. In some embodiments including all of the above, at least one end roller has a roller diameter greater than 5 cm. In some embodiments including all of the above, at least one end roller has a roller diameter greater than 6 cm. In some embodiments including all of the above, at least one end roller has a roller diameter greater than 7 cm. In some embodiments including all of the above, at least one end roller has a roller diameter greater than 8 cm. In some embodiments including all of the above, at least one end roller has a winding tension greater than 20 g per 1 cm of straight web width.

[0257]

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

[0258]

[0277] In some embodiments, including all of the above, the upper and lower voids of the bilayer are configured such that the bilayer contains at least 95% by weight of lithium after processing compared to before processing in the processing apparatus.

[0259]

[0278] In some embodiments that include any of the above, the processing apparatus comprises at least two end rollers.

[0260]

[0279] In some embodiments, including all of the above, the green body comprises unsintered lithium-filled garnet or a chemical precursor of lithium-filled garnet.

[0261]

[0280] In some embodiments, including all of the above, the processing apparatus comprises a sintered bilayer body wound around at least one end roller.

[0262]

[0281] In some embodiments that include any of the above, the sintered bilayer body includes a lithium-filled garnet sintered body. In some embodiments that include any of the above, the sintered bilayer body includes a lithium aluminum germanium phosphate sintered body. In some embodiments that include any of the above, the sintered bilayer body includes a lithium aluminum titanium phosphate sintered body.

[0263]

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

[0264]

[0283] In some embodiments that include any of the above, the green compound includes a dispersant. In some embodiments that include any of the above, the green compound includes a plasticizer.

[0265]

[0284] In some embodiments that include any of the above, the Greene compound comprises a solvent or a combination of solvents.

[0266]

[0285] In some embodiments, including all of the above, the processing apparatus is configured to advance the two-layer body through at least one furnace at a speed of at least 2 inches per minute.

[0267]

[0286] In some embodiments, including all of the above, the processing apparatus is configured to advance the two layers through the sintering section at a speed of at least 2 inches per minute.

[0268]

[0287] In some embodiments including all of the above, the processing apparatus comprises a curved ramp in front of at least one furnace. In some embodiments including all of the above, the processing apparatus comprises a curved ramp in front of the binder burnout section. In some embodiments including all of the above, the processing apparatus comprises a curved ramp in front of the bisque firing section. In some embodiments including all of the above, the processing apparatus comprises a curved ramp in front of the sintering section. In some embodiments including all of the above, the processing apparatus comprises a curved ramp inside at least one furnace. In some embodiments including all of the above, the processing apparatus comprises a curved ramp inside the binder burnout section. In some embodiments including all of the above, the processing apparatus comprises a curved ramp inside the bisque firing section. In some embodiments including all of the above, the processing apparatus comprises a curved ramp inside the sintering section. In some embodiments including all of the above, the curved ramp is coated.

[0269]

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

[0270]

[0289] In some embodiments that include all of the above, the coating is a boron nitride coating.

[0271]

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

[0272]

[0291] In some embodiments that include all of the above, the ceramics are silicon carbide, boron nitride, alumina, zirconia, and lithium aluminate.

[0273]

[0292] In some embodiments, including all of the above, the ramps are made of SS 430, SS 304, Kovar, Invar, Haynes 214, alumina with more than 99.5% (w / w), carbon composites, boron nitride, or a combination thereof. In some embodiments, speed bumps are placed on the runway. In some embodiments, speed bumps are placed on a flat runway. In some embodiments, speed bumps are placed on a curved runway. These bumps relieve stress on the metal layer that is always in contact with the runway. These bumps create a “gap” when the membrane rides over and passes over the “speed bumps”. In some embodiments, there are speed bumps on the runway spaced about 1 inch apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced about 2 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced about 3 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 4 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 5 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 6 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 7 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 8 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 9 inches apart from the next speed bump. In some embodiments, there are speed bumps on the runway spaced approximately 10 inches apart from the next speed bump.

[0274]

[0293] A unique atmosphere, in this context, means that the gaseous or vapor environment in one furnace is substantially different from the gaseous or vapor environment in another furnace. For example, a substantial difference between one oven and another could, but are not limited to, a difference of 5% or more in total pressure, a difference of 5% or more in partial pressure, a difference of twice the concentration or amount of a given gas (e.g., O2, H2, N2, Ar, Xe, or H2O), or a 50% difference in the flow rate of one or more gases (e.g., a gas mixture) between one oven and another. For example, one furnace may contain a sufficient amount of H2O and / or O2 so that organic materials can burn when heated to their ignition temperature. This could be a condition for a binder burnout section. In such an example, if another furnace has a low concentration of O2, combustion may not be sustained there even at its combustion temperature, which could demonstrate a substantial difference between one oven and another. 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 higher than parts per million (ppm), while another oven may contain water vapor at a concentration of less than 100 ppm. This difference in H2O partial pressure can also demonstrate a substantial difference between one oven and another. In yet another example, one oven may be under vacuum while another is at 1 atmosphere, and this difference can represent a substantial difference between one oven and another. In yet 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 can represent a substantial difference between one oven and another.

[0275]

[0294] In certain embodiments, the binder burnout oven may contain an oxidizing agent mixed in the gas or atmosphere in contact with the green tape. Such oxidizing agents may include H2O, O2, or clean, dry air. In certain embodiments, the sintering oven does not contain an oxidizing agent mixed in the gas or atmosphere in contact with the film being sintered.

[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 contains hydrogen (H2) gas.

[0279]

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

[0280]

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

[0281]

[0300] In some embodiments, the pressurized enclosure further includes an inert gas, but is not limited to N2, H2, Ar, and mixtures thereof, for example, 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 parts per ten million (ppm). In some embodiments, including any of the above, O2 is present at 5-10 ppm.

[0282]

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

[0283]

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

[0284]

[0303] In some embodiments, including all of the above, O2 is present in the binder burnout oven at a concentration of 5–10 ppm.

[0285]

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

[0286]

[0305] In some embodiments, which include all of the above, O2 is placed in a sintering oven for 10 -16 ~10 -20 It exists in Pa.

[0287]

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

[0288]

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

[0289]

[0308] In certain embodiments, rapid sintering occurs within a closed space. The closed space may have an atmosphere that helps reduce lithium loss during LLZO sintering and retain a stoichiometric amount of lithium in a given LLZO formula. The closed space may be a portion of the oven through which the sintering film passes as it progresses. Certain processes described herein include a step of suspending the film using tension without contact with the surface. The tension may be applied by weights, roller motors, load cells, or other means for applying tension. Certain processes described herein include a step of suspending the film using tension without contact with the surface while the film progresses through the aforementioned closed space. In this specification, the suspended portion of the film is not in contact with the surface, but the mechanism used to apply tension is in contact with other portions of the film. In some embodiments, only the suspended portion of the film is sintered, while the film does not touch other surfaces. Certain processes described herein include a step of bringing only one surface into contact during sintering (for example, the bottom surface of the tape or film may be in contact with a roller, tensioning mechanism, or substrate). Certain processes described herein include a step of suspending the film without contact with a surface using tension, gas flow, or a combination of both tension and gas flow. In this specification, “without contact with a surface” specifically refers to the film being sintered as it moves through the oven. While in the sintering stage, any portion of the green tape being sintered does not come into contact with any surface that could cause sintering defects on the surface of the green tape. When the green tape exits the oven, it may come into contact with rollers, rewinders, pins, posts, tensioning mechanisms, etc., which come into contact with the surface of the green tape. Similarly, when the film being sintered 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 specific process described herein includes the step of continuously peeling the green tape from a Mylar substrate on which the green tape is placed.This may be done at the beginning of the sintering process, when the green tape is unwound from the roller and the peeled green tape is introduced into the binder burnout oven. Specific processes described herein include applying tension to the green film while it is being sintered. Specific processes described herein include avoiding reaction with water / oxygen in the surrounding environment while the green tape is being processed from green tape to sintered LLZO film. In some embodiments, metal foil is used instead of 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 iron-nickel combination is more than 1% iron and the remainder nickel. In certain embodiments, the iron-nickel combination is more than 2% iron and the remainder nickel. In certain embodiments, the iron-nickel combination is more than 3% iron and the remainder nickel. In certain embodiments, the iron-nickel combination is more than 4% iron and the remainder nickel. In certain embodiments, the iron-nickel combination is more than 5% iron and the remainder nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 6% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 7% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 8% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 9% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 10% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 11% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 12% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 13% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 14% and the remainder is nickel.In certain embodiments, the combination of iron and nickel is such that iron exceeds 15% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 16% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 17% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 18% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 19% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 20% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 11% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 12% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 13% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 14% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 15% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 16% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 17% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 18% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 19% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 20% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 11% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 12% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 13% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 14% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 15% is iron and the remainder is nickel.In certain embodiments, the combination of iron and nickel is such that iron exceeds 16% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 17% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 18% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 19% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 20% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 21% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 22% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 23% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 24% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 25% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 26% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 27% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 28% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 29% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 30% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 31% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 32% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 33% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 34% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 35% and the remainder is nickel. In certain embodiments, the combination of iron and nickel consists of more than 36% iron and the remainder being nickel.In certain embodiments, the combination of iron and nickel is such that iron exceeds 37% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 38% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 39% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 40% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 41% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 42% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 43% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 44% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 45% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 46% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 47% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 48% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 49% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 50% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 51% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 52% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 53% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 54% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 55% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 56% and the remainder is nickel. In certain embodiments, the combination of iron and nickel consists of more than 57% iron and the remainder being nickel.In certain embodiments, the iron-nickel combination is more than 58% iron and the remainder being nickel. In certain embodiments, the iron-nickel combination is more than 59% iron and the remainder being nickel. In certain embodiments, the iron-nickel combination is more than 60% iron and the remainder being nickel. In certain embodiments, the iron-nickel combination is more than 61% iron and the remainder being nickel. In certain embodiments, the iron-nickel combination is more than 62% iron. In certain embodiments, the combination of iron and nickel is such that iron exceeds 63% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 64% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 65% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 66% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 67% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 68% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 69% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 70% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 71% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that iron exceeds 72% and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 73% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 74% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 75% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 76% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 77% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 78% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 79% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 80% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 81% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 82% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel consists of more than 83% iron and the remainder being nickel.In certain embodiments, the combination of iron and nickel is such that more than 84% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 85% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 86% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 87% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 88% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 89% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 90% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 91% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 92% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 93% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 94% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 95% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 96% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 97% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 98% is iron and the remainder is nickel. In certain embodiments, the combination of iron and nickel is such that more than 99% is iron and the remainder is nickel.

