Processing apparatus and method of using same

Abstract

The present application describes a method of making a sintered bilayer comprising: providing a green bilayer comprising a green layer and a metal layer under a tension of 1-300 N per meter of coil width; moving the green bilayer through a first heating zone to produce a debonder bilayer (debonder bilayer); moving the debonded double layer to pass through a second heating zone to obtain a sintered double layer; when the debonding double layers move to pass through the second heating area, the debonding double layers are arched; the debonded bilayer lasts in the second heating zone for about 1 second to about 3 minutes; the temperature in the second heating area ranges from 1050 DEG C to 1250 DEG C; and the thickness of the sintering double layer is less than 100 microns.

Description

[0001] Cross-references

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 406,711, filed on September 14, 2022, the entire contents of which are incorporated herein by reference in their entirety for all purposes. Technical Field

[0003] The present application relates to methods for calcining, debinding and / or sintering ceramics. In some examples, these ceramics are deposited as a layer on top of a metal layer. Such two layers form a double-layer structure. The double-layer structure is heated in a continuous processing device. Background Art

[0004] Certain methods of sintering lithium-filled garnets (lithium lanthanum zirconium oxide; LLZO), such as batch sintering of LLZO, have been described in, for example, U.S. Pat. No. 10,563,918 B2 or US Pat. No. 10,840,544 B2. Containerless sintering of certain ceramics is disclosed in U.S. Patent Application No. 2004 / 0206470 A1; and PCT International Patent Application Publication No. WO 2014 / 103662 A1.

[0005] Despite this background, there is still a need for methods of making thin film ceramics or ceramic bilayers, such as lithium filled garnets in sintered thin film or bilayer form. There is also a need for high throughput continuous sintering processes, such as roll-to-roll processes. Summary of the invention

[0006] In one embodiment, the present application describes a method for preparing a sintered bilayer, which includes: providing a green bilayer under a tension of 1N-300N per meter of coil width, the green bilayer including a green layer and a metal layer; moving the green bilayer through a first heating zone to obtain a debonded bilayer (debonded bilayer); moving the debonded bilayer through a second heating zone to obtain a sintered bilayer; when the debonded bilayer moves through the second heating zone, the debonded bilayer is arched; the debonded bilayer persists in the second heating zone for about 1 second to about 3 minutes; the temperature in the second heating zone is 1050°C to 1250°C; the thickness of the sintered bilayer is less than 100 μm.

[0007] In some embodiments, the present application describes a processing device comprising: a front roller; at least one furnace comprising at least three heating zones; and a runway having a surface selected from the following materials: nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite, aluminum oxide (Al2O3), zirconium oxide (ZrO2), boron nitride, silicon carbide, magnesium oxide, or a combination thereof.

[0008] In other embodiments, the present application describes a processing device comprising: a front roller; at least one furnace, the furnace comprising at least three heating zones; and at least one of the following: baffles within the heating zones; baffles between two heating zones; curtain purges between two heating zones; a device for controlling at least two different pressure zones within the at least three heating zones; a device for exhausting through the center of the at least one furnace; a device for exhausting through the center of a runway; a purge gas device between the two heating zones; a device for isolating the gas between the two heating zones; a device for mechanically separating the two heating zones; or a combination thereof.

[0009] In some other embodiments, the present application describes a processing device comprising: a front roller; at least one oven comprising at least three heating zones; and a double layer maintained under tension, wherein the tension is in the range of 0.1 g / cm to 500 g / cm of the web width.

[0010] In certain other embodiments, the present application describes a processing device comprising: a front roller; at least one furnace, the furnace comprising at least three heating zones; a double layer; at least two or more rollers; the double layer is wound on one of the at least two or more rollers, and the wrap angle is between 0 and 40°.

[0011] In other embodiments, the present application describes a method using a continuous processing device, which includes the following operations: (a) heating the green double layer as the green double layer moves through at least one furnace to form a double layer having an organic content of less than 1 weight percent (wt%); and (b) winding the double layer having an organic content of less than 1 wt% onto a roller.

[0012] In certain embodiments, the present application describes a method using a continuous processing apparatus comprising the following operations: (a) providing or having provided a processing apparatus as disclosed in the present application; (b) heating the bilayer as the bilayer moves through the at least one furnace to form a bisqued bilayer; and (c) winding the bisqued bilayer.

[0013] In some other embodiments, the present application describes a method using a continuous processing device, the method comprising the following operations: (a) providing or having provided a processing device as disclosed in the present application; (b) heating the bilayer as the bilayer moves through the at least one furnace to produce a sintered bilayer. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG. 1 shows one embodiment of a processing apparatus having multiple heating and / or cooling zones and a series of internal rollers arranged in an arcuate ramp.

[0015] FIG. 2 shows a part of an embodiment of a processing device.

[0016] FIG. 3 shows a series of tube furnaces in one embodiment of a processing apparatus.

[0017] FIG. 4 shows a series of tube furnaces in one embodiment of a processing apparatus.

[0018] FIG5 shows a picture of an embodiment of a processing device.

[0019] FIG. 6 shows an image of the bilayer produced in Example 8.

[0020] Figure 7 shows a top-down scanning electron microscope (SEM) image of a bilayer, showing the lithium-stuffed garnet layer in the bilayer prepared in Example 8. The lithium-stuffed garnet top layer has a porosity of less than 1% by volume.

[0021] Figure 8 shows a scanning electron microscope (SEM) cross-sectional image of a sintered oxide containing lithium-filled garnet in the bilayer prepared in Example 8. The porosity of the lithium-filled garnet top layer is less than 1 volume %.

[0022] FIG. 9 shows a green bilayer and a sintered bilayer wound on a roll.

[0023] Figure 10 shows a Keyence microscopic image of the bilayer flatness as a function of the tension on the bilayer. The Keyence microscope flatness analysis is measured on the surface of the sintered oxide layer of the bilayer rather than on the surface of the metal layer in the bilayer. The flatness measures the flatness of the sintered oxide layer surface.

[0024] FIG. 11 shows a table quantifying the amount of flatness of different bi-layers as a function of the tension applied to the bi-layer during sintering.

[0025] FIG. 12 shows an embodiment of a processing device described in the present application.

[0026] FIG. 13 shows the electrochemical cycling results from Example 7.

[0027] FIG. 14 shows a table quantifying the flatness as a function of tension on a bi-layer sintered on a curved track.

[0028] Figure 15 shows a Keyence microscopic image height map of a double layer made on a flat racetrack.

[0029] Figure 16 shows a Keyence microscopic height map of a bilayer produced on a curved (ie, arcuate) racetrack.

[0030] FIG. 17 shows the flatness as a function of the tension on the bilayer during heat treatment.

[0031] FIG. 18 shows the flatness as a function of the tension on the bilayer during heat treatment.

[0032] FIG. 19 shows the flatness as a function of the tension on the bilayer during heat treatment.

[0033] FIG. 20 shows the flatness as a function of the tension on the bilayer during heat treatment. DETAILED DESCRIPTION

[0034] A. Introduction

[0035] The following description is provided to enable one of ordinary skill in the art to make and use the present invention and to incorporate it in the context of a particular application. Various modifications and various uses in different applications will be apparent to those skilled in the art, and the general principles defined in this application can be applied to a wide range of embodiments. Therefore, the present invention is not intended to be limited to the embodiments presented, but should be given the widest scope consistent with the principles and novel features disclosed in this application.

[0036] In the following detailed description, many specific details are described to provide a more thorough understanding of the present invention. However, it is apparent to those skilled in the art that the present invention can be implemented without being limited to these specific details. In other examples, in order to avoid obscuring the present application, well-known structures and devices are shown in block diagram form rather than in detail.

[0037] Unless otherwise expressly stated, all features disclosed in this specification (including any attached claims, abstracts and drawings) may be replaced by alternative features of the same, equivalent or similar purpose. Therefore, unless otherwise expressly stated, each feature disclosed is only an example of a series of general equivalent or similar features.

[0038] Although shown in horizontal form, in some embodiments, the continuous production line in the drawings of the present application can be assembled in a vertical form, where the green belt or double layer moves in a parallel or anti-parallel direction relative to the gravity pull directly downward on the earth's surface. For example, in a vertical form, the green belt or double layer is processed on the ground so that it moves upward or downward and is perpendicular to (90°; i.e., a right angle) the ground. In addition, there may be angles between the various ovens so that the green belt deviates from a straight line and bends when being processed. The drawings of the present application are presented as representative, non-limiting embodiments of the present application. The present application covers other configurations and orientations of ovens and sintering lines. In some configurations, the green belt moves parallel to gravity. For example, the green belt can be hung like a curtain under the weight applied by gravity. In some configurations, the belt moves perpendicular to gravity; for example, the green belt can move in a direction parallel to the ground.

[0039] As described herein, the raw film moving through the processing device can be described in x, y, and z dimensions. The x and y directions of the raw film describe the length and width of the raw film, and the z direction describes the thickness of the raw film. As the raw film moves through the processing device, or moves in the machine direction (MD), the film moves in the x dimension or web dimension. The cross-web dimension (or cross direction (CD)) describes the y dimension in the same plane as the web. The z dimension is perpendicular to the web and describes the thickness of the web.

[0040] This application describes an apparatus and method for obtaining high quality, fast processing ceramic electrolyte membranes. This application describes a high throughput continuous process for sintering thin film ceramics. The ceramics may include, but are not limited to, lithium aluminum titanium phosphate (LATP), lithium-filled garnet oxides (e.g., Li7La3Zr2O 12 and Li7La3Zr2O 12 ·Al2O3; also known as LLZO), lithium lanthanum titanate, and lithium aluminum germanium phosphate (LAGP). In certain embodiments, the method includes a sintering step, wherein the sintered film (i.e., the green body on the green film or bilayer is sintered into a film or sintered into a bilayer) does not contact any surface during its sintering. In some embodiments, when a bilayer is used, the metal layer can contact the surface, but the green body does not contact the surface of the processing device during the passage of the green body through one or more furnaces. Due to the lack of contact with other surfaces during the sintering process, the sintered ceramic membrane prepared by the method of the present invention has unexpectedly advantageous properties, such as low flatness. For lithium-filled garnets, the processing device has unexpectedly advantageous properties, namely the ability to maintain the stoichiometric amount of lithium in a given LLZO formula, as well as an advantageous LLZO microstructure (e.g., high density, small particle size, and combinations thereof). In some embodiments, by not contacting other surfaces, the prepared material has no surface defects. In some embodiments, by not allowing the green body to contact the surface, the bilayer prepared in the present application has no surface defects on the ceramic side of the bilayer. In some embodiments, by not contacting other surfaces, the resulting material does not have problems such as adhesion to the substrate. In addition, these sintered LLZOs are prepared by a novel fast sintering method. From a per unit volume product point of view, this method is faster than other methods for preparing sintered LLZO films.

[0041] This application describes a method for continuously processing bilayers comprising: step 1) binder burnout (BBO), which occurs between room temperature and moderately elevated temperatures to remove organic material from the bilayer; and step 2) sintering, which converts the ceramic powder into a dense solid at very high temperatures.

[0042] During both stages and subsequent cooling to room temperature, the temperature profile and gas environment are controlled and the double layer coil is treated to ensure that the final product is flat and defect free. The specific requirements to achieve this quality are described in this application as follows.

[0043] In some processes, both processing stages (BBO and sintering) occur in one tool. In other embodiments, separate tools are used for each stage, i.e., one tool for BBO and another tool for sintering.

[0044] B. Definition

[0045] In the present application, when a number is limited, such as about 15% weight % (% w / w), the term "about" refers to the limited value, and may also include values ​​within the range of ± 10% of the value. For example, about 15% w / w includes 15% w / w and 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 and 67 ° C, 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.

[0046] In the present application, "selected from" refers to a single member from the group, a plurality of members from the group, or a combination of members from the group. For example, the members selected from the group consisting of A, B, and C may include only A, only B, or only C, or may include A and B, A and C, B and C, or A, B, and C.

[0047] As used herein, a "roller" refers to a rotating cylinder or other shape on which something moves, or which is used to convey, move, press, shape, spread, or flatten something. The roller does not have to be a perfect mathematical cylinder. The roller can be any shape on which a belt or film can move or bend; or on which a belt or film can be wound. In some embodiments, the roller has an outer diameter equal to or greater than 6 cm. In some embodiments, the roller has a winding tension equal to or greater than 20 g / cm. The roller can have a convex or concave profile. The roller has an axis of rotational symmetry.

[0048] The "double layer" of the present application includes a ceramic layer deposited on a metal layer. The ceramic layer can be a green body or a sintered body. In some embodiments, the green body is continuous, and in other embodiments, the green body is deposited in the form of a patch coating. After sintering, the thickness of the ceramic layer of the double layer is 10-50 μm, and the thickness of the metal layer is 2-20 μm. The thickness of the ceramic layer of the double layer can be 20-30 μm, and the thickness of the metal layer can be 3-10 μm.

[0049] Unless otherwise specified, a green bi-layer comprises a thin metal foil and a thicker layer of green ceramic material deposited thereon, prior to binder burnout and sintering. The green ceramic layer consists of ceramic powder particles embedded in an organic matrix. The green bi-layer in this application comprises a green layer and a metal layer.

[0050] The sintered double layer is a green double layer processed in the processing device described in the present application, and the sintered double layer is composed of a sintered body and a metal layer.

[0051] The term "green film" or "green tape" as used herein refers to an unsintered tape or film comprising a lithium-filled garnet, a precursor of a lithium-filled garnet, or a combination thereof, and at least one of a binder, a plasticizer, carbon, a dispersant, a solvent, or a combination thereof. The term "green film tape" as used herein refers to a green film roll, a continuous layer, or a cut portion thereof of a dried or undried cast tape. Green can be used interchangeably with green film or green tape. Green tape can also include a green body sheet (i.e., a flaky coating of a metal layer) deposited on a metal layer.

[0052] As used herein, a "green body" is a material deposited from a slurry that includes a ceramic or ceramic precursor and at least one selected from a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof. Before heating the green body to remove organic materials such as solvents, binders, dispersants, plasticizers, surfactants; or before sintering the ceramic component of the green body, the green body is considered to be a green material. The green body is prepared by depositing the slurry onto a substrate, and the deposited slurry may also be dried.

[0053] The "front roll" described in the present application refers to a roll that is located at the beginning of the processing device and unwinds or unrolls the unsintered film, green film or green body bilayer.

[0054] The "rear roller" described herein refers to a roller that is located at the end of a processing device and winds or rolls up a sintered film, a bi-layer, a debonded film or a bi-layer.

[0055] The "sintered product receiving device" described in this application refers to any device, including but not limited to a back roller or any machine for cutting and stacking sintered films. The "oven" or "furnace" described in this application is a partially or completely enclosed compartment in which materials can be heated to a temperature above room temperature. For example, an oven can be heated to up to 1,200°C. Binder burnout ovens are typically heated to below 750°C. Green blank ovens are typically heated to 600–900°C. Sintering ovens are typically heated to 900°C to 1,450°C. In some instances, at least one oven is enclosed in an atmosphere. In other instances, the processing device is enclosed in an atmosphere. Ovens and furnaces are used interchangeably in this application.

[0056] As used herein, "atmosphere control" refers to a system that controls moisture content, oxygen content, gas flow rate, gas temperature, gas content, gas concentration, total pressure, vacuum, and combinations thereof in a closed or confined space. Atmosphere control can be dynamic, i.e., the system responds to sensed conditions and adjusts the atmosphere so as to better meet certain predetermined conditions. In this case, the atmosphere refers to the gas environment that is in direct contact with the green belt being heated, calcined, sintered, or cooled; or the gas environment that is in direct contact with the sintered belt being heated, sintered, annealed, or cooled. In some examples described herein, atmosphere control includes controlling the flow rate of any gas inlet of oxygen, argon, nitrogen, helium, and / or hydrogen. In some examples described herein, atmosphere control includes controlling the amount of water, oxygen, and lithium in a gaseous state that is in direct contact with the green belt being heated, calcined, sintered, or cooled, or in direct contact with the sintered belt being heated, sintered, annealed, or cooled. Atmosphere control may use various gas curtains, gas densities, gas flow rates, gas flow directions, or gas pulses in the oven, furnace, any inlet or outlet, and in / around and near any holes where the green strip or sintered article enters or exits the oven or furnace. Atmosphere control may refer to systems that use nitrogen, argon, forming gas, dry air, or humidified air in an enclosed or confined space. Atmosphere control may refer to systems that apply a partial vacuum, such as when the pressure is less than atmospheric pressure.

[0057] The "gas curtain" described in this application refers to the gas flow rate determined at certain inlets or outlets of the oven (such as the green tape inlet and the sintered film outlet). For example, the gas flow rate can be between 1-50 liters / minute at standard pressure and temperature. For example, the gas flow rate can be greater than 50 liters / minute at standard pressure and temperature. The gas curtain can be configured to reach a certain amount of gas flow per unit time in the compartment, such as exchanging the compartment volume once per minute. For example, if the volume of gas contained in a compartment is 30 liters, the gas curtain STP can be configured to flow 30 liters per minute, thereby achieving flow once per minute. The gas curtain can be provided with a pressure sensor at the outlet. The gas curtain flows through the inlet or outlet of the oven to control the gas flow in the oven. The gas curtain can help maintain a specific atmosphere in the oven by partially or completely preventing gas from leaving or entering the oven.

[0058] "Dry air" as used herein refers to air with reduced humidity. Dry air may be supplied in a clean room. Dry air may be characterized by a dew point below -20°C, below -30°C, below -40°C, below -50°C, below -60°C, or below -70°C.

[0059] The "solid separator" described in this application refers to a Li-ion battery that is substantially electronically insulating. + Ion-conducting materials (e.g., lithium ion conductivity is at least 10 times greater than electronic conductivity)3 times, and usually 10 6 times) and acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell.

[0060] As used herein, "annealing" refers to heating a material in a controlled atmosphere such as dry air or argon, for example, from 100° C. to 1400° C., or 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. Some exemplary annealing methods can be found in U.S. Pat. No. 9,966,630 B2, which is incorporated herein by reference in its entirety for all purposes.

[0061] Unless otherwise stated, the area specific resistance (ASR) described in this application is measured by electrochemical cycling using an Arbin, Maccor or Biologic instrument. ASR is calculated by measuring the voltage drop ΔV after 30-180 seconds in response to current interruption, ASR = ΔV / J, where J is A / cm 2 The current density in units.

[0062] The ionic conductivity described in this application is measured by electrical impedance spectroscopy method known in the art.

[0063] As used herein, "ambient conditions" refers to room temperature and a natural atmosphere, such as the Earth's atmosphere comprising approximately 78% N2 and 21% O2; and / or the presence of moisture. Ambient conditions include standard temperature and pressure, with a relative humidity of at least 1%.

[0064] As used herein, "electrolyte" refers to a material that conducts ions but is electrically insulating. The electrolyte is used to electrically insulate the positive and negative electrodes of a rechargeable battery while allowing ions (e.g., Li + ) is conducted through the electrolyte.

[0065] "Film" or "film" as used herein refers to a film having a thickness greater than 10 nm and less than 0.5 mm. The lateral dimension of the film is greater than 5 mm. "Film" or "film" can be produced by continuous processes such as tape-casting, spraying or slip casting. In some instances, production can include batch processing. In some instances, production can include screen printing.

[0066] "Film thickness" as used in this application refers to the distance or median measured distance between the top and bottom surfaces of the film. The top and bottom surfaces as used in this application refer to the sides of the film with the largest surface area. The thickness as used in this application is measured by cross-sectional scanning electron microscopy. Cross-sectional scanning electron microscopy can also be used to measure the thickness of the metal layer and sintered oxide on the double layer. The thickness of the sintered oxide refers to the distance from the plane of the largest surface area of ​​the sintered oxide to the interface between the metal layer and the sintered oxide. The thickness of the metal layer refers to the distance from the plane of the largest surface area of ​​the metal layer to the interface between the metal layer and the sintered oxide.

[0067] "Binder" as described in this application refers to a polymer having the ability to increase the adhesion and / or polymerization of a solid in a material such as a green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene alpha-olefin copolymers. "Binder" refers to a material that helps another material adhere. For example, polyvinyl butyral as described in this application is a binder because it can be used to bond garnet materials. Other binders may include polycarbonate. Other binders may include polyacrylates and polymethacrylates. The examples of these binders do not limit the entire scope of the binders considered in this application, but are only used as examples. Binders that can be used in the present application 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-1-octene (PE-co-PO), polyethylene-co-poly(methylene cyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylic resins), acrylic acid, polyvinyl acetal resin, ethyl methacrylate, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, etc. In some examples, including any of the foregoing examples, the binder is selected from the following polymers: polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (P mmA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (PVP), polyethylene oxide poly (allyl glycidyl ether) (PEO-AGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly (allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene fluoride hexafluoropropylene (PVDF-HFP), ethylene propylene rubber (EPR), nitrile rubber (NPR), styrene butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, α-polyolefin, ethylene α-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR) and polyethyl acrylate (PEA).

[0068] The solvents used in this application are selected from alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, and other types of organic solvents such as ethers and aromatic solvents, including but not limited to dibutyl ether, diethyl ether, diisopropylethyl 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).

[0069] In certain instances, the dispersants used are selected from fish oil, Mehaden Blown Fish Oil, mineral oil, phosphate esters, Rhodaline TM 、Rhodoline 4160, phosphine-131 TM 、BYK TM 22124, BYK-22146 TM 、HypermerKD1 TM 、Hypermer KD6 TM and Hypermer KD7 TM 。

[0070] As used in this application, "casting a film" refers to the process of transporting or transferring a liquid or slurry into a mold or onto a substrate such that the liquid or slurry forms a film. Casting can be accomplished by a doctor blade, Meyer rod, comma coater, gravure coater, microgravure printing, reverse comma coater, slot die, dip coating and / or tape casting, and other methods.

[0071] As used in this application, "lithium-filled garnet" refers to an oxide having a crystal structure related to the garnet crystal structure. Lithium-filled garnets include compounds having the formula Li A La B Zr C O F 、Li A La B M' C M” D Ta E O F or Li A La B M' C M” D Nb E O F where 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2; 0 < E < 2.5, 10 < F < 13, and M' and M" are each independently selected from Al, Mo, W, Nb, Ga, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta in each case; or Lia La b Zr c Al d Me” e O f , where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 < d < 2; 0 < e < 2, 10 < f < 13 and Me” is a metal selected from Nb, V, W, Mo, Ta, Ga, and Sb. The garnets used in this application also include the above garnets doped with Al or Al2O3. In addition, the garnets used in this application include, but are not limited to, Li A La B Zr C O F +yAl2O3, where x is from 5.8 to 7.0 and y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0; 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2; 10 < F < 13. In addition, the garnets used in this application include, but are not limited to, Li x La3Zr2O 12 +yAl2O3, where x is from 5.8 to 7.0 and y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0. The garnets described in this application do not include YAG-garnets (i.e., yttrium aluminum garnets, or e.g., Y3Al5O 12 ). The garnets do not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, topazolite, or cinnamon stone, tsavorite, uvarovite, and andradite, as well as solid solutions of pyrope-almandine-spessartine and uvarovite-grossular-andradite. The garnets in this application do not include nesosilicates with the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn; and Y is Al, Fe, and / or Cr.

