CN117015688A - Quick ceramic processing technology and equipment - Google Patents
Quick ceramic processing technology and equipment Download PDFInfo
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- CN117015688A CN117015688A CN202280019709.9A CN202280019709A CN117015688A CN 117015688 A CN117015688 A CN 117015688A CN 202280019709 A CN202280019709 A CN 202280019709A CN 117015688 A CN117015688 A CN 117015688A
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- 238000005516 engineering process Methods 0.000 title description 3
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Landscapes
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Abstract
The application provides a rapid and high-quality film sintering process, which comprises high-flux continuous sintering of lithium-lanthanum zirconium oxide (lithium filled garnet). The present disclosure sets forth an apparatus and method for manufacturing a high quality, fast-machining ceramic electrolyte membrane. These processes include high throughput continuous sintering of lithium-lanthanum zirconium oxide used as an electrolyte membrane. In some processes, the film is not in contact with any surface during sintering (i.e., during the sintering phase).
Description
Cross Reference to Related Applications
The present application claims priority and benefit from U.S. patent application Ser. No.63/158,861 entitled "Rapid ceramic processing techniques and apparatus", filed on day 3 and 9 of 2021, and U.S. patent application Ser. No.63/233,684 entitled "Rapid ceramic processing techniques and apparatus", filed on day 8 and 16 of 2021; the entire contents of both applications are incorporated herein by reference for all purposes.
Technical Field
The present application relates to a method of calcining, debonding and/or sintering ceramics such as, but not limited to, lithium aluminum titanium phosphate, lithium stuffed garnet oxide, lithium lanthanum titanate and lithium aluminum germanium phosphate. In some examples, these ceramics are deposited as layers on top of a metal layer. Such two layers form a bilayer.
Background
U.S. patent nos. US10,563,918B2 or US10,840,544B2, for example, describe certain methods of sintering lithium-filled garnet (lithium lanthanum zirconium oxide; LLZO), such as batch sintering of LLZO. U.S. Pat. No. 10,766,165B2, international PCT patent application publication WO2017/003980A1, discloses high throughput continuous sintering of certain ceramics; U.S. patent application No. US2004/0206470 A1 and International PCT patent application publication WO2014/103662A1 disclose the container-less sintering of certain ceramics. US 2019/00777774 A1 discloses non-contact sintering of certain ceramics. Literature on sintered Lithium Aluminum Titanium Phosphate (LATP) and Lithium Lanthanum Titanium Oxide (LLTO) includes, for example, "influence of sintering temperature on electrical conductivity and mechanical behavior of solid electrolyte LATP", published by Yan, g. Et al, ceramics International, volume 45, 12 th edition, 2019, pages 14697-14703, ISSN 0272-8842, https:// doi.org/10.1016/j. Ceramine.2019.04.191; geng, H.et al, "sintering temperature vs. different lithium content Li 3x La 2/3-x TiO 3 Effects of microstructure and transport Properties "Ecectrochimica Acta, volume 56, 9 th, 2011, pages 3406-3414, ISSN 0013-4686, https::
ori/10.1016/j. Electric acta.2010.06.031; waetzig et al, "have improved Li + Li of conductivity 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) ceramic electrolyte synthesis and sintering ", journals of Alloys and Compounds, volume 818, 2020, 153237, ISSN 0925-8388, https:// doi.org/10.1016/j.java com 2019.153237; geng et al, "sintering atmosphere vs Li 0.5 La 0.5 TiO 3 Solid electrolyte ion conduction and structural influence ", materials Science and Engineering: volume 164, phase 2, 2009, pages 91-95, ISSN 0921-5107, https:// doi.org/10.1016/j.mseb.2009.07.011.
Despite this background, methods of sintering lithium-filled garnet in thin film or bilayer form, as well as methods using high throughput continuous sintering methods (e.g., roll-to-roll methods), have not been fully disclosed. Accordingly, there is a need in the relevant art for a high throughput continuous sintering process for making thin film lithium-stuffed garnet.
Disclosure of Invention
In one embodiment, the present application provides a continuous production line (CML) comprising a front roll, a rear roll (end roll), and at least one sealing oven between the front roll and the rear roll, the at least one sealing oven comprising: (a) a binder burn-out section; (b) a biscuit section; (c) a sintering section; further, the CML includes at least one atmosphere controller for controlling at least one condition of gas flow rate, flow direction, gas composition, pressure, and combinations thereof in the furnace.
In another embodiment, the present application provides a continuous production line (CML) comprising a front roll, a back roll, and at least one sealing oven between the front roll and the back roll, the at least one sealing oven comprising: (a) a binder burn-out section; (b) a green billet; (c) a sintering section; further, the CML includes at least one atmosphere controller for controlling at least one condition of gas flow rate, flow direction, gas composition, pressure, and combinations thereof in the furnace.
In yet another embodiment, the present application is directed to a continuous production line (CML) comprising a front roll, a back roll, and at least one sealed oven between the front roll and the back roll, and at least one atmosphere controller for controlling at least one condition of gas flow rate, flow direction, gas composition, pressure, and combinations thereof in the oven; the front roller is wound with a double layer, and the double layer comprises a metal layer and a green body layer.
In yet another embodiment, the present application provides a method of using a continuous production line comprising the operations of: (a) providing or having provided a CML as disclosed herein; (b) Moving the green body through the at least one furnace to sinter the green body, producing a sintered body; (c) winding the sintered body around a rear roller.
In some other embodiments, the present application contemplates sintered articles made by the methods of the present application.
In still other embodiments, the application contemplates rechargeable batteries made by the methods of the application.
Drawings
Fig. 1 shows an embodiment of a continuous production line.
Fig. 2 shows another embodiment of a continuous production line.
Fig. 3 shows an embodiment of a partially continuous production line.
Fig. 4 shows a cross-sectional Scanning Electron Microscope (SEM) image of a lithium-filled garnet sintering film on a metal foil. The scale bar is 40 μm.
Fig. 5 shows a top-down SEM image of a lithium-filled garnet sintered film. The scale bar is 10 μm.
Fig. 6 shows a ramp (ramp) and furnace/oven assembly of a continuous production line.
Fig. 7A illustrates a ramp assembly for a continuous line. Fig. 7B illustrates a ramp assembly for a continuous line.
FIG. 8 shows the grain size (μm, y-axis) and grain size (d) 10 、d 50 、d 90 、d 95 And d 99 ) Is a graph of the relationship of (1).
Fig. 9 shows a cross-sectional Scanning Electron Microscope (SEM) image of a lithium-filled garnet sintering film on a metal foil. The scale bar is 20 μm.
Fig. 10 shows a cross-sectional Scanning Electron Microscope (SEM) of a lithium-filled garnet sintering film on a metal foil. The scale bar is 50 μm.
Fig. 11 shows a top-down SEM image of a lithium-filled garnet sintered film. The scale bar is 10 μm.
Fig. 12 shows a curved ramp component of a continuous production line.
Fig. 13 shows another embodiment of a continuous production line.
Fig. 14 shows another embodiment of a continuous production line.
Fig. 15 shows a unwind roller (spreader) assembly of a continuous production line.
Fig. 16 shows a bilayer with a green body deposited in a die-coated manner (i.e., a die-coated tape).
Fig. 17 shows the belt in a horizontal treatment orientation.
Fig. 18 shows the belt in the shade processing direction.
Fig. 19 shows the tape in a vertical processing orientation.
Fig. 20 shows an example of a deceleration strip assembly for a curved runway on a continuous production line.
Fig. 21 shows a voltage versus run time graph.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the application and to incorporate it into the context of a particular application. Various modifications and various uses in different applications will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to a wide variety of embodiments. Thus, the present application is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the application. It will be apparent, however, to one skilled in the art that the application may be practiced without limitation to these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present disclosure.
All the features disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
Although shown in a horizontal form, in some examples, the continuous line in the present figures may be assembled in a vertical form, wherein the green tape or bilayer is moved in parallel or anti-parallel directions relative to the direct downward pulling force of gravity on the earth's surface. For example, in the case of a vertical version, the green tape or bilayer may be moved up or down (90 °; i.e. at right angles) relative to the ground surface during processing. Furthermore, there may be angles between the different ovens such that the green tape forms a curve away from the straight line during processing. The drawings in the present application are to be regarded as illustrative, non-restrictive examples of the application. Other configurations and arrangements of ovens and sintering lines are contemplated by the present application. In some configurations, the green tape moves parallel to gravity. For example, the green tape may hang like a curtain under gravity. In some configurations, the belt moves perpendicular to gravity; for example, the green tape may be moved in a direction parallel to the ground.
The movement of the green film through the CML described in the present application can be described in three dimensions, x, y and z. The x-direction and y-direction of the green film describe the length and width of the green film, and the z-direction describes the thickness of the green film. The film is moved in the x-dimension or film stock dimension as the green film passes through the CML or moves along the Machine (MD). The y-dimension describes the transverse dimension (or Cross Direction (CD)) in the same plane as the film. The z dimension is perpendicular to the membrane and describes the thickness of the membrane.
Described are an apparatus and a method for obtaining a high quality, fast-processing ceramic electrolyte membrane. Described herein is a high throughput continuous process for sintering thin film ceramics. Ceramics include, but are not limited to, lithium Aluminotitanophosphate (LATP), lithium-filled garnet oxides (e.g., li) 7 La 3 Zr 2 O 12 And Li (lithium) 7 La 3 Zr 2 O 12 Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Also known as LLZO), lithium lanthanum titanate, and Lithium Aluminum Germanium Phosphate (LAGP). In certain embodiments, the method includes a sintering step wherein the film (i.e., green film or green body on a bilayer, i.e., to be sintered into a film or into a bilayer) is not in contact with any surface during sintering. In some examples, when a bilayer is used, the metal layer may contact the surface, but the green body does not contact the surface of the CML during its passage through the one or more melters. The sintered ceramic membranes produced by the present method have unexpected advantageous properties, such as low flatness, due to the lack of contact with other surfaces during sintering. For lithium-filled garnet, CML has unexpected advantageous properties: a stoichiometric amount of lithium can be retained in a given LLZO formulation while having an advantageous LLZO microstructure (e.g., high density, small grain size, and combinations thereof). In some examples, the resulting material is free of surface defects because it does not contact other surfaces. In some examples, the bilayers made according to the present application have no surface defects on the ceramic side, as the green body is not in contact with other surfaces. In some examples, the resulting material does not present problems such as adhesion to a substrate, as it does not contact other surfaces. In addition, these sintered LLZO are prepared by a novel and rapid sintering process. The process produces a higher rate of production per unit volume of product than all known LLZO burns The fabrication process of the junction film is fast.
A. Definition of the definition
The term "about", when used herein, defines a value, such as about 15% w/w, includes the defined value, as well as ranges within + -10% of the defined 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 ℃ includes 75 ℃ and 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, or 83 ℃.
"selected from" as used herein is selected from the group consisting of a single member from the group, a plurality of members from the group, or a combination of members from the group. Members selected from A, B and C include, for example, a only, B only, or C only, and a and B, A and C, B and C, and A, B, C.
A "roll" as used herein refers to a rotatable cylinder or other shape over or on which an object moves, or is used to convey, move, press, shape, spread or smooth an object. The roller need not be a perfect mathematical cylinder. The roll may be of any shape and the tape or film may be passed over, around or wound around the roll. In some examples, the outer diameter of the roller is equal to or greater than 6cm. In some examples, the roll has a winding tension equal to or greater than 20 g/cm.
The "green body" as used herein is a material deposited from a slurry comprising a ceramic precursor and at least one selected from the group consisting of solvents, binders, dispersants, plasticizers, surfactants, or combinations thereof. The green body is referred to as a green body prior to being heated to remove the organic material (e.g., solvent, binder, dispersant, plasticizer, surfactant, or combinations thereof) or prior to sintering the ceramic components of the green body. The green body is prepared by depositing the slurry onto a substrate, and the preparing of the green body may also include drying the deposited slurry.
The term "bilayer" as used herein includes a green body deposited onto a metal layer. In some examples, the green body is continuous, while in other examples, the green body is deposited in the form of a platelet coating. After sintering, the thickness of the ceramic layer of the double layer can be 10-40 μm, and the thickness of the metal layer is 2-20 μm. The bilayer may have a ceramic layer thickness of 20-30 μm thick and a metal layer thickness of 3-10 μm.
The term "green film" or "green tape" as used herein refers to an unsintered tape or film comprising lithium-filled garnet, a precursor of lithium-filled garnet, or a combination thereof, and at least one of a binder, plasticizer, carbon, dispersant, solvent, or combination thereof. "green film tape" as used herein refers to a roll, continuous layer, or cut portion thereof of a green film (dry or non-dry) casting tape. The green body may be used interchangeably with green film or green tape. The green tape may also include green body platelets deposited on the metal layer (i.e., platelet coating on the metal layer).
The "front roll" as used herein refers to a roll that is positioned at the beginning of the CML and unwinds or winds up the unfired film.
The "back roll" as used herein refers to a roll that is positioned at the end of the CML and unwinds or winds up the sintered film.
The term "sintered article receiving device" as used herein refers to any device including, but not limited to, a back roll or any machine that cuts and stacks sintered films. An "oven" or "furnace" as used herein is a partially or completely enclosed compartment in which materials can be heated to a temperature above room temperature. For example, the oven may be heated up to 1,200 ℃. The binder burn-out oven is typically heated to below 750 ℃. The greenbody oven is typically heated to 600-900 ℃. The sintering oven is typically heated to 900 ℃ to 1,450 ℃. In some examples, at least one oven is enclosed in an atmosphere. In other examples, the CML is enclosed in an atmosphere. The oven and furnace are used interchangeably in the present application.
The term "atmosphere control" as used herein 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 enclosed space. Atmosphere control may be dynamic, i.e. the system responds to sensed conditions and adjusts the atmosphere so that certain predetermined conditions are more met. In this case, the atmosphere refers to a gaseous environment in direct contact with the green tape being heated, calcined, sintered or cooled; or a gaseous environment that directly contacts the sintering belt being heated, sintered, annealed, or cooled. In some examples described herein, atmosphere control includes controlling the flow rate of any one of the gas inlets of oxygen, argon, nitrogen, helium, and/or hydrogen. In some examples described herein, atmosphere control includes controlling the amount of water, oxygen, and lithium present in a gaseous state that is in direct contact with a green tape being heated, calcined, sintered, or cooled, or in direct contact with a sintered tape being heated, sintered, annealed, or cooled. Atmosphere control various gas curtains, gas densities, gas flow rates, gas flow directions or gas pulses may be used in/around and near the oven, the furnace, any inlet or outlet, and any holes where the green tape or sintered article enters/exits the oven or furnace. Atmosphere control may refer to systems that use nitrogen, argon, synthesis gas, dry air, or humidified air within an enclosed or closed space. Atmosphere control may refer to a system that applies a partial vacuum, for example when the pressure is less than atmospheric pressure.
As used herein, the term "gas curtain" refers to a defined gas flow rate at certain inlets or outlets of the oven (e.g., green tape inlet and sintered film outlet). For example, the gas flow rate may be between 1 and 50 liters/minute at standard pressure and temperature. For example, the gas flow rate may be greater than 50 liters/minute at standard pressure and temperature. The air curtain may have a pressure sensor at the outlet. The air curtain flows through the inlet or outlet of the oven to control the flow of air within the oven. The air curtain may help maintain a particular atmosphere within the oven by partially or completely preventing gases from exiting or entering the oven.
The "dry air" as used herein refers to air having a reduced humidity. Dry air may be supplied in the clean room. The dry air is characterized by a dew point below-20 ℃, below-30 ℃, below-40 ℃, below-50 ℃, below-60 ℃ or below-70 ℃.
The "solid separator" as referred to in the present application means Li which is substantially electrically insulating + Ion conductive materials (e.g., lithium ion conductivity is at least 10 of electron conductivity 3 Multiple, and typically 10 6 Multiple) and act as a physical barrier or separator between the positive and negative electrodes in an electrochemical cell.
"annealing" as used herein refers to heating a material in a controlled atmosphere, such as dry air or argon, for example from 100 ℃ to 1400 ℃, or such as 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, or 1450 ℃. Some exemplary annealing methods can be found in U.S. patent No.9,966,630B2, which is incorporated by reference herein in its entirety for all purposes.
Unless stated to the contrary, the specific area resistance (ASR) described in the present application is measured by electrochemical cycling using an Arbin or biological instrument. ASR is calculated by measuring the voltage drop av in response to a current interruption of 30-180 seconds, ASR = av/J, where J is in a/cm 2 Current density in units.
The ionic conductivity described in the present application is measured by electrical impedance spectroscopy methods known in the art.
As used herein, "ambient conditions" refers to room temperature and natural atmosphere, e.g., including about 78% N 2 And 21% O 2 Is the earth atmosphere; and/or moisture is also present. Ambient conditions include standard temperature and pressure, and a relative humidity of at least 1%.
The "electrolyte" as used herein refers to an ion-conductive and electrically insulating material. The electrolyte serves to electrically insulate the positive and negative electrodes of the rechargeable battery while allowing ions (e.g., li + ) Through electrolyte conduction.
The term "film" or "thin film" as used herein refers to a film having a thickness of less than 0.5mm and a thickness of more than 10 nm. The transverse dimension of the film is greater than 5mm. "films" or "films" may be produced by continuous processes such as tape casting, spraying or slip casting. In some examples, the production may include a batch process. In some examples, the producing may include screen printing.
The "film thickness" as used herein refers to the distance between the top and bottom surfaces of the film or the median measured distance. The top and bottom surfaces as used herein refer to the sides of the film having the greatest surface area. The thickness described in the present application is measured by a cross-sectional scanning electron microscope.
"pellet" as used herein refers to any small unit of any of a variety of shapes and sizes, such as cylindrical, rectangular or spherical, formed by compression of a bulk material. The compressed material is disc-shaped, with a diameter of 0.5-20 cm and a height of 0.5 mm-2 cm. Typically, the compressed material is disc-shaped, 10mm in diameter and 1mm in height. The pellets may also contain additional reagents to aid in bonding the material compressed into the pellets. In some examples, these additional agents are referred to as binders, including, but not limited to, polymers such as polyethylene oxide. In some examples, polyvinyl butyral is used as the binder. Pellets are typically made by extruding a powder material in an extruder. The powder materials are made to adhere to each other by extrusion and the densification is increased relative to the powder materials before extrusion. In some cases, the powder material is heated and/or an electrical current is passed through the powder material during extrusion.
As used herein, "compressed pellets" refers to pellets that have been further compressed by compression (e.g., 5000 PSI).
By "adhesive" as used herein is meant a polymer having the ability to increase the adhesion and/or polymerization of materials such as solids in green tape. Suitable binders include, but are not limited to, PVDF-HFP, SBR, and ethylene alpha-olefin copolymers. By "adhesive" is meant a material that aids in the adhesion of another material. For example, the polyvinyl butyral described in the present application is an adhesive because it can be used to adhere garnet materials. Other adhesives may include polycarbonate. Other binders may include polyacrylates and polymethacrylates. These examples of adhesives are not limiting to the full scope of adhesives contemplated by the present application, but are intended to be exemplary only. Adhesives useful 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), polyolefin, 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, and the like. In some examples, including any of the preceding examples, the binder is selected from the following polymers: polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (pmma), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly (allyl glycidyl ether) (PEO-AGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-mege), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly (allyl glycidyl ether) (PEO-mege-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), polyisoprene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR) and polyethyl acrylate (PEA).
The solvents used in the present application are selected from alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, and other classes of organic solvents such as ethers and aromatic solvents including, but not limited to, dibutyl ether, diethyl ether, diisopropyl ether, dimethoxy ethane, diethoxy ethane, tetrahydrofuran, toluene, xylene, toluene: ethanol, acetone, N-methyl-2-pyrrolidone (NMP), diacetone alcohol, ethyl acetate, acetonitrile, hexane, nonane, dodecane, and Methyl Ethyl Ketone (MEK).
In some examples, the dispersant used is selected from fish oil, mehaden Blown Fish Oil, mineral oil, phosphate esters, rhodoline TM Rhodline 4160, phosphine-131 TM 、BYK TM 22124、BYK-22146 TM 、Hypermer KD1 TM 、Hypermer KD6 TM And Hypermer KD7 TM 。
"casting film" as used herein refers to the process of delivering or transferring a liquid or slurry to a mold or substrate such that the liquid or slurry forms a film. Casting may be accomplished by doctor blades, meyer bars, comma coaters, gravure coaters, micro-gravure, reverse comma coaters, slot die, slip and/or tape casting, among other methods.
"high throughput continuous" as used herein refers to roll-to-roll processes as well as roll-to-sheet processes. Some roll-to-sheet processes have one roll at the beginning of the process, but at the end, the sintered film is cut at the exit instead of being rolled into a finished product.
The "lithium-filled garnet" as referred to in the present application means an oxide having a crystal structure related to the garnet crystal structure. The lithium filled garnet includes a material having the formula Li A La B Zr C O F 、Li A La B M' CM ” D Ta E O F Or Li (lithium) A La B M' CM ” D Nb E O F Of (2), wherein 4<A<8.5、1.5<B<4、0<C≤2、0<D<2;0 < E < 2.5, 10 < F < 13, and M' are in each case independently selected from Al, mo, W, nb, ga, sb, ca, ba, sr, ce, hf, rb and Ta; or Li (lithium) a La b Zr c Al d Me” e O f Wherein a is more than 5 and less than 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. Garnet used in the present application also includes those doped with Al or Al 2 O 3 The garnet of (2) above. In addition, garnet materials useful in the present application include, but are not limited to, li A La B Zr C O F +yAl 2 O 3 Wherein x is 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. Furthermore, the applicationGarnet used includes but is not limited to Li x La 3 Zr 2 O 12 +yAl 2 O 3 Wherein x is 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 garnet described in the present application does not include YAG-garnet (i.e. yttrium aluminum garnet, or e.g. Y 3 Al 5 O 12 ). Garnet does not include silicate-based garnet such as magnesia-alumina garnet, iron-alumina garnet, manganese-alumina garnet, lime-alumina garnet, gold-alumina garnet or cinnamon garnet, sha Fulai garnet, lime-chromite and lime-iron garnet, and solid solution magnesia-alumina garnet-manganese-alumina garnet and lime-chromite-lime garnet. Garnet according to the application does not include garnet having the general formula X 3 Y 2 (SiO 4 ) 3 Wherein X is Ca, mg, fe and/or Mn; y is Al, fe, and/or Cr.
