Process and materials for casting and sintering green garnet thin films

Abstract

To provide: precursor materials of inorganic thin films (e.g., green tapes or sintered films made from green tapes); methods for using these precursors to make sintered thin films; and sintered thin films made by the processes set forth herein.SOLUTION: Set forth herein are processes and materials for making ceramic thin films by casting ceramic source powders and precursor reactants, binders, and functional additives into unsintered thin films and subsequently sintering the thin films under controlled atmospheres and on specific substrates. The green tapes which are set forth herein and used for making sintered thin films have a higher solid loading than known green tapes. The sintered thin films prepared by the processes herein have a lower porosity, a higher density, and less defects, and / or are prepared in higher yield than known sintered thin films.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] This application claims priority and the benefit thereof to U.S. Provisional Patent Application No. 62 / 195,172, filed Jul. 21, 2015, the content of which is hereby incorporated by reference in its entirety for all purposes. (Processes and Materials for Casting and Sintering Green Garnet Thin Films)

[0002] (Field) The present disclosure relates to precursors of inorganic thin films (e.g., green tapes or sintered films made from green tapes), methods of making sintered thin films using these precursors, and sintered thin films made by the processes shown herein. In some examples, the sintered thin films made by the processes shown herein are useful as solid electrolytes for rechargeable batteries. In many examples, the green tapes shown herein and used to make sintered thin films have a higher solid loading than known green tapes. The sintered thin films prepared by the processes in this specification have lower porosity, higher density, fewer defects, and / or are prepared with a higher yield than known sintered thin films.

Background Art

[0003] (Background) Solid ceramics such as lithium-filled garnet materials and lithium borohydride, lithium oxide, lithium sulfide, lithium oxyhalide, and lithium halide are fuels ​​​​​​​​​​​Ion-conducting electrolyte membranes in various electrochemical devices, including batteries and rechargeable batteries. It has several advantages as a material for separators. Compared to its liquid-based counterparts. When compared, the aforementioned solid ceramics offer not only safety and economic advantages, but also these materials When the material is incorporated into an electrochemical device as an electrolyte separator, it exhibits a considerably high volumetric effect. It also possesses advantages in terms of solid and density of materials that enable gravitational energy density. On-conducting ceramics have high ionic conductivity and electrical insulation properties in solids. Furthermore, its chemical compatibility with various types of lithium metals and its performance across a wide voltage range. Due to its stability, it is well-suited for solid-state electrochemical devices.

[0004] Solid ion-conducting ceramics have a series of advantages and beneficial properties, but these materials , the formation of a green film (i.e., green tape) and the subsequent sintering of these green films They are plagued by a wide range of problems related to this. Solid ion-conducting ceramics are typically used as thin films. When combined and sintered, do these films tend to adhere to the substrate on which they are prepared? , due to processing conditions, it tends to crack or deform, or is too brittle after sintering, And it cannot be manipulated. In particular, during the sintering of thin films, these films tend to crack. It may either deform, have a tendency to warp, or exhibit surface degradation in another form.

[0005] Therefore, although not limited to, ceramic greens such as garnet and lithium sulfide Casting the green tape, and sintering these green tapes to produce high-density garnet A series of problems exist in related fields concerning the preparation of thin films. For example, new methods for casting and sintering green tape. This disclosure relates to materials and processes. In addition to such materials and processes, this disclosure also relates to their manufacturing and It shows usage and other solutions to problems in related fields. [Overview of the project]

[0006] (overview) In one embodiment, the present disclosure shows a method for casting a thin film tape, where the The method generally involves providing at least one source powder and modifying the at least one source powder. To modify and prepare a modified source powder, and to provide a slurry of the modified source powder. The slurry is then cast to form a green tape, and the green tape is dried. This includes causing the green tape to be sintered to form a sintered thin film.

[0007] In a second embodiment, the present disclosure shows a slurry for casting green tape. The slurry comprises a source powder, optionally a precursor of the source powder, and a binder. - comprises at least one component selected from a dispersant and a solvent.

[0008] In a third embodiment, the present disclosure relates to a method for sintering green tape, wherein (a) less (b) to provide at least one source powder; (b) to modify the at least one source powder. (c) preparing a source powder; (d) providing a slurry of the modified source powder; (c) the slurry (e) to cast the material to form a green tape; (a) to dry the green tape; and (f) sintering the green tape; thereby including sintering the green tape, The method is shown.

[0009] In a fourth embodiment, the disclosure relates to a slurry for preparing a cast green film. hand: The following: Methanol, ethanol, MEK, isopropanol, acetone, cyclohexanone, A solvent selected from the group consisting of ruene, acetic acid, and benzene; A group consisting of fish oil, PVB, KD1, acrylic acid, triton, phosphate esters, and their derivatives. The binder to be selected; A plasticizer selected from the group consisting of benzylbutyl phthalate or dibutyl phthalate; pH modifier; A sintering aid selected from the constituent group; and Selected source powder from lithium-filled garnet This indicates a slurry containing at least two of the following.

[0010] In the fifth embodiment, this disclosure is: source powder; solvent; Binder; and Dispersant; This includes, where green tape has a pycnometric density greater than 3.9 and less than 5.0. They are doing it.

[0011] In a sixth embodiment, the present disclosure relates to the following steps: (a) providing a slurry; (b) by (c) to provide a binder mixture; (a) to mix the slurry with the binder mixture to make a mixed slurry (d) to form a leaf; and (d) to cast the mixed slurry to provide a green tape. This includes, where the green tape has a total organic content of approximately 10-25% w / w. This shows how to make tape. [Brief explanation of the drawing]

[0012] (Brief explanation of the drawing) [Figure 1] Figure 1 shows an example flowchart of an embodiment of the method described herein.

[0013] [Figure 2] Figure 2 shows a scanning electron microscope (SEM) image of a green tape prepared by the casting method shown in Example 1. The tape contains 15% binder, and the garnet has a d50 of approximately 180 nm and a density of 2.3 g / cm³. The organic portion is labeled 201, and the inorganic portion is labeled 202.

[0014] [Figure 3] Figure 3 shows the optical image of the 100-200 μm sintered green tape prepared according to Example 3.

[0015] [Figure 4] Figure 4 shows scanning electron microscope (SEM) images of the sintered tape prepared in Example 2 using slurry composition 1 and binder composition 1.

[0016] The drawings are for illustrative purposes only and illustrate various embodiments of the present disclosure. Those skilled in the art will understand the following. From observation, without departing from the principles described herein, the structure and It will be readily apparent that alternative embodiments of the method may be utilized. [Modes for carrying out the invention]

[0017] The following description is intended for those skilled in the art to create and use the disclosed subject matter and relate it to specific uses. It is presented so that it can be incorporated into various modifiers and different uses. Various uses will be immediately apparent to those skilled in the art, and the general principles defined herein apply to a wide range of applications. This disclosure can be applied to embodiments. Therefore, this disclosure is not limited to the embodiments presented. It is not intended to be done in a manner consistent with the principles and novel features disclosed herein. The broadest possible range should be recognized.

[0018] In the following detailed explanation, numerous specific examples are provided to give a more thorough understanding of this disclosure. The details are shown. However, it is not necessarily limited to these specific details. It will be obvious to those skilled in the art that this disclosure can be implemented. In other examples, this disclosure is ambiguous. To avoid this, well-known structures and devices are shown in block diagram form rather than in detail. It will be shown.

[0019] (Detailed explanation) The disclosures herein include green tapes, processes for producing these tapes, and This shows the process for sintering these tapes. The process described herein is conventional Compared to films prepared by known methods, it has improved surface quality. Sintered thin films are produced. Some of the films prepared by the methods described herein are uniform. Firstly, they are prepared with a rough (i.e., smooth) surface. These films are polished or It is suitable for integration into electrochemical devices without further processing such as wrapping. It has a sintered surface. Depending on the specific application, it can be polished or lapped. There may be cases where the sintered film prepared in this specification needs to be processed, but for other applications... The films sintered by the methods described herein are suitable for electrochemical device applications. In some examples, the films prepared herein have a surface roughness of less than 5 μm after sintering. To possess.

[0020] (A.Definition) As used herein, “to provide” means to provide, produce, or present what is provided. It refers to supplying or providing something. Providing includes making something available. For example, powder The powder can be used as shown in the method described herein. This refers to the process of making powder available or supplying powder. If provided, the means of providing are to measure, weigh, move, and combine It also means to combine or blend.

[0021] As used herein, “casting” means applying a casting solution or slurry onto a substrate. It means to supply, deposit, or deliver. Casting is called slot casting. This includes, but is not limited to, immersion coating and doctor blade application. Not possible. As used herein, the phrase "slot casting" means a solution, liquid. A body, slurry, etc., is placed adjacent to, in contact with, a substrate on which deposition or coating is to be performed, or By pouring the solution into a fixed-size slot or mold placed on the substrate, the solution is applied to the substrate. This refers to a deposition process in which liquids, slurries, etc., are coated or deposited. Slot casting involves slot openings of approximately 1 to 100 μm. In this case, the phrases "immersion casting" or "immersion coating" refer to the substrate being coated with a solution. By moving the liquid, slurry, etc., in and out of the substrate, often vertically, This refers to a deposition process in which a solution, liquid, slurry, etc., is coated or deposited. In such cases, "casting the slurry" means depositing or bonding the slurry onto the substrate. This refers to the process of casting. Casting includes slot casting and dipping casting. This may include, but is not limited to, the following. When used herein, "slot flow" The phrase "to extend" refers to the process of depositing or coating a substrate with a solution, liquid, slurry, etc. Fixed-size slots or castings adjacent to, in contact with, or positioned on the substrate Deposition is the process of coating or depositing a substrate with a solution, liquid, slurry, etc., by pouring it into a mold. This refers to the process. In some cases, slot casting involves slots of approximately 1-100 μm. Includes a pit opening. When used herein, "immersion casting" or "immersion coating" The phrase "to do something" often refers to moving the substrate vertically, in and out of a solution, liquid, slurry, etc. By moving it, a solution, liquid, slurry, etc., is coated or deposited on the substrate. This refers to the deposition process. As used herein, casting means casting solution or casting solution This also includes depositing, coating, or diffusing the rally onto a substrate. When used, the phrase "casting a film" means that a liquid or slurry forms a film. Alternatively, the liquid or slurry is supplied to or transferred to a mold or substrate so that it forms a film. It refers to the process. The process involves using a doctor blade, a Meyer rod, and a comma coater. Gravure coater, microgravure, reverse comma coater, slot die, slicing This can be done by casting and / or tape casting, and by other methods known to those skilled in the art. .

[0022] As used herein, the phrase "casting a film" means that a liquid or slurry is cast into a film. To form a film or to form a film, the liquid or slurry is supplied to a mold or substrate. This refers to the process of supplying or transferring. The process involves using a doctor blade, a Meyer rod, etc. Comma coater, gravure coater, microgravure, reverse comma coater, s By lot die, slip and / or tape casting, and other methods known to those skilled in the art It is possible to do so.

[0023] As used herein, the phrase "slot casting" means a solution, liquid, or slot Layers, etc., are placed adjacent to, in contact with, or on the substrate where the deposition or coating is to be performed. By pouring the solution or liquid into a fixed-size slot or mold placed on top of the substrate, the solution is applied to the substrate. This refers to a deposition process in which a slurry or similar material is covered or deposited. In some examples, Lot casting includes slot openings of approximately 1 to 100 μm.

[0024] As used herein, the terms “immersion casting” or “immersion coating” The phrase refers to moving a substrate in and out of a solution, liquid, slurry, etc., often vertically. This refers to a deposition process in which a solution, liquid, slurry, or the like is coated or deposited onto a substrate. vinegar.