[0072] The lithium-filled garnets used in this application include, but are not limited to, compounds having the following chemical formulas: Li7La3Zr2O 12 Al2O3; Li 6-7 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- 7La3Zr2O 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- 7La3Zr2O 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- 7La3Zr2O 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- 7La3Zr2O 12-13 (1.0)Al2O3; or Li 7-3x La3Zr2O 12 Al x Where x is from 0 to 2.

[0073] In certain embodiments, the lithium-filled garnet comprises: Li 7-3x La3Zr2O 12 Al x, 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 certain embodiments, the lithium-filled garnet comprises: Li 7-3x La3Zr2O 12 Al x , where x is 0.25, 0.5, or 0.75.

[0074] The "garnet precursor chemical" or "chemical precursor of garnet-type electrolyte" mentioned in this application refers to the chemical substance that reacts to form the lithium-filled garnet material described in this application. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., Li2O), lithium carbonate (e.g., Li2CO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), aluminum oxide (e.g., Al2O3), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO3), aluminum nitrate nonahydrate, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., Ta2O5).

[0075] The “d 50 "Diameter" refers to the median size in a size distribution as measured by microscopy or other particle size analysis techniques such as, but not limited to, scanning electron microscopy or dynamic light scattering. 50 It can be represented as “the quantity d 50 " or "volume d 50 ”, where “the number d 50 ” refers to the diameter at which 50% of the particles have a smaller diameter, and “volume d 50 " is the diameter at which 50% of the smallest particle volume has a smaller diameter. Unless otherwise specified, d in this application 50 refers to the volume d 50 , that is, the characteristic size when 50% of the particles by volume are smaller than the stated size.

[0076] The “D 90 "Diameter" refers to the size in the size distribution measured by microscopy or other particle size analysis techniques (such as but not limited to scanning electron microscopy or dynamic light scattering). 90 It refers to the characteristic size when 90% of the particles by volume are smaller than the stated size.

[0077] The "flatness" of a surface as described in this application refers to the maximum normal distance between the lowest point on the surface and the plane containing the three highest points on the surface, or the maximum normal distance between the highest point on the surface and the plane containing the three lowest points on the surface. It can be measured using an atomic force microscope (AFM), a high-precision optical microscope, a 3D vision system, or surface laser interferometer height mapping. Keyence VR-3000 is an example of an optical microscope that can measure flatness using structured light. Unless otherwise specified, flatness is measured using Keyence VR-3000 in this application.

[0078] The term "speed bump" as used herein refers to a raised surface on a runway or on a processing device surface over which the bi-layer moves when passing through the processing device. The speed bump contacts the metal layer in the bi-layer disclosed in the present application; the speed bump helps to apply a normal force to the bi-layer through the contact between the bi-layer and the speed bump. Unless otherwise specified, the metal layer in the bi-layer is the layer of the bi-layer that can contact the speed bump when the bi-layer passes through the speed bump.

[0079] The term "heating zone" as used herein refers to a space heated by one or more heating elements, measured by one or more temperature sensors, and feedback control is performed between the sensors and the set point. In some embodiments, the first heating zone and the second heating zone are both contained in a single furnace or a single oven. In some other embodiments, the first heating zone and the second heating zone are each located in a furnace or oven different from the furnace or oven used for the other heating zones.

[0080] The term "track" as used herein refers to a material having a length of at least 10 cm, a width at least as wide as the strip to be treated and a thickness of at least 100 μm, which can make point contact or line contact with the strip to be treated in the heating zone.

[0081] The term "green bilayer" as used herein refers to a bilayer having an organic content of less than 1% by weight and a ceramic layer porosity of at least 10 vol%. In this application, the organic content includes carbon-containing compounds.

[0082] The term "binder-free film" as used herein refers to a green body having a binder content of less than 1% by weight.

[0083] The term "coil width" as used herein refers to the width of the metal layer in the double layer.

[0084] As used herein, the term "green bi-layer" refers to a green film or green body, as defined above, having an underlying metal substrate layer attached or bonded to the green film or green body.

[0085] The term "Invar" as used in this application refers to Ni / Fe material.

[0086] The term "vertical processing" as used herein refers to the bilayer being oriented in a vertical processing as it passes through the CML. Vertical processing means that the bilayer moves parallel or antiparallel to the earth's gravity.

[0087] As used herein, the term "curtain treatment" means that the bi-layer is oriented to be curtain treated as it passes through the CML. Curtain treatment means that the edges of the bi-layer are turned over so that both the metal layer and the green layer are moving parallel to the ground, but the metal layer is not below the green layer; instead, the metal layer and the green layer are side by side. Curtain treatment helps prevent debris from falling onto the upper surface of the green layer. Curtain treatment helps prevent the bi-layer from sagging.

[0088] As used herein, "under tension" refers to applying tension to the bilayer using physical means, such as, but not limited to, at least one roller, at least one weight, at least one load cell, at least one motor, at least one tension controller device, a series of devices, or a combination thereof. In some embodiments, under tension includes using a load cell in a feedback loop having at least one roller, at least one weight, at least one motor, at least one tension controller device, a series of devices, or a combination thereof. The bilayer resting on a flat surface has a natural internal tension that holds the structure of the bilayer together even without any object attached other than the bilayer itself. "Under tension" as used herein refers to an amount of tension in addition to the natural tension of the material. Tension is applied to the bilayer from the outside, such as to stretch, expand, flatten, or conform the bilayer to size.

[0089] The "10% or less tolerance" described in this application, when used to describe a tension controller, means that the tension controller can maintain a tension on the double layer with a tolerance of ten percent. For example, if the tension on the double layer is set to 150N per meter of web width, a tolerance of 10% or less means that the tension controller can maintain a tension on the double layer between 135N and 165N per meter of web width. "Or less" means that the tension controller has a tighter tolerance range. For example, for a tension controller set to 150N per meter of web width, a tolerance of 5% or less means that the tension controller can maintain a tension on the double layer between 142.5N and 157.5N per meter of web width.

[0090] The term "arched shape characterized by a radius of curvature" as used herein means that the bilayer is bent in a curved form when it rests under tension against a runway, at least one speed bump or at least one roller. Mathematically, the curvature of the bilayer can be approximately represented by the radius of curvature of the bilayer bend. The radius of curvature includes the radius of the arc of the curve that is closest to the point. For a surface, the radius of curvature is the radius of the arc of the normal section that best fits the contact surface of the bilayer. Unless otherwise specified, the contact surface is the metal layer of the bilayer.

[0091] C. Processing device

[0092] FIG. 1 shows an embodiment of a processing device disclosed in the present application. The processing device 100 includes a front roller 101 with a green double layer wound thereon. The processing device 100 includes a rear roller 102 with a green double layer or a sintered double layer wound thereon. The processing device 100 includes a plurality of zones 103 for heating, cooling, maintaining temperature, or a combination thereof. Five zones 103 are shown in FIG. 1 , however, more or fewer zones 103 are contemplated herein. For example, the processing device 100 may include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-12 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-11 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-10 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-9 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-8 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-7 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-6 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-5 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-4 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-3 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. For example, the processing device 100 may include 1-2 zones 103 for heating, cooling, maintaining temperature, or a combination thereof. In some embodiments, including any of the foregoing, one zone 103 is larger than another zone 103. In certain embodiments, the bilayer moves through the processing device at a certain speed. In these embodiments, the residence time in zone 103 will depend on the speed and length of the bilayer through zone 103.

[0093] Within region 103 are rollers 102. Rollers 102 are arranged in the shape of a ramp. The ramp may have a parabolic shape. The ramp may have an elliptical shape. The ramp may have a circular shape. The ramp may have a catenary shape. In some examples, the ramp may be symmetrical. In other examples, the ramp may not be symmetrical. When passing through each roller, the angle formed by the belt is in the range of 0-40°. The height difference between the highest and lowest rollers may be in the range of 0-10m.

[0094] In certain embodiments, the width of the above-mentioned slope is 120mm-800mm. In certain embodiments, including any of the foregoing, the length of each region is 100-1000mm long. In certain embodiments, including any of the foregoing, the height of each region is 10mm-1000mm.

[0095] FIG. 2 shows a portion of a processing device 200. A heating zone 201 is a furnace or oven capable of burning, evaporating, or a combination thereof, the binder in the green body double layer. In some embodiments, the zone 201 is a binder burnout zone. On one side of the 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 can be a heating lamp, a heating coil, an induction heater, or any heat source. The curved runway includes a plurality of rollers that are spaced apart on the curved runway. The roller 202 can be locked (fixed), overdriven (the rotation speed of the roller edge is faster than the web speed at the contact point), underdriven (the rotation speed of the roller edge is slower than the web speed at the contact point), or driven at the same speed as the web. The roller 202 can have a cylindrical profile, a convex profile, or a concave profile. The roller surface may comprise metal (including iron, nickel, molybdenum, tungsten, stainless steel) or ceramic (including silicon carbide, aluminum oxide, zirconium oxide, spinel, tungsten carbide, magnesium oxide, boron nitride and similar high temperature ceramics).

[0096] Here the susceptor absorbs energy, such as heat, from the heater and reradiates the heat to the film.

[0097] FIG3 shows a processing device 300. The processing device 300 includes at least one tube furnace 305 and at least one tube furnace 306. Additional tube furnaces may be present. In some embodiments, the tube furnace is a heating zone such as area 103 in FIG1, and the processing device 300 includes an exhaust port 301, which is located at the entrance and exit of each tube furnace 305 and 306. The processing device 300 includes rollers 302, which are located at the front and rear of the tube furnaces 305 and 306. In some embodiments, including any of the foregoing, the rollers 302 can be replaced with a tension control device. FIG3 shows a tube furnace entrance 303. FIG3 also shows a controller 304, which is used to control the temperature or atmosphere or a combination thereof in the tube furnace. The distance between the tube furnaces 305 and 306 can be adjusted by moving the furnaces relative to each other.

[0098] FIG. 4 shows a processing device 400. The processing device 400 includes at least one tube furnace 405 and at least one tube furnace 406. Additional tube furnaces may be present. In some embodiments, the tube furnace is a heating zone such as area 103 in FIG. 1, and the processing device 400 includes an exhaust port 401, which is located at the entrance and exit of each tube furnace 405 and 406. The processing device 400 includes a roller 402, which is located at the front and rear of the tube furnaces 405 and 406. In some embodiments, including any of the foregoing, the roller 402 can be replaced with a tension control device. FIG. 4 shows a tube furnace entrance 403. FIG. 4 also shows a controller 404, which is used to control the temperature or atmosphere or a combination thereof in the tube furnace. The distance between the tube furnaces 405 and 406 can be adjusted by moving the furnaces relative to each other.

[0099] In some embodiments, the present application describes a continuous production line, as described in International Patent Application No. PCT / US2022 / 019641, entitled “Rapid Ceramic Processing Techniques and Equipment,” filed on March 9, 2022, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0100] In some embodiments, the present application describes a processing device comprising: a front roller; at least one furnace comprising at least three heating zones; and a runway having a surface of a material selected from the following: nickel (Ni), iron (Fe), anodized aluminum, Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite; aluminum oxide (Al2O3), zirconium oxide (ZrO2), silicon carbide, magnesium oxide, molybdenum alloys such as titanium-zirconium-molybdenum (TZM) or molybdenum-lanthanum (MoLa), tungsten alloy or a combination thereof.

[0101] In some examples, the racetrack has an aluminum oxide surface. In certain instances, the racetrack comprising aluminum oxide contacts the back side (metal side) of the bilayer.

[0102] In some examples, the racetrack has a magnesium oxide surface. In certain instances, the racetrack comprising magnesium oxide contacts the back side (metal side) of the bilayer.

[0103] In some examples, the racetrack has a boron nitride surface. In certain instances, a racetrack comprising magnesium oxide contacts the back side (metal side) of the bilayer.

[0104] In some examples, the racetrack has a boron nitride surface. In certain instances, the racetrack comprising boron nitride contacts the back side (metal side) of the bilayer.

[0105] In some examples, the racetrack has a silicon carbide surface. In certain instances, the racetrack comprising silicon carbide does not contact the bilayer but is located within 0.5 cm to 5 cm of the bilayer.

[0106] In some examples, the racetrack has a surface comprising graphite. In certain instances, the racetrack comprising graphite does not contact the bilayer but is located within 0.5 cm to 5 cm of the bilayer.

[0107] In some examples, the track has a carbon fiber composite surface. In some instances, the track comprising the carbon fiber composite does not contact the bilayer, but is located within 0.5 cm to 5 cm of the bilayer. In some instances, the carbon fiber composite is coated with boron nitride.

[0108] In some examples, the racetrack has a surface containing molybdenum (Mo). In some examples, the racetrack has a surface containing tungsten (W). In certain instances, the racetrack containing Mo or W does not contact the bilayer, but is located within 0.5 cm to 5 cm of the bilayer.

[0109] In some embodiments, a racetrack is provided in the binder burnout zone.

[0110] In some embodiments, a racetrack is provided in the green area.

[0111] In some embodiments, a racetrack is provided in the sintering zone. In some such embodiments, the racetrack has an alumina surface. In some such embodiments, the racetrack has a surface comprising a refractory material.

[0112] In some embodiments, racetracks are provided in the green zone and the sintering zone.

[0113] In some embodiments, racetracks are provided in the binder burnout zone and the green body zone.

[0114] In some embodiments, racetracks are provided in the binder burnout zone and the sintering zone.

[0115] In some embodiments, racetracks are provided in the binder burnout zone, the green zone, and the sintering zone.

[0116] In some embodiments, a raceway is provided in the cooling zone. In some such embodiments, the raceway has a carbonaceous surface.

[0117] In some embodiments, including any of the preceding embodiments, the track includes rollers.

[0118] In certain embodiments, the roller contacts only the metal layer of the bilayer disclosed herein.

[0119] In certain embodiments, the roller contacts only the metal layer on the double layer disclosed in the present application. In some embodiments, the roller does not contact the ceramic layer on the double layer disclosed in the present application. In some embodiments, when the temperature of the double layer exceeds 30°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 60°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 90°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 150°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 200°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 250°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 300°C, The roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 400°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 500°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 600°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 700°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 800°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application; in some embodiments, when the temperature of the double layer exceeds 900°C, the roller does not contact the ceramic layer on the double layer disclosed in the present application. In some embodiments, the roller does not contact the ceramic layer on the double layer disclosed in the present application until after the sintering zone of the processing device.

[0120] In some embodiments, the present application describes a processing device comprising: a front roller; at least one furnace, the furnace comprising at least three heating zones; and at least one of the following: a baffle within a heating zone; a baffle between two heating zones; a curtain purge between two heating zones; a device for controlling at least two different pressure zones within the at least three heating zones; a device for exhausting through the center of the at least one furnace; a device for exhausting through the center of a runway; a purge gas device between two heating zones; a device for isolating gas between two heating zones; a device for mechanically separating two heating zones; or a combination thereof.

[0121] In some embodiments, including any of the foregoing embodiments, the racetrack includes an exhaust system. In some examples, the exhaust system is in the middle of the racetrack. In some examples, the exhaust system is located at a number of points along the binder burnout path. In some embodiments, the airflow flows in a cross direction of the web. In some embodiments, the exhaust system is heated from the furnace to the cold trap.

[0122] In some embodiments, the present application describes a processing device comprising: a front roller; at least one oven, the oven comprising at least three heating zones; and a double layer maintained under tension, wherein the tension is in the range of 0.1 g / cm to 500 g / cm. The left side of Figure 10 shows a double-layer film prepared under high tension of 30-100 g / cm web width. The right side of Figure 10 shows a double-layer film prepared under low tension of 1-15 g / cm web width. In some embodiments, the present application describes a processing device comprising: a front roller; at least one oven, the oven comprising at least three heating zones; and a double layer maintained under tension, wherein the tension is in the range of 1-15 g / cm web width. When the double layer is unrolled from the roller, before the double layer is heated to burn out the adhesive, the tension is measured using a load cell. In some examples, the tension range is 1-14 g / cm web width. In some examples, the tension range is 1 to 13 g / cm web width. In some examples, the tension range is 1 to 12 g / cm web width. In some examples, the tension range is 1 to 11 g / cm web width. In some examples, the tension range is 1 to 10 g / cm web width. In some examples, the tension range is 1 to 9 g / cm web width. In some examples, the tension range is 1 to 8 g / cm web width. In some examples, the tension range is 1 to 7 g / cm web width. In some examples, the tension range is 1 to 6 g / cm web width. In some examples, the tension range is 1 to 5 g / cm web width. In some examples, the tension range is 1 to 4 g / cm web width. In some examples, the tension range is 1 to 3 g / cm web width. In some examples, the tension range is 1 to 2 g / cm web width. In some examples, the tension range is 1 to 15 g / cm web width. In some examples, the tension range is 2 to 15 g / cm web width. In some examples, the tension range is 3 to 15 g / cm web width. In some instances, the tension range is 4 to 15 g / cm of web width. In some instances, the tension range is 5 to 15 g / cm of web width. In some instances, the tension range is 6 to 15 g / cm of web width. In some instances, the tension range is 7 to 15 g / cm of web width. In some instances, the tension range is 8 to 15 g / cm of web width. In some instances, the tension range is 9 to 15 g / cm of web width. In some instances, the tension range is 10 to 15 g / cm of web width. In some instances, the tension range is 11 to 15 g / cm of web width. In some instances, the tension range is 12 to 15 g / cm of web width. In some instances, the tension range is 13 to 15 g / cm of web width. In some instances, the tension range is 14 to 15 g / cm of web width.

[0123] In some embodiments, the bilayer is maintained at a tension of 30 g on a 100 mm wide roll that includes a 10 μm thick Ni foil layer in the bilayer. In some examples, the tension is 3 kg / cm 2 (cross sectional area). In certain embodiments, the bilayer maintains a tension of 0.01 g / cm to 10 g / cm of web width.

[0124] In certain embodiments, for green bilayers, the bilayer is maintained at a tension in the range of 0.01 g / cm to 100 g / cm.

[0125] In certain embodiments, for a green bilayer, the bilayer is maintained at a tension in the range of 0.01 g / cm to 500 g / cm.

[0126] In some embodiments, the tension is not equal in different areas of the processing device. For example, the tension in the unwinding and rewinding areas may be higher than the tension in the high temperature area. In some embodiments, the tension is isolated using nip rolls, vacuum rolls, and / or rolls with wrap angles that increase or decrease cross-roll tension. In some embodiments, the tension in the winding and / or unwinding areas is greater than 5 kg / cm 2 , or greater than 10kg / cm 2 , or greater than 15kg / cm 2 , or greater than 20kg / cm 2 or greater than 25kg / cm 2 In some embodiments, the tension in the winding area is greater than 5 kg / cm 2 , or greater than 10kg / cm 2 , or greater than 15kg / cm 2 , or greater than 20kg / cm 2 or greater than 25kg / cm 2 In some embodiments, the tension in the unwinding zone is greater than 5 kg / cm 2 , or greater than 10kg / cm 2 , or greater than 15kg / cm 2 , or greater than 20kg / cm 2 or greater than 25kg / cm 2 In some embodiments, in at least one region where the temperature exceeds 800°C, the tension is less than 6 kg / cm 2 , or less than 5kg / cm 2 , or less than 4kg / cm 2 , or less than 3kg / cm 2 , or less than 2kg / cm 2 , or less than 1kg / cm 2 , or less than 0.5kg / cm 2 Cross-sectional area of ​​the coil.

[0127] In some embodiments, the present application describes a processing device comprising: a front roller; at least one furnace, the furnace comprising at least three heating zones; a double layer; and at least two or more rollers; wherein the double layer is wrapped around one of the at least two or more rollers at a wrap angle of 0-40°.

[0128] In some embodiments, including any of the foregoing embodiments, the two aligned rollers are parallel to each other. The wrap angle describes the angle between entering the double layer and leaving the double layer relative to the roller. In some instances, the double layer is wrapped around one of the at least two or more rollers at a wrap angle of 5° to 10°. In some examples, the rollers for handling the coils are aligned with each other with a maximum deviation of 0.0005-0.005 degrees. In some examples, the rollers are circular within a tolerance of 0.001", or a tolerance of 0.002", or a tolerance of 0.003", or a tolerance of 0.004", or a tolerance of 0.005". In some instances, at least one roller has a diameter of at least 7 cm. In some instances, at least one roller has a diameter of at least 8 cm. In some instances, at least one roller has a diameter of at least 9 cm. In some instances, at least one roller has a diameter of at least 10 cm. In some instances, at least one roller has a diameter of at least 15 cm.

[0129] In some embodiments, including any of the preceding embodiments, the double layer is wrapped around one of the at least two or more rollers at a wrap angle of 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, 22°, 23°, 24°, 25°, 26°, 27°, 28°, 29°, 30°, 31°, 32°, 33°, 34°, 35°, 36°, 37°, 38°, 39° or 40°.

[0130] In some embodiments, including any of the preceding embodiments, the processing device comprises a double layer.

[0131] In some embodiments, including any of the preceding embodiments, the three different heating zones include: (a) a binder burnout section; (b) a green billet section; and (c) a sintering section.

[0132] In some embodiments, including any of the preceding embodiments, the processing device includes a rear roller.

[0133] In some embodiments, including any of the preceding embodiments, the front roller is mechanically coupled to the at least one furnace.

[0134] In some embodiments, including any of the preceding embodiments, the front roller is provided with a motor, and the motor is sealed from the at least one furnace.

[0135] In some embodiments, including any of the foregoing embodiments, the processing device includes a runway, which includes a material selected from the following: nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber, graphite; aluminum oxide (Al2O3), zirconium oxide (ZrO2) or a combination thereof. In some embodiments, including any of the foregoing embodiments, the runway may be coated with a material selected from the following: nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber, graphite; aluminum oxide (Al2O3), zirconium oxide (ZrO2) or a combination thereof. In some embodiments, the runway comprises nickel, carbon or carbon fiber. In some embodiments, the runway is coated with at least one layer of iron, Ni-Fe alloy, silicon carbide or boron nitride.

[0136] In some embodiments, including any of the preceding embodiments, the raceway is located inside at least one furnace.

[0137] In some embodiments, including any of the foregoing embodiments, the racetrack is located inside the sintering section.