The "garnet precursor chemical species" or "chemical precursor of garnet-type electrolyte" in the present application refers to chemical species that react to form the lithium-filled garnet material of the present application. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., liOH), lithium oxide (e.g., li) 2 O), lithium carbonate (e.g. Li 2 CO 3 ) Zirconia (e.g. ZrO 2 ) Lanthanum oxide (e.g. La 2 O 3 ) Alumina (e.g. Al 2 O 3 ) Aluminum (e.g., al), aluminum nitrate (e.g., alNO) 3 ) Aluminum nitrate nonahydrate, niobium oxide (e.g. Nb) 2 O 5 ) Tantalum oxide (e.g. Ta 2 O 5 )。
"d" as described in the present application 50 Diameter "refers to the median size in a size distribution measured by microscopy or other particle size analysis techniques such as, but not limited to, scanning electron microscopy or dynamic light scattering. D (D) 50 Can be characterized as "number D 50 Or volume D 50 ", wherein" number D 50 "means that 50% of the particles have a smaller diameter," volume D 50 "is the diameter at which 50% of the smallest particle volume has a smaller diameter. D in the present application unless otherwise specified 50 Refers to the volume D 50 I.e. 50% by volume of particlesFeature sizes smaller than the dimensions.
"d" as described in the present application 90 Diameter "refers to the dimension 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. D (D) 90 Meaning that 90% by volume of the particles are smaller than the characteristic size of the size.
The term "flatness" of a surface as used herein refers to the maximum normal distance between the lowest point on the surface and a plane containing the three highest points on the surface, or the maximum normal distance between the highest point on the surface and a plane containing the three lowest points on the surface. It can be measured using Atomic Force Microscopy (AFM), high precision optical microscopy, or surface laser interference height mapping.
B. Continuous line (CML) apparatus or plant
In some embodiments, the application provides a continuous production line (CML) comprising: a front roller; a rear roller; and at least one sealing oven between the front roll and the rear roll, the at least one furnace comprising: (a) a binder burn-out section; (b) a green billet; (c) a sintering section; and at least one atmosphere controller for controlling at least one condition of gas flow rate, flow direction, gas composition, pressure, and combinations thereof within the furnace. In some examples, at least one atmosphere controller controls the gas flow rate in at least one furnace. In some examples, at least one atmosphere controller controls the direction of flow in at least one furnace. In some examples, at least one atmosphere controller controls the composition of gases in at least one furnace. In some examples, at least one atmosphere controller controls pressure in at least one furnace. In some examples, at least one atmosphere controller controls a combination of gas flow rate, flow direction, gas composition, and pressure in at least one furnace.
The batch process for making ceramic membranes may be a process in which the membranes are produced in groups or batches rather than in a continuous manner. A discontinuous amount of film or product may come from a batch process. Batch processes for ceramic membrane production include the use of shims or shim plate stacks. In contrast, a continuous process can produce a certain amount of product or film without any time interruption during the process. Continuous processes have many advantages, such as time and cost savings.
In some examples, including any of the preceding, the CML comprises a bilayer comprising a metal layer and a green layer wound on a front roll. In certain examples, the green body is a continuous layer deposited on the metal layer. In certain other examples, the green body is a platelet or discontinuous layer deposited on the metal layer. In some examples, the CML includes a roll of metal on a front roll that forms a bilayer when the metal is unwound from the front roll while casting a green body onto the metal layer. In some examples, after the bilayer is formed as described herein, it is passed to the binder burn-out section as it moves through the CML.
In some embodiments, the application provides a continuous production line (CML) comprising: a front roller having a bilayer wound thereon, wherein the bilayer comprises a metal layer and a green layer; a rear roller; at least one melting furnace between the front roller and the rear roller; and at least one atmosphere controller that controls at least one condition of gas flow rate, flow direction, gas composition, pressure, and combinations thereof within the furnace.
In some examples, including any of the preceding, the green layer comprises unsintered lithium-filled garnet.
In some examples, including any of the preceding examples, the green layer comprises a chemical precursor of lithium-stuffed garnet.
In some examples, including any of the above, the at least one furnace comprises: (a) a binder burn-out section; (b) a green billet; (c) a sintering section.
In some examples, including any of the above, the at least one furnace comprises: a single furnace having a cooling section, a binder burn-out section; a green billet; the sintering section is followed by another cooling section. In some examples, there is an additional cooling section between the binder burn-out section and the green section or between the green section and the sintering section.
In some examples, including any of the preceding examples, the sintered segment is not directly exposed to the earth atmosphere. This means a sintered segmentHaving a different atmosphere than the earth (e.g. 78% N 2 、21％O 2 ) Is in contact with the membrane or bilayer portions that are sintered inside the sintering section. In contrast, in the sintering section, the gas contacting the film or bilayer being sintered is an inert gas or a reducing gas, e.g. Ar, N 2 、H 2 Or a combination thereof. This can be achieved by sealing the sintered section (partially or completely) in a way that isolates it from the earth atmosphere. This can be achieved by flowing gas into or out of the sintering section to isolate it from the earth atmosphere. This can be achieved by placing the sintering section in a space filled with an inert gas or a reducing gas.
In some examples, including any of the preceding examples, the at least one furnace is not directly exposed to the earth's atmosphere. This means that the at least one furnace has a different atmosphere (e.g., 78% N) 2 、21％O 2 ) Is in contact with the portion of the film or bilayer being sintered inside the at least one furnace. In contrast, in at least one furnace, the gas contacting the sintered film or bilayer is an inert gas or a reducing gas, e.g. Ar, N 2 、H 2 Or a combination thereof. This may be achieved by sealing at least one furnace from the earth atmosphere. This may be achieved by flowing gas into or out of at least one furnace, isolating it from the earth's atmosphere. This may be achieved by placing at least one furnace in a space filled with an inert gas or a reducing gas.
In some examples, including any of the above, sealing the at least one furnace such that the at least one atmosphere controller controls gas flow into and out of the at least one furnace.
In some examples, including any of the foregoing, the flow rate in the binder burn-out section is higher than the flow rate in the green section, higher than the flow rate in the sinter section, or both.
In some examples, including any of the preceding examples, the atmosphere controller maintains continuous atmosphere conditions inside the at least one furnace.
In some examples, including any of the preceding examples, the atmosphere controller maintains continuous atmosphere conditions within the binder burn-out section.
In some examples, including any of the preceding examples, the atmosphere controller maintains continuous atmosphere conditions inside the green compact.
In some examples, including any of the preceding, the atmosphere controller maintains continuous atmosphere conditions within the sintering section.
In some examples, including any of the preceding examples, the CML includes at least one gas curtain coupled to at least one furnace.
In some examples, including any of the above, the CML includes an air curtain at the inlet of the at least one furnace. In some examples, a dynamic barrier is created to move the gas flow laterally relative to the gas curtain gas flow to reduce the gas flow into or out of the furnace.
In some examples, including any of the above, the CML comprises an air curtain at the outlet of the at least one furnace. In some examples, a dynamic barrier is created to move the gas flow laterally relative to the gas curtain gas flow to reduce the gas flow into or out of the furnace.
In some examples, including any of the preceding examples, the CML includes a pressurized gas line between the green compact and the sintering section through which gas is pumped into the green compact and the sintering section. In some examples, gas flows into at least one furnace between the green compact and the sintering section and is directed into the green compact and the sintering section. In some examples, the gas flow is assisted by a vacuum pump connected to the sintering section. In some examples, the gas flow is assisted by a vacuum pump connected to the green compact.
If the atmosphere controller does not control the atmosphere in at least one of the furnaces, the ceramic surface of the bilayer will include a defect layer of lithium-filled garnet. For example, a bilayer ceramic surface may have Li thereon 2 CO 3 A layer. This is one benefit of using the atmosphere controller of the present application.
In some examples, including any of the preceding examples, the CML includes a vent located on the binder burn-out section, the green body section, the sintering section, or a combination thereof. In some examples, the CML is configured to expel as much air as possible from the binder burn-out stage such that volatile materials and combustion residues that may be present in the binder burn-out stage are rapidly removed from the at least one furnace and do not deposit onto the bilayer.
In some examples, including any of the preceding examples, the at least one furnace is enclosed in a sealed container.
In some examples, including any of the preceding, the CML is enclosed in a sealed space.
In some examples, including any of the preceding examples, the adhesive burn-out segment is enclosed in a sealed container.
In some examples, including any of the preceding, the greenbody segments are enclosed in a sealed container.
In some examples, including any of the preceding examples, the sintered segment is enclosed in a sealed container.
In some examples, including any of the preceding examples, the sealed container comprises Ar, N 2 、H 2 O、H 2 Or a combination thereof.
In some examples, including any of the preceding examples, the atmosphere controller maintains a reducing atmosphere in the green compact.
In some examples, including any of the preceding, the atmosphere controller maintains argon (Ar), nitrogen (N) 2 ) Hydrogen (H) 2 ) A gas or mixture thereof.
In some examples, including any of the preceding, the atmosphere controller maintains a reducing atmosphere in the sintering section.
In some examples, including any of the preceding, the atmosphere controller maintains argon (Ar), nitrogen (N) in the sintering zone 2 ) Hydrogen (H) 2 ) A gas or mixture thereof.
In some examples, including any of the preceding examples, the atmosphere controller maintains a composition comprising less than 500ppm O in the green body section, the sinter section, or both the green body section and the sinter section 2 Is a gas atmosphere of (a).
In some examplesIncluding any of the preceding examples, the atmosphere controller maintains less than 400ppm O in the green body section, the sinter section, or both the green body section and the sinter section 2 Is a gas atmosphere of (a).
Maintaining less than 300ppm O in the green body section, the sinter section, or both the green body section and the sinter section 2 Is a gas atmosphere of (a).
In some examples, including any of the preceding examples, the atmosphere controller maintains less than 200ppm O in the green section, the sinter section, or both the green section and the sinter section 2 Is a gas atmosphere of (a).
In some examples, including any of the preceding examples, the atmosphere controller maintains less than 100ppm O in the green section, the sinter section, or both the green section and the sinter section 2 Is a gas atmosphere of (a).
In some examples, including any of the preceding examples, the atmosphere controller maintains less than 10ppm O in the green section, the sinter section, or both the green section and the sinter section 2 Is a gas atmosphere of (a).
In some examples, including any of the preceding examples, the atmosphere controller is maintained at less than 5% v/v H in the binder burn-out section 2 O atmosphere.
In some examples, including any of the preceding examples, H 2 The gas is present at about 1, 2, 3, 4 or 5% v/v.
In some examples, including any of the preceding examples, H 2 The gas is present at about 2.9% v/v.
In some examples, including any of the preceding examples, H 2 The gas is present at about 5% v/v.
In some examples, including any of the preceding examples, the at least one furnace or portion thereof is under vacuum at a pressure of less than 1 atmosphere (atm).
In some examples, including any of the preceding examples, the at least one furnace or portion thereof is under vacuum at a pressure of less than 100 torr.
In some instances herein, at least one furnace is evacuated to a low vacuum to evacuate the air from its interior, which is then backfilled with an inert or reducing gas. For example, the at least one melting furnace may be N 2 And (5) backfilling. Example(s)For example, the at least one furnace may be operated with Ar/H 2 And (5) backfilling. For example, the at least one furnace may be backfilled with Ar.
In some examples, including any of the preceding examples, the atmosphere in the binder burn-out section is different than the atmosphere in the green compact section.
In some examples, including any of the preceding examples, the atmosphere in the binder burn-out section is different than the atmosphere in the sintering section.
In some examples, including any of the preceding examples, the atmosphere in the green stage is different than the atmosphere in the sintering stage.
In some examples, including any of the preceding examples, O in the binder burn-out section 2 The amount of (2) is less than 0.2% by volume.
In some examples, including any of the preceding examples, the CO in the binder burn-out section 2 The amount of (2) is less than 0.2% by volume.
In some examples, including any of the preceding examples, the sintering stage is from CO 2 The amount of carbon is less than 100 parts per million (ppm).
In some examples, including any of the preceding examples, the sintering stage is from CO 2 The amount of carbon is about 50ppm to 100ppm.
In some examples, including any of the preceding, the bilayer shrinks primarily in the z-direction as it moves through the sintering section. The z-direction is the direction perpendicular to the bilayer surface; the x-direction is the direction in which the bilayer moves across the CML; the y-direction is perpendicular to the x-direction and in the same plane as the bilayer; the z-direction is perpendicular to the x-direction and the y-direction.
In some examples, including any of the preceding, the CML is configured to heat the bilayer at a rate greater than 2.5 ℃/minute.
In some examples, including any of the preceding examples, the CML is configured to heat the bilayer at a rate greater than 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, 25 ℃/min, 30 ℃/min, 35 ℃/min, 40 ℃/min, 45 ℃/min, 50 ℃/min, 55 ℃/min, 60 ℃/min, 65 ℃/min, 70 ℃/min, 75 ℃/min, 80 ℃/min, 85 ℃/min, 90 ℃/min, 100 ℃/min, 200 ℃/min, or 300 ℃/min.
In some examples, including any of the preceding examples, the CML is configured to heat the bilayer at a rate of about 5 ℃/minute to about 50 ℃/minute. If the bilayer heats too slowly, the material may not be properly dense. Slowing the heating rate can cause premature necking of the ceramic particles in the bilayer.
In some examples, including any of the preceding, the CML includes an infrared heater for heating the bilayer.
In some examples, including any of the preceding examples, the CML comprises an induction carbon plate heater. In some examples, the carbon plate does not contact the green body. In some examples, the carbon plate does not contact the bilayer.
In some examples, including any of the preceding examples, the CML uses carbon sheet/induction heating to heat the bilayer.
In some examples, including any of the preceding, the CML includes heating the bilayer based on lamp heating.
In some examples, including any of the preceding, the CML comprises oven-based heating.
According to an embodiment, the heating element used in the present application may be a carbon plate or a carbon paper. In some examples, the carbon sheet or carbon paper comprises conductive carbon. According to an embodiment, the heating element may be a molybdenum plate or molybdenum paper. In some examples, the molybdenum plate or molybdenum paper comprises conductive molybdenum. An electric current may be applied to heat the conductive carbon sheet or conductive carbon paper element at a suitable rate to sinter within the temperature ranges described herein.
In one embodiment, the heating element is 1 to 200mm from the material to be sintered. In one embodiment, the heating element is 1 to 190mm from the material to be sintered. In one embodiment, the heating element is 1 to 180mm from the material to be sintered. In one embodiment, the heating element is 1 to 170mm from the material to be sintered. In one embodiment, the heating element is 1 to 160mm from the material to be sintered. In one embodiment, the heating element is 1 to 150mm from the material to be sintered. In one embodiment, the heating element is 1 to 140mm from the material to be sintered. In one embodiment, the heating element is 1 to 130mm from the material to be sintered. In one embodiment, the heating element is 1 to 120mm from the material to be sintered. In one embodiment, the heating element is 1 to 110mm from the material to be sintered. In one embodiment, the heating element is 1 to 100mm from the material to be sintered. In one embodiment, the heating element is 1 to 90mm from the material to be sintered. In one embodiment, the heating element is 1 to 80mm from the material to be sintered. In one embodiment, the heating element is 1 to 70mm from the material to be sintered. In one embodiment, the heating element is 1 to 60mm from the material to be sintered. In one embodiment, the heating element is 1 to 50mm from the material to be sintered. In one embodiment, the heating element is 1 to 40mm from the material to be sintered. In one embodiment, the heating element is 1 to 30mm from the material to be sintered. In one embodiment, the heating element is 1 to 20mm from the material to be sintered. In one embodiment, the heating element is 1 to 10mm from the material to be sintered.
In one embodiment, the heating temperature is in the range of 900 ℃ to 2000 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1900 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1800 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1800 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1700 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1600 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1500 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1400 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1300 ℃. In one embodiment, the heating temperature is in the range of 900 ℃ to 1200 ℃.
In one embodiment, the heating time is in the range of 5 seconds to 30 minutes. In one embodiment, the heating time is in the range of 5 seconds to 25 minutes. In one embodiment, the heating time is in the range of 5 seconds to 20 minutes. In one embodiment, the heating time is in the range of 5 seconds to 15 minutes. In one embodiment, the heating time is in the range of 5 seconds to 10 minutes. In one embodiment, the heating time is in the range of 5 seconds to 5 minutes. In one embodiment, the heating time is in the range of 5 seconds to 4 minutes. In one embodiment, the heating time is in the range of 5 seconds to 3 minutes. In one embodiment, the heating time is in the range of 5 seconds to 4 minutes. In one embodiment, the heating time is in the range of 5 seconds to 1 minute.
In some examples, the heating element may have the same area as the material to be heated. In some examples, the heating element may be longer than and as wide as the material to be heated. In some examples, the heating element may be the same length as the material to be heated and wider than the material to be heated. In some examples, the heating element may be shorter than the material to be heated. In embodiments where a single heating element is present, the heating element may have any of the aforementioned area relationships with the material being heated.
In some examples, including any of the preceding examples, the CML is provided with a cooling zone after the sintering section. For example, in a 60 inch furnace, there is a 20 inch hot zone with two 20 inch cooling zones before and after the hot zone.
In some examples, the at least one furnace has a gap of 1mm above the green body. In some examples, the at least one furnace has a gap of 2mm above the green body. In some examples, the at least one furnace has a gap of 3mm above the green body. In some examples, the at least one furnace has a gap of 4mm above the green body. In some examples, the at least one furnace has a gap of 5mm above the green body. The gap prevents lithium from escaping from the green body.
In some examples, including any of the preceding examples, the CML is configured to reduce or eliminate cross-web wrinkles (e.g., as shown in fig. 15) by applying an appropriate tension.
In some examples, including any of the preceding examples, the CML is configured to use rollers at the inlet or outlet of the at least one furnace to reduce or eliminate lateral wrinkles (e.g., as shown in fig. 15). A slide roller, drive roller, underdrive roller, or other roller may be used.
In some examples, including any of the preceding, the CML is configured such that the residence time in the sintering section is two minutes or less.
In some examples, including any of the preceding, the CML is configured such that the residence time in the sintering section is one minute, thirty seconds, or less.
In some examples, including any of the preceding, the CML is configured such that the residence time in the sintering section is one minute or less.
In some examples, including any of the preceding, the CML is configured such that the residence time in the sintering section is about thirty seconds or less.
In some examples, including any of the preceding examples, the CML is configured such that the residence time in the sintering section is about thirty seconds.
In some examples, including any of the preceding examples, the CML is configured such that the residence time in the binder burn-out section is about ten times the residence time in the sintering section.
In some examples, including any of the preceding examples, the CML includes at least one tension adjuster.
In some examples, including any of the preceding examples, the double layer tension after the front roller is 270g.
In some examples, including any of the preceding, the double layer tension before the back roller is 500g.
In some examples, including any of the preceding, the width of the bilayer is 8cm.
In some examples, including any of the preceding, the bilayer has a tension of about 34g/cm.
In some examples, including any of the preceding examples, the bilayer has a tension of about 35N/10 μm.
In some examples, including any of the preceding, the tensile force of the bilayer is less than 50% of its yield strength.
In some examples, including any of the preceding examples, the tensile force of the bilayer is less than 50% of the yield strength of the metal layer.
In some examples, including any of the preceding examples, the tensile force of the bilayer is about 25% to 50% of its yield strength.
In some examples, including any of the preceding examples, the tensile force of the bilayer is about 25% to 50% of the yield strength of the metal layer.
In some examples, including any of the preceding, the green body is green tape.
In some examples, including any of the preceding examples, the green body is a green tape of platelets. By platelet coating is meant that the green body is not continuously deposited on the metal layer. Platelet coating refers to depositing a green body on a metal layer at intervals. The metal layer may be scored or partially cut between the dies. The metal between the tabs may be used as lugs in the battery cell, for example, fig. 16 shows a tab coating.
Referring to fig. 16, the metal layer is spread under the slot die. The slot die applies rectangular die coating onto the metal layer, which results in intermittent application with an uncoated metal layer surface between the rectangular die coating. The arrow and label "web direction" refer to the direction in which the metal layer expands and passes under the slot die. When a die coating is employed, the front roll in the CML may have only a rolled metal foil roll, thereby forming a bilayer as the metal foil roll unrolls from the front roll, passes under the slot die, and into the adhesive burn-out section. In some other embodiments, the front roll has a double layer wound roll with a metal foil having a die coating thereon, the metal foil and die coating being wound together on the front roll.
In some examples, including any of the preceding examples, the bilayer is oriented for horizontal processing as the bilayer moves through the CML. Horizontal processing refers to the bilayer moving through the CML such that the metal layer moves parallel to the ground and below the green layer. Fig. 17 shows an example of a horizontal processing orientation. As shown in FIG. 17, tape 1701 is moved horizontally from position 1702 to position 1703 over the top portion of CML 1702. Before position 1702 and after position 1703, the belt rotates and moves vertically.
In some examples, including any of the preceding examples, the bilayer is oriented for curtain treatment as the bilayer moves through the CML. Curtain treatment means turning over the edges of the bilayer so that both the metal layer and the green layer move parallel to the ground but the metal layer is not under the green layer; instead, the metal layer and the green layer are side-by-side. Curtain treatment is advantageous in preventing chips from falling onto the upper surface of the green body. Curtain treatment is advantageous in preventing double layer sagging. Fig. 18 shows an example of a curtain treatment orientation. As shown in fig. 18, the belt 1801 moves through the CML 1802 in the shade processing direction.
In some examples, including any of the preceding examples, the bilayer is oriented for vertical processing as the bilayer moves through the CML. Perpendicular processing refers to the movement of the bilayer parallel or anti-parallel to the earth's gravity. Fig. 19 shows an example for vertical processing orientation. As shown in fig. 19, the belt 1901 moves through the CML 1902 in the vertical process direction. Fig. 19 also shows a nitrogen line 1903 that serves as a curtain or air knife.
In some examples, including any of the preceding, the CML includes an intermediate roll after the binder burn-out section, upon which the bilayer is wound as it moves through the CML.
In some examples, including any of the preceding examples, the bilayer on the intermediate roll does not include a binder in the green body.
In some examples, including any of the preceding examples, the at least one furnace has a green tape inlet.
In some examples, including any of the preceding examples, the double-layered metal layer is selected from nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.
In some examples, including any of the preceding examples, the double metal layer is an alloy of Fe and Ni.
In some examples, including any of the preceding examples, the double metal layer is an alloy of Fe and Ni, the amount of Fe being 1% to 25% (w/w), the remainder being Ni.
In some examples, including any of the preceding examples, the bilayer metal layer has a thickness of 1 μm to 20 μm.
In some examples, including any of the preceding examples, the thickness of the metal layer of the bilayer is from 1 μm to 10 μm.
In some examples, including any of the preceding examples, the thickness of the metal layer of the bilayer is from 5 μm to 10 μm.
In some examples, including any of the preceding examples, the bilayer is free of air bearing support as it moves through the CML.
In some examples, including any of the examples previously described, the bilayer is suspended (suspended) as it moves through the CML.
In some examples, including any of the preceding, the bilayer is suspended as it moves through the binder burn-out section.
In some examples, including any of the preceding, the bilayer is suspended as it moves through the green compact.
In some examples, including any of the preceding, the bilayer is suspended as it moves through sintering.
In some examples, including any of the preceding examples, the binder burn-out stage is a binder burn-out oven.
In some examples, including any of the preceding examples, the binder burn-out furnace is a furnace that can be heated to a temperature sufficient to volatilize, pyrolyse, burn, or decompose the binder in the green body.