[0025] As used herein, the term “layering” means one precursor species, for example Then, layers of lithium precursor species are continuously deposited on the substrate, and then further layers are added. Using two precursor species, for example, transition metal precursor species, continuous deposition occurs in already deposited layers. This refers to the process of creating a layer. By repeating this layering process, several layers of deposited gaseous phase are created. It can be raised. As used herein, the term "to stack" means to load. A layer containing an electrode, for example, a layer containing a positive electrode or cathode active material, is made of another material, for example, garnet. This also refers to the process of bringing the material into contact with a layer containing an electrolyte. The lamination process involves bringing the layer to be laminated into contact with the material. The reaction or use of a binder that adheres or physically maintains contact between layers being laminated It may be included. Lamination involves bonding unsintered, i.e., "green" ceramic films. It also refers to the process of combining.

[0026] As used herein, the terms "green tape" or "green film" are used in a legal sense. Garnet material, garnet material precursor, binder, solvent, carbon, dispersant, or similar This refers to an unsintered film containing at least one component selected from the combinations of these.

[0027] As used herein, the term "film thickness" refers to the distance between the upper and lower surfaces of a film. Refers to distance or median of measured distance. When used herein, the upper surface and lower surface are This refers to the side of the membrane that has the largest surface area.

[0028] As used herein, "garnet precursor chemicals" and "garnet-type electrolyte chemicals" are used. The terms "chemical precursor" or "garnet chemical precursor" are used in this specification in reference to the reaction of chemical precursors. This refers to the chemical substances that form the lithium-filled garnet material. These chemical precursors Examples include lithium hydroxide (e.g., LiOH), lithium oxide (e.g., Li2O), and lithium carbonate. (e.g., LiCO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), acid Aluminum oxide (e.g., Al2O3), aluminum (e.g., Al), aluminum nitrate (e.g., , AlNO3), aluminum nitrate notahydrate, (oxy)aluminum hydroxide (gibbsite and ve -mite), gallium oxide, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., T Examples include a2O5, but are not limited to these.

[0029] When used herein, "subscripts and molar coefficients in empirical formulas are as given in the examples provided." The phrase "based on the amount of raw materials initially batched for production" means, Subscripts (for example, Li7La3Zr2O) 12 The coefficients 7, 3, 2, 12, and 0.35 in Al2O3 (0.35) are, Given material (for example, Li7La3Zr2O 12 Chemical precursors used to produce 0.35Al2O3 For example, it refers to the elemental ratios in LiOH, La2O3, ZrO2, and Al2O3. As used herein, the phrase “characterized by formula” means that the characterization Whether the materials were batch-formulated or experimentally determined during the process of producing them. This refers to the molar ratio of any of the constituent atoms.

[0030] As used herein, the term “solvent” refers to any component or material described herein. This refers to a liquid suitable for dissolving or solvating a substance. For example, a suitable solvent is garnet calcinate. Components used in the binding process, for example, a suitable liquid for dissolving the binder, for example Toluene is one example.

[0031] As used herein, the phrase "remove the solvent" means to remove the solvent as specified herein. This refers to the process of extracting or separating a component or material from a given substance. Removing the solvent is limited It is not specified, but includes evaporating the solvent. Removing the solvent is not limited to, This involves using a vacuum or reduced pressure to remove the solvent from the mixture, for example, an unsintered thin film. In some examples, the solvent is evaporated, and the solvated bit is added to the thin film after the solvent has been removed. To remove the binder, the thin film containing the binder and solvent is heated, or optionally vacuumed. Also, place it in a reducing atmosphere environment.

[0032] As used herein, "thin" is limited to films, membranes, etc. When doing so, dimensions less than 200 μm, more preferably less than 100 μm, and in some cases, 0.1 to 60 μm. It means...

[0033] As used herein, "membrane tape" means that it is sintered or can be sintered. Rolls or continuous sheets of cast tape, either dry or undried. It refers to a layer.

[0034] As used herein, “binder” refers to a material that helps to bond two materials together. For example, as used herein, polyvinyl butyral is used to bond garnet material. It is a binder because it is useful for organizing. Other binders include polycarbonate One example is [this]. Another example of a binder is polymethyl methacrylate. These examples of binders cover the entire range of binders assumed herein. This disclosure is not limited to, but merely serves as an example. Useful binders include polypropylene (PP), atactic polypropylene (aPP), Isotactive polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene Copolymer (EPC), polyisobutylene (PIB), styrene-butadiene rubber (SBR), polyolefin In, polyethylene-co-poly-1-octene (PE-co-PO), PE-co-poly(methylenecyclopentene) (PE-co-PMCP), polymethyl-methacrylate (and other acrylates), acrylates, polyvinyl acetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin , stereoblock polypropylene, polypropylene polymethylpentene copolymer, poly ethylene oxide (PEO), PEO block copolymer, silicone, and the like, but are not limited to these. As used herein, the phrase "lithium-filled garnet electrolyte" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. The lithium-filled garnet has the formula Li

[0035] La M' M'' A Zr B O c D E F A B C D E F A B C D E F a b c d e f 3+ + 7.0 t1 t t3 12 (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 13, and M' and M'' are each independently, in each instance, selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb , or Ta), or Li a b c d e f 3+ + 7.0 t1 ​​​​ <c≦2.5; 0≦d<2; 0≦e<2、10<f<13であり、かつMe''は、Nb、Ta、V、W、Mo、Ga、 A compound having (or a metal selected from Sb and as described herein) This includes the above garnet which is doped with Al2O3. Garnet is also included. Garnet as used herein is Al 3+ Li + to replace This also includes the above garnets that are doped in this manner. When used herein, lith Li-filled garnets, and garnets, are not limited to Li-filled garnets. 7.0 La3(Zr t1 +Nb t 2+Ta t3 )O 12 +0.35Al2O3 is included; here, the La:(Zr / Nb / Ta) ratio is 3:2, (t1+t2 +t3 = subscript 2). Furthermore, the garnet used herein is not limited to However, Li x La3Zr2O 12 +yAl2O3 (where x is in the range of 5.5 to 9, and y is in the range of 0 to 1) It is included. In some examples, x is between 6 and 7, and y is 1.0. In this case, x is 7 and y is 0.35. In some examples, x is 6 to 7 and y is 0.7. In some examples, x is between 6 and 7, and y is 0.4. Also, Honmei The garnet used in the fine writing is not limited to, but Li x La3Zr2O 12 Contains +yAl2O3 A non-limiting example of a lithium-filled garnet electrolyte is, for example, published on July 16, 2015. This can be seen in U.S. Patent Application Publication No. 2015-0200420 A1.

[0036] As used herein, garnet refers to YAG-garnet (i.e., yttrium garnet). Aluminum garnet, or for example, Y3 Al5O 12 ) does not include. Used herein In this case, garnet contains pyrope, almandine, spessartine, and grossular crystals. , hessonite or cinnamon stone, tsavorite, uvarovite, and andrad Ito, as well as the solid solutions pyrope-almandine-spessarite and uvaroxapine. This does not include silicate garnets such as bite-grossular-andradite. In the specification, garnet is defined by the general formula X3Y2(SiO4)3 (wherein X is Ca, Mg, Fe, and / or M It does not contain nesosilicates having n (where Y is Al, Fe, and / or Cr).

[0037] As used herein, the term "garnet-type electrolyte" is used in accordance with the terms described herein. This refers to an electrolyte containing lithium-filled garnet material as an ion conductor. The advantage of solid electrolytes is that they are different from the flammable liquid electrolytes commonly used in lithium rechargeable batteries. Many of them serve as substitutes for other things.

[0038] When used herein, "d 50 The term "diameter" is not limited to scanning electron microscopes. The diameter is measured by microscopy techniques such as microscopy or dynamic light scattering, or by other particle size analysis techniques. This refers to the median diameter in the distribution of . 50 50% of the particles are smaller than the listed size. The characteristic dimensions are included.

[0039] When used herein, "d 90The term "diameter" is not limited to scanning electron microscopes. The diameter is measured by microscopy techniques such as microscopy or dynamic light scattering, or by other particle size analysis techniques. This refers to the median diameter in the distribution of . 90 90% of the particles are smaller than the listed size. The characteristic dimensions are included.

[0040] As used herein, the “thickness” that characterizes a film refers to the upper and lower surfaces of the film. Refers to the distance between or the median of the measured distance. When used herein, the upper surface and the lower The surface refers to the side of the film that has the largest surface area.

[0041] When used herein, "subscripts and molar coefficients in empirical formulas are as given in the examples provided." The phrase "based on the amount of raw materials initially blended in the batch to produce" is a subscript. (For example, Li7La3Zr2O 12 The coefficients 7, 3, 2, 12, and 0.35 in Al2O3 (0.35) are given material ( For example, Li7La3Zr2O 12 • 0.35Al2O3) used as a chemical precursor (e.g., L This refers to the elemental ratios in IOH, La2O3, ZrO2, and Al2O3.

[0042] As used herein, the phrase "sintering a film" means thermal sintering or electric field assisted sintering. The use of sintering can be used to densify (make denser, or This refers to the process of making a material have reduced porosity. Sintering is the process of transforming a solid mass of material into a solid mass. A process that forms the solid mass by heat and / or pressure without melting it to its complete liquefaction point. Including Rothes

[0043] As used herein, the term “plasticizer” means that the green tape is flexible or pliable. This refers to an additive that imparts one of the following properties to the binder: flexibility, workability, or expansion. It may be a substance or material used to increase flexibility. Flexibility means being able to bend without breaking. Plasticity is the ability to change shape permanently.

[0044] As used herein, the phrase "relieving stress" refers to drying and associated shrinkage. This refers to the process of removing residual stress in green tape cast during the process. One method is to use a temperature that exceeds the glass transition temperature of the organic components in the green tape. The tape is heated, and the structural rearrangement and stress rearrangement in the cast green tape remain. This includes enabling the removal of stress. Another method of stress relief is cast gri The green tape is heated to 70°C, allowing the cast green tape to relax from stress. This includes maintaining that temperature for a certain period of time.

[0045] As used herein, the term "pH modifier" means a better composition of the cast slurry. To achieve dispersion stability, it is added to the slurry to adjust its acidity or alkalinity. This refers to an acid or base that can modify pH. Examples of pH modifiers include citric acid and ammonium hydroxide. Hmm , Other equivalent pH modifiers are also included, but are not limited to.

[0046] As used herein, the phrase “batch-formulated” means the first batch formulated at the start of the synthesis. This refers to the molar amount of each component mixed or provided. For example, a batch-formulated Li 7La3Zr2O 12 Li7La3Zr2O 12Li, La, Zr, and O in the reagents used to prepare This means the ratio was 7:3:2:12.

[0047] As used herein, pycnometry density refers to Micromeritics AccuPycII 1340 C The measurement is performed using an alibrate device. Using this device, a controlled amount of the powder sample is measured in a cup. Place it in a container and measure its mass. Using this device, measure the volume and determine the density by mass / volume. Calculate the degree.

[0048] As used herein, the term "sintering aid" means that, in other cases, sintering aid may be used without it. Used to form a liquid phase with a melting point lower than the required melting point, or otherwise as a sintering aid. Sintering aids refer to any additive that enables faster sintering than would be possible without them. This helps the diffusion / dynamics of the atoms being sintered. For example, LiAlO2 has garnet. It can be used as an additive during rallies, but that is because LiAlO2 is at approximately 1050-1100°C. A liquid containing garnet can be formed, thereby allowing more garnet to be produced during sintering. This is because it leads to rapid densification.

[0049] As used herein, particle size distribution (hereinafter referred to as "PSD") refers to, for example, Horiba LA-950 V2 particles. The measurement is performed by light scattering using a radial analyzer, and the solvent used in the analysis is Tolué. The analysis includes ions, IPA, or acetonitrile, and the analysis includes a 1-minute sonication treatment before measurement. ru.