[0138] In some embodiments, including any of the preceding embodiments, the runway includes an exhaust port.

[0139] In some embodiments, including any of the preceding embodiments, the runway includes a speed bump.

[0140] In some embodiments, including any of the preceding embodiments, the top track is center-less.

[0141] In some embodiments, including any of the preceding embodiments, the racetrack includes holes on a top surface thereof.

[0142] In some embodiments, including any of the preceding embodiments, the at least one furnace is sealed.

[0143] In some embodiments, including any of the preceding embodiments, the processing device includes a cooling section.

[0144] In some embodiments, including any of the foregoing embodiments, the processing device includes at least one atmosphere controller that controls at least one of the gas flow rate, flow direction, gas composition, pressure, and combinations thereof in the furnace.

[0145] In some embodiments, including any of the preceding embodiments, the double layer is wound on a front roller.

[0146] In some embodiments, including any of the preceding embodiments, the bilayer includes a metal layer and a green layer.

[0147] In some embodiments, including any of the preceding embodiments, the at least one furnace comprises a multiple zone tunnel kiln (MZTK).

[0148] In some embodiments, including any of the preceding embodiments, the roller comprises a material selected from silicon carbide, Ni, stainless steel, or combinations thereof.

[0149] In some embodiments, including any of the preceding embodiments, the rollers can be mechanically aligned to within 0.005 inches. In some embodiments, including any of the preceding embodiments, the rollers can be mechanically aligned to within 0.001 inches.

[0150] In some embodiments, including any of the preceding embodiments, the rollers can be mechanically aligned in three dimensions.

[0151] In some embodiments, including any of the preceding embodiments, the processing device includes nip rollers. Nip rollers are two rollers that contact the top and bottom of the double layer at the same position. Nip rollers are used to isolate tension zones - the tension on either side of the nip roller can be different.

[0152] In some embodiments, including any of the foregoing embodiments, the processing device includes at least two pairs of nip rollers. In some examples, a pair of nip rollers is positioned after the unwind section. In some examples, a pair of nip rollers is positioned before the rewind section. In some examples, the nip rollers isolate the tension so that a larger tension (greater than 6 g / cm) can be applied in the unwind and rewind, while a smaller tension (less than 6 g / cm) can be applied in the hot zone.

[0153] In some embodiments, including any of the preceding embodiments, the at least one oven comprises a heated roller.

[0154] In some embodiments, including any of the preceding embodiments, the at least one furnace includes rollers configured as a ramp.

[0155] In some embodiments, including any of the foregoing embodiments, the MZTK has a roller configured as a dome within the MZTK. In some examples, the dome is as shown in FIG. 1 .

[0156] In some embodiments, including any of the preceding embodiments, the MZTK includes one to twenty rollers configured as a ramp.

[0157] In some embodiments, including any of the foregoing embodiments, the MZTK is hermetically sealed.

[0158] In some embodiments, including any of the foregoing embodiments, the MZTK is vacuum sealed.

[0159] In some embodiments, including any of the foregoing embodiments, the front roller has a motor, and a vacuum seal is formed between the motor and the MZTK.

[0160] In some embodiments, including any of the preceding embodiments, the method includes a baffle between each heating zone.

[0161] In some embodiments, including any of the preceding embodiments, the wrap angle around the roller is in the range of 0° to 40°.

[0162] In some embodiments, including any of the preceding embodiments, the wrap angle around the roller in the binder burnout section ranges from 0° to 40°.

[0163] In some embodiments, including any of the preceding embodiments, the wrap angle around the roller in the sintering section is in the range of 0° to 40°.

[0164] In some embodiments, including any of the foregoing embodiments, the handling device comprises nip rollers, wherein the top roller contacts each edge of the web, the distance between the two being 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 foregoing embodiments, the handling device comprises nip rollers, wherein the top roller contacts the top of the web. In some embodiments, including any of the foregoing embodiments, the handling device comprises speed bumps, air bearings, or combinations thereof.

[0165] In some embodiments, including any of the preceding embodiments, the bilayer is suspended in MZTK. In some embodiments, including any of the preceding embodiments, the bilayer travels vertically in at least one zone heated to above 600°C.

[0166] In some embodiments, including any of the preceding embodiments, the at least one furnace comprises: (a) a binder burnout section; (b) a green billet section; and (c) a sintering section.

[0167] In some embodiments, including any of the foregoing embodiments, the at least one furnace is sealed so that at least one atmosphere controller controls the flow of gas into and out of the at least one furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 100 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 90 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 80 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 70 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 60 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 50 ppm by weight is maintained in the sealed furnace. In some instances, when the furnace is purged with a N2 gas flow, an oxygen partial pressure of less than 40 ppm by weight is maintained in the sealed furnace. In some examples, an oxygen partial pressure of less than 30 ppm by weight is maintained in the sealed furnace when the furnace is purged with a flow of N2.

[0168] In some embodiments, including any of the preceding embodiments, the processing apparatus includes a pressurized gas line between the green billet segment and the sintering segment, the pressurized gas line pumping gas into the green billet segment and the sintering segment.

[0169] In some embodiments, including any of the preceding embodiments, the at least one furnace is enclosed in a sealed container.

[0170] In some embodiments, including any of the foregoing embodiments, the sealed container contains an atmosphere of Ar, N2, H2O, H2 or a combination thereof.

[0171] In some embodiments, including any of the preceding embodiments, an atmosphere controller maintains a reducing atmosphere in the sintering section.

[0172] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere including argon (Ar); nitrogen (N2); hydrogen (H2) gas or a mixture thereof in the sintering section. In some embodiments, including any of the foregoing embodiments, moisture is introduced in the temperature zone below 800° C. by gas flow configuration. In some embodiments, including any of the foregoing embodiments, the gas in the temperature zone below 800° C. is isolated from the environment in the temperature zone above 900° C. by gas flow configuration.

[0173] In some embodiments, including any of the foregoing embodiments, the O2 atmosphere is maintained at less than 500 ppm by an atmosphere controller in the green billet section, the sintering section, or both the green billet section and the sintering section.

[0174] In some embodiments, including any of the foregoing embodiments, the H 2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0175] In some embodiments, including any of the preceding embodiments, the green layer is a green tape.

[0176] In some embodiments, including any of the preceding embodiments, the green layer is a patch-coated green tape. In some embodiments, including any of the preceding embodiments, the green layer is a coated green tape.

[0177] In some embodiments, including any of the preceding embodiments, curtain processing is performed as the bi-layer moves through the processing device.

[0178] In some embodiments, including any of the preceding embodiments, vertical processing is performed as the bilayer moves through the processing device.

[0179] In some embodiments, including any of the foregoing embodiments, the metal layer comprises a metal selected from nickel (Ni), iron (Fe), copper (Cu), titanium, tungsten, molybdenum, alloys thereof, or combinations thereof.

[0180] In some embodiments, including any of the preceding embodiments, the metal layer is an alloy of Fe and Ni.

[0181] In some embodiments, including any of the foregoing embodiments, the metal layer is an alloy of Fe and Ni, and the amount of Fe is 1% to 25% (w / w), and the rest is Ni. In some embodiments, including any of the foregoing embodiments, the metal layer is a double layer of Fe and Ni, and the amount of Fe is 1% to 25% (w / w), and the rest is Ni.

[0182] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 1 μm to 20 μm. In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 4 μm to 10 μm. In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 6 μm to 10 μm. In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 8 μm to 10 μm.

[0183] In some embodiments, including any of the preceding embodiments, the bi-layer is suspended while moving through the sintering zone.

[0184] In some embodiments, including any of the preceding embodiments, the processing device includes a sintered bi-layer wound on the at least one back roller.

[0185] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered lithium-filled garnet.

[0186] In some embodiments, including any of the preceding embodiments, the processing device moves the bilayer through the at least one furnace at a rate of at least 2 inches per minute.

[0187] In some embodiments, including any of the foregoing embodiments, the processing apparatus is capable of producing at least 200,000 sintered bi-layers per week. In some embodiments, including any of the foregoing embodiments, the processing apparatus is capable of producing at least 1,000 m 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 1 m per hour 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 2 m per hour. 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 3m per hour 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 4 m per hour 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 5m per hour 2 In some embodiments, including any of the foregoing embodiments, the processing device is capable of producing at least 6 m per hour 2 Sintered double layer.

[0188] In some embodiments, including any of the preceding embodiments, the processing apparatus produces double layers cut to a size of 73 mm x 90 mm.

[0189] In some embodiments, including any of the foregoing embodiments, the minimum web speed required for the processing device to achieve this throughput is 1.0 m / min, which will be the assumed web speed in the following sections.

[0190] In some embodiments, including any of the foregoing embodiments, the processing device produces a double layer length of 400m-1500m. This corresponds to a maximum incoming coil diameter of 295mm-485mm (if a 6-inch core is used) and a maximum coil weight of 50-180kg.

[0191] In some embodiments, including any of the foregoing embodiments, the processing apparatus produces a double layer having a maximum output coil diameter of 360-450 mm (if using a 12 inch core) and a maximum coil weight of 40-140 kg.

[0192] In some embodiments, including any of the preceding embodiments, the binder burnout zone and the sintering zone are positioned parallel to each other.

[0193] In some embodiments, including any of the preceding embodiments, the binder burnout zone is located above the sintering zone.

[0194] In some embodiments, including any of the preceding embodiments, the processing device includes a second binder burnout zone.

[0195] In some embodiments, including any of the preceding embodiments, the entire processing device is placed under vacuum.

[0196] In some embodiments, including any of the foregoing embodiments, the at least one furnace comprises a single furnace having a cooling section, a binder burnout section; a green billet section; a sintering section; and then another cooling section. In some implementations, there is an additional cooling section between the binder burnout section and the green billet section or between the green billet section and the sintering section.

[0197] In some embodiments, including any of the foregoing embodiments, the sintering section is not directly exposed to the earth's atmosphere. This means that in the sintering section, the atmosphere in contact with the sintered membrane or bilayer within the sintering section inside the sintering section is unique, and the unique atmosphere is not the earth's atmosphere (e.g., 78% N2, 21% O2). Instead, in the sintering section, the gas contacting the sintered membrane or bilayer is an inert or reducing gas, such as Ar, N2, H2, or a combination thereof. This can be achieved by partially or completely sealing the sintering section, thereby isolating the sintering section from the earth's atmosphere. This can be achieved by allowing gas to flow into or out of the sintering section, isolating it from the earth's atmosphere. This can be achieved by placing the sintering section in a chamber filled with an inert or reducing gas.

[0198] In some embodiments, including any of the foregoing embodiments, the at least one furnace is not directly exposed to the earth's atmosphere. This means that the at least one furnace has a unique atmosphere, and the sintered film or double layer inside the at least one furnace is in contact with the unique atmosphere, which is not the earth's atmosphere (e.g., 78% N2, 21% O2). Instead, in the at least one furnace, the gas contacting the sintered film or double layer is an inert or reducing gas, such as Ar, N2, H2, or a combination thereof. This can be achieved by sealing the at least one furnace, isolating it from the earth's atmosphere. This can be achieved by allowing gas to flow into or out of the at least one furnace, isolating it from the earth's atmosphere. This can be achieved by placing the at least one furnace in a chamber filled with an inert or reducing gas.

[0199] In some embodiments, including any of the preceding embodiments, the at least one furnace is sealed such that the at least one atmosphere controller controls the flow of gas into and out of the at least one furnace.

[0200] In some embodiments, including any of the foregoing embodiments, the flow rate in the binder burnout section is higher than the flow rate in the green billet section, or higher than the flow rate in the sintering section, or higher than both the flow rate in the green billet section and the flow rate in the sintering section.

[0201] In some embodiments, including any of the foregoing embodiments, an atmosphere controller maintains consistent atmospheric conditions within the at least one furnace.

[0202] In some embodiments, including any of the preceding embodiments, an atmosphere controller maintains consistent atmosphere conditions within the binder burnout section.

[0203] In some embodiments, including any of the foregoing, an atmosphere controller maintains consistent atmosphere conditions within the green billet.

[0204] In some embodiments, including any of the foregoing embodiments, an atmosphere controller maintains consistent atmosphere conditions within the sintering section.

[0205] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere in the green billet that includes argon (Ar); nitrogen (N2); hydrogen (H2) gas; or a mixture thereof.

[0206] In some embodiments, including any of the preceding embodiments, an atmosphere controller maintains a reducing atmosphere in the sintering section.

[0207] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere including argon (Ar) gas; nitrogen (N2); hydrogen (H2) gas; or a mixture thereof in the sintering section.

[0208] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains an atmosphere of less than 500 ppm O2 in the green section, the sintering section, or both.

[0209] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere of less than 400 ppm O2 in the green section, the sintering section, or both.

[0210] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere of less than 300 ppm O2 in the green section, the sintering section, or both.

[0211] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains an atmosphere of less than 200 ppm O2 in the green section, the sintering section, or both the green section and the sintering section.

[0212] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains an atmosphere of less than 100 ppm O2 in the green section, the sintering section, or both the green section and the sintering section.

[0213] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains an atmosphere of less than 10 ppm O2 in the green section, the sintering section, or both the green section and the sintering section.

[0214] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains the H2O atmosphere in the binder burnout section at less than 5% v / v.

[0215] In some embodiments, including any of the foregoing embodiments, the H 2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0216] In some embodiments, including any of the foregoing embodiments, the H 2 gas is present at about 2.9% v / v.

[0217] In some embodiments, including any of the foregoing embodiments, the H 2 gas is present at about 5% v / v.

[0218] In some embodiments, including any of the preceding embodiments, the at least one furnace or a portion thereof is under a vacuum of less than 1 atmosphere (atm).

[0219] In some embodiments, including any of the preceding embodiments, the at least one furnace or portion thereof is under a vacuum of less than 100 Torr.

[0220] In some cases, the at least one furnace is pumped to a low vacuum to evacuate the air in the at least one furnace, and then the at least one furnace is backfilled with an inert or reducing gas. For example, the at least one furnace can be backfilled with N2. For example, the at least one furnace can be backfilled with Ar / H2. For example, the at least one furnace can be backfilled with Ar.

[0221] In some embodiments, including any of the preceding embodiments, the atmosphere in the binder burnout section is different from the atmosphere in the green billet section.

[0222] In some embodiments, including any of the preceding embodiments, the atmosphere in the binder burnout section is different from the atmosphere in the sintering section.

[0223] In some embodiments, including any of the foregoing, the atmosphere in the green segment is different from the atmosphere in the sintered segment.

[0224] In some embodiments, including any of the foregoing embodiments, the amount of O2 in the binder burnout section is less than 0.2 vol%.

[0225] In some embodiments, including any of the foregoing embodiments, the amount of CO 2 in the binder burnout section is less than 0.2 vol %.

[0226] In some embodiments, including any of the foregoing embodiments, the amount of carbon from the CO 2 in the sintering stage is less than 100 parts per million (ppm).

[0227] In some embodiments, including any of the foregoing embodiments, the amount of carbon from the CO 2 in the sintering stage is about 50 ppm to 100 ppm.

[0228] In some embodiments, including any of the foregoing embodiments, the bilayer contracts primarily in the z-direction as it moves through the sintering section. The z-direction as used herein is a direction directly perpendicular to the surface of the bilayer. The x-direction is the direction in which the bilayer moves through the processing device. The y-direction is perpendicular to the x-direction and is in the same plane as the bilayer. The z-direction is perpendicular to the x- and y-directions.

[0229] In some embodiments, including any of the preceding embodiments, the processing device heats the bilayer at a rate greater than 2.5°C / minute.

[0230] In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a rate greater than 5°C / minute, 10°C / minute, 15°C / minute, 20°C / minute, 25°C / minute, 30°C / minute, 35°C / minute, 40°C / minute, 45°C / minute, 50°C / minute, 55°C / minute, 60°C / minute, 65°C / minute, 70°C / minute, 75°C / minute, 80°C / minute, 85°C / minute, 90°C / minute, 100°C / minute, 200°C / minute or 300°C / minute.

[0231] In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a rate of about 5°C / minute to about 50°C / minute.

[0232] In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 0.5°C / cm to about 50°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 1°C / cm to about 5°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 0.5°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 1°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 2°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 3°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 4°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 5°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 6°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the double layer at a spatial rate of about 7°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a spatial rate of about 8°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a spatial rate of about 9°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a spatial rate of about 10°C / cm. In some embodiments, including any of the foregoing embodiments, the processing device heats the bilayer at a spatial rate of about 11°C / cm.

[0233] In some embodiments, including any of the preceding embodiments, the processing device includes an infrared heater for heating the bilayer.

[0234] In some embodiments, including any of the foregoing embodiments, the processing device comprises an induction carbon plate heater. In some embodiments, the carbon plate does not contact the green body. In some embodiments, the carbon plate does not contact the bilayer.

[0235] In some embodiments, including any of the foregoing embodiments, the processing device uses a carbon plate / heats the bilayer by induction heating.

[0236] In some embodiments, including any of the foregoing embodiments, the treatment device includes lamp-based heating to heat the bilayer. In some embodiments, including those embodiments that are lamp-based heating, the treatment device further includes a susceptor that can absorb at least 20% of the radiation emitted by the lamp.

[0237] In some embodiments, including any of the preceding embodiments, the processing apparatus includes furnace-based heating.

[0238] According to an embodiment, the heating element used in the present application can be a carbon plate or carbon paper. In some embodiments, the carbon plate or carbon paper includes conductive carbon. According to an embodiment, the heating element can be a molybdenum plate or molybdenum paper. In some embodiments, the molybdenum plate or molybdenum paper can include conductive molybdenum. An electric current can be applied to heat the conductive carbon plate or conductive carbon paper element to a certain temperature at an appropriate rate so as to sinter within the temperature range described in the present application.

[0239] In one embodiment, the maximum heating temperature may be in the range of 900°C to 2000°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1900°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1800°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1700°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1600°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1500°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1400°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1300°C; in one embodiment, the maximum heating temperature may be in the range of 900°C to 1200°C.

[0240] In one embodiment, the time in the highest temperature heating zone can be in the range of 5 seconds to 30 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 25 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 20 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 15 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 10 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 5 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 4 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 3 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 4 minutes. In one embodiment, the range of the heating period can be from 5 seconds to 1 minute.

[0241] In some embodiments, the heating element may have the same area as the material to be heated. In some embodiments, the heating element may be longer than the material to be heated and as wide as the material to be heated. In some embodiments, the heating element may have the same length as the material to be heated and be wider than the material to be heated. In some embodiments, the heating element may be shorter than the material to be heated. In embodiments where there is a single heating element, the area relationship of the heating element to the material to be heated may be any of the above.

[0242] In some embodiments, including any of the foregoing embodiments, the processing device is provided with a cooling zone after the sintering section. For example, in a 60-inch furnace, there may be a 20-inch preheating zone, a 20-inch high temperature zone, and a 20-inch cooling zone.

[0243] In some examples, the at least one furnace has a 1 mm gap above the green body. In some examples, the at least one furnace has a 2 mm gap above the green body. In some examples, the at least one furnace has a 3 mm gap above the green body. In some examples, the at least one furnace has a 4 mm gap above the green body. In some examples, the at least one furnace has a 5 mm gap above the green body. The gap prevents lithium from escaping from the green body.

[0244] In some embodiments, including any of the foregoing embodiments, a suitable amount of tension is applied by the processing device to reduce or eliminate transverse wrinkles of the web. For example, to avoid plastic deformation of the foil substrate at high temperatures, the tension can be kept relatively low. In some examples, the tension on the foil during sintering is 0.4N to 4N.

[0245] In some embodiments, including any of the foregoing embodiments, when a separate tool is used for binder burnout, or when the tension between the sintering section and the binder burnout section is separated, the tension on the foil during binder burnout can be 1.2N to 12N.

[0246] In some embodiments, including any of the foregoing embodiments, rollers are used at the entrance or exit of at least one furnace by the processing device to reduce or eliminate transverse wrinkles of the coil. Sliding rollers, driven rollers, lower driven rollers, upper driven rollers, or other rollers may be used.

[0247] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the sintering zone is two minutes or less.

[0248] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the sintering zone is one minute and thirty seconds or less.

[0249] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the sintering zone is one minute or less.

[0250] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the sintering zone is about thirty seconds or less.

[0251] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the sintering zone is about thirty seconds.

[0252] In some embodiments, including any of the preceding embodiments, the processing apparatus is configured such that the residence time in the binder burnout zone is about ten times the residence time in the sintering zone.

[0253] In some embodiments, including any of the preceding embodiments, the processing device includes at least one tension regulator.

[0254] In some embodiments, including any of the preceding embodiments, the tension of the bi-layer after the front roller is about 270 g.

[0255] In some embodiments, including any of the preceding embodiments, the tension of the bi-layer before the back roller is about 500 g.

[0256] In some embodiments, including any of the preceding embodiments, the width of the double layer is 8 cm.

[0257] In some embodiments, including any of the foregoing embodiments, the tension applied to the bilayer is about 34 g / cm.

[0258] In some embodiments, including any of the preceding embodiments, the tension applied to the bilayer is about 0.1 N / μm thickness.

[0259] In some embodiments, including any of the preceding embodiments, the tension applied to the bilayer is less than 50% of its yield strength.

[0260] In some embodiments, including any of the preceding embodiments, the tension applied to the bilayer is less than 50% of the yield strength of the metal layer.

[0261] In some embodiments, including any of the preceding embodiments, the tension applied to the bilayer is between about 25% and 50% of its yield strength.

[0262] In some embodiments, including any of the preceding embodiments, the tension of the bi-layer is between about 25% and 50% of the yield strength of the metal layer.

[0263] In some embodiments, including any of the preceding embodiments, the green body is a green tape.

[0264] In some embodiments, including any of the foregoing embodiments, 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 certain intervals. The metal layer between the sheets can be scored or partially cut. The metal between the sheets can be used as a connector in the battery cell.

[0265] In some embodiments, including any of the preceding embodiments, the binder burnout stage is a binder burnout furnace.

[0266] In some embodiments, including any of the preceding embodiments, the binder burnout furnace is a furnace that is heated to a temperature sufficient to volatilize, pyrolyze, burn, or decompose the binder present in the green body.

[0267] In some embodiments, including any of the preceding embodiments, the temperature in the binder burnout furnace is between 80°C and 500°C.

[0268] In some embodiments, including any of the preceding embodiments, the temperature in the binder burnout furnace is between 100°C and 500°C.

[0269] In some embodiments, including any of the preceding embodiments, the temperature in the binder burnout furnace is between 80°C and 800°C.

[0270] In some embodiments, including any of the preceding embodiments, the binder burnout furnace contains oxygen. In some of these embodiments, the sintering furnace does not contain oxygen.

[0271] In some embodiments, including any of the preceding embodiments, the china segment is a china furnace.

