Garnet material for lithium-ion batteries

Abstract

To provide a lithium-loaded garnet in a thin film and powder form as catholytes, electrolytes, and anolytes for a solid-state lithium secondary battery.SOLUTION: A bilayer includes a metal foil or metal powder disposed in contact with a lithium-filled garnet thin film which is a thin sintered garnet film having a thickness of less than 50 μm and greater than 10 nm and being bonded to the metal foil or metal powder on at least one side of the film, and is selected from a particular formula.SELECTED DRAWING: Figure 36

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application, filed on October 7, 2013, concerns the formation of garnet material using a sintering process. Method and system for forming garnet materials with sint U.S. Provisional Patent Application No. 61 / 887,451, entitled "RING PROCESS", filed on January 13, 2014. U.S. Provisional Patent Application No. 61 / 9, entitled "GARNET THIN FILM ELECTROLYTE" Patent No. 26,910, filed on June 4, 2014, describes a method for forming garnet material using reaction sintering. Methods and systems for forming garnet material with reactive U.S. Provisional Patent Application No. 62 / 007,417, entitled SINTERING, filed on July 18, 2014, Fine-grained lithium-ion conductive thin film garnet ceramics U.S. Provisional Patent Application No. 62 / 026,271, entitled "N CONDUCTING THIN FILM GARNET CERAMICS", and A patent application filed on July 18, 2014, relating to garnet cassolite and solid-state electrochemical devices and Sintering of components (Garnet Catholyte and Sintering of Solid State Electrical Devices) Claiming priority to U.S. Provisional Patent Application No. 62 / 026,440, entitled "AND COMPONENTS" Each of these provisional patent applications is fully disclosed herein by reference for any purpose. It will be incorporated inside. [Background technology]

[0002] (Background of the invention) There is a great demand for cleaner forms of energy storage. An example is Li during discharge. + Rechargeable lithium (Li) where ions move from the negative electrode to the positive electrode. Ion batteries (i.e., lithium-ion rechargeable batteries) are one example. They have numerous applications (for example, portable electronic devices) In containers and transport, due to safety and energy density considerations, liquid components (for example, In contrast to batteries containing flammable liquid electrolytes, solid-state lithium-ion batteries are made entirely of solid materials. It is advantageous to do so. Solid lithium-ion batteries incorporating a lithium-metal anode are significantly lower It is also advantageous that the electrode has a large capacitance and a correspondingly increased energy density.

[0003] A crucial component of a solid-state battery is the electrolyte, which electrically isolates the positive and negative electrodes. In this case, the cathode active material is tightly mixed with the material to improve ionic conductivity within it. It also contains cassolite. In some lithium-ion batteries, the third important component is the anode material. An anodized material (i.e., negative electrode material; for example, Li-metal) is laminated with or in contact with it. It is light. However, currently available electrolytes, catholites, and anolite materials Even within the operating voltage range of a solid-state battery, certain cathode or anode active materials (for example) Furthermore, it is not stable when in contact with metal fluorides.

[0004] Garnet (e.g., Li-filled garnet) is used as a catholite, electrolyte, and in all-solid-state batteries. Alternatively, it is a class of oxides that may be suitable for use as anolite. However, garnet materials still do not have a suitable form (e.g., thin film or nanostructured powder). So as to have sufficient conductivity and / or particle bonding properties to function well. It is not manufactured. Specific garnet materials and processing techniques are known (for example, in the United States). U.S. Patent Nos. 8,658,317, 8,092,941, and 7,901,658; U.S. Patent Application Publication No. 2013 / 00850 Issues 55, 2011 / 0281175, 2014 / 0093785, and 2014 / 0170504; furthermore, Bonderer et al.'s paper, "Free-Standing Ultrathin Ceramic Foils", J Ournal of the American Ceramic Society, 2010, 93(11):3624-3631; and Murugan et al. (See reference, Angew Chem. Int. Ed. 2007, 46, 7778-7781), these materials and techniques are, This includes, but is not limited to, processing conditions that result in insufficient conductivity or are incompatible with certain solid battery components. I am plagued by various flaws.

[0005] Therefore, in particular, garnet films and garnet powder and cathode activators in all-solid-state batteries Regarding the integration of materials, there is a need for methods to produce and process improved garnet materials. The following disclosures are, firstly, to these and to the relevant fields to which this disclosure relates. It offers many solutions to other problems. [Overview of the project]

[0006] (Summary of the invention) Disclosed herein are catholites, electrolytes, and anions for solid lithium secondary batteries. Lithium-stuffed garnet in thin film and powder form as a light source This is a novel and inventive method for manufacturing and using. Also disclosed herein is a novel Garnet catholite, electrolytes, and anolite, and novel materials incorporating these materials This is an electrochemical device. In contrast to known garnets, the method described herein The materials are uniquely designed for electrochemical devices (e.g., solid-state batteries), and lithium Suitable form, conductivity, density, porosity, and surface properties (e.g., roughness) for use in batteries. (Flatness, lack of surface cracks and defects), as well as chemical stability, temperature stability, and voltage stability. It has a sexual nature. [Brief explanation of the drawing]

[0007] (Brief explanation of the drawing) [Figure 1] This specification shows an example of liquid-phase sintering by the flux sintering method described herein.

[0008] [Figure 2] This shows a plot of oxygen partial pressure as a function of calcination temperature for producing a specific calcined oxide.

[0009] [Figure 3] This shows a three-layer battery component in which a metal layer (e.g., metal powder or metal foil) is placed between and in contact with two electrolyte layers (e.g., Li-filled garnet).

[0010] [Figure 4] This specification describes a method for calcining or sintering garnet particles or garnet-metal-garnet triple layers, comprising applying pressure to these layers using a plate (which may be a die plate or a setter plate) during the calcining or sintering process.

[0011] [Figure 5] Examples of methods for calcining or sintering garnet layers (e.g., garnet double layers, triple layers, garnet-active material composite layers) are shown, where the weight of the die (or setter) plate provides the only external pressure applied to the calcined or sintered layer.

[0012] [Figure 6] Scanning electron microscopy (SEM) and focused ion beam (FIB) microscopy observations of thin garnet films fabricated by the reaction sintering method described herein, which uses applied pressure but does not use additional lithium source powder, are shown.

[0013] [Figure 7] The image shows the X-ray diffraction (XRD) pattern (intensity on the y-axis, 2-θ on the x-axis) of a thin garnet film fabricated by reaction sintering at approximately 1150°C without further lithium source powder. The labeled peaks [(112), (312), (400), (204), (224)] correspond to the crystalline phase of Li7La3Nb2O13.

[0014] [Figure 8] This image shows a high-density garnet thin film produced by reaction sintering under pressure. The scale bar in the left image is 10 μm. The scale bar in the right image is 100 μm.

[0015] [Figure 9]This specification shows a spatial conduction map of lithium-lanthanum-zirconia-alumina, exhibiting the total conductivity (at 20°C) as a function of Li and Al in LixLa3Zr2O12·yAl2O3 (where x is in the range of 5.5 to 9 (the x-axis of the plot is 5.5 to 9.0); and y is in the range of 0 to 1 (the y-axis of the plot is 0 to 2)), manufactured by the method described herein, for several different processing temperature / time combinations. The left image is of material processed at 1075°C; the middle image is of material processed at 1150°C; and the right image is of material processed at 1200°C.

[0016] [Figure 10] The plots above show the grain size (top plot), density (middle plot), and conductivity (bottom plot) as a function of Li content and processing temperature / time for LixLa3Zr2O12·yAl2O3 (where x is in the range of 5.5 to 9 and y is in the range of 0 to 1). Compositions marked A, B, C, and D were sintered at 1075°C for 6 hours. These compositions possess both small grain size and conductivity >10⁻⁴ S / cm. Composition A is characterized by Li6.3La3Zr2O12·0.35Al2O3; composition B is characterized by Li6.3La3Zr2O12·0.67Al2O3; composition C is characterized by Li7La3Zr2O12·0.67Al2O3; and composition D is characterized by Li7La3Zr2O12·Al2O3. The subscripts and molar coefficients in these compositions describe the respective amounts of raw materials used to manufacture them.

[0017] [Figure 11]This specification shows comparative examples of lithium-lanthanum-zirconia-alumina compared to the inventive compositions A, B, C, and D described herein. Composition A is characterized by Li6.3La3Zr2O12·0.35Al2O3; Composition B is characterized by Li6.3La3Zr2O12·0.67Al2O3; Composition C is characterized by Li7La3Zr2O12·0.67Al2O3; and Composition D is characterized by Li7La3Zr2O12·Al2O3. The subscripts and molar coefficients of these compositions describe the respective amounts of raw materials used to manufacture these compositions.

[0018] [Figure 12] The image shows a scanning electron microscope image of a lithium-filled garnet film LixLa3Zr2O12·yAl2O3 (where x is in the range of 5.5 to 9 and y is in the range of 0 to 1), manufactured by thermal sintering at 1075°C and having a variable Li:Al ratio.

[0019] [Figure 13] This specification shows conductivity plots as a function of Li:Al in the lithium-filled garnet film LixLa3Zr2O12·yAl2O3 (where x is in the range of 5.5 to 9 and y is in the range of 0 to 1).

[0020] [Figure 14] The density plots shown herein are a function of Li:Al content in the lithium-filled garnet film LixLa3Zr2O12·yAl2O3 (where x is in the range of 5.5 to 9 and y is in the range of 0 to 1, and the film was heat-sintered at 1075°C for 6 hours (left plot), 1150°C for 6 hours (middle plot), or 1200°C for 15 minutes (right plot)) (the x-axis is in the range of 5.0 to 9.0; the y-axis is in the range of 0 to 2.0 in each plot).

[0021] [Figure 15] This shows an example of sintering cylindrical shape element materials.

[0022] [Figure 16] This shows a film sintered by a sintering system in which sintered electrodes are in electrical contact with the film at two locations on the film surface.

[0023] [Figure 17] This shows a film sintered using a setter plate having individually addressable electrical contact points.

[0024] [Figure 18] This example shows how to sinter a film using a calender roller that conducts electric current.

[0025] [Figure 19] This example demonstrates the sintering of a film using a calender roller, in which one roller has individually addressable electrical contact points and the other roller is the ground electrode.

[0026] [Figure 20] This shows a film sintered using a sintering plate, where one or more metal foils are inserted between the sintered film and the setter plate.

[0027] [Figure 21] This shows a film sintered using a sintering plate, where one or more metal powders are inserted between the sintered film and the setter plate.

[0028] [Figure 22] The image shows a film sintered using a calender roller, where one of the rollers has a movable spiral design, allowing the contact point between the spiral roller and the thin film to be controlled during the sintering process.

[0029] [Figure 23] Examples of films and rectangular shape elements (e.g., thin films) that can be sintered according to the methods described herein are shown.

[0030] [Figure 24] This shows sintering, where an electric current is passed through the sintered film.

[0031] [Figure 25] This specification describes a method for fabricating embodiments of the invention disclosed herein.

[0032] [Figure 26] An example of a composite electrode for a solid-state battery, manufactured according to the method described herein, is shown, comprising an active electrode material with electrolyte particles dispersed in it, prior to sintering. This layer may also contain conductive additives (e.g., carbon) (not shown).

[0033] [Figure 27] A schematic diagram of an example of a well-sintered solid composite electrode is shown.

[0034] [Figure 28] This shows the arrangement for fast sintering of the electrolyte membrane used in lithium-ion solid-state batteries.

[0035] [Figure 29] This shows the configuration for fast sintering of an electrolyte-cathode combination that is expected to operate as a solid-state battery.

[0036] [Figure 30] Scanning electron microscope (SEM) images of self-supporting films fabricated according to the methods described herein are shown. The scale bar is 100 μm. Arrows indicate terminal boundaries. The films are imaged with their edges facing upwards.

[0037] [Figure 31]The left image shows a 40-micron thick, freestanding (i.e., substrate-free) garnet film produced by sintering an unsintered film between support setter plates, also made of garnet material. Figure 31 (right) shows a magnified portion of the image on the left.

[0038] [Figure 32] This shows the particle size distribution of garnet precursor powder before and after grinding.

[0039] [Figure 33] This shows the particle size distribution of lithium hydroxide and lanthanum oxide powders before grinding.

[0040] [Figure 34] This shows the particle size distribution of lithium hydroxide and lanthanum oxide after grinding.

[0041] [Figure 35] This image shows a cross-sectional SEM of a garnet film bilayer formed by sintering garnet powder. The upper layer is nickel (Ni), and the lower layer is lithium-filled garnet. The scale bar is 30 μm.

[0042] [Figure 36] Figure 35 shows the conductivity plot of the bilayer.