[0050] As used herein, the term "source powder" refers to the slurry shown herein. This refers to the inorganic material used. In some examples, the source powder is lithium-filled garnet. Yes, for example, the source powder is Li7La3Zr2O 12 It may contain powder of 0.5Al2O3.

[0051] As used herein, the term "phosphate ester" means, for example, Hypermer KD- 23(TM), Hypermer KD-24(TM), Phoschem PD(TM), Phoschem R-6(TM), Phosphora n PS-131 (trademark), and Rhodoline 41 60 This refers to a phosphate ester known as (trademark).

[0052] As used herein, the term "DBP" refers to a molecule having a molecular weight of 278.35 g / mol. , formula C 16 H 22 This refers to dibutyl phthalate, a chemical substance containing O4.

[0053] As used herein, the term "BBP" refers to a molecule having a molecular weight of 312.37 g / mol. , benzylbutyl phthalate C 19 H 20 This refers to O4.

[0054] As used herein, the term "PEG" refers to polyethylene glycol. Unless otherwise specified, the molecular weight of PEG is between 400 and 6000 g / mol.

[0055] (B. Green Tape) In some examples shown herein, cast by the method shown herein The green tape is formulated as fire-resistant ceramic particles densely mixed with a binder. It contains materials and / or ceramic materials. The purpose of this binder is, firstly, to protect the ceramics. It assists in the sintering of particles, and after sintering, forms a uniform and thin film or layer of refractory or ceramic material. This is what is caused. During the sintering process, the binder is burned away from the sintered thin film. (For example, calcination). In some cases, this binder is used at temperatures below 700°C, below 450°C, Below 400°C, below 350°C, below 300°C, below 250°C, or in some cases, below 200°C , or in some cases, temperatures below 150°C, or in some cases, temperatures below 100°C The sintered film is then completely burned away. During binder removal, the partial pressure of oxygen and water vapor (water p It can control (artificial pressure).

[0056] (C. Manufacturing Method) The composite materials described herein can be prepared by various methods. In this method, a slurry containing source powder is prepared, and this slurry is applied to a substrate or setter. Cast onto a plate, then the slurry is dried and sintered, dried and sintered A solid ion-conducting ceramic is prepared. In one example, the substrate is, for example, Mylar. Silicone-coated Mylar, polymer-coated surface, surface-modified polymer, or bonded to a surface Examples include a surface-structured monolayer that is attached or bonded.

[0057] In one example, the method described herein is generally as shown in Figure 1. Figure 1 Method 100 is described therein. In this method, the first step includes slip preparation 101. This involves combining a solvent, a dispersant, and a source powder, such as garnet, in a reaction vessel (e.g., For example, it involves putting it into a 50ml Nalgene bottle. A grinding medium is also added. Step 102 odor Then, the combined contents are ground for 1 hour to 3 days. In the third step 103, the binder - Add a plasticizer and / or homogenizer to the reaction vessel to form a slurry. In step 4, 104, the slurry is rotated by rotating the reaction vessel, and the binder Blend the dahl. In the fifth step 105, the slurry is degassed by a degassing process. Then, the gas is removed. In the sixth step 106, the slurry is passed by the doctor blade method. Then it is cast onto a substrate (for example, silicone-coated Mylar). In the seventh step 107, the cast film Dry it. In this step 107, in order to avoid the formation of cracks or defects in the film, Drying is achieved in a controlled manner. In one example, the slurry contains approximately 3 μm d 50 possess 70g garnet powder, 16g MEK solvent, 1.4g phosphate ester, 50% wt (w / w) MEK 8.4 g of polymethyl methacrylate binder, 3.5 g of plasticizer (e.g., S-160), and 1.6 It contained g of cyclohexanone.

[0058] (D. Slurry) In some examples, suitable for use with the slurry described herein As an inder, it is a binder used to promote adhesion with Li-filled garnet particles. These include polypropylene (PP), polyvinyl butyral (PVB), and polyethylene. Polymethacrylate (PEMA), polyvinylpyrrolidone (PVP), atactic polypropylene (aP P), isotactive polypropylene ethylene propylene rubber (EPR), ethylene pentene Polymer (EPC), polyisobutylene (PIB), styrene-butadiene rubber (SBR), polyolefin Polyethylene-copoly-1-octene (PE-co-PO); PE-co-poly(methylenecyclopentane) (PE-CO-PMCP); Stereoblock polypropylene, polypropylene polymethylpentene Polymer, polypropylene carbonate, methyl methacrylate (or PMMA), ethyl methacrylate This includes, but is not limited to, acrylate (or PEMA) and silicone. Other by The materials used include polypropylene (PP), atactic polypropylene (aPP), and isotactic polypropylene. Polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene-butadiene (SBR), polyolefin, polyethylene Len-co-poly-1-octene (PE-co-PO), PE-co-poly(methylenecyclopentene) (PE-co-PMCP) ), Stereoblock polypropylene, polypropylene polymethylpentene, polyethylene Selected from PEO oxides, PEO block copolymers, silicones, and combinations thereof. A binder that can be used is one example.

[0059] Examples of dispersants include phosphate esters, esters, for example, fish oil, surfactants, and fluorine. Losurfactant, polyvinylpyridine (PVP), polyvinyl butadiene (PVB), polyal Examples include, but are not limited to, chilenamines and acrylic polymers.

[0060] In some cases, the slurry may also contain a surfactant. Suitable surfactants A non-restrictive list of these includes cetylpyridinium chloride and cetylpyridinium bromide (cetylpy Examples include ridium bromide and sodium dodecylbenzenesulfonate.

[0061] In some cases, the slurry may also contain a pH modifier. Examples of pH modifiers include Examples include glacial acetic acid, NH4OH, monoethanolamine, NaOH, Na2CO3, and KOH, but These are not the only options.

[0062] In some cases, the slurry may also contain a plasticizer. Examples of plasticizers include: Examples include dibutyl phthalate, dioctyl phthalate, and benzyl butyl phthalate. However, it is not limited to these.

[0063] In some cases, the slurry strongly interacts with the solvent or organic binder. - Net powder or precursor, and Li garnet that increases slurry viscosity by re-aggregation. It contains powder or precursors. In some examples, re-aggregation is performed on high-quality slurry and casting. It is at a high level that does not generate tape. In these specific examples, the process To ensure stable dispersion in the slurry, an agent that changes the pH of the slurry is added. Therefore, it can be controlled. In these specific examples, the process involves less reactive solvents. It can also be controlled by adding a medium and / or binder. In these examples, Lee has excellent dispersibility, low viscosity, and minimal organic content.

[0064] (E. Ryuen) Several tape trailing methods are publicly known in the relevant fields, and their entirety is for any purpose The texts of Mistler, RE and Twiname, E. R are incorporated herein in full by citation. Dedication, Tape Casting: Theory and Practice, First Edition, Wiley-Amer This includes the methods described in the ICAN Ceramic Society; 1st edition (December 1, 2000). The entirety of this work is incorporated herein by reference in full for all purposes, Dolhert, L. For E, a green tape casting system using an atactic polypropylene binder Lean burning (CLEAN BURNING GREEN TAPE CAST SYSTEM USING ATACTIC POLYPROPYLENE BI) Other casting methods and materials as shown in U.S. Patent No. 5,256,609, titled NDER.

[0065] In some of the methods described herein, the method involves a tape of ceramic source powder Substrate (e.g., porous or non-porous alumina, zirconia, garnet, alumina-zirconia) This includes casting onto lanthanum alumina-zirconia. In some examples, The tape is a silicone-coated substrate (for example, silicone-coated Mylar, or silicone on alumina) It is prepared on a substrate such as a cone-coated Mylar.

[0066] In some of the methods described herein, the sintered film releases volatile components. The components of this product allow these volatile components to evaporate or volatilize from the sintered film. Unless a rate is used, cracks or surface degradation can often occur in the sintered film. In certain cases, porous setter plates are used to aid in the evaporation of these volatile components. It would be advantageous to do so.

[0067] (F. Tape drying after casting) In some examples, the methods described herein involve cast tapes (e.g., green films). This includes drying. In some methods, drying is, for example, casting film A heating bed on which the tape is placed or deposited, infrared (IR) heating, or convection heating of the cast tape. This includes controlling the temperature of the cast tape by using [a certain method]. Drying is not limited to, but is permitted in non-flowing and / or flowing environments (for example) Using environmental control methods such as atmospheric air, dry air, inert gas, nitrogen gas, and argon gas, This may include managing or controlling the amount of solvent in a dry environment. Drying is done to control the rate of solvent removal, and to allow the cast film to dry away from the substrate. It is used to ensure that drying occurs from the substrate to the surface, rather than from the substrate to the surface.

[0068] In some cases, before the cast green tape dries, the cast green tape is , containing a solvent that is an azeotropic mixture. In some examples, this azeotropic mixture is green te The solvent contains 10-25% by weight of cyclohexanone. In some examples, azeotropic The weight percentage of cyclohexanone in the mixture is 10% by weight. In some examples... The weight percentage of cyclohexanone in the azeotropic mixture is 11% by weight. In some examples... In this case, the weight percentage of cyclohexanone in the azeotropic mixture is 12% by weight. In this example, the weight percentage of cyclohexanone in the azeotropic mixture is 13% by weight. In some examples, the weight percentage of cyclohexanone in the azeotropic mixture is 14% by weight. In some cases, the weight percentage of cyclohexanone in the azeotropic mixture is 15% by weight. It is %. In some examples, the weight percentage of cyclohexanone in an azeotropic mixture is It is 16% by weight. In some examples, the weight portion of cyclohexanone in the azeotropic mixture The nitrate is 17% by weight. In some examples, the weight of cyclohexanone in the azeotropic mixture The percentage is 18% by weight. In some examples, cyclohexanone in azeotropic mixtures. The weight percentage is 19% by weight. In some examples, cyclohex in azeotropic mixtures The weight percentage of sanone is 20% by weight. In some examples, sic in azeotropic mixtures The weight percentage of lohexanone is 21% by weight. In some examples, in azeotropic mixtures... The weight percentage of cyclohexanone is 22% by weight. In some examples, azeotropic mixture The weight percentage of cyclohexanone in the compound is 23% by weight. In some examples, The weight percentage of cyclohexanone in the azeotropic mixture is 24% by weight. In some examples... Furthermore, the weight percentage of cyclohexanone in the azeotropic mixture is 25% by weight. In the example, the solvent is a MEK:IPA combination. In one example, the MEK:IPA ratio is 1:1. In one example, the MEK:IPA ratio is 2:1. In another example, the MEK:IPA ratio is 3:1. In one example, the MEK:IPA ratio is 4:1. In another example, the MEK:IPA ratio is 5:1. In one example, the MEK:IPA ratio is 5:1. In another example, the MEK:IPA ratio is 7:1. In one example, the MEK:IPA ratio is 8:1. In another example, the MEK:IPA ratio is 5:1. In one example, the MEK:IPA ratio is 5:2. In another example, the MEK:IPA ratio is 6:2. In one example, the MEK:IPA ratio is 7:2. In another example, the MEK:IPA ratio is 8:2. In one example, the MEK:IPA ratio is 9:2. In another example, the MEK:IPA ratio is 10:3. Yes. In one example, the MEK:IPA ratio is 11:3. In another example, the MEK:IPA ratio is 5:3. In one example, the MEK:IPA ratio is 6:3. In another example, the MEK:IPA ratio is 7:3. In one example, the MEK:IPA ratio is 8:3. In another example, the MEK:IPA ratio is 9:3. In one example, the MEK:IPA ratio is 10:3. In another example, the MEK:IPA ratio is 11 :3.