[0290]

[0309] In some embodiments, the binder burnout chimney is replaced by a Watlow heater cartridge embedded in a plate, which is perforated so that the gas can diffuse through it. The plate may incorporate a gas diffuser, gas manifold, channel, or other means of directing the gas flow over one or more product surfaces. The unit is equipped with an exhaust port for removing the debinder product.

[0291]

[0310] In some embodiments, a 6-inch diameter Lindbergh bisque tubular furnace is used. In some embodiments, this furnace is 650°C. The furnace can be 200-900°C. The furnace may incorporate multiple temperature zones. The furnace may include members for supporting the product in transit; these members may be made of Inconel, Hastelloy, Haynes alloy 214, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, alumina, or other ceramics or metals. The support members may include coatings of Haynes alloy, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, alumina, or other ceramics or metals.

[0292] D. Usage Process

[0311] In some embodiments, this specification describes a process for using a continuous process apparatus, which includes the following operations: (a) heating the green bilayer as it moves through at least one furnace to produce a bilayer with an organic content of less than 1%; and (b) winding the bilayer with an organic content of less than 1% onto rollers.

[0293]

[0312] In some embodiments, this specification describes a process for using a continuous process apparatus, which includes the following operations: (a) providing or leaving the process apparatus disclosed herein; (b) producing a bisque-fired bilayer by heating the bilayer as it moves through at least one furnace; and (c) winding up the bisque-fired bilayer.

[0294]

[0313] In some embodiments that include any of the above, the process includes step (d) unwinding the bisque-fired bilayer.

[0295]

[0314] In some embodiments that include any of the above, the process includes step (e) sintering the two layers.

[0296]

[0315] In some embodiments that include any of the above, the process includes winding the sintered bilayer onto an end roller.

[0297]

[0316] In some embodiments, which include any of the above, a sintered bilayer body as a cut strip.

[0298]

[0317] In some embodiments, which include all of the above, the bisque-fired bilayer after step (c) is wound onto a roller until it is subsequently sintered.

[0299]

[0318] In some embodiments, this specification describes a process for using a continuous process apparatus, which includes the following operations: (a) providing or leaving a process apparatus disclosed herein; and (b) producing a sintered bilayer by heating the bilayer as it progresses through at least one furnace.

[0300]

[0319] During this process, various embodiments of use are possible depending on the specific conditions and the articles 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 mechanical fastening 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 the surface (e.g., setter). During the sintering process, the green tape is suspended in certain embodiments so that it does not come into contact with the surface (e.g., setter). This suspension can be achieved by various means. For example, the green tape may 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 tape being sintered will move through a narrow gap made of nickel-plated metal plates. In some embodiments, these metal plates are stainless steel metal plates. In some embodiments, this gap is less than 5 mm thick, where thickness is the maximum distance between nickel-plated metal plates perpendicular to one surface of those metal plates. In some embodiments, this gap is less than 4.5 mm. In some embodiments, this gap is less than 4 mm. In some embodiments, this gap is less than 3.5 mm. In some embodiments, this gap is less than 3 mm. In some embodiments, this gap is less than 2.5 mm. In some embodiments, this gap is less than 2 mm. In some embodiments, this gap is less than 1.5 mm. In some embodiments, this gap is less than 1 mm. In some embodiments, this gap is less than 0.5 mm. In some embodiments, this gap is less than 500 μm. In some embodiments, this gap is less than 400 μm.In some embodiments, this gap is less than 300 μm. In some embodiments, this gap is less than 200 μm. In some embodiments, this gap is less than 100 μm. In some embodiments, this narrow gap helps prevent lithium loss from the sintered product during the sintering process.

[0301]

[0320] In some embodiments, the flatness of the green tape is controlled by applying tension to the green tape. In some embodiments, the flatness of the green tape is controlled by precise tape slitting such that the stress on the edges of the sintered product is minimized. In some embodiments, the flatness of the green tape is controlled by laser cutting of the edges of the article before or after sintering. In some embodiments, the flatness of the green tape is controlled by adjusting the lateral heating profile, for example, by heating the center of the film first. In some embodiments, the flatness is controlled by the precise alignment of the tensioning roller and other rollers in the processing apparatus.

[0302]

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

[0303]

[0322] In some embodiments, the process will utilize atmosphere control. This may include, for example, controlling the amount of O2 in the sintering oven to less than 100 ppm or lower. In some embodiments, atmosphere control may include forming a gas curtain around the oven (e.g., around the oven inlet and outlet) using N2, Ar, or other inert gases. In some embodiments, atmosphere control may include using vortices around the oven inlet and outlet. In some embodiments, atmosphere control may include using narrow openings around the oven inlet and outlet. In some embodiments, atmosphere control may include using gas injection near the center of the oven. This gas injection may result in laminar flow from the center of the oven to both ends. In some embodiments, atmosphere control may include 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, atmosphere control involves using an enclosure to provide a confined environment with atmosphere control around or near the oven. For example, the enclosure may be filled with nitrogen, with a portion of it exposed to a reducing environment. A reducing environment can be achieved by providing H2 or CO at a certain partial pressure.

[0305]

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

[0306]

[0325] To avoid surface contamination of the sintered product or the article before sintering as it passes through the processing apparatus, the film may be cooled to below 40°C. In some embodiments, the sintered film is maintained in an atmosphere with a low H2O content. For example, the H2O 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] Due to the mechanical properties of the two-layer green tape, it will shrink when processed in the processing apparatus; therefore, a different tape speed (e.g., different roller rotation speeds) may be used in the green tape stage compared to the binder burnout stage or the sintering stage. The tape speed may also differ from part to part of the line. Such variable speeds can be achieved in some embodiments by independent tension control (e.g., a dancer after firing, tension control after sintering).

[0308]

[0327] Due to lateral shrinkage during sintering, the two-layer structure may shrink laterally. Therefore, the length of the sintering zone (along the tape direction) may be made larger compared to the lateral shrinkage distance. This will result in a smaller tape edge angle.

[0309]

[0328] The strength of the green tape may change as it is processed in the processing apparatus. To accommodate this, the tape tension may be variable throughout the entire processing apparatus. For example, in a binder burnout oven, the tape may be under one tension setting; in a bisque oven, the tape may be under a different tension setting; and in a sintering oven, the tape may be under yet another different tension. In the winding and unwinding sections, the tape may be under higher tension than in the burnout oven, bisque oven, or sintering oven.

[0310]

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

[0311]

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

[0312]

[0331] In some embodiments, the green tape moves through the processing device at a speed of approximately 2 to 25 inches per minute. In some embodiments, the green tape moves through the processing device at a speed of approximately 3 to 6 inches per minute. In some embodiments, the green tape moves through the processing device at a speed of approximately 1 to 5 inches per minute. In some embodiments, the green tape moves through the processing device at a speed of approximately 5 to 10 inches per minute.

[0313]

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

[0314]

[0333] In some embodiments, including all of the above, the speed at which the tape moves through the processing apparatus refers to the distance traveled and the time taken to travel through the sintering oven.

[0315]

[0334] Figure 12 shows one embodiment of the processing apparatus in a vertical processing orientation. The two-layer body 1101 is unwound as a two-layer body 1109 as it moves through the first heating zone 1102, the second heating zone 1104, the third heating zone 1106, and the fourth heating zone 1107. Heating zone 1107 may also be a cooling zone. Rollers 1103 and 1105 help guide the two-layer body and maintain the appropriate tension on the two-layer body. The final product is shown as a sintered roll 1108, which may also be a bisque roll 1108 if sintering did not occur in the heating zones. The two-layer body 1109 moves vertically upward, away from the ground, as it moves through zone 1102. The two-layer body 1109 moves downward, towards the ground, as it moves through zone 1106. The two-layer body 1109 moves parallel to the ground, as it moves through zone 1104.

[0316] E. Materials formed by the processes disclosed herein

[0335] In some embodiments, the Specified Material shows bisque products prepared by the processes of the Specified Material.

[0317]

[0336] In some embodiments, this specification shows sintered articles prepared by the processes described herein.

[0318]

[0337] In some embodiments, this specification shows a bisque bilayer containing lithium-filled garnet, where the bisque bilayer is wound onto a roller and the bilayer is less than 100 μm thick.

[0319]

[0338] In some embodiments that include all of the above, the two-layer body 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 that include all of the above, the grain size of the two-layer ceramic sintered layer is d 90 The ceramic sintered layer has a porosity of <5 μm, or <4 μm, or <3 μm, or <2 μm, or <1 μm. The ceramic sintered layer has a porosity of <10 vol%, or <8 vol%, or <6 vol%, or <5 vol%, or <4 vol%, or <3 vol%, or <2 vol%, or <1 vol%, or <0.5 vol%. The interfacial porosity (porosity within 5 μm closest to the bilayer interface) is <2 vol%, or <1.5 vol%, or <1 vol%, or <0.5 vol%. These variables can be controlled by the sintering atmosphere used in the production of the sintered bilayer. These characteristics can be achieved by controlling the gas atmosphere, ramp rate, and sintering holding time. The slurry contains particles less than 1 μm, less than 0.5 μm, less than 0.25 μm, or less than 0.1 μm. 50 It may contain ceramic particles having a particle size of [specify particle size].

[0321]

[0340] In some embodiments, this specification shows a sintered bilayer containing lithium-filled garnet, where the bilayer is wound around a roller and the bilayer is less than 100 μm thick.