[0043] [Figure 37] This shows reaction-sintered Li7La3Zr2O12 using 100% lithium-filled garnet precursor. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 10 μm. The film was fabricated by doctor braiding with a slot gap of 5 mil.

[0044] [Figure 38]The image shows reaction-sintered Li7La3Zr2O12 using 75% w / w lithium-filled garnet precursor and 25% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 5 μm. The film was fabricated by doctor braiding with a slot gap of 5 mil.

[0045] [Figure 39] The image shows reaction-sintered Li7La3Zr2O12 using 50% w / w lithium-filled garnet precursor and 50% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 10 μm. The film was fabricated by doctor brading with a slot gap of 5 mil.

[0046] [Figure 40] The image shows reaction-sintered Li7La3Zr2O12 using 25% w / w lithium-filled garnet precursor and 75% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 5 μm. The film was fabricated by doctor brading with a slot gap of 5 mil.

[0047] [Figure 41] The image shows reaction-sintered Li7La3Zr2O12 using 75% w / w lithium-filled garnet precursor and 25% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 5 μm. The film was fabricated by doctor brading with a slot gap of 10 mils.

[0048] [Figure 42]The image shows a 10-mil sintered Li7La3Zr2O12 formed by the reaction of a 50% w / w lithium-filled garnet precursor and a 50% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 5 μm. The film was fabricated by doctor braiding with a slot gap of 10 mils.

[0049] [Figure 43] The image shows reaction-sintered Li7La3Zr2O12 using 25% w / w lithium-filled garnet precursor and 75% w / w lithium-filled garnet powder. The scale bar in the upper left image is 100 μm; the scale bar in the upper right image is 10 μm; and the scale bar in the lower image is 10 μm. The film was fabricated by doctor brading with a slot gap of 10 mils.

[0050] [Figure 44] Various layer structures that can be sintered according to the sintering method described herein are illustrated: A) Self-supporting lithium-filled garnet material; B) Self-supporting lithium-filled garnet material optionally containing an active material, binder, solvent, and / or carbon; C) A double layer having one layer of lithium-filled garnet and one layer of metal powder, metal foil, or metal sheet; D) A double layer having one layer of lithium-filled garnet material optionally containing an active material, binder, solvent, and / or carbon and one layer of metal powder, metal foil, or metal sheet; E) A triple layer having two layers of lithium-filled garnet and one layer of metal powder, metal foil, or metal sheet between and in contact with the garnet layers; and F) A triple layer having two layers of lithium-filled garnet material optionally containing an active material, binder, solvent, and / or carbon, and one layer of metal powder, metal foil, or metal sheet between and in contact with the garnet layers.

[0051] [Figure 45]This describes a sintering method in which sintered electrodes, which are electrically in contact with the film, are deposited or sputter-deposited at two locations on the film surface, and an electric current is passed between them.

[0052] [Figure 46] The image shows an optical image of a high-density, self-supporting garnet film pellet, and also a SEM image of this self-supporting film.

[0053] [Figure 47] Figure 46 shows the conductivity plot of the SEM film with Ni backing.

[0054] [Figure 48] Figure 46 shows the plating / deplating of the film at high current density.

[0055] [Figure 49] The X-ray diffraction pattern (XRD) of composition C is shown.

[0056] [Figure 50] The impedance spectrum of the pellet of composition C, measured at 30°C, is shown.

[0057] [Figure 51] This shows the charge-discharge curve of an electrochemical cell having pellets of composition C as an electrolyte, cycled at 20 μA / cm2.

[0058] [Figure 52] This plot shows the density (g / cm³) as a function of flux volume percentage for a 1:1 molar mixture of Li₂CO₃ and B₂O₃.

[0059] [Figure 53] This shows the impedance spectrum of a lithium-filled garnet bilayer (garnet-Ni).

[0060] [Figure 54]This image shows low-magnification SEM images of bilayers produced under various oxygen partial pressure conditions (scale bars in each image represent 100 μm).

[0061] [Figure 55] The images show high-magnification SEM images of garnet-nickel bilayers fabricated under various oxygen partial pressure conditions (scale bar in each image is 20 μm).

[0062] [Figure 56] The images show SEM images of garnet-nickel bilayers fabricated under various oxygen partial pressure conditions (scale bars in the top and bottom rows are 100 μm; scale bars in the middle row are 20 μm).

[0063] [Figure 57] SEM images of FAST-sintered lithium-filled garnet powder are shown. (Top left and bottom left -800°C; 3 ampere product) (Top right and bottom right -800°C; 2 ampere product) (Scale bars in top left and top right are 100 μm) (Scale bars in bottom left and bottom right are 10 μm).

[0064] [Figure 58] SEM images of FAST-sintered lithium-filled garnet powder are shown. (Top left and bottom left -800°C; 2 amp product) (Top right and bottom right -900°C; 2 amp product) (Scale bars in top left and top right are 100 μm) (Scale bars in bottom left and bottom right are 10 μm).

[0065] [Figure 59] This shows the setup for a half-cell experiment using a garnet-nickel bilayer electrolyte.

[0066] [Figure 60] This shows a self-supporting lithium-filled garnet film.

[0067] [Figure 61]The electrochemical impedance spectroscopy (EIS) of lithium-filled garnet comparing Pt setter plates and ceramic setter plates (the y-axis is the imaginary impedance shown in Ω, and the x-axis is the real impedance shown in Ω) and the lower specific area resistance (ASR) of lithium-filled garnet produced by a sintering method using ceramic setter plates are shown.

[0068] [Figure 62] It shows impedance comparisons for pellet sintering in Ar, Ar / H2, or air.

[0069] [Figure 63] It shows an EIS showing less than 10 Ωcm2 for the self-supporting film of FIG. 46, where the film was cut to be a 13 mm disc with a 7 mm diameter Li deposited thereon.

Embodiments for Carrying Out the Invention

[0070] (Detailed Description of the Invention) The following description is presented to enable those skilled in the art to make and use the inventions described herein and to incorporate them in connection with specific applications. Various modifications, and various uses in different applications will be readily apparent to those skilled in the art, and the general principles defined herein can be applied to a wide range of embodiments. Accordingly, the present invention is not intended to be limited to the embodiments presented, but rather should be accorded the widest scope consistent with the principles and novel features disclosed herein. The attention of the reader is directed to all documents and papers filed simultaneously with this specification and made available to the public for inspection with this specification, and the contents of all such documents and papers are hereby incorporated by reference into this specification.

[0071] The attention of the reader is directed to all documents and papers filed simultaneously with this specification and made available to the public for inspection with this specification, and the contents of all such documents and papers are hereby incorporated by reference into this specification, and the contents of all such documents and papers are hereby incorporated by reference into this It is incorporated in the specification. Unless otherwise expressly stated, each disclosed feature is only one example of a series of general equivalent or similar features. It is only one example of a series of general equivalent or similar features.

[0072] Furthermore, any element in a claim that does not expressly recite a “means for” performing a particular function or a “step for” performing a particular function should not be construed as a “means” or “step” clause as defined in paragraph 6 of 35 U.S.C. § 112. In particular, the use of “step of” or “act of” in the claims of the present specification is not intended to invoke the provisions of paragraph 6 of 35 U.S.C. § 112. In the claims, where no element expressly recites a “means for” performing a particular function or a “step for” performing a particular function, such element should not be construed as a “means” or “step” clause as defined in paragraph 6 of 35 U.S.C. § 112. In particular, the use of “step of” or “act of” in the claims of the present specification is not intended to invoke the provisions of paragraph 6 of 35 U.S.C. § 112. When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. It should be noted that they are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object.

[0073] When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. It should be noted that they are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. It should be noted that they are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. It should be noted that they are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. When used, the terms right, left, front, rear, top, bottom, clockwise, counterclockwise, and the like are used for convenience only and are not intended to imply any particular fixed direction. It should be noted that they are used for convenience only and are not intended to imply any particular fixed direction. In fact, they are used to indicate the relative position and / or orientation between various parts of an object. <00遂に、特定の機能を実施する「ための手段」又は特定の機能を実施する「ための工程 (I. Definitions) As used herein, the term “NASICON” refers to a sodium (Na) superionic conductor often characterized by the chemical formula Na Zr2Si 1+x Zr2Si x P 3-x O 12 4-x, 0 < x < 3 (optionally, where Na, Zr, and / or Si are replaced by isovalent elements). As used herein, the term “NASICON” refers to a sodium (Na) superionic conductor often characterized by the chemical formula Na4-xZr2SixP4O12, 0 < x < 3 (optionally, where Na, Zr, and / or Si are replaced by isovalent elements). As used herein, the term “NASICON” refers to a sodium (Na) superionic conductor often characterized by the chemical formula Na4-xZr2SixP4O12, 0 < x < 3 (optionally, where Na, Zr, and / or Si are replaced by isovalent elements). [[ID=]

[0075] As used herein, the term “LISICON” refers to a lithium (Li) superionic conductor often characterized by the chemical formula Li 学式Li 2+2x Zn 1-xRefers to a lithium (Li) superionic conductor often characterized by GeO4 means.

[0076] As used herein, the term "positive electrode" refers to the electrode in a secondary battery towards which positive ions, such as Li flow in or move during battery discharge. As used herein + the term "negative electrode" refers to the electrode in a secondary battery from which positive ions, such as Li flow out or move during battery discharge. In a battery composed of a Li-metal electrode and a conversion + electrode (i.e., active material; e.g., NiF (0000010 x )), the electrode with the conversion chemical substance is called the positive electrode. In some common usages, the cathode is used instead of the positive electrode, and the anode is used instead of the negative electrode. When charging a Li-secondary battery Li ions move from the positive electrode (e.g., NiF (0000011 s to the negative electrode (Li-metal). When discharging a Li- x secondary battery, Li ions move from the negative electrode (e.g., Li-metal; i.e., anode) to the positive electrode (e.g., NiF (0000012 ; i.e., cathode). x ; i.e., cathode).

[0077] As used herein, the term "current collector" is a component or layer in a secondary battery through which electrons conduct in and out of the electrode to complete an external circuit, and is in direct contact with the electrode through which electrons conduct in and out of it. In some examples, the current collector is a metal (e.g., Al, Cu, or Ni, steel, alloys thereof, or a combination thereof) layer laminated on the positive or negative electrode. During charge and discharge, electrons move in the opposite direction to the flow of Li ions a metal (e.g., Al, Cu, or Ni, steel, alloys thereof, or a combination thereof) layer laminated on the positive or negative electrode. During charge and discharge, electrons move in the opposite direction to the flow of Li ions 、When entering and leaving the electrode, it passes through the current collector.

[0078] As used herein, the phrase "at least one member selected from the group" includes a single member from the group, a plurality of members from the group, or a combination of members from the group. At least one member selected from the group consisting of A, B , and C includes, for example, only A, only B, or only C, as well as A and B, and A and C, and B and C, and A, B, and C, or any other all combinations of A, B, and C.

[0079] As used herein, the phrase "slot casting" refers to a deposition process in which a solution, liquid, slurry , etc. is flowed into, in contact with, or onto a substrate adjacent to, in contact with, or on which deposition or coating is to be performed, through a slot or mold of fixed dimensions arranged on the substrate to apply or deposit a solution, liquid, slurry, etc. on the substrate. In some examples, slot casting includes a slot opening of about 1 to 100 μm.

[0080] As used herein, the phrase "dip casting" or "dip coating" refers to a deposition process in which a substrate is moved, often vertically, in and out of a solution, liquid, slurry, etc. to apply or deposit a solution, liquid, slurry, etc. on the substrate .

[0081] As used herein, the term "laminating" refers to a process of continuously depositing a layer of one precursor species, for example , a lithium precursor species, on a deposition substrate, and then continuously depositing a further layer using a second precursor species, for example, a transition metal precursor species, on the already deposited layer. By repeating this lamination process, several layers of the deposited gas phase are created . It can be raised. As used herein, the term “stacked” means that the electrodes A layer containing, 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 an electrolyte-containing layer into contact with another layer. The lamination process involves bonding the layers to be laminated. This includes the reaction or use of a binder that physically maintains contact between the stacked layers. It's okay.

[0082] As used herein, the terms “solid cassolite” or “cassolite” are used in this specification. The term refers to a cathode (i.e., positive electrode) active material (for example, a metal containing lithium as an option). This refers to an ionic conductor that is tightly mixed with or surrounded by ions (or ions).

[0083] As used herein, the term "electrolyte" means an ionic conductive and electrically insulating substance. This refers to the material. The electrolyte is the ions in the electrolyte, for example, Li + It enables conduction and It is useful for electrically insulating the positive and negative electrodes of a secondary battery.