[0069] In some cases, after drying the green tape, the total amount of material other than the source powder is This is approximately 10-25% by weight of the lean tape. In some examples, the total amount of material other than the source powder. This is 10% by weight of the green tape. In some examples, the total amount of materials other than the source powder is It is 11% by weight of the green tape. In some examples, the total amount of materials other than the source powder is It is 12% by weight of the lean tape. In some examples, the total amount of material other than the source powder is glycerin. It is 13% by weight of the green tape. In some examples, the total amount of material other than the source powder is green It is 14% by weight of the tape. In some examples, the total amount of material other than the source powder is green It is 15% by weight of the tape. In some examples, the total amount of material other than the source powder is green tape. It is 16% by weight of the pith. In some examples, the total amount of materials other than the source powder is green tape. It is 17% by weight of the powder. In some examples, the total amount of material other than the source powder is green tape. This is 18% by weight. In some examples, the total amount of materials other than the source powder is the same as the amount of the green tape. It is 19% by weight. In some examples, the total amount of material other than the source powder is 20% of the green tape. This is expressed as a percentage by weight. In some examples, the total amount of material other than the source powder is 21 times the amount of green tape. The amount is in percent. In some examples, the total amount of material other than the source powder is 22 times the weight of the green tape. It is %. In some examples, the total amount of materials other than the source powder is 23% by weight of the green tape. In some cases, the total amount of materials other than the source powder is 24% by weight of the green tape. Yes. In some cases, the total amount of materials other than the source powder is 25% by weight of the green tape. In some of these examples, the amount of source powder is 60, 65, 70, 75 of the green tape. Alternatively, it is 80% by weight.

[0070] (G. Setter Plate) In the method described herein, the contents of both patent applications are drawn for any purpose. International PCT patent application filed on April 15, 2016, which is fully incorporated herein by use. The set shown in PCT / US16 / 27886 and PCT / US16 / 27922, filed on April 15, 2016 Tarplate and sintering method.

[0071] In some cases, by the methods described herein and those incorporated by reference, The green film prepared is sintered between setter plates. In some examples... These setter plates are made of metal, oxide, nitride, or have an organic or silicone surface. It is composed of a metal, oxide, or nitride having a laminate layer. In one example, Plaster plates include platinum (Pt) setter plates, palladium (Pd) setter plates, and gold (Au) setter plates. Setter plates, copper (Cu) setter plates, aluminum (Al) setter plates, aluminum Minasetter plates, porous alumina setter plates, steel setter plates, Zirconium (Zr) setter plate, zirconia setter plate, porous zirconia setter plate Setter plate, lithium oxide setter plate, porous lithium oxide setter plate Lanthanum oxide setter plate, porous lanthanum oxide setter plate, garnet setter Setter plate, porous garnet setter plate, lithium-filled garnet setter Plates, porous lithium-filled garnet setter plates, and combinations thereof Selected from the group. In some examples, the setter plate is a garnet setter. It is a plate or a porous garnet setter plate.

[0072] In some cases, by the methods described herein and those incorporated by reference, The green film prepared is sintered on at least one setter plate. In that example, these setter plates are metals, oxides, nitrides, and organic materials on their surface. Alternatively, it may consist of a metal, oxide, or nitride having a silicone laminate layer. One example... In this context, the setter plate is a platinum (Pt) setter plate, a palladium (Pd) setter plate. Setters, gold (Au) setter plates, copper (Cu) setter plates, aluminum (Al) setter plates Plates, alumina setter plates, porous alumina setter plates, steel setter Setter plates, zirconium (Zr) setter plates, zirconia setter plates, porous Porous zirconia setter plate, lithium oxide setter plate, porous lithium oxide setter plate Setter plate, lanthanum oxide setter plate, lithium zirconium oxide (Li2ZrO3) Setter plate, lithium aluminum oxide (LiAlO2) setter plate, porous aluminum oxide Garnet setter plate, garnet setter plate, porous garnet setter plate Lithium-filled garnet setter plate, porous lithium-filled garnet setter - Selected from a group consisting of plates and combinations of the aforementioned.

[0073] In some cases, by the methods described herein and those incorporated by reference, The green film prepared is sintered between setter plates, where the metal powder is set It is positioned between the tamper plate and the green film. In some examples, these cells The tamper plate is made of metal, oxide, or nitride, with an organic or silicone laminate layer on its surface. It is composed of a metal, oxide, or nitride having [a certain characteristic]. In one example, a setter plate Platinum (Pt) setter plates, palladium (Pd) setter plates, gold (Au) setter plates Setter plates, copper (Cu) setter plates, aluminum (Al) setter plates, alumina setter Plates, porous alumina setter plates, steel setter plates, zirconium (Zr) setter, zirconia setter plate, porous zirconia setter plate, oxidation Lithium setter plate, porous lithium oxide setter plate, lanthanum oxide setter - Plate, lithium zirconium oxide (Li2ZrO3) setter plate, lithium aluminum oxide Minium (LiAlO2) setter plate, porous lanthanum oxide setter plate, lithium acid Zirconium oxide (Li2ZrO3) setter plate, lithium aluminum oxide (LiAlO2) setter - Plate, garnet setter plate, porous garnet setter plate, lithium Lithium-filled garnet setter plate, and porous lithium-filled garnet setter plate The group is selected from the combination of the aforementioned items. In these specific examples, The metal powder is selected from Ni powder, Cu powder, Au powder, Fe powder, or a combination thereof.

[0074] In some cases, by the methods described herein and those incorporated by reference, The green film prepared is sintered between setter plates, where the metal layer or film is They are positioned between the setter plate and the green film. In some examples, these The setter plate is made of metal, oxide, nitride, or has an organic or silicone laminate on its surface. It is composed of a metal, oxide, or nitride having a setter layer. In one example, the setter plate The setter plates are made of platinum (Pt), palladium (Pd), and gold (Au). Plates, copper (Cu) setter plates, aluminum (Al) setter plates, alumina setter plates Setter plates, porous alumina setter plates, steel setter plates, zirconia Zirconia (Zr), zirconia setter plate, porous zirconia setter plate, lithium oxide Lithium oxide setter plate, porous lithium oxide setter plate, lanthanum oxide setter plate Plate, porous lanthanum oxide setter plate, garnet setter plate, porous gar - Net setter plate, lithium-filled garnet setter plate, porous lithium Filled garnet setter plate, magnesia setter plate, porous magnesia setter Selected from the group consisting of tarplates. In these particular examples, the metal powder is Ni powder. The powder is selected from Cu powder, Mg powder, Mn powder, Au powder, Fe powder, or a combination thereof.

[0075] During specific sintering conditions, a layer of particles (e.g., a setter sheet) or powder is set with a green film. It can be placed between the tar plates to help with the sintering of the green film. As it forms, it tends to contract and densify, and therefore, if not controlled... This can lead to cracks or other mechanical defects in the membrane. In some of these examples, The particle layer contains a uniform layer of particles. In some other examples of these, the particles The layer contains a uniform layer of particles that are inert, i.e., do not react with the green film. Under these sintering conditions, the layer of particles is provided as a sheet of particles. In some examples... The thickness of the particle sheet or layer is approximately equal to the size of the particles in the sheet or layer. In the example, the inert particles are located between the green films, and the setter plate is the green film It is positioned between the contact surface and the portion of the sintered green film. Several consecutive In the sintering process, between the setter plate and / or the setter plate and the green film The particles, layers, or sheets to be placed are prepared in a continuous process by a continuous roll of sintered films. These continuous processes can be moved or rearranged during the sintering process. In the setter plate, the setter plate and particles, layers, or sheets are sintered green film The part in question should be in contact with the particles, layer, or sheet that are also in contact with the setter plate. It moves in accordance with the movement of the film. In some cases, the layer or sheet moves in accordance with the warping of the tape and To prevent surface degradation, it is prepared using specific weights.

[0076] In some of the examples described herein, inert and / or homogeneous particles (or A layer or sheet of powder becomes a film as it sinters, its volume decreases and its density increases. To prevent distortion, the film and the setter plate are subjected to sintering by creating minimal friction between them. Supports the process. By reducing friction on the film, the green film supports the sintering process. During this process, it can contract with minimal stress. This allows it to adhere to the setter plate. Improved sintered film that does not deform during the sintering process, and sintered film An improved sintered film is provided that does not crack during or after the sect.

[0077] In some examples described herein, other setter plates have a high melting point and high As long as it has lithium activity and stability in a reducing environment, other setter plates can be used. For example, in combination with the lithium-filled garnet setter plate described herein. It can be used. Some examples of these other materials include Li2ZrO3, xLi2O-(1- x)SiO2 (where x = 0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a + b + c = 1), Li A portion selected from LaO2, LiAlO2, Li2O, Li3PO4, Li-filled garnet, or a combination thereof. Materials are mentioned. Furthermore, these other setter plates are made from sintered film setter plates. The chemical potential in the sintered film that leads to Li diffusion into the film should not be introduced. The materials used are aluminum lanthanum oxide, pyrochlore, and 0.01 mol / cm³. 3 Exceeding Examples include materials having a lithium concentration. In some examples, the setter material is a powder. It can be provided as or in a non-planar shape.

[0078] (H. Solvent) In some examples, slurry is optionally used with a binder (e.g., PVB), and Optionally, along with a plasticizer, isopropanol, water, butanol, and tetrahydrofuran (THF) It contains a solvent selected from the following. In some examples, the solvent is approximately 10–30% w / w isopropyl alcohol. Butanol, 1-10% w / w water, 1-10% w / w butanol, and 10-30% w / w tetrahydro Contains furan (THF) [for example, 100 grams of garnet, 12 grams of binder, 12 grams DBP, 20-30 grams of solvent. In some examples, the solvent is approximately 20-30% w / w isop Lopanol, 3-6% w / w water, 3-6% w / w butanol, and 20-30% w / w tetrahydro Contains furan (THF). In some examples, the binder is 5% w / w. In these cases, the plasticizer is 5% w / w. In these examples, garnet or calcined precursor material is , which corresponds to the remaining %w / w (e.g., 40, 50, 60%, 70%, or 75%w / w). Some examples include In this process, a dispersant is used during the grinding process. In some examples, the dispersant is phosphoric acid. It is an ester. In some cases, the plasticizer is dibutyl thalate. Alternatively, the solvent is benzylbutyl phthalate. In some examples, the solvent is butanol and TH13. It is F. In some examples, the solvents are butanol, water, and THF. In the example, the solvents are butanol, water, toluene, and THF. The solvents are butanol and toluene. In some examples, the solvent is butanol , water, and THF.

[0079] Examples of solvents include toluene, ethanol, diacetone alcohol, and combinations thereof. Examples of solvents include isopropanol (IPA, anhydrous) and butanol. One example is the combination with toluene. Other examples of solvents include methanol, ethanol, and iso Propanol, butanol, pentanol, hexanol, toluene, xylene, xylene :Butyl alcohol, cyclohexanone, tetrahydrofuran, toluene:ethanol, Acetone, N-methyl-2-pyrrolidone (NMP), diacetone alcohol, ethyl acetate, aceton Tolyl, hexane, nonane, dodecane, methyl ethyl ketone (MEK), and combinations thereof. These are some examples.

[0080] In some examples, the solvent is a MEK:IPA combination. In one example, the ratio of MEK:IPA The ratio is 1:1. In one example, the MEK:IPA ratio is 2:1. In one example, the MEK:IPA ratio The ratio is 3:1. In one example, the MEK:IPA ratio is 4:1. In one example, the MEK:IPA ratio The ratio is 5:1. In some examples, the MEK:IPA ratio is 5:1. In some examples, the MEK:IPA ratio The ratio is 7:1. In one example, the MEK:IPA ratio is 8:1. In one example, the MEK:IPA ratio The ratio is 5:1. In one example, the MEK:IPA ratio is 5:2. In one example, the MEK:IPA ratio The ratio is 6:2. In one example, the MEK:IPA ratio is 7:2. In one example, the MEK:IPA ratio The ratio is 8:2. In one example, the MEK:IPA ratio is 9:2. In one example, the MEK:IPA ratio The ratio is 10:3. In one example, the MEK:IPA ratio is 11:3. In one example, the MEK:IPA ratio is The ratio is 5:3. In one example, the MEK:IPA ratio is 6:3. In one example, the MEK:IPA ratio The ratio is 7:3. In one example, the ratio of MEK:IPA is 8:3. In one example, the ratio of MEK:IPA is 9:3. In one example, the ratio of MEK:IPA is 10:3. In one example, MEK:IPA has a ratio of 11:3.