[0322]

[0341] In some embodiments that include all of the above, the two-layer body 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 all of the above, the metal foil layer comprises nickel, iron, or a combination thereof.

[0324]

[0343] In some embodiments, this specification shows a sintered bilayer body prepared by the process described herein.

[0325]

[0344] In some embodiments that include any of the above, the sintered bilayer body contains lithium-filled garnet.

[0326]

[0345] In some embodiments that include all of the above, the two-layer body 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 all of the above, the metal foil layer comprises nickel, iron, or a combination thereof.

[0328]

[0347] In some embodiments, including all of the above, the green layer comprises unsintered lithium-filled garnet.

[0329]

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

[0330]

[0349] In some embodiments, including all of the above, 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 all of the above, the metal layer of the bilayer is an alloy of Fe and Ni.

[0332]

[0351] In some embodiments, including all of the above, the two-layer metal layer is an alloy of Fe and Ni, with Fe making up 1% to 25% (w / w) and the remainder being Ni.

[0333]

[0352] In some embodiments that include all of the above, the thickness of the metal layer in the two-layer structure is 1 μm to 20 μm.

[0334]

[0353] In some embodiments that include all of the above, the thickness of the metal layer in the two-layer structure is 1 μm to 10 μm.

[0335]

[0354] In some embodiments, including all of the above, the processing apparatus comprises a green tape wrapped around at least one front roller.

[0336]

[0355] In some embodiments, the sintering of the LLZO film is carried out without a portion of the LLZO film in contact with other surfaces, such as the surface of the processing apparatus, during the sintering process. Unexpectedly, this non-contact of a portion of the film during sintering can result in advantageous properties such as low flatness, retention of stoichiometric amounts of lithium in a given LLZO formula, and favorable microstructure (e.g., high density, small grain size, and combinations thereof). Because the upper surface of the film is not in contact with other surfaces, surface defects such as scratches or tears are reduced.

[0337]

[0356] In some embodiments that include all of the above, the sintered product comprises a two-layer body. In some embodiments, the two-layer body comprises a metal foil and a ceramic film. In some embodiments, the sintered product comprises a three-layer body, 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 layer is 17 μm thick. In some embodiments, the Ni layer is 18 μm thick. In some embodiments, the Ni layer is 19 μm thick. In some embodiments, the Ni layer is 20 μm thick.

[0338]

[0357] In some embodiments, a slurry may be deposited on a foil strip to form a green tape with a backing foil. In some embodiments, the foil is Mylar foil. The green tape with the backing foil can be wound onto a roll to form a roll of unsintered film with a backing foil. The roll of unsintered film with a backing foil can be loaded into an apparatus as described herein. In some embodiments, the method of using the apparatus may include (a) loading the roll of unsintered film with a backing foil onto a front roller, (b) spreading out the roll of unsintered film, (c) sintering the unsintered film to produce a sintered film with a backing foil, and (d) rolling the sintered film with a backing foil onto an end roller, all of which are performed in a controlled atmosphere. In some embodiments, the backing foil may include nickel metal or nickel foil.

[0339]

[0358] In some embodiments, the green film sintered using the processing apparatus is a two-layer or three-layer structure.

[0340]

[0359] In some embodiments, various layer configurations are envisioned and can be sintered according to the sintering methods shown herein: A) Self-supporting lithium-filled garnet material; B) Self-supporting lithium-filled garnet material optionally containing an active substance, binder, solvent, and / or carbon; C) Two-layer body having one lithium-filled garnet layer and one metal powder layer, metal foil layer, or metal sheet layer; D) Two-layer body having one lithium-filled garnet layer and one layer containing metal powder, metal foil, or metal sheet; E) One lithium-filled garnet material layer optionally containing an active substance, binder, solvent, and / or carbon, and one metal powder layer, metal F) A two-layer body having a metal foil layer or a metal sheet layer; G) A three-layer body having two lithium-filled garnet layers and one layer of metal powder, metal foil, or metal sheet between the garnet layers and in contact with them; and H) A three-layer body having two lithium-filled garnet material layers in which each garnet layer optionally contains an active substance, binder, solvent, and / or carbon, and one layer of metal powder, metal foil, or metal sheet between the garnet layers and in contact with them.

[0341]

[0360] In some cases, a two-layer body may be sintered using the apparatus described herein. In some cases, a three-layer body may be sintered using the apparatus described herein.

[0342]

[0361] The three-layer structure may include a lithium-filled garnet layer, a metal layer, and a second lithium-filled garnet layer on the opposite side of the metal layer. The two-layer film may pass through the processing apparatus with the lithium-filled garnet layer facing upwards and the second lithium-filled garnet layer facing downwards.

[0343]

[0362] The two-layer structure may comprise a lithium-filled garnet layer and a metal foil layer. In some embodiments, the metal layer may comprise Ni, Fe, Cu, Al, Sn, In, Ag, Au, steel, alloys, or combinations thereof. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may comprise 90% Ni and 10% Fe. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may comprise 91% Ni and 9% Fe. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may comprise 92% Ni and 8% Fe. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may comprise 93% Ni and 7% Fe. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may comprise 94% Ni and 6% Fe. For example, the metal layer may comprise Ni and Fe. For example, the metal layer may contain 95% Ni and 5% Fe. For example, the metal layer may contain Ni and Fe. For example, the metal layer may contain 96% Ni and 4% Fe. For example, the metal layer may contain Ni and Fe. For example, the metal layer may contain 97% Ni and 3% Fe. For example, the metal layer may contain Ni and Fe. For example, the metal layer may contain 98% Ni and 2% Fe. For example, the metal layer may contain Ni and Fe. For example, the metal layer may contain 99% Ni and 1% Fe. In some embodiments, the metal layer is a sheet of metal. In some embodiments, the metal layer is a sheet of aluminum. In some embodiments, the metal layer is a sheet of 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 described herein have a thickness of 1 μm to 100 μm. In certain embodiments, such films are co-sintered with a mixed amount 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 a film. In some embodiments, the film contains a uniform mixture of lithium-filled garnet and metal. The relative amounts of lithium-filled garnet and metal can vary from 1% lithium-filled garnet with the remainder being metal, on a volume percentage basis, to up to 99% lithium-filled garnet with the remainder being metal.

[0345]

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

[0346]

[0365] The processing systems and processes described herein are useful for the manufacture of various materials. Such materials include, but are not limited to, lithium-filled garnet films. Such materials include, but are not limited to, two-layer structures in which a lithium-filled garnet film is located on a metal layer, or three-layer structures in which a metal layer is located between two lithium-filled garnet films.The processing systems and processes described herein are not limited to, but include, PCT / US2016 / 043428, filed on 21 July 2016 and published as International Publication No. 2017015511A1, titled "PROCESSES AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS"; PCT / US2019 / 056584, filed on 16 October 2019 and published as International Publication No. 2020081718A1, titled "SINTERING LARGE AREA CERAMIC FILMS"; and PCT / US2016 / 15209, filed on 27 January 2016 and published as International Publication No. 2017131676A1, titled "ANNEALED GARNET ELECTROLYTE PCT / US2017 / 039069, filed on January 23, 2017 and published as International Publication No. 2018236394A1 - Title of invention: "LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS", and PCT / US2019 / 54117, filed on October 1, 2019 and published as International Publication No. 2020072524A1 - Title of invention: "METHODS OF MAKING AND USING AN ELECTROCHEMICAL CELL COMPRISING AN INTERLAYER; including any of the sintered films or film-containing materials shown in U.S. Patent No. 10,403,931; No. 10,290,895; No. 9,966,630B2; No. 10,347,937B2; and No. 10,103,405 (each of these vessels is incorporated herein by reference as a whole for any purpose), is useful for the manufacture of lithium-filled garnet films or composite materials.

[0347]

[0366] In some embodiments, including all of the above, the ceramic-metal film may 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 contains both 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 ceramics is 70% and the volume percentage of metal is 30%. In some embodiments, the volume percentage of ceramics is 80% and the volume percentage of metal is 20%. In some embodiments, the volume percentage of ceramics is 90% and the volume percentage of metal is 10%. In some embodiments, the volume percentage of ceramics is 5% and the volume percentage of metal is 95%. In some embodiments, the volume percentage of ceramics is 15% and the volume percentage of metal is 85%. In some embodiments, the volume percentage of ceramics is 25% and the volume percentage of metal is 75%. In some embodiments, the volume percentage of ceramics is 35% and the volume percentage of metal is 65%. In some embodiments, the volume percentage of ceramics is 45% and the volume percentage of metal is 55%. In some embodiments, the volume percentage of ceramics is 55% and the volume percentage of metal is 45%. In some embodiments, the volume percentage of ceramics is 65% and the volume percentage of metal is 32%. In some embodiments, the volume percentage of ceramics is 75% and the volume percentage of metal is 25%.In some embodiments, the volume percentage of ceramics is 85% and the volume percentage of metal is 15%. In some embodiments, the volume percentage of ceramics is 95% and the volume percentage of metal is 5%.

[0348]

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

[0350]

[0369] In some embodiments, including all of the above, the ceramics 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, Li2ZrO3, xLi2O-(1-x)SiO2 (wherein x=0.01~0.99), aLi2O-bB2O3-cSiO2 (wherein a+b+c=1), LiLaO2, LiAlO2, Li2O, Li3PO4, or combinations thereof.

[0351]

[0370] In some embodiments, the three-layer structure includes a metal foil and green ceramic films on both sides of the metal foil. The metal foil of the two-layer or three-layer structure may have a thickness of 0.5 μm to 50 μm. The metal foil of the two-layer or three-layer structure may have a thickness of 3 μm to 30 μm. In some embodiments, the metal foil of the two-layer or three-layer structure may have a thickness of 5 to 20 μm. In other embodiments, the metal foil of the two-layer or three-layer structure may have a thickness of 5 μm to 15 μm.

[0352]

[0371] In some embodiments that include any of the above, the sintered product includes LLZO.

[0353]

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

[0354]

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

[0355]

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

[0356]

[0375] In some embodiments, including all of the above, the sintered ceramic film is less than 5 μm thick. 90 It has a grain size.