In some examples, including any of the preceding examples, the temperature in the binder burn-out oven is between 80 ℃ and 500 ℃.
In some examples, including any of the preceding examples, the temperature in the binder burn-out oven is between 100 ℃ and 500 ℃.
In some examples, including any of the preceding examples, the temperature in the binder burn-out oven is between 80 ℃ and 800 ℃.
In some embodiments, including any preceding embodiment, the binder burn-out furnace comprises oxygen. In some of these examples, the sintering furnace does not contain oxygen.
In some examples, including any preceding example, the greenware section is a greenware oven.
In some examples, including any of the preceding examples, the green body furnace is a furnace that heats the green body to a temperature sufficient to form it into a green body after binder removal.
In some examples, including any of the preceding examples, the temperature in the greenbody oven is between 100 ℃ and 800 ℃.
In some examples, including any of the preceding examples, the sintering section is a sintering furnace.
In some examples, including any of the preceding examples, the sintering furnace is a furnace heated to a temperature sufficient to sinter the green body.
In some examples, including any of the preceding examples, the sintering furnace is a furnace heated to a temperature sufficient to sinter the lithium-stuffed garnet.
In some examples, including any of the preceding examples, the temperature in the sintering furnace is between 500 ℃ and 1300 ℃.
In some examples, including any of the preceding examples, the temperature in the sintering furnace is between 1000 ℃ and 1300 ℃.
In some examples, including any of the preceding examples, the temperature in the sintering furnace is between 1100 ℃ and 1300 ℃.
In some examples, including any of the preceding examples, the binder burn-out furnace is hermetically coupled to the green body furnace, and the green body furnace is hermetically sealed to the sintering furnace.
In some examples, including any of the preceding examples, the at least one furnace is a single furnace.
In some examples, including any of the preceding examples, the at least one back roller has a roller diameter greater than 4 cm.
In some examples, including any of the preceding examples, the at least one back roller has a roller diameter greater than 5 cm.
In some examples, including any of the preceding examples, the at least one back roller has a roller diameter greater than 6 cm.
In some examples, including any of the preceding examples, the at least one back roller has a roller diameter greater than 7 cm.
In some examples, including any of the preceding examples, the at least one back roller has a roller diameter greater than 8 cm.
In some examples, including any of the preceding examples, the at least one back roller has a winding tension greater than 20 g/linear cm.
In some examples, including any of the preceding examples, the air spaces above and below the bilayer are configured to maintain a lithium-rich atmosphere in contact with the sintered film.
In some examples, including any of the preceding examples, the air space above and below the bilayer is configured to hold at least 95 wt% lithium in the lithium-stuffed garnet.
In some examples, including any of the preceding examples, the CML includes at least two back rollers.
In some examples, including any of the preceding examples, the green body comprises unsintered lithium-filled garnet or a chemical precursor of lithium-filled garnet.
In some examples, including any of the preceding examples, the CML comprises a sintered bilayer wound on the at least one rear roller.
In some examples, including any of the preceding, the sintered bilayer comprises a sintered lithium-stuffed garnet.
In some examples, including any of the preceding examples, the green body comprises a binder.
In some examples, including any of the preceding examples, the green body comprises a dispersant.
In some examples, including any of the preceding, the green body comprises a solvent or a combination of solvents.
In some examples, including any of the preceding examples, the CML is configured to move the bilayer through the at least one furnace at a rate of at least 2 inches/minute.
In some examples, including any of the preceding, the CML is configured to move the bilayer through the sintering section at a rate of at least 2 inches/minute.
In some examples, including any of the examples above, the CML includes a curved ramp (curved ramp) prior to the at least one furnace.
In some examples, including any of the preceding, the CML includes a curved ramp prior to the binder burn-out section.
In some examples, including any of the preceding, the CML includes a curved ramp prior to the green billet.
In some examples, including any of the preceding, the CML includes a curved ramp prior to the sintering section.
In some examples, including any of the above, the CML includes a curved ramp inside the at least one furnace.
In some examples, including any of the preceding, the CML includes a curved ramp inside the binder burn-out section.
In some examples, including any of the preceding, the CML includes a curved ramp inside the green billet.
In some examples, including any of the preceding, the CML includes a curved ramp inside the sintered segment.
In some examples, including any of the preceding examples, the curved ramp has a coating thereon.
In some examples, including any of the preceding, the coating is a lithium aluminate coating.
In some examples, including any of the preceding, the coating is a boron nitride coating.
In some examples, including any of the preceding examples, the curved ramp upper surface is made of ceramic.
In some examples, including any of the preceding examples, the ceramic is silicon carbide, boron nitride, aluminum oxide, zirconium oxide, lithium aluminate.
In some examples, including any of the preceding examples, the ramp is made of SS 430, SS 304, kovar, invar, haynes, greater than 99.5% (w/w) alumina, carbon composite, boron nitride, or a combination thereof.
In some examples, including any of the preceding, the CML includes a deceleration strip over which the bilayer passes as the bilayer moves past the CML. Fig. 20 shows a deceleration strip 2001, with the strip 2002 being tensioned over the deceleration strip 2001 as the strip 2002 moves across the curved runway 2003.
In some examples, the speed bump is disposed on a runway (runway). In some examples, the speed bump is disposed on a flat runway. In some examples, the speed bump is disposed on a curved runway. These bumps break the stress of the metal layer that continuously contacts the racetrack. These bumps form "airspace" as the film rises and passes over the "deceleration strip". In some examples, there is a deceleration strip on the runway that is spaced about 1 inch from the next deceleration strip. In some examples, there is a speed bump on the runway that is spaced about 2 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 3 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 4 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 5 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 6 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 7 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 8 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 9 inches from the next speed bump. In some examples, there is a speed bump on the runway that is spaced about 10 inches from the next speed bump.
In some examples, the CML includes a curved racetrack that curves in the lateral direction. Similar to a bicycle tire, wherein the tire is curved in the y-direction and the x-direction. This curved track helps to reduce double layer wrinkling. The metal foil may expand as it passes through the CML, which bending allows the metal to expand and disengage from the CML track.
In some examples, including any of the preceding examples, the CML includes at least one curved runway.
In some examples, including any of the examples above, the CML includes at least one curved runway that curves in the y and x directions.
In some examples, including any of the preceding examples, the racetrack is made of SS 430, SS 304, kovar, invar, haynes, greater than 99.5% (w/w) alumina, carbon-carbon composite, boron nitride, or a combination thereof.
In some examples, the racetrack is made of a woven carbon-carbon composite material. In some examples, a runway made of woven carbon-carbon composite is used only on the hot portion of the CML over which the belt can move. In some other examples, the entire runway or the surface of the entire runway of the CML is a braided carbon-carbon composite.
An exemplary continuous production line (100) is shown in fig. 1. The CML includes a front portion (101) and a rear portion (103), with an intermediate portion (102) therebetween. Between and cooperating with the front and rear portions are at least three ovens. In some examples, one oven has multiple heating zones that can accomplish the task that three separate ovens can accomplish separately. In other examples, there are two ovens. In still other examples, there may be more ovens. The front portion has one or more rollers on which green tape (i.e., unsintered) is provided. The roll may be referred to as a rewinder, laminator, drive, brake, master, slave or dancer roll (dancer). There may be additional rollers, pins and pulleys in the front to apply tension, flatten, wind up, curl, emboss or direct the green tape from the front to the green tape entrance of the adhesive burn-off oven and/or oven (not shown). The rear portion has one or more rollers onto which the sintered tape is received through the oven outlet. There may be additional rollers, pins and pulleys at the rear to apply tension, flatten, roll up, curl, emboss or direct the sintered tape from the exit of the oven to the front. Weights may also be used to apply tension.
In some examples, a motor is used to apply tension to the green tape or sintered film. In this example, the tension is proportional to the motor torque (for a given drum diameter). In some examples, torque may be controlled by current flowing through the motor (for a dc motor).
In some examples, a movable "dancer" roller (dancer roller) is used to apply tension to the green tape or sintered film. In some examples, the tension is controlled by the weight suspended on a "dancer roll".
In some examples, a large oven is used, with one green tape inlet and one sinter tape outlet. In some other examples, multiple ovens are used, some ovens having a green tape inlet and an outlet of the green tape that has not been fully sintered. The treated green tape will enter another oven inlet for sintering and then exit the other oven through a sintered film outlet. In some examples, a large oven is enclosed in an enclosure that provides a controlled atmosphere in contact with the green tape. In other examples, multiple ovens are enclosed in a single enclosure that provides a controlled atmosphere in contact with the green tape. In other examples, the plurality of ovens are enclosed in a plurality of enclosures that provide a controlled atmosphere in contact with the green tape.
An oven may be used instead of a furnace.
In some examples, the roller has an inner diameter of between 2cm to 100cm, 5cm to 50cm, or 5cm to 15 cm. The rollers may comprise a metal, such as nickel, steel, stainless steel, copper, aluminum, or combinations thereof. The roller may be made of: nickel, steel, stainless steel, copper, aluminum, kovar, invar, zirconia on another substrate, zirconia on a ceramic, zirconia on a metal, alumina, quartz, boron nitride, silicon carbide, ceramic on a metal, LLZO on Ni, or combinations thereof. The rollers may be made of SS 430, SS 304, kovar, invar, haynes 214, greater than 99.5% (w/w) alumina, carbon-carbon composites, boron nitride, or combinations thereof.
In some examples, after the sintered membrane passes through the oven, the sintered membrane is passed through a tool, the sintered membrane is cut to a desired size and the cut membrane is stored in a sintered article receiving device. The tool may comprise an in-line laser cutter. The tool can cut the sintered film to the desired dimensions (parallel and/or perpendicular to the direction of travel through the CML).
In some examples, the oven (102) is a biscuit oven. In some examples, the oven (102) has multiple distinct heating zones in the oven, such as a greenfield and a sintering field.
In some examples, the oven (103) is a sintering oven. In some examples, the oven (103) has multiple distinct heating zones in the oven, such as a greenization zone and a sintering zone.
In this case, the 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, substantial differences of one oven relative to another oven may include, but are not limited to, one ovenA difference of 5% or more of partial pressure relative to the other oven total pressure, a difference of 5% or more of partial pressure, a given gas (e.g., O 2 、H 2 、N 2 Ar, xe or H 2 O) a two-fold difference in concentration or amount, or a ten-fold difference in flow rate of one or more gases (e.g., gas mixtures). For example, a furnace may include a sufficient amount of O 2 So that the organic material burns if heated to its ignition temperature. This is the case for the binder burn-out section. In such a case, if the other furnace has a low concentration of O 2 So that combustion cannot continue therein even at the combustion temperature, which shows a substantial difference of one melting furnace with respect to another melting furnace. For example, sintering ovens have lower oxygen concentrations than binder burn-out ovens. In another example, the water vapor concentration in one furnace is greater than 1,000 parts per million (ppm) and the water vapor concentration in another oven is less than 100ppm. H 2 The difference in partial pressure of O also shows a substantial difference in one oven relative to another. In another example, one oven is under vacuum and the other oven is at a pressure of 1atm, the difference being a substantial difference of one oven relative to the other. In another example, two ovens have similar gas mixtures, but one oven has a total pressure that is 5% or more lower than the other oven, the difference being a substantial difference of one oven relative to the other.
In certain examples, the binder burn-out furnace includes an oxidant mixed into a contact green tape gas or atmosphere. These oxidizing agents may include H 2 O、O 2 Or clean dry air. In some examples, the sintering furnace does not include an oxidizing agent mixed into the gas or atmosphere contacting the sintering film.
In some examples, argon (Ar) gas is contained in the pressurized enclosure.
In some examples, the pressurized enclosure contains nitrogen (N 2 )。
In some examples, the pressurized housing also contains hydrogen (H 2 )。
In some examples, H 2 The gas is present at about 5% v/v.
In some implementationsIn the example, the pressurized housing also contains water (H 2 O) gas.
In some examples, the pressurized housing also includes an inert gas, such as, but not limited to, N 2 、H 2 Ar and mixtures thereof, e.g. N 2 And H 2 . In some examples, the mixture is 2.9% H 2 And 97.1% N 2 . In some examples, the mixture is 0%H 2 And 100% N 2 . In some examples, the mixture is 1%H 2 And 99% N 2 . In some examples, the mixture is 2% H 2 And 98% N 2 . In some examples, the mixture is 3%H 2 And 97% N 2 . In some examples, the mixture is 4%H 2 And 98% N 2 . In some examples, the mixture is 5%H 2 And 96% N 2 . In some examples, the mixture is 6%H 2 And 94% N 2 . In some examples, the mixture is 7%H 2 And 93% N 2 . In some examples, the mixture is 8%H 2 And 92% N 2 . In some examples, the mixture is 9%H 2 And 91% N 2 . In some examples, the mixture is 10% H 2 And 90% N 2 . In some examples, the mixture is 0-10% H 2 And 90-100% N 2 . In some examples, the mixture is 0-5%H 2 And 95-100% N 2 . In some examples, including any of the preceding examples, O 2 Is present in an amount less than 10 parts per million (ppm). In some examples, including any of the preceding examples, O 2 Is present in an amount of 5 to 10ppm.
In some embodiments, including any preceding embodiments, O 2 The amount in the binder burn-out furnace is less than 10ppm.
In some embodiments, including any preceding embodiments, O 2 The amount in the sintering furnace is less than 10ppm.
In some examples, including any of the preceding examples, O 2 Is present in the binder burn-out oven at 5-10 ppm.
In some examples, including any of the preceding examples, O 2 In a sintering furnace at a ratio of 5-10ppm is present.
In some examples, including any of the preceding examples, O 2 At 10 in a sintering furnace -16 To 10 -20 Pa is present.
In some examples, the oven includes 1 to 500ppm H 2 O。
In some examples, the oven includes 1 to 1000ppm H 2 O。
In some examples, the green tape, the tape being sintered, or the open gap or hole through which the sintered tape passes has a cylindrical, oval, rectangular, or square shape with the size of the gap or hole (e.g., the diameter of the gap in the case of a circular gap, one side in the case of a square gap, or one side in the case of a rectangular gap, and the length of one axis in the case of an oval gap) being less than 10cm but greater than 1cm. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20 centimeters wide and 1 to 20mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 1mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 2mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 3mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 4mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 5mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 6mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 7mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 8mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 9mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 10mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 11mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 12mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 13mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 14mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 15mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 16mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 17mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 18mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 19mm high. In some examples, the shape of the opening gap resembles a rectangle about 5 to 20cm wide and 20mm high. In some examples, the size of the gap or hole is 9cm. In some examples, the size of the gap or hole is 8cm. In some examples, the size of the gap or hole is 7cm. In some examples, the size of the gap or hole is 6cm. In some examples, the size of the gap or hole is 5cm. In some examples, the size of the gap or hole is 4cm. In some examples, the size of the gap or hole is 3cm. In some examples, the size of the gap or hole is 2cm. In some examples, the size of the gap or hole is 1cm. In some examples, the size of the gap or hole is 500 μm. In some examples, the size of the gap or hole is 400 μm. In some examples, the size of the gap or hole is 8mm. In some examples, the size of the gap or hole is 300 μm. In some examples, the size of the gap or hole is 6mm. In some examples, the size of the gap or hole is 200 μm. In some examples, the size of the gap or hole is 4mm. In some examples, the size of the gap or hole is 100 μm. In some examples, the size of the gap or hole is 50 μm. In some examples, the size of the gap or aperture at the gap or aperture is also the same as the size of the gap or aperture through the oven as the green tape passes through the oven. In some examples, this narrowest dimension at the gap or aperture is also the same as the size of the gap or aperture through the oven as the green tape passes through the oven. The open gap or the gap of the holes through which the green tape or the sintered tape passes may be not more than 5 meters. In some examples, the largest dimension of the opening gap may be between 1cm and 5 meters, 1cm and 4 meters, 1cm and 3 meters, 1cm and 2 meters, 1cm and 1 meter, 1cm and 50 cm, or 1cm and 5cm.
In some examples, the length of the green tape or sintered film roll is between 10 meters and 10,000 meters. In some examples, the length of the green tape or sintered film roll is between 10 meters and 1000 meters. In some examples, the length of the green tape or sintered film roll is between 10 meters and 500 meters. In some examples, the length of the green tape or sintered film roll is between 10 meters and 100 meters.
In certain examples, rapid sintering occurs within a closed space. The closed space has an atmosphere that reduces lithium loss during the LLZO sintering process, helping to maintain a stoichiometric amount of lithium in a given LLZO formulation. The enclosed space may be part of an oven through which the film being sintered moves as it is sintered. Certain methods of the present application include the step of suspending the film using tension without contacting the surface. The tension may be applied by a weight or other means of applying tension. Certain methods of the present application include the step of suspending the film using tension as the film moves through the enclosed space without contacting the surface. Where the suspended portion of the membrane does not contact the surface, but the means for applying tension contacts other portions of the membrane. In some examples, only the suspended portion of the film is sintered when it does not contact other surfaces. Certain methods proposed by the present application include the step of contacting only one surface (e.g., the lower surface of a belt or film contacting a roller, tensioner or substrate) during sintering. Certain methods proposed by the present application include the step of suspending the film without contacting the surface using tension, air flow, or a combination of both tension and air flow. By "non-contact surface" is meant herein in particular the film being sintered as it moves through the oven. During the sintering phase, the portion of the green tape that is sintered is not in contact with any surface that may introduce sintering defects into the green tape surface. As the green tape moves out of the oven, the green tape may encounter rollers, rewinders, pins, posts, tensioners, etc. that contact the surface of the green tape. Similarly, as the sintered film moves out of the oven, the sintered film may encounter rollers, rewinders, pins, posts, etc. that contact the sintered film. In this case, the contact occurs after film sintering, rather than during sintering. Certain methods of the present application include the step of continuously stripping the green tape from the mylar substrate upon which it is disposed. This occurs at the beginning of the sintering process by unwinding the green tape from the roll and introducing the stripped green tape into the binder burn-out oven. Certain methods of the present application include the step of applying tension to the green film as it is sintered. Certain methods of the present application include the step of avoiding reaction with water/oxygen in the environment when processing green tape into LLZO sintered films. In some examples, a metal foil is used in place of the mylar substrate. In some examples, the metal foil is an iron foil, a copper foil, a nickel foil, alloys thereof, or combinations thereof. In some examples, the metal foil is a combination of iron and nickel. In certain embodiments, the combination of iron and nickel has more than 1% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 2% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 3% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 4% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 5% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 6% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 7% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 8% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 9% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 10% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 11% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 12% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 13% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 14% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 15% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 16% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 17% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 18% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 19% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 20% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 11% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 12% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 13% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 14% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 15% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 16% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 17% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 18% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 19% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 20% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 11% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 12% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 13% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 14% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 15% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 16% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 17% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 18% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 19% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 20% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 21% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 22% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 23% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 24% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 25% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 26% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 27% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 28% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 29% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 30% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 31% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 32% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 33% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 34% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 35% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 36% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 37% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 38% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 39% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 40% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 41% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 42% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 43% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 44% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 45% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 46% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 47% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 48% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 49% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 50% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 51% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 52% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 53% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 54% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 55% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 56% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 57% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 58% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 59% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 60% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 61% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 62% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 63% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 64% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 65% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 66% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 67% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 68% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 69% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 70% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 71% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 72% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 73% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 74% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 75% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 76% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 77% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 78% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 79% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 80% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 81% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 82% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 83% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 84% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 85% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 86% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 87% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 88% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 89% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 90% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 91% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 92% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 93% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 94% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 95% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 96% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 97% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 98% iron, with the remainder being nickel. In certain embodiments, the combination of iron and nickel has more than 99% iron, with the remainder being nickel.
In one example, the application sets forth a continuous production line (CML) comprising: a front portion comprising a front roller; a rear portion comprising a rear roller, a sintered article receiving device, or a combination thereof; and a middle portion between the front and rear portions comprising at least one oven, the at least one oven comprising a green tape inlet and a sintered film outlet, and an atmosphere controller that maintains atmosphere conditions within the at least one oven.
In another example, the application sets forth a continuous production line (CML) comprising: a front portion comprising at least one front roller; a rear portion comprising at least one rear roller, at least one sintered article receiving device, or a combination thereof; a middle portion between the front and rear portions comprising at least one oven, the at least one oven comprising at least one green tape inlet and at least one sintered film outlet, the at least one green tape inlet having an open gap with a height of less than 5 mm.
In another example, the application sets forth a continuous production line (CML) comprising: a front portion comprising at least one front roller; a rear portion comprising at least one sintered article receiving device; a middle portion between the front and rear portions including a binder burn-out furnace and a green body furnace, the middle portion including a curved ramp prior to the binder burn-out furnace or prior to the green body furnace.
In another example, the application sets forth a method of using a continuous production line comprising the operations of: (a) Providing or already providing a wound green tape on a front roller located at the front; (b) unwinding the green tape into an inlet of an oven; (c) Sintering the green tape in an oven as the green tape moves through the oven to produce a sintered film; (d) Winding the sintered film onto a back roll after exiting the oven through an outlet; (e) The atmosphere in contact with the green tape being sintered is or has been controlled.
In another example, the application sets forth a method of using a continuous production line comprising the operations of: (a) Moving the green tape under tension at a rate of at least two inches per minute through at least two ovens; (b) the green tape thickness is less than 200 μm; (c) Sintering the green tape while moving the green tape to produce a sintered film; (d) The atmosphere in contact with the green tape being sintered is or has been controlled.
In certain methods described herein, the film is sintered without the use of a shim or any surface during sintering. This advantageously avoids sticking, particle transfer, pull-out and scratching, yielding high quality films. The pullout described herein is a particle of material that pulls out of the film due to adhesion. For example, when the film is sintered on a surface, particles from the surface may transfer to the surface of the film. Particles from the surface of the membrane may also transfer to the surface as the membrane sinters on the surface.
In certain methods of the present application, the production of sintered films is higher than before. For example, in certain methods of the application, the continuous binder burn-out, sintering, and cooling cycles are within one hour rather than about twenty-four hours or more.