[0272] In some embodiments, including any of the preceding embodiments, the china furnace is a furnace heated to a temperature sufficient to form the green body into a china body after the binder is removed.

[0273] In some embodiments, including any of the preceding embodiments, the temperature in the bisque furnace is between 100°C and 800°C.

[0274] In some embodiments, including any of the preceding embodiments, the sintering section is a sintering furnace.

[0275] In some embodiments, including any of the preceding embodiments, the sintering furnace is a furnace heated to a temperature sufficient to sinter the green body.

[0276] In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature sufficient to sinter the lithium-filled garnet. In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature sufficient to sinter lithium aluminum titanium phosphate. In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature sufficient to sinter lithium aluminum germanium phosphate. In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature of 800-900°C. In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature of 900-1000°C. In some embodiments including any of the foregoing, the sintering furnace is a furnace heated to a temperature of 1000-1100°C. In some embodiments, including any of the foregoing embodiments, the sintering furnace is a furnace heated to a temperature of 1100-1200°C.

[0277] In some embodiments, including any of the preceding embodiments, the temperature in the sintering furnace is between 500°C and 1300°C.

[0278] In some embodiments, including any of the preceding embodiments, the temperature in the sintering furnace is between 1000°C and 1300°C.

[0279] In some embodiments, including any of the preceding embodiments, the temperature in the sintering furnace is between 1100°C and 1300°C.

[0280] In some embodiments, including any of the foregoing embodiments, the binder burnout furnace is sealedly connected to the biscuit furnace, and the biscuit furnace is sealedly connected to the sintering furnace.

[0281] In some embodiments, including any of the foregoing embodiments, the at least one furnace is a single furnace. In some embodiments, including any of the foregoing embodiments, the at least one rear roller has a roller diameter greater than 4 cm. In some embodiments, including any of the foregoing embodiments, the at least one rear roller has a roller diameter greater than 5 cm. In some embodiments, including any of the foregoing embodiments, the at least one rear roller has a roller diameter greater than 6 cm. In some embodiments, including any of the foregoing embodiments, the at least one rear roller has a roller diameter greater than 7 cm. In some embodiments, including any of the foregoing embodiments, the at least one rear roller has a roller diameter greater than 8 cm. In some embodiments, including any of the foregoing embodiments, the winding tension of the at least one rear roller is greater than 20 g per centimeter of linear web width.

[0282] In some embodiments, including any of the foregoing embodiments, the spaces above and below the bilayer are configured to maintain a lithium-rich atmosphere in contact with the sintered film.

[0283] In some embodiments, including any of the foregoing embodiments, the spaces above and below the bi-layer are configured such that the bi-layer contains at least 95% lithium by weight after treatment in the treatment device relative to before treatment.

[0284] In some embodiments, including any of the preceding embodiments, the processing device includes at least two endrollers.

[0285] In some embodiments, including any of the preceding embodiments, the green body includes an unsintered lithium-stuffed garnet or a chemical precursor to a lithium-stuffed garnet.

[0286] In some embodiments, including any of the preceding embodiments, the processing device includes a sintered bilayer wound on at least one back roller.

[0287] In some embodiments, including any of the foregoing embodiments, the sintered bilayer comprises sintered lithium-filled garnet. In some embodiments, including any of the foregoing embodiments, the sintered bilayer comprises sintered lithium aluminum germanium phosphate. In some embodiments, including any of the foregoing embodiments, the sintered bilayer comprises sintered lithium aluminum titanium phosphate.

[0288] In some embodiments, including any of the preceding embodiments, the green body includes a binder.

[0289] In some embodiments, including any of the preceding embodiments, the green body includes a dispersant. In some embodiments, including any of the preceding embodiments, the green body includes a plasticizer.

[0290] In some embodiments, including any of the preceding embodiments, the green body comprises a solvent or a combination of solvents.

[0291] In some embodiments, including any of the preceding embodiments, the processing device moves the bilayer through the at least one furnace at a rate of at least 2 inches per minute.

[0292] In some embodiments, including any of the preceding embodiments, the handling device moves the bi-layer through the sintering section at a rate of at least 2 inches per minute.

[0293] In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope before at least one furnace. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope before the binder burnout section. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope before the billet section. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope before the sintering section. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope within at least one furnace. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope within the binder burnout section. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope located within the billet section. In some embodiments, including any of the foregoing embodiments, the processing device includes a curved slope within the sintering section. In some embodiments, including any of the foregoing embodiments, the curved slope is coated.

[0294] In some embodiments, including any of the foregoing embodiments, the coating is a lithium aluminate coating. In some embodiments, including any of the foregoing embodiments, the coating is an aluminum oxide coating. In some embodiments, including any of the foregoing embodiments, the coating is a silicon carbide coating.

[0295] In some embodiments, including any of the preceding embodiments, the coating is a boron nitride coating.

[0296] In some embodiments, including any of the foregoing embodiments, a top surface of the curved slope is made of ceramic.

[0297] In some embodiments, including any of the foregoing embodiments, the ceramic is silicon carbide, boron nitride, aluminum oxide, zirconium oxide, or lithium aluminate.

[0298] In some embodiments, including any of the foregoing embodiments, the ramp is made of SS 430, SS 304, Kovar, Invar, Haynes 214, greater than 99.5% (w / w) alumina, carbon composite, boron nitride, or a combination thereof. In some embodiments, a speed bump is provided on the runway. In some embodiments, a speed bump is provided on a flat runway. In some embodiments, a speed bump is provided on a curved runway. These bumps destroy the stress of the metal layer from the continuous contact with the runway. When the film speed increases and exceeds the "speed bump", these impacts create "airspace". In some embodiments, there is a speed bump on the runway that is approximately 1 inch apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 2 inches apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 3 inches apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 4 inches apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 5 inches apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 6 inches apart from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 7 inches from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 8 inches from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 9 inches from the next speed bump. In some embodiments, there is a speed bump on the runway that is approximately 10 inches from the next speed bump.

[0299] As used herein, a unique atmosphere means that the gas or vapor environment in one furnace is substantially different from the gas or vapor environment in another furnace. For example, a substantial difference in one oven relative to another oven includes, but is not limited to, a total pressure difference of 5% or greater, a partial pressure difference of 5% or greater, a two-fold difference in 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) in one oven relative to another oven. For example, one furnace may include sufficient amounts of H2O and / or O2 so that organic materials can burn if heated to the ignition temperature of the organic materials. This may be a condition in the binder burnout stage. In such an instance, if the other furnace has a low concentration of O2 such that combustion cannot be maintained therein even at the combustion temperature, this indicates a substantial difference in one furnace relative to the other furnace. For example, a sintering furnace may have a lower oxygen concentration than a binder burnout furnace. In another example, one furnace may include water vapor at a concentration greater than 1,000 parts per million (ppm); while the other furnace may include water vapor at a concentration less than 100 ppm. This difference in the partial pressure of HO will also indicate a substantial difference in one oven relative to the other. In another example, one oven may be under vacuum while the other oven may be at 1 atm pressure, with this difference being a substantial difference in one oven relative to the other. In another example, both ovens may have similar gas mixtures, but one oven may have a total pressure that is 5% or more lower than the other oven, with this difference being a substantial difference in one oven relative to the other oven.

[0300] In certain embodiments, the binder burnout furnace contains an oxidant mixed into the gas or atmosphere that contacts the green tape. These oxidants may include H2O, O2, or clean, dry air. In certain embodiments, the sintering furnace does not include an oxidant mixed into the gas or atmosphere that contacts the sintered film.

[0301] In some embodiments, the pressurized enclosure contains argon (Ar) gas.

[0302] In some embodiments, the pressurized enclosure contains nitrogen (N2).

[0303] In some embodiments, the pressurized envelope also contains hydrogen (H2).

[0304] In some embodiments, H 2 gas is present in an amount of about 5% v / v.

[0305] In some embodiments, the pressurized enclosure also contains water (H2O) gas.

[0306] In some embodiments, the pressurized envelope also contains an inert gas, such as, but not limited to, N2, H2, Ar, and mixtures thereof, such as 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 foregoing embodiments, O2 is less than 10 ppm. In some embodiments, including any of the foregoing embodiments, O2 is present in an amount of 5-10 ppm.

[0307] In some embodiments, including any of the foregoing embodiments, O2 is present in the binder burnout furnace in an amount less than 10 ppm.

[0308] In some embodiments, including any of the foregoing embodiments, O2 is present in an amount of less than 10 ppm in the sintering furnace. In some embodiments, including any of the foregoing embodiments, O2 is present in an amount of less than 100 ppm in the cooling section after the sintering furnace. In some embodiments, including any of the foregoing embodiments, O2 is present in an amount of less than 70 ppm in the cooling section after the sintering furnace. In some embodiments, including any of the foregoing embodiments, O2 is present in an amount of less than 50 ppm in the cooling section after the sintering furnace.

[0309] In some embodiments, including any of the foregoing embodiments, O2 is present in the binder burnout furnace in an amount of 5-10 ppm.

[0310] In some embodiments, including any of the foregoing embodiments, O2 is present in the sintering furnace in an amount of 5-10 ppm.

[0311] In some embodiments, including any of the foregoing embodiments, O2 is present in the sintering furnace in an amount of 10 -16 Up to 10 -20 Pa.

[0312] In some embodiments, the oven includes 1-500 ppm H2O.

[0313] In some embodiments, the oven includes 1-1000 ppm H2O.

[0314] In certain embodiments, rapid sintering occurs in a confined space. The confined space has an atmosphere that reduces lithium loss during LLZO sintering and helps to maintain a stoichiometric amount of lithium in a given LLZO formula. A portion of the furnace through which the sintered film moves during sintering can be the confined space. Some methods described herein include using a tension suspension film without contacting the surface. Tension can be applied using a weight, a roller motor, a force sensor, or other methods for applying tension. Some methods described herein include using a tension suspension film without contacting the surface when moving through the above-mentioned confined space. Here, the suspended portion of the film does not contact the surface, but the device for applying tension contacts the other parts of the film. In some embodiments, only the suspended portion of the sintered film, and it does not contact other surfaces. Some methods described herein include contacting only one surface (e.g., the bottom surface of the belt or film can contact a roller, a tension device, or a substrate) during sintering. Some methods described herein include using tension, airflow, or a combination of tension and airflow to suspend the film without contacting the surface. Here, "not contacting the surface" specifically refers to when the sintered film moves through the furnace. During the sintering stage, the portion of the green tape to be sintered does not contact any surface, otherwise sintering defects will be introduced into the surface of the green tape. When the green tape is moved outside the oven, the green tape may pass through rollers, rewinders, pins, columns, tension devices, etc., which will contact its surface. Similarly, when the sintered film is moved outside the oven, the sintered film will pass through rollers, rewinders, pins, columns, etc., which will contact the sintered film. The contact in this case occurs after the film is sintered rather than during sintering. Certain methods described in the present application include the step of continuously peeling the green tape on it from the polyester film substrate. This can occur at the beginning of the sintering process to unwind the green tape from the roller and introduce the peeled green tape into the binder burnout furnace. Certain methods described in the present application include the step of applying tension to the green film during the sintering process. Certain methods described in the present application include the step of avoiding reaction with water / oxygen in the environment while processing the green tape from the green tape into the LLZO sintered film. In some embodiments, a metal foil is used instead of a polyester film substrate. In some embodiments, the metal foil is an iron foil, a copper foil, a nickel foil, an alloy thereof, or a combination thereof. In some embodiments, the metal foil is a combination of iron and nickel. In some embodiments, the combination of iron and nickel contains more than 1% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 2% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 3% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 4% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 5% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 6% iron, the remainder being nickel. In some embodiments, the combination of iron and nickel contains more than 7% iron, the remainder being nickel.In certain embodiments, the combination of iron and nickel contains more than 8% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 9% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 10% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 11% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 12% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 13% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 14% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 15% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 16% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 17% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 18% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 19% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 20% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 11% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 12% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 13% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 14% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 15% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 16% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 17% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 18% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 19% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 20% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 11% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 12% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 13% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 14% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 15% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 16% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 17% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 18% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 19% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 20% iron, the remainder being nickel.In certain embodiments, the combination of iron and nickel contains more than 21% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 22% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 23% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 24% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 25% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 26% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 27% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 28% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 29% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 30% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 31% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 32% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 33% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 34% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 35% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 36% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 37% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 38% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 39% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 40% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 41% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 42% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 43% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 44% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 45% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 46% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 47% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 48% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 49% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 50% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 51% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 52% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 53% iron, the remainder being nickel.In certain embodiments, the combination of iron and nickel contains more than 54% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 55% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 56% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 57% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 58% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 59% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 60% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 61% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 62% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 63% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 64% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 65% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 66% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 67% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 68% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 69% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 70% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 71% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 72% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 73% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 74% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 75% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 76% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 77% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 78% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 79% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 80% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 81% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 82% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 83% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 84% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 85% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 86% iron, the remainder being nickel.In certain embodiments, the combination of iron and nickel contains more than 87% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 88% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 89% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 90% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 91% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 92% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 93% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 94% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 95% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 96% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 97% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains more than 98% iron, the remainder being nickel. In certain embodiments, the combination of iron and nickel contains greater than 99% iron with the remainder being nickel.

[0315] In some embodiments, the binder burnout chimney is replaced by a Watlow heater cartridge embedded in a plate with perforations so that the gas can diffuse through them. These plates may incorporate gas diffusers, gas manifolds, channels or other devices to direct the gas flow across the product surface. The unit includes an exhaust port to remove the product of the binder.

[0316] In some embodiments, a 6 inch diameter Lindbergh Bisque tube furnace is used. In some embodiments, the furnace is at 650°C. The furnace can be at 200-900°C, and the furnace can incorporate multiple temperature zones. The furnace may include a member to support the product during transportation; the member may be made of Inconel, Hastelloy, Haynes Alloy 214, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, aluminum oxide or other ceramic or metal. A coating of Haynes alloy, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, aluminum oxide or other ceramic or metal may be provided on the support member.

[0317] D. How to use

[0318] In some embodiments, the present application describes a method using a continuous processing device, which includes the following operations: (a) heating the green double layer as the green double layer moves through at least one furnace to form a double layer with an organic content of less than 1%, and (b) winding the double layer with an organic content of less than 1% onto a roller.

[0319] In some embodiments, the present application describes a method using a continuous processing device, which includes the following operations: (a) providing or having provided a processing device disclosed in the present application; (b) heating the double layer as the double layer moves through the at least one furnace to form a blank double layer; (c) winding the blank double layer.

[0320] In some embodiments, including any of the foregoing embodiments, the method comprises step (d): unwinding the blank double layer.

[0321] In some embodiments, including any of the preceding embodiments, the method includes step (e): sintering the bilayer.

[0322] In some embodiments, including any of the preceding embodiments, the method includes winding the sintered bi-layer onto a back roll.

[0323] In some embodiments, including any of the preceding embodiments, the sintered bilayer is cut strips.

[0324] In some embodiments, including any of the preceding embodiments, after step (c) and prior to subsequent sintering, the green body bi-layer is wound onto a roll.

[0325] In some embodiments, the present application describes a method using a continuous processing device, which includes the following operations: (a) providing or having provided a processing device disclosed in the present application; (b) heating the double layer as the double layer moves through the at least one furnace to form a sintered double layer.

[0326] In this process, various embodiments can be used depending on certain conditions and the product to be produced. In some examples, a guide tape will be used. The guide tape will be attached to the green tape by high temperature ceramic (e.g., zirconium oxide) epoxy resin, or metal welding, or mechanical connection such as staples. In some embodiments, during the binder burnout process, the green tape is suspended so that the green tape does not contact the surface (e.g., positioner). In some embodiments, during the sintering process, the green tape is suspended so that the green tape does not contact the surface (e.g., positioner). This suspension can be achieved in various ways, such as tension, air bearings or other devices can be used to suspend the green tape. In some embodiments, for example, before or after sintering, the surface of the roller that the green tape contacts may be coated with nickel or an inert coating containing nickel. During sintering, in some embodiments, the sintered tape is moved through a narrow gap formed by a nickel-plated metal plate. In some embodiments, the metal plate is a stainless steel metal plate. In some embodiments, the thickness of the gap is less than 5 mm, and the thickness refers to the maximum distance between the nickel-plated metal plates (perpendicular to the surface of one of the metal plates). In some embodiments, the gap is less than 4.5 mm. In some embodiments, the gap is less than 4 mm. In some embodiments, the gap is less than 3.5 mm. In some embodiments, the gap is less than 3 mm. In some embodiments, the gap is less than 2.5 mm. In some embodiments, the gap is less than 2 mm. In some embodiments, the gap is less than 1.5 mm. In some embodiments, the gap is less than 1 mm. In some embodiments, the gap is less than 0.5 mm. In some embodiments, the gap is less than 500 μm. In some embodiments, the gap is less than 400 μm. In some embodiments, the gap is less than 300 μm. In some embodiments, the gap is less than 200 μm. In some embodiments, the gap is less than 100 μm. In some embodiments, the narrow gap helps prevent the loss of lithium in the sintered article during the sintering process.

[0327] In some embodiments, the flatness of the green tape will be controlled by applying tension to the green tape. In some embodiments, the flatness of the green tape will be controlled by precise tape cutting, which imparts minimal stress to the edges of the sintered article. In some embodiments, the flatness of the green tape is controlled by laser cutting the edges on the article before or after sintering. In some embodiments, the flatness of the green tape will be controlled by adjusting the lateral heating profile, for example, heating the center of the film first. In some embodiments, the flatness is controlled by precise alignment of the tensioning roller and other rollers in the processing device.

[0328] In some embodiments, the sintered microstructure (high density, small particles) of the sintered product is controlled by fast sintering. In some embodiments, the sintered microstructure (high density, small particles) of the sintered product is controlled by temperature ramp control, belt speed, multiple heating zones or a combination thereof.

[0329] In some embodiments, the atmosphere is controlled in the method. This may include, for example, controlling the amount of O2 in the sintering furnace to be less than 100ppm or even lower. In some embodiments, atmosphere control includes using N2, Ar or other inert gases to form a gas curtain around the furnace (e.g., around the entrance and exit of the furnace). In some embodiments, atmosphere control includes using excess flow around the entrance and exit of the furnace. In some embodiments, atmosphere control includes using narrow openings around the entrance and exit of the furnace. In some embodiments, atmosphere control includes using gas injection near the center of the furnace. This gas injection can result in laminar flow from the center of the furnace to both ends. In some embodiments, atmosphere control includes using passive or active overpressure in the furnace using high airflow and low opening size around the entrance and exit of the furnace.

[0330] In some embodiments, the atmosphere control includes using a capsule to provide a closed environment around or near the furnace in which the atmosphere can be controlled. For example, a capsule filled with nitrogen with a portion of the area exposed to a reducing environment. The reducing environment can be achieved by providing a partial pressure of H2 or CO.

[0331] In some embodiments, the green tape is sintered quickly. The time that any given portion of the film is processed at a temperature higher than room temperature can be between 15 seconds and 20 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 10 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 5 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 2 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 90 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 75 minutes. In other embodiments, the time that any given portion of the film is processed at a temperature higher than room temperature can be between 1 minute and 60 minutes.

[0332] In order to avoid surface contamination of the sintered article or the article to be sintered as it moves through the processing device, the film can be cooled to less than 40°C. In some embodiments, the sintered film is maintained in an atmosphere with a low H2O content. For example, the H2O content is less than 10ppm. In some embodiments, the sintered film is maintained in an atmosphere that is mainly argon. In some embodiments, the sintered film is maintained in an atmosphere that is mainly nitrogen. In some embodiments, the sintered film is maintained in clean dry air (CDA).

[0333] Because the mechanical properties of the green body double layer shrink when processed in the processing device, different belt speeds (e.g., different roller rotation speeds) can be used in the green body belt stage compared to the binder burnout stage or the sintering stage. Different belt speeds can be set for each part of the production line. In some embodiments, these different speeds can be achieved by independent tension control (e.g., dancers after the green body furnace, tension control after sintering).

[0334] Due to the lateral shrinkage during sintering, the bilayer will shrink laterally during sintering and the length of the sintered zone (along the ribbon direction) can be greater than the lateral shrinkage distance. This will make the angle of the ribbon edge smaller.

[0335] The green tape strength may change as it is processed in the processing unit. To accommodate this, the tape tension may vary throughout the processing unit. For example, in the binder burnout furnace, the tape is at one tension setting; in the biscuit furnace, the tape may be at another tension setting; in the sintering furnace, the tape is at yet another tension. The tension of the double layer is higher in the winding and unwinding sections than in the binder burnout furnace or the biscuit furnace or the sintering furnace.

[0336] In some embodiments, the green tape is peeled off the polyester film substrate before moving through a continuous production line. This can be achieved using a sharp knife edge (e.g., 180° angle at the knife edge), tension control, and other devices.

[0337] In some embodiments, the method comprises: (a) loading a film roll to be sintered onto a front roller, (b) unwinding the film to be sintered, (c) sintering the film to be sintered to form a sintered film, (d) winding the sintered film onto a rear roller, wherein the operations are performed in a controlled atmosphere. Rollers can be used to hold the green film or sintered film in a desired position.

[0338] In some embodiments, the green tape moves through the processing device at a rate of about 2 inches to 25 inches per minute. In some embodiments, the green tape moves through the processing device at a rate of about 3 inches to 6 inches per minute. In some embodiments, the green tape moves through the processing device at a rate of about 1 inch to 5 inches per minute. In some embodiments, the green tape moves through the processing device at a rate of about 5 inches to 10 inches per minute.

[0339] In some embodiments, the belt moves through the processing device at a rate of about 2-25 inches per minute. In some embodiments, the belt moves through the processing device at a rate of about 3-6 inches per minute.

[0340] In some embodiments, including any of the preceding embodiments, the rate at which the strip moves through the processing device refers to the distance and time it takes to move through the sintering furnace.

[0341] FIG. 12 shows an embodiment of a processing device in a vertical processing position. The double layer 1101 is unfolded into a double layer 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. The heating zone 1107 may also be a cooling zone. Rollers 1103 and 1105 help guide the double layer and maintain appropriate tension on the double layer. The final product is embodied as a sintered roll 1108; if sintering does not occur in the heating zones, it may also be embodied as a green roll 1108. When moving through area 1102, the double layer 1109 moves vertically upward and away from the ground. When moving through area 1106, the double layer 1109 moves downward toward the ground. When moving through area 1104, the double layer 1109 moves parallel to the ground.

[0342] E. Products made by the method disclosed in this application

[0343] In some embodiments, the present application describes a greenware article prepared by the method of the present application.

[0344] In some embodiments, the present application describes a sintered article prepared by the method of the present application.