[0357]

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

[0358]

[0377] In some embodiments, including all of the above, the sintered film has an aspect ratio (height / diameter) greater than 1 and a perimeter of 1000 μm. 2 The surface defect density is such that there are fewer than 100 protrusions per square centimeter that are taller than 2 microns, based on the median height of the surface area.

[0359]

[0378] In some embodiments, including all of the above, the sintered film has an aspect ratio (height / diameter) greater than 1 and a perimeter of 1000 μm. 2 Based on the median height of the area, the surface has a defect density of fewer than 100 valleys per square centimeter with a depth exceeding 2 microns from the surface.

[0360]

[0379] In some embodiments, including all of the above, the sintered film has a surface defect density of fewer 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 all of the above, the sintered film has a surface defect density of fewer than 100 valleys per square centimeter at the interface between the lithium-filled garnet film and the metal layer, where the aspect ratio (height / diameter) is greater than 1.

[0362]

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

[0363]

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

[0364]

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

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

[0384] The processing apparatus disclosed herein can be used for sintering lithium-filled garnet onto a metal foil. 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 ceramics. In some of these embodiments, the ceramics are 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 a combination thereof. In some embodiments, the metal foil is produced at least in part by rolling annealing. In some embodiments, the metal foil is produced at least in part by electrodeposition.

[0367] In certain embodiments, 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 contains 5-20% Fe and 80-95% Ni. In some of these embodiments, the metal foil contains 10-20% Fe and 80-90% Ni.

[0368]

[0386] In certain embodiments, 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 contains 5-20% Cu and 80-95% Ni. In some of these embodiments, the metal foil contains 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 may 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 and can instead be sintered directly onto the metal. The green tape and metal may be rolled together before the green tape is advanced through the processing apparatus. In some embodiments, a backing layer is added to the metal, which is rolled together with the green tape onto the metal. In some embodiments, an interleaf layer is used when the metal is rolled together with the green tape on the metal. The interleaf provides a filler between the layers being rolled.

[0370]

[0388] In some embodiments, the processing apparatus is used for sintering lithium-filled garnet without an underlying substrate.

[0371]

[0389] In some embodiments, the apparatus is used for sintering a green lithium-filled garnet layer adjacent to a green oxide / metal mixture layer. The green oxide / metal mixture layer may contain 0.0001 to 25 wt% Ni powder, 1 to 25 wt% Fe powder, or a combination thereof. In some cases, the green oxide / metal mixture layer contains 1 to 20 wt% Ni and 1 to 10 wt% Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal mixture layer contains 5 to 15 wt% Ni and 1 to 5 wt% Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal mixture layer contains 10 to 15 wt% Ni and 3 to 5 wt% Fe, with the remainder being lithium-filled garnet.

[0372]

[0390] Other configurations are also considered in this specification. For example, the configuration of a bare film may be as follows: a sintered LLZO film without other metal-containing layers.

[0373]

[0391] For example, a co-sintered structure may include a two-layer body of green LLZO and a green metal-ceramic layer. The metal-ceramic layer is a mixture of metal and ceramic powders while in the green state.

[0374]

[0392] For example, a configuration on a metal foil may 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 does not contain ceramics and can be purchased, typically made by processes other than sintering (e.g., electrodeposition or rolling-annealing). The metal layer may contain less than 10 vol% additional ceramic inclusions.

[0375] G. Two-layer and additional embodiments

[0393] In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 700 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 600 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 500 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 400 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 300 mm.

[0376]

[0394] In some embodiments that include all of the above, the width of the two layers to be processed is approximately 250 mm.

[0377]

[0395] In some embodiments that include all of the above, the width of the two layers to be processed is approximately 200 mm.

[0378]

[0396] In some embodiments that include all of the above, the width of the two layers to be processed is approximately 150 mm.

[0379]

[0397] In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 100 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 90 mm. In some embodiments that include all of the above, the width of the two-layer body to be processed is approximately 80 mm.

[0380]

[0398] In some embodiments that include all of the above, the width of the two layers to be processed is approximately 50 mm.

[0381]

[0399] In some embodiments, including all of the above, the metal foil in the two-layer tape is an alloy of nickel, essentially made of Ni, essentially made of pure Ni, or made of pure Ni alone.

[0382]

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

[0383]

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

[0384]

[0402] In some embodiments including all 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 where there is no ceramic layer; such areas may be up to 15 mm wide. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 3 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 4 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 5 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 6 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 7 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of about 8 mm. In some embodiments including all of the above, the metal foil has one or two uncoated edges of 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 all of the above, the average thickness of the sintered dense ceramic layer ranges from 18 μm to 42 μm in the central region of the ceramic layer, and the thickness may vary locally by up to ±1.5 μm across the width and length of the web.

[0386]

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

[0387]

[0405] In some embodiments that include all of the above, the incoming two-layer material will be in the form of a roll wound around a core with a diameter of 3 to 6 inches.

[0388]

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

[0389]

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

[0390]

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

[0391] H. Gas and atmosphere I. Configuration

[0409] In some examples, each heating zone has its own individually controllable gas outlet and exhaust port, thus allowing different gases, different total flow rates, and different exhaust openings to flow through each zone. In these examples, the gas flow within each zone shall be perpendicular to the direction of web movement (i.e., machine). This means that flows perpendicular to the web or flows across the web are both permitted, but flows in the direction of the machine are not.

[0392] II. Available Gases

[0410] The systems and apparatus described herein shall allow the flow of the following gases or mixtures thereof: nitrogen (N2), foaming gas (N2 + H2, H2 < 5%), wet nitrogen, and wet foaming gas.

[0393] III. Requirements for Atmosphere

[0411] In some embodiments, while only N2 gas is flowing through all zones, the O2 levels, as measured by individually sampling the gas from each zone using an O2 analyzer, are maintained to be below 10 ppm to 50 ppm throughout the tool (e.g., furnace).

[0394]

[0412] In some embodiments, the H2O level requirements, as measured by sampling the gas individually from each zone using a dew point analyzer while the tool is in its typical gas flow configuration (which may include flowing a forming gas and wet nitrogen and wet forming gas), differ for each different section of the temperature profile.

[0395] IV. Gas Flow

[0413] In some embodiments, during the BBO stage, the maximum refresh rate is 1 to 3 exchanges per minute. 1 exchange per minute means that the gas flow rate, in terms of volume per minute, is equal to the internal volume available to the gas. 2 exchanges per minute means that the gas flow rate, in terms of volume per minute (in STP), is twice the internal volume available to the gas. In some embodiments, during the sintering stage, the maximum refresh rate is 0.3 to 3 exchanges per minute.

[0396] V. Wastewater Management

[0414] Organic vapors from binder removal tend to condense and leave residues on cooler surfaces. Any condensation on the inner surface of the tool must be avoided by heating the inner surface into which the binder waste liquid enters; this heating should be carried out continuously without cold spots until it reaches the building's exhaust system or cooling trap.

[0397] VI. Atmosphere Control

[0415] Atmosphere control can be provided by enclosing a complete processing system, or various components of a processing system (e.g., an oven), within an enclosure.

[0398]

[0416] Atmosphere control can be provided by using various gas curtains in a complete processing system or in various components of a processing system (e.g., an oven).

[0399]

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

[0400]

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

[0401]

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

[0402]

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

[0403]

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

[0404]

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

[0405]

[0423] In some embodiments, the process will utilize atmosphere control. This may include, for example, controlling the amount of O2 in the sintering oven to less than 100 ppm or lower. In some embodiments, atmosphere control may include forming a gas curtain around the oven (e.g., around the oven inlet and outlet) using N2, Ar, or other inert gases. In some embodiments, atmosphere control may include using vortices around the oven inlet and outlet. In some embodiments, atmosphere control may include using narrow openings around the oven inlet and outlet. In some embodiments, atmosphere control may include using gas injection near the center of the oven. This gas injection may result in laminar flow from the center of the oven to both ends. In some embodiments, atmosphere control may include 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, atmosphere control involves using an enclosure to provide a confined environment with atmosphere control around or near the oven. For example, the enclosure may be filled with nitrogen, with a portion of it exposed to a reducing environment. A reducing environment can be achieved by providing H2 or CO at a certain partial pressure.

[0407]

[0425] In some embodiments, parts of the production line are enclosed in a container or room with atmosphere control. For example, the production line may be completely enclosed in a cleanroom. The inlet and / or outlet of the processing equipment may be enclosed in a cleanroom. In certain embodiments of these, a gas is introduced into a particle-free enclosed container or room (e.g., a cleanroom). CDA refers to clean dry air, which is air or gas from which particles have been removed based on particle size by filtration. Examples of gases 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, this specification includes Front roller and; A furnace comprising at least three heating zones; It's a runway, Nickel (Ni), iron (Fe), Ni alloys, Fe alloys, Ni-Fe alloys, stainless steel, pyrolytic carbon, carbon fiber composites (CFCs), graphite, alumina (Al2O3), zirconia (ZrO2), boron nitride, silicon carbide, magnesium oxide, or combinations thereof. A runway having a surface containing a material selected from A processing device comprising the above is shown.

[0410]

[0428] In some embodiments, this specification includes Front rollers; and at least one furnace including at least three heating zones; Baffles located within the heating zone; A baffle located between the two heating zones; Curtain purging between the two heating zones; Means for controlling at least two separate pressure zones within at least three heating zones; Exhaust means for at least one furnace; A means of purging gas between two heating zones; A means of isolating gas between two heating zones; Means for mechanically separating the two heating zones; or These combinations A processing device comprising at least one of the following is shown.

[0411]

[0429] In some embodiments, this specification includes Front roller and; A furnace comprising at least three heating zones; A two-layer structure that is kept under tension, wherein the tension is in the range of 0.1 g / cm to 500 g / cm per web width. A processing device comprising the above is shown.

[0412]

[0430] In some embodiments, this specification includes Front roller and; A furnace comprising at least three heating zones; A two-layer body; At least two rollers and A processing apparatus comprising, A processing apparatus is shown in which a two-layer material is wound onto one of at least two rollers at a winding angle in the range of 0 to 40°.