[0084] As used herein, the term "anolite" means an anode material or an anode material. It is mixed with the node current collector, or superimposed on them, or stacked on them. This refers to layers of ion-conducting material.

[0085] As used herein, the term "green film" refers to garnet material, garnet A precursor, binder, solvent, carbon, dispersant, or combination thereof of the set material is selected. This refers to an unsintered film containing at least one component.

[0086] As used herein, the phrase "depositing a cathode current collector" is not limited to... However, metals such as copper, nickel, aluminum, or combinations thereof can be used as cathodes. Castholite, or combinations thereof, or anode, anolite, or combinations thereof The metal is supplied in the form of vapor or spray so as to come into contact with the surfaces and form an adhesive layer with them. This refers to the process of supplying or providing a metal layer on the cathode or anode. This results in the formation of a metal layer, which then electrically communicates with the cathode or anode.

[0087] As used herein, the term “to manufacture” means to form an object to be manufactured. It refers to a process or method of forming or causing to form. For example, energy Fabricating energy storage electrodes is a process for forming electrodes for energy storage devices. Including process steps or methods. The final result of the steps constituting the fabrication of an energy storage electrode is This involves creating materials that function as electrodes.

[0088] As used herein, the term “energy storage electrode” means, for example, “energy storage electrode.” For use in ghee storage devices, for example, in rechargeable lithium batteries or Li-secondary batteries. This refers to an electrode suitable for rechargeable batteries. As used herein, such an electrode is a rechargeable battery. It can conduct electrons and lithium ions necessary for charging and discharging the battery.

[0089] As used herein, the phrase “to provide” means to provide, to give, to give, to give, to give It refers to completion, presentation, or supply.

[0090] As used herein, the phrase "provides an unsintered thin film" means an unsintered thin film Refers to providing, generating, or presenting, or supplying. For example, providing an unsintered thin film means making the unsintered thin film available or supplying the unsintered thin film in such a way that it can be used as described in the methods described herein. film, so that it can be used as described in the methods described herein, refers to a process of making the unsintered thin film available or supplying the unsintered thin film.

[0091] As used herein, the term "unsintered thin film" refers to a thin film that contains the components and materials described herein but has not been sintered by the sintering methods described herein. Thin means, for example, a film having an average thickness dimension of about 10 nm to about 100 μm. In some examples, thin refers to a film having a thickness less than about 1 μm, 10 μm, or 50 μm.

[0092] As used herein, the term "lithium-filled garnet" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Lithium-filled garnets include the formula Li A La B M' c M'' D Zr E O F A La B M' C M'' D Ta E O F A La B M' C M'' D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4,​​​​​​​​c Al d Me'' e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f < 13, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb ) and contains a compound as described herein. The garnets used herein also include the above garnets doped with Al2O3. The garnets used herein also include the above garnets doped such that Al 3+ replaces Li + . As used herein, lithium-filled garnets, and garnets generally, but not limited to, contain Li La3(Zr 7.0 +Nb<000004​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​As used herein, garnet includes YAG-garnet (i.e., yttrium garnet). Aluminum garnet, or for example, Y3Al5O 12 ) does not include. Used herein Garnet contains pyrope, almandine, spessartine, and grosche La, hessonite, or cinnamon stone, tsavorite, uvarovite, and Luddite, and its solid solution pyrope-almandine-spessarite and It does not include silicate garnets such as barovite, grossular, andradite. The garnets described herein are of the general formula X3Y2(SiO4)3 (wherein X is Ca, Mg, Fe, and / or Mn It does not contain nesosilicates having (and Y is Al, Fe, and / or Cr).

[0094] As used herein, "garnet precursor chemical" or "garnet-type electrolyte" The phrase "chemical precursor of" refers to the reaction of lithium-filled garnet as described herein. This refers to the chemical substances that form the material. Examples of these chemical precursors include lithium hydroxide ( For example, LiOH, lithium oxide (e.g., Li2O), lithium carbonate (e.g., LiCO3), zirconium oxide Nium (e.g., ZrO2), lanthanum oxide (e.g., La2O3), aluminum oxide (e.g., Al2O3) 3) Aluminum (e.g., Al), aluminum nitrate (e.g., AlNO3), aluminum nitrate Examples include niobium nohydrate, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., Ta2O5), This is not limited to these.

[0095] As used herein, the term "garnet-type electrolyte" is defined as follows: This refers to an electrolyte containing garnet or lithium-filled garnet material as an ion conductor. vinegar.

[0096] As used herein, the phrase “alumina-doped” means “using Al2O3.” This means replacing a specific component of garnet with another material, such as Al2O3. Lithium-filled garnets that are doped with aluminum (Al) are lithium-filled garnets. Garnet is a substance that replaces an element in the chemical formula of a compound (which could be, for example, Li or Zr). It refers to a set.

[0097] As used herein, the term “aluminum reaction vessel” means a vessel used to carry out a chemical reaction. So, the precursor chemicals used to produce the product, for example, lithium-filled garnet material It refers to a container or vessel into which something is placed.

[0098] As used herein, the term "high conductivity" means 10 at room temperature. -5 Exceeding S / cm This refers to conductivity, for example, ionic conductivity. In some cases, high conductivity is 10 at room temperature. -5 Includes conductivity values ​​exceeding S / cm.

[0099] As used herein, the phrase “partially replace Zr with a species with a higher valence” The phrase is, Zr 4+ For example, 5 + or 6 + This refers to substitution with a species having a charge. For example, several Nb 5+ However, Zr atoms are present in the lattice positions within the garnet crystal structure, and in that case, 4+ to If substitution is possible, partially replace Zr with Nb. This is also known as niobium doping. I was called.

[0100] As used herein, "subscripts and molar coefficients in empirical formulas are as described in the examples." The phrase "based on the amount of raw materials initially batched to produce" is a subscript. Letters (for example, Li7La3Zr2O) 12 The coefficients 7, 3, 2, 12, and 0.35 in Al2O3 (0.35) are given the material (For example, Li7La3Zr2O 12 Chemical precursors used to produce 0.35Al2O3 (e.g., This refers to the elemental ratios in LiOH, La2O3, ZrO2, and Al2O3.

[0101] As used herein, the term “electrochemical device” refers to an energy storage device. Vice, for example, electrochemical reactions, for example, conversion chemical reactions, for example, [ka] This refers to a lithium-ion secondary battery that operates or generates electricity or electric current.

[0102] As used herein, the term "film thickness" refers to the distance between the top and bottom surfaces of a film or This refers to the median of the measured distance. As used herein, the top and bottom surfaces are the largest surface. This refers to the side surface of a membrane that has a cross-section.

[0103] As used herein, the term “crystal grain” refers to a crystal grain separated from the rest of the material. It refers to regions of material within the bulk of a material that have a distinguishing physical boundary. For example, several In materials, in many cases, both the crystalline and amorphous components of materials with the same chemical composition are... Both are distinguished from each other by the boundary between crystalline and amorphous components. Crystalline component or amorphous The approximate diameter of the boundary between components is referred to as the grain size in this specification.

[0104] As used herein, "d 50 The term "diameter" is not limited to scanning electrons. 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 diameter distribution. 50 50% of the particles are larger than the listed size. Small characteristic dimensions are included.

[0105] As used herein, the terms “active electrode material” or “active material” are used in a more accurate sense. Suitable for use as a rechargeable Li-ion battery, and undergoing chemical reactions during charge-discharge cycles. It refers to materials that enable the discharge cycle of rechargeable lithium batteries. For example, "active cathode material" refers to the discharge cycle of rechargeable lithium batteries. It contains metal fluorides that are converted into metal and lithium fluoride.

[0106] As used herein, the term “active anode material” is defined above. Anode material suitable for use in rechargeable Li-cells containing active cathode materials such as This refers to the active material, which in some cases is lithium metal. In some of the methods, the sintering temperature is used as the active anode material. It is tall enough to melt the thium metal.

[0107] As used herein, the term "conductive additive" refers to a substance that improves the conductivity of a cathode. This refers to a material that is mixed with a cathode active material to increase its activity. Examples include carbon, and various other materials. Various forms of carbon, for example, Ketjenblack, VGCF, acetylene black, graphite Examples include t, graphene, nanotubes, nanofibers, and combinations thereof. However, it is not limited to these.

[0108] As used herein, the term “solvent” refers to the components or This refers to a liquid suitable for dissolving or solvating materials. For example, garnet is a suitable solvent. Components used in the sintering process, for example, a suitable liquid for dissolving the binder, e.g. Toluene is one example.

[0109] As used herein, the phrase “remove the solvent” means that the solvent is not specified herein. This refers to the process of extracting or separating components or materials. 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 leave the binder, the thin film containing the binder and solvent is heated, or optionally vacuumed or It can also be placed in a reducing atmosphere environment.

[0110] As used herein, the phrase "sinter a film" means thermal sintering or electric field-assisted sintering. The use of the bond densifies (makes denser or lower the density of) the thin films described herein. Sintering refers to the process of making a solid mass of material have a porous structure. This process includes forming the solid mass by heat and / or pressure without melting it completely. nothing.

[0111] As used herein, the term "FAST" refers to the acronym for electric field-assisted sintering. In some cases, FAST also refers to flash sintering.

[0112] As used herein, the phrase "apply a DC or AC electric field" means that in the material The electric field is changed or generated by the power source, current flows through the material, and direct current (DC) is supplied from the power source. The process of electrically connecting a power source to a material so that it results in either alternating current (AC) or alternating current (AC). It refers to.

[0113] As used herein, the term “binder” refers to a substance that helps to bond two materials together. It refers to the material. For example, as used herein, polyvinyl butyral is garnet It is a binder because it is useful for bonding materials together. Other binders include: Polycarbonate is one example. Another binder is polymethyl methacrylate. These examples of binders represent the entire range of binders intended here. This is not limited to that specific case, but merely serves as an example.

[0114] As used herein, the phrase “casting a film” means that a liquid or slurry is cast into a film. A liquid or slurry is poured into a mold or onto a substrate to form or to form a film. This refers to the process of supplying or transferring to a doctor blade, a meyer rod, and a cone. Mac coater, gravure coater, microgravure, reverse comma coater, slot This can be done by die casting, slip casting, and / or tape casting, and other methods known to those skilled in the art. It is possible.

[0115] As used herein, the phrase “apply pressure” means an external device, for example A calendar is a process that induces pressure in another material.

[0116] As used herein, the term “about” refers to a numerical limit that is approximately the same as the word “about”. In some cases, "approximately" refers to a number centered around ±5, which is restricted by the word "approximately". This includes a range of ~10%. For example, evaporating a solvent at approximately 80°C is equivalent to 79°C, 80°C, or 81°C. This includes evaporating the solvent.

[0117] As used herein, the phrase "approximately 1 to approximately 600 minutes" means from 0.1 to 1.1 to 540 to 660 minutes. This refers to a range of minutes and the minute values ​​within that range. As used herein, "approximately 10 μm to approximately 100 μm" The term "9μm" refers to the range from 9μm to 11μm and 90μm to 110μm, as well as integer values ​​within that range.

[0118] As used herein, the phrase "approximately 500°C to approximately 900°C" means from 450°C to 550°C. This refers to the temperature range of 810°C to 990°C, and integer temperature values ​​within that range.

[0119] As used herein, “burning the binder or calcining the unsintered film” The phrase means to burn the binder, or to expel or remove the binder. Chemical reactions such as combustion, or processes that result in higher density or lower porosity of the binder To induce a chemical reaction that sinters a film containing a binder, the film containing the binder is subjected to oxidation species For example, it refers to a process of arbitrarily heating in an environment containing O2.

[0120] As used herein, the term “composite electrode” refers to a device composed of multiple materials. This refers to electrodes that are active in a tight mixture or ordered layer. For example, as a composite electrode, active in a tight mixture or ordered layer. A cathode material and a garnet-type electrolyte, or a combination of the active material and the electrolyte Examples of active cathode materials and garnet-type electrolytes include, but are not limited to, these. It is not determined.

[0121] As used herein, the term “inert setter plate” generally refers to a flat This refers to a plate that does not react with the material being sintered. An inert setter plate is, They can be metal or ceramic, and optionally, these setter plates are sintered. When the material is actually sintered, it causes the diffusion of gases and vapors passing through it. It can be porous.

[0122] As used herein, the phrase "operate in constant voltage amplitude mode" means that the material While maintaining the magnitude of the applied DC voltage amplitude or AC voltage RMS amplitude at a constant value, the current However, electrochemical properties that allow the resistance, or impedance, of the material to change as a function of the material Regarding Rothes

[0123] As used herein, the phrase "operate in constant current amplitude mode" means constant A DC current or an AC current with RMS amplitude flows through a material, and the applied voltage is such that the resistance or impedance of the material is overcome. —Refers to an electrochemical process that allows for variation as a function of dance.