[0345] In some embodiments, the present application describes a green bi-layer comprising lithium-filled garnet, wherein the green bi-layer is wound on a roll, the bi-layer having a thickness of less than 100 μm.

[0346] In some embodiments, including any of the preceding embodiments, the bilayer includes a lithium-stuffed garnet layer and a metal foil layer, wherein the lithium-stuffed garnet layer is 10 μm to 30 μm thick and the metal foil layer is 2 μm to 10 μm thick.

[0347] In some embodiments, including any of the foregoing embodiments, the particle size D of the ceramic sintered layer in the double layer is 90 <5μm, or <4μm, or <3μm, or <2μm, or <1μm. The volume % porosity of the ceramic sintered layer is <10 volume %, or <8 volume %, or <6 volume %, or <5 volume %, or <4 volume %, or <3 volume %, or <2 volume %, or <1 volume %, or <0.5. The interface porosity (the porosity within 5μm closest to the double layer interface) is <2 volume %, or <1.5 volume %, or <1 volume %, or <0.5 volume %. These parameters can be controlled by the sintering atmosphere for preparing the sintered double layer. These characteristics can be obtained by controlling the gas atmosphere, the heating rate, and the sintering residence time. The slurry may include d 50 Ceramic particles with a particle size of less than 1 μm, less than 0.5 μm, less than 0.25 μm or less than 0.1 μm.

[0348] In some embodiments, the present application describes a sintered bilayer comprising lithium-filled garnet, the bilayer being wound on a roll, the bilayer having a thickness of less than 100 μm.

[0349] In some embodiments, including any of the foregoing embodiments, the bilayer includes a lithium-filled garnet layer and a metal foil layer, the lithium-filled garnet layer having a thickness of 10-30 μm, and the metal foil layer having a thickness of 2-10 μm.

[0350] In some embodiments, including any of the preceding embodiments, the metal foil layer includes nickel, iron, or a combination thereof.

[0351] In some embodiments, the present application describes a sintered bilayer prepared by the method of the present application.

[0352] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a lithium-filled garnet.

[0353] In some embodiments, including any of the foregoing embodiments, the bilayer includes a lithium-stuffed garnet layer and a metal foil layer, wherein the lithium-stuffed garnet layer has a thickness of 10-30 μm and the metal foil layer has a thickness of 2-10 μm.

[0354] In some embodiments, including any of the preceding embodiments, the metal foil layer includes nickel, iron, or a combination thereof.

[0355] In some embodiments, including any of the preceding embodiments, the green layer comprises an unsintered lithium-filled garnet.

[0356] In some embodiments, including any of the preceding embodiments, the green layer comprises a chemical precursor of a lithium-stuffed garnet.

[0357] In some embodiments, including any of the foregoing embodiments, the metal layer in the bilayer comprises a metal selected from nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.

[0358] In some embodiments, including any of the foregoing embodiments, the metal layer in the bilayer is an alloy of Fe and Ni.

[0359] In some embodiments, including any of the foregoing embodiments, the metal layer in the bilayer is an alloy of Fe and Ni, with Fe in an amount of 1% to 25% (w / w) and the remainder being Ni.

[0360] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer in the double layer is 1 μm to 20 μm.

[0361] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer in the double layer is 1 μm to 10 μm.

[0362] In some embodiments, including any of the preceding embodiments, the processing device includes a green tape that is wound around the at least one front roller.

[0363] In some embodiments, sintering is performed without contacting other surfaces, such as surfaces of processing equipment, with the portion of the LLZO film to be sintered during sintering. Lack of contact with the film to be sintered can produce unexpectedly favorable properties, such as low flatness, retention of stoichiometric amounts of lithium in a given LLZO formula, and favorable microstructures (e.g., high density, small particle size, and combinations thereof). Lack of contact with the top surface of the film can produce fewer surface defects, such as scratches or tears.

[0364] In some embodiments, including any of the foregoing embodiments, the sintered article comprises a double layer. In an embodiment, the double layer comprises a metal foil and a ceramic film. In some embodiments, the sintered article comprises three layers, two of which are ceramic layers, with a metal layer sandwiched in between. In some embodiments, the metal is Ni. In some embodiments, the Ni is 1 μm thick. In some embodiments, the Ni is 2 μm thick. In some embodiments, the Ni is 3 μm thick. In some embodiments, the Ni is 4 μm thick. In some embodiments, the Ni is 5 μm thick. In some embodiments, the Ni is 6 μm thick. In some embodiments, the Ni is 7 μm thick. In some embodiments, the Ni is 8 μm thick. In some embodiments, the Ni is 9 μm thick. In some embodiments, the Ni is 10 μm thick. In some embodiments, the Ni is 11 μm thick. In some embodiments, the Ni is 12 μm thick. In some embodiments, the Ni is 13 μm thick. In some embodiments, the Ni is 14 μm thick. In some embodiments, the Ni is 15 μm thick. In some embodiments, the Ni is 16 μm thick. In some embodiments, the Ni is 17 μm thick. In some embodiments, the Ni is 18 μm thick. In some embodiments, the Ni is 19 μm thick. In some embodiments, the Ni is 20 μm thick.

[0365] In some embodiments, the slurry is deposited onto a foil to form a green tape with a foil backing. In some embodiments, the foil is a polyester film foil. The green tape with a foil backing can be rolled into a roll to form an unsintered film roll with a foil backing. The unsintered film roll with a foil backing can be loaded onto a processing device described herein. In some embodiments, the method of using the processing device includes: (a) loading the unsintered film roll with a foil backing onto a front roller, (b) unwinding the unsintered film, (c) sintering the unsintered film to form a sintered film with a foil backing, (d) winding the sintered film with a foil backing onto a rear roller, and the operation is performed in a controlled atmosphere. In some embodiments, the foil backing can include nickel metal or nickel foil.

[0366] In some embodiments, the green film sintered using the processing apparatus is a bi-layer or a tri-layer.

[0367] In some embodiments, various layer architectures can be envisioned and sintered according to the sintering methods described in this application: A) a free-standing lithium-filled garnet material; B) a free-standing lithium-filled garnet material, which optionally contains active materials, binders, solvents and / or carbon; C) a bi-layer having a layer of lithium-filled garnet and a layer of metal powder, foil or sheet; D) a bi-layer having a layer of lithium-filled garnet and another layer containing metal powder, foil or sheet; E) a bi-layer having a layer of lithium-filled garnet, optionally containing active materials, binders, solvents and / or carbon; The invention relates to a method for preparing an active material of the present invention and comprising: ...

[0368] In some cases, a double layer can be sintered using the processing apparatus described herein. In some cases, a triple layer can be sintered using the processing apparatus described herein.

[0369] The three layers may include a lithium-filled garnet layer, a metal layer, and another lithium-filled garnet layer on the opposite side of the metal layer. A bilayer membrane passes through the processing device with one lithium-filled garnet layer facing up and the other lithium-filled garnet layer facing down.

[0370] The double layer may include a lithium-filled garnet layer and a metal foil layer. In some embodiments, the metal layer includes Ni, Fe, Cu, Al, Sn, In, Ag, Au, steel, alloys, or combinations thereof. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 90% Ni and 10% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 91% Ni and 9% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 92% Ni and 8% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 93% Ni and 7% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 94% Ni and 6% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 95% Ni and 5% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 96% Ni and 4% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 97% Ni and 3% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 98% Ni and 2% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 99% Ni and 1% Fe. In some embodiments, the metal layer is a metal sheet. In some embodiments, the metal layer is an aluminum sheet. In some embodiments, the metal layer is a nickel sheet. In some embodiments, the metal layer may be ductile. 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.

[0371] In some embodiments, the lithium-filled garnet-metal sintered film of the present application has a thickness of 1 μm to 100 μm. In certain embodiments, these films are co-sintered with mixed amounts of lithium-filled garnet and metal. The metal may be selected from Ni, Mg, Li, Fe, Al, Cu, Au, Ag, Pd, Pt, Ti, steel, alloys thereof, and combinations thereof. The lithium-filled garnet and the metal are mixed as powders and then sintered together to form a film. In some embodiments, the film includes a uniform mixture of lithium-filled garnet and metal. The relative amounts of lithium-filled garnet and metal may vary by volume from 1% lithium-filled garnet to 99% lithium-filled garnet, with the remainder being metal.

[0372] In some embodiments, including any of the preceding embodiments, the lithium filled garnet is sintered onto a ceramic-metal film.

[0373] The processing device system and method described in the present application can be used to manufacture various materials. These materials include but are not limited to lithium-filled garnet films. These materials include but are not limited to a double layer formed by a lithium-filled garnet film on a metal layer, or a triple layer formed by two lithium-filled garnet films and a metal layer therebetween. The processing device system and method described in the present application can be used to manufacture lithium-filled garnet films or composite materials, including but not limited to sintered films or film-containing materials described in any of the following documents: PCT / US2016 / 043428, filed on July 21, 2016, published as WO2017015511A1, entitled PROCESS AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS; PCT / US2019 / 056584, filed on October 16, 2019, published as WO2020081718A1, entitled SINTERING LARGEAREA CERAMIC FILMS; PCT / US2016 / 15209, filed on January 27, 2016, published as WO2017131676A1, entitled ANNEALED GARNET ELECTROLYTE SEPARATRS; PCT / US2017 / 039069, filed on January 23, 2017, published as WO2018236394A1, entitled LITHIUM-STUFFED GARNETELECTROLYTES WITH SECONDARY PHASE INCLUSIONS; PCT / US2019 / 54117, filed on October 1, 2019, published as WO2020072524A1, entitled METHODS OF MAKING AND USING AN ELECTROCHEMICAL CELL COMPRISING AN INTERLAYERS; and U.S. Patents 10,403,931; 10,290,895; 9,966,630B2; 10,347,937B2; 10,103,405. The entire contents of each are hereby incorporated by reference for all purposes.

[0374] In some embodiments, including any of the foregoing embodiments, the ceramic-metal film can be an oxide-metal film. In some embodiments, the film has a ceramic layer and a metal layer. In other embodiments, the film is a uniform mixture of ceramic and metal. In some embodiments, the ceramic-metal film contains ceramic and metal. In some embodiments, the volume percentage of ceramic is 10%, and the volume percentage of metal is 90%. In some embodiments, the volume percentage of ceramic is 20%, and the volume percentage of metal is 80%. In some embodiments, the volume percentage of ceramic is 30%, and the volume percentage of metal is 70%. In some embodiments, the volume percentage of ceramic is 40%, and the volume percentage of metal is 60%. In some embodiments, the volume percentage of ceramic is 50%, and the volume percentage of metal is 50%. In some embodiments, the volume percentage of ceramic is 60%, and the volume percentage of metal is 40%. In some embodiments, the volume percentage of ceramic is 70%, and the volume percentage of metal is 30%. In some embodiments, the volume percentage of ceramic is 80%, and the volume percentage of metal is 20%. In some embodiments, the volume percentage of ceramic is 90%, and the volume percentage of metal is 10%. In some embodiments, the volume percentage of ceramic is 5% and the volume percentage of metal is 95%. In some embodiments, the volume percentage of ceramic is 15% and the volume percentage of metal is 85%. In some embodiments, the volume percentage of ceramic is 25% and the volume percentage of metal is 75%. In some embodiments, the volume percentage of ceramic is 35% and the volume percentage of metal is 65%. In some embodiments, the volume percentage of ceramic is 45% and the volume percentage of metal is 55%. In some embodiments, the volume percentage of ceramic is 55% and the volume percentage of metal is 45%. In some embodiments, the volume percentage of ceramic is 65% and the volume percentage of metal is 35%. In some embodiments, the volume percentage of ceramic is 75% and the volume percentage of metal is 25%. In some embodiments, the volume percentage of ceramic is 85% and the volume percentage of metal is 15%. In some embodiments, the volume percentage of ceramic is 95% and the volume percentage of metal is 5%.

[0375] In some embodiments, including any of the foregoing embodiments, 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 the oxide is 5% and the volume percentage of the metal is 95%. In some embodiments, the volume percentage of the oxide is 15% and the volume percentage of the 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 35%. 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%.

[0376] In some embodiments, including any of the foregoing embodiments, the ceramic-metal film may be an oxide-metal film. In some embodiments, the ceramic-metal film contains ceramic and metal. In some embodiments, the weight percentage of the ceramic is 10% and the weight percentage of the metal is 90%. In some embodiments, the weight percentage of the ceramic is 20% and the weight percentage of the metal is 80%. In some embodiments, the weight percentage of the ceramic is 30% and the weight percentage of the metal is 70%. In some embodiments, the weight percentage of the ceramic is 40% and the weight percentage of the metal is 60%. In some embodiments, the weight percentage of the ceramic is 50% and the weight percentage of the metal is 50%. In some embodiments, the weight percentage of the ceramic is 60% and the weight percentage of the metal is 40%. In some embodiments, the weight percentage of the ceramic is 70% and the weight percentage of the metal is 30%. In some embodiments, the weight percentage of the ceramic is 80% and the weight percentage of the metal is 20%. In some embodiments, the weight percentage of the ceramic is 90% and the weight percentage of the metal is 10%. In some embodiments, the weight percentage of the ceramic is 5% and the weight percentage of the metal is 95%. In some embodiments, the weight percentage of ceramic is 15% and the weight percentage of metal is 85%. In some embodiments, the weight percentage of ceramic is 25% and the weight percentage of metal is 75%. In some embodiments, the weight percentage of ceramic is 35% and the weight percentage of metal is 65%. In some embodiments, the weight percentage of ceramic is 45% and the weight percentage of metal is 55%. In some embodiments, the weight percentage of ceramic is 55% and the weight percentage of metal is 45%. In some embodiments, the weight percentage of ceramic is 65% and the weight percentage of metal is 35%. In some embodiments, the weight percentage of ceramic is 75% and the weight percentage of metal is 25%. In some embodiments, the weight percentage of ceramic is 85% and the weight percentage of metal is 15%. In some embodiments, the weight percentage of ceramic is 95% and the weight percentage of metal is 5%.

[0377] In some embodiments, including any of the foregoing embodiments, the ceramic in the ceramic-metal film is 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, zirconium oxide, Li2ZrO3, xLi2O-(1-x)SiO2 (where x = 0.01-0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, LiAlO2, Li2O, Li3PO4 or a combination thereof.

[0378] In an embodiment, the three layers include a metal foil and a green ceramic film on both sides of the metal foil. The thickness of the metal foil in the double or triple layer may be between 0.5 μm and 50 μm. The metal foil in the double or triple layer has a thickness of 3 μm to 30 μm. In some embodiments, the metal foil in the double or triple layer has a thickness of 5-20 μm. In other embodiments, the metal foil in the double or triple layer has a thickness of 5 μm to 15 μm.

[0379] In some embodiments, including any of the foregoing embodiments, the sintered article contains LLZO.

[0380] In some embodiments, the d of the sintered ceramic membrane is 50 The particle size is less than 5 μm. In some embodiments, the d 50 The particle size is less than 4 μm. In some embodiments, the d 50 The particle size is less than 3 μm. In some embodiments, the d 50 The particle size is less than 2 μm. In some embodiments, the d 50 The particle size is less than 1 μm. In some embodiments, the d 50 The particle size is less than 0.9 μm. In some embodiments, the d 50 The particle size is less than 0.8 μm. In some embodiments, the d 50 The particle size is less than 0.7 μm. In some embodiments, the d 50 The particle size is less than 0.6 μm. In some embodiments, the d 50 The particle size is less than 0.5 μm. In some embodiments, the d 50 The particle size is less than 0.4 μm. In some embodiments, the d 50 The particle size is less than 0.3 μm. In some embodiments, the d 50 The particle size is less than 0.2 μm. In some embodiments, the d 50 The particle size is less than 0.1 μm. In some embodiments, the D 90 The particle size is less than 5 μm. In some embodiments, the D 90 The particle size is less than 4 μm. In some embodiments, the D 90 The particle size is less than 3 μm. In some embodiments, the D 90 The particle size is less than 2 μm. In some embodiments, the D 90 The particle size is less than 1 μm. In some embodiments, the D 90The particle size is less than 0.9 μm. In some embodiments, the D 90 The particle size is less than 0.8 μm. In some embodiments, the D 90 The particle size is less than 0.7 μm. In some embodiments, the D 90 The particle size is less than 0.6 μm. In some embodiments, the D 90 The particle size is less than 0.5 μm. In some embodiments, the D 90 The particle size is less than 0.4 μm. In some embodiments, the D 90 The particle size is less than 0.3 μm. In some embodiments, the D 90 The particle size is less than 0.2 μm. In some embodiments, the D 90 The particle size is less than 0.1 μm. In some embodiments, the porosity of the sintered ceramic membrane is less than 5 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 4 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 3 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 2 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 1 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 0.5 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 0.4 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 0.3 volume%. In some embodiments, the porosity of the sintered ceramic membrane is less than 0.2 volume%. In some embodiments, the density of the sintered ceramic membrane is greater than 95 volume%. In some embodiments, the density of the sintered ceramic membrane is greater than 96 volume%. In some embodiments, the density of the sintered ceramic membrane is greater than 97 volume%. In some embodiments, the density of the sintered ceramic membrane is greater than 98% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99.5% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99.6% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99.7% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99.8% by volume. In some embodiments, the density of the sintered ceramic membrane is greater than 99.9% by volume.

[0381] In some embodiments, the sintered film roll may further include additional backing material sandwiched between the roll layers.

[0382] In some embodiments, including any of the foregoing embodiments, the d 50 The particle size is less than 5 microns (μm).

[0383] In some embodiments, including any of the foregoing embodiments, the D of the sintered ceramic membrane 90 The particle size is less than 5μm.

[0384] In some embodiments, including any of the foregoing embodiments, the sintered ceramic membrane has a porosity of less than 5% by volume.

[0385] In some embodiments, including any of the foregoing embodiments, the surface defect density of the sintered film is less than 100 protrusions / cm2, wherein the aspect ratio (height / diameter) is greater than 1, and the height is greater than 1000 μm relative to the surrounding 2 The median height of the area is greater than 2 microns.

[0386] In some embodiments, including any of the foregoing embodiments, the surface defect density of the sintered film is less than 100 valleys / square centimeter, wherein the aspect ratio (height / diameter) is greater than 1, and the height is greater than 1000 μm relative to the surrounding 2 The median height of the area is greater than 2 microns.

[0387] In some embodiments, including any of the foregoing embodiments, the sintered film has a surface defect density of less than 100 protrusions / cm2 at the interface of the lithium-filled garnet film and the metal layer, wherein the aspect ratio (height / diameter) is greater than 1.

[0388] In some embodiments, including any of the foregoing embodiments, the sintered film has a surface defect density of less than 100 valleys / cm2 at the interface between the lithium-filled garnet film and the metal layer, wherein the aspect ratio (height / diameter) is greater than 1.

[0389] In some embodiments, including any of the foregoing embodiments, d 50 The particle size is at least 10 nm.

[0390] In some embodiments, including any of the foregoing embodiments, d 50 The particle size is at least 50 nm.

[0391] In some embodiments, including any of the foregoing embodiments, d 50 The particle size is at least 0.5 μm.

[0392] F. Lithium-filled garnet sintered on metal foil

[0393] The processing apparatus disclosed in the present application can be used to sinter lithium-filled garnet on a metal foil. In some embodiments, the metal foil is a dense metal layer. In certain embodiments, the metal foil is a dense metal layer including a ceramic. In some such embodiments, the ceramic is a lithium-filled garnet.

[0394] In some embodiments, the metal foil or metal layer is nickel, steel, stainless steel, copper, aluminum, Kovar alloy, Invar alloy, ceramic, Haynes216 or a combination thereof. In some embodiments, the metal foil is produced at least in part by roll annealing. In some embodiments, the metal foil is produced at least in part by an electrodeposition process. In certain embodiments, LLZO is sintered on the 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, in some of these embodiments, the metal foil comprises 5-20% Fe and 80-95% Ni. In some of these embodiments, the metal foil comprises 10-20% Fe and 80-90% Ni.

[0395] In certain embodiments, LLZO is sintered on a metal foil. In some of these embodiments, the metal foil is pure Cu. In some of these embodiments, the metal foil comprises 5-20% Cu and 80-95% Ni. In some of these embodiments, the metal foil comprises 10-20% Cu and 80-90% Ni. In some of these embodiments, the metal foil is a combination of Cu and Fe.

[0396] In some embodiments, unlike the deposition on polyester film foil described above, the green tape is deposited on the metal layer. The metal can be nickel, steel, stainless steel, copper, aluminum, Kovar alloy, Invar, ceramic, Haynes216 or a combination thereof. In this example, the green tape does not need to be peeled off from the polyester film and can be sintered directly on the metal. Before the green tape moves through the processing device, the green tape and the metal can be rolled together. In some embodiments, a backing layer is applied to the metal, and the backing layer can be rolled together with the green tape on the metal. In some embodiments, an interlayer is used when the metal is rolled up with the green tape on it. The interlayer provides a pad between the rolled layers.

[0397] In some embodiments, the processing apparatus is used to sinter lithium-filled garnets without an underlying substrate.

[0398] In some embodiments, the processing device is used to sinter a green lithium-filled garnet layer adjacent to a green oxide / metal hybrid layer. The green oxide / metal hybrid layer may include 0.0001-25 wt % Ni powder, 1-25 wt % Fe powder, or a combination thereof. In some cases, the green oxide / metal hybrid layer includes 1-20 wt % Ni and 1-10 wt % Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal hybrid layer includes 5-15 wt % Ni and 1-5 wt % Fe, with the remainder being lithium-filled garnet. In some cases, the green oxide / metal hybrid layer includes 10-15 wt % Ni and 3-5 wt % Fe, with the remainder being lithium-filled garnet.

[0399] Other configurations are also contemplated herein, for example a bare film configuration may be as follows: sintered LLZO film, without other metal-containing layers.

[0400] For example, the co-fired structure can include a bilayer formed of a LLZO green layer and a metal-ceramic green layer. The metal-ceramic layer is metal and ceramic powder in a green state.

[0401] For example, the construction on the foil can be as follows. This involves casting a LLZO green body on a metal layer / foil. The metal layer is a dense layer, not a powder. In this case, there is no ceramic in the foil, which can be purchased and is usually made by a process other than sintering (such as electrodeposition or roll annealing). The metal layer can additionally include <10% by volume of ceramic.

[0402] G. Dual-layer and additional embodiments

[0403] In some embodiments, including any of the foregoing embodiments, the width of the double layer to be processed is about 700 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be processed is about 600 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be processed is about 500 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be processed is about 400 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be processed is about 300 mm.

[0404] In some embodiments, including any of the foregoing embodiments, the width of the bilayer to be treated is about 250 mm.

[0405] In some embodiments, including any of the preceding embodiments, the width of the bilayer to be treated is about 200 mm.

[0406] In some embodiments, including any of the preceding embodiments, the width of the bilayer to be treated is about 150 mm.