[0413]

[0431] In some embodiments that include all of the above, the processing apparatus comprises a two-layer body.

[0414]

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

[0415]

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

[0416]

[0434] In some embodiments that include any of the above, the processing apparatus includes an end roller.

[0417]

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

[0418]

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

[0419]

[0437] In some embodiments, including all of the above, the runway is located inside at least one furnace. In some embodiments, including all of the above, the runway is located inside a sintering section. In some embodiments, including all of the above, the runway includes an exhaust port. In some embodiments, including all of the above, the runway includes speed bumps. In some embodiments, including all of the above, the uppermost runway is centerless. In some embodiments, including all of the above, the runway has holes on its upper surface. In some embodiments, including all of the above, at least one furnace is sealed.

[0420]

[0438] In some embodiments that include any of the above, the processing apparatus includes a cooling section.

[0421]

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

[0422]

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

[0423]

[0441] In some embodiments that include any of the above, the two layers include a metal layer and a ceramic layer.

[0424]

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

[0425]

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

[0426]

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

[0427]

[0445] In some embodiments that include any of the above, the processing apparatus includes rollers that can be mechanically aligned to within 0.005 inches. In some embodiments that include any of the above, the processing apparatus includes rollers that can be mechanically aligned to within 0.001 inches. In some embodiments that include any of the above, the processing apparatus includes rollers that can be mechanically aligned in three dimensions.

[0428]

[0446] In some embodiments that include any of the above, the processing apparatus includes a nip roller. In some embodiments that include any of the above, at least one furnace includes a hot roller.

[0429]

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

[0430]

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

[0431]

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

[0432]

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

[0433]

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

[0434]

[0452] In some embodiments, including all of the above, the winding angle with respect to the roller is in the range of 0° to 40°. In some embodiments, including all of the above, the winding angle with respect to the roller is in the range of 0° to 40° in the binder burnout section. In some embodiments, including all of the above, the winding angle with respect to the roller is in the range of 0° to 40° in the sintering section. In some embodiments, including all of the above, the processing apparatus comprises a nip roller on the edge, a speed bump, an air bearing, or a combination thereof.

[0435]

[0453] In some embodiments, including all of the above, the two-layer body is suspended in the process apparatus.

[0436]

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

[0437]

[0455] In some embodiments, including all of the above, at least one furnace is sealed, and the inflow and outflow of gases into that at least one furnace is controlled by at least one atmosphere controller.

[0438]

[0456] In some embodiments, including all of the above, the processing apparatus includes a pressurized gas line between the bisque section and the sintering section, which pressurizes and delivers gas into the bisque section and the sintering section.

[0439]

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

[0440]

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

[0441]

[0459] In some embodiments, including all 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 sintered section containing argon (Ar) gas; nitrogen (N2) gas; hydrogen (H2) gas; or a mixture thereof.

[0443]

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

[0444]

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

[0445]

[0463] In some embodiments that include all of the above, the ceramic layer is green, or green tape.

[0446]

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

[0447]

[0465] In some embodiments, including all of the above, the two-layer body is positioned in a curtain-processing orientation as it moves through the process apparatus.

[0448]

[0466] In some embodiments, including all of the above, the two-layer body is positioned in a vertical processing orientation as it moves through the process apparatus.

[0449]

[0467] In some embodiments, including any of the above, 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 all of the above, the metal layer is an alloy of Fe and Ni.

[0451]

[0469] In some embodiments that include all of the above, the metal layer is an alloy of Fe and Ni, with Fe making up 1% to 25% (w / w) and the remainder being Ni.

[0452]

[0470] In some embodiments, including all of the above, the thickness of the metal layer is 1 μm to 20 μm. In some embodiments, including all of the above, the bilayer is suspended as it moves through the sintering zone. In some embodiments, including all of the above, the processing apparatus comprises a sintered bilayer wound around at least one end roller. In some embodiments, including all of the above, the sintered bilayer includes a metal layer and a sintered oxide layer. In some embodiments, including all of the above, the sintered bilayer includes a metal layer and a lithium-filled garnet sintered layer. In some embodiments, including all of the above, the process apparatus 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 all of the above, the binder burnout zone and the sintering zone are located parallel to each other.

[0453]

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

[0454]

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

[0455]

[0473] In some embodiments that include all of the above, the entire process apparatus is under vacuum.

[0456]

[0474] In some embodiments, this specification describes a process for using a continuous process apparatus, namely, the following operations: (a) To produce a bilayer with an organic content of less than 1% by heating the green bilayer as it passes through at least one furnace, and (b) Winding a two-layer material with an organic content of less than 1% onto a roller. The process including this is shown. In some embodiments, this specification describes a process for using a continuous process apparatus, namely, the following operations: (a) To provide or keep in place a process apparatus as shown herein; (b) Preserving a two-layered bisque by heating the two-layered body as it passes through at least one furnace, and (c) Rolling up the unglazed clay The process including this is shown. In some embodiments that include any of the above, the process further includes (d) unwinding the bisque-fired bilayer. In some embodiments that include any of the above, the process further includes (e) sintering the two layers.

[0457]

[0475] In some embodiments that include any of the above, the process further includes winding the sintered bilayer onto an end roller.

[0458]

[0476] In some embodiments, which include any of the above, a sintered bilayer body as a cut strip.

[0459]

[0477] In some embodiments that include all of the above, the two-layered unglazed body after step (c).

[0460]

[0478] In some embodiments, this specification shows bisque products prepared by the processes described herein.

[0461]

[0479] In some embodiments, this specification shows sintered articles prepared by the processes described herein.

[0462]

[0480] In some embodiments, this specification shows a bisque bilayer containing lithium-filled garnet, where the bisque bilayer is wound onto a roller and the bilayer is less than 100 μm thick.

[0463]

[0481] In some embodiments that include all of the above, the two-layer body 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, this specification shows a sintered bilayer containing lithium-filled garnet, where the bilayer is wound around a roller and the bilayer is less than 100 μm thick.

[0465]

[0483] In some embodiments that include all of the above, the two-layer body 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 all of the above, the metal foil layer comprises nickel, iron, or a combination thereof.

[0467]

[0485] In some embodiments, this specification describes a process for using a continuous process apparatus, which includes the following operations: (a) providing or leaving the process apparatus described herein; and (b) producing a sintered bilayer by heating the bilayer as it progresses through at least one furnace.

[0468]

[0486] In some embodiments, this specification shows a sintered bilayer body prepared by the process described above.

[0469]

[0487] In some embodiments that include any of the above, the process includes lithium-filled garnet.

[0470]

[0488] In some embodiments that include all of the above, the two-layer body 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 all of the above, the metal foil layer comprises nickel, iron, or a combination thereof.

[0472] I. Additional Embodiments

[0490] In at least one embodiment, this specification provides 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; producing a debindered bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debindered bilayer through a second heating zone; wherein the debindered bilayer is arched as it advances through the second heating zone; the debindered 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 that include all of the above, the tension is 10N to 200N per meter of web width.

[0474]

[0492] In some embodiments, which include all of the above, the tension is 40N to 200N per meter of web width.

[0475]

[0493] In some embodiments that include all of the above, the tension is 80N to 150N per meter of web width.

[0476]

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

[0477]

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

[0478]

[0496] In some embodiments, including all of the above, the debindered bilayer is under the described tension in the second heating zone.

[0479]

[0497] In some embodiments that include all 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 all 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 that include all 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 all 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 all 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 all 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 arched runway. In certain examples, the radius of curvature of the arch is 3 to 5 meters.

[0485]

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

[0486]

[0504] A process according to any of the above embodiments, further comprising cooling the sintered bilayer. In certain examples, this process includes cooling the sintered bilayer to room temperature.

[0487]

[0505] In some embodiments that include any of the above, the green layer comprises ceramic powder and a binder.

[0488]

[0506] In some embodiments that include any of the above, the sintered bilayer includes a sintered oxide layer.

[0489]

[0507] In some embodiments that include all of the above, the sintered bilayer body includes a lithium-filled garnet sintered body.

[0490]

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

[0491]

[0509] In some embodiments that include all of the above, the thickness of the metal layer is 1 μm to 10 μm.

[0492]

[0510] In some embodiments that include all of the above, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0493]

[0511] In some embodiments that include all of the above, the width of the sintered bilayer is 300 mm or less.

[0494]

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

[0495]

[0513] In some embodiments, including all of the above, the length of the sintered bilayer is at least 1 meter.

[0496]

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

[0497]

[0515] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 1 cm / min to 200 cm / min.

[0498]

[0516] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of 5 cm / min to 100 cm / min.

[0499]

[0517] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 8 cm / min to 80 cm / min.

[0500]

[0518] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 20 cm / min to 80 cm / min.

[0501]

[0519] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 80 cm / min.

[0502]

[0520] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0503]

[0521] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0504]

[0522] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, or 4.0 m.

[0505]

[0523] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1 meter.

[0506]

[0524] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0507]

[0525] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0508]

[0526] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0509]

[0527] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, or 4.0 m.

[0510]

[0528] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1 meter.

[0511]

[0529] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0512]

[0530] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 5.0 meters.

[0513]

[0531] In some embodiments, including all of the above, at least one runway provides an arched shape. This means that the runway is used with tension that causes the two layers to curve into an arched shape.

[0514]

[0532] In some embodiments, including all of the above, at least one roller provides an arch shape. This means that at least one roller is used with tension to curve the two layers into an arch shape.

[0515]

[0533] In some embodiments, including all of the above, at least one speed bump provides an arch shape. This means that at least one or more speed bumps are used with tension to curve the two-layer body into an arch shape.

[0516]

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

[0517]

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

[0518]

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

[0519]

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

[0520]

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

[0521]

[0539] In yet another embodiment, this specification provides a process for manufacturing a sintered bilayer, comprising: providing a green bilayer comprising a green layer and a metal layer; producing a debindered bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debindered bilayer through a second heating zone; wherein the debindered bilayer is arched as it advances through the second heating zone; the debindered 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 that include all of the above, the tension is 10N to 200N per meter of web width.