[0124] As used herein, the term "self-supporting thin film" means a film that is adhered to or attached by a substrate. This refers to an unsupported film. In some cases, a self-supporting thin film is attached to or fixed to it. A self-supporting film that does not require a specific substrate and can be mechanically manipulated or moved. That is the case.

[0125] As used herein, the term "porous" refers to pores, e.g., nanopores, mesopores. , or refers to a material containing micropores.

[0126] As used herein, the term "thermal decomposition" refers to high temperature in the absence of oxygen. This refers to the thermochemical decomposition of organic materials.

[0127] As used herein, the term "electroplating" refers to the process of plating a material, such as a metal. This refers to the process of depositing materials in conjunction with the use of electricity.

[0128] As used herein, the phrase "average pore diameter dimensions of approximately 5 nm to approximately 1 μm" means pore A material having such that the inner diameter of the pores therein is, for example, about 5 nm for nanopores, For example, micropores refer to materials that are physically separated by approximately 1 μm.

[0129] As used herein, the phrase "the polymer is stable at voltages above approximately 3.8V" When a voltage greater than 3.8V is applied to the lithium reference electrode, destructive chemical reactions occur. This refers to polymers that do not react. The destructive chemical reactions used herein are therefore polymers. A polymer is a chemical reaction that degrades the function of the polymer it is used in. For example, if the polymer... If it is ionic and useful as a Li-conductor in a Li-cell, the destructive reaction is, Under useful operating conditions for temperature and cycling, conductivity in S / cm units over the lifetime of the product. When measured, the polymer's ability to conduct Li ions was reduced or deteriorated by more than 10%. It is a reaction that causes something to happen.

[0130] As used herein, the term “penetrated” means that one material has penetrated another material. This refers to a state in which something enters another state, or a state in which one material is made to come together with another material. However, when carbon is impregnated into porous garnet, this means that the carbon is inside the porous garnet. It refers to the process of getting in and mixing it closely with something else.

[0131] As used herein, the phrase "operated with ramp voltage" means that the applied voltage is This refers to an electrical process that gradually or systematically increases or decreases over a period of time.

[0132] As used herein, the phrase "operated by lamp power" means that the applied power is This refers to a process of gradually or systematically increasing or decreasing something over a period of time.

[0133] As used herein, the phrase "operated by lamp current" means that the applied current is This refers to an electrical process that gradually or systematically increases or decreases over a period of time.

[0134] As used herein, the terms “nanostructure” or “nano-dimensional” refer to a structure. This refers to composite materials in which components are separated by nanoscale dimensions. For example, a nanoscale composite material Examples include Li-containing compounds, such as LiF, and Fe-containing compounds, such as Fe. Here, the Fe region and the LiF region are visually contrasting regions in various nanoscale regions. When measured by TEM microscopy based on identification, the range is approximately 1-100 nm, or 2-50 nm, or 1-10 nm. or have a median physical dimension of 2-5 nm, or 5-15 nm, or 5-20 nm.

[0135] (II. Garnet Materials) Disclosed herein are powders based on nanostructured lithium-filled garnet. Also disclosed herein are physical dimensions less than 10 μm, for example, d 50 Crystal grain size is 10 μm It is also a lithium-filled garnet thin film containing crystal grains smaller than a certain size. Furthermore, these films have a thickness of less than 50 μm. In some of these examples... Films with a thickness of less than 50 μm are several meters to several kilometers in length. In that example, the film has high conductivity, which in some examples is 10 -4 S / It is greater than cm. In some cases, the film is strong, has good mechanical integrity, and is lithium It prevents lithium dendrites from entering when used as an electrolyte in secondary batteries. Some of these films contain cathode-active materials, and optionally, binders and dispersants. It is tightly mixed with a solvent and other electron and ionic conductors. Also described herein The method described is for fabricating these example membranes.

[0136] In other examples described herein, alumina is doped and high Several lithium-filled glass possess a unique combination of ionic conductivity and minute crystal grain size. It is a net composition. In some examples, these compositions are lithium-filled garnet. Lower temperatures and shorter reaction time conditions than previously known to be possible. It is manufactured under the following conditions. In addition, in some examples, novel sintering methods are used, among which Some of these utilize an argon gas environment instead of air, and new lithium-filled gas To manufacture nets. Furthermore, in some examples, finely ground garnet powder, and Alternatively, by using garnet precursors and / or metal powders, unique thin film structures can be created. is manufactured as follows. The disclosure herein describes several novel lithium-filled garnet ceramics that have aluminum therein, for example, as alumina (Al2O3), which, conveniently and surprisingly, have the properties of high ionic conductivity and small crystal grain size.

[0137] (a. Lithium-filled garnet) (i. Electrolyte) In one example, the method described herein is Li A La B M' c M'' D Zr E O F Li A La B M' C M'' D T a E O F Li A La B M' C M''[[ID=A47]] D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2 , 10 < F < 14, and M' and M' are each, independently in each case, selected from Al, Mo, W, Nb, Sb, Ca, Ba , Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (where 5 < a < 7.7; < 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f < 14, and Me'' is a metal selected from Nb, Ta, V , W, Mo, or Sb), a garnet-type electrolyte material is included.

[0138] ​In one example, the method described herein is Li A La B M' c M'' D Zr E O F 、Li<00th="0000093">La B M' C M''<00th="0000096">T a E O F 、Li A La B M' C M'' D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2;​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​It contains a garnet-type electrolyte selected from

[0140] In one example, the method described herein is Li A La B M' C M'' D Nb E O F (where 4 < A < 8 .5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 13, and M' and M' are each, respectively independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta in each case ) It contains a garnet-type electrolyte selected from

[0141] In one example, the method described herein is Li a La b Zr c Al d [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In some embodiments, the garnet materials described herein are used as electrolytes . In some of these embodiments, the garnet has the formula [Chemical formula] ; where 5.0 < x < 9 and 0.1 < y < 1.5. In some of these examples , the electrolyte is Li x La3Zr2O 12 ·0.35Al2O3. In other ones of these examples , the electrolyte is Li7La3Zr2O 12 ·0.35Al2O3.

[0144] In some examples where the garnet is an electrolyte, the garnet contains neither Nb, nor Ta , nor W, nor Mo, which means herein that the concentration of these elements (e.g., Nb, Ta, W, or M o) is 10 parts per million (ppm) or less. In some examples , the concentration of these elements (e.g., Nb, Ta, W, or Mo) is 1 part per million (ppm) or less. In some examples, the concentration of these elements (e.g., Nb, Ta, W, or Mo) is 0.1 part per million (ppm) or less.

[0145] In some examples, the lithium-filled garnets described herein have the general formula Li x A 3B2O 12 (where 5 < x < 7). In some of these examples , A is a large ion that occupies an eight-fold coordination lattice site. In some of these examples<00014​​In this case, B is a smaller, more charged ion that occupies an octahedral site. In some of these examples, B is Zr, Hf, Nb, Ta, Sb, V, or a combination thereof. In some of these examples, the composition is Li x A3B2O 12 0.3 to 1 mole per unit It is doped with a certain amount of Al. In some of these examples, the composition is Li x A3B2O 12 Each unit is doped with 0.35 moles of Al.

[0146] In some cases, lithium-filled garnet is Li7La3Zr2O 12 (LLZ) and also A Lumina is doped. In one example, LLZ is the antimicrobial agent used to make LLZ. The mixture of the responding material precursor is doped by adding Al2O3. In some other examples, Then, LLZ is doped with aluminum in an aluminum reaction vessel in contact with LLZ. ru.

[0147] In some cases, alumina-doped LLZ is, for example, 10 at room temperature. -4 S / cm or more It has high conductivity.

[0148] In some cases, higher conductivity is due to a portion of Zr being a higher valence species, for example, This is observed when Nb, Ta, Sb, or combinations thereof are partially substituted. And the conductivity is 10 at room temperature. -3 It can reach a height of S / cm.

[0149] In some examples, the compositions described herein, Li x A3B2O 12 0.35 moles per unit Al doped Li x A3B2O 12 In some of these examples, x is 5. In one other example, x is 5.5. In yet another example, x is 6.0. How many? In one other example, x is 6.5. In yet another example, x is 7.0. In this example, x is 7.5.

[0150] In some examples, garnet-based compositions include Li x A3B2O 12 The winning probabilities were 0.3, 0.35, 0.4, and 0. 45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or 1 mole of Al It is being promoted.

[0151] In some examples, garnet-based compositions include Li x A3B2O 12 0.35 moles of Al per unit It is being linked.

[0152] In the examples specified herein, the subscripts and molar coefficients in the empirical formulas are used to prepare the examples described. This is based on the amount of raw materials that are initially batch-processed.

[0153] In some examples, the present disclosure describes compositions comprising lithium-filled garnet and Al2O3. To provide. In one example, lithium-filled garnet is doped with alumina. In some cases, lithium-filled garnet is empirically formulated Li A La B M' c M'' D Zr E O F by Characterized, in the formula, 4 <A<8.5、1.5<B<4、0≦C≦2、0≦D≦2; 0≦E≦2、10<F≦13で Yes, M' and M'' are either absent or, in each case independently, Al, Mo, W, Nb, Sb, Ca, It is either independently selected from Ba, Sr, Ce, Hf, Rb, or Ta; and Net: The molar ratio of Al2O3 is 0.05 to 0.7.

[0154] In some examples, the present disclosure describes compositions comprising lithium-filled garnet and Al2O3. To provide. In one example, lithium-filled garnet is doped with alumina. In some cases, lithium-filled garnet is empirically formulated Li A La B M' c M'' D Zr E O F by Characterized, in the formula, 4 <A<8.5、1.5<B<4、0≦C≦2、0≦D≦2; 0≦E≦2、10<F≦13で Yes, M' and M'' are either absent or, in each case independently, Al, Mo, W, Nb, Sb, Ca, It is either independently selected from Ba, Sr, Ce, Hf, Rb, or Ta; and Li: The molar ratio of Al is between 0.05 and 0.7.

[0155] In some examples, the present disclosure describes compositions comprising lithium-filled garnet and Al2O3. To provide. In one example, lithium-filled garnet is doped with alumina. In some cases, lithium-filled garnet is empirically formulated Li A La B M' c M'' D Zr E O F by Characterized in that, in the formula, 2 < A < 10, 2 < B < 6, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E ≤ 3, 8 < F ≤ 14 , M' and M'' are, in each case independently, either non-existent or each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta; and the molar ratio of garnet:Al2O3 is 0.01 - 2.

[0156] In some examples, the present disclosure provides a composition comprising a lithium-filled garnet and Al2O3. In one example, the lithium-filled garnet is doped with alumina. In some examples, the lithium-filled garnet has the empirical formula Li A La B M' c M'' D Zr E O<00001​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​- including a pant, where 0 < e < 2. In some examples, the lithium-filled garnet is the entire content of which is hereby incorporated by reference in its entirety for all purposes a method and system for forming garnet materials with a sintering process filed on October 7, 2013 and described in U.S. Provisional Patent Application No. 61 / 887,451 entitled "METHOD AND SYSTEM FOR FORMING GARNET MATERIALS WITH SINTERING PROCESS" .

[0158] In some of the above examples, A is 6. In some other examples, A is 6.5 . In other examples, A is 7.0. In some other examples, A is 7.5. In still other examples, A is 8.0.

[0159] In some of the above examples, B is 2. In some other examples, B is 2.5 . In other examples, B is 3.0. In some other examples, B is 3.5. In still other examples, B is 3.5. In still other examples, B is 4.0.

[0160] In some of the above examples, C is 0.5. In other examples, C is 0.6. In some other examples, C is​​​​​​​In one other example, C is 1.6. In another example, C is 1.7. In yet another example... In one example, C is 1.8. In another example, C is 1.9. In yet another example, C is 2.0. Yes. In other examples, C is 2.1. In some other examples, C is 2.2. In a few other examples, C is 2.3. In one other example, C is 2.4. In another example, In one example, C is 2.5. In yet another example, C is 2.6. In one example, C is 2.7. Yes. In another example, C is 2.8. In yet another example, C is 2.9. Several In other examples, C is 3.0.