[0407] In some embodiments, including any of the foregoing embodiments, the width of the double layer to be treated is about 100 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be treated is about 90 mm. In some embodiments, including any of the foregoing embodiments, the width of the double layer to be treated is about 80 mm.

[0408] In some embodiments, including any of the preceding embodiments, the width of the bilayer to be treated is about 50 mm.

[0409] In some embodiments, including any of the foregoing embodiments, the metal foil in the dual-layer tape is a nickel alloy, consists essentially of Ni, or consists essentially of pure Ni, or consists only of pure Ni.

[0410] In some embodiments, including any of the foregoing embodiments, the average thickness of the metal foil is in the range of 4.5 μm to 10.5 μm. In some instances, the average thickness is 4, 5, 6, 7, 8, 9, 10, or 11 μm. In some instances, the average thickness is 4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, or 11.5 μm. Unless otherwise stated, thickness is measured by scanning electron microscopy (SEM).

[0411] In some embodiments, including any of the preceding embodiments, the thickness of the foil varies by up to ±1.25 μm in both the width and length directions.

[0412] In some embodiments, including any of the foregoing embodiments, the ceramic layer covers most of the width of the metal foil, but there are areas without any ceramic layer at the two edges of the foil; the width of these areas does not exceed 15mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 3mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 4mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 5mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 6mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 7mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 8mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 9mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 10mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 11mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 12 mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 13 mm. In some embodiments, including any of the foregoing embodiments, the metal foil has one or two uncovered edges of about 14 mm.

[0413] In some embodiments, including any of the foregoing embodiments, the sintered dense ceramic layer has an average thickness of 18 μm to 42 μm in a central region of the ceramic layer, with the thickness varying locally by up to ±1.5 μm across the width and length of the coil.

[0414] In some embodiments, including any of the foregoing embodiments, the thickness of the ceramic layer before processing is greater, up to 2.25 times the sintered thickness. Thus, before sintering, the average thickness of the ceramic layer in the central region is up to 95 μm, and it can vary by ±3.4 μm in width and length.

[0415] In some embodiments, including any of the preceding embodiments, the input bi-layer is in the form of a coil wound on a core having a diameter of 3 inches to 6 inches.

[0416] In some embodiments, including any of the foregoing embodiments, at the end of the process, the sintered ribbon is again wound onto a roll having a minimum core diameter of 6-12 inches.

[0417] In some embodiments, including any of the foregoing embodiments, if BBO and sintering are performed in separate tools, the ribbon is wound into a coil (core minimum diameter 6-12 inches) after BBO processing so that it can be delivered to the sintering tool in coil form.

[0418] In some embodiments, including any of the preceding embodiments, the maximum output roll diameter is 360 mm to 450 mm (if a 12 inch core is used), and the maximum roll weight is 40 kg to 140 kg.

[0419] H. Gases and atmosphere

[0420] I. Configuration

[0421] In some examples, each heating zone is provided with its own individually controllable gas outlet and exhaust, thereby allowing different gases to flow in each zone, different total flow rates, and different exhausts. In these examples, the airflow within each zone should be perpendicular to the web moving (i.e., machine) direction. This means that flow perpendicular to the web or across the web would be acceptable, but flow in the machine direction would not be acceptable.

[0422] II. Available Gases

[0423] The system and apparatus of the present application allow the following gases or mixtures thereof to flow: nitrogen (N2), synthetic gas (N2+H2, wherein H2<5%), wet nitrogen, and wet synthetic gas.

[0424] III. Atmosphere requirements

[0425] In some embodiments, the O2 level should be maintained below 10 ppm-50 ppm throughout the equipment (e.g., furnace), measured by sampling the gas from each zone individually using an O2 analyzer, while flowing only N2 gas in all zones.

[0426] In some embodiments, the H2O level requirements are different for different parts of the temperature profile. When the tool is in its typical gas flow configuration (which may include flowing forming gas and wet nitrogen and wet forming gas), the gas is sampled from each zone individually using a dew point analyzer to measure the H2O level.

[0427] IV. Gas Flow

[0428] In some embodiments, during the BBO stage, the maximum renewal rate is 1-3 exchanges per minute. 1 exchange per minute means that the gas flow rate by volume per minute is equal to the internal volume accessible to the gas. 2 exchanges per minute means that the gas flow rate by volume per minute (at STP) is twice the internal volume accessible to the gas. In some embodiments, the maximum renewal rate during the sintering stage is 0.3-3 exchanges per minute.

[0429] V. Effluent Treatment

[0430] Organic vapors generated by adhesive removal tend to condense and leave residue on cooler surfaces. Any condensation on the inner surfaces of the tool can be avoided by heating the inner surfaces of the output adhesive exhaust; heating continues without cold spots until it reaches the building exhaust system or a cooled trap.

[0431] VI. Atmosphere Control

[0432] The processing apparatus as a complete system or its various components (eg, an oven) may be placed in an atmosphere-controlled enclosure.

[0433] Various gas curtains may be used with processing equipment, either as a complete system, or with various components of processing equipment (eg, a furnace) to provide atmosphere control.

[0434] In some embodiments, atmosphere control includes using a narrow oven opening.

[0435] In some embodiments, atmosphere control includes using excess gas flow at the furnace inlet and outlet. In some embodiments, atmosphere control includes using a glove box filled with N2 or Ar around various components such as rollers. In some embodiments, atmosphere control includes using overpressure in the furnace. In some embodiments, the pressure in the furnace is at least 0.1 inches of water column greater than ambient pressure. In some embodiments, the pressure in the furnace is at least 0.3 inches of water column greater than ambient pressure. In some embodiments, the pressure in the furnace is at least 0.5 inches of water column greater than ambient pressure. In some embodiments, the pressure in the furnace is at least 0.7 inches of water column greater than ambient pressure. In some embodiments, the pressure in the furnace is at least 0.9 inches of water column greater than ambient pressure. In some embodiments, the pressure in the furnace is at least 1 inch of water column greater than ambient pressure.

[0436] In some embodiments, atmosphere control comprises controlling the amount of H2O in the oven. In some embodiments, atmosphere control comprises controlling the amount of O2 in the oven. In some embodiments, atmosphere control comprises controlling the amount of O2 in the oven to a level of less than 100 ppm. In some embodiments, atmosphere control comprises controlling the amount of O2 in the oven to a level of less than 10 ppm. In some embodiments, atmosphere control comprises controlling the amount of O2 in the oven to a level of less than 1 ppm. In some embodiments, atmosphere control comprises controlling the amount of H2 in the oven. In some embodiments, atmosphere control comprises controlling the amount of N2 in the oven.

[0437] In some embodiments, the gas curtain is a N2 curtain.

[0438] In some embodiments, a bellows (tunnel configuration) is used with the exhaust.

[0439] In some embodiments, a wind box with a feedback loop is used to form a gas supply tube. In some embodiments, an O2 sensor in the oven is also included.

[0440] In some embodiments, the method uses atmosphere control. This may include, for example, controlling the amount of O2 in the sintering furnace to less than 100ppm or even lower. In some embodiments, atmosphere control includes using N2, Ar or other inert gases to form a gas curtain around the furnace (e.g., around the entrance and exit of the furnace). In some embodiments, atmosphere control includes using excess flow around the entrance and exit of the furnace. In some embodiments, atmosphere control includes using narrow openings around the entrance and exit of the furnace. In some embodiments, atmosphere control includes injecting gas near the center of the furnace. This gas injection can result in laminar flow from the center of the furnace to both ends. In some embodiments, atmosphere control includes using high airflow and low opening size around the entrance and exit of the furnace, thereby generating passive or active overpressure in the furnace.

[0441] In some embodiments, the atmosphere control includes using a capsule to provide an atmosphere controlled closed environment around or near the furnace. For example, a capsule filled with nitrogen, wherein a portion of the area is exposed to a reducing environment. The reducing environment can be achieved by providing a partial pressure of H2 or CO.

[0442] In some embodiments, a portion of the production line is enclosed in a container or chamber that is atmosphere controlled. For example, the production line can be completely enclosed in a clean room. The inlet and / or outlet of the processing device can be enclosed in a clean room. In some such embodiments, a particle-free gas is introduced into a closed container or chamber (e.g., a clean clean room). CDA refers to clean dry air, which is air or gas that has been filtered to remove particles based on the size of the particles. The gas may include N2, Ar, synthetic gas (Ar / H2; or N2 / H2) or a combination thereof.

[0443] The pressure was measured with a manometer and the gas flow was controlled by a mass flow controller.

[0444] In some embodiments, the present application describes a processing device, including:

[0445] front roller;

[0446] at least one furnace comprising at least three heating zones; and

[0447] A runway, wherein the runway surface contains a material selected from the following: nickel (Ni), iron (Fe), Ni alloy, Fe alloy, Ni-Fe alloy, stainless steel, pyrolytic carbon, carbon fiber composite (CFC), graphite, aluminum oxide (Al2O3), zirconium oxide (ZrO2), boron nitride, silicon carbide, magnesium oxide or a combination thereof.

[0448] In some embodiments, the present application describes a processing device comprising: a front roller; at least one furnace, the at least one furnace comprising at least three heating zones; and at least one of the following:

[0449] Baffles within the heating zone;

[0450] a baffle between two heating zones;

[0451] A curtain purge device between two heating zones;

[0452] means for controlling at least two different pressure zones in the at least three heating zones;

[0453] means for exhausting at least one furnace;

[0454] means for purging the gas between the two heating zones;

[0455] means for isolating the gas between two heating zones;

[0456] Means for mechanically isolating two heating zones; or

[0457] and combinations thereof.

[0458] In some embodiments, the present application describes a processing device, including:

[0459] front roller;

[0460] at least one furnace comprising at least three heating zones; and

[0461] The bilayers are held under tension, wherein the tension is between 0.1 g / cm and 500 g / cm of web width.

[0462] In some embodiments, the present application describes a processing device, including:

[0463] front roller;

[0464] at least one furnace, the at least one furnace comprising at least three heating zones;

[0465] Double layer; and

[0466] at least two or more rollers;

[0467] The double layer is wound around one of the at least two or more rollers at a wrap angle of 0 to 40°.

[0468] In some embodiments, including any of the preceding embodiments, the processing device comprises a double layer.

[0469] In some embodiments, including any of the foregoing embodiments, the bilayer is a metal-ceramic bilayer.

[0470] In some embodiments, including any of the preceding embodiments, the three different heating zones include: (a) a binder burnout section; (b) a green billet section; and (c) a sintering section.

[0471] In some embodiments, including any of the preceding embodiments, the processing device includes a rear roller.

[0472] In some embodiments, including any of the preceding embodiments, the front roller is mechanically coupled to the at least one furnace.

[0473] In some embodiments, including any of the preceding embodiments, the front roller has a motor that is sealed from the at least one furnace.

[0474] In some embodiments, including any of the foregoing embodiments, the racetrack is disposed inside the at least one furnace. In some embodiments, including any of the foregoing embodiments, the racetrack is disposed within the sintering section. In some embodiments, including any of the foregoing embodiments, the racetrack includes an exhaust port. In some embodiments, including any of the foregoing embodiments, the racetrack includes a speed bump. In some embodiments, including any of the foregoing embodiments, the top racetrack is centerless. In some embodiments, including any of the foregoing embodiments, the racetrack includes holes on its top surface. In some embodiments, including any of the foregoing embodiments, the at least one furnace is sealed.

[0475] In some embodiments, including any of the preceding embodiments, the processing device includes a cooling section.

[0476] In some embodiments, including any of the foregoing embodiments, the processing apparatus includes at least one atmosphere controller that controls at least one of a gas flow rate, a flow direction, a gas composition, a pressure, and a combination thereof in the furnace.

[0477] In some embodiments, including any of the preceding embodiments, the double layer is wound on a front roller.

[0478] In some embodiments, including any of the foregoing embodiments, the double layer includes a metal layer and a ceramic layer.

[0479] In some embodiments, including any of the preceding embodiments, the ceramic layer is green, bisque, or sintered.

[0480] In some embodiments, including any of the preceding embodiments, the at least one furnace comprises a multi-zone tunnel kiln (MZTK).

[0481] In some embodiments, including any of the preceding embodiments, the roller comprises a material selected from silicon carbide, Ni, stainless steel, or combinations thereof.

[0482] In some embodiments, including any of the foregoing embodiments, the processing device includes rollers that can be mechanically aligned to within 0.005 inches. In some embodiments, including any of the foregoing embodiments, the processing device includes rollers that can be mechanically aligned to within 0.001 inches. In some embodiments, including any of the foregoing embodiments, the processing device includes rollers that can be mechanically aligned in three dimensions.

[0483] In some embodiments, including any of the preceding embodiments, the processing device comprises nip rolls. In some embodiments, including any of the preceding embodiments, the at least one oven comprises heated rolls.

[0484] In some embodiments, including any of the foregoing embodiments, the at least one furnace includes rollers configured as a ramp. In some embodiments, including any of the foregoing embodiments, the MZTK has rollers disposed in an arched shape within the MZTK. In some embodiments, including any of the foregoing embodiments, the processing device includes 1 to 30 rollers disposed in a ramp. In some embodiments, including any of the foregoing embodiments, the processing device includes 1 to 20 rollers disposed in a ramp.

[0485] In some embodiments, including any of the foregoing embodiments, the MZTK is hermetically sealed.

[0486] In some embodiments, including any of the foregoing embodiments, the MZTK is vacuum sealed.

[0487] In some embodiments, including any of the foregoing embodiments, the front roller has a motor, and the motor and the MZTK are vacuum-sealed.

[0488] In some embodiments, including any of the preceding embodiments, the processing device includes a baffle between each heating zone.

[0489] In some embodiments, including any of the foregoing embodiments, the wrap angle around the roller is in the range of 0° to 40°. In some embodiments, including any of the foregoing embodiments, the wrap angle around the roller in the binder burnout section is in the range of 0° to 40°. In some embodiments, including any of the foregoing embodiments, the wrap angle around the roller in the sintering section is in the range of 0° to 40°. In some embodiments, including any of the foregoing embodiments, the handling device includes a nip roller, a speed reduction bump, an air bearing, or a combination thereof on the edge.

[0490] In some embodiments, including any of the preceding embodiments, the bilayer is suspended in a processing device.

[0491] In some embodiments, including any of the preceding embodiments, the at least one furnace comprises: (a) a binder burnout section; (b) a green billet section; and (c) a sintering section.

[0492] In some embodiments, including any of the preceding embodiments, the at least one furnace is sealed such that at least one atmosphere controller controls the flow of gases into and out of the at least one furnace.

[0493] In some embodiments, including any of the preceding embodiments, the processing apparatus includes a pressurized gas line between the green billet segment and the sintering segment, the pressurized gas line pumping gas into the green billet segment and the sintering segment.

[0494] In some embodiments, including any of the preceding embodiments, the at least one furnace is enclosed in a sealed container.

[0495] In some embodiments, including any of the foregoing embodiments, the sealed container contains an atmosphere of Ar, N2, H2 or a combination thereof.

[0496] In some embodiments, including any of the preceding embodiments, an atmosphere controller maintains a reducing atmosphere in the sintering section.

[0497] In some embodiments, including any of the foregoing embodiments, the atmosphere controller maintains an atmosphere containing argon (Ar) gas; nitrogen (N2); hydrogen (H2) gas; or a mixture thereof in the sintering section.

[0498] In some embodiments, including any of the preceding embodiments, the atmosphere controller maintains an atmosphere of less than 500 ppm O2 in the green section, the sintering section, or both.

[0499] In some embodiments, including any of the foregoing embodiments, the H 2 gas is present at about 1, 2, 3, 4, or 5% v / v.

[0500] In some embodiments, including any of the preceding embodiments, the ceramic layer is a green body, a green body tape.

[0501] In some embodiments, including any of the preceding embodiments, the ceramic layer is a green body that is a sheet-coated green tape.

[0502] In some embodiments, including any of the preceding embodiments, the bi-layer is positioned for curtain treatment as it moves through the treatment device.

[0503] In some embodiments, including any of the preceding embodiments, the bi-layer is positioned for vertical processing as it moves through the processing device.

[0504] In some embodiments, including any of the foregoing embodiments, the metal layer comprises a metal selected from nickel (Ni), iron (Fe), copper (Cu), titanium, tungsten, molybdenum, alloys thereof, or combinations thereof.

[0505] In some embodiments, including any of the preceding embodiments, the metal layer is an alloy of Fe and Ni.

[0506] In some embodiments, including any of the foregoing embodiments, the metal layer is an alloy of Fe and Ni, wherein the amount of Fe is 1% to 25% (w / w) and the remainder is Ni.

[0507] In some embodiments, including any of the foregoing embodiments, the metal layer has a thickness of 1 μm to 20 μm. In some embodiments, including any of the foregoing embodiments, the bilayer is suspended as it moves through the sintering zone. In some embodiments, including any of the foregoing embodiments, the handling device comprises a sintered bilayer wound on the at least one rear roller. In some embodiments, including any of the foregoing embodiments, the sintered bilayer comprises a metal layer and a sintered oxide layer. In some embodiments, including any of the foregoing embodiments, the sintered bilayer comprises a metal layer and a sintered lithium-filled garnet layer. In some embodiments, including any of the foregoing embodiments, the handling device moves the bilayer through the at least one furnace at a rate of at least 2 inches per minute. In some embodiments, including any of the foregoing embodiments, the binder burnout zone and the sintering zone are positioned parallel to each other.

[0508] In some embodiments, including any of the preceding embodiments, the binder burnout zone is located above the sintering zone.

[0509] In some embodiments, including any of the preceding embodiments, the processing device further comprises a second binder burnout zone.

[0510] In some embodiments, including any of the foregoing embodiments, the entire processing device is disposed in a vacuum.

[0511] In some embodiments, the present application describes a method of using a continuous processing apparatus comprising the following operations:

[0512] (a) heating the green bilayer as it moves through at least one furnace to produce a bilayer having an organic content of less than 1%;

[0513] (b) Winding the double layer having an organic matter content of less than 1% onto a roll.

[0514] In some embodiments, the present application describes a method of using a continuous processing apparatus comprising the following operations:

[0515] (a) providing or having provided a processing device as described in this application;

[0516] (b) heating the bilayer to form a green bilayer as the bilayer moves through the at least one furnace;

[0517] (c) Winding the green blank into two layers.

[0518] In some embodiments, including any of the foregoing embodiments, the method further comprises: (d) unfolding the two layers of the blank.

[0519] In some embodiments, including any of the foregoing embodiments, the method further comprises: (e) sintering the bilayer.

[0520] In some embodiments, including any of the preceding embodiments, the method further comprises winding the sintered bi-layer onto a back roll.

[0521] In some embodiments, including any of the preceding embodiments, the sintered bilayer is a cut strip.

[0522] In some embodiments, including any of the preceding embodiments, the green sheet is double-layered after step (c).

[0523] In some embodiments, described herein are greenware articles prepared by the methods described herein.

[0524] In some embodiments, described herein are sintered articles prepared by the methods described herein.

[0525] In some embodiments, the present application describes a green bi-layer comprising lithium-filled garnet, wherein the green bi-layer is wound on a roll, the bi-layer having a thickness of less than 100 μm.

[0526] In some embodiments, including any of the foregoing embodiments, the bilayer includes a lithium-filled garnet layer and a metal foil layer, wherein the lithium-filled garnet layer has a thickness of 10 μm-30 μm and the metal foil layer has a thickness of 2 μm-10 μm.

[0527] In some embodiments, the present application describes a sintered bilayer comprising lithium-filled garnet, wherein the bilayer is wound on a roll, the bilayer having a thickness of less than 100 μm.

[0528] In some embodiments, including any of the foregoing embodiments, the bilayer includes a lithium-filled garnet layer and a metal foil layer, the lithium-filled garnet layer having a thickness of 10 μm to 30 μm, and the metal foil layer having a thickness of 2 μm to 10 μm.

[0529] In some embodiments, including any of the preceding embodiments, the metal foil layer includes nickel, iron, or a combination thereof.

[0530] In some embodiments, the present application describes a method using a continuous processing device, which includes the following operations: (a) providing or having provided a processing device described in the present application; (b) heating the bilayer to form a sintered bilayer as the bilayer moves through the at least one furnace.

[0531] In some embodiments, the present application describes a sintered bilayer prepared by the above method.

[0532] In some embodiments, including any of the preceding embodiments, the processing device comprises a lithium-filled garnet.

[0533] In some embodiments, including any of the foregoing embodiments, the bilayer includes a lithium-filled garnet layer and a metal foil layer, the lithium-filled garnet layer having a thickness of 10 μm to 30 μm, and the metal foil layer having a thickness of 2 μm to 10 μm.

[0534] In some embodiments, including any of the preceding embodiments, the metal foil layer includes nickel, iron, or a combination thereof.

[0535] I. Other Implementation Schemes

[0536] In at least one embodiment, the present application describes a method for preparing a sintered bilayer, which includes: providing a green bilayer under a tension of 1N to 300N per meter of coil width, the green bilayer including a green layer and a metal layer; moving the green bilayer through a first heating zone to form a debonded bilayer; moving the debonded bilayer through a second heating zone to form a sintered bilayer; when the debonded bilayer moves through the second heating zone, the debonded bilayer presents an arched configuration; wherein the debonded bilayer persists in the second heating zone for about 1 second to about 3 minutes; the temperature in the second heating zone is 1050°C to 1250°C; the thickness of the sintered bilayer is less than 100 μm.

[0537] In some embodiments, including any of the foregoing embodiments, the tension is 10N to 200N per meter of web width.

[0538] In some embodiments, including any of the foregoing embodiments, the tension is 40N to 200N per meter of web width.

[0539] In some embodiments, including any of the foregoing embodiments, the tension is 80N to 150N per meter of web width.

[0540] In some embodiments, including any of the foregoing embodiments, the tension is 125N to 200N per meter of web width.

[0541] In some embodiments, including any of the preceding embodiments, the green bi-layer is under the tension in the first heating zone.

[0542] In some embodiments, including any of the preceding embodiments, the debonded bilayer is under tension in the second heating zone.

[0543] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is different from the tension in the second heating zone.

[0544] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is lower than the tension in the second heating zone.

[0545] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of coil width; and the tension in the second heating zone is 10N to 200N per meter of coil width.

[0546] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of coil width; and the tension in the second heating zone is 40N to 200N per meter of coil width.

[0547] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 3N to 35N per meter of web width; the tension in the second heating zone is 3N to 35N per meter of web width. In some examples, a flat runway is used to apply the tension.

[0548] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of web width; the tension in the second heating zone is 40N to 190N per meter of web width. In some examples, a runway with an arched configuration is used to apply the tension. In some examples, the radius of curvature of the arched configuration is 3-5 meters.