In some examples, the sintered film has a width of about 0.8mm to about 5 meters. In certain examples, the sintered films of the present disclosure have a width of about 5.0 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.9 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.8 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.7 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.6 meters. In certain embodiments, the sintered films of the present application have a width of about 4.5 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.4 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.3 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.2 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.1 meters. In certain examples, the sintered films of the present disclosure have a width of about 4.0 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.9 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.8 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.7 meters. In certain embodiments, the sintered films of the present application have a width of about 3.6 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.5 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.4 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.3 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.2 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.1 meters. In certain examples, the sintered films of the present disclosure have a width of about 3.0 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.9 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.8 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.7 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.6 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.5 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.4 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.3 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.2 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.1 meters. In certain examples, the sintered films of the present disclosure have a width of about 2.0 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.9 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.8 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.7 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.6 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.5 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.4 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.3 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.2 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.1 meters. In certain examples, the sintered films of the present disclosure have a width of about 1.0 meter. In certain examples, the sintered films of the present disclosure have a width of about 0.9 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.8 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.7 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.6 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.5 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.45 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.4 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.35 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.3 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.275 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.25 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.225 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.2 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.18 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.16 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.15 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.14 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.13 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.12 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.11 meters. In certain examples, the sintered films of the present disclosure have a width of about 0.1 meters. In certain examples, the sintered films of the present disclosure have a width of about 9 cm. In certain embodiments, the sintered films of the present application have a width of about 8 cm. In certain examples, the sintered films of the present disclosure have a width of about 7 cm. In certain examples, the sintered films of the present disclosure have a width of about 6 cm. In certain examples, the sintered films of the present disclosure have a width of about 5 cm. In certain examples, the sintered films of the present disclosure have a width of about 4 cm. In certain examples, the sintered films of the present disclosure have a width of about 3 cm. In certain examples, the sintered films of the present disclosure have a width of about 2 cm. In certain examples, the sintered films of the present disclosure have a width of about 1 cm. In certain embodiments, the sintered films of the present application have a width of about 9 mm. In certain examples, the sintered films of the present disclosure have a width of about 8 mm. In certain embodiments, the sintered films of the present application have a width of about 7 mm. In certain embodiments, the sintered films of the present application have a width of about 6 mm. In certain embodiments, the sintered films of the present application have a width of about 5 mm. In certain embodiments, the sintered films of the present application have a width of about 4 mm. In certain examples, the sintered films of the present disclosure have a width of about 3 mm. In certain examples, the sintered films of the present disclosure have a width of about 2 mm. In certain embodiments, the sintered films of the present application have a width of about 1 mm. In certain embodiments, the sintered films of the present application have a width of about 0.9 mm. In certain embodiments, the sintered films of the present application have a width of about 0.8 mm.
In some examples, the sintered film has a width of 0.8mm to 5 meters. In certain embodiments, the sintered films of the present application have a width of 5.0 meters. In certain embodiments, the sintered films of the present application have a width of 4.9 meters. In certain embodiments, the sintered films of the present application have a width of 4.8 meters. In certain embodiments, the sintered films of the present application have a width of 4.7 meters. In certain embodiments, the sintered films of the present application have a width of 4.6 meters. In certain embodiments, the sintered films of the present application have a width of 4.5 meters. In certain embodiments, the sintered films of the present application have a width of 4.4 meters. In certain embodiments, the sintered films of the present application have a width of 4.3 meters. In certain embodiments, the sintered films of the present application have a width of 4.2 meters. In certain embodiments, the sintered films of the present application have a width of 4.1 meters. In certain embodiments, the sintered films of the present application have a width of 4.0 meters. In certain embodiments, the sintered films of the present application have a width of 3.9 meters. In certain embodiments, the sintered films of the present disclosure have a width of 3.8 meters. In certain embodiments, the sintered films of the present application have a width of 3.7 meters. In certain embodiments, the sintered films of the present application have a width of 3.6 meters. In certain embodiments, the sintered films of the present application have a width of 3.5 meters. In certain embodiments, the sintered films of the present application have a width of 3.4 meters. In certain embodiments, the sintered films of the present application have a width of 3.3 meters. In certain embodiments, the sintered films of the present application have a width of 3.2 meters. In certain embodiments, the sintered films of the present application have a width of 3.1 meters. In certain embodiments, the sintered films of the present application have a width of 3.0 meters. In certain embodiments, the sintered films of the present application have a width of 2.9 meters. In certain embodiments, the sintered films of the present application have a width of 2.8 meters. In certain embodiments, the sintered films of the present application have a width of 2.7 meters. In certain embodiments, the sintered films of the present application have a width of 2.6 meters. In certain embodiments, the sintered films of the present application have a width of 2.5 meters. In certain embodiments, the sintered films of the present application have a width of 2.4 meters. In certain embodiments, the sintered films of the present application have a width of 2.3 meters. In certain embodiments, the sintered films of the present application have a width of 2.2 meters. In certain embodiments, the sintered films of the present application have a width of 2.1 meters. In certain embodiments, the sintered films of the present application have a width of 2.0 meters. In certain embodiments, the sintered films of the present application have a width of 1.9 meters. In certain embodiments, the sintered films of the present application have a width of 1.8 meters. In certain embodiments, the sintered films of the present application have a width of 1.7 meters. In certain embodiments, the sintered films of the present application have a width of 1.6 meters. In certain embodiments, the sintered films of the present application have a width of 1.5 meters. In certain embodiments, the sintered films of the present application have a width of 1.4 meters. In certain embodiments, the sintered films of the present application have a width of 1.3 meters. In certain embodiments, the sintered films of the present application have a width of 1.2 meters. In certain embodiments, the sintered films of the present application have a width of 1.1 meters. In certain embodiments, the sintered films of the present application have a width of 1.0 meter. In certain embodiments, the sintered films of the present application have a width of 0.9 meters. In certain embodiments, the sintered films of the present application have a width of 0.8 meters. In certain embodiments, the sintered films of the present application have a width of 0.7 meters. In certain embodiments, the sintered films of the present application have a width of 0.6 meters. In certain embodiments, the sintered films of the present application have a width of 0.5 meters. In certain embodiments, the sintered films of the present application have a width of 0.4 meters. In certain embodiments, the sintered films of the present application have a width of 0.35 meters. In certain embodiments, the sintered films of the present application have a width of 0.3 meters. In certain embodiments, the sintered films of the present application have a width of 0.2 meters. In certain embodiments, the sintered films of the present disclosure have a width of 0.18 meters. In certain embodiments, the sintered films of the present disclosure have a width of 0.17 meters. In certain embodiments, the sintered films of the present application have a width of 0.16 meters. In certain embodiments, the sintered films of the present application have a width of 0.15 meters. In certain embodiments, the sintered films of the present application have a width of 0.14 meters. In certain embodiments, the sintered films of the present application have a width of 0.13 meters. In certain embodiments, the sintered films of the present application have a width of 0.12 meters. In certain embodiments, the sintered films of the present application have a width of 0.11 meters. In certain embodiments, the sintered films of the present application have a width of 0.1 meters. In certain embodiments, the sintered films of the present application have a width of 9 cm. In certain embodiments, the sintered films of the present application have a width of 8 cm. In certain embodiments, the sintered films of the present application have a width of 7 cm. In certain embodiments, the sintered films of the present application have a width of 6 cm. In certain embodiments, the sintered films of the present application have a width of 5 cm. In certain embodiments, the sintered films of the present application have a width of 4 cm. In certain embodiments, the sintered films of the present application have a width of 3 cm. In certain embodiments, the sintered films of the present application have a width of 2 cm. In certain embodiments, the sintered films of the present application have a width of 1 cm. In certain embodiments, the sintered films of the present application have a width of 9 mm. In certain embodiments, the sintered films of the present application have a width of 8 mm. In certain embodiments, the sintered films of the present application have a width of 7 mm. In certain embodiments, the sintered films of the present application have a width of 6 mm. In certain embodiments, the sintered films of the present application have a width of 5 mm. In certain embodiments, the sintered films of the present application have a width of 4 mm. In certain embodiments, the sintered films of the present application have a width of 3 mm. In certain embodiments, the sintered films of the present application have a width of 2 mm. In certain embodiments, the sintered films of the present application have a width of 1 mm. In certain embodiments, the sintered films of the present application have a width of 0.9 mm. In certain embodiments, the sintered films of the present application have a width of 0.8 mm.
In some examples, the sintered film has a width of 0.8mm to 4 meters. In some examples, the sintered film has a width of 0.8mm to 3 meters. In some examples, the sintered film has a width of 0.8mm to 2 meters. In some examples, the sintered film has a width of 0.8mm to 1 meter. In some examples, the sintered film has a width of 0.8mm to 0.5 meters. In some examples, the sintered film has a width of 0.8mm to 0.4 meters. In some examples, the sintered film has a width of 0.8mm to 0.3 meters. In some examples, the sintered film has a width of 0.8mm to 0.2 meters. In some examples, the sintered film has a width of 0.8mm to 0.1 meters.
In some examples, the sintered film has a width of 1cm to 25 cm. In some examples, the sintered film has a width of 2cm to 22 cm. In some examples, the sintered film has a width of 4cm to 22 cm. In some examples, the sintered film has a width of 6cm to 22 cm. In some examples, the sintered film has a width of 8cm to 22 cm. In some examples, the sintered film has a width of 10cm to 22 cm. In some examples, the sintered film has a width of 12cm to 22 cm. In some examples, the sintered film has a width of 14cm to 22 cm. In some examples, the sintered film has a width of 16cm to 22 cm.
In some examples, the sintered bi-layer has a width of 1 cm. In some examples, the sintered bi-layer has a width of 1cm to 25 cm. In some examples, the sintered bi-layer has a width of 2cm to 22 cm. In some examples, the sintered bi-layer has a width of 4cm to 22 cm. In some examples, the sintered bi-layer has a width of 6cm to 22 cm. In some examples, the sintered bi-layer has a width of 8cm to 22 cm. In some examples, the sintered bi-layer has a width of 10cm to 22 cm. In some examples, the sintered bi-layer has a width of 12cm to 22 cm. In some examples, the sintered bi-layer has a width of 14cm to 22 cm. In some examples, the sintered bi-layer has a width of 16cm to 22 cm.
In some examples, the sintered film has a width of 2cm to 25 cm. In some examples, the sintered film has a width of 4cm to 25 cm. In some examples, the sintered film has a width of 6cm to 25 cm. In some examples, the sintered film has a width of 8cm to 25 cm. In some examples, the sintered film has a width of 10cm to 25 cm. In some examples, the sintered film has a width of 12cm to 25 cm. In some examples, the sintered film has a width of 14cm to 25 cm. In some examples, the sintered film has a width of 16cm to 25 cm.
In some examples, the sintered bi-layer has a width of 2cm to 25 cm. In some examples, the sintered bi-layer has a width of 4cm to 25 cm. In some examples, the sintered bi-layer has a width of 6cm to 25 cm. In some examples, the sintered bi-layer has a width of 8cm to 25 cm. In some examples, the sintered bi-layer has a width of 10cm to 25 cm. In some examples, the sintered bi-layer has a width of 12cm to 25 cm. In some examples, the sintered bi-layer has a width of 14cm to 25 cm. In some examples, the sintered bi-layer has a width of 16cm to 25 cm.
In some examples, the sintered film has a width of 1 cm. In some examples, the sintered film has a width of 2 cm. In some examples, the sintered film has a width of 1 cm. In some examples, the sintered film has a width of 3 cm. In some examples, the sintered film has a width of 4 cm. In some examples, the sintered film has a width of 5 cm. In some examples, the sintered film has a width of 6 cm. In some examples, the sintered film has a width of 7 cm. In some examples, the sintered film has a width of 8 cm. In some examples, the sintered film has a width of 9 cm. In some examples, the sintered film has a width of 10 cm. In some examples, the sintered film has a width of 11 cm. In some examples, the sintered film has a width of 12 cm. In some examples, the sintered film has a width of 13 cm. In some examples, the sintered film has a width of 14 cm. In some examples, the sintered film has a width of 15 cm. In some examples, the sintered film has a width of 16 cm. In some examples, the sintered film has a width of 17 cm. In some examples, the sintered film has a width of 18 cm. In some examples, the sintered film has a width of 19 cm. In some examples, the sintered film has a width of 20 cm. In some examples, the sintered film has a width of 21 cm. In some examples, the sintered film has a width of 22 cm. In some examples, the sintered film has a width of 23 cm. In some examples, the sintered film has a width of 24 cm. In some examples, the sintered film has a width of 25 cm.
In some examples, the green tape, sintered film, or bilayer is moved through the CML at a rate of greater than 0.1mm per minute. The distance "0.1mm" as referred to herein is measured in the direction of travel. In some examples, the green tape or sintered film is moved through the CML at a rate of greater than 1mm per minute. In some examples, the green tape or sintered film is moved through the CML at a rate of greater than 10mm per minute. In some examples, the green tape or sintered film is moved through the CML at a rate of greater than 100mm per minute. In some examples, the green tape or sintered film is moved through the CML at a rate of greater than 1000mm per minute.
In some examples, the sintered film or sintered bilayer moves through the CML at a rate between 2 centimeters per minute (cm/min) and 100 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 5 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 60 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 50 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 25 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 15 cm/min. In some examples, the sintered membrane moves through the CML at a rate of about 10 cm/min. The time herein refers to the time taken to move through the sintering furnace.
In some examples, the sintered film or the sintered bilayer has a thickness of less than 200 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 100 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 60 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 30 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 25 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 20 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 10 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 5 μm. In some examples, including any of the preceding examples, the sintered film or the sintered bilayer has a thickness between 5 μm and 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of at least 10 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of at least 20 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of at least 30 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of at least 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of at least 50 μm.
In some examples, the sintered film or the sintered bilayer has a thickness of about 200 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 100 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 90 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 80 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 70 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 60 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 30 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 25 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 20 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 10 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of about 5 μm. In some examples, including any of the preceding examples, the sintered film or the sintered bilayer has a thickness between 5 μm and 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 40 μm.
In some examples, the sintered film or the sintered bilayer has a thickness of 200 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 100 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 90 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 80 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 70 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 60 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 45 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 35 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 30 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 25 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 20 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 18 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 16 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 10 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness of 5 μm. In some examples, including any of the preceding examples, the sintered film or the sintered bilayer has a thickness between 5 μm and 50 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 40 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 60 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 70 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 10 μm and 80 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 60 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 70 μm. In some examples, including any of the preceding examples, the sintered film or sintered bilayer has a thickness between 20 μm and 80 μm.
In some methods of the present disclosure, the ceramic film in the double layer after sintering has a thickness of about 10 μm to about 50 μm. In some methods of the present disclosure, the ceramic film in the double layer after sintering has a thickness of about 20 μm to about 40 μm. In some methods of the present disclosure, the ceramic film in the double layer after sintering has a thickness of about 20 μm to about 30 μm.
The method of the present application includes a method for producing a sintered film roll. This approach reduces the number of cutting and stacking operations typically required in sintered film batch processing. The method of the present application reduces a number of process steps. These reduced process steps may introduce variability, particles and other defects into the sintered film. The form and processing conditions of the rolls proposed by the present application are more easily maintained. The sintered film is easier to transport than the sintered film produced in the conventional manner due to the production manner and the winding manner after production. The sintered film roll forms according to the present application may be used in downstream continuous processing steps such as, but not limited to, coating of interlayers, protective layers, adhesive layers, or other functional layers.
In some examples set forth herein, the continuous production line includes three furnaces: one furnace for burning out the binder, one furnace for firing the green body, and one furnace for sintering. The first furnace, the second furnace, and/or the third furnace may each have a plurality of temperature zones, individually or collectively. The first furnace, the second furnace, and/or the third furnace may each have a plurality of atmosphere control zones, individually or collectively.
In some examples set forth herein, the continuous production line includes two melters: a furnace is used to burn out the binder and to fire the green body. In some examples, the furnace used to burn out the binder and fire the greenware has multiple heating zones within the furnace. In this example, a second furnace is used for sintering. The second furnace may have a plurality of heating zones. The first furnace and/or the second furnace may have a plurality of atmosphere control zones.
In other examples set forth herein, the continuous line includes two melters. The first furnace is used to burn off the binder. In some examples, the furnace used to burn off the binder has multiple heating zones within the furnace. The second furnace is used for firing the greenware and sintering. The second furnace has a plurality of heating zones. The first furnace and/or the second furnace has a plurality of atmosphere control zones.
In some examples set forth herein, the continuous production line includes a furnace having a plurality of heating zones. The one furnace performs all or at least one of binder burn-out, green body firing, and sintering. The one furnace has a plurality of atmosphere control zones.
Fig. 2 shows an example of a continuous production line (200). The front portion (201) has at least one roller. In some examples, the front portion includes additional rollers (not shown). During operation of the CML (200), the green tape is unwound from a roll. In some examples, the green tape is disposed on the mylar substrate prior to winding on a roll. As the green tape unwinds from the roll, the underlying mylar substrate is removed. The removed mylar substrate may be wound onto another roll. The green tape without the mylar substrate is moved into an adhesive burn-out oven (202) and then into a greenware oven (203). The green tape passing through the binder burn-out furnace and the green body furnace is moved into the sintering furnace (204) after exiting the green body furnace by various rollers, pins, and tensioners. There may be various sensors and metrology tools in the middle to evaluate the quality of the passing belt. The tape then enters a sintering furnace (205). After exiting the sintering furnace, the sintered article reaches the rear (206). The sintered product taken out of the CML is guided and rolled on rollers at the rear for further processing. The rear portion (206) may also include another device. The rear portion (206) may have an enclosure for controlling the atmosphere surrounding the sintered article. In some examples, the rear portion (206) collects the sintered lithium-filled garnet film. In some examples, an adhesive burn-out furnace (202) is enclosed in an enclosure that provides a controlled atmosphere in contact with green tape. In other examples, the greenware oven (203) is enclosed in an enclosure that provides a controlled atmosphere in contact with the green tape. In other examples, the sintering furnace (205) is enclosed in a housing that provides a controlled atmosphere in contact with the green tape.
The middle section may also have these metrology analysis tools (not shown). These metrology analysis tools include lasers, X-ray devices, electron microscope devices, or combinations thereof. These metrology analysis tools are used to analyze the sintered article being produced.
The above figures are only intended to illustrate some examples that are contemplated. In some examples, there may be 1, 2, or 3 ovens, one for burning out binder, one for firing greenware, and one for sintering. In some examples, one oven has multiple heating zones. In some examples, there is a cool down zone or cooling zone at the end of the CML. The number of rollers is merely exemplary. More or fewer rolls may be used for various combinations with different types and numbers of furnaces. Various suction devices can be used to move the belt and sintered article. Various sensors and feedback devices may be employed for quality control.
Although the CML in FIGS. 1-3, 6-7A, 7B, 12-20 are shown in a horizontal form, in some examples the CML may be used in a vertical form in other examples.
The present application contemplates the placement of metrology analysis tools at different locations along the CML. For example, the metrology tool may evaluate the surface quality (e.g., defect density, defect type, protrusion size), film thickness, film uniformity, camber, bow, crystallinity, grain size, grain shape, flatness, roughness, density, refractive index, transparency, chemical analysis, crystalline phase, and combinations thereof of the sintered film or green tape being processed into the sintered film. These metrology analysis tools include lasers, X-ray devices, profilers, atomic force microscopes, electron microscope devices, imaging systems, raman microscopes, X-ray diffractometers, and combinations thereof. These metrology tools are used to analyze the sintered article being processed.
The present application contemplates a continuous apparatus with high throughput wherein green tape is processed from a spool by a CML that produces a sintered film that is wound onto the spool at the end of the process. The present application contemplates a reel-to-reel apparatus in which the green tape is processed from a reel by a CML that produces sintered films that are cut (or slit) into sheets and then stacked at the end of the production line.
The entire system of the CML or various components of the CML (e.g., the oven) may be enclosed in one or more enclosures, which provide for atmosphere control.
Various air curtains may be used with the overall system of the CML or various components of the CML (e.g., the oven) to provide atmosphere control.
In some examples, atmosphere control includes the use of a narrow oven opening.
In some examples, atmosphere control includes using excess flow at the oven inlet and outlet. In some examples, atmosphere control includes using N around various components (e.g., rollers) 2 Or an Ar filled glove box. In some examples, atmosphere control includes using overpressure within the oven.
In some examples, atmosphere control includes controlling H in an oven 2 The amount of O. In some examples, atmosphere control includes controlling O in an oven 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 100 ppm. In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 10 ppm. In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 1 ppm. In some examples, atmosphere control includes controlling H in an oven 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes controlling N in an oven 2 Amount of the components.
In some examples, atmosphere control includes controlling H in the binder burn-out furnace 2 The amount of O. In some examples, atmosphere control includes controlling O in a binder burn-out furnace 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes burning O in a binder burn-out furnace 2 Is controlled to a level of less than 100 ppm. In some examples, atmosphere control includes burning O in a binder burn-out furnace 2 Is controlled to a level of less than 10 ppm. In some examples, atmosphere control includes burning O in a binder burn-out furnace 2 Is controlled to a level of less than 1 ppm. In some examples, atmosphere control includes controlling H in the binder burn-out furnace 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes controlling N in the binder burn-out furnace 2 Amount of the components.
In some examples, atmosphere control includes controlling H in a sintering furnace 2 The amount of O. In some examples, atmosphere control includes controlling O in a sintering furnace 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes placing O in a sintering furnace 2 Is controlled to a level of less than 100 ppm. In some examples, atmosphere control includes placing O in a sintering furnace 2 Is controlled to a level of less than 10 ppm. In some examples, atmosphere control includes placing O in a sintering furnace 2 Is controlled to a level of less than 1 ppm. In some examples, atmosphere control includes controlling H in a sintering furnace 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes controlling a sintering furnaceN of (a) 2 Is a combination of the amounts of (a) and (b).
In some examples, the gas curtain includes N 2 And (5) an air curtain. In some examples, the gas curtain comprises an argon gas curtain. In some examples, the gas curtain includes a helium gas curtain.
In some examples, atmosphere control includes the use of synthesis gas in an oven. In some examples, the synthesis gas is hydrogen (H 2 ) And Ar. In some examples, atmosphere control includes the use of synthesis gas in an oven. In some examples, the synthesis gas is hydrogen (H 2 ) And nitrogen (N) 2 ) Is a mixture of (a) and (b). In some examples, atmosphere control includes the use of synthesis gas in an oven. In certain examples, the synthesis gas is H 2 Ar and N 2 Is a mixture of (a) and (b). In some such examples, H 2 Several percent of the synthesis gas volume. For example, in certain instances, H 2 Is present in the synthesis gas at 1%, 2%, 3%, 4%, 6%, 7%, 8%, 9% or 10% by volume. In certain other examples, H 2 Is present in the synthesis gas at about 1%, about 2%, about 3%, about 4%, about 6%, about 7%, about 8%, about 9%, or about 10% by volume. In certain other examples, H 2 Is present in the synthesis gas at about 1-2%, about 2-3%, about 3-4%, about 4-5%, about 6-7%, about 7-8%, about 8-9%, or about 9-10% v/v. In still other embodiments, H 2 Is present in the synthesis gas at 1-2%, 2-3%, 3-4%, 4-5%, 6-7%, 7-8%, 8-9%, or 9-10% v/v. In still other embodiments, H 2 Is present in the synthesis gas in an amount of 1-5%, 2-5%, 3-5%, 5-9%, 5-7%, 4-6%, 3-7% or 2-8% v/v.
In other examples, atmosphere control includes using Ar gas, N in an oven 2 Gas or a combination thereof. In certain examples, the gas is Ar. In some examples, the gas is N 2 . In other examples, the gases are Ar and N 2 Is a mixture of (a) and (b).