[0161] In some of the examples above, D is 0.5. In other examples, D is 0.6. In some other examples, D is 0.7. In some other examples, D is 0.8. In one other example, D is 0.9. In another example, D is 1.0. In yet another example... In one example, D is 1.1. In another example, D is 1.2. In yet another example, D is 1.3. In some other examples, D is 1.4. In some other examples, D is 1.5. In one other example, D is 1.6. In yet another example, D is 1.7. In one example, D is 1.8. In another example, D is 1.9. In yet another example, D is 2.0. Yes. In other examples, D is 2.1. In some other examples, D is 2.2. In a few other examples, D is 2.3. In one other example, D is 2.4. In another example, In one example, D is 2.5. In yet another example, D is 2.6. In one example, D is 2.7. Yes. In another example, D is 2.8. In yet another example, D is 2.9. Several In other examples, D is 3.0.

[0162] In some of the examples above, E is 0.5. In other examples, E is 0.6. In some other examples, E is 0.7. In some other examples, E is 0.8. In one other example, E is 0.9. In another example, E is 1.0. In yet another example... In one example, E is 1.1. In another example, E is 1.2. In yet another example, E is 1.3. In some other examples, E is 1.4. In some other examples, E is 1.5. In one other example, E is 1.6. In yet another example, E is 1.7. In one example, E is 1.8. In another example, E is 1.9. In yet another example, E is 2.0. Yes. In other examples, E is 2.1. In some other examples, E is 2.2. In a few other examples, E is 2.3. In one other example, E is 2.4. In another example, In one example, E is 2.5. In yet another example, E is 2.6. In one example, E is 2.7. Yes. In another example, E is 2.8. In yet another example, E is 2.9. Several In other examples, E is 3.0.

[0163] In some of the examples above, F is 11.1. In other examples, F is 11.2. In some other examples, F is 11.3. In some other examples, F is 11.4. In one other example, F is 11.5. In another example, F is 11.6. In one example, F is 11.7. In another example, F is 11.8. In yet another example, F is 11. It is 9. In some other examples, F is 12. In some other examples, F is 12. It is 1. In one other example, F is 12.2. In another example, F is 12.3. In another example, F is 12.3. In one example, F is 12.4. In yet another example... In one example, F is 12.5. In another example, F is 12.6. In several other examples, F It is 12.7. In some other examples, F is 12.8. In one other example, E is 12 It is 0.9. In another example, F is 13.

[0164] In some examples, the empirical formulas provided herein are [ka] A composition characterized by; here, 5.0 <x<9かつ0.1<y<1.5である。いく In a few examples, x is 5. In other examples, x is 5.5. In some examples, In some cases, x is 6. In others, x is 6.5. In still other cases, x is 7. In some examples, x is 7.5. In other examples, x is 8. In some cases, y is 0.35. In other cases, y is 0.4. Yes. In some cases, y is 0.45. In some cases, y is 0.5. In other examples, y is 0.55. In some examples, y is 0.6. In other examples, In some cases, y is 0.7. In other cases, y is 0.8. Yes. In some examples, y is 0.85. In other examples, y is 0.9. How many? In that example, y is 0.95. In the other example, y is 1.0.

[0165] In some examples, the empirical formula Li is provided herein. 7.0 La3(Zr t1 +Nb t2 +Ta t 3)O 12 This composition is characterized by +0.35Al2O3. In this formula, La and (Zr+Nb t1 + t2 + t3 = subscript 2 such that the molar ratio of the combined amount of +Ta) is 3:2.

[0166] In some examples, the empirical formula Li7La3Zr2O is provided herein. 12 0.35Al2O3 It is a composition characterized by the following.

[0167] In some of the examples above, A is 5, 6, 7, or 8. In one example, A It is 7.

[0168] In some of the examples above, M' is Nb and M'' is Ta.

[0169] In some of the examples above, E is 1, 1.5, or 2. In one example, E The answer is 2.

[0170] In some of the examples above, C and D are 0.

[0171] In some examples provided herein, the molar ratio of garnet:Al2O3 is 0.1 The composition has a ratio of approximately 0.65. In some examples, the Li:Al ratio is 7:0.2 to 7:1.3. In some cases, the Li:Al ratio is 7:0.3 to 7:1.2. The ratio is between 7:0.3 and 7:1.1. In some examples, the Li:Al ratio is between 7:0.4 and 7:1.0. In some cases, the Li:Al ratio is 7:0.5 to 7:0.9. The ratio is 7:0.6 to 7:0.8. In some examples, the Li:Al ratio is approximately 7:0.7. In that example, the Li:Al ratio is 7:0.7.

[0172] In some examples provided herein, the molar ratio of garnet:Al2O3 is 0.15 This is a composition with a value of ~0.55.

[0173] In some examples, provided herein, the molar ratio of garnet:Al2O3 is 0.25 This is a composition with a value of ~0.45.

[0174] In some examples, provided herein, the molar ratio of garnet:Al2O3 is 0.35 It is a composition.

[0175] In some examples provided herein, the molar ratio of Al to garnet is 0.35. It is a certain composition.

[0176] In some examples provided herein, lithium-filled garnet is empirically formulated Li7La3Zr2O 12 A composition characterized by and doped with aluminum ru.

[0177] In some cases, lithium-filled garnet is Li7La3Zr2O 12 (LLZ) and also A Lumina is doped. In one example, LLZ is the antimicrobial agent used to make LLZ. The mixture of the responding material precursor is doped by adding Al2O3. In some other examples, Then, LLZ is doped with aluminum in an aluminum reaction vessel in contact with LLZ. When LLZ is doped with alumina, it increases the conductivity of lithium-filled garnet. Conducting holes are introduced. In some cases, this increased conductivity is due to increased ions. (For example, Li + This is called conductivity.

[0178] (ii. Cassolite) Cassolais suitable for use with the components, devices, and methods described herein. While not limited to specific materials, Li A La B M' c M'' D Zr E O F Li A La B M' C M'' D Ta E O F , Li A La B M' C M'' D Nb E O F (Here, 4 <A<8.5、1.5<B<4、0≦C≦2、0≦D≦2; 0≦E<2、10< F < 14, and M' and M'' are, in each case, independently Al, Mo, W, Nb, Sb, Ca, Ba, Sr (Selected from Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (Here, 5 <a<7 .7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f < 14, and Me'' is a metal selected from Nb, Ta, V, W , Mo, or Sb). Garnet materials selected therefrom are exemplified . In some embodiments, the garnet material is Li A La B M' c M'' D Zr E O F . In some other embodiments, the garnet material is Li A La B M' C M'' D Ta E O F . In other embodiments, the garnet material is Li A La B M' C M'' D Nb E O F .

[0179] In the above examples, the values of the subscripts (4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14) characterize the ratio of the reactants used to produce the garnet material . Some degree of deviation from these reactant ratios may be present in the garnet product . As used herein, the garnet precursor refers to the reactants used to produce or synthesize the garnet

[0180] In the above examples, the values of the subscripts (e.g., 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F ≤ 13) characterize the ratio of the reactants used to produce the garnet material . Some degree of deviation from these reactant ratios may be present in the garnet product This is also acceptable. As used in this specification, the garnet precursor refers to the reactant used to produce garnet.

[0181] In the above examples, as the values of the subscripts, 4 < A < 8.5, 1.5 < B < 4, C < 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14 can also be cited. In some examples, C is equal to or less than 1.99

[0182] In the above examples, as the values of the subscripts, 4 < A < 8.5, 1.5 < B < 4, C < 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F ≤ 13 can also be cited. In some examples, C is equal to or less than 1.99

[0183] In one embodiment, the garnet is a lithium-filled garnet.

[0184] In some embodiments, the garnet is a Li b La c Zr d Al e Me'' f is characterized by O, where the subscript is characterized by the above values.

[0185] In some embodiments, the lithium-filled garnet is lithium lanthanum zirconium oxide mixed with aluminum oxide. In some of these examples the lithium lanthanum zirconium oxide is characterized by the formula Li La3Zr2O 7.0 +0.35Al2O3, where the subscripts and coefficients represent the molar ratios determined based on the reactants used to make the garnet. 12 ​​​​​​

[0186] In some embodiments, the ratio of La:Zr is 3:2. In some other examples, Garnet is Li 7.0 La3(Zr t1 +Nb t2 +Ta t3 )O 12 It is +0.35Al2O3; where La:(Zr / Nb / Ta) (t1 + t2 + t3 = subscript 2) such that the ratio is 3:2.

[0187] In some cases, the garnet is Li x La3Zr2O 12 +yAl2O3, where x is 5.5 The range is ~9; and y is in the range of 0~1. In some examples, x is 7 and y is 0. It is 35.

[0188] The catholites described herein, in some embodiments, are carbon electron conductive additives. Lithium conductive gas filled with additives, lithium conductive polymer binder, and active material - Includes a hierarchical structure with a net scaffold. The amount of active material packed is high energy density. It can be more than 50 volume percent to allow for a certain degree. In some examples, The garnet is sintered and retains a porosity of >70% to accommodate the volume of other components. The disclosure herein addresses several issues associated with the assembly of solid energy storage devices. This overcomes the problem, and this includes, for example, but is not limited to, well-developed particle indirect Reduced interparticle spacing allows for greater current flow without contact points and significant voltage drops. Sintering a composite electrode having electrical resistance; also, processing the entire device (electrode and electrolyte) in one process. A manufacturing method that involves producing the product in a certain time; also, in some cases, the use of flammable liquid electrolytes that may pose a safety hazard. A manufacturing method for creating a solid energy storage device that eliminates the need for using FAS; and a film for FAS A method for reducing the process time and cost of fabricating electrochemical devices by sintering; and FAST Sintering is performed to densify the components of the electrode composite material without significant interdiffusion or harmful chemical reactions. There is a way to do it.

[0189] (iii. Composite materials) In some embodiments, the methods described herein are disclosed. It is a composite electrochemical device manufactured by [the means of]. In some examples, the device is Selected from the group consisting of active electrode materials, electrolytes, conductive additives, and combinations thereof. A layer comprising a component; and a layer comprising a garnet-type electrolyte. In some examples, the composite material has the structure shown in Figure 26 or Figure 27.

[0190] In some embodiments, the device comprises at least one active anode material It further includes layers of carbon, silicon, silicon oxide, tin, etc. as active anode materials. Examples include, but are not limited to, these alloys and combinations thereof.

[0191] In some embodiments, the following are disclosed herein: an anode and anode current collector. A body containing at least one layer; a small amount containing a garnet solid electrolyte (SSE) in contact with the anode. at least one layer; at least one layer containing porous garnet in contact with the garnet SSE. Here, the porous garnet may optionally contain carbon, a lithium conductive polymer, and an activated carbon A material and at least one component selected from the group consisting of combinations thereof is permeated. is present; and at least one layer including an aluminum cathode current collector in contact with the porous garnet where the porous garnet layer is at least 70% porous by volume; and where the garnet is Li A La B M' c M'' D Zr E O F 、Li A La B M' C M'' D Ta E O F 、Li A La B M' C M'' D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14, and M' and M'' are each, independently in each case, selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f ≤ 13, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb ), and is selected from the materials including; the active electrode material is NCA (lithium nickel cobalt aluminum oxide), LMNO (lithium manganese nickel oxide) ), NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide, i.e., LiCoO2), nickel fluoride (NiF x , where x is 0 to 2.5), copper fluoride (CuF y , and Here, y is 0 to 2.5), or FeF z (Here, z is selected from 0 to 3.5) It is a cathode material, a layered material for electrochemical devices. In some examples, The layered structure is essentially as shown in Figure 25.

[0192] In one embodiment, both sides of the layer containing the anode and the anode current collector are independently, It is in contact with the garnet SSE layer, and each garnet SSE layer is independently a porous garnet. It is in contact with the layer.