[0549] In some embodiments, including any of the preceding embodiments, the tension is maintained by a tension controller with a tolerance of ±10% or less.

[0550] The method of any of the preceding embodiments further comprises cooling the sintered bilayer. In some examples, the method comprises cooling the sintered bilayer to room temperature.

[0551] In some embodiments, including any of the preceding embodiments, the green layer includes ceramic powder and a binder.

[0552] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered oxide layer.

[0553] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered lithium-filled garnet.

[0554] In some embodiments, including any of the foregoing embodiments, the metal layer includes nickel, iron, or alloys thereof.

[0555] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 1 μm to 10 μm.

[0556] In some embodiments, including any of the foregoing embodiments, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0557] In some embodiments, including any of the foregoing embodiments, the width of the sintered bilayer is 300 mm or less.

[0558] In some embodiments, including any of the preceding embodiments, the width of the sintered bilayer is at least 0.5 μm.

[0559] In some embodiments, including any of the preceding embodiments, the sintered bi-layer has a length of at least 1 meter.

[0560] In some embodiments, including any of the foregoing embodiments, the sintered double layer is less than 500 meters in length.

[0561] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 1 cm / min to 200 cm / min.

[0562] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 5 cm / min to 100 cm / min.

[0563] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 8 cm / min to 80 cm / min.

[0564] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 20 cm / min to 80 cm / min.

[0565] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 80 cm / min.

[0566] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0567] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0568] In some embodiments, including any of the foregoing embodiments, the debonded bilayer is in an arched configuration characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0569] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arcuate configuration characterized by a radius of curvature of 1 meter.

[0570] In some embodiments, including any of the foregoing embodiments, the debonded bilayer is in an arched configuration characterized by a curvature of 3.8 meters.

[0571] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0572] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0573] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1.0 meter, 2.0 meter, 3.0 meter, or 4.0 meter.

[0574] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1 meter.

[0575] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 3.8 meters.

[0576] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 5.0 meters.

[0577] In some embodiments, including any of the preceding embodiments, the at least one raceway provides the arched configuration. This means that a raceway with tension is used to bend the double layer into an arched structure.

[0578] In some embodiments, including any of the foregoing embodiments, at least one roller provides an arched configuration. This means that at least one or more rollers with tension are used to bend the bilayer into an arched structure.

[0579] In some embodiments, including any of the above embodiments, at least one speed bump provides the arched configuration. This means that at least one or more speed bumps with tension are used to bend the double layer into an arched structure.

[0580] In some embodiments, including any of the preceding embodiments, the length of the first heating zone is 60 inches.

[0581] In some embodiments, including any of the preceding embodiments, the length of the second heating zone is 60 inches.

[0582] In some embodiments, including any of the preceding embodiments, the debonded bilayer is in the second heating zone for about 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.

[0583] In some embodiments, including any of the preceding embodiments, the green body bilayer moves horizontally through the first heating zone.

[0584] In some embodiments, including any of the preceding embodiments, the green body bilayer moves vertically through the first heating zone.

[0585] In another embodiment, the present application describes a method for preparing a sintered bilayer, which includes: providing a green bilayer including a green layer and a metal layer; moving the green bilayer through a first heating zone to form a debonded bilayer; moving the debonded bilayer through a second heating zone to form a sintered bilayer; when the debonded bilayer moves through the second heating zone, the debonded bilayer presents an arched configuration; the debonded bilayer persists in the second heating zone for about 1 second to about 3 minutes; the temperature in the second heating zone is 1050°C to 1250°C; the thickness of the sintered bilayer is less than 100 μm.

[0586] In some embodiments, including any of the foregoing embodiments, the tension is 10N to 200N per meter of roll width.

[0587] In some embodiments, including any of the foregoing embodiments, the tension is 40N to 200N per meter of roll width.

[0588] In some embodiments, including any of the foregoing embodiments, the tension is 80N to 150N per meter of roll width.

[0589] In some embodiments, including any of the foregoing embodiments, the tension is 125N to 200N per meter of roll width.

[0590] In some embodiments, including any of the foregoing embodiments, the tension is 150N to 200N per meter of roll width.

[0591] In some embodiments, including any of the foregoing embodiments, the tension is 180N to 200N per meter of roll width.

[0592] In some embodiments, including any of the preceding embodiments, the green bi-layer is under the tension in the first heating zone.

[0593] In some embodiments, including any of the preceding embodiments, the debonded bilayer is under tension in the second heating zone.

[0594] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is different from the tension in the second heating zone.

[0595] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is lower than the tension in the second heating zone.

[0596] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of roll width; and the tension in the second heating zone is 10N to 200N per meter of roll width.

[0597] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of roll width; and the tension in the second heating zone is 40N to 200N per meter of roll width.

[0598] In some embodiments, including any of the preceding embodiments, the tension is maintained by a tension controller with a tolerance of ±10% or less.

[0599] The method according to the above embodiment further comprises cooling the sintered bilayer. In some examples, the method comprises cooling the sintered bilayer to room temperature.

[0600] In some embodiments, including any of the preceding embodiments, the green layer includes ceramic powder and a binder.

[0601] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered oxide layer.

[0602] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered lithium-filled garnet.

[0603] In some embodiments, including any of the foregoing embodiments, the metal layer includes nickel, iron, or alloys thereof.

[0604] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 1 μm to 10 μm.

[0605] In some embodiments, including any of the foregoing embodiments, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0606] In some embodiments, including any of the foregoing embodiments, the width of the sintered bilayer is 300 mm or less.

[0607] In some embodiments, including any of the preceding embodiments, the width of the sintered bilayer is at least 0.5 μm.

[0608] In some embodiments, including any of the preceding embodiments, the sintered bi-layer has a length of at least 1 meter.

[0609] In some embodiments, including any of the foregoing embodiments, the sintered double layer is less than 500 meters in length.

[0610] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 1 cm / min to 200 cm / min.

[0611] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 5 cm / min to 100 cm / min.

[0612] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 8 cm / min to 80 cm / min.

[0613] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 20 cm / min to 80 cm / min.

[0614] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 80 cm / min.

[0615] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0616] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0617] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0618] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 1 meter.

[0619] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 3.8 meters.

[0620] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arched configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0621] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arched configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0622] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, or 4.0 meters.

[0623] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arched configuration characterized by a radius of curvature of 1 meter.

[0624] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arched configuration characterized by a radius of curvature of 3.8 meters.

[0625] In some embodiments, including any of the preceding embodiments, at least one racetrack provides the arcuate configuration.

[0626] In some embodiments, including any of the preceding embodiments, at least one roller provides the arcuate configuration.

[0627] In some embodiments, including any of the preceding embodiments, at least one speed bump provides the arcuate configuration.

[0628] In some embodiments, including any of the preceding embodiments, the length of the first heating zone is 60 inches.

[0629] In some embodiments, including any of the preceding embodiments, the length of the second heating zone is 60 inches.

[0630] In some embodiments, including any of the foregoing embodiments, the debonded bilayer is in the second heating zone for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 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, 4 9 seconds, 30 seconds, 31 seconds, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds or 90 seconds.

[0631] In some embodiments, including any of the preceding embodiments, the green body bilayer moves horizontally through the first heating zone.

[0632] In some embodiments, including any of the preceding embodiments, the green body bilayer moves vertically through the first heating zone.

[0633] In another embodiment, the present application describes a method for preparing a sintered bilayer, which includes: providing a green bilayer including a green layer and a metal layer under a tension of 1N to 300N per meter of roll width; moving the green bilayer through a first heating zone to form a debonded bilayer; moving the debonded bilayer through a second heating zone to form a sintered bilayer; the debonded bilayer is maintained in the second heating zone for about 1 second to about 3 minutes; the temperature in the second heating zone is 1050°C to 1250°C; the thickness of the sintered bilayer is less than 100 μm.

[0634] In some embodiments, including any of the preceding embodiments, the debonded bi-layer assumes an arcuate configuration as the debonded bi-layer moves through the second heating zone.

[0635] In some embodiments, including any of the preceding embodiments, the debonded bi-layer is in a flat configuration as it moves through the second heating zone.

[0636] In some embodiments, including any of the foregoing embodiments, the tension is 3N to 100N per meter of roll width.

[0637] In some embodiments, including any of the foregoing embodiments, the tension is 3N to 80N per meter of roll width.

[0638] In some embodiments, including any of the foregoing embodiments, the tension is 3N to 50N per meter of roll width.

[0639] In some embodiments, including any of the foregoing embodiments, the tension is 3N to 35N per meter of roll width.

[0640] In some embodiments, including any of the foregoing embodiments, the tension is 3N to 30N per meter of roll width.

[0641] In some embodiments, including any of the foregoing embodiments, the tension is 10N to 20N per meter of roll width.

[0642] In some embodiments, including any of the preceding embodiments, the green bi-layer is under the tension in the first heating zone.

[0643] In some embodiments, including any of the preceding embodiments, the debonded bilayer is under tension in the second heating zone.

[0644] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is different from the tension in the second heating zone.

[0645] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is lower than the tension in the second heating zone.

[0646] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 3N to 50N per meter of roll width; the tension in the second heating zone is 3N to 50N per meter of roll width.

[0647] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 3N to 35N per meter of roll width; the tension in the second heating zone is 3N to 35N per meter of roll width.

[0648] In some embodiments, including any of the preceding embodiments, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0649] The method according to the above embodiment further comprises cooling the sintered bilayer. In some examples, the method comprises cooling the sintered bilayer to room temperature.

[0650] In some embodiments, including any of the preceding embodiments, the green layer includes ceramic powder and a binder.

[0651] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered oxide layer.

[0652] In some embodiments, including any of the preceding embodiments, the sintered bilayer comprises a sintered lithium-filled garnet.

[0653] In some embodiments, including any of the foregoing embodiments, the metal layer includes nickel, iron, or alloys thereof.

[0654] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 1 μm to 10 μm.

[0655] In some embodiments, including any of the foregoing embodiments, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0656] In some embodiments, including any of the foregoing embodiments, the width of the sintered bilayer is 300 mm or less.

[0657] In some embodiments, including any of the preceding embodiments, the width of the sintered bilayer is at least 0.5 μm.

[0658] In some embodiments, including any of the preceding embodiments, the sintered bi-layer has a length of at least 1 meter.

[0659] In some embodiments, including any of the foregoing embodiments, the sintered double layer is less than 500 meters in length.

[0660] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 1 cm / min to 200 cm / min.

[0661] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 5 cm / min to 100 cm / min.

[0662] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 8 cm / min to 80 cm / min.

[0663] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 20 cm / min to 80 cm / min.

[0664] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 80 cm / min.

[0665] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0666] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0667] In some embodiments, including any of the foregoing embodiments, the debonded bilayer is in an arched configuration characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, 4.0 meters, or 5.0 meters.

[0668] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arcuate configuration characterized by a radius of curvature of 1 meter.

[0669] In some embodiments, including any of the foregoing embodiments, the debonded bilayer has an arched configuration characterized by a radius of curvature of 3.8 meters.

[0670] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arched configuration characterized by a radius of curvature of 0.5 meters to 6.0 meters.

[0671] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

[0672] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 2.0 meters to 4.0 meters.

[0673] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1.0 meter, 2.0 meter, 3.0 meter, 4.0 meter, or 5.0 meter.

[0674] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1 meter.

[0675] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 3.8 meters.

[0676] In some embodiments, including any of the foregoing embodiments, the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 5.0 meters.

[0677] In some embodiments, including any of the preceding embodiments, at least one racetrack provides the arcuate configuration.

[0678] In some embodiments, including any of the preceding embodiments, at least one roller provides the arcuate configuration.

[0679] In some embodiments, including any of the preceding embodiments, at least one speed bump provides the arcuate configuration.

[0680] In some embodiments, including any of the foregoing embodiments, the first heating zone is 60 inches long.

[0681] In some embodiments, including any of the foregoing embodiments, the second heating zone is 60 inches long.

[0682] In some embodiments, including any of the preceding embodiments, the debonded bilayer is in the second heating zone for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 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.

[0683] In some embodiments, including any of the preceding embodiments, the green body bilayer moves horizontally through the first heating zone.

[0684] In some embodiments, including any of the preceding embodiments, the green body bilayer moves vertically through the first heating zone.

[0685] In another embodiment, the present application describes a method for sintering a double layer, the method comprising: providing the double layer under a tension of 1N to 300N; the thickness of the double layer is 1μm to 100μm; the double layer comprises a layer containing ceramics disposed on a metal layer; and sintering the double layer at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0686] In some embodiments, including any of the foregoing embodiments, the ceramic layer comprises ceramic powder.

[0687] In some embodiments, including any of the preceding embodiments, the ceramic layer is a sintered ceramic.

[0688] In some embodiments, including any of the preceding embodiments, the ceramic layer comprises lithium-filled garnet.

[0689] In some embodiments, including any of the foregoing embodiments, the metal layer is nickel foil.

[0690] In some embodiments, including any of the foregoing embodiments, the bilayer has a thickness of 1 μm to 50 μm.

[0691] In some embodiments, including any of the foregoing embodiments, the ceramic layer has a thickness less than 25 μm.

[0692] In some embodiments, including any of the foregoing embodiments, the metal layer has a thickness less than 25 μm.

[0693] In some embodiments, including any of the foregoing embodiments, the double layer width is 300 mm or less.

[0694] In some embodiments, including any of the preceding embodiments, the double layer length is at least 1 meter long.

[0695] In some embodiments, including any of the preceding embodiments, the bilayer is sintered at about 1100°C to about 1200°C.

[0696] In some embodiments, including any of the foregoing embodiments, the bilayer moves at a rate of about 5 cm / min to about 100 cm / min.

[0697] In some embodiments, including any of the preceding embodiments, the double layer is disposed on a flat runway.

[0698] In some embodiments, including any of the foregoing embodiments, the double layer is disposed on a curved runway.

[0699] In some embodiments, including any of the foregoing embodiments, the tension is 10N to 200N per meter of roll width.

[0700] In some embodiments, including any of the foregoing embodiments, the tension is 40N to 200N per meter of roll width.

[0701] In some embodiments, including any of the foregoing embodiments, the tension is 80N to 150N per meter of roll width.

[0702] In some embodiments, including any of the foregoing embodiments, the tension is 125N to 200N per meter of roll width.

[0703] In some embodiments, including any of the preceding embodiments, the bilayer is under the tension as it moves through the first heating zone.

[0704] In some embodiments, including any of the preceding embodiments, the bilayer is under the tension as it moves through the second heating zone.

[0705] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is different from the tension in the second heating zone.

[0706] In some embodiments, including any of the preceding embodiments, the tension in the first heating zone is lower than the tension in the second heating zone.

[0707] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of roll width; and the tension in the second heating zone is 10N to 200N per meter of roll width.

[0708] In some embodiments, including any of the foregoing embodiments, the tension in the first heating zone is 125N to 250N per meter of roll width; and the tension in the second heating zone is 40N to 200N per meter of roll width.

[0709] In some embodiments, including any of the preceding embodiments, tension is maintained by a tension controller with a tolerance of ±10% or less.

[0710] In the method of the foregoing embodiment, the method further comprises cooling the bilayer. In some examples, the method comprises cooling the bilayer to room temperature.

[0711] In some embodiments, including any of the preceding embodiments, the bi-layer comprises a green layer comprising a ceramic powder and a binder.

[0712] In some embodiments, including any of the preceding embodiments, the bilayer comprises a sintered oxide layer.

[0713] In some embodiments, including any of the preceding embodiments, the bilayer comprises a sintered lithium-filled garnet.

[0714] In some embodiments, including any of the foregoing embodiments, the metal layer includes nickel, iron, or alloys thereof.

[0715] In some embodiments, including any of the foregoing embodiments, the thickness of the metal layer is 1 μm to 10 μm.

[0716] In some embodiments, including any of the foregoing embodiments, the thickness of the sintered oxide layer is 5 μm to 40 μm.

[0717] In some embodiments, including any of the foregoing embodiments, the width of the sintered bilayer is 300 mm or less.

[0718] In some embodiments, including any of the preceding embodiments, the width of the sintered bilayer is at least 0.5 μm.

[0719] In some embodiments, including any of the foregoing embodiments, the sintered double layer is at least 1 meter long. In some instances, the sintered double layer is at least 2 meters long. In some instances, the sintered double layer is at least 3 meters long. In some instances, the sintered double layer is at least 4 meters long. In some instances, the sintered double layer is at least 5 meters long. In some instances, the sintered double layer is at least 6 meters long. In some instances, the sintered double layer is at least 7 meters long. In some instances, the sintered double layer is at least 8 meters long. In some instances, the sintered double layer is at least 9 meters long. In some instances, the sintered double layer is at least 10 meters long. In some instances, the sintered double layer is at least 20 meters long. In some instances, the sintered double layer is at least 30 meters long. In some instances, the sintered double layer is at least 40 meters long. In some instances, the sintered double layer is at least 50 meters long. In some examples, the sintered double layer is at least 60 meters long. In some examples, the sintered double layer is at least 70 meters long. In some examples, the sintered double layer is at least 80 meters long. In some examples, the sintered double layer is at least 90 meters long. In some examples, the sintered double layer is at least 100 meters long.

[0720] In some embodiments, including any of the foregoing embodiments, the sintered double layer is less than 500 meters in length.

[0721] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 1 cm / min to 200 cm / min.

[0722] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 5 cm / min to 100 cm / min.

[0723] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 8 cm / min to 80 cm / min.

[0724] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of 20 cm / min to 80 cm / min.

[0725] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 10 cm / min.

[0726] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 20 cm / min.

[0727] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 30 cm / min.

[0728] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 40 cm / min.

[0729] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 50 cm / min.

[0730] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 60 cm / min.

[0731] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 70 cm / min.

[0732] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 80 cm / min.

[0733] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 90 cm / min.

[0734] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 100 cm / min.

[0735] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 110 cm / min.

[0736] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 120 cm / min.

[0737] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 130 cm / min.

[0738] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 140 cm / min.

[0739] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 150 cm / min.

[0740] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 160 cm / min.

[0741] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 170 cm / min.

[0742] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 180 cm / min.

[0743] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 190 cm / min.

[0744] In some embodiments, including any of the preceding embodiments, the bilayer moves through the second heating zone at a rate of about 200 cm / min.

[0745] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 0.5 meters to 6.0 meters.

[0746] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 0.5 meters to 4.0 meters.

[0747] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 2.0 meters to 4.0 meters.

[0748] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 2.0 meters to 6.0 meters.

[0749] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 1.0 meter, 2.0 meter, 3.0 meter, 4.0 meter or 5.0 meter.

[0750] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 1 meter.

[0751] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 3.8 meters.

[0752] In some embodiments, including any of the foregoing embodiments, the double layer has an arched configuration, and the radius of curvature of the arch is 5.0 meters.

[0753] In some embodiments, including any of the preceding embodiments, at least one racetrack provides the arcuate configuration.

[0754] In some embodiments, including any of the preceding embodiments, at least one roller provides the arcuate configuration.

[0755] In some embodiments, including any of the preceding embodiments, at least one speed bump provides the arcuate configuration.

[0756] In some embodiments, including any of the preceding embodiments, the length of the first heating zone is 60 inches.

[0757] In some embodiments, including any of the preceding embodiments, the length of the second heating zone is 60 inches.

[0758] In some embodiments, including any of the preceding embodiments, the double layer is in the second heating zone for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds. 10 seconds, 15 seconds, 16 seconds, 17 seconds, 18 seconds, 19 seconds, 20 seconds, 21 seconds, 22 seconds, 23 seconds, 24 seconds, 25 seconds, 26 seconds, 27 seconds, 28 seconds, 29 seconds, 30 seconds, 31 seconds, 32 seconds, 33 seconds, 34 seconds, 35 seconds, 36 seconds, 37 seconds, 38 seconds, 39 seconds, 40 seconds, 41 seconds, 42 seconds, 43 seconds, 44 seconds, 45 seconds, 46 seconds, 47 seconds, 48 ​​seconds, 49 seconds, 50 seconds, 51 seconds, 52 seconds, 53 seconds, 54 seconds, 55 seconds, 56 seconds, 57 seconds, 58 seconds, 59 seconds, 60 seconds, 70 seconds, 80 seconds, or 90 seconds.

[0759] In some embodiments, including any of the preceding embodiments, the bilayer moves horizontally through the first heating zone.

[0760] In some embodiments, including any of the preceding embodiments, the bilayer moves vertically through the first heating zone.

[0761] In another embodiment, the present application describes a method for sintering a double layer, comprising: providing the double layer under a tension of 5N to 100N; the thickness of the double layer is 1μm to 100μm; the double layer includes a layer containing ceramics disposed on a metal layer; and sintering the double layer in an arched configuration at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0762] In another embodiment, the present application describes a method for sintering a bilayer, comprising providing a bilayer; the bilayer has a thickness of 1 μm to 100 μm; the bilayer comprises a layer containing ceramic disposed on a metal layer; and sintering the bilayer in an arched configuration at about 1050°C to about 1250°C for about 1 second to about 3 minutes.

[0763] In some embodiments, including any of the preceding embodiments, the bilayer is under a tension of 5N to 100N.

[0764] In some embodiments, including any of the foregoing embodiments, the double-layer curvature radius is 2 meters to 4 meters.

[0765] In some embodiments, including any of the foregoing embodiments, the double-layer curvature radius is 2 meters to 6 meters.

[0766] In some embodiments, including any of the foregoing embodiments, the ceramic layer includes ceramic powder and a binder.

[0767] In some embodiments, including any of the preceding embodiments, the ceramic layer is a sintered ceramic.

[0768] In some embodiments, including any of the preceding embodiments, the ceramic layer is a sintered lithium-filled garnet.

[0769] In some embodiments, including any of the foregoing embodiments, the metal layer is nickel foil.

[0770] In some embodiments, including any of the foregoing embodiments, the bilayer has a thickness of 1 μm to 50 μm.

[0771] In some embodiments, including any of the foregoing embodiments, the ceramic layer has a thickness less than 25 μm.

[0772] In some embodiments, including any of the foregoing embodiments, the metal layer has a thickness less than 10 μm.

[0773] In some embodiments, including any of the foregoing embodiments, the double layer width is 300 mm or less.

[0774] In some embodiments, including any of the preceding embodiments, the double layer length is at least 1 meter long.

[0775] In some embodiments, including any of the preceding embodiments, the bilayer is sintered at about 1100°C to about 1200°C.

[0776] In some embodiments, including any of the preceding embodiments, the bilayer moves at a rate between about 5 cm / min and 80 cm / min.

[0777] In some embodiments, including any of the foregoing embodiments, the double layer is disposed on a curved runway.