In some examples, the atmosphere control includes oxidizing gas in some parts of the production line, such as parts of the production line where sintering is not performed. For example, H 2 O can be aloneUsed or used in combination with the gases in the preceding paragraph. For example, O 2 May be used alone or in combination with the gases in the preceding paragraphs. For example, CDA (clean dry air) may be used alone or in combination with the gases in the preceding paragraph.
In some examples, an air box (tunnel configuration) is used with the exhaust.
In some examples, the gas supply tube and O in the furnace are formed with an air box having a feedback loop 2 A sensor.
In some examples, the adhesive burn-out chimney is replaced with a Watlow heater cartridge embedded in a plate that has perforations to allow gas to diffuse through them. The plates may incorporate gas diffusers, gas manifolds, channels or other means to direct the gas flow across the product surface. The apparatus includes a vent for removing the de-binding agent product (products of debindering).
In some examples, a Lindbergh biscuit tube furnace with a diameter of 6 inches is used. In some examples, the temperature of the furnace is 650 ℃. The furnace temperature may be in the range 200-900 ℃. The furnace may include a plurality of temperature zones. The furnace may include components that support the product during transport, which may be made of inconel, hastelloy, hay 214, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, aluminum oxide, or other ceramics or metals. The support member may comprise a coating of a haynes alloy, nickel, steel, stainless steel, boron nitride, silicon carbide, aluminum nitride, aluminum oxide, or another ceramic or metal.
In some examples, a 3 inch diameter furnace is used. In some examples, the temperature of the furnace is 1000 ℃. In some examples, the temperature of the furnace is 1010 ℃. In some examples, the temperature of the furnace is 1020 ℃. In some examples, the temperature of the furnace is 1030 ℃. In some examples, the temperature of the furnace is 1040 ℃. In some examples, the temperature of the furnace is 1050 ℃. In some examples, the temperature of the furnace is 1060 ℃. In some examples, the temperature of the furnace is 1070 ℃. In some examples, the temperature of the furnace is 1080 ℃. In some examples, the temperature of the furnace is 1090 ℃. In some examples, the temperature of the furnace is 1110 ℃. The furnace may include a Haynes Alloy 214 moving support.
In some examples, a 6 inch diameter furnace is used. In some examples, the temperature of the furnace is 1000 ℃. In some examples, the temperature of the furnace is 1010 ℃. In some examples, the temperature of the furnace is 1020 ℃. In some examples, the temperature of the furnace is 1030 ℃. In some examples, the temperature of the furnace is 1040 ℃. In some examples, the temperature of the furnace is 1050 ℃. In some examples, the temperature of the furnace is 1060 ℃. In some examples, the temperature of the furnace is 1070 ℃. In some examples, the temperature of the furnace is 1080 ℃. In some examples, the temperature of the furnace is 1090 ℃. In some examples, the temperature of the furnace is 1110 ℃. In some examples, the temperature of the furnace is 1100 ℃. In some examples, the temperature of the furnace is 1120 ℃. In some examples, the temperature of the furnace is 1130 ℃. In some examples, the temperature of the furnace is 1140 ℃. In some examples, the temperature of the furnace is 1150 ℃. In some examples, the temperature of the furnace is 1160 ℃. In some examples, the temperature of the furnace is 1170 ℃. In some examples, the temperature of the furnace is 1180 ℃. The furnace includes a Haynes Alloy 214 moving support.
In some examples, a furnace having a diameter of 1-10 inches (e.g., 1 inch, 2 inches, 3 inches, 4 inches, 5 inches, 6 inches, 7 inches, 8 inches, 9 inches, or 10 inches) is used. In some examples, the temperature of the furnace is 1000 ℃. In some examples, the temperature of the furnace is 1010 ℃. In some examples, the temperature of the furnace is 1020 ℃. In some examples, the temperature of the furnace is 1030 ℃. In some examples, the temperature of the furnace is 1040 ℃. In some examples, the temperature of the furnace is 1050 ℃. In some examples, the temperature of the furnace is 1060 ℃. In some examples, the temperature of the furnace is 1070 ℃. In some examples, the temperature of the furnace is 1080 ℃. In some examples, the temperature of the furnace is 1090 ℃. In some examples, the temperature of the furnace is 1110 ℃. The furnace includes a Haynes Alloy 214 moving support.
In some examples, including any of the preceding, the CML is a three-stage system comprising a binder burn-out furnace, a green body furnace, and a sintering furnace. As used herein, a green body refers to a material that is heated to partially neck down the particles, but not as dense as the sintered material.
In some examples, including any of the preceding, the CML is a two-stage system comprising a binder burn-out furnace and a green furnace, and a sintering furnace.
In some examples, including any of the preceding, the CML is a one-stage system including one furnace for binder burn-out, green body, and sintering. In some such examples, the furnace has a plurality of different heating zones.
An example of a continuous production line (1300) is shown in fig. 13. The CML (1300) includes a front portion (1301) and a rear portion (1304). Between the front (1301) and rear (1304) and in line with the front (1301) and rear (1304) are at least three ovens (shown as 1302, 1303, 1305). In some examples, one oven has multiple heating zones that can accomplish the task of three separate ovens individually. In other examples, there are two ovens (not shown). In still other examples, there may be more ovens. The front portion (1301) has one or more rollers on which green tape (i.e., unsintered) is provided. These rolls may be referred to as rewinders, laminators or dancer rolls (dancer). Additional rollers, pins, and pulleys may be present in the front portion (1301) to apply tension, flatten, roll up, curl, emboss, or guide the green tape from the front portion (1301) to the adhesive burn-out oven (1305) and/or the green tape inlet (not shown) of the oven (1302). The rear portion (1304) has one or more rollers that receive the sinter band through an oven (1303) outlet (1307). There may be additional rollers, pins, and pulleys in the rear (1304) to apply tension, flatten, roll up, curl, imprint, or direct the sintered tape from the outlet (1307) of the oven (1303) to the front (1301).
Fig. 13 also shows a second portion (1308). The second portion (1308) has one or more rollers on which the green tape is provided. Additional rollers and pulleys may be present in the second section (1308) to apply tension, flatten, roll up, curl, imprint, or direct the green tape from the outlet (1306) of the greens oven (1302) to the green tape inlet of the oven (1303). Fig. 6 shows examples of rollers, pins, and pulleys that may be used in some examples of the rear (1304) of the CML (1300). There may be additional rollers and pulleys in the second section (1308) to apply tension to the belt, flatten it, roll it up, curl it, emboss it or direct it from the outlet (1307) of the oven (1303) to the front (1301). Weights may also be used to apply tension to the green tape or sintered film. The belt has been partially or fully sintered as it passes through the second portion (1308). As the tape passes through the second portion (1308), the organic material in the tape has burned off the tape.
In some examples, the greenware oven (1302) is an oven that heats the green tape after the binder has been burned out of the green tape. In some examples, the oven (1302) has a plurality of different heating zones in the oven.
In some examples, oven (1303) is a sintering oven. In some examples, the oven (1303) has a plurality of different heating zones in the oven.
Fig. 13 also shows a binder burn-out oven (1305). The adhesive burn-out oven (1305) is used to control and/or measure the thickness of the green tape before it enters the green tape inlet (not shown) of the oven (1302). The binder burn-out oven (1305) is used to partially heat or sinter the green tape before it enters the green tape inlet (not shown) of the greenware oven (1302). In some examples, the oven (1305) is a binder burn-out oven. The tape may have been partially sintered or fully sintered as it passes through the second portion (1305). As the tape passes through the second portion (1305), the organic material in the tape may have burned off the tape. A heater cartridge may also be used in place of the oven at location (1305) to effect the burn-out of adhesive from the green tape.
Fig. 13 shows a horizontal tube oven (1302) used as a greenware oven, and a horizontal tube oven (1303) used as a sintering oven. In some examples, horizontal tube oven (1302) and horizontal tube oven (1303) are the same type of oven. In some other examples, horizontal tube oven (1302) and horizontal tube oven (1303) are different types of ovensA box. In still other examples, horizontal tube oven (1302) and horizontal tube oven (1303) are the same type of oven, but each has a unique atmosphere within the oven. In still other embodiments, the horizontal tube oven (1303) includes Ar, N 2 、H 2 Or a combination thereof. In still other embodiments, the horizontal tube oven (1303) includes Ar, N 2 、H 2 Or a combination thereof. In some examples, the horizontal tube oven (1303) does not include O 2 . In some examples, the horizontal tube oven (1303) contains no more than 100 parts per million O 2 . In this case, a unique atmosphere means that the gas or vapor environment in one oven is substantially different from the gas or vapor environment in another oven. For example, substantial differences from one oven to another oven may include, but are not limited to, differences of 5% or greater of total pressure, differences of 5% or greater of partial pressure, given a gas (e.g., O 2 、H 2 、N 2 Ar, xe or H 2 O) a two-fold difference in concentration or amount, or a ten-fold difference in flow rate in one oven relative to one or more gases (e.g., gas mixture) in another oven. For example, a furnace may include a sufficient amount of O 2 So that the organic material burns if heated to its ignition temperature. This may be the case for the binder burn-out section. In such an example, if another furnace has a low concentration of O 2 So that combustion cannot continue therein even at the ignition temperature, which shows a substantial difference in one oven relative to the other. For example, a sintering oven has a lower oxygen concentration than a binder burn-out oven. In another example, one oven contains water vapor at a concentration greater than 1,000 parts per million (ppm), and another oven may contain water vapor at a concentration less than 100ppm (by molecular count). H 2 This difference in partial pressure of O also shows a substantial difference in one oven relative to another.
In some examples, the binder burn-out furnace has a higher flow rate than other furnaces in the CML line, and the sintering furnace has a lower flow rate and inert gas.
In fig. 13, each of the horizontal tube ovens (1302) and (1303) has a green tape inlet (not shown due to perspective) and an outlet. The horizontal tube oven (1302) has an outlet (1306) and the horizontal tube oven (1303) has an outlet (1307). In some examples, the green tape, the tape being sintered, or the sintered tape will pass through an open gap or aperture having a cylindrical, oval, rectangular, or square shape, the aperture having a size of less than 10 centimeters. In some examples, the size of the gap or hole is 9cm. In some examples, the size of the gap or hole is 8cm. In some examples, the size of the gap or hole is 7cm. In some examples, the size of the gap or hole is 6cm. In some examples, the size of the gap or hole is 5cm. In some examples, the size of the gap or hole is 4cm. In some examples, the size of the gap or hole is 3cm. In some examples, the size of the gap or hole is 2cm. In some examples, the size of the gap or hole is 1cm. In some examples, the size of the gap or hole is 500 μm. In some examples, the size of the gap or hole is 400 μm. In some examples, the size of the gap or hole is 8mm. In some examples, the size of the gap or hole is 300 μm. In some examples, the size of the gap or hole is 6mm. In some examples, the size of the gap or hole is 200 μm. In some examples, the size of the gap or hole is 4mm. In some examples, the size of the gap or hole is 100 μm. In some examples, the size of the gap or hole is 50 μm. In some examples, the size of the gap or aperture at the gap or aperture is also the same as the size of the gap or aperture through the oven as the green tape passes through the oven.
Fig. 14 shows an example of a continuous production line (1400). Shown is a front portion (1413) having a rolled green tape roll (not shown). In some examples, the front portion (1413) includes a first roller (not shown). During operation of the CML (1400), green tape is unwound from a roll and moved into an adhesive burn-out oven (1411). Directly above the binder burn-out oven (1411) is a chimney (1407) to accommodate combustion and other gaseous products. A greenware oven (1405) enclosed in the enclosure (1406) is also shown. A sintering oven (1402) enclosed in a housing (1403) is also shown. In some examples, housings (1403) and (1406) are the same housing (not shown). In some examples, housing (1414) is used in place of housings (1403) and (1406). In some examples, the segments (1404) have various rollers, pins, and tensioners to guide green tape from the greenware oven to the sintering oven. Weights may also be used to apply tension. Controllers (1409 and 1410) control the heating and cooling of the oven, atmosphere control, and the rate at which the green tape moves through the CML (1400). Line (1408) represents the path of green tape travel, starting from the binder burn-out oven (1411), through the greenware oven (1405), and then into and out of the sintering oven (1402). Finally, the sintered article, after exiting the sintering oven (1402), reaches the rear (1401), where it is wound on a roll or cut and stacked. Fig. 14 shows that a device (1412) is provided at the beginning of the binder burn-out oven.
In some examples, there are transition zones between ovens where tension on the green tape and/or the sintered film can be adjusted. On opposite sides of the transition zone, the green tape or sintered film may exert unequal tension.
In some examples, there is a transition zone between ovens where the green tape or sintered film is bent around corners or around rollers. In some examples, the bend has a radius of curvature of about 6 inches. In some examples, the bend has a radius of curvature of about 7 inches. In some examples, the bend has a radius of curvature of about 8 inches.
In some examples, the residence time of the belt or bilayer moving through the CML in the oven is less than 60 minutes. In some examples, less than 30 minutes. In some other examples, less than 20 minutes. In still other examples, less than 15 minutes. In other examples, less than 10 minutes.
As the length of the CML oven increases, the speed at which the tape or bilayer moves through the oven also increases to achieve a certain residence time as described above. In some embodiments, some water is contained in the atmosphere, which aids in binder removal, thereby promoting binder burn-out.
In some examples, the CML includes a ramp to the oven inlet, such as an adhesive burn-out oven, a green body oven, and/or a sintering oven. In some examples, the ramp is curved. In some examples, the ramp may be heated or cooled. The ramp helps to apply tension to the green tape or sintered film. The ramp helps smooth the green tape or sinter the film. The ramp helps prevent wrinkling of the green tape or sintered film.
Fig. 7A shows an example of a curved ramp component 700 of a continuous production line. The curved ramp member 700 includes a top 701 and a bottom 702. 701 and 702 have thermal controls (not explicitly shown) for heating or cooling purposes. 701 and 702 may be made of metal, such as steel, copper, nickel, and the like. 701 and 702 are coated with an oxide such as, but not limited to, lithium-filled garnet, zirconia, or lithium zirconium phosphate. Between 701 and 702 is a film 703. The film 703 may be a green film, a film being sintered, or a sintered film.
Fig. 7B illustrates another example of a curved ramp component 700 of a continuous production line. The curved ramp component 700 includes a top 701 and a bottom 702. 701 and 702 have heating or cooling purpose thermal controls 704 and 705. 701 and 702 are made of metal, such as steel, copper, nickel, etc. 701 and 702 are coated with an oxide such as, but not limited to, lithium-filled garnet, zirconia, or lithium zirconium phosphate. Between 701 and 702 is a film 703. The film 703 may be a green film, a film being sintered, or a sintered film.
The flatness, tension, presence or absence of wrinkles, or other surface features of a film placed in contact with a curved ramp may be controlled by adjusting the curved ramp component of a continuous production line. For example, as shown in FIG. 12, curved ramp member 1203 has end rollers 1201 and 1202. In some examples, the end roller helps to maintain contact between the surfaces of film and 1203. Arrow 1205 indicates the direction of movement of the film through the curved ramp member relative to the rotation of the end rollers 1201 and 1202.
The continuous production line may contain the unwind rollers at different points of the production line or at only one point. An example of a spreader roll is shown in fig. 15. The unwind roll 1500 has a film 1501 with wrinkles or other surface imperfections thereon. The unwind roller 1500 produces an angular displacement at positions 1502 and 1503. These angular displacements stretch, flatten, the film at location 1504. 1505 represents the entrance point size of the membrane and 1506 represents the size after deployment.
In some examples, the foregoing ramp is characterized by a radius of curvature, as shown in fig. 6 (600). In some examples, the ramp (601) leads to an inlet (604) of a furnace/oven (605). The curvature of the ramp is indicated by (602). The curvature corresponds to a circle having a radius (603). In some examples, including any of the preceding, the radius of curvature is about 10cm-50cm. In some examples, including any of the preceding examples, the radius of curvature is about 10cm-40cm. In some examples, including any of the preceding, the radius of curvature is about 20cm-50cm. In some examples, including any of the preceding, the radius of curvature is about 20cm-40cm. In some examples, including any of the preceding, the radius of curvature is about 20cm-30cm. In some examples, including any of the preceding, the radius of curvature is about 30cm-50cm. In some examples, including any of the preceding, the radius of curvature is about 40cm-50cm. In some examples, including any of the preceding, the radius of curvature is about 30cm-40cm. In some examples, including any of the preceding examples, the radius of curvature is about 10cm. In some examples, including any of the preceding examples, the radius of curvature is about 10cm. In some examples, including any of the preceding examples, the radius of curvature is about 11cm. In some examples, including any of the preceding examples, the radius of curvature is about 12cm. In some examples, including any of the preceding examples, the radius of curvature is about 13cm. In some examples, including any of the preceding examples, the radius of curvature is about 14cm. In some examples, including any of the preceding examples, the radius of curvature is about 15cm. In some examples, including any of the preceding examples, the radius of curvature is about 16cm. In some examples, including any of the preceding examples, the radius of curvature is about 17cm. In some examples, including any of the preceding examples, the radius of curvature is about 18cm. In some examples, including any of the preceding examples, the radius of curvature is about 19cm. In some examples, including any of the preceding examples, the radius of curvature is about 20cm. In some examples, including any of the preceding examples, the radius of curvature is about 21cm. In some examples, including any of the preceding examples, the radius of curvature is about 22cm. In some examples, including any of the preceding examples, the radius of curvature is about 23cm. In some examples, including any of the preceding examples, the radius of curvature is about 24cm. In some examples, including any of the preceding examples, the radius of curvature is about 25cm. In some examples, including any of the preceding examples, the radius of curvature is about 26cm. In some examples, including any of the preceding examples, the radius of curvature is about 27cm. In some examples, including any of the preceding examples, the radius of curvature is about 28cm. In some examples, including any of the preceding examples, the radius of curvature is about 29cm. In some examples, including any of the preceding examples, the radius of curvature is about 30cm. In some examples, including any of the preceding examples, the radius of curvature is about 31cm. In some examples, including any of the preceding examples, the radius of curvature is about 32cm. In some examples, including any of the preceding examples, the radius of curvature is about 33cm. In some examples, including any of the preceding examples, the radius of curvature is about 34cm. In some examples, including any of the preceding examples, the radius of curvature is about 35cm. In some examples, including any of the preceding examples, the radius of curvature is about 36cm. In some examples, including any of the preceding examples, the radius of curvature is about 37cm. In some examples, including any of the preceding examples, the radius of curvature is about 38cm. In some examples, including any of the preceding examples, the radius of curvature is about 39cm. In some examples, including any of the preceding examples, the radius of curvature is about 40cm. In some examples, including any of the preceding examples, the radius of curvature is about 41cm. In some examples, including any of the preceding examples, the radius of curvature is about 42cm. In some examples, including any of the preceding examples, the radius of curvature is about 43cm. In some examples, including any of the preceding examples, the radius of curvature is about 44cm. In some examples, including any of the preceding examples, the radius of curvature is about 45cm. In some examples, including any of the preceding examples, the radius of curvature is about 46cm. In some examples, including any of the preceding examples, the radius of curvature is about 47cm. In some examples, including any of the preceding examples, the radius of curvature is about 48cm. In some examples, including any of the preceding examples, the radius of curvature is about 49cm. In some examples, including any of the preceding examples, the radius of curvature is about 50cm.
In some examples, including any of the preceding, the radius of curvature is about 6 inches to 8 inches.
In some examples, including any of the preceding examples, the radius of curvature is about 6 inches.
In some examples, including any of the preceding examples, the radius of curvature is about 7 inches.
In some examples, including any of the preceding examples, the radius of curvature is about 8 inches.
In some examples, the ramp may be made of nickel, steel, stainless steel, copper, aluminum, kovar, invar, haynes216, ceramic on metal, LLZO on Ni, or a combination thereof. In some examples, ni is very thin, e.g., 1 μm to 100 μm thick. In some examples, the ramp is a substrate having a zirconia coating thereon.
In some examples, the CML has components substantially as shown in fig. 3. In fig. 3, the green tape is unwound and enters the oven. Using the CML configuration shown in fig. 3, the process can operate as follows. In the first step, the tape is first passed through the CML in the opposite direction to the arrow in fig. 3, i.e., first into an adhesive burn-off (BBO) oven, heated to no more than 750 ℃ (625 ℃ in some examples). The strip then enters a furnace and is heated to 600-900 ℃ (850 ℃ in some examples) to fire the greenware. In a second step, after this is completed, the tape is reversed in direction (so it now matches the arrow in the figure) and sintered by passing through a furnace heated to 900 ℃ -1450 ℃ (1150 ℃ in some examples). After that, the mixture was passed through a BBO oven, but the oven was turned off (at room temperature).
In some examples, including any of the above, the application sets forth a continuous production line (CML) comprising: a front portion comprising at least one front roller; a rear portion comprising at least one sintered article receiving device; and a middle portion between the front and rear portions including an adhesive burn-out oven and a greenware oven, the middle portion including a curved ramp prior to the adhesive burn-out oven or prior to the greenware oven.
In some examples, the curved ramp is located inside the sintering oven. In certain other examples, the curved ramp is located inside the greenbody oven. In still other examples, the curved ramp is located inside the adhesive burn-out oven. In other examples, the curved ramp is located between ovens.
In some examples, the curved ramp is located in front of the sintering furnace. In certain other examples, the curved ramp is located in front of the greenbody furnace. In still other examples, the curved ramp is located in front of the binder burn-out furnace. In other examples, curved ramps are located between the furnaces.
In some examples, including any of the preceding examples, the middle portion further includes a sintering oven.
In some examples, including any of the preceding examples, the adhesive burn-out oven is enclosed in an atmosphere enclosure.
In some examples, including any of the preceding examples, the oven of the CML has a lower oxygen and moisture partial pressure (at least 10 times) than outside the oven.
In some examples, including any of the preceding examples, the bilayer used is made of 90% or more by weight lithium-filled garnet.
In some examples, including any of the preceding examples, a bilayer made with two Li electrodes has less than 20ohm-cm at room temperature 2 Is a non-linear variable (ASR) of the system. The ceramic portion of the bilayer is about 40 μm thick.
In some examples, including any of the preceding examples, the greenbody oven is enclosed in an atmosphere enclosure.
In some examples, including any of the preceding examples, the sintering oven is enclosed in an atmosphere enclosure.
In some examples, including any of the preceding examples, the atmosphere enclosure of the closed sintering oven comprises Ar, N 2 、H 2 O、H 2 Or a combination thereof.
In some examples, including any of the preceding examples, the atmosphere enclosure enclosing the binder burn-out oven comprises Ar, N 2 、H 2 O、H 2 、O 2 Or a combination thereof.
In some examples, including any of the preceding examples, the atmosphere enclosure of the closed greenware oven comprises Ar, N 2 、H 2 O、H 2 、O 2 Or a combination thereof.
In some examples, including any of the preceding examples, the CML comprises a green tape wound on the at least one front roll.
In some examples, sintering of the LLZO film occurs without other surfaces (e.g., CML surfaces) contacting the LLZO film during sintering. The non-contact film portion being sintered has unexpected advantageous properties such as low flatness, retention of stoichiometric amounts of lithium in a given LLZO formula, and advantageous microstructures (e.g., high densification, small grain size, and combinations thereof).