[0193] (b. powder) (i. Nanocrystalline powder) In some examples, the lithium-filled garnet powder described herein is nanoscale. It is a nanostructure or a molecular structure. Therefore, these powders are crystalline lithium-filled garnet. Including domains, where the median diameter of the crystalline domain is approximately the same as the physical dimension (e.g., diameter). The size ranges from 0.5 nm to approximately 10 μm. In some examples, the crystalline domain has a diameter of approximately 0.5 nm. Yes. In some other examples, the crystalline domain has a diameter of about 1 nm. In this example, the crystalline domain has a diameter of approximately 1.5 nm. Furthermore, in another example, the crystalline The domain has a diameter of approximately 2 nm. In another example, the crystalline domain has a diameter of approximately 2 It is 0.5 nm. In some examples, the crystalline domain has a diameter of approximately 3.0 nm. In other examples, the crystalline domain has a diameter of approximately 3.5 nm. The crystalline domain has a diameter of approximately 4.0 nm. In some examples, the crystalline domain is The diameter is approximately 5 nm. In some other examples, the crystalline domain has a diameter of approximately 5.5 nm. In other examples, the crystalline domain has a diameter of approximately 6.0 nm. Furthermore, the crystalline domain has a diameter of approximately 6.5 nm. In other examples, the crystalline domain The in has a diameter of approximately 7.0 nm. In some examples, the crystalline domain has a diameter of approximately 7 It is 0.5 nm. In another example, the crystalline domain has a diameter of approximately 8.0 nm. In the example, the crystalline domain has a diameter of approximately 8.5 nm. In some examples, the The crystalline domain has a diameter of approximately 8.5 nm. In some other examples, the crystalline domain In one example, the diameter of the crystalline domain is approximately 9 nm. In another example, the diameter of the crystalline domain is approximately 9.5 nm. In another example, the crystalline domain has a diameter of approximately 10 nm. The crystalline domain has a diameter of approximately 10.5 nm. In some examples, the crystalline domain The domain has a diameter of approximately 11.0 nm. In other examples, the crystalline domain has a diameter of approximately 11 It is 0.5 nm. In other examples, the crystalline domain has a diameter of approximately 12.0 nm. In this example, the crystalline domain has a diameter of approximately 12.5 nm. In some other examples, The crystalline domain has a diameter of approximately 13.5 nm. In other examples, the crystalline domain is straight The diameter is approximately 14.0 nm. In another example, the crystalline domain has a diameter of approximately 14.5 nm. In other examples, the crystalline domain has a diameter of approximately 15.0 nm. In this example, the crystalline domain has a diameter of approximately 15.5 nm. Furthermore, in another example, the crystalline The domain has a diameter of approximately 16.0 nm. In other examples, the crystalline domain has a diameter of approximately 16 It is 0.5 nm. In some examples, the crystalline domain has a diameter of approximately 17 nm. In another example, the crystalline domain has a diameter of approximately 17.5 nm. The crystalline domain has a diameter of approximately 18 nm. In other examples, the crystalline domain is The diameter is approximately 18.5 nm. In another example, the crystalline domain has a diameter of approximately 19 nm. In some examples, the crystalline domain has a diameter of approximately 19.5 nm. In yet another example... In this example, the crystalline domain has a diameter of approximately 20 nm. In another example, the crystalline domain The diameter is approximately 20.5 nm. In some examples, the crystalline domain has a diameter of approximately 21 nm. In some other examples, the crystalline domain has a diameter of approximately 21.5 nm. In one example, the crystalline domain has a diameter of approximately 22.0 nm. In yet another example, the The crystalline domain has a diameter of approximately 22.5 nm. In other examples, the crystalline domain is straight The diameter is approximately 23.0 nm. In some examples, the crystalline domain has a diameter of approximately 23.5 nm. In other examples, the crystalline domain has a diameter of approximately 24.0 nm. The crystalline domain has a diameter of approximately 24.5 nm. In some examples, the crystalline domain The in has a diameter of approximately 25.5 nm. In some other examples, the crystalline domain has a diameter In one example, the crystalline domain has a diameter of approximately 26 nm. In other examples, the crystalline domain has a diameter of approximately 27 nm. The crystalline domain has a diameter of approximately 27.5 nm. In some examples, the crystalline domain is The diameter is approximately 28.0 nm. In another example, the crystalline domain has a diameter of approximately 28.5 nm. In other examples, the crystalline domain has a diameter of approximately 29.0 nm. The crystalline domain has a diameter of approximately 29.5 nm. In some other examples, the crystal The crystalline domain has a diameter of approximately 30 nm. In other examples, the crystalline domain has a diameter of approximately 30 It is 0.5 nm. In another example, the crystalline domain has a diameter of approximately 31 nm. In this example, the crystalline domain has a diameter of approximately 32 nm. In some examples, the The crystalline domain has a diameter of approximately 33 nm. In other examples, the crystalline domain is straight The diameter is approximately 34 nm. In other examples, the crystalline domain has a diameter of approximately 35 nm. In that example, the crystalline domain has a diameter of approximately 40 nm. In some other examples... The crystalline domain has a diameter of approximately 45 nm. In other examples, the crystalline domain is straight The diameter is approximately 50 nm. In another example, the crystalline domain has a diameter of approximately 55 nm. In other examples, the crystalline domain has a diameter of approximately 60 nm. The crystalline domain has a diameter of approximately 65 nm. In another example, the crystalline domain In one example, the diameter of the crystalline domain is approximately 70 nm. In another example, the diameter of the crystalline domain is approximately 80 nm. In some examples, the crystalline domain has a diameter of approximately 85 nm. In some other examples... In this example, the crystalline domain has a diameter of approximately 90 nm. In another example, the crystalline domain In one example, the crystalline domain has a diameter of approximately 100 nm. In other examples, the crystalline domain has a diameter of approximately 150 nm. In one example, the crystalline domain has a diameter of approximately 200 nm. In yet another example, the The crystalline domain has a diameter of approximately 250 nm. In other examples, the crystalline domain has a diameter of It is approximately 300 nm. In some examples, the crystalline domain has a diameter of approximately 350 nm. In some other examples, the crystalline domain has a diameter of approximately 400 nm. The crystalline domain has a diameter of approximately 450 nm. In other examples, the crystalline domain The domain has a diameter of approximately 500 nm. In another example, the crystalline domain has a diameter of approximately 550 nm. In some cases, the crystalline domain has a diameter of approximately 600 nm. In this example, the crystalline domain has a diameter of approximately 650 nm. In other examples, the crystalline The domain has a diameter of approximately 700 nm. In some examples, the crystalline domain has a diameter of It is approximately 750 nm. In some other examples, the crystalline domain has a diameter of approximately 800 nm. In other examples, the crystalline domain has a diameter of approximately 850 nm. The crystalline domain has a diameter of approximately 900 nm. In another example, the crystalline domain The domain has a diameter of approximately 950 nm. In some examples, the crystalline domain has a diameter of approximately 100 It is 0 nm.

[0194] (ii. Microcrystalline granular powder) Grain size is determined by microscopy, as used herein, unless otherwise specified, for example. , measured by transmission electron microscopy or scanning electron microscopy, or by X-ray diffraction. It can be done.

[0195] In some examples, the specified material is less than 10 μm 50Crystals with diameter It is a membrane having granules. In one example, the membrane has d particles less than 9 μm. 50 It has crystal grains with a diameter. In other examples, the crystal grains are less than 8 μm in diameter. 50 It has a diameter. In some examples The crystal grains are less than 7 μm in diameter. 50 It has a diameter. In one example, the film is less than 6 μm in diameter. 50 diameter It has crystalline grains. In other examples, the film has d less than 5 μm. 50 It has crystal grains with a diameter. In some cases, the film is less than 4 μm thick. 50 It has crystal grains with a diameter. In the example, the film is less than 3 μm thick. 50 It has crystal grains with a diameter. In one example, the film is d less than 2 μm 50 It has crystal grains with a diameter. In other examples, the film has d less than 1 μm. 50 straight It has crystal grains with a diameter.

[0196] As used herein, the microcrystalline grains in the films described herein are 10 nm to 10 μm. d 50 It has a diameter. In some examples, the microcrystalline grains in the film described herein are 1 d 00nm~10μm 50 It has a diameter.

[0197] In some examples, the films described herein have a Young's modulus of approximately 130–150 GPa. In some other examples, the films described herein have a Vickers hardness of approximately 5–7 GPa. So.

[0198] In some cases, the films described herein have a porosity of less than 20%. In the example described herein, the film has a porosity of less than 10%. Furthermore, the films described herein have a porosity of less than 5%. In other examples, The film described in the specification has a porosity of less than 3%. Porosity is, in some examples It is measured by pycnometry or mercury porosimetry.

[0199] (c.membrane) (i. Uncalcined film) This specification describes a membrane containing a garnet precursor which optionally contains calcined garnet. and powder. Before heating these films and powders, or when forming lithium-filled garnets Before sufficient time has elapsed for the precursor to react, these films and powders are used. It is uncalcined. In some cases, several layers of lithium-filled garnet are made up. To achieve this, the slurry of the following garnet precursors is used to create a calcined film of lithium-filled garnet. It is layered, deposited, or stacked. In some examples, calcined lithium-filled garnet The slurry of the garnet precursor described below is to penetrate into the empty or porous spaces within the container. This is layered, deposited, or laminated onto a calcined film of lithium-filled garnet.

[0200] In some cases, what is described herein is a garnet precursor or, optionally, a provisional This is a thin, self-supporting garnet film containing calcined garnet. In some examples, this These membranes contain at least one selected from a binder, solvent, dispersant, or a combination thereof. This also includes one component. In some examples, the amount of garnet solid filling is at least 30% by weight. It is (w / w). In some cases, the film thickness is less than 100 μm.

[0201] In one example, the dispersant is fish oil, Mehaden Blown Fish Oil, phosphate ester, rhodal ine(trademark), Rhodoline 4160, phospholan-131(trademark), BYK(trademark) 22124, BYK-22146(trademark) These are Hypermer KD1(trademark), Hypermer KD6(trademark), and Hypermer KD7(trademark).

[0202] In some examples, the film includes a substrate adhered to it. In one example, the substrate This is a polymer, metal foil, or metal powder. In some of these examples, The substrate is a metal foil. In some examples, the substrate is a metal powder. These examples In some of these, the metal is Ni, Cu, Al, steel, alloys thereof, or combinations thereof. Selected from the combination.

[0203] The film according to claim 1, wherein the solid filler content is at least 35% w / w.

[0204] In some cases, the film has a solid filler content of at least 40% w / w. In this example, the film has a solid filler content of at least 45% w / w. The film has a solid filler content of at least 50% w / w. In other examples, the solid filler content is , at least 55% w / w. In some other examples, the solid fill amount is at least 60 It is %w / w. In some examples, the solid fill volume is at least 65%w / w. In another example, the solid filler is at least 70% w / w. In yet another example, The solid fill weight is at least 75% w / w. In some examples, the solid fill weight is small. At most, it's 80% w / w.

[0205] In some cases, the uncalcined film has thicknesses of less than 75 μm and greater than 10 nm. In one example, the uncalcined film has thicknesses of less than 50 μm and more than 10 nm. Several examples In this case, the uncalcined film has particles whose maximum physical size is less than 1 μm. In that example, the uncalcined film has a median grain size of 0.1 μm to 10 μm. In this example, the unbaked film is not adhered to any substrate.

[0206] In some cases, what is described herein is a garnet precursor or, optionally, a provisional This is a thin, self-supporting garnet film containing calcined garnet. In some examples, this These membranes contain at least one selected from a binder, solvent, dispersant, or a combination thereof. This also includes one component. In some examples, the amount of garnet solid filling is at least 30% by volume. The ratio is (v / v). In some cases, the film thickness is less than 100 μm.

[0207] In some cases, the film has a solid filler content of at least 40% v / v. In this example, the film has a solid filler content of at least 45% v / v. The film has a solid filler content of at least 50% v / v. In other examples, the solid filler content is , at least 55% v / v. In some other examples, the solid filling amount is at least 60 It is %v / v. In some examples, the solid filler amount is at least 65%v / v. In one other example, the solid filler is at least 70% v / v. In yet another example, The solid filler content is at least 75% v / v. In some examples, the solid filler content is small. At most, it is 80% v / v.

[0208] (a. Tempered film) The uncalcined film described herein is obtained by heating the film to approximately 200°C to 1200°C for approximately 20 minutes to 10 hours or by crystallization. Tempering can be achieved by heating until chemical reactions occur.

[0209] (ii. Unsintered film) In some cases, garnet-based films are unsintered and referred to as "green" films. It exists, and its length extends for kilometers.

[0210] In one embodiment, this disclosure relates to a method for fabricating an energy storage electrode. A method for providing an unsintered thin film, wherein the unsintered thin film is a garnet-type electrolyte. From the group consisting of active electrode materials, conductive additives, solvents, binders, and combinations thereof Includes at least one selected component; remove the solvent if present in the unsintered thin film. Optionally, laminating the film onto the surface; removing the binder if present in the film. t; sintering the film (where sintering is thermal sintering or electric field assisted sintering (FAST)). This includes; where thermal sintering means heating the film at a temperature range of about 700°C to about 1200°C for about 1 to about 600°C. This includes heating for minutes and in an atmosphere having an oxygen partial pressure of 1e-1 to 1e-15 atmospheres; and FA ST sintering involves heating the film in the range of approximately 500°C to approximately 900°C and applying DC or The document describes a method that includes applying an AC electric field.