[0081] In the above examples, the solvent further contains 10 to 25 wt% cyclohexanone. In some examples, the weight percent of cyclohexanone in the slurry is 10 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 11 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 12 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 13 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 14 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 15 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 16 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 17 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 18 wt%. In some examples, the weight percent of cyclohexanone in the slurry is [[ID=3()]] 19 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 20 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 21 wt%. In some examples, the weight percent of cyclohexanone in the slurry is 22 wt%. In some examples, the weight percent of cyclohexanone in the slurry is The weight percentage of cyclohexanone is 23% by weight. In some examples, the weight percentage of cyclohexanone in the slurry is 24% by weight. In some examples, the slurry the weight percentage of cyclohexanone in is 25% by weight. In some examples, the solvent is a combination of MEK:IPA. In one example, the ratio of MEK:IPA is 1:1. In one example, the ratio of MEK:IPA is 2:1. In one example, the ratio of MEK:IPA is 3:1. In one example, the ratio of MEK:IPA is 4:1. In one example, the ratio of MEK:IPA is 5:1. In one example, the ratio of MEK:IPA is 5:1. In one example, the ratio of MEK:IPA is 7:1. In one example, the ratio of MEK:IPA is 8:1. In one example, the ratio of MEK:IPA is 5:1. In one example, the ratio of MEK:IPA is 5:2. In one example, the ratio of MEK:IPA is 6:2. In one example, the ratio of MEK:IPA is 7:2. In one example, the ratio of MEK:IPA is 8:2. In one example, the ratio of MEK:IPA is 9:2. In one example, the ratio of MEK:IPA is 10:3. In one example the ratio of MEK:IPA is 11:3. In one example, the ratio of MEK:IPA is 5:3. In one example the ratio of MEK:IPA is 6:3. In one example, the ratio of MEK:IPA is 7:3. In one example the ratio of MEK:IPA is 8:3. In one example, the ratio of MEK:IPA is 9:3. In one example the ratio of MEK:IPA is 10:3. In one example, the ratio of MEK:IPA is 11:3.

[0082] In some examples, the solvent in the slurry contains MEK:IPA and cyclohexanone. In a In this example, the weight percentage of cyclohexanone in the slurry is 10% by weight. In one example, the weight percentage of cyclohexanone in the slurry is 11% by weight. In some cases, the weight percentage of cyclohexanone in the slurry is 12% by weight. In some cases, the weight percentage of cyclohexanone in the slurry is 13% by weight. In some cases, the weight percentage of cyclohexanone in the slurry is 14 times. It is expressed as a percentage by weight. In some examples, the weight percentage of cyclohexanone in the slurry is It is 15% by weight. In some cases, the weight percentage of cyclohexanone in the slurry The amount is 16% by weight. In some examples, the weight of cyclohexanone in the slurry is 16% by weight. The cent is 17% by weight. In some examples, the weight of cyclohexanone in the slurry The percentage is 18% by weight. In some examples, cyclohexanone in slurry The weight percentage is 19% by weight. In some examples, cyclohexano in slurry The weight percentage of is 20% by weight. In some examples, cyclohexyl in slurry The weight percentage of Sanon is 21% by weight. In some examples, cyclo in slurry The weight percentage of hexanone is 22% by weight. In some examples, the syllium in the slurry is The weight percentage of chlorohexanone is 23% by weight. In some examples, in the slurry... The weight percentage of cyclohexanone is 24% by weight. In some examples, slurry - The weight percentage of cyclohexanone in it is 25% by weight. In some examples, The solvent is a MEK:IPA combination. In one example, the MEK:IPA ratio is 1:1. In one example, the MEK:IPA ratio is 2:1. In another example, the MEK:IPA ratio is 3:1. In one example, the MEK:IPA ratio is 4:1. In another example, the MEK:IPA ratio is 5:1. In one example, the MEK:IPA ratio is 5:1. In another example, the MEK:IPA ratio is 7:1. In one example, the MEK:IPA ratio is 8:1. In another example, the MEK:IPA ratio is 5:1. In one example, the MEK:IPA ratio is 5:2. In another example, the MEK:IPA ratio is 6:2. In one example, the MEK:IPA ratio is 7:2. In another example, the MEK:IPA ratio is 8:2. In one example, the MEK:IPA ratio is 9:2. In another example, the MEK:IPA ratio is 10:3. In one example, the MEK:IPA ratio is 11:3. In another example, the MEK:IPA ratio is 5:3. In one example, the MEK:IPA ratio is 6:3. In another example, the MEK:IPA ratio is 7:3. In one example, the MEK:IPA ratio is 8:3. In another example, the MEK:IPA ratio is 9:3. In one example, the MEK:IPA ratio is 10:3. In another example, the MEK:IPA ratio is 11:3.

[0083] In one example, the MEK:IPA ratio is 7:3.

[0084] In some examples, the solvent is a combination of MEK, IPA, and cyclohexanone.

[0085] In some examples, the solvents used herein further include water.

[0086] (I. Sintering) The green film described herein can be sintered by a sintering method known in the relevant art. It is possible. PCT / US2014 / 059578, filed on October 7, 2014, Garnet Materials for Li Secondary Batteries Materials and Methods of Making and Using Garnet Materials (Garnet Materials for Li Secondary B atteries and Methods of Making and Using Garnet Materials) are incorporated herein by reference in their entirety for all purposes.

[0087] The green films shown herein can be sintered in an oven exposed to an atmosphere. In some examples, the film is sintered in an O2-rich atmosphere. In other examples, the film is sintered in an argon-rich atmosphere. In still other examples, the film is sintered in an argon / H2 atmosphere. In other examples, the film is sintered in an argon / H2O atmosphere. In some examples, the atmosphere used to sinter the film is not the same as the atmosphere used to cool the film after sintering the film.

[0088] In some examples, the method includes sintering a film, where sintering the film includes heat sintering. In some of these examples, heat sintering the film includes heating the film in an atmosphere having an oxygen partial pressure in the range of about 700 °C to about 1200 °C, about 1 to about 600 minutes, and 1e-1 atm to 1e-15 atm.

[0089] In any of the methods shown herein, heat sintering the film includes heating the film to about 700 °C to about 1250 °C; or about 800 °C to about 1200 °C; or about 900 °C to about 1200 °C; or about 1000 °C to about 1200 °C; or This may include heating in the range of approximately 1100°C to approximately 1200°C. In either case, heating and sintering the film is performed at approximately 700°C to approximately 1100°C; or approximately 700°C to approximately 1 This includes heating to 000°C; or to a range of approximately 700°C to approximately 900°C; or to a range of approximately 700°C to approximately 800°C. Yes, it is possible. In any of the methods shown herein, heating and sintering the film can be about 70 0℃, approximately 750℃, approximately 850℃, approximately 800℃, approximately 900℃, approximately 950℃, approximately 1000℃, approximately 1050℃, approximately 1100℃, This may include heating to approximately 1150°C or approximately 1200°C. (Method as described herein) In any of these cases, heating and sintering the film at 700°C, 750°C, 850°C, 800°C, or 900°C. This includes heating up to 950°C, 1000°C, 1050°C, 1100°C, 1150°C, or 1200°C. Yes, it is possible. In any of the methods shown herein, heating and sintering can be used to make the film about 700 This may include heating to °C. In any of the methods shown herein, Heat sintering may include heating the film to approximately 750°C. In any of the methods, heating and sintering involves heating the film to approximately 850°C. It may include. In any of the methods shown herein, heating and sintering is This may include heating the membrane to approximately 900°C. Any of the methods described herein. In this process, heating and sintering may involve heating the film to approximately 950°C. In any of the methods described in the specification, heating and sintering involves heating the film to about 1000°C. This may include heating and sintering in any of the methods shown herein. This may include heating the film to approximately 1050°C. In either case, heating and sintering involves heating the film to approximately 1100°C. Yes, it is possible. In any of the methods shown herein, heating and sintering can be used to make the film about 1125 This may include heating to °C. In any of the methods shown herein, Heat sintering may include heating the film to approximately 1150°C. In any of the methods, heating and sintering involves heating the film to approximately 1200°C. It can include.

[0090] In any of the methods described herein, the method involves heating the membrane for about 1 to about 600 minutes. This may include the following: In any of the methods shown herein, the method involves the film This may include heating for approximately 20 to 600 minutes, or any of the methods shown herein. In this specification, the method may include heating the membrane for about 30 to about 600 minutes. In any of the methods shown, the method includes heating the membrane for about 40 to about 600 minutes. It is possible to do so. In any of the methods shown herein, the method involves making the film about 50 to about This may include heating for 600 minutes in any of the methods shown herein. The method may include heating the membrane for about 60 to about 600 minutes. In any of the methods, the method may include heating the membrane for about 70 to about 600 minutes. Yes, it is possible. In any of the methods shown herein, the method involves drying the film for about 80 to about 600 minutes. This may include heating. In any of the methods shown herein, the method This may include heating the membrane for about 90 to about 600 minutes. In either case, the method may include heating the membrane for about 100 to about 600 minutes. In any of the methods described herein, the method involves heating the membrane for about 120 to about 600 minutes. This may include the following: In any of the methods shown herein, the method involves the film This may include heating for approximately 140 to 600 minutes, or any of the methods described herein. In this specification, the method may include heating the membrane for about 160 to about 600 minutes. In any of the methods shown, the method includes heating the membrane for about 180 to about 600 minutes. It is possible to do so. In any of the methods shown herein, the method involves making a film about 200~ This may include heating for approximately 600 minutes. Any of the methods shown herein may cause odor The method may include heating the membrane for about 300 to about 600 minutes. In any of the methods, the method includes heating the membrane for about 350 to about 600 minutes. This can be done. In any of the methods shown herein, the method involves drying the film for about 400 to about 600 minutes. Intermittent heating may be included. In any of the methods shown herein, the method The method may include heating the membrane for approximately 450 to 600 minutes. In either of these methods, the method may include heating the membrane for about 500 to about 600 minutes. In any of the methods described herein, the method involves heating the membrane for about 1 to about 500 minutes. This may include the following: In any of the methods shown herein, the method involves the film This may include heating for approximately 1 to 400 minutes. The method may include heating the membrane for about 1 to about 300 minutes. In any of the methods, the method includes heating the membrane for about 1 to about 200 minutes. This can be done. In any of the methods shown herein, the method involves drying the film for about 1 to about 100 minutes. This may include heating. In any of the methods shown herein, the method This may involve heating the membrane for approximately 1 to 50 minutes.

[0091] In some cases, the sintering process may further include a filtration step.

[0092] In some cases, the sintering process may further include a degassing step.

[0093] In some cases, the sintering process is carried out in a closed but not sealed furnace. That is, it may include sintering in an oven or heating chamber. In some cases, the sintered film, along with any setter sheet or layer therein, The sintered film is placed between setter plates, adjacent to or very close to the Li sacrificial source. This Li sacrificial source helps prevent Li loss due to evaporation from the sintered garnet. In some cases, the closed system is argon gas, argon gas and hydrogen gas, or water. This includes any mixture, air, purified air, or nitrogen. Some of these examples include Furthermore, the Li sacrificial source has a larger surface area than the surface area of ​​the green tape being sintered. In some cases, the Li source and sintered green film are the same type of lithium-filled garnet. It has a to.