C. Sintered articles (e.g., films, monoliths, wafers, sheets, continuous strips, compressed powder pellets, and ingots)
The present application proposes a sintered article having a density of greater than 95%.
The present application contemplates sintered articles substantially as shown in figures 4-5 and 9-11.
In some examples, including any of the preceding, the sintered article comprises a bilayer. In an example, the bilayer includes a metal foil and a ceramic membrane. In some examples, the sintered article comprises three layers. In some examples, the metal is Ni. In some examples, the thickness of Ni is 1 μm. In some examples, the thickness of Ni is 2 μm. In some examples, the thickness of Ni is 3 μm. In some examples, the thickness of Ni is 4 μm. In some examples, the thickness of Ni is 5 μm. In some examples, the thickness of Ni is 6 μm. In some examples, the thickness of Ni is 7 μm. In some examples, the thickness of Ni is 8 μm. In some examples, the thickness of Ni is 9 μm. In some examples, the thickness of Ni is 10 μm. In some examples, the thickness of Ni is 11 μm. In some examples, the thickness of Ni is 12 μm. In some examples, the thickness of Ni is 13 μm. In some examples, the thickness of Ni is 14 μm. In some examples, the thickness of Ni is 15 μm. In some examples, the thickness of Ni is 16 μm. In some examples, the thickness of Ni is 17 μm. In some examples, the thickness of Ni is 18 μm. In some examples, the thickness of Ni is 19 μm. In some examples, the thickness of Ni is 20 μm.
In some examples, the slurry may be deposited onto a foil to form a green tape of foil backing. In some examples, the foil is a mylar foil. The green tape with foil backing may be wound into a roll to form an unsintered film roll with foil backing. An unsintered film roll with a foil backing may be loaded onto a CML as described herein. In some examples, a method of using CML may comprise: (a) Loading an unsintered film roll with a foil backing onto a front roll; (b) unrolling the unsintered film; (c) sintering the green film to produce a sintered film; (d) The sintered film with foil backing is wound onto a back roll in a controlled atmosphere. In some examples, the foil backing comprises nickel metal or nickel foil.
In some examples, the green film sintered with CML is a bilayer or trilayer.
In some examples, various layer structures may be envisaged and sintered according to the sintering method set forth in the present application: a) A lithium-filled garnet material alone; b) A separate lithium-stuffed garnet material, optionally including an active material, a binder, a solvent, and/or carbon; c) A bilayer having a layer of lithium-filled garnet and a layer of metal powder, foil or sheet; d) Having a layer of lithium-stuffed garnet and a bilayer comprising a metal powder, foil or sheet; e) A bilayer having a layer of lithium-filled garnet material, optionally comprising an active material, a binder, a solvent, and/or carbon and a layer of metal powder, foil or sheet; f) Three layers having two layers of lithium-filled garnet and one layer of metal powder, foil or sheet, the latter being located between and in contact with the garnet layers; g) Three layers having two lithium-filled garnet layers and one layer comprising metal powder, foil or sheet, the latter being located between and in contact with the garnet layers; h) Three layers having two layers of lithium-stuffed garnet material and one layer of metal powder, foil or sheet between and in contact with the garnet layers, wherein each garnet layer optionally comprises an active material, binder, solvent and/or carbon.
In some cases, the CML described herein may be used to sinter bilayers. In some cases, the CML described in the present application may be used to sinter three layers.
The bilayer structure may include a layer of lithium-stuffed garnet, a layer of metal, and a second layer of lithium-stuffed garnet on the opposite side of the metal. The bilayer membrane may be passed through a CML with one layer of lithium-filled garnet facing upward and a second layer of lithium-filled garnet facing downward.
The bilayer may include a layer of lithium-filled garnet and a layer of metal foil. In some examples, the metal layer comprises Ni, fe, cu, al, sn, in, ag, au, steel, an alloy, or a combination thereof. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 90% Ni and 10% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 91% Ni and 9% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 92% Ni and 8% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 93% Ni and 7% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 94% Ni and 6% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 95% Ni and 5% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 96% Ni and 4% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 97% Ni and 3% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 98% Ni and 2% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 99% Ni and 1% Fe. In some examples, the metal layer is a metal sheet. In some examples, the metal layer is an aluminum sheet. In some examples, the metal layer is a nickel sheet. In some examples, the metal layer may be ductile. In some examples, the metal layer has a thickness of 1 μm. In some examples, the thickness of the metal layer is 2 μm. In some examples, the thickness of the metal layer is 3 μm. In some examples, the thickness of the metal layer is 4 μm. In some examples, the metal layer has a thickness of 5 μm. In some examples, the thickness of the metal layer is 6 μm. In some examples, the thickness of the metal layer is 7 μm. In some examples, the metal layer has a thickness of 8 μm. In some examples, the thickness of the metal layer is 9 μm. In some examples, the metal layer has a thickness of 10 μm. In some examples, the thickness of the metal layer is 11 μm. In some examples, the thickness of the metal layer is 12 μm. In some examples, the metal layer has a thickness of 13 μm. In some examples, the thickness of the metal layer is 14 μm. In some examples, the thickness of the metal layer is 15 μm. In some examples, the thickness of the metal layer is 16 μm. In some examples, the thickness of the metal layer is 17 μm. In some examples, the metal layer has a thickness of 18 μm. In some examples, the thickness of the metal layer is 19 μm. In some examples, the metal layer has a thickness of 20 μm.
In some examples, the lithium-filled garnet-metal sintering films of the present application have a thickness of 1 μm to 100 μm. In certain examples, these films are sintered together with a mixed amount 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 in powder form and then sintered together to form a thin film. In some examples, the film comprises a homogeneous mixture of lithium-filled garnet and metal. The relative amounts of lithium-filled garnet and metal vary from 1% lithium-filled garnet to up to 99% lithium-filled garnet by volume percent, with the remainder being metal.
In some examples, including any of the preceding examples, the lithium-stuffed garnet is sintered to the ceramic-metal film.
The CML systems and processes described herein can be used to fabricate a variety of materials. These materials include, but are not limited to, lithium-filled garnet films. These materials include, but are not limited to, a bilayer formed from a lithium filled garnet film on a metal layer, or a trilayer formed from two lithium filled garnet films with a metal layer in between. The CML systems and processes set forth herein may be used to make lithium filled garnet films or composites, including but not limited to any sintered film or film-containing material disclosed in the following documents: PCT/US2016/043428, publication number WO2017015511A1, entitled "PROCESSES AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS", filed at 7/21 of 2016; PCT/US2019/056584, filed on 10 months 16 days 2019, publication No. WO2020081718A1, titled "SINTERING LARGE AREACERAMIC FILMS"; PCT/US2016/15209, published under number WO2017131676A1, entitled "ANNEALED GARNET ELECTROLYSE SEPERATORS", filed on 1-27 date 2016; PCT/US2017/039069, publication No. WO2018236394A1, titled "list-STUFFED GARNET ELECTRO-LYES WITH SECONDARYPHASEINCLUDES", filed 1/23/2017; PCT/US2019/54117, filed on 10/1/2019, publication No. WO2020072524A1, titled "METHODS OF MAKING AND USING AN ELECTROCHEMICAL CELL COMPRISING AN INTERLAYER"; us 10,403,931;10,290,895;9,966,630B2;10,347,937B2;10,103,405 and 10,103,405. The entire contents of each of the above documents are incorporated by reference in their entirety for all purposes.
In some examples, including any of the preceding, the ceramic-metal film may be an oxide-metal film. In some examples, the membrane has a ceramic layer and a metal layer. In other examples, the membrane is a homogeneous mixture of ceramic and metal. In some examples, the ceramic-metal film comprises a ceramic and a metal. In some examples, the volume percent of the ceramic is 10% and the volume percent of the metal is 90%. In some examples, the ceramic is 20% by volume and the metal is 80% by volume. In some examples, the volume percent of the ceramic is 30% and the volume percent of the metal is 70%. In some examples, the volume percent of the ceramic is 40% and the volume percent of the metal is 60%. In some examples, the volume percent of the ceramic is 50% and the volume percent of the metal is 50%. In some examples, the volume percent of the ceramic is 60% and the volume percent of the metal is 40%. In some examples, the volume percent of the ceramic is 70% and the volume percent of the metal is 30%. In some examples, the volume percent of the ceramic is 80% and the volume percent of the metal is 20%. In some examples, the volume percent of the ceramic is 90% and the volume percent of the metal is 10%. In some examples, the volume percent of the ceramic is 5% and the volume percent of the metal is 95%. In some examples, the volume percent of the ceramic is 15% and the volume percent of the metal is 85%. In some examples, the volume percent of the ceramic is 25% and the volume percent of the metal is 75%. In some examples, the volume percent of the ceramic is 35% and the volume percent of the metal is 65%. In some examples, the volume percent of the ceramic is 45% and the volume percent of the metal is 55%. In some examples, the volume percent of the ceramic is 55% and the volume percent of the metal is 45%. In some examples, the volume percent of the ceramic is 65% and the volume percent of the metal is 32%. In some examples, the volume percent of the ceramic is 75% and the volume percent of the metal is 25%. In some examples, the volume percent of the ceramic is 85% and the volume percent of the metal is 15%. In some examples, the volume percent of the ceramic is 95% and the volume percent of the metal is 5%.
In some examples, including any of the preceding examples, the ceramic-metal film comprises an oxide and a metal. In some examples, the volume percent of oxide is 10% and the volume percent of metal is 90%. In some examples, the volume percent of oxide is 20% and the volume percent of metal is 80%. In some examples, the volume percent of oxide is 30% and the volume percent of metal is 70%. In some examples, the volume percent of oxide is 40% and the volume percent of metal is 60%. In some examples, the volume percent of oxide is 50% and the volume percent of metal is 50%. In some examples, the volume percent of oxide is 60% and the volume percent of metal is 40%. In some examples, the volume percent of oxide is 70% and the volume percent of metal is 30%. In some examples, the volume percent of oxide is 80% and the volume percent of metal is 20%. In some examples, the volume percent of oxide is 90% and the volume percent of metal is 10%. In some examples, the volume percent of oxide is 5% and the volume percent of metal is 95%. In some examples, the volume percent of oxide is 15% and the volume percent of metal is 85%. In some examples, the volume percent of oxide is 25% and the volume percent of metal is 75%. In some examples, the volume percent of oxide is 35% and the volume percent of metal is 65%. In some examples, the volume percent of oxide is 45% and the volume percent of metal is 55%. In some examples, the volume percent of oxide is 55% and the volume percent of metal is 45%. In some examples, the volume percent of oxide is 65% and the volume percent of metal is 35%. In some examples, the volume percent of oxide is 75% and the volume percent of metal is 25%. In some examples, the volume percent of oxide is 85% and the volume percent of metal is 15%. In some examples, the volume percent of oxide is 95% and the volume percent of metal is 5%.
In some examples, including any of the preceding, the ceramic-metal film is an oxide-metal film. In some examples, the ceramic-metal film comprises a ceramic and a metal. In some examples, the weight percent of ceramic is 10% and the weight percent of metal is 90%. In some examples, the weight percent of ceramic is 20% and the weight percent of metal is 80%. In some examples, the weight percent of ceramic is 30% and the weight percent of metal is 70%. In some examples, the weight percent of ceramic is 40% and the weight percent of metal is 60%. In some examples, the weight percent of ceramic is 50% and the weight percent of metal is 50%. In some examples, the weight percent of ceramic is 60% and the weight percent of metal is 40%. In some examples, the weight percent of ceramic is 70% and the weight percent of metal is 30%. In some examples, the weight percent of ceramic is 80% and the weight percent of metal is 20%. In some examples, the weight percent of ceramic is 90% and the weight percent of metal is 10%. In some examples, the weight percent of ceramic is 5% and the weight percent of metal is 95%. In some examples, the weight percent of ceramic is 15% and the weight percent of metal is 85%. In some examples, the weight percent of ceramic is 25% and the weight percent of metal is 75%. In some examples, the weight percent of ceramic is 35% and the weight percent of metal is 65%. In some examples, the weight percent of ceramic is 45% and the weight percent of metal is 55%. In some examples, the weight percent of ceramic is 55% and the weight percent of metal is 45%. In some examples, the weight percent of ceramic is 65% and the weight percent of metal is 35%. In some examples, the weight percent of ceramic is 75% and the weight percent of metal is 25%. In some examples, the weight percent of ceramic is 85% and the weight percent of metal is 15%. In some examples, the weight percent of ceramic is 95% and the weight percent of metal is 5%.
In some examples, including any of the preceding examples, the ceramic in the ceramic-metal film is selected from the group consisting of alumina, silica, titania, lithium-filled garnet, lithium aluminate, aluminum hydroxide, aluminosilicate, lithium zirconate, lanthanum aluminate, lanthanum zirconate, lanthanum oxide, lithium lanthanum oxide, zirconium oxide, li 2 ZrO 3 、xLi 2 O-(1-x)SiO 2 (where x=0.01-0.99), aLi 2 O-bB 2 O 3 -cSiO 2 (wherein a+b+c=1), liLaO 2 、LiAlO 2 、Li 2 O、Li 3 PO 4 Or a combination thereof.
In an example, the three layers include a metal foil and green ceramic films on both sides of the metal foil. The double-or triple-layered metal foil may have a thickness of 0.5 μm to 50 μm. The double-or triple-layered metal foil may have a thickness of 3 μm to 30 μm. In some examples, the double-or triple-layered metal foil may have a thickness of 5-20 μm. In other examples, the double-or triple-layered metal foil may have a thickness of 5 μm to 15 μm.
In some examples, including any of the preceding, the sintered article comprises LLZO.
In some examples, the sintered film has a D of less than 5 μm 50 Grain size. In some examples, the sintered film has a D of less than 4 μm 50 Grain size. In some examples, the sintered film has a D of less than 3 μm 50 Grain size. In some examples, the sintered film has a D of less than 2 μm 50 Grain size. In some examples, the sintered film has a D of less than 1 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.9 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.8 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.7 μm 50 Grain size. In some examples, the sintered film has a small sizeD at 0.6 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.5 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.4 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.3 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.2 μm 50 Grain size. In some examples, the sintered film has a D of less than 0.1 μm 50 Grain size. In some examples, the sintered film has a D of less than 5 μm 90 Grain size. In some examples, the sintered film has a D of less than 4 μm 90 Grain size. In some examples, the sintered film has a D of less than 3 μm 90 Grain size. In some examples, the sintered film has a D of less than 2 μm 90 Grain size. In some examples, the sintered film has a D of less than 1 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.9 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.8 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.7 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.6 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.5 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.4 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.3 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.2 μm 90 Grain size. In some examples, the sintered film has a D of less than 0.1 μm 90 Grain size. In some examples, the sintered film has a porosity of less than 5%. In some examples, the sintered film has a porosity of less than 4%. In some examples, the sintered film has a porosity of less than 3%. In some examples, the sintered film has a porosity of less than 2%. In some examples, the sintered film has a porosity of less than 1%. In some examples, the sintered film has a porosity of less than 0.5%. In some examples, the sintered film has a porosity of less than 0.4%. In some examples, the sintered film has a porosity of less than 0.3%. At the position of In some examples, the sintered film has a porosity of less than 0.2%. In some examples, the sintered film has a density (density) of greater than 95%. In some examples, the sintered film has a density of greater than 96%. In some examples, the sintered film has a density of greater than 97%. In some examples, the sintered film has a density of greater than 98%. In some examples, the sintered film has a density of greater than 99%. In some examples, the sintered film has a density of greater than 99.5%. In some examples, the sintered film has a density of greater than 99.6%. In some examples, the sintered film has a density of greater than 99.7%. In some examples, the sintered film has a density of greater than 99.8%. In some examples, the sintered film has a density of greater than 99.9%.
In some examples, the sintered film roll may also include additional liners.
In some examples, including any of the preceding, the sintered film has a D of less than 5 micrometers (μm) 50 Grain size.
In some examples, including any of the preceding, the sintered film has a D of less than 5 microns 90 Grain size.
In some examples, including any of the preceding examples, the sintered film has a porosity of less than 5% by volume.
In some examples, including any of the preceding examples, the sintered film has an aspect ratio (height/diameter) of less than 100 protrusions per square centimeter of defect density on a surface greater than 1.
In some examples, including any of the preceding examples, the sintered film has an aspect ratio (height/diameter) of less than 100 depressions per square centimeter of defect density (valley) on a surface greater than 1.
In some examples, including any of the preceding examples, the sintered film has a defect density of less than 100 protrusions per square centimeter at an interface between the lithium-filled garnet film and the metal layer having an aspect ratio (height/diameter) greater than 1.
In some examples, including any of the preceding examples, the sintered film has less than 100 depressions per square centimeter of defect density at an interface between the lithium-filled garnet film and the metal layer having an aspect ratio (height/diameter) greater than 1.
In some examples, including any of the preceding examples, D 50 The grain size is at least 10nm.
In some examples, including any of the preceding examples, D 50 The grain size is at least 50nm.
In some examples, including any of the preceding examples, D 50 The grain size is at least 1 μm.
a. Sintered lithium filled garnet on metal foil
The CML disclosed in the present application can be used to sinter lithium filled garnet on metal foil. In some examples, the metal foil is a dense metal layer. In certain examples, the metal foil is a dense metal layer that also includes ceramic. In some such examples, the ceramic is a lithium-filled garnet.
In some examples, the metal foil or metal layer is nickel, steel, stainless steel, copper, aluminum, kovar, invar, ceramic, haynes216, or combinations thereof.
In some examples, LLZO is sintered onto a metal foil. In some of these examples, the metal foil is pure nickel. In some such examples, the metal foil is a combination of Ni and Fe. In some such examples, the metal foil is Ni/Fe 93%/7%.
In some examples, LLZO is sintered onto a metal foil. In some of these examples, the metal foil is pure copper. In some such examples, the metal foil is Cu/Fe 93%/7%. In some such examples, the metal foil is a combination of Cu and Fe.
In some examples, curvature is prevented from forming in the sintered film by CTE matching. CTE matching causes the Coefficients of Thermal Expansion (CTE) of the two layers to be the same. The interface between the two layers is formed/fixed during sintering at > 1000C. When the film cools to room temperature, if the CTE is different, one layer will shrink more than the other, forming a film that curves to one side (the more shrunk side), which is undesirable.
As used herein, "Invar" is a Ni/Fe material.
In some examples, the green tape deposited on the mylar foil described above is deposited on a metal layer. The metal may be nickel, steel, stainless steel, copper, aluminum, kovar, invar, ceramic on metal, haynes216, LLZO on Ni, or combinations thereof. In this example, the green tape need not be peeled from the mylar, but rather sintered directly to the metal. The green tape may be rolled with the metal before the green tape moves through the CML. In some examples, a backing layer is added to the metal, the backing layer and green tape being wound together on the metal. In some examples, interlayers are used when rolling up metal with green tape on top of the metal. The interlayer provides a cushion between the rolled layers.
b. Sintered lithium-filled garnet without substrate
In some examples, CML is used to sinter lithium-filled garnet without an underlying substrate.
c. Sintered lithium-filled garnet with co-sintered current collector
In some examples, CML is used to sinter a lithium-filled garnet layer adjacent to a co-sintered current collector (CSC). The CSC layer may comprise 0.0001-25 wt% Ni, 1-25 wt% Fe, or a combination thereof. In some cases, the CSC layer comprises 1-20 wt% Ni and 1-10 wt% Fe, with the remainder being lithium-stuffed garnet. In some cases, the CSC layer comprises 5-15 wt% Ni and 1-5 wt% Fe, with the remainder being lithium-stuffed garnet. In some cases, the CSC layer comprises 10-15 wt% Ni and 3-5 wt% Fe, with the remainder being lithium-stuffed garnet.
Other configurations are contemplated by the present application. For example, the bare film is configured as follows: sintered LLZO films without other metal-containing layers.
For example, the CSC or co-sintered configuration may include a bilayer of LLZO green films and cermet layer green films. The metal-ceramic layer is a metal and ceramic powder in the green state.
For example, the configuration on the foil may be as follows. This involves casting LLZO raw stock on the metal layer/foil. The metal layer is a dense layer, not a powder. In this case, the foil is free of ceramic and is commercially available and is typically made by a process other than sintering (e.g., electrodeposition or roll annealing). For example, ceramic-metal foils may also be employed for the on-foil construction. This includes the use of common metal foils, starting from metal-ceramic foils, so the final product resembles a CSC.
D. Atmosphere control
The complete system of the CML or various components of the CML (e.g., the oven) may be enclosed in an enclosure, which provides atmosphere control.
Various air curtains may be used with the CML complete system or various components thereof (e.g., ovens) to provide atmosphere control.
In some examples, atmosphere control includes the use of a narrow oven opening.
In some examples, atmosphere control includes using excess flow at the oven inlet and outlet. In some examples, atmosphere control includes using N around various components (e.g., rollers) 2 Or an Ar filled glove box. In some examples, atmosphere control includes using overpressure within the oven.
In some examples, the atmosphere control includes H in an oven 2 The amount of O. In some examples, atmosphere control includes controlling O in an oven 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 100 ppm. In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 10 ppm. In some examples, atmosphere control includes placing O in an oven 2 The amount is controlled to a level of less than 1 ppm. In some examples, atmosphere control includes controlling H in an oven 2 Is a combination of the amounts of (a) and (b). In some examples, atmosphere control includes controlling N in an oven 2 Amount of the components.
In some examples, the gas curtain is N 2 A curtain.
In some examples, an air box (tunnel configuration) is used with the exhaust.
In some examples, the gas supply tube is formed with an air tank having a feedback loop. In some examples, also include O in an oven 2 A sensor.
In some examples, the process will use atmosphere control. This may include, for example, placing O in a sintering furnace 2 Is controlled to an amount of less than 100ppm or even moreLow. In some examples, atmosphere control includes using N 2 Ar or other inert gas to form a curtain of gas around the furnace (e.g., around the inlet and outlet of the furnace). In some examples, atmosphere control includes using excess flow around the inlet and outlet of the oven. In some examples, atmosphere control includes the use of narrow openings around the inlet and outlet of the oven. In some examples, atmosphere control includes injecting a gas near the center of the oven. Such gas injection may result in laminar flow from the center to both ends of the oven. In some examples, atmosphere control includes achieving passive or active overpressure within the oven by using high airflow and low opening sizes around the inlet and outlet of the oven.
In some examples, atmosphere control includes providing an enclosed environment using an enclosure, such that atmosphere control is performed around or near the oven. Such as a nitrogen-filled enclosure, with some areas exposed to a reducing environment. The reducing environment can be realized by providing H 2 Or partial pressure of CO.
In some examples, the production line is partially enclosed within an atmosphere-controlled container or room. For example, the production line is completely enclosed in a clean room. In some such examples, the gas is introduced into a closed container or room (e.g., a clean room) that is free of particles. CDA refers to clean dry air, which is air or gas that is filtered to remove particles according to particle size. The gas may include N 2 Ar, synthesis gas (Ar/H) 2 Or N 2 /H 2 ) Or a combination thereof.