[0211] In some of the methods disclosed herein, the unsintered thin film is approximately 10 μm to approximately 100 μm It has a thickness of μm. In some other methods disclosed herein, The unsintered thin film has a thickness of approximately 20 μm to approximately 100 μm. Among the methods disclosed herein In some cases, the unsintered thin film has a thickness of approximately 30 μm to approximately 100 μm. Disclosed herein In other methods, the unsintered thin film has a thickness of approximately 40 μm to approximately 100 μm. In further methods disclosed herein, the unsintered thin film is approximately 50 μm to approximately 100 μm. It has a thickness of about 60 μm. In other methods disclosed herein, the unsintered thin film is about 60 μm thick. It has a thickness of approximately 100 μm. In several other methods disclosed herein, The unsintered thin film has a thickness of approximately 70 μm to approximately 100 μm. Among the methods disclosed herein In some cases, the unsintered thin film has a thickness of approximately 80 μm to approximately 100 μm. Disclosed herein In some of the other methods, the unsintered thin film is approximately 90 μm to 100 μm thick. It has thickness.

[0212] In some of the methods disclosed herein, the unsintered thin film is approximately 10 μm to approximately 90 It has a thickness of μm. In some other methods disclosed herein, The unsintered thin film has a thickness of approximately 20 μm to approximately 80 μm. Among the methods disclosed herein In this case, the unsintered thin film has a thickness of approximately 30 μm to approximately 70 μm. In other methods, the unsintered thin film has a thickness of approximately 40 μm to approximately 60 μm. In yet another method disclosed in the specification, the unsintered thin film has a thickness of about 50 μm to about 90 μm. It has. In other methods disclosed herein, the unsintered thin film is about 60 μm to about 90 μm thick. Having a thickness of . In several other methods disclosed herein, an unsintered thin film It has a thickness of approximately 70 μm to approximately 90 μm. Some of the methods disclosed herein The unsintered thin film has a thickness of approximately 80 μm to approximately 90 μm. In some other cases, the unsintered thin film has a thickness of approximately 30 μm to approximately 60 μm.

[0213] In some cases, the unsintered film is approximately 50 percent larger in volume than the sintered film. In several examples, the sintered film has a thickness of approximately 1 to 150 μm. In one case, the sintered film has a thickness of approximately 1 μm. In some other examples, the sintered film is It has a thickness of approximately 2 μm. In one example, the sintered film has a thickness of approximately 3 μm. Another example In this case, the sintered film has a thickness of approximately 4 μm. In some other examples, the sintered film is approximately It has a thickness of 5 μm. In some examples, the sintered film has a thickness of approximately 6 μm. In some of the examples, the sintered film has a thickness of approximately 7 μm. The sintered film has a thickness of approximately 8 μm. In some other examples, the sintered film is approximately 9 μm thick. It has thickness. In one example, the sintered film has a thickness of approximately 10 μm.

[0214] In some cases, sintering reduces the film length to approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or greater than 25% Without causing any damage, the film thickness is reduced by approximately 50, 40, 30, 20, 10, or 5%. As used in the specification, thickness refers to the average thickness in the z-direction (as shown in Figure 23). As used in [the context of the text], length refers to the average length in the x-direction or y-direction (as shown in Figure 23). In the example described herein, the sintering is proportionally greater in the z-direction than in the x-direction or y-direction. The thickness of the film in the x-direction is reduced (shown in Figure 23). In some cases, sintering is mainly in the x-direction or This reduces the film thickness in the z-direction by a much larger proportion than in either the y-direction. In this example, sintering reduces the length of the film in the x-direction or y-direction proportionally to the rate at which sintering reduces the length of the film in the x-direction or y-direction. This substantially reduces the film thickness in the z-direction (as shown in Figure 23). In effect, more significantly, at least 50%, at least 60%, at least 70%, less This includes, but is not limited to, 80%, at least 90%, or at least 100%.

[0215] (iii. Sintered film) In some of these examples, the sintered film has a thickness of approximately 10 nm. In other examples, the sintered film has a thickness of approximately 11 nm. In one example, the sintered film has a thickness of approximately 12 nm. It has a thickness of . In one other example, the sintered film has a thickness of about 13 nm. In this example, the sintered film has a thickness of approximately 14 nm. In some examples, the sintered film is approximately It has a thickness of 15 nm. In some of these examples, the sintered film has a thickness of approximately 16 nm. It has. In some examples, the sintered film has a thickness of about 17 nm. In some other examples... In one example, the sintered film has a thickness of approximately 18 nm. It has. In some of these examples, the sintered film has a thickness of about 20 nm. In several other examples, the sintered film has a thickness of approximately 21 nm. In one example, the sintered film is It has a thickness of approximately 22 nm. In another example, the sintered film has a thickness of approximately 23 nm. In one other example, the sintered film has a thickness of approximately 24 nm. In some examples, the sintered film It has a thickness of approximately 25 nm. In some examples, the sintered film has a thickness of approximately 26 nm. In some of these examples, the sintered film has a thickness of approximately 27 nm. Some examples In this case, the sintered film has a thickness of approximately 28 nm. In some other examples, the sintered film is approximately It has a thickness of 29 nm. In one example, the sintered film has a thickness of approximately 30 nm. In some of our cases, the sintered film has a thickness of approximately 31 nm. In some other examples... The sintered film has a thickness of approximately 32 nm. In one example, the sintered film has a thickness of approximately 33 nm. In one other example, the sintered film has a thickness of approximately 34 nm. In several other examples, The sintered film has a thickness of approximately 35 nm. In some examples, the sintered film has a thickness of approximately 36 nm. In some of these examples, the sintered film has a thickness of approximately 37 nm. In that example, the sintered film has a thickness of approximately 38 nm. In some other examples, the sintered film It has a thickness of approximately 39 nm. In one example, the sintered film has a thickness of approximately 40 nm. In some of the examples, the sintered film has a thickness of approximately 41 nm. In some other examples... In one example, the sintered film has a thickness of approximately 42 nm. It has. In one other example, the sintered film has a thickness of about 44 nm. In some other examples... In some cases, the sintered film has a thickness of approximately 45 nm. It has a thickness of approximately 47 nm. In some examples, the sintered film has a thickness of approximately 48 nm. In some other examples, The sintered film has a thickness of approximately 49 nm. In one example, the sintered film has a thickness of approximately 50 nm. In some of these examples, the sintered film has a thickness of approximately 51 nm. In one example, the sintered film has a thickness of approximately 52 nm. In another example, the sintered film has a thickness of approximately 53 nm. It has thickness. In one other example, the sintered film has a thickness of about 54 nm. In one example, the sintered film has a thickness of approximately 55 nm. In some examples, the sintered film has a thickness of approximately 56 nm. It has a thickness of nm. In some of these examples, the sintered film has a thickness of approximately 57 nm. In some cases, the sintered film has a thickness of approximately 58 nm. In some other cases... In one example, the sintered film has a thickness of approximately 59 nm. do.

[0216] In some of these examples, the sintered film has a thickness of approximately 11 μm. In other examples, the sintered film has a thickness of approximately 12 μm. In one example, the sintered film is approximately 1 It has a thickness of 3 μm. In another example, the sintered film has a thickness of approximately 14 μm. In one other example, the sintered film has a thickness of approximately 15 μm. In some examples, sintered The film has a thickness of approximately 16 μm. In some of these examples, the sintered film is approximately 17 It has a thickness of μm. In some cases, the sintered film has a thickness of approximately 18 μm. In another example, the sintered film has a thickness of approximately 19 μm. In one example, the sintered film is It has a thickness of approximately 20 μm. In some of these examples, the sintered film has a thickness of approximately 21 μm. It has a thickness of approximately 22 μm. In some other examples, the sintered film has a thickness of approximately 22 μm. In one example, the sintered film has a thickness of approximately 23 μm. In another example, the sintered film is approximately 24 μm thick. It has thickness. In some other examples, the sintered film has a thickness of about 25 μm. In that example, the sintered film has a thickness of approximately 26 μm. In some of these examples... The sintered film has a thickness of approximately 27 μm. In some examples, the sintered film is approximately 28 μm thick. It has thickness. In some other examples, the sintered film has a thickness of approximately 29 μm. In this case, the sintered film has a thickness of approximately 30 μm. In some of these examples, The sintered film has a thickness of approximately 31 μm. In some other examples, the sintered film has a thickness of approximately 32 μm. It has a thickness of approximately 33 μm in one example. The sintered film has a thickness of approximately 34 μm. In some other examples, the sintered film is approximately 35 μm thick. It has thickness. In some examples, the sintered film has a thickness of approximately 36 μm. These examples In some of these cases, the sintered film has a thickness of approximately 37 μm. The sintered film has a thickness of approximately 38 μm. In some other examples, the sintered film is approximately 39 μm thick. It has thickness. In one example, the sintered film has a thickness of approximately 40 μm. In some cases, the sintered film has a thickness of approximately 41 μm. In some other cases, The sintered film has a thickness of approximately 42 μm. In one example, the sintered film has a thickness of approximately 43 μm. In one other example, the sintered film has a thickness of approximately 44 μm. In several other examples... The sintered film has a thickness of approximately 45 μm. In some examples, the sintered film has a thickness of approximately 46 μm. In some of these examples, the sintered film has a thickness of approximately 47 μm. In some cases, the sintered film has a thickness of approximately 48 μm. In some other cases... The sintered film has a thickness of approximately 49 μm. In one example, the sintered film has a thickness of approximately 50 μm. In some of these examples, the sintered film has a thickness of approximately 51 μm. In another example, the sintered film has a thickness of approximately 52 μm. In one example, the sintered film is It has a thickness of approximately 53 μm. In another example, the sintered film has a thickness of approximately 54 μm. In some other examples, the sintered film has a thickness of approximately 55 μm. The conjunctiva has a thickness of approximately 56 μm. In some of these examples, the sintered film is approximately 5 It has a thickness of 7 μm. In some examples, the sintered film has a thickness of approximately 58 μm. In several other examples, the sintered film has a thickness of approximately 59 μm. In one example, the sintered film is It has a thickness of approximately 60 μm.

[0217] In some of these examples, the sintered film has a thickness of approximately 61 μm. In other examples, the sintered film has a thickness of approximately 62 μm. In one example, the sintered film is approximately 6 It has a thickness of 3 μm. In another example, the sintered film has a thickness of approximately 64 μm. In one other example, the sintered film has a thickness of approximately 65 μm. In some examples, sintered The film has a thickness of approximately 66 μm. In some of these examples, the sintered film is approximately 67 It has a thickness of μm. In some examples, the sintered film has a thickness of approximately 68 μm. In another example, the sintered film has a thickness of approximately 69 μm. In one example, the sintered film is It has a thickness of approximately 70 μm. In some of these examples, the sintered film has a thickness of approximately 71 μm. It has a thickness of approximately 72 μm. In some other examples, the sintered film has a thickness of approximately 72 μm. In one example, the sintered film has a thickness of approximately 73 μm. In another example, the sintered film is approximately 74 μm thick. It has thickness. In some other examples, the sintered film has a thickness of about 75 μm. In that example, the sintered film has a thickness of approximately 76 μm. In some of these examples... In some cases, the sintered film has a thickness of approximately 77 μm. It has thickness. In some other examples, the sintered film has a thickness of approximately 79 μm. In this case, the sintered film has a thickness of approximately 80 μm. In some of these examples, The sintered film has a thickness of approximately 81 μm. In some other examples, the sintered film has a thickness of approximately 82 μm. It has a thickness of approximately 83 μm in one example. The sintered film has a thickness of approximately 84 μm. In some other examples, the sintered film is approximately 85 μm thick. It has thickness. In some examples, the sintered film has a thickness of approximately 86 μm. These examples In some of these cases, the sintered film has a thickness of approximately 87 μm. The sintered film has a thickness of approximately 88 μm. In some other examples, the sintered film is approximately 89 μm thick. It has thickness. In one example, the sintered film has a thickness of approximately 90 μm. In some cases, the sintered film has a thickness of approximately 91 μm. In some other cases, The sintered film has a thickness of approximately 92 μm. In one example, the sintered film has a thickness of approximately 93 μm. In one other example, the sintered film has a thickness of approximately 94 μm. In several other examples... The sintered film has a thickness of approximately 95 μm. In some examples, the sintered film has a thickness of approximately 96 μm. In some of these examples, the sintered film has a thickness of approximately 97 μm. In some cases, the sintered film has a thickness of approximately 98 μm. In some other cases... The sintered film has a thickness of approximately 99 μm. In one example, the sintered film has a thickness of approximately 100 μm. do.

[0218] In one other example, the sintered film has a thickness of approximately 100 nm. In another example, the sintered film is It has a thickness of approximately 500 nm. In another example, the sintered film has a thickness of approximately 1 μm. In this example, the sintered film has a thickness of approximately 2 μm. In some examples, the sintered film is approximately It has a thickness of 250 nm. In some other examples, the sintered film has a thickness of approximately 2 μm. In some cases, the sintered film has a thickness of approximately 5 μm. The film has a thickness of approximately 3 μm. In other examples, the sintered film has a thickness of approximately 4 μm. In one example, the sintered film has a thickness of approximately 300 nm. In several examples, the sintered film It has a thickness of approximately 400 nm. In some examples, the sintered film has a thickness of approximately 200 nm. .