[0523]

[0541] In some embodiments, which include all of the above, the tension is 40N to 200N per meter of web width.

[0524]

[0542] In some embodiments that include all of the above, the tension is 80N to 150N per meter of web width.

[0525]

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

[0526]

[0544] In some embodiments that include all of the above, the tension is 150N to 200N per meter of web width.

[0527]

[0545] In some embodiments that include all of the above, the tension is 180N to 200N per meter of web width.

[0528]

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

[0529]

[0547] In some embodiments, including all of the above, the debindered bilayer is under the described tension in the second heating zone.

[0530]

[0548] In some embodiments that include all 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 all 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 that include all 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 all 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 all of the above, the tension is maintained by a tension controller having a tolerance of ±10% or less.

[0535]

[0553] A process of the above-described embodiment, further comprising cooling the sintered bilayer. In a particular example, this process includes cooling the sintered bilayer to room temperature.

[0536]

[0554] In some embodiments that include any of the above, the green layer comprises ceramic powder and a binder.

[0537]

[0555] In some embodiments that include any of the above, the sintered bilayer includes a sintered oxide layer.

[0538]

[0556] In some embodiments that include all of the above, the sintered bilayer body includes a lithium-filled garnet sintered body.

[0539]

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

[0540]

[0558] In some embodiments that include all of the above, the thickness of the metal layer is 1 μm to 10 μm.

[0541]

[0559] In some embodiments that include all of the above, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0542]

[0560] In some embodiments that include all of the above, the width of the sintered bilayer is 300 mm or less.

[0543]

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

[0544]

[0562] In some embodiments, including all of the above, the length of the sintered bilayer is at least 1 meter.

[0545]

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

[0546]

[0564] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 1 cm / min to 200 cm / min.

[0547]

[0565] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of 5 cm / min to 100 cm / min.

[0548]

[0566] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 8 cm / min to 80 cm / min.

[0549]

[0567] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 20 cm / min to 80 cm / min.

[0550]

[0568] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 80 cm / min.

[0551]

[0569] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0552]

[0570] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0553]

[0571] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, or 4.0 m.

[0554]

[0572] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1 meter.

[0555]

[0573] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0556]

[0574] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0557]

[0575] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0558]

[0576] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, or 4.0 m.

[0559]

[0577] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1 meter.

[0560]

[0578] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0561]

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

[0562]

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

[0563]

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

[0564]

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

[0565]

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

[0566]

[0584] In some embodiments including any of the above, the debindered bilayer is approximately 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, 3 It remains 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 all of the above, the green bilayer moves horizontally through the first heating zone.

[0568]

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

[0569]

[0587] In yet another embodiment, this specification provides a process for manufacturing a sintered bilayer, comprising: providing a green bilayer containing a green layer and a metal layer under a tension of 1 N to 300 N per meter of web width; producing a debindered bilayer by advancing the green bilayer through a first heating zone; and preparing a sintered bilayer by advancing the debindered bilayer through a second heating zone; wherein the debindered 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 all of the above, the debindered bilayer is arched as it moves through the second heating zone.

[0571]

[0589] In some embodiments, including all of the above, the debindered bilayer is flat as it moves through the second heating zone.

[0572]

[0590] In some embodiments that include all of the above, the tension is 3N to 100N per meter of web width.

[0573]

[0591] In some embodiments that include all of the above, the tension is 3N to 80N per meter of web width.

[0574]

[0592] In some embodiments that include all of the above, the tension is 3N to 50N per meter of web width.

[0575]

[0593] In some embodiments that include all of the above, the tension is 3N to 35N per meter of web width.

[0576]

[0594] In some embodiments that include all of the above, the tension is 3N to 30N per meter of web width.

[0577]

[0595] In some embodiments that include all of the above, the tension is 10N to 20N per meter of web width.

[0578]

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

[0579]

[0597] In some embodiments, including all of the above, the debindered bilayer is under the described tension in the second heating zone.

[0580]

[0598] In some embodiments that include all 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 all 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 that include all 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 that include all 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 all of the above, the tension is maintained by a tension controller having a tolerance of ±10% or less.

[0585]

[0603] A process of the above-described embodiment, further comprising cooling the sintered bilayer. In a particular example, this process includes cooling the sintered bilayer to room temperature.

[0586]

[0604] In some embodiments that include any of the above, the green layer comprises ceramic powder and a binder.

[0587]

[0605] In some embodiments that include any of the above, the sintered bilayer includes a sintered oxide layer.

[0588]

[0606] In some embodiments that include all of the above, the sintered bilayer body includes a lithium-filled garnet sintered body.

[0589]

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

[0590]

[0608] In some embodiments that include all of the above, the thickness of the metal layer is 1 μm to 10 μm.

[0591]

[0609] In some embodiments that include all of the above, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0592]

[0610] In some embodiments that include all of the above, the width of the sintered bilayer is 300 mm or less.

[0593]

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

[0594]

[0612] In some embodiments, including all of the above, the length of the sintered bilayer is at least 1 meter.

[0595]

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

[0596]

[0614] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 1 cm / min to 200 cm / min.

[0597]

[0615] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of 5 cm / min to 100 cm / min.

[0598]

[0616] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 8 cm / min to 80 cm / min.

[0599]

[0617] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 20 cm / min to 80 cm / min.

[0600]

[0618] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 80 cm / min.

[0601]

[0619] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0602]

[0620] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0603]

[0621] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, 4.0 m, or 5.0 m.

[0604]

[0622] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 1 meter.

[0605]

[0623] In some embodiments, including all of the above, the debindered bilayer is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0606]

[0624] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 0.5 meters to 6.0 meters.

[0607]

[0625] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0608]

[0626] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0609]

[0627] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, 4.0 m, or 5.0 m.

[0610]

[0628] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 1 meter.

[0611]

[0629] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0612]

[0630] In some embodiments, including all of the above, the green two-layer structure is arched in shape, characterized by a radius of curvature of 5.0 meters.

[0613]

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

[0614]

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

[0615]

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

[0616]

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

[0617]

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

[0618]

[0636] In some embodiments including any of the above, the debindered bilayer is approximately 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, 3 It remains 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 all of the above, the green bilayer moves horizontally through the first heating zone.

[0620]

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

[0621]

[0639] In another embodiment, this specification provides a sintering process for a bilayer body, comprising: providing a bilayer body under a tension of 1 N to 300 N; the thickness of the bilayer body being 1 μm to 100 μm; the bilayer body comprising a layer containing ceramics 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 that include any of the above, the ceramic layer comprises ceramic powder.

[0623]

[0641] In some embodiments that include any of the above, the ceramic layer comprises sintered ceramics.

[0624]

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

[0625]

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

[0626]

[0644] In some embodiments that include all of the above, the thickness of the bilayer is 1 μm to 50 μm.

[0627]

[0645] In some embodiments that include all of the above, the thickness of the ceramic layer is less than 25 μm.

[0628]

[0646] In some embodiments, including all of the above, the thickness of the metal layer is less than 25 μm.

[0629]

[0647] In some embodiments that include all of the above, the width of the two-layer structure is 300 mm or less.

[0630]

[0648] In some embodiments, including all of the above, the length of the two layers is at least 1 meter.

[0631]

[0649] In some embodiments, including all of the above, the two layers are sintered at approximately 1100°C to approximately 1200°C.

[0632]

[0650] In some embodiments, including all of the above, the two layers move at a speed of approximately 5 cm / min to approximately 100 cm / min.

[0633]

[0651] In some embodiments, including all of the above, the two-layer structure is placed on a flat runway.

[0634]

[0652] In some embodiments, including all of the above, the two-layer structure is positioned on a curved runway.

[0635]

[0653] In some embodiments that include all of the above, the tension is 10N to 200N per meter of web width.

[0636]

[0654] In some embodiments, which include all of the above, the tension is 40N to 200N per meter of web width.

[0637]

[0655] In some embodiments that include all of the above, the tension is 80N to 150N per meter of web width.

[0638]

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

[0639]

[0657] In some embodiments, including all of the above, the two layers are under the described tension as they move through the first heating zone.

[0640]

[0658] In some embodiments, including all of the above, the two layers are under the described tension as they move through the second heating zone.

[0641]

[0659] In some embodiments that include all 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 all 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 that include all 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 all 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 all of the above, the tension is maintained by a tension controller having a tolerance of ±10% or less.

[0646]

[0664] A process of the aforementioned embodiment, further comprising cooling the bilayer. In a particular example, this process includes cooling the bilayer to room temperature.

[0647]

[0665] In some embodiments that include any of the above, the two-layer body includes a green layer comprising ceramic powder and a binder.

[0648]

[0666] In some embodiments that include any of the above, the two-layer body includes a sintered oxide layer.

[0649]

[0667] In some embodiments that include any of the above, the two-layer body includes a lithium-filled garnet sintered body.

[0650]

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

[0651]

[0669] In some embodiments that include all of the above, the thickness of the metal layer is 1 μm to 10 μm.

[0652]

[0670] In some embodiments that include all of the above, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0653]

[0671] In some embodiments that include all of the above, the width of the sintered bilayer is 300 mm or less.

[0654]

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

[0655]

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

[0656]

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

[0657]

[0675] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 1 cm / min to 200 cm / min.

[0658]

[0676] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of 5 cm / min to 100 cm / min.

[0659]

[0677] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 8 cm / min to 80 cm / min.

[0660]

[0678] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of 20 cm / min to 80 cm / min.

[0661]

[0679] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of approximately 10 cm / min.

[0662]

[0680] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 20 cm / min.

[0663]

[0681] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 30 cm / min.

[0664]

[0682] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of approximately 40 cm / min.

[0665]

[0683] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 50 cm / min.

[0666]

[0684] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 60 cm / min.

[0667]

[0685] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of approximately 70 cm / min.

[0668]

[0686] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 80 cm / min.

[0669]

[0687] In some embodiments, including all of the above, the two-layer body moves through the second heating zone at a speed of approximately 90 cm / min.

[0670]

[0688] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 100 cm / min.