The pressure is measured by a pressure gauge and the gas flow is controlled by a mass flow controller.
E. Method of using CML and producing sintered articles
In some examples, the application sets forth a method of using a continuous production line comprising the operations of: (a) Providing or already providing a wound green tape on a front roller located at the front; (b) unwinding the green tape into an inlet of an oven; (c) burn out the binder; (d) firing the greenware; (e) Sintering the green tape in an oven as the green tape moves through the oven to produce a sintered film; (f) After leaving the oven through the outlet, the sintered film is wound onto a back roll; (g) The atmosphere in contact with the green tape being sintered is or has been controlled.
In this process, there are various examples of use, depending on certain conditions and the article to be produced. In some examples, a guide belt will be used. The guide tape is attached to the green tape with a high temperature ceramic (e.g., zirconia) epoxy. During the binder burn-out process, in some examples, the green tape is suspended such that the green tape is not in contact with a surface (e.g., a backing plate). During sintering, in some instances, the green tape is suspended such that the green tape is not in contact with a surface (e.g., a backing plate). This suspension can be achieved in a number of ways. For example, tension, air bearings, or other devices may be used to suspend the green tape. In some examples, the surfaces contacted before or after sintering of the green tape, such as the surfaces of the rolls, may be coated with nickel or an inert coating comprising nickel. During sintering, in some examples, the tape being sintered moves through a narrow gap made of nickel plated metal sheet. In some examples, the metal plate is a stainless steel metal plate. In some examples, the gap has a thickness of less than 5mm, the thickness being the maximum distance between the nickel plated metal plates perpendicular to one side of the metal plates. In some examples, the gap is less than 4.5mm. In some examples, the gap is less than 4mm. In some examples, the gap is less than 3.5mm. In some examples, the gap is less than 3mm. In some examples, the gap is less than 2.5mm. In some examples, the gap is less than 2mm. In some examples, the gap is less than 1.5mm. In some examples, the gap is less than 1mm. In some examples, the gap is less than 0.5mm. In some examples, the gap is less than 500 μm. In some examples, the gap is less than 400 μm. In some examples, the gap is less than 300 μm. In some examples, the gap is less than 200 μm. In some examples, the gap is less than 100 μm. In some examples, the narrow gap helps prevent lithium loss of the sintered article during sintering.
In some examples, the flatness of the green tape will be controlled by applying tension to the green tape. In some examples, the flatness of the green tape will be controlled by precise tape cutting, which applies minimal stress to the edges of the sintered article. In some examples, the flatness of the green tape will be controlled by laser cutting the edges of the article before or after sintering. In some examples, the flatness of the green tape will be controlled by adjusting the lateral heating profile, for example, by first heating the center of the film. In some examples, flatness is controlled by precise alignment of the tension applying roller with other rollers in the CML.
In some examples, the sintered microstructure (high density, small grains) of the sintered article produced is controlled by rapid sintering. In some examples, the sintered microstructure (high density, small grains) of the sintered article produced is controlled by a rate of temperature rise, by a belt speed, by multiple heating zones, or a combination thereof.
In some examples, the process will use atmosphere control. This may include, for example, placing O in a sintering furnace 2 Is controlled to an amount of less than 100ppm or even lower. In some examples, atmosphere control includes using N 2 Ar or other inert gas to form a curtain of gas around the furnace (e.g., around the inlet and outlet of the furnace). In some examples, atmosphere control includes using excess flow around the inlet and outlet of the oven. In some examples, atmosphere control includes the use of narrow openings around the inlet and outlet of the oven. In some examples, atmosphere control includes injecting a gas near the center of the oven. Such gas injection may result in laminar flow from the center to both ends of the oven. In some examples, atmosphere control includes achieving passive or active overpressure within the oven by using high airflow and low opening sizes around the inlet and outlet of the oven.
In some examples, atmosphere control includes using an enclosure to provide an enclosed environment, which is atmosphere controlled around or near an oven. Such as a nitrogen-filled enclosure, with some areas exposed to a reducing environment. The reducing environment can be realized by providing H 2 Or partial pressure of CO.
In some examples, green tape is rapidly sintered. Any given portion of the film spends between 15 seconds and 20 minutes at a temperature above room temperature. In other examples, any given portion of the film spends between 1 minute and 10 minutes at a temperature above room temperature. In other examples, any given portion of the film spends between 1 minute and 5 minutes at a temperature above room temperature. In other examples, any given portion of the film spends between 1 minute and 2 minutes at a temperature above room temperature.
To avoid surface contamination of the sintered or presintered article as it passes through the CML, the film may be cooled to below 40 ℃. In some examples, the membrane is maintained at low H 2 And the atmosphere with O content. For example, H 2 The O content is less than 10ppm. In some examples, the film is maintained in an atmosphere of primarily argon. In some examples, the membrane is maintained in an atmosphere of primarily nitrogen. In some examples, the membrane is maintained in Clean Dry Air (CDA).
Because the green tape shrinks during the CML process, a different tape speed (e.g., a different roll rotation speed) may be used in the green tape stage than in the binder burn-out stage or the sintering stage. Each section of the production line may have a different belt speed. In some examples, these different speeds may be achieved by independent tension control (e.g., a jump after greens oven (dander), tension control after sintering).
Due to the lateral shrinkage during sintering, the length of the sintered zone (in the belt direction) may be greater than the lateral shrinkage distance. This will cause the angle of the belt to become slightly lower.
The green tape strength may change during the CML process. To accommodate this, the tension in the strap may be varied throughout the CML. For example, in a binder burn-out oven, the belt is under one tension setting, but in a greenware oven the belt may be under a different tension setting, and in a sintering oven the belt may also be under another different tension.
In some examples, the green tape is peeled from the mylar substrate prior to passing through a continuous production line. This can be accomplished using sharp blades (e.g., 180 ° angle at the blade), tension control devices, and other devices.
In some examples, the method includes: (a) loading the green film roll on a front roll; (b) unwinding the green film; (c) sintering the green film to produce a sintered film; (d) The sintered film was wound onto a back roll in a controlled atmosphere. Rollers may be used to hold the green or sintered film in a desired position.
In some examples, the green tape is moved through the CML at a rate of about 2 to 25 inches per minute. In some examples, the green tape is moved through the CML at a rate of about 3 to 6 inches per minute. In some examples, the green tape is moved through the CML at a rate of about 1 inch to 5 inches per minute. In some examples, the green tape is moved through the CML at a rate of about 5 inches to 10 inches per minute.
In some examples, the belt moves through the CML at a rate of about 2-25 inches/minute. In some examples, the belt moves through the CML at a rate of about 3-6 inches/minute.
In some examples, including any of the preceding examples, the rate at which the belt moves through the CML refers to the distance and time spent moving through the sintering furnace.
Description of the embodiments
Embodiment 1: a continuous production line (CML), comprising:
a front roller;
a rear roller;
at least one sealed furnace located between the front roll and the rear roll, wherein the at least one furnace comprises: (a) a binder burn-out section; (b) a green billet; (c) a sintering section;
at least one atmosphere controller that controls at least one of the following conditions within the furnace: gas flow rate, flow direction, gas composition, pressure, and combinations thereof.
Embodiment 2: the CML of embodiment 1, further comprising a bilayer comprising a metal layer and a green layer wound on the front roll.
Embodiment 3: a continuous production line (CML), comprising:
a front roller having a double layer wound thereon, the double layer comprising a metal layer and a green layer;
a rear roller;
at least one melting furnace between the front roller and the rear roller;
at least one atmosphere controller that controls at least one of the following conditions within the furnace: gas flow rate, flow direction, gas composition, pressure, and combinations thereof.
Embodiment 4: the CML of embodiment 3, wherein the green layer comprises unsintered lithium-filled garnet.
Embodiment 5: the CML of embodiments 3 or 4, wherein the at least one furnace comprises: (a) a binder burn-out section; (b) a green billet; (c) a sintering section.
Embodiment 6: the CML of any of embodiments 1-2 or 5, wherein the sintered segment is not directly exposed to the earth's atmosphere.
Embodiment 7: the CML of any of embodiments 3 or 4, wherein the at least one furnace is not directly exposed to the earth's atmosphere.
Embodiment 8: the CML of any of embodiments 1-7, wherein the at least one furnace is sealed such that the at least one atmosphere controller controls gas flow into and out of the at least one furnace.
Embodiment 9: the CML of any of embodiments 1-8, wherein the flow rate in the binder burn-out section is higher than the flow rate in the green section, higher than the flow rate in the sinter section, or higher than the flow rates of both the green section and the sinter section.
Embodiment 10: the CML of any of embodiments 1-9, wherein the atmosphere controller maintains continuous atmospheric conditions within the at least one furnace.
Embodiment 11: the CML of any of embodiments 1-2 and 5-9, wherein the atmosphere controller maintains continuous atmospheric conditions within the binder burn-out section.
Embodiment 12: the CML of any of embodiments 1-2 and 5-11, wherein the atmosphere controller maintains continuous atmospheric conditions within the greenbody section.
Embodiment 13: the CML of any of embodiments 1-2 and 5-12, wherein the atmosphere controller maintains continuous atmospheric conditions within the sintering section.
Embodiment 14: the CML of any of embodiments 1-13, further comprising at least one air curtain coupled to the at least one furnace.
Embodiment 15: the CML of embodiment 14, comprising an air curtain at the inlet of the at least one furnace.
Embodiment 16: the CML of embodiments 14 or 15, comprising an air curtain at the outlet of the at least one furnace.
Embodiment 17: the CML of any of embodiments 1-16, comprising a pressurized gas line between the green compact and the sintering section that pumps gas into the green compact and the sintering section.
Embodiment 18: the CML of any of embodiments 1-17, comprising a vent in the binder burn-out section, green compact section, sintering section, or a combination thereof.
Embodiment 19: the CML of any of embodiments 1-18, wherein the at least one oven is enclosed in a sealed container.
Embodiment 20: the CML of any of embodiments 1-19, wherein embodiment 1: the CML is enclosed in a sealed chamber.
Embodiment 21: the CML of any of embodiments 1-19, wherein the adhesive burn-out section is enclosed in a sealed container.
Embodiment 22: the CML of any of embodiments 1-19, wherein the green compact is enclosed in a sealed container.
Embodiment 23: the CML of any of embodiments 1-19, wherein the sintered segment is enclosed in a sealed container.
Embodiment 24: the CML of any of embodiments 21-23, wherein the sealed container comprises Ar, N 2 、H 2 O、H 2 Or a combination thereof.
Embodiment 25: the CML of any of embodiments 1-24, wherein the atmosphere controller maintains a reducing atmosphere in the green compact.
Embodiment 26: the CML of any of embodiments 1-25, wherein the atmosphere controller maintains an atmosphere in the plain billet comprising argon (Ar), nitrogen (N) 2 ) Hydrogen (H) 2 ) A gas or a mixture thereof.
Embodiment 27: the CML of any of embodiments 1-26, wherein the atmosphere controller maintains a reducing atmosphere in the sintering section.
Embodiment 28: the CML of any of embodiments 1-27, wherein the atmosphere controller maintains an atmosphere in the sintering section comprising argon (Ar), nitrogen (N) 2 ) Hydrogen (H) 2 ) A gas or a mixture thereof.
Embodiment 29: the CML of any of embodiments 1-28, wherein the atmosphere controller maintains less than 500ppm O in the green body section, the sinter section, or both the green body section and the sinter section 2 Is a gas atmosphere of (a).
Embodiment 30: the CML of any of embodiments 1-24, wherein the atmosphere controller maintains less than 5% v/v H in the binder burn-out section 2 O atmosphere.
Embodiment 31: the CML of any of embodiments 26-30, wherein H 2 The gas is present at about 1, 2, 3, 4 or 5% v/v.
Embodiment 32: the CML of any of embodiments 26-31, wherein H 2 The gas is present at about 2.9% v/v.
Embodiment 33: the CML of any of embodiments 26-31, wherein H 2 The gas is present at about 5% v/v.
Embodiment 34: the CML of any of embodiments 1-33, wherein the at least one furnace or a portion thereof is under vacuum at a pressure of less than 1 atmosphere (atm).
Embodiment 35: the CML of any of embodiments 1-34, wherein the at least one furnace or a portion thereof is under vacuum at a pressure of less than 100 torr.
Embodiment 36: the CML of any of embodiments 1-35, wherein the ambient atmosphere in the binder burn-out section is different than the ambient atmosphere in the green compact section.
Embodiment 37: the CML of any of embodiments 1-36, wherein the ambient atmosphere in the binder burn-out section is different than the ambient atmosphere in the sintering section.
Embodiment 38: the CML of any of embodiments 1-37, wherein the ambient atmosphere in the green compact is different from the ambient atmosphere in the sintered compact.
Embodiment 39: the CML of any of embodiments 1-37, wherein the O in the binder burn-out section 2 The amount of (2) is less than 0.2% by volume.
Embodiment 40: the CML of any of embodiments 1-38, wherein the CO in the binder burn-out section 2 The amount of (2) is less than 0.2% by volume.
Embodiment 41: the CML of any of embodiments 1-40, wherein the sintered segment is derived from CO 2 The amount of carbon in (c) is less than 100 parts per million (ppm).
Embodiment 42: the CML of any of embodiments 1-40, wherein in the sintering section is derived from CO 2 The amount of carbon is about 50ppm to 100ppm.
Embodiment 43: the CML of any of embodiments 2-42, wherein the bilayer shrinks primarily in the z-direction as it moves through the sintering section.
Embodiment 44: the CML of any of embodiments 2-43, wherein embodiment 1: the CML is configured to heat the bilayer at a rate of greater than 2.5 ℃/minute.
Embodiment 45: the CML of any of embodiments 2-44, wherein embodiment 1: the CML is configured to heat the bilayer at a rate of greater than 5 ℃/minute, 50 ℃/minute, or 300 ℃/minute.
Embodiment 46: the CML of any of embodiments 2-43, wherein embodiment 1: the CML is configured to heat the bilayer at a rate of about 5 ℃/minute to about 50 ℃/minute.
The CML of any of embodiments 1-46, comprising an infrared heater.
The CML of any of embodiments 1-48, comprising an induction carbon plate heater.
The CML of any of embodiments 2-48, wherein embodiment 1: the CML is configured to have a residence time in the sintering section of two minutes or less.
Embodiment 50: the CML of any one of embodiments 2-49, wherein embodiment 1: the CML is configured to have a residence time in the sintering section of about thirty seconds.
Embodiment 51: the CML of any of embodiments 2-50, wherein embodiment 1: the CML is configured such that the residence time in the binder burn-out section is about ten times the residence time in the sintering section.
Embodiment 52: the CML of any of embodiments 1-51 comprising at least one tension adjuster.
Embodiment 53: the CML of embodiment 52, wherein the tension of the bi-layer after the front roll is 270g.
Embodiment 54: the CML of embodiments 52 or 53 wherein the tension of the bi-layer prior to the back roll is 500g.
Embodiment 55: the CML of any of embodiments 52-54, wherein the bilayer has a width of 8cm.
Embodiment 56: the CML of any of embodiments 52-55, wherein the bilayer has a tension of about 34g/cm.
Embodiment 58: the CML of any of embodiments 52-55, wherein the bilayer has a tension of about 35N/10 μm.
Embodiment 58: the CML of any of embodiments 52-55, wherein the bilayer has a tension less than 50% of its yield strength.
Embodiment 59: the CML of any of embodiments 52-55, wherein the bilayer has a tension less than 50% of the yield strength of the metal layer.
Embodiment 60: the CML of any of embodiments 52-55, wherein the bilayer has a tension of about 25% to 50% of its yield strength.
Embodiment 61: the CML of any of embodiments 52-55, wherein the bilayer has a tensile force of about 25% to 50% of the yield strength of the metal layer.
Embodiment 62: the CML of any of embodiments 1-61, wherein the green body is a green tape.
Embodiment 63: the CML of any of embodiments 1-62, wherein the green body is a small piece of green tape.
Embodiment 64: the CML of any of embodiments 2-63, wherein as the bilayer moves through embodiments: CML, it is oriented for curtain processing.
Embodiment 65: the CML of any of embodiments 2-64 wherein as the bilayer moves through embodiments: CML, it is oriented for vertical processing.
Embodiment 66: the CML of any of embodiments 1-65, having an intermediate roll after the binder burn-out section as the bilayer moves through the embodiment: in CML, the bilayer is wound around the intermediate roll.
Embodiment 67: the CML of embodiment 66, wherein the two layers on the intermediate roll do not comprise an adhesive in the green body.
Embodiment 68: the CML of any of embodiments 1-67, wherein the at least one furnace is provided with a green tape inlet.
Embodiment 69: the CML of any of embodiments 1-68, wherein the metal layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.
Embodiment 70: the CML of embodiment 69, wherein the metal layer is an alloy of Fe and Ni.
Embodiment 71: the CML of embodiments 69 or 70, wherein the metal layer is an alloy of Fe and Ni, the amount of Fe being 1% to 25% (w/w), the remainder being Ni.
Embodiment 72: the CML of any of embodiments 1-71, wherein the metal layer has a thickness of 1 μm to 20 μm.
Embodiment 73: the CML of any of embodiments 1-71, wherein the metal layer has a thickness of 1 μm to 10 μm.
Embodiment 74: the CML of any of embodiments 1-71, wherein the metal layer has a thickness of 5 μm to 10 μm.
Embodiment 75: the CML of any of embodiments 1-74 wherein the bilayer moves through embodiments as it moves: CML is not supported by air bearings.
Embodiment 76: the CML of any of embodiments 1-75 wherein the bilayer moves through embodiments as it moves: CML is suspended.
Embodiment 77: the CML of any of embodiments 1-76, wherein the bilayer is suspended as the bilayer moves through the binder burn-out section.
Embodiment 78: the CML of any of embodiments 1-77, wherein the bilayer is suspended as it moves through the green compact.
Embodiment 79: the CML of any of embodiments 1-78, wherein the bilayer is suspended as it moves through the sintering section.
Embodiment 80: the CML of any of embodiments 1-79, wherein the binder burn-out section is a binder burn-out oven.
Embodiment 81: the CML of embodiment 80, wherein the binder burn-out furnace is a furnace heated to a temperature sufficient to volatilize, pyrolyse, burn, or decompose the binder in the green body.
Embodiment 82: the CML of embodiment 81, wherein the temperature in the binder burn-out oven is between 100 ℃ and 500 ℃.
Embodiment 83: the CML of embodiments 81 or 82 wherein the binder burn-out oven comprises some oxygen.
Embodiment 84: the CML of any of embodiments 1-83, wherein the green compact segments are green compact furnaces.
Embodiment 85: the CML of embodiment 84, wherein the green body oven is a furnace heated to a temperature sufficient for the green body to be greened after the binder is removed.
Embodiment 86: the CML of embodiment 85, wherein the temperature in the greenbody oven is between 100 ℃ and 800 ℃.
Embodiment 87: the CML of any of embodiments 1-86, wherein the sintering section is a sintering furnace.
Embodiment 88: the CML of embodiment 87, wherein the sintering furnace is a furnace heated to a temperature sufficient to sinter the green body.
Embodiment 89: the CML of embodiments 87 or 88, wherein the sintering furnace is a furnace heated to a temperature sufficient to sinter the lithium-stuffed garnet.
Embodiment 90: the CML of embodiments 87 or 88, wherein the temperature in the sintering furnace is between 500 ℃ and 1300 ℃.
Embodiment 91: the CML of any of embodiments 80-91, wherein the adhesive burn-up oven is hermetically coupled to the green body oven and the green body oven is hermetically sealed to the sintering oven.
Embodiment 92: the CML of any of embodiments 1-91, wherein the at least one furnace is a single furnace.
The CML of any of embodiments 1-92, wherein the at least one back roll has a diameter greater than 6cm.
Embodiment 94: the CML of any of embodiments 1-93, wherein the at least one back roll has a winding tension greater than 20 g/linear cm.
Embodiment 95: the CML of any of embodiments 1-94, wherein the air spaces above and below the bilayer are configured to maintain a lithium-rich atmosphere in contact with the sintered membrane.
Embodiment 96: the CML of any of embodiments 1-95, wherein the air spaces above and below the bilayer are configured to hold at least 95 wt% lithium in the lithium filled garnet.
Embodiment 97: the CML of any of embodiments 1-96, comprising at least two back rollers.
Embodiment 98: the CML of any of embodiments 2-97, wherein the green body comprises unsintered lithium-filled garnet or a chemical precursor of lithium-filled garnet.
Embodiment 99: the CML of any of embodiments 1-98, comprising a sintered bilayer wound on the at least one back roll.
Embodiment 100: the CML of embodiment 99, wherein the sintered bilayer comprises a sintered lithium-stuffed garnet.
Embodiment 101: the CML of any of embodiments 1-100, wherein the green body comprises a binder.
Embodiment 102: the CML of any of embodiments 1-101, wherein the green body comprises a dispersant.
Embodiment 103: the CML of any of embodiments 1-102, wherein the green body comprises a solvent or a combination of solvents.
Embodiment 105: the CML of any of embodiments 2-103, wherein embodiments: the CML is configured to move the bilayer through at least one furnace at a rate of at least 2 inches/minute.
Embodiment 105: the CML of any of embodiments 2-103, wherein embodiments: the CML is configured to move the bilayer through the sintering section at a rate of at least 2 inches/minute.
Embodiment 106: the CML of any of embodiments 1-103, further comprising a curved ramp prior to the at least one furnace.
Embodiment 107: the CML of any of embodiments 1-103, further comprising a curved ramp prior to the binder burn-out section.
Embodiment 108: the CML of any of embodiments 1-103, further comprising a curved ramp prior to the green billet.
Embodiment 109: the CML of any of embodiments 1-103, further comprising a curved ramp prior to the sintering section.
Embodiment 110: the CML of any of embodiments 1-103, further comprising a curved ramp inside the at least one furnace.
Embodiment 111: the CML of any of embodiments 1-103, further comprising a curved ramp inside the burn-up section.
Embodiment 112: the CML of any of embodiments 1-103, further comprising a curved ramp inside the greenbody section.
Embodiment 113: the CML of any of embodiments 1-103, further comprising a curved ramp inside the sintering section.
Embodiment 114: the CML of any of embodiments 106-113, wherein the curved ramp has a coating thereon.
Embodiment 115: the CML of embodiment 114, wherein the coating is a lithium aluminate coating.
Embodiment 116: the CML of embodiment 114, wherein the coating is a boron nitride coating.
Embodiment 117: the CML of any of embodiments 106-114, wherein the upper surface of the curved ramp is made of ceramic.
Embodiment 118: the CML of embodiment 115, wherein the ceramic is silicon carbide, boron nitride, aluminum oxide, zirconium oxide, lithium aluminate.
Embodiment 119: the CML of any of embodiments 106-118, wherein 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.