[0778] J. Examples

[0779] Unless otherwise specified, the solvents used in the present application are selected from alcohols (e.g., methanol, ethanol, isopropanol, butanol, pentanol, hexanol) and other types of organic solvents, such as ethers and aromatic solvents, including but not limited to dibutyl ether, diethyl ether, diisopropyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, toluene, xylene, toluene: ethanol, acetone, N-methyl-2-pyrrolidone (NMP) diacetone alcohol, ethyl acetate, acetonitrile, hexane, nonane, dodecane and methyl ethyl ketone (MEK).

[0780] Unless stated to the contrary, reagents, chemicals and materials were purchased commercially.

[0781] The pouch cell container was purchased from Showa Denko.

[0782] The electrochemical potentiostat used was an Arbin potentiostat.

[0783] Electrical impedance spectroscopy (EIS) was performed using a Biologic VMP3, VSP-300, SP-150, or SP-200.

[0784] Electron microscopy was performed on a FEI Quanta SEM, Apreo SEM, Helios 600i, or Helios 660 FIB-SEM.

[0785] X-ray powder diffraction (XRD) was performed in a Bruker D8 Advance A25 with Cu K-α radiation at room temperature (e.g., 21° C.-23° C.). Cu-Ka source, wavelength 1.54. X-ray parameters 40 kV, 25 mA X. Detector: LYNXEYE_XE, PSD opening 2.843. Divergence slit was 0.6 mm, anti-scatter slit was 5.0 mm.

[0786] Grinding was performed using a Retsch PM 400 planetary ball mill. Mixing was performed using a Fischer Scientific vortex mixer, a Flaktek Speed ​​mixer or a Primix Filmix homogenizer unless otherwise stated.

[0787] Casting was done on a TQC stretching table. Calendering was done on an IMC calender unless otherwise stated.

[0788] Light scattering was performed on a Partica model Horiba, model: LA-950V2, general term: laser scattering particle size distribution analyzer.

[0789] Unless otherwise specified, the lithium nickel cobalt manganese oxide (NMC) used in the examples is LiNi 0.85 Co 0.1 Mn 0.05 O2.

[0790] Example 1 - Preparation of Sintered Coil - Prophetic Example

[0791] In these examples, a slurry was prepared by mixing lithium filled garnet, solvent, binder and plasticizer. The following slurry compositions were used.

[0792] Slurry 1: Disperse LLZO powder in ethanol containing 2 wt% polyacrylic acid using an ultrasonic horn. Allow larger particles to settle. Pour off the supernatant and dry the resulting powder in air. Add the collected powder, polyvinyl butyral, benzyl butyl phthalate, acetone, and ethanol in a weight ratio of 37:3:3:29:29 to a vial and ball mill with 2.0 mm diameter ZrO2 beads for 10 to 24 hours. Use a spatula to cast the slurry onto a metal substrate; control the film thickness by adjusting the blade height. Dry the raw film and wrap it around a core of at least 8 cm in diameter.

[0793] Slurry 2: LLZO powder containing 3 weight percent (wt%) polyacrylic acid was dispersed in ethanol. Polyvinyl butyral, benzyl butyl phthalate and acetone were mixed in a weight ratio of 1:1:10 to form a second solution. The second solution and the first solution were mixed in equal volumes. The resulting slurry was milled with ZrO2 beads for 8-16 hours. The slurry was cast onto a metal substrate using a scraper, and the thickness was controlled by the scraper height. The raw film was dried and wound on a core with a diameter of at least 8 cm.

[0794] Slurry 3: Dissolve methylcellulose, polyethylene glycol and glycerol in water to make a polymer aqueous solution. The weight ratio of the components is water: methylcellulose: polyethylene glycol: glycerol = 100: 1: 4: 4. Add LLZO (lithium filled garnet) powder to the polymer solution in an equal weight ratio. Mix the slurry with ZrO2 beads for 5-60 minutes. Pour the slurry on the metal foil with a spatula; the thickness is controlled by the gap of the spatula. Dry the raw film and wrap it on a core with a diameter of at least 8 cm.

[0795] Slurry 4: Ball mill LLZO in a mixture of equal parts of ethanol, xylene and toluene. Add herring oil dropwise for 30 minutes at 2-5 wt% of the weight of LLZO. Add 6-10 wt% polyvinyl butyral relative to LLZO, 2-4 wt% polyethylene glycol relative to LLZO and 3-7 wt% benzyl butyl phthalate relative to LLZO and mix. Cast the tape on a metal substrate with a spatula. After drying at 45°C for 1-6 hours, wrap the tape around a core of at least 8 cm in diameter.

[0796] Slurry 5: 100 g LLZO powder, 2-4 g triolein, 100-200 g n-propyl propionate, and 15-25 g elvan E-2046 were mixed and ball-milled to prepare a slurry. The slurry was cast onto a metal foil substrate by a spatula, dried, and wound.

[0797] Slurry 6: 20g LLZO powder, 25-40g solvent mixture (ethanol: butanol: propylene glycol, volume percentage 70-80: 15-25: 0-5), 1-3g dibutyl phthalate, 1-4g PVB and 0.1-1g dispersant were mixed in a grinder to make a slurry. The dispersant can be, for example, BYK Anti-terra-202 dispersant. After mixing, the slurry was filtered, degassed, and cast onto a metal substrate by comma coating. The green tape was dried and wound.

[0798] Slurry 7: 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 Innovation) were mixed in a grinder for at least one hour to make a slurry. After mixing, the slurry was filtered, degassed, and cast onto a metal substrate by slot die coating. The green tape was dried and wound.

[0799] Slurry eight: Grind LLZO powder in a mixed solvent of toluene and isopropanol plus fish oil. Mix the mixture for 1-5 hours to make a slurry. Mix toluene and isopropanol plus polyvinyl butyral and butyl benzyl phthalate to make a binder solution. Add the binder solution to the slurry and mix. Degas the mixture, filter and cast onto a metal support. Dry the green tape and wind it up.

[0800] Slurry nine: 80g of calcined LLZO powder was mixed with 50ml of 33% w / w solution of polyvinyl butyral in toluene and 4g of plasticizer dibutyl phthalate to prepare calcined LLZO slurry. A polyacrylic binder was added according to 3 wt% of the solution. The slurry was cast onto a metal substrate using a scraper. The cast mixed slurry was dried at room temperature for 2-6 hours to form a green film. The dried green film was wound on a core of at least 8 cm diameter.

[0801] After drying, the dried slurry on the nickel foil was placed on a continuous processing unit.

[0802] In the first step, the binder is burned off by heating the green bilayer to produce a debonded bilayer.

[0803] In the second step, the green tape is heated in a china furnace to produce a china double layer.

[0804] In the third step, the green tape is sintered at about 1100° C. to produce a sintered bilayer.

[0805] The sintered double-layer film can be wound on a rear roll. The sintered double-layer can also be cut into thin sheets.

[0806] In the second processing unit, the green double layer will move back and forth between the biscuit furnace and the binder burnout furnace. The oven is opened and closed to selectively heat the film in the biscuit furnace or the binder burnout furnace. For sintering, the biscuit furnace temperature is increased to the sintering temperature.

[0807] Example 2 - Preparation of Sintered Coils - Prophetic Example

[0808] In this example, a slurry was prepared by mixing lithium filled garnet, solvent, binder, and plasticizer.

[0809] Specifically, lithium-filled garnet was mixed with an acrylic binder and benzyl butyl phthalate in an aprotic solvent to form a slurry. The slurry was cast onto a Ni foil to form a double layer. The slurry was dried and then rolled up.

[0810] After drying, the dried slurry on the nickel foil is placed on a continuous production line. As the slurry dries on the nickel foil, a green bilayer is formed. The belt is then moved through the apparatus.

[0811] The bilayer was moved through the processing apparatus at a speed of 5 cm / min and maintained at about 1100° C. for about 10 minutes in the sintering section.

[0812] Example 3 - Preparation of Debonded Coil with Controlled Particle and Granule Size

[0813] Dispersion of lithium-filled garnet powders (d 50 <1μm) to prepare a slurry, wherein the content of binder and plasticizer is 8-20% by weight of the solid. Xylene is added to control the viscosity in the range of 50-1000cP at a shear rate of 20Hz. Using a comma coater, the slurry is cast on a nickel foil of 60mm to 150mm width at a fixed gap distance of 200μm-400μm. The double layer is dried and wound on a core of about 9cm in diameter. The thickness of the green ceramic layer is 50μm to 80μm; the thickness of the metal layer is 5μm to 15μm. The roll is transferred to a processing device, unwound, unfolded, and passed through a temperature zone at a feed rate of 5-20cm / min, in which the double layer is debonded (i.e., the binder is removed from the double layer). The temperature zone is set to 600-900℃, where the atmosphere is configured to remove organic burnout products and reduce lithium loss. After removing the binder, the product is rolled up. The debonded bi-layer material rolls were stored for subsequent sintering, testing and analysis.

[0814] Example 4 - Preparation of green coil with controlled particle size and grain size

[0815] Dispersion of lithium-filled garnet powders (d 50 <1μm) to prepare a slurry, wherein the content of binder and plasticizer is 8-20% by weight of solids. Solvent is added to control the viscosity in the range of 50-1000cP at a shear rate of 20Hz. Using a comma coater, the slurry is cast on a metal foil of 60mm to 150mm width at a fixed gap distance of 200μm to 400μm. The double layer is dried and wound on a core of about 9cm in diameter. The thickness of the green ceramic layer is 50μm to 80μm; the thickness of the metal layer is 5μm to 15μm. The roll is transferred to a processing device, unwound, unfolded, and passed through a temperature zone at a feed rate of 5cm / min to 20cm / min, where the double layer is debonded. The temperature zone is set to 600-900℃, where the atmosphere is configured to remove organic burnout products and reduce lithium loss.

[0816] Example 5 - Preparation of Sintered Coil with Controlled Grain and Particle Size

[0817] Dispersion of lithium-filled garnet powders (d 50 <1μm) to prepare a slurry, wherein the content of binder and plasticizer is 8-20% by weight of the solid. A solvent is added to control the viscosity in the range of 50-1000cP at a shear rate of 20Hz. Using a comma coater, the slurry is cast on a metal foil of 60mm to 150mm width at a fixed gap distance of 200μm to 400μm. The double layer is dried and wound on a core of about 9cm in diameter. The thickness of the green ceramic layer is 50μm to 80μm; the thickness of the metal layer is 5μm to 15μm. The roll is transferred to a processing device, unwound, unfolded, and passed through multiple temperature zones at a feed rate of 5cm / min-20cm / min, in which the double layer is debonded, formed into a green body and sintered. The temperature zone is set to 600-1300℃, where the atmosphere is configured to remove organic burnout products and reduce lithium loss. After sintering, the product is rolled up. Coils of sintered bilayer material were stored for later testing and analysis.

[0818] Example 6 - Testing of Sintered Coils

[0819] Sintered films were prepared as in Example 5, and the area specific resistance (ASR) was measured by current interruption measurement.

[0820] The separator of the battery cell is cut from the sintered film roll, 3mAh / cm 2 The cathode is loaded with NMC (Li (Ni 1-x- y Mn x Coy The battery was charged and discharged at 30°C using intermittent current pulses with a constant current density of 0.33 mA / cm 2 , operating voltage is 3V-4.2V. A current pulse is applied for 30 minutes, the current is stopped, and the system relaxes under open circuit conditions for 3 minutes. This intermittent pulse is repeated until the battery voltage reaches 4.2V during charging and 3V during discharge. The area specific resistance (ASR) of the battery cell is obtained by reading the voltage drop during the relaxation step during charging. The ASR is measured to be 15-25Ωcm at 30°C 2 .

[0821] Example 7 - Preparation and Testing of Sintered Bilayers

[0822] The sintered bilayer was prepared as in Example 5. Specifically, the lithium-filled garnet was mixed with an acrylic binder and benzyl butyl phthalate in an aprotic solvent to form a slurry. The slurry was cast onto a Ni foil to form a bilayer.

[0823] The two-layer coil (referred to as coil) was moved through the CML at 5 cm / min and held at about 1100° C. for about 10 minutes in the sintering section.

[0824] A 30 × 30 mm double-layer separator was cut from the sintered coil and combined with a 3.1 mAh / cm 2 The battery is assembled with a cathode. The cathode is infiltrated with a liquid or gel catholyte containing a lithium salt and a solvent that dissolves the salt. The battery is cycled at 30°C, 50 pounds per square inch (PSI) (~3.4atm) with a 1C charge rate, 1C discharge rate. After 800 cycles of 100% discharge depth, the battery retains more than 90% of its initial capacity. See Figure 13.

[0825] Example 8 - Preparation of the materials in Figures 6, 7 and 8

[0826] Unless otherwise stated, the D 90 It is for sintered particles.

[0827] The slurry is prepared by dispersing lithium filled garnet powder with solvent, binder and plasticizer, wherein the content of binder and plasticizer is 8-20% by weight of solids. The solvent is added and the viscosity is controlled in the range of 50-1000 cP at a shear rate of 20 Hz. The slurry is cast on a metal foil (width 60-150 mm) using a comma coater with a fixed gap distance of 200-400 μm, dried and rolled into a roll. The thickness of the green ceramic layer is 50 μm-80 μm; the thickness of the metal layer is 5-15 μm. The roll is transferred to a processing device for unwinding, unwinding, and passing through multiple temperature zones at a feed rate of 5-20 cm / min, where it is debonded, formed into a green body and sintered.

[0828] The binder burnout temperature zone is configured to remove the atmosphere for organic burnout. The sintering temperature zone is set to 900-1250°C to promote densification. After sintering, the product is rolled up. The sintered coil is transferred to a cutting machine and cut into 11 mm discs, 30×30 mm squares, and 70×85 mm rectangular sizes for testing and analysis. The product is shown in Figures 6 and 7.

[0829] The cross-section of the bilayer prepared in this application was imaged using a scanning electron microscope (SEM). The thickness of the lithium-filled garnet top layer was ~32 μm. Particle size D 90 The lithium-filled garnet side of the bilayer has a porosity of less than 1% by volume.

[0830] Porosity is calculated as volume % through image segmentation. A deep learning model is used to identify porous regions in the image; the model is trained based on manual segmentation of the image to label dark regions as pores.

[0831] Example 10 - Sintering a double layer using a flat racetrack

[0832] Lithium filled garnet powder (d) was dispersed with xylene, acrylic binder, plasticizer and acrylate dispersant. 50<1μm), to form a slurry, wherein the content of binder, plasticizer and dispersant is 10-20% by weight of solid. Solvent is added to control the viscosity in the range of 50-1000cP at a shear rate of 20Hz. Using a comma coater, the slurry is cast on a metal foil of 60mm to 150mm width at a fixed gap distance of 100μm to 200μm. The thickness of the green ceramic layer is 20μm to 50μm; the thickness of the metal layer is 5μm to 10μm. The coil is transferred to a processing device, unwound, unwound, and passed through a first heating zone at a feed rate of 5cm / min to 80cm / min to form a debonded double layer. The temperature of the first heating zone is 700℃ to 900℃.

[0833] The coil is then passed through a second heating zone at a feed rate of 40 cm / min to 200 cm / min to form a sintered bilayer. The temperature of the second heating zone is 1050°C to 1250°C. The second heating zone is a tubular furnace with a length of about 60 inches. A flat runway extends from the opening of the second heating zone to the exit. The debonded bilayer is conformed to the runway by applying a tension of 3N to 35N per meter of coil width to the debonded bilayer.

[0834] After sintering, the product is cut into sheets and stored for later testing and analysis.

[0835] Example 11 - Sintered Bilayer Using a Racetrack in an Arched Configuration

[0836] Lithium filled garnet powder (d) was dispersed with xylene, acrylic binder, plasticizer and acrylate dispersant. 50 <1μm), to form a slurry in which the content of binder, plasticizer and dispersant is 10-20% by weight of the solid. A solvent is added to control the viscosity in the range of 50-1000cP at a shear rate of 20Hz. Using a comma coater, the slurry is cast on a metal foil of 60mm to 150mm width at a fixed gap distance of 100μm to 200μm. The double layer is dried and wound on a core of about 9cm in diameter. The thickness of the green ceramic layer is 20μm to 50μm; the thickness of the metal layer is 5μm to 10μm. The coil is transferred to a processing device, unwound, unwound, and passed through a first heating zone at a feed rate of 20cm / min to 200cm / min to form a debonded double layer. The temperature of the first heating zone is 700℃ to 900℃.

[0837] The coil then passes through a second heating zone at a feed rate of 10 cm / min, 20 cm / min, 40 cm / min or 101 cm / min to form a sintered double layer. The temperature of the second heating zone is 1050°C to 1250°C. The second heating zone is a tubular furnace with a length of about 60 inches. The double layer passes through the second heating zone between 90 seconds and 5 minutes. An arched runway with a radius of curvature of 5.0 meters extends from the opening of the second heating zone to the exit. The debonded double layer is made to conform to the runway by applying a tension of 40N-187.5N per meter of coil width to the debonded double layer.

[0838] After sintering, the bilayer is cut into sheets.

[0839] FIG. 16 shows a height map of the bilayer produced in Example 11.

[0840] Figures 17-20 show the flatness of the double layers obtained using the heat treatment method, where the different tensions are listed in N / m of web width.

[0841] The web speed in Figure 17 is 10 cm / min; the web speed in Figure 18 is 20 cm / min; the web speed in Figure 19 is 40.5 cm / min; and the web speed in Figure 20 is 101 cm / min. The speeds listed in Figures 17-20 are in inches per minute.

[0842] Table 1 shows the average roughness of the data of Figures 17-20, measured using a Keyence microscope.

[0843] Table 1

[0844]

[0845]

[0846] The embodiments and examples described above are merely illustrative and non-limiting. A person of ordinary skill will recognize or confirm based on routine experiments that there are many equivalents for specific compounds, materials and steps. All of these equivalents are within the scope of protection and are included in the appended claims.

Claims

1. A method for preparing a sintered double layer, comprising: Providing a green double layer under a tension of 1N-300N per meter of coil width, the green double layer comprising a green layer and a metal layer; moving the green bilayer through a first heating zone to produce a debonded bilayer; moving the debonded bilayer through a second heating zone to produce a sintered bilayer; When the debonded double layer moves through the second heating zone, the debonded double layer assumes an arched shape; The debonding bilayer lasts from about 1 second to about 3 minutes in the second heating zone; The temperature in the second heating zone is 1050° C. to 1250° C.; and the thickness of the sintered double layer is less than 100 μm.

2. The method according to claim 1, wherein the tension is 10N to 200N per meter of coil width.

3. The method according to claim 1 or 2, wherein the tension is 40N to 200N per meter of coil width.

4. The method according to any one of claims 1 to 3, wherein the tension is 80N to 150N per meter of coil width.

5. The method according to any one of claims 1 or 2, wherein the tension is 125N to 200N per meter of coil width.

6. The method of any one of claims 1-5, wherein the green bi-layer is under the tension in the first heating zone.

7. The method of any one of claims 1-6, wherein the debonded bilayer is under the tension in the second heating zone.

8. The method of any one of claims 1-7, wherein the tension in the first heating zone is different from the tension in the second heating zone.

9. The method of any one of claims 1 to 8, wherein the tension in the first heating zone is lower than the tension in the second heating zone.

10. The method according to any one of claims 1-3 and 5-9, wherein the tension in the first heating zone is 125N to 250N per meter of coil width; and the tension in the second heating zone is 10N to 200N per meter of coil width.

11. The method according to any one of claims 1-3 and 5-9, wherein the tension in the first heating zone is 125N to 250N per meter of coil width; and the tension in the second heating zone is 40N to 200N per meter of coil width.

12. The method of any one of claims 1-11, wherein the tension is maintained by a tension controller with a tolerance of ±10% or less.

13. The method of claim 12, comprising cooling the sintered bilayer to room temperature.

14. The method according to any one of claims 1 to 13, wherein the green layer comprises ceramic powder and a binder.

15. The method of any one of claims 1-14, wherein the sintered bilayer comprises a sintered oxide layer.

16. The method of any one of claims 1-15, wherein the sintered bilayer comprises a sintered lithium-filled garnet.

17. The method according to any one of claims 1 to 16, wherein the metal layer comprises nickel, iron or an alloy thereof.

18. The method according to any one of claims 1 to 17, wherein the metal layer has a thickness of 1 μm to 10 μm.

19. The method according to any one of claims 16 to 18, wherein the sintered oxide layer has a thickness of 5 to 40 μm.

20. The method according to any one of claims 1 to 19, wherein the width of the sintered double layer is 300 mm or less.

21. The method according to any one of claims 1 to 20, wherein the sintered double layer has a length of at least 1 meter.

22. The method of any one of claims 1-21, wherein the bilayer moves through the second heating zone at a rate of 1 cm / min to 200 cm / min.

23. The method of any one of claims 1-22, wherein the bilayer moves through the second heating zone at a rate of 5 cm / min to 100 cm / min.

24. The method of any one of claims 1-23, wherein the bilayer moves through the second heating zone at a rate of 8 cm / min to 80 cm / min.

25. The method of any one of claims 1-24, wherein the bilayer moves through the second heating zone at a rate of 20 cm / min to 80 cm / min.

26. The method of any one of claims 1-25, wherein the debonded bilayer is in an arcuate configuration characterized by a radius of curvature of 0.5 meters to 6.0 meters.

27. The method of any one of claims 1-26, wherein the debonded bilayer is in an arcuate configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

28. The method of any one of claims 1-27, wherein the debonded bilayer is in an arcuate configuration characterized by a radius of curvature of 1.0 meters, 2.0 meters, 3.0 meters, 4.0 meters, 5.0 meters, or 6.0 meters.

29. The method of any one of claims 1-28, wherein the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 0.5 meters to 6.0 meters.

30. The method of any one of claims 1-29, wherein the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 0.5 meters to 4.0 meters.

31. The method of any one of claims 1-30, wherein the green body bi-layer has an arcuate configuration characterized by a radius of curvature of 1.0 meter, 2.0 meter, 3.0 meter, 4.0 meter, 5.0 meter, or 6.0 meter.

32. The method of any one of claims 1-31, wherein at least one racetrack provides the arcuate configuration.

33. The method of any one of claims 1-32, wherein at least one roller provides the arcuate configuration.

34. The method of any one of claims 1-33, wherein at least one speed bump provides the arcuate configuration.

35. The method of any one of claims 1-34, wherein the debonded bilayer is in the second heating zone for about 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.

36. The method of any one of claims 1 to 35, wherein the green body bilayer is moved horizontally through a first heating zone.

37. The method of any one of claims 1-35, wherein the green body bilayer is moved vertically through a first heating zone.

38. A sintered bilayer made according to the method of any one of claims 1 to 37.

39. An electrochemical cell comprising the sintered bilayer of claim 38.

40. A battery comprising the electrochemical cell of claim 39 or the sintered bilayer of claim 38.

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