[0671]

[0689] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 110 cm / min.

[0672]

[0690] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 120 cm / min.

[0673]

[0691] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 130 cm / min.

[0674]

[0692] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 140 cm / min.

[0675]

[0693] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 150 cm / min.

[0676]

[0694] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 160 cm / min.

[0677]

[0695] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 170 cm / min.

[0678]

[0696] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 180 cm / min.

[0679]

[0697] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 190 cm / min.

[0680]

[0698] In some embodiments, including all of the above, the two layers move through the second heating zone at a speed of approximately 200 cm / min.

[0681]

[0699] In some embodiments, including all of the above, the two-layer structure is arched in shape, characterized by a radius of curvature of 0.5 meters to 6.0 meters.

[0682]

[0700] In some embodiments, including all of the above, the two layers are arched in shape, characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0683]

[0701] In some embodiments, including all of the above, the two layers are arched in shape, characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0684]

[0702] In some embodiments, including all of the above, the two-layer structure is arched in shape, characterized by a radius of curvature of 2.0 meters to 6.0 meters.

[0685]

[0703] In some embodiments, including all of the above, the two layers are arched in shape, characterized by a radius of curvature of 1.0 m, 2.0 m, 3.0 m, 4.0 m, or 5.0 m.

[0686]

[0704] In some embodiments, including all of the above, the two layers are arched in shape, characterized by a radius of curvature of 1 meter.

[0687]

[0705] In some embodiments, including all of the above, the two-layer structure is arched in shape, characterized by a radius of curvature of 3.8 meters.

[0688]

[0706] In some embodiments, including all of the above, the two layers are arched in shape, characterized by a radius of curvature of 5.0 meters.

[0689]

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

[0690]

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

[0691]

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

[0692]

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

[0693]

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

[0694]

[0712] In some embodiments including any of the above, the two layers are approximately 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, It remains 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 all of the above, the two-layer body moves horizontally through the first heating zone.

[0696]

[0714] In some embodiments, including all of the above, the two layers move vertically through the first heating zone.

[0697]

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

[0698]

[0716] In another embodiment, this specification provides a bilayer; the bilayer has a thickness of 1 μm to 100 μm; the bilayer includes a layer comprising ceramics disposed on a metal layer; and a bilayer sintering process is described, comprising sintering the bilayer in an arch shape at approximately 1050°C to approximately 1250°C for approximately 1 second to approximately 3 minutes.

[0699]

[0717] In some embodiments, including all of the above, the two-layer body is under a tension of 5N to 100N.

[0700]

[0718] In some embodiments, including all of the above, the radius of curvature of the two layers is 2 to 4 meters.

[0701]

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

[0702]

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

[0703]

[0721] In some embodiments that include any of the above, the ceramic layer comprises sintered ceramics.

[0704]

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

[0705]

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

[0706]

[0724] In some embodiments that include all of the above, the thickness of the bilayer is 1 μm to 50 μm.

[0707]

[0725] In some embodiments that include all of the above, the thickness of the ceramic layer is less than 25 μm.

[0708]

[0726] In some embodiments that include all of the above, the thickness of the metal layer is less than 10 μm.

[0709]

[0727] In some embodiments that include all of the above, the width of the two-layer structure is 300 mm or less.

[0710]

[0728] In some embodiments, including all of the above, the length of the two layers is at least 1 meter.

[0711]

[0729] In some embodiments, including all of the above, the two layers are sintered at approximately 1100°C to approximately 1200°C.

[0712]

[0730] In some embodiments, including all of the above, the two layers move at speeds of approximately 5 cm / min and 80 cm / min.

[0713]

[0731] In some embodiments, including all of the above, the two-layer structure is positioned on a curved runway. [Examples]

[0714] J. Examples

[0732] Unless otherwise specified, the solvents used herein are selected from other classes of organic solvents, including alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, and hexanol, and, 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), as well as ethers and aromatic solvents.

[0715]

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

[0716]

[0734] The pouch cell containers were purchased from Showa Denko.

[0717]

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

[0718]

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

[0719]

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

[0720]

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

[0721]

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

[0722]

[0740] Casting was performed using the TQC drawdown table. Calendar processing was performed using the IMC calendar unless otherwise specified.

[0723]

[0741] The light scattering method was performed using a Horiba Partica laser particle size distribution analyzer (model number LA-950V2).

[0724]

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

[0725] Example 1 - Manufacturing of a sintered roll - Virtual example

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

[0726]

[0744] Slurry 1: Using an ultrasonic horn, the LLZO powder may be dispersed in ethanol containing 2 wt% polyacrylic acid. Larger particles may be allowed to settle. The supernatant may be decanted and the collected powder 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 ground with 2.0 mm diameter ZrO2 beads in a ball mill 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 in diameter.

[0727]

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

[0728]

[0746] Slurry 3: A polymer aqueous 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. To this polymer solution, LLZO (lithium-filled garnet) powder may be added in an amount equal to the solution. The slurry may be mixed with ZrO2 beads for 5 to 60 minutes. This slurry may be cast onto metal foil with a doctor blade; the thickness may be controlled by the gap in the doctor blade. This green film may be dried and wound onto a core with a diameter of at least 8 cm.

[0729]

[0747] Slurry 4: LLZO was ball-milled in a mixture of equal parts ethanol, xylene, and toluene. 2-5 wt% herring oil may be added dropwise to the LLZO over 30 minutes. 6-10 wt% polyvinyl butyral, 2-4 wt% polyethylene glycol, and 3-7 wt% benzyl butyl phthalate may be added and mixed with the LLZO. The tape may be cast onto a metal substrate using 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 in diameter.

[0730]

[0748] Slurry 5 can be prepared by mixing 100g of LLZO powder, 2-4g of glyceryl trioleate, 100-200g of n-propyl propionate, and 15-25g of elvacite E-2046, and then grinding it in a ball mill. This slurry can then be cast onto a metal foil substrate using a doctor blade, dried, and rolled up.

[0731]

[0749] A slurry can be prepared by milling 6:20 g of LLZO powder, 25-40 g of 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 dispersant. The dispersant may 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.

[0732]

[0750] Slurry 7: The slurry can be prepared by mixing water (30 parts by mass), LLZO powder (12-18 parts by mass), and binder solution (8 parts by mass of WB4101, WB40B-44, 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.

[0733]

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

[0734]

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

[0735]

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

[0736]

[0754] In the first step, the binder can be burned off by heating the green bilayer to produce a binder-free bilayer.

[0737]

[0755] In the second step, the green tape may be heated in an unglazed oven to create a two-layered unglazed body.

[0738]

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

[0739]

[0757] The sintered bilayer film may be rolled into a roll on an end roller. Alternatively, the sintered bilayer may be cut into sheets.

[0740]

[0758] In the second processing apparatus, the green bilayer may be moved back and forth between a bisque oven and a binder burnout oven. These ovens may be switched on and off to selectively heat the film in either the bisque oven or the binder burnout oven. For sintering, the temperature of the bisque oven may be increased to the sintering temperature.

[0741] Example 2 - Manufacturing of Sintered Rolls - Virtual Example

[0759] In this embodiment, a slurry can be prepared by mixing lithium-filled garnet, a solvent, a binder, and a plasticizer.

[0742]

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

[0743]

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

[0744]

[0762] The two layers will move through the processing apparatus at a rate of 5 cm / min and may be held at approximately 1100°C for about 10 minutes in the sintering section.

[0745] Example 3 - Production of binder-free rolls with controlled grain size and particle size

[0763] Lithium-filled garnet powder (d 50A slurry was prepared by dispersing particles (<1 μm) in 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 to a range of 50-1000 cP at a shear rate of 20 Hz. This slurry was cast onto nickel foil 60 mm-150 mm wide using a comma coater with a fixed gap distance of 200 μm-400 μm. This two-layer body was dried and rolled around a core of approximately 9 cm in diameter. The thickness of the green ceramic layer was 50 μm-80 μm; the thickness of the metal layer was 5 μm-15 μm. The roll was transferred to a process apparatus, unwound, and fed at a rate of 5-20 cm / min through a temperature zone configured for de-bindering the two-layer body (i.e., for removing the binder from it). The temperature zone was set to 600-900°C, where the atmosphere was configured to remove burnout organic byproducts and reduce lithium loss. After debinding, the product was rolled into a roll. This debinding two-layer material roll was stored for subsequent sintering, testing, and analysis.

[0746] Example 4 - Manufacturing of ceramic rolls with controlled grain size and texture

[0764] Lithium-filled garnet powder (d 50 A slurry was prepared by dispersing particles (<1 μm) in a solvent, binder, and plasticizer (where the binder and plasticizer content was 8 wt% to 20 wt% of the solids). The solvent was added to control the viscosity to a range of 50 to 1000 cP at a shear rate of 20 Hz. Using a comma coater with a fixed gap distance of 200 μm to 400 μm, this slurry was cast onto metal foil with a width of 60 mm to 150 mm. This two-layer body 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 roll was transferred to a process apparatus, unwound, and fed at a rate of 5 cm / min to 20 cm / min through a temperature zone configured for debinding the two-layer body. The temperature zone was set to 600-900°C, and the atmosphere within this zone was configured to remove burnout organic products and reduce lithium loss.

[0747] Example 5 - Manufacturing of sintered rolls with controlled grain size and texture

[0765] Lithium-filled garnet powder (d 50 A slurry was prepared by dispersing particles (<1 μm) in a solvent, binder, and plasticizer (where the binder and plasticizer content was 8-20 wt% of the solids). The solvent was added to control the viscosity to a range of 50-1000 cP at a shear rate of 20 Hz. Using a comma coater with a fixed gap distance of 200 μm-400 μm, this slurry was cast onto metal foil 60 mm-150 mm wide. This two-layer body was dried and rolled around a core of approximately 9 cm in diameter. The thickness of the green ceramic layer was 50 μm-80 μm; the thickness of the metal layer was 5 μm-15 μm. The roll was transferred to a process apparatus and fed at a rate of 5 cm / min-20 cm / min through temperature zones configured for unwinding, debinding, firing, and sintering of the two-layer body. The temperature zone was set to 600-1300°C, and the atmosphere was configured to remove burnout organic products and reduce lithium loss. After sintering, the product was rolled into a roll. This roll of sintered two-layer material was stored for later testing and analysis.