[0094] (J. Sintering with other device components) In one example, when the green film was used in an electrochemical device, the sintered film was It is sintered while in contact with other components it is combined with. For example, in some cases Then, after the green film is sintered, the sintered film adheres to the positive electrode assembly. It is layered or laminated on the finished product. In another example, the green film is made of metal powder (e.g., nickel). It is sintered while in contact with the (Ni) powder. The green film is sintered, and the metal powder becomes a solid metal foil. In this state, the sintered film bonds to the metal foil. The advantages of these sintering conditions are for electrochemical devices. Multiple components can be prepared in a single step, thus saving manufacturing time and resources. That is what can be done.

[0095] (K. Crushed) As described herein, several listed methods relate to the mixing process. The process includes steps relating to grinding and / or crushing. Crushing includes ball crushing. Crushing includes, Not limited to, but including ethanol, isopropanol, toluene, ethyl acetate, methyl acetate, This also includes grinding methods using inert solvents such as acetone, acetonitrile, or combinations thereof. It is possible. Depending on the material being ground, the solvent does not have to be inert. Some of these examples In this regard, pulverization is not limited to ethanol, isopropanol, toluene, acetic acid. Solvents such as ethyl acetate, methyl acetate, acetone, acetonitrile, MEK, or combinations thereof. This includes grinding using a grinding method.

[0096] In some cases, the crushing is ball crushing. In some cases, the crushing is horizontal It is grinding. In some cases, grinding is grinding by grinding machine. In some cases, The grinding is immersion grinding. In some cases, the grinding is jet grinding. In the example, the grinding is steam jet grinding. In some examples, the grinding is high energy This is high-energy grinding. In some cases, the high-energy grinding process is performed at approximately 100 nm. 50 This results in a grinding particle size distribution having [specific characteristics]. In some cases, grinding is immersion grinding.

[0097] In some cases, a high-energy grinding process is used to produce particles with a d50 of approximately 100 nm. A radial distribution is achieved. In some examples, the solvent is toluene. In some examples, The solvent is isopropyl alcohol (IPA). In some examples, the solvent is ethanol It is a solvent. In some examples, the solvent is diacetone alcohol. In this case, the solvent is a polar solvent suitable for achieving the listed d50 sizes.

[0098] In some cases, grinding is performed using a 0.3 mm yttrium-stabilized zirconium oxide grinding medium. This includes a high-energy wet grinding process using body beads. In some examples, ball Grinding, horizontal grinding, abrasive grinding, or immersion grinding can be used. Some examples include... Furthermore, using a high-energy grinding process, a particle size distribution of d50 from approximately 100 nm to 5000 nm is produced. To do.

[0099] In some cases, grinding involves sieving, centrifugation, or different sizes and / or qualities. This may include classification steps such as other known laboratory tests to separate particles in quantities. [Examples]

[0100] (L. Example) SEM electron microscopy observations were performed using a Helios 600i or FEI Quanta. Surface roughness was measured at height. An optical microscope capable of measuring and calculating roughness values, such as Keyence VR. It was done.

[0101] The sintering apparatus used was equipped with a custom-made temperature and gas flow control system, operating at 1e-1 to 1e-20°C. It included a 3-inch experimental tube furnace with a controlled atmosphere and a range of oxygen partial pressures.

[0102] (Example 1 - Method for producing and sintering green tape) 12.25g isopropanol, 1.875g polyvinyl butyral, 1.875g dibutylphthalate 18.75 g of phosphate mixed with 2.81 g of phosphate ester and 9 g of tetrahydrofuran Lithium-filled garnet (batch compound, Li 7.1 Zr2La3O 12 The first slurry contains (+0.5Al2O3) source powder. —was prepared.

[0103] 12.25g isopropanol, 1.875g polyvinyl butyral, 1.875g dibutylphthalate 18.75g lithium-filled gas mixed with 2.81g of phosphate ester and 9g of toluene. A second slurry containing the net source powder was prepared.

[0104] 12.25 g of a mixed solvent containing isopropanol and 20% by weight of butanol, and 1.875 g Polyvinyl butyral, 1.875 g of dibutyl phthalate, and 2.81 g of phosphate ester, This product contains 18.75 g of lithium-filled garnet source powder mixed with 9 g of tetrahydrofuran. A third slurry was prepared.

[0105] 12.25 g of mixed solvent containing isopropanol and 20% by weight butanol, 1.875 g of polyvinyl Nilbutyral, 1.875 g of dibutyl phthalate, 2.81 g of phosphate ester, and 9 g of A fourth slurry was prepared containing 18.75 g of lithium-filled garnet source powder mixed with ruen. did.

[0106] Lithium-filled garnet source powder before and after friction grinding for each slurry. teeth Particle shape status That is .

[0107] In this example, a slurry of lithium-filled garnet is prepared by doctor blading. The material is cast onto a substrate, and then the cast slurry is placed between two porous garnet setter plates. By placing it there and sintering it, a green tape is prepared, and then , and removed from the setter plate. In one embodiment, the tape cast from the slurry was 1100°C In another embodiment, the tape was sintered at 1125°C for 1 to 5 hours. In this example, the tape was sintered at 1150°C for 1 to 5 hours. Before sintering, the binder was subjected to high-pressure O2(P It was burned out in O2 and H2O. During sintering, the atmosphere around the sintered film was 0.5-10 -20 atmospheric pressure It had a range PO2.

[0108] The green tape produced in this example using slurry composition 1 is shown in Figure 2. The analysis was performed using SEM microscopy.

[0109] (Example 2 - Method for producing and sintering green tape) In this example, the following slurry contains the following components in the listed weight percentages (%). Slurry 1, Slurry 2, and Slurry 3 were prepared. The source powder was batch-formulated Li7 .1 Zr2La3O 12 The result was +0.5Al2O3. 。 [Table 1]

[0110] In this example, the following binder has the following components listed in weight percent (%). - A mixture was prepared: [Table 2]

[0111] Slurry 1 was mixed with binder mixture 1 in a weight ratio of 2.4 to form a mixed slurry. Mix slurry 2 with binder mixture 2 in a weight ratio of 2.1 to form the mixed slurry. This was done. Slurry 3 was mixed with binder mixture 3 and 2 in the weight ratio, and the mixed slurry — was formed.

[0112] In this example, each mixed slurry is cast onto the substrate by doctor bladening. Then, the cast slurry is placed between two porous garnet setter plates. By sintering it, the green tape is prepared, and then setter plate It was removed from the tape. In one embodiment, the tape cast from the slurry was sintered at 1100°C for 1 to 5 hours. In another embodiment, the tape was sintered at 1125°C for 1 to 5 hours. The material was sintered at 1150°C for 1 to 5 hours. Before sintering, the binder was heated in high-pressure O2 (PO2) and H2O. It was burned to ashes. During sintering, the atmosphere around the sintered film was 0.5-10 -20 The PO2 has a range of atmospheric pressure. They were doing it.

[0113] The sintered film produced in this example using slurry composition 1 and binder mixture 1 is shown in Figure 4. The analysis was performed using SEM microscopy as shown.

[0114] (Example 3 - Method for layering and sintering green tape) In this embodiment, the slurry and binder mixture were prepared in the same manner as in Example 2, and combined Next, each mixed slurry is cast onto the substrate by doctor bladening. Green tape was prepared by the following method. The cast mixture slurry was dried in the air, and then the green tape was prepared. A layer of green tape was formed. Next, a second layer of green tape was dried. They were piled on top of each other. This process continued until five layers of green tape were stacked on top of each other. The process was repeated. Then, the layered green tape was placed in two porous garnet setter plates. By placing it between the sets, it is sintered, and then removed from the setter plate. In one embodiment, the laminated green tape was sintered at 1100°C for 1 to 5 hours. In one example, the tape was sintered at 1125°C for 1 to 5 hours. In another example, the tape was sintered at 1150°C for 1 Sintering was performed for approximately 5 hours. Before sintering, the binder was completely burned off in high-pressure O2 (PO2) and H2O. During sintering, the atmosphere around the sintered film was 0.5-10°C. -20 It had a PO2 within a certain atmospheric pressure range.

[0115] The sintered film produced using the aforementioned green tape in this embodiment is shown in Figure 3. The analysis was performed using optical imaging.