Embodiment 120: the CML of any of embodiments 1-119, comprising a deceleration strip, the bilayer being moveable through the embodiments: CML passes over the deceleration strip.
Embodiment 121: the CML of any of embodiments 1-120 comprising at least one curved racetrack.
Embodiment 122: the CML of any of embodiments 1-121, comprising at least one curved racetrack that curves in the z-and x-directions.
Embodiment 123: the CML of embodiments 121 or 122, the racetrack is made of SS 430, SS 304, kovar, invar, haynes 214, greater than 99.5% (w/w) alumina, carbon-carbon composite, boron nitride, or a combination thereof.
Embodiment 124: a method of using a continuous production line comprising the operations of:
(a) Providing or having provided a CML as described in any one of embodiments 1-123;
(b) Sintering the green body as it moves through at least one furnace to produce a sintered body;
(c) The sintered body was wound around a rear roll.
Embodiment 125: the method of embodiment 124, comprising controlling or having controlled an atmosphere in the at least one furnace.
Embodiment 126: the method of any of embodiments 124-125, comprising moving the green body or the resulting sintered body through the at least one furnace at a rate of at least two inches per minute in a direction of movement of the green tape.
Embodiment 127: the method according to any of embodiments 124-125, wherein the bilayer has a thickness of less than 200 μm.
Embodiment 128: a sintered article made by the method of any one of embodiments 124-127.
Embodiment 129: the sintered article of embodiment 128, wherein the metal layer is less than 10 weight percent (w/w) of the total weight of the bilayer.
Embodiment 130: the sintered article of embodiment 128 or 129, wherein the bilayer has less than 20 Ω -cm at room temperature 2 Is a surface specific resistivity of (c).
Embodiment 131: the sintered article of any of embodiments 128-130, wherein the bilayer has less than 20 Ω -cm at 20 ℃ 2 Is a surface specific resistivity of (c).
Embodiment 132: the sintered article of any of embodiments 128-131, wherein the bilayer has a thickness from about 30 μιη to 50 μιη.
Embodiment 133: the sintered article of any of embodiments 128-132, wherein the bilayer has a thickness of about 30 μιη, 40 μιη, or 50 μιη.
Embodiment 134: the sintered article of any of embodiments 128-133, wherein the surface of the bilayer opposite the metal layer is free of defects.
Embodiment 135: the sintered article of any of embodiments 128-134, wherein the bilayer has a D of about 50 μιη 90 Ceramic grain size.
Embodiment 136: the sintered article of any of embodiments 128-135, wherein the bilayer has a D of about 25 μιη 90 Ceramic grain size.
Embodiment 137: the sintered article of any of embodiments 128-136, wherein the bilayer has a D of about 5 μιη 90 Ceramic grain size.
Embodiment 138: the sintered article of any of embodiments 128-137, wherein the bilayer comprises a sintered lithium-stuffed garnet oxide.
Embodiment 139: the sintered article of any of embodiments 128-138, wherein the bilayer has less than 5 volume percent porosity as determined by Scanning Electron Microscopy (SEM).
Embodiment 140: the sintered article of any of embodiments 128-139, wherein the bilayer has less than 0% porosity as measured by BET surface area analysis.
Embodiment 141: the sintered article of any of embodiments 128-140, wherein the bilayer has less than 0 volume percent porosity as measured by the helium leak test.
Embodiment 142: a sintered film or bilayer comprising lithium-filled garnet, wherein the film is wound on a roll and the film thickness is less than 100 μm.
Embodiment 143: the sintered film or bilayer of embodiment 142 the lithium-stuffed garnet is in excess of 100 μm 2 Area of (2)There are no defects.
Embodiment 144: the sintered film or bilayer of embodiment 142 above the lithium-stuffed garnet over more than 100mm 2 Is free of defects in the area of (a).
Embodiment 145: the sintered film or bilayer of embodiment 142 above the lithium-stuffed garnet over more than 100cm 2 Is free of defects in the area of (a).
Embodiment 146: the sintered film or bilayer of any of embodiments 142-145 over more than 100mm on a lithium filled garnet 2 Is free of defects in the area of (a).
Embodiment 147: the sintering film or bilayer of any of embodiments 142-146 wherein the lithium filled garnet has a D of about 50 μm 90 Grain size.
Embodiment 148: the sintered film or bilayer of any of embodiments 142-147 wherein the lithium filled garnet has a D of about 25 μm 90 Grain size.
Embodiment 149: the sintering film or bilayer of any of embodiments 142-148 wherein the lithium filled garnet has a D of about 5 μm 90 Grain size.
Embodiment 150: the sintering film or bilayer of any of embodiments 142-149 wherein embodiment: the sintered film or bilayer comprises a lithium-filled garnet oxide.
Embodiment 151: the sintering film or bilayer of any of embodiments 142-150 wherein embodiment: the sintered film or bilayer has a porosity of less than 5% by volume as determined by Scanning Electron Microscopy (SEM).
Embodiment 152: the sintering film or bilayer of any of embodiments 142-151 wherein embodiment: the sintered film or bilayer has a porosity of 0% as measured by BET surface area analysis.
Embodiment 153: the sintering film or bilayer of any of embodiments 142-152 wherein embodiment: the sintered film or bilayer has a porosity of 0% by volume as measured by the helium leak test.
Embodiment 154: the sintering film or bilayer of any of embodiments 142-153 wherein embodiment: the sintered film or bilayer has a D of less than 5 micrometers (μm) 50 Grain size.
Embodiment 155: the sintering film or bilayer of any of embodiments 142-154 wherein embodiment: the sintered film or bilayer has a D of less than 5 μm 90 Grain size.
Embodiment 156: the sintering film or bilayer of any of embodiments 142-155 wherein embodiment: the sintered film or bilayer has a porosity of less than 5 volume percent as measured by SEM.
Embodiment 157: the sintered film or bilayer of any of embodiments 142-156 wherein the lithium filled garnet has less than 100 protrusions per square centimeter of defect density on a surface having an aspect ratio (height/diameter) greater than 1.
Embodiment 158: the sintered film or bilayer of any of embodiments 142-157 wherein the lithium filled garnet has less than 100 depressions per square centimeter of defect density on a surface having an aspect ratio (height/diameter) greater than 1.
Embodiment 159: the sintered film or bilayer of embodiment 142 or 158 wherein the lithium-stuffed garnet D 50 The grain size is at least 10nm.
Embodiment 160: the sintered film or bilayer of embodiment 142 or 159 wherein the lithium fills garnet D 50 The grain size is at least 50nm.
Embodiment 161: the sintered film or bilayer of embodiment 142 or 160 wherein the lithium-stuffed garnet D 50 The grain size is at least 1 μm.
Embodiment 162: the sintering film or bilayer of any of embodiments 142-155 wherein embodiment: the sintered film or bilayer is free of wrinkles in the transverse direction.
Embodiment 163: the method of any of embodiments 124-127, wherein the bilayer moves across the CML with only the metal layer contacting the surface of the CML.
Embodiment 125: the method of embodiment 124 or 125, further comprising manufacturing a rechargeable battery using the sintered body.
Examples
Unless stated to the contrary, reagents, chemicals, and materials are commercially available.
Soft pack battery (pouch cell) containers were purchased from Showa Denko.
The electrochemical potentiostat used was an Arbin potentiostat.
Electrical Impedance Spectroscopy (EIS) tests were performed using biological VMP3, VSP-300, SP-150 or SP-200.
Electron microscopy scans were performed in FEIQuanta SEM, apreo SEM, helios 600i or Helios 660 FIB-SEM.
Transmission electron microscopy measurements were performed as follows.
Sample preparation: samples for TEM measurements were prepared using a Ga ion source focused ion beam (nanoDUE' T NB5000, hitachi High-Technologies). To protect the material surface from Ga ion beam, a multilayer protective layer is deposited before sampling: first, a metal layer is deposited by a plasma coater, and then a carbon protective layer and a tungsten layer are deposited by high vacuum evaporation and focused ion beam, respectively. Sheet sampling is performed by focusing the ion beam. The prepared samples were measured by TEM.
X-ray powder diffraction (XRD) was performed with Cu K-. Alpha.radiation in Bruker D8 Advance A25 at room temperature (e.g., between 21℃and 23 ℃). The light source is Cu-Ka, and the wavelength is X-rays at 40kV and 25 mA. The detector comprises: lynxeye_xe, PSD opening 2.843. The divergent slit is fixed at 0.6mm and the anti-scatter fixed at 5.0mm.
Milling was performed with a Retsch PM 400 planetary ball mill. Mixing was performed using a Fischer Scientific vortex mixer, a fluktek high speed mixer, or a Primix filmix homogenizer.
Casting was performed on a TQC calender station. Calendering was performed on an IMC calender.
Light scattering was performed on Horiba, model: particle, model: LA-950V2, common name: laser scattering particle size distribution analyzer.
The lithium nickel cobalt manganese oxide (NMC) used in the examples was LiNi 0.85 Co 0.1 Mn 0.05 O 2 Unless otherwise indicated.
Example 1: making sintered rolls (prophetic example)
In this example, a slurry was prepared by mixing lithium-filled garnet, a solvent, a binder and a plasticizer. The following slurry compositions were used.
Slurry one: LLZO powder was dispersed in ethanol containing 2wt% polyacrylic acid using an ultrasonic horn. Allowing larger particles to settle. The supernatant was decanted and the recovered powder was dried in air. The collected powder, polyvinyl butyral, butyl benzyl phthalate, acetone and ethanol were added to a vial in a weight ratio of 37:3:3:29:29, and ZrO 2.0mm in diameter was used 2 Ball milling for 10-24 hours. Casting the slurry onto a polyester film substrate using a doctor blade; the thickness of the film is controlled by adjusting the height of the blade. The dried green film was manually peeled from the mylar substrate and cut to the desired size.
And (3) slurry II: LLZO powder containing 3wt% polyacrylic acid was dispersed in ethanol. Polyvinyl butyral, butyl benzyl 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 are mixed in equal volume ratio. Mixing the obtained slurry with ZrO 2 The beads were milled together for 8-16 hours. The slurry was cast onto a polyester film substrate using a doctor blade and the film thickness was controlled by adjusting the blade height. The green film dried in air was manually peeled from the mylar substrate and cut to the desired dimensions.
And (3) slurry III: methyl cellulose, polyethylene glycol and glycerin are dissolved in water to prepare a polymer aqueous solution. The weight ratio of the components is water, methylcellulose, polyethylene glycol and glycerin=100:1:4:4. The same weight of LLZO (lithium filled garnet) powder as the solution was added to the polymer solution. With ZrO 2 The beads mix the slurry for 5-60 minutes. Casting the slurry onto a polyester film substrate using a doctor blade by conditioning Blade gap to control film thickness. After drying in air, the green film was manually peeled from the mylar substrate and cut to size.
And (3) slurry IV: LLZO was ball milled in equal parts of a mixture of ethanol, xylene, toluene. 2-5wt% of herring oil relative to LLZO was added dropwise over 30 minutes. 6 to 10% by weight of polyvinyl butyral, 2 to 4% by weight of polyethylene glycol and 3 to 7% by weight of butyl benzyl phthalate are added relative to LLZO and mixed. The tape was formed by doctor blade casting onto a mylar substrate. After drying at 45 ℃ for 1-6 hours, the tape was peeled from the mylar substrate and cut to size.
Slurry five: 100g LLZO powder, 2-4g triolein, 100-200g n-propyl propionate, 15-25g Elvacite E-2046 were mixed and ball milled to prepare a slurry. The slurry was cast onto the substrate with a doctor blade, dried and peeled off the substrate.
Slurry six: 20g of LLZO powder, 25-40g of mixed solvent (ethanol: butanol: propylene glycol according to the volume percentage of 70-80:15-25:0-5), 1-3g of dibutyl phthalate, 1-4g of PVB and 0.1-1g of dispersing agent are placed into a grinding machine to be mixed, and a slurry is prepared. The dispersant may be, for example, an Anti-terra-202 dispersant from BYK. After mixing, the slurry was filtered, degassed, and cast onto a substrate by reverse comma coating. The green tape was dried, peeled from the substrate, and cut to size.
Slurry seven: water (30 parts by mass), LLZO powder (12-18 parts by mass) and a binder solution (WB 4101, WB40B-44, WB40B-53,8 parts by mass from Polymer Innovations) were mixed in a mill for at least 1 hour to prepare a slurry. After mixing, the slurry was filtered, degassed and coated onto a substrate through a slot die. The green tape was dried, peeled from the substrate, and cut to size.
Slurry eight: the LLZO powder was milled in a mixed solvent of toluene and isopropanol plus fish oil. Mixing for 1-5 hours, and making the mixture into slurry. Toluene, isopropanol, polyvinyl butyral, and butyl benzyl phthalate were mixed to form a binder solution. The binder solution is added to the slurry and mixed. The mixture was degassed, filtered and cast onto a polymer support. The green tape was dried and cut into 10-40 cm long sheets. The sheet is peeled from the carrier and cut to size.
And (3) slurry nine: 80g of calcined LLZO powder was mixed with 50ml of a 33% w/w toluene solution of polyvinyl butyral and 4g of the plasticizer dibutyl phthalate to produce a calcined LLZO slurry. The content of polyacrylic acid binder was 3% by weight of the solution. The slurry was cast onto a silicone coated mylar substrate using a doctor blade. The cast mixed slurry was dried at room temperature for 2 to 6 hours to form a green film. The green film was cut into 10-40 cm long sheets. The sheet is peeled from the carrier and cut to size.
The slurry may be cast onto nickel foil and dried and then rolled up.
After drying, the dried slurry on the nickel foil was placed on a continuous production line. Green tape is formed as the slurry dries on a nickel foil and moves through the apparatus shown in fig. 3.
In the first step, the green tape is heated to burn off the adhesive.
And secondly, heating the green tape in a biscuit baking oven.
Third, the green tape is sintered at about 1100 ℃ to form a sintered film.
The sintered film may be wound on a back roll as shown in fig. 3.
The green tape is moved back and forth between the green body oven and the binder burn-out oven. The film is selectively heated in either the greenware oven or the adhesive burn-out oven by opening and closing the oven. For sintering, the temperature of the greenbody oven is raised to the sintering temperature.
Example 2: manufacturing sintered coil
In this example, a slurry was prepared by mixing lithium-filled garnet, a solvent, a binder and a plasticizer.
Specifically, lithium-stuffed garnet is mixed with an acrylic binder and butyl benzyl phthalate in an aprotic solvent to form a slurry. The slurry was poured onto nickel foil to form a bilayer. The slurry was dried and then rolled up.
After drying, the dried slurry on the nickel foil was placed on a continuous production line. Green tape is formed when the slurry is dried over a nickel foil. The green tape then moves through the apparatus shown in fig. 3.
The bilayer was passed through the CML at a rate of 5 cm/min and was left in the sintering zone at a temperature of about 1100 ℃ for about 10 minutes.
A cross-sectional scanning electron microscope image of the sintered film produced by this process is shown in fig. 4. The sintered lithium fills the garnet Dan Zhimi and is combined with the underlying nickel film. The porosity of the lithium-filled garnet is less than 2% v/v.
A top-down scanning electron microscope image of the sintered film produced by this process is shown in fig. 5. The sintered lithium fills the garnet Dan Zhimi without defects on the surface.
Example 3: manufacture of sintered rolls with controlled grain and grain size
In this example, a slurry was prepared as in example 2.
The slurry is processed by batch and continuous processes.
The grain size of the sintered film was measured by SEM. The particle size of the added reactants was measured by a particle size analyzer. The results are shown in FIG. 8. The films treated by the batch process are shown in dashed lines and the films treated by the continuous process are shown in solid lines.
The results show that as the particle size of the added reactants increases, so does the grain size.
The sintered film produced by this process is shown in fig. 5 in Plan View (PV) or top-down scanning electron microscope images. Sintered lithium fills garnet Dan Zhimi without defects. Fig. 5 shows a relatively small grain size. D (D) 50 About 1.1 μm.
A cross-sectional scanning electron microscope image of the sintered film produced by this process is shown in fig. 9. The sintered lithium fills the garnet Dan Zhimi and is bonded to the underlying nickel film. The film shown in fig. 10 was sintered at 1140 ℃. The porosity of the membrane was 1.8% v/v. The bottom of the film shows a foil of 5 μm ED.
A cross-sectional scanning electron microscope image of the sintered film produced by this process is shown in fig. 10. The sintered lithium fills the garnet Dan Zhimi and is bonded to the underlying nickel film. The film shown in fig. 10 was sintered at 1140 ℃. The porosity of the membrane was 1.8% v/v. The bottom of the film shows a foil of 5 μm ED.
A top-down scanning electron microscope image of the sintered film produced by this process is shown in fig. 11. The sintered lithium fills the garnet Dan Zhimi without surface defects.
Example 4: test sintering roll
Sintered films were prepared as in example 2. The Area Specific Resistance (ASR) was measured by electrical impedance spectroscopy.
On average, ΔASR was 39 Ω cm 2 。
The battery cell was prepared and then at 30℃and constant current density of 0.33mA/cm 2 And an operating voltage of 3V to 4.2V. A current pulse was applied for 30 minutes, the current stopped, and the relaxation (relaxation) system was stopped for 3 minutes. The intermittent pulse is repeated until the battery voltage reaches 4.2V during charging and 3V during discharging. The Area Specific Resistance (ASR) of the cell is obtained by reading the voltage drop during the relaxation step (relaxation steps) during charging.
Example 5: manufacture and testing of sintered bilayers
A sintered bilayer membrane was prepared as in example 2. Specifically, lithium-stuffed garnet is mixed with an acrylic binder and butyl benzyl phthalate in an aprotic solvent to form a slurry. The slurry was cast onto nickel foil to form a bilayer.
A bilayer (known as a web) was formed, the web was moved through the CML at a speed of 5 cm/min and held at a temperature of about 1100 ℃ in the sintering section for about 10 minutes.
The cell was cycled at a 1C charge rate, a 1C discharge rate, at 30℃and 50 pounds Per Square Inch (PSI) (-3.4 atm). The results are shown in FIG. 21.
The foregoing embodiments and examples are illustrative only and not intended to be limiting. Based on routine experimentation, one of ordinary skill in the art will recognize or be able to ascertain many equivalents to the specific compounds, materials, and processes. All such equivalents are within the scope of the application and are intended to be covered by the following claims.
Claims (32)
1. A continuous production line (CML), comprising:
a front roller;
a rear roller;
at least one sealed furnace located between the front roll and the rear roll, wherein the at least one furnace comprises: (a) a binder burn-out section; (b) a green billet; (c) a sintering section;
at least one atmosphere controller that controls at least one of the following conditions within the furnace: gas flow rate, flow direction, gas composition, pressure, and combinations thereof.
2. The CML of claim 1, further comprising a bilayer comprising a metal layer and a green layer wound on the front roll.
3. A continuous production line (CML), comprising:
a front roller having a double layer wound thereon, the double layer comprising a metal layer and a green layer;
a rear roller;
at least one melting furnace between the front roller and the rear roller;
at least one atmosphere controller that controls at least one of the following conditions within the furnace: gas flow rate, flow direction, gas composition, pressure, and combinations thereof.
4. A CML as claimed in claim 3 wherein the at least one furnace comprises: (a) a binder burn-out section; (b) a green billet; (c) a sintering section.
5. The CML of any of claims 1-4, wherein 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.
6. The CML of any of claims 1-5, comprising a pressurized gas line between the green compact and the sintering section that pumps gas into the green compact and the sintering section.
7. The CML of any of claims 1-6, wherein the at least one furnace is enclosed in a sealed container.
8. The CML of claim 7, wherein the sealed container comprises Ar, N 2 、H 2 O、H 2 Or a combination thereof.
9. The CML of any one of claims 1-8, wherein the atmosphere controller maintains a reducing atmosphere in the sintering section.
10. The CML of any one of claims 1-9, wherein the atmosphere controller maintains an atmosphere in the sintering section comprising argon (Ar), nitrogen (N) 2 ) Hydrogen (H) 2 ) A gas or a mixture thereof.
11. The CML of any of claims 1-10, wherein the atmosphere controller maintains less than 500ppm O in the green block section, the sinter section, or both the green block section and the sinter section simultaneously 2 Is a gas atmosphere of (a).
12. The CML of claim 10 or 11, wherein H 2 The gas is present at about 1, 2, 3, 4 or 5% v/v.
13. The CML of any of claims 1-12, wherein the green body is a green tape.
14. The CML of any of claims 1-13, wherein the green body is a small piece green tape.
15. A CML according to any one of claims 2-14 wherein the bilayer is oriented for curtain treatment as it moves through the CML.
16. A CML according to any one of claims 2-15 wherein the bilayer is oriented for vertical processing as it moves through the CML.
17. The CML of any one of claims 1-16, wherein the metal layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.
18. The CML of claim 17, wherein the metal layer is an alloy of Fe and Ni.
19. A CML as claimed in claim 17 or 18, wherein the metal layer is an alloy of Fe and Ni, the amount of Fe being 1% to 25% (w/w), the remainder being Ni.
20. The CML of any one of claims 1-19, wherein the metal layer has a thickness of 1 μιη to 20 μιη.
21. A CML according to any one of claims 1-20, wherein the bilayer is suspended as it moves through the CML.
22. The CML of any of claims 1-21, comprising a sintered bilayer wound on the at least one back roller.
23. The CML of claim 22, wherein the sintered bilayer comprises a sintered lithium filled garnet.
24. The CML of any of claims 2-23, wherein CML is configured to move the bilayer through the at least one furnace at a rate of at least 2 inches/minute.
25. The CML of any of claims 1-24, further comprising a curved ramp prior to the sintering section.
26. The CML of any of claims 1-25, further comprising a curved ramp inside the at least one furnace.
27. A method of using a continuous production line comprising the operations of:
(a) Providing or having provided a CML as defined in any one of claims 1-26;
(b) Sintering the green body as it moves through the at least one furnace to produce a sintered body;
(c) The sintered body was wound around a rear roll.
28. The method of claim 27, comprising controlling or having controlled an atmosphere in the at least one furnace.
29. A sintered article produced by the method of claim 27 or 28.
30. A bilayer comprising a lithium filled garnet, the bilayer film being wound on a roll and the bilayer thickness being less than 100 μm.
31. The bilayer of claim 30 wherein the bilayer comprises a layer of lithium-filled garnet and a layer of metal foil, wherein the lithium-filled garnet layer has a thickness of 10-30 μιη and the metal foil layer has a thickness of 2-10 μιη.
32. The bilayer of claim 31 wherein the metal foil layer comprises nickel, iron or a combination thereof.
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| US63/158,861 | 2021-03-09 | ||
| US202163233684P | 2021-08-16 | 2021-08-16 | |
| US63/233,684 | 2021-08-16 | ||
| PCT/US2022/019641 WO2022192464A1 (en) | 2021-03-09 | 2022-03-09 | Rapid ceramic processing techniques and equipment |
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| CN117015688A true CN117015688A (en) | 2023-11-07 |
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