[0748] Example 6 - Testing of sintered rolls

[0766] As described in Example 5, a sintered film was manufactured. The specific area resistance (ASR) was measured using the current interruption method.

[0749]

[0767] Separator cut from a roll of sintered film and 3mAh / cm² 2 Load capacity NMC(Li(Ni 1-x-y Mn x Co y Battery cells were manufactured from the cathode of an active material (O2). 0.33 mA / cm² 2The battery was charged and discharged at 30°C with intermittent current pulses of constant current density and an operating voltage range of 3V to 4.2V. The current pulse was applied for 30 minutes, then the current was stopped, and the system was relaxed in an open-circuit state for 3 minutes. This intermittent pulse was repeated until the cell voltage reached 4.2V during charging and 3V during discharging. The specific area resistance (ASR) of the battery cell was determined by reading the voltage drop during the relaxation phase of charging. The ASR was 15-25 Ωcm at 30°C. 2 It was measured as follows.

[0750] Example 7 - Manufacturing and testing of a sintered bilayer body

[0768] A sintered bilayer film was manufactured as described in Example 5. Specifically, lithium-filled garnet was mixed with an acrylic binder and benzyl butyl phthalate in an aprotic solvent to form a slurry. This slurry was then cast onto a Ni foil to form a bilayer.

[0751]

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

[0752]

[0770] A 30 x 30 mm two-layer separator cut from a sintered roll and a 3.1 mAh / cm² battery. 2 A battery was assembled with a cathode containing a load-capacity NMC active material. This cathode was impregnated with a cathode solution or cathode gel containing a lithium salt and a solvent to dissolve the salt. The cell was cycled at 1C charge and 1C discharge rates at 30°C and 50 pounds per square inch (PSI) (approximately 3.4 atm). The cell retained more than 90% of its initial capacity after 800 cycles at 100% depth of discharge. See Figure 13.

[0753] Example 8 - Manufacturing of the materials shown in Figures 6, 7, and 8

[0771] In this specification, D 90 Unless otherwise specified, this refers to sintered crystal grains.

[0754]

[0772] A slurry was prepared by dispersing lithium-filled garnet powder with a solvent, binder, and plasticizer (where the binder and plasticizer content was 8-20 wt% of the solids). The solvent was added and the viscosity was controlled to a range of 50-1000 cP at a shear rate of 20 Hz. Using a comma coater with a fixed gap distance of 200-400 μm, the slurry was cast onto metal foil (60-150 mm wide), dried, and rolled into a roll. 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 process apparatus and fed at a rate of 5-20 cm / min through temperature zones configured for unwinding, de-bindering of the layers, bisque firing, and sintering. The binder burnout temperature zone included an atmosphere configured to remove organic burnout. The sintering temperature zone was set to 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 11mm discs, 30x30mm squares, and 70x85mm rectangles for testing and analysis. The products are imaged in Figures 6 and 7.

[0755]

[0773] A cross-section of the bilayer material manufactured according to this specification was imaged using scanning electron microscopy (SEM). The top layer of lithium-filled garnet is approximately 32 μm thick. Grain size D 90 The porosity is 1.3 to 1.9 μm. Figure 6 shows an optical image of the lithium-filled garnet side of the bilayer. Figure 7 shows a top view of the lithium-filled garnet side of the bilayer obtained by scanning electron microscopy (SEM). Figure 8 shows a cross-sectional image of the bilayer produced by the process apparatus described herein, obtained by scanning electron microscopy (SEM). The uppermost layer of the lithium-filled garnet has a porosity of less than 1 volume%.

[0756]

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

[0757] Example 10 - Sintering of a two-layer body using a flat runway

[0775] Lithium-filled garnet powder (d 50 A slurry was prepared by dispersing (<1 μm) particles with xylene, an acrylic binder, a plasticizer, and an acrylate dispersant (where the binder, plasticizer, and dispersant content was 10-20 wt% of the solids). A solvent was added to control the viscosity to a range of 50-1000 cP at a shear rate of 20 Hz. This slurry was cast onto metal foil 60 mm to 150 mm wide using a comma coater with a fixed gap distance of 100 μm to 200 μm. The thickness of the green ceramic layer was 20 μm to 50 μm; the thickness of the metal layer was 5 μm to 10 μm. A debindered bilayer was prepared by transferring the roll to the process apparatus, unwinding it, and feeding it through a first heating zone at a speed of 5 cm / min to 80 cm / min. The temperature of the first heating zone was 700°C to 900°C.

[0758]

[0776] Next, a sintered bilayer was prepared by feeding this roll through a second heating zone at a speed of 40 cm / min to 200 cm / min. The temperature of the second heating zone was 1050°C to 1250°C. The second heating zone was a tubular furnace approximately 60 inches long. A flat runway extended from the opening of the second heating zone to the point of entry. The debindered bilayer was molded to the same shape as the runway by applying a tension of 3 to 35 N per meter of web width to the debindered bilayer.

[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-filled garnet powder (d 50A slurry was prepared by dispersing (<1 μm) particles with xylene, an acrylic binder, a plasticizer, and an acrylate dispersant (where the binder, plasticizer, and dispersant content was 10-20 wt% of the solids). A solvent was added to control the viscosity to a range of 50-1000 cP at a shear rate of 20 Hz. This slurry was cast onto metal foil 60 mm to 150 mm wide using a comma coater with a fixed gap distance of 100 μm to 200 μm. The two layers were dried and rolled around a core with a diameter of approximately 9 cm. The thickness of the green ceramic layer was 20 μm to 50 μm; the thickness of the metal layer was 5 μm to 10 μm. The rolls were transferred to a process apparatus, unwound, and fed through a first heating zone at a speed of 20 cm / min to 200 cm / min to prepare a binder-free two-layer body. The temperature of the first heating zone was between 700°C and 900°C.

[0761]

[0779] Next, a sintered bilayer was prepared by feeding this roll through a second heating zone at speeds of 10 cm / min, 20 cm / min, 40 cm / min, or 101 cm / min. The temperature of the second heating zone was 1050°C to 1250°C. The second heating zone was a tubular furnace approximately 60 inches long. The bilayer was passed through the second heating zone for a period of 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 debindered bilayer was molded to the same shape as the runway by applying a tension of 40 to 187.5 N per meter of web width to the debindered bilayer.

[0762]

[0780] After sintering, the two-layer body was cut into small pieces.

[0763]

[0781] Figure 16 shows the height map of the two-layer body produced in this Example 11.

[0764]

[0782] Figures 17 to 20 show the flatness of two-layer bodies obtained by manufacturing them using various different heat treatment processes, as listed in the table, with tension in N per meter of web width.

[0765]

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

[0766]

[0784] Table 1 shows the average roughness of the data from Figures 17-20 when 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 verify, numerous equivalents of specific compounds, materials, and procedures using conventional methods. All such equivalents are deemed to be within and encompassed by the appended claims.

Claims

1. To provide a two-layer green body comprising a green body layer and a metal layer containing nickel, iron, or an alloy thereof, under a tension of 1 N to 300 N per meter of web width; A binder-free bilayer is produced by passing the aforementioned green bilayer through a first heating zone; A sintered bilayer is prepared by passing the aforementioned debinder bilayer through a second heating zone. A method for manufacturing a sintered bilayer containing; When the two layers of debinder move through the second heating zone, the two layers of debinder are in an arch shape; The temperature of the second heating zone is 1050°C to 1250°C; and A method wherein the thickness of the sintered bilayer is less than 100 μm.

2. The method according to claim 1, wherein the green two-layer body is under a tension of 1 N to 300 N in the first heating zone.

3. The method according to claim 1, wherein the tension in the first heating zone is different from the tension in the second heating zone.

4. The method according to claim 1, wherein the tension in the first heating zone is lower than the tension in the second heating zone.

5. The method according to claim 1, wherein the tension applied to the green two-layer body as it moves through the first heating zone is 3N to 35N per meter of web width in the first heating zone.

6. The method according to claim 1, wherein the tension applied to the green two-layer body as it moves through the first heating zone is 3N to 30N per meter of web width in the first heating zone.

7. The method according to claim 1, wherein the tension applied to the green two-layer body as it moves through the first heating zone is 10 N to 20 N per meter of web width in the first heating zone.

8. The method according to claim 1, wherein the sintered bilayer body includes a sintered lithium-filled garnet layer.

9. The method according to claim 1, wherein the thickness of the metal layer is 1 μm to 10 μm.

10. The method according to claim 8, wherein the thickness of the sintered lithium-filled garnet layer is 5 μm to 40 μm.

11. The method according to claim 1, wherein the length of the sintered bilayer is at least 1 meter.

12. The method according to claim 1, wherein the debindered bilayer is arch-shaped, characterized by a radius of curvature of 0.5 m to 6.0 m.

13. The method according to claim 1, wherein at least one runway provides the arch shape.

14. The method according to claim 1, wherein at least one roller provides the arch shape.

15. The method according to claim 1, wherein at least one speed bump provides the arch shape.

16. The method according to claim 1, wherein the debindered bilayer is heated at a rate faster than 300°C / min.

17. The method according to claim 1, wherein the tension applied to the debindered bilayer as it moves through the second heating zone is 3 to 35 N per meter of web width in the second heating zone.

18. The method according to claim 1, wherein the tension applied to the debindered bilayer as it moves through the second heating zone is 40 to 187.5 N per meter of web width in the second heating zone.

19. The method according to claim 1, wherein the debindered bilayer body moves through the second heating zone at a speed of 10 cm / min to 80 cm / min.

20. The method according to claim 19, wherein the speed is 20 cm / min to 80 cm / min.

21. The method according to claim 1, wherein the tension applied to the debindered bilayer as it moves through the second heating zone is 10 N to 200 N per meter of web width in the second heating zone.

Images