[0116] The above description of embodiments of this disclosure is presented for illustrative purposes only; it is not comprehensive. Furthermore, it is not intended to limit the claims to the exact form disclosed. Related fields Those skilled in the art can, by routine experimentation alone, determine that numerous equivalents, modifiers, and variations are as described above. It can be understood that this is possible in light of the disclosure. This application provides an invention having the following configuration: (Composition 1) A method for sintering green tape: (a) Provide at least one source powder; (b) Modifying at least one source powder to prepare a modified source powder; (c) To provide a slurry of the modified source powder; (d) Cast the slurry to form a green tape; (e) drying the green tape; and (f) Sintering the green tape The method, including the method described above. (Configuration 2) The amount of source powder in the green tape is at least 50% by weight, 55% by weight, 60% by weight, 65% by weight The composition described in Configuration 1 is % by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, or 90% by weight. method. (Composition 3) The amount of source powder in the green tape is at least 60% by weight or at least 70% by weight. The method described in Configuration 2. (Composition 4) The at least one source powder is lithium-filled garnet, lithium-filled garnet It consists of a lithium-filled garnet containing a chemical precursor and an aluminum oxide dopant. A method selected from the group, as described in one of the three items (Construction 1 to 3). (Composition 5) The at least one of the source powders is lithium-filled garnet powder, of the configurations 1 to 4 The method described in one of the items. (Composition 6) The aforementioned at least one source powder is Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 It is one of configurations 1 to 5. The method described in item 1. (Composition 7) The above at least one source powder is lithium-filled garnet, one of the configurations 1 to 5 The method described in the section. (Composition 8) Modifying the at least one source powder results in the particle size distribution of the at least one source powder. A method described in any one of the items 1 to 5 of the composition, including modifying to have. (Composition 9) The particle size distribution is centered around 100 nm, 200 nm, 300 nm, 400 nm, 1 μm, 2 μm, 3 μm, or 4 μm. The method described in Configuration 8. (Composition 10) The method according to configuration 8, wherein the particle size distribution is centered around 0.1 to 1 μm. (Composition 11) Modifying the at least one source powder involves grinding the at least one source powder. A method described in any one of items 1 to 10 of the composition, including the above. (Composition 12) Modifying the at least one source powder increases the surface area of ​​the at least one source powder. A method described in any one of the items 1 to 11 of the configuration, including making something larger. (Composition 13) The aforementioned grinding methods include dry grinding, friction grinding, ultrasonic grinding, high-energy grinding, wet grinding, and The method according to configuration 11, selected from the group consisting of wet grinding and low-temperature grinding. (Composition 14) The pulverization includes using a solvent selected from isopropanol or butanol. The method described in configuration 11. (Composition 15) The aforementioned grinding is performed using a solvent selected from methyl ethyl ketone (MEK) or toluene. The method described in configuration 11, which includes the above. (Composition 16) The pulverization process is carried out using a solvent containing methyl ethyl ketone (MEK), as described in configuration 11. The method. (Composition 17) The method according to configuration 16, further comprising isopropanol (IPA) as the solvent. (Composition 18) The method according to configuration 17, wherein the solvent further comprises cyclohexanone. (Composition 19) The MEK:IPA ratio is 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8 w / w, and the composition is 15-18. Either one of the methods described in item 1. (Composition 20) The method according to any one of the components 17 to 18, wherein the amount of cyclohexanone is approximately 10 to 25% by weight. 。 (Composition 21) The method according to any one of claims 15 to 20, wherein the solvent is an azeotropic mixture. (Composition 22) The surface area of ​​the at least one source powder is such that while the at least one source powder is being modified , at least 3m 2 The method described in any one of the constructs 11 to 20, which increases to / g. (Composition 23) The surface area of ​​the at least one source powder is such that while the at least one source powder is being modified , at least 5m 2 The method described in configuration 22 increases to / g. (Composition 24) The surface area of ​​the at least one source powder is such that while the at least one source powder is being modified , at least 8m 2 / g and 15m 2 The method described in configuration 22, which increases to less than / g. (Composition 25) Modifying the at least one source powder means that the average of the particles of the at least one source powder A method according to any one of the claims 1 to 24, comprising reducing the particle size. (Composition 26) The method according to configuration 13, wherein the grinding is wet grinding or high-energy grinding. (Composition 27) The aforementioned grinding process involves a protonating Li in an aprotic solvent, organic solvent, and lithium-filled garnet. This includes using solvents selected from the group consisting of non-exchangeable solvents and combinations thereof. Hmm, the method described in configuration 13. (Composition 28) The aforementioned pulverization process involves methanol, ethanol, propanol, isopropanol, and butanol. Isobutanol, t-butanol, pentanol, hexanol, cyclohexanol, Cyclohexanone, methyl acetate, ethyl acetate, methyl ethyl ketone (MEK), acetone, Use a solvent selected from the group consisting of ruene, hexane, acetic acid, and combinations thereof. The method described in configuration 13, which includes the following. (Composition 29) The modified source powder has wavelengths of 100nm to 200nm, 200nm to 300nm, 300nm to 400nm, and 400nm to 500nm. , 500nm~600nm, 600nm~700nm, 700nm~800nm, 800nm~900nm, 900nm~1000nm, 1000nm ~1100nm, 2000nm~2200nm, 3000nm~3300nm, or 4000nm~4400nm 50 grains with a specific particle size A method having a diameter distribution, as described in any one of the configurations 1 to 28. (Composition 30) The modified source powder has wavelengths of 100nm to 200nm, 200nm to 300nm, 300nm to 400nm, and 400nm to 500nm. , 500nm~600nm, 600nm~700nm, 700nm~800nm, 800nm~900nm, or 900nm~1000nm 50 A method according to any one of the constructs 1 to 28, having a particle size distribution with particle size. (Composition 31) The aforementioned d 50 However, the range is 100nm to 200nm, 200nm to 300nm, or 300nm to 400nm, as described in configuration 30. Law. (Composition 32) The structure further includes relieving the stress on the green tape before the sintering process. The method described in any one of items 1 to 31. (Composition 33) Any one of configurations 1 to 32, further including the layering of multiple green tapes together. Method of description. (Composition 34) Configuration 1 further includes layering one green tape on top of a second green tape. The method described in any one of the items ~32. (Composition 35) Before step (d), the slurry of the modified source powder and polypropylene (PP), ATACT Polypropylene (aPP), isotactic polypropylene (iPP), polyvinyl butyral (PVB), Acrylic, Polyethyl Methacrylate (PMMA), Polyethyl Methacrylate (PEMA) Polyvinylpyrrolidone (PVP), Atactic polypropylene (aPP), Isotactic poly Propylene ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyiso Butylene (PIB), styrene-butadiene rubber (SBR), polyolefin, polyethylene-copoly- 1-octene (PE-co-PO); PE-co-poly(methylenecyclopentane) (PE-co-PMCP); stereo- block polypropylene, polypropylene polymethylpentene copolymer, polypropylene carbonate, methyl methacrylate, ethyl methacrylate, silicone, and combinations thereof, further comprising mixing a binder selected from the group consisting of, the method according to any one of Configurations 1 to 32. (Configuration 36) The slurry is polypropylene (PP), atactic polypropylene (aPP), isotactic polypropylene (iPP), polyvinyl butyral (PVB), acrylic, polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyvinyl pyrrolidone (PVP), atactic polypropylene (aPP), isotactic polypropylene ethylene propylene rubber ( EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene-butadiene rubber (SBR), polyolefin, polyethylene-copoly-1-octene (PE-co-PO); PE-co-poly( (methylenecyclopentane) (PE-co-PMCP); stereoblock polypropylene, polypropylene polymethylpentene copolymer, polypropylene carbonate, methyl methacrylate , ethyl methacrylate, silicone, and a binder selected from the group consisting of combinations thereof, the method according to any one of Configurations 1 to 35. (Configuration 37) The at least one source powder is of the formula Li x La y Zr z O t ·qAl 2 O 3 (where 4 < x < 10, 1 < y < 4, 1 < z < 3, 6 < t < 14, 0 ≦ q ≦ 1), a Li-filled garnet compound characterized by, the method according to any one of Configurations 1 to 36. (Configuration 38) The at least one source powder is of the formula Li 7-x La 3 Zr 2 O 12 ·qAl 2 O 3 (where q is 0, 0.3, 0.35 , 0.5, 0.75, or 1.0, and 0 ≦ x ≦ 1), a Li-filled garnet compound characterized by, the method according to any one of Configurations 1 to 37. (Configuration 39) Modifying the at least one source powder comprises grinding the at least one source powder, ni trotoluene, nitrile butadiene rubber, carboxymethyl cellulose (CMC), styrene-butad En rubber (SBR), PVDF-HFP, PAN, water-compatible polymer, atactic polypropylene (aPP) ), silicone, polyisobutylene (PIB), ethylene propylene rubber (EPR), PMX-200 PDMS ( Polydimethylsiloxane / polysiloxane (i.e., PDMS, or silicone), polyacrylate Lilonitrile (PAN), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl Rubityral (PVB), polyfluoride (vinylidene)-hexafluoropropylene PVDF-HFP, and This includes incorporating a dispersant or polymer selected from the group consisting of these combinations. The method described in any one of items 1 to 38. (Composition 40) Providing the aforementioned slurry includes the following: Methanol, MEK, ethanol, propanol, isopropanol (IPA), acetone, cyanoacrylate Select from the group consisting of chlorohexanol, toluene, acetate, benzene, and combinations thereof. The solvent that is used; Fish oil, PVB, KD1, acrylic acid, triton, phosphate esters, their derivatives, and combinations thereof A binder selected from a group consisting of combinations; A plasticizer selected from the group consisting of benzylbutyl phthalate or dibutyl phthalate; pH modifier; Selected sintering aids; and Selected source powder from lithium-filled garnet The slurry is formulated by mixing at least two of the following: The method described in any one of items 1 to 39 of the configuration. (Composition 41) The benzylbutyl phthalate is benzylbutyl phthalate 9S-160 (trademark), composition Method described in 40. (Composition 42) The modification includes classifying the at least one source powder based on particle size. The method described in any one of items 1 to 41 of the composition. (Composition 43) Classification is a group of processes that include sieving, centrifugation, and separating particles of different sizes. The method described in configuration 42, which is a technique selected from among them. (Composition 44) Classification is a group of processes that include sieving, centrifugation, and separating particles of different masses. The method described in configuration 42 is a technique selected from among the methods. (Composition 45) The slurry has a solid load of 1% to 99 wt%, where the solid load refers to the amount of source powder. The method described in any one of items 1 to 42 of the configuration. (Composition 46) The slurry, when dried, has approximately 80% w / w of source powder, one of the constituents 1 to 42. The method described in the section. (Composition 47) When the slurry dries, it has an organic content of approximately 10-25% w / w, where the organic The method according to any one of the constituents 1 to 42, wherein the content refers to slurry components other than the source powder. (Composition 48) When the slurry dries, it contains approximately 10-25% w / w of organic matter, where the organic matter The contained substance refers to slurry components other than the source powder, and the source powder is lithium-filled garnet. or the method described in any one of items 1 to 42 of the composition. (Composition 49) The amount of binder and plasticizer in the slurry is approximately 10-25% w / w of organic matter. Here, the organic content refers to slurry components other than the source powder, and the source powder is lithium-filled gas - A network, using one of the methods described in item 1 to 42. (Composition 50) The source powder is d 50nm~5μm 50 A particle size distribution having the following characteristics, according to any one of the configurations 1 to 49. method. (Composition 51) The method according to any one of the configurations 1 to 50, wherein the source powder is lithium-filled garnet. (Composition 52) The aforementioned source powder is of formula Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 Characterized by, the composition 1 to 50 The method described in one of the items. (Composition 53) The aforementioned source powder is batch-formulated, Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 Characterized by or the method described in any one of items 1 to 50 of the composition. (Composition 54) A slurry for preparing a cast green film: Methanol, ethanol, propanol, isopropanol, butanol, isobutanol t-butanol, pentanol, hexanol, cyclohexanone, cyclohexano Toluene, methyl acetate, ethyl acetate, methyl ethyl ketone (MEK), acetone, toluene, hexyl acetate A solvent selected from the group consisting of ethanol, acetic acid, and combinations thereof; Fish oil, polyvinylbutylene (PVB), KD1, acrylic acid, triton, phosphate ester, and so A binder selected from the group consisting of derivatives of; A plasticizer selected from the group consisting of benzylbutyl phthalate or dibutyl phthalate; Optionally, pH modifiers; Optionally, a sintering aid; and Selected source powder from lithium-filled garnet The slurry comprising at least two of the following. (Composition 55) The amount of source powder is at least 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight A slurry according to composition 54, which is % by weight, 80% by weight, 85% by weight, or 90% by weight. (Composition 56) The amount of source powder is at least 60% by weight, 65% by weight, 70% by weight, or 75% by weight, configuration 54 The slurry described. (Composition 57) The aforementioned source powder includes lithium-filled garnet, a chemical precursor of lithium-filled garnet, and Selected from the group consisting of lithium-filled garnets containing aluminum oxide dopant. , a slurry according to any one of items 54 to 56. (Composition 58) A slurry according to any one of the components 54 to 57, comprising a plasticizer, a pH modifier, and a sintering aid. (Composition 59) The aforementioned source powder is approximately 3 μm in size d50 It contains finely ground garnet powder, and the binder is in MEK A slurry according to any one of the constituents 54 to 58, comprising polymethyl methacrylate. (Composition 60) The description of any one of the items 54 to 59, comprising MEK, phosphate ester, and cyclohexanone. The slurry. (Composition 61) The solvent is selected from methyl ethyl ketone (MEK) or toluene, of the configurations 54-60 A slurry as described in one of the items. (Composition 62) The slurry according to any one of the constructs 54 to 61, wherein the solvent comprises methyl ethyl ketone (MEK) —. (Composition 63) The solvent further comprises isopropanol (IPA) according to any one of the configurations 54 to 62. Rally. (Composition 64) The slurry according to any one of the constructs 54 to 63, wherein the solvent further comprises cyclohexanone. 。 (Composition 65) MEK:IPA ratios of 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8 w / w, composition of 54-64 w / w A slurry as described in one of the items. (Composition 66) A slurry according to any one of items 54 to 65, wherein the amount of cyclohexanone is approximately 10 to 25% by weight. Lee. (Composition 67) The slurry according to any one of the claims 54 to 66, wherein the solvent is an azeotropic mixture. (Composition 68) The slurry according to any one of the configurations 54 to 67, wherein the source powder is lithium-filled garnet. —. (Composition 69) The amount of lithium-filled garnet in the slurry is at least 70% w / w, according to configuration 68. A slurry containing a load. (Composition 70) The concentration of the source powder in the slurry is approximately 50 wt%, and the concentration of the binder in the slurry is A slurry according to any one of items 54 to 69, comprising approximately 50 wt%. (Composition 71) The concentration of the source powder in the slurry is approximately 2-80% w / w, as described in any one of the configurations 54-70. The slurry. (Composition 72) The concentration of the source powder in the slurry is approximately 50 wt%, and the concentration of the binder in the slurry is A slurry according to any one of items 54 to 70, comprising approximately 30 wt%. (Composition 73) A slurry according to composition 54 to 68, comprising approximately 47.5 wt% of a solvent and 0.5 wt% of a plasticizer. (Composition 74) The aforementioned green film is 100 / mm 2 It contains flocs of less than a certain density, where the flocs are green When measured by FIB cross-sectional SEM of the film, it was found to be a binder aggregate with a diameter of >5 μm, comprising 5 A slurry as described in any one of items 4 to 73. (Composition 75) source powder; solvent; Binder; and Dispersant; A green tape containing 3.9 g.cm 3 Super and 5.0g.cm 3 Less than pic The green tape having a nomometric density. (Composition 76) The configuration according to configuration 75 further comprises a component selected from a plasticizer, a pH modifier, and a sintering aid. Tape. (Composition 77) The dispersant is selected from KD-1, fish oil, and Rhodline 4160, according to configuration 75. Tape. (Composition 78) The green tape according to configuration 75, wherein the plasticizer is selected from DBP, BBP, and PEG. (Composition 79) The green according to composition 75, comprising a pH modifier selected from citric acid or ammonium hydroxide. tape. (Composition 80) MgO, Al 2 O 3 The green according to configuration 75, comprising a sintering aid selected from a combination thereof, and a green Tape. (Composition 81) A green tape according to any one of the items 75 to 80, wherein the solvent is an azeotropic mixture. (Composition 82) Green according to any one of the constructs 75 to 81, wherein the solvent is a polar aprotic azeotropic mixture. tape. (Composition 83) The solvents are methyl ethyl ketone (MEK), tetrahydrofuran, toluene, acetone, and 1-bronze. Butanol, 2-butanol, cyclohexane, cyclohexanol, ethanol, isopropyl alcohol Panol, methanol, 1-propanol, propylene carbonate, hexane, 1-propanol A compound selected from ol, m-xylene, and pentane, as described in any one of items 75 to 82. Lean tape. (Composition 84) The solvent is selected from methyl ethyl ketone (MEK) or toluene, and the composition of 75-83 The green tape described in item 1. (Composition 85) The solvent comprises methyl ethyl ketone (MEK) as described in any one of the claims 75 to 84. Tape. (Composition 86) The solvent further comprises isopropanol (IPA), according to any one of the configurations 75 to 85. Lean tape. (Composition 87) The Green according to any one of the configurations 75 to 86, wherein the solvent further comprises cyclohexanone. tape. (Composition 88) MEK:IPA ratios of 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, or 2:8 w / w, composition 75-87 The green tape described in item 1. (Composition 89) The amount of cyclohexanol is approximately 10-25% by weight, as described in any one of the components 87-88. Lean tape. (Composition 90) A green tape according to any one of the configurations 75 to 89, having a polarity index greater than 3. (Composition 91) 4 g / cm³ 3 A source powder of lithium-filled garnet having a density; and a solvent containing MEK and IPA. Green tape as described in any one of items 75 to 90, including the above. (Composition 92) 4 g / cm³ 3 Lithium-filled garnet source powder having density; as well as MEK, IPA, and cyclo A green tape according to any one of the items 75 to 91, comprising a solvent containing hexanone. (Composition 93) A method for making green tape, (a) Provide a slurry; (b) Provide a binder mixture; (c) Mixing the slurry with the binder mixture to form a mixed slurry; and (d) Cast the mixed slurry to provide a green tape. The method, including the method described above. (Composition 94) The slurry, Methanol, ethanol, propanol, isopropanol, butanol, isobutanol t-butanol, pentanol, hexanol, cyclohexanol, methyl acetate, Ethyl acetate, methyl ethyl ketone (MEK), acetone, toluene, hexane, acetic acid, and A solvent selected from the group consisting of these combinations; Fish oil, polyvinylbutylene (PVB), KD1, acrylic acid, triton, phosphate ester, and so A binder selected from the group consisting of derivatives of; A plasticizer selected from the group consisting of benzylbutyl phthalate or dibutyl phthalate; Optionally, pH modifiers; Optionally, a sintering aid; and Selected source powder from lithium-filled garnet The method according to configuration 93, comprising at least two of the following. (Composition 95) The method according to any one of the configurations 92 to 93, further comprising sintering the green tape. Law. (Composition 96) The description of any one of the configurations 92 to 93, which includes grinding the slurry before step (a). The method. (Composition 97) The slurry is pulverized so that the particle size of the particles in the slurry is 100 nm to 200 nm, 200 nm ~300nm, 300nm~400nm, 400nm~500nm, 500nm~600nm, 600nm~700nm, 700nm~800nm, 8 00nm~900nm, 900nm~1000nm, 1000nm~1100nm, 2000nm~2200nm, 3000nm~3300nm, or d 50 Any one of the items of item 96, which includes grinding until a particle size is obtained. The method. (Composition 98) The method according to any one of the constructs 92 to 97, wherein the slurry includes the following: (Table 1) TIFF0007881646000003.tif34170 。 (Composition 99 places) The method according to any one of the constructs 92 to 97, wherein the slurry includes the following: (Table 2) TIFF0007881646000004.tif35170 。 (Configuration 100) The method according to any one of the constructs 92 to 97, wherein the slurry includes the following: (Table 3) TIFF0007881646000005.tif30170 。 (Composition 101) The method according to any one of the constructs 92 to 97, wherein the slurry includes the following: (Table 4) TIFF0007881646000006.tif35170 。 (Composition 102) The method according to any one of claims 92 to 97, wherein the binder mixture comprises the following: (Table 5) TIFF0007881646000007.tif36170 。 (Composition 103) The green tape has a solid load greater than 50% w / w, in any of configurations 92 to 102. The method described in item 1. (Composition 104) The green tape has a solid load greater than 60% w / w, in any of configurations 92 to 103. The method described in item 1. (Composition 105) The green tape has a solid load greater than 70% w / w, any of configurations 92 to 104. The method described in item 1. (Composition 106) The green tape has a solid load greater than 80% w / w, any of configurations 92 to 105. The method described in item 1. (Composition 107) The green tape has a solid load greater than 90% w / w, any of configurations 92 to 106. The method described in item 1. (Composition 108) The green tape is a thin film having a thickness of less than 200 μm and more than 1 nm, configuration 92-1 The method described in any one of item 07. (Composition 109) The green tape is a thin film having a thickness of less than 100 μm and more than 1 nm, configuration 92-108 The method described in any one of the items. (Configuration 110) The green tape is a thin film having a thickness of less than 75 μm and more than 1 nm, configuration 92-109 The method described in any one of the items. (Composition 111) The green tape is a thin film having a thickness of less than 50 μm and more than 1 nm, configuration 92-110 The method described in any one of the items. (Composition 112) The green tape is a thin film having a thickness of less than 25 μm and more than 1 nm, configuration 92-111 The method described in any one of the items. (Composition 113) The green tape is a thin film having a thickness of less than 10 μm and more than 1 nm, configuration 92-112 The method described in any one of the items. (Composition 114) (e) any one of the provisions of 92 to 113, further comprising drying the green tape. Method of loading. (Composition 115) (e) Dry the green tape until it has an organic content of approximately 10-25% w / w. This further includes, where the organic content is a content other than the source powder, configuration 92~ The method described in any one of item 113. (Composition 116) (f) Laminate the second green tape onto the green tape described in configuration 92, The method according to any one of the constructs 92 to 113, further comprising preparing a laminate of the same. (Composition 117) The configuration according to any one of the claims 92 to 115, further comprising sintering the green tape. method. (Composition 118) The configuration further includes sintering the laminate of the green tape, any one of configurations 92 to 116 The method described in the section.

Claims

1. A method for sintering green tape, wherein the method is (a) Cast the slurry to form a green tape. Here, the slurry comprises at least one source powder, an aprotic solvent, a binder, and a dispersant. The amount of the at least one source powder in the green tape is at least 75% by weight, and The at least one source powder has d particles ranging from 50 nm to 5 μm. 50 Having a particle size distribution; (b) Dry the green tape; (c) Relieving the stress on the green tape after drying; and (d) Sintering the green tape Includes, The at least one source powder is of the following formula: Li x La y Zr z O t ・qAl 2 O 3 (wherein 4 < x < 10, 1 < y < 4, 1 < z < 3, 6 < t < 14, and 0 ≤ q ≤ 1); Li x Zr 2 La 3 O 12 yAl 2 O 3 (where x is in the range of 5 to 9 and y is in the range of 0 to 1); Li 7-x La 3 Zr 2 O 12 ・qAl 2 O 3 (wherein q is 0, 0.3, 0.35, 0.5, 0.75, or 1.0 and 0 ≤ x ≤ 1); or Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 The method, wherein the lithium-filled garnet compound is characterized by one of the following.

2. The aforementioned at least one source powder is of formula Li x La y Zr z O t qAl 2 O 3 The method according to claim 1, wherein the lithium-filled garnet compound is characterized by the formula (wherein 4 < x < 10, 1 < y < 4, 1 < z < 3, 6 < t < 14, and 0 ≤ q ≤ 1).

3. wherein the at least one source powder is Li x Zr 2 La 3 O 12 yAl 2 O 3 (where x ranges from 5 to 9 and y ranges from 0 to 1), the method according to claim 1.

4. The aforementioned at least one source powder is of formula Li 7-x La 3 Zr 2 O 12 qAl 2 O 3 The method according to claim 1, wherein the lithium-filled garnet compound is characterized by the formula (wherein q is 0, 0.3, 0.35, 0.5, 0.75, or 1.0, and 0 ≤ x ≤ 1).

5. The aforementioned at least one source powder is of formula Li 7.1 Zr 2 La 3 O 12 +0.5Al 2 O 3 The method according to claim 1, characterized by the above.

6. The method according to claim 1, wherein the slurry is cast onto a metal substrate.

7. The method according to claim 6, wherein the metal substrate is a metal foil.

8. The method according to claim 7, wherein the metal foil comprises nickel, copper, gold, iron, or a combination thereof.

9. The method according to claim 1, wherein the slurry, when dried, has 80% w / w of the at least one source powder.

10. The method according to claim 1, wherein the slurry, when dried, has an organic content of 10% w / w, wherein the organic content refers to components of the slurry other than the at least one source powder.

11. The method according to claim 1, wherein the aprotic solvent is selected from toluene, xylene, cyclohexanone, tetrahydrofuran, acetone, N-methyl-2-pyrrolidone (NMP), ethyl acetate, acetonitrile, hexane, nonane, dodecane, methyl ethyl ketone (MEK), and combinations thereof.

12. The method according to claim 11, wherein the aprotic solvent is xylene.

13. The aforementioned binder is polypropylene (PP), atactic polypropylene (aPP), isotactive polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefin, polyethylene-co-poly-1-octene (PE-co-PO), PE-co-poly(methylenecyclopentane) (PE-co-PMCP), polymethyl methacrylate, acrylic polymer, acrylic, polyvinyl acetal resin, poly The method according to claim 1, comprising a material selected from vinyl butyral resin, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, polyvinyl butyral (PVB), polyethyl methacrylate (PEMA), polyvinylpyrrolidone, polypropylene carbonate, methyl methacrylate (or PMMA), ethyl methacrylate (or PEMA), isotactic polypropylene (iPP), and combinations thereof.

14. The method according to claim 13, wherein the binder is an acrylic polymer selected from polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, and combinations thereof.

15. The method according to claim 1, wherein the dispersant is selected from phosphate esters, fish oil, surfactants, fluorosurfactants, polyvinylpyridine, polyvinyl butadiene (PVB), polyalkyleneamines, acrylic polymers, and combinations thereof.

16. The method according to claim 1, wherein the slurry further comprises a plasticizer.

17. The method according to claim 16, wherein the plasticizer is selected from dibutyl phthalate, dioctyl phthalate, benzyl butyl phthalate, and combinations thereof.

18. The method according to claim 1, wherein the amount of the at least one source powder in the green tape is at least 80% by weight.

19. The method according to claim 1, wherein the amount of the at least one source powder in the green tape is at least 85% by weight.

20. The method according to claim 1, wherein the amount of the at least one source powder in the green tape is at least 90% by weight.

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