[0219] In some of these examples, the sintered film has a thickness of approximately 101 μm. In other examples, the sintered film has a thickness of approximately 102 μm. In one example, the sintered film is approximately It has a thickness of 103 μm. In another example, the sintered film has a thickness of approximately 104 μm. In several other examples, the sintered film has a thickness of approximately 105 μm. The conjunctiva has a thickness of approximately 106 μm. In some of these examples, the sintered film is approximately It has a thickness of 107 μm. In some examples, the sintered film has a thickness of approximately 108 μm. In several other examples, the sintered film has a thickness of approximately 10⁹ μm. In one example, the sintered film It has a thickness of approximately 110 μm. In some of these examples, the sintered film is approximately 111 It has a thickness of μm. In some other examples, the sintered film has a thickness of approximately 112 μm. In one example, the sintered film has a thickness of approximately 113 μm. In another example, the sintered film is It has a thickness of approximately 114 μm. In some other examples, the sintered film has a thickness of approximately 115 μm. In some examples, the sintered film has a thickness of approximately 116 μm. In some cases, the sintered film has a thickness of approximately 117 μm. In some examples, the sintered film is It has a thickness of approximately 118 μm. In some other examples, the sintered film has a thickness of approximately 119 μm. In one example, the sintered film has a thickness of approximately 120 μm. In one case, the sintered film has a thickness of approximately 121 μm. In some other examples, the sintered film is It has a thickness of approximately 122 μm. In one example, the sintered film has a thickness of approximately 123 μm. In other examples, the sintered film has a thickness of approximately 124 μm. In some other examples, sintered The film has a thickness of approximately 125 μm. In some examples, the sintered film has a thickness of approximately 126 μm. In some of these examples, the sintered film has a thickness of approximately 127 μm. In one example, the sintered film has a thickness of approximately 128 μm. In several other examples, the sintered film has a thickness of approximately 128 μm. The conjunctiva has a thickness of approximately 129 μm. In one example, the sintered film has a thickness of approximately 130 μm. In some of these examples, the sintered film has a thickness of approximately 131 μm. In other examples, the sintered film has a thickness of approximately 132 μm. In one example, the sintered film is approximately It has a thickness of 133 μm. In another example, the sintered film has a thickness of approximately 134 μm. In some other examples, the sintered film has a thickness of approximately 135 μm. The conjunctiva has a thickness of approximately 136 μm. In some of these examples, the sintered film is approximately It has a thickness of 137 μm. In some examples, the sintered film has a thickness of approximately 138 μm. In several other examples, the sintered film has a thickness of approximately 139 μm. In one example, the sintered film It has a thickness of approximately 140 μm.

[0220] In some of these examples, the sintered film has a thickness of approximately 141 μm. In other examples, the sintered film has a thickness of approximately 142 μm. In one example, the sintered film is approximately It has a thickness of 143 μm. In another example, the sintered film has a thickness of approximately 144 μm. In some other examples, the sintered film has a thickness of approximately 145 μm. The conjunctiva has a thickness of approximately 146 μm. In some of these examples, the sintered film is approximately It has a thickness of 147 μm. In some examples, the sintered film has a thickness of approximately 148 μm. In several other examples, the sintered film has a thickness of approximately 149 μm. In one example, the sintered film It has a thickness of approximately 150 μm.

[0221] (iv. Nanocrystalline films and microcrystalline granular films) In some examples, the specifications provided herein are d 50 Crystals with diameter It is a film having granules. In one example, the film has d particles less than 9 nm. 50 It has crystal grains with a diameter. In other examples, the crystal grains are less than 8 nm in size. 50 It has a diameter. In some examples, The grain size is less than 7 nm. 50 It has a diameter. In one example, the film has a diameter of less than 6 nm. 50 Having a diameter It has crystalline grains of less than 5 nm. In other examples, the film has d 50 Having crystal grains with a diameter In some cases, the film has a d of less than 4 nm. 50 It has crystal grains with a diameter. In this film, the film has a d of less than 3 nm 50 It has crystal grains with a diameter. In one example, the film is d less than 2nm 50 It has crystal grains with a diameter. In other examples, the film has d of less than 1 nm. 50 diameter It has crystal grains that have [specific characteristics].

[0222] In some examples, the specified material is less than 10 μm 50 Crystals with diameter It is a membrane having granules. In one example, the membrane has d particles less than 9 μm. 50 It has crystal grains with a diameter. In other examples, the crystal grains are less than 8 μm in diameter. 50 It has a diameter. In some examples The crystal grains are less than 7 μm in diameter. 50 It has a diameter. In one example, the film has a diameter of less than 6 μm. 50 diameter It has crystal grains having . In other examples, the film has d less than 5 μm. 50 Crystal grains with diameter It has. In some examples, the film has a thickness of less than 4 μm. 50 Having crystal grains with a diameter In other examples, the film is less than 3 μm thick. 50 It has crystal grains with a diameter. The film is less than 2 μm thick. 50It has crystal grains with a diameter. In another example, the film is 1 μ d less than m 50 It has crystal grains with a diameter.

[0223] As used herein, the microcrystalline grains in the films described herein are 10 nm to 10 μm. d 50 It has a diameter. In some examples, the microcrystalline grains in the film described herein are 1 d 00nm~10μm 50 It has a diameter.

[0224] (v. free-standing membrane) In some cases, this disclosure is provided herein by means of the methods described herein. This describes a self-supporting, thin-film garnet-type electrolyte that is manufactured using this method.

[0225] In some embodiments, the methods described herein are disclosed. It is a self-supporting thin-film garnet-type electrolyte manufactured by [the specified method].

[0226] In some embodiments, the thickness of the self-supporting film is less than 50 μm. In this example, the thickness of the film is less than 40 μm. In some embodiments, the thickness of the film is 30 It is less than μm. In some other embodiments, the thickness of the film is less than 20 μm. In this embodiment, the thickness of the film is less than 10 μm. In yet another embodiment, the film The thickness is less than 5 μm.

[0227] In some embodiments, the thickness of the film is less than 45 μm. In one embodiment The thickness of the film is less than 35 μm. In some embodiments, the thickness of the film is less than 25 μm. In some other embodiments, the thickness of the film is less than 15 μm. In this embodiment, the thickness of the film is less than 5 μm. In yet another embodiment, the thickness of the film is It is less than 1 μm.

[0228] In some embodiments, the thickness of the film is approximately 1 μm to approximately 50 μm. In this case, the thickness of the film is approximately 10 μm to approximately 50 μm. In some embodiments, the film The thickness is approximately 20 μm to approximately 50 μm. In some other embodiments, the thickness of the film is The thickness is approximately 30 μm to approximately 50 μm. In other embodiments, the thickness of the film is approximately 40 μm to approximately 50 μm. ru.

[0229] In some embodiments, the thickness of the film is approximately 1 μm to approximately 40 μm. In this case, the thickness of the film is approximately 10 μm to approximately 40 μm. In some embodiments, the film The thickness is approximately 20 μm to approximately 40 μm. In some other embodiments, the thickness of the film is The thickness is approximately 30 μm to approximately 40 μm. In other embodiments, the thickness of the film is approximately 20 μm to approximately 30 μm. ru.

[0230] In some examples, the following are described herein: thin, self-supporting sintered garnets. The film is a film, where the film thickness is less than 50 μm and greater than 10 nm, and the film is substantially flat. and the garnet optionally contains metal or metal powder on at least one side of the film. It is bonded to the current collector (CC) film.

[0231] In some cases, thin, self-supporting sintered garnet films are less than 20 μm or less than 10 μm thick. It has a thickness of 5 μm. In some examples, thin and self-supporting sintered garnet films have a thickness of 5 μm. It has a surface roughness of less than . In some examples, thin and self-supporting sintered garnet films are , having a surface roughness of less than 4 μm. In some examples, thin and self-supporting sintered garnets The film has a surface roughness of less than 2 μm. In some examples, thin and self-supporting sintered glass - The garnet film has a surface roughness of less than 1 μm. In one example, the garnet has a surface roughness of 0.1 μm. The median grain size is ~10 μm. In one example, the garnet has grain sizes of 2.0 μm to 5.0 μm. It has a median grain size of .

[0232] (vi. Film bonded to a substrate) In some of the films described herein, the film is made of a polymer, glass, or metal. It is bonded to a selected substrate. In some of these examples, the film is bonded to or The substrate to which it is bonded is a current collector (CC). In some of these examples, the CC film These are made from nickel (Ni), copper (Cu), steel, stainless steel, combinations thereof, and alloys thereof. The film includes a metal selected from the group. In some of these examples, the film is It is coupled to a metal current collector (CC) on one side. In some other examples, the film is coupled to both sides of the film. It is coupled to a metal current collector (CC) on the side. In yet another example, the CC consists of two garnet films. It is positioned between them and in contact with them.

[0233] (vii. Double and triple layers) In some examples, two different lithium-filled garnets are described herein. A triple layer containing metal foil or metal powder placed between and in contact with a thin film. In some examples, the middle layer is metal foil. In some other examples, The middle layer is metal powder. In some examples, the metal is Ni. In other examples... In some cases, the metal is Al. In other cases, the metal is Fe. In some cases, gold The genus is steel or stainless steel. In some examples, the metal is Ni, Cu, Al, or Fe It is an alloy or combination of the above. In some examples, the triple layer has the structure shown in Figure 3. In some cases, the triple layer has the structure shown in Figure 4 below. In some examples, the triple layer has the structure shown in Figure 29 below. In some examples, the triple The layered structure is shown in Figures 44(E) and 44(F).

[0234] In some examples, the lithium-filled garnet thin film is described herein in conjunction with It is a double layer containing metal foil or metal powder arranged in contact with each other. In some examples, the two One layer of the double layer is metal foil. In another example, one layer of the double layer is metal powder. In some examples, the metal is Ni. In other examples, the metal is Al. In other examples, the metal is Fe. In some examples, the metal is steel or stainless steel. It is a steel. In some examples, the metal is an alloy or combination of Ni, Cu, Al, or Fe. In some examples, the double layer has the structure shown in Figures 44(C) and 44(D). In the example shown, the double layer has the structure shown between the sintered plates in Figure 20 or Figure 21. ru.

[0235] In some of the double and triple layers described herein, garnet is given by the following formula : LiALaBM'cM''DZrEOF, LiALaBM'CM''DTaEOF, LiALaBM'CM''DNbEOF (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 selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta) , or LiaLabZrcAldMe''eOf (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f ≤ 13, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb) ); LiALaBM'cM''DZrEOF (where the molar ratio of Al2O3 to garnet is 0.05 - 0.7); or LigLa3Zr2O12 - Al2O3 (where 5.5 < g < 8.5 and the molar ratio of Al2O3 to garnet is 0.05 - 1.0), characterized by one of them. (viii.Multilayer) In some examples, what is described herein is a number of stacks or combinations of the aforementioned layers, bilayers, and / or trilayers. In some examples, two or more bilayers are stacked in a continuous combination. In some other examples, two or more trilayers are stacked in a continuous combination. In some examples, what is inserted between these continuous combination stacks is a cathode active material, an anode active material, and / or a current collector.

[0236] (ix.Film Dimensions) In some examples, the thin films described herein have a thickness of less than 50 μm. In some other examples, the thin films described herein have a thickness of less than 45 μm. In one example, the thin films described herein have a thickness of less than 40 μm. In still other examples , the thin films described herein have a thickness of less than 35 μm. In yet other examples, the thin films described herein have a thickness of less than 30 μm. In still other examples , the thin films described herein have a thickness of less than 25 μm. In yet other examples, the thin films described herein have a thickness of less than 20 μm. In still other examples , the thin films described herein have a thickness of less than 15 μm. In yet other examples, the thin films described herein have a thickness of less than 10 μm. In still other examples , the thin films described herein have a thickness of less than 5 μm. In yet other examples, the thin films described herein have a thickness of less than 1 μm. (ix.Film Dimensions)

[0237] (ix.Film Dimensions) In some examples, the thin films described herein have a thickness of less than 50 μm. In some other examples, the thin films described herein have a thickness of less than 45 μm. In one example, the thin films described herein have a thickness of less than 40 μm. Also in other examples , the thin films described herein have a thickness of less than 35 μm. In yet other examples, the thin films described herein have a thickness of less than 30 μm. In still other examples , the thin films described herein have a thickness of less than 25 μm. In yet other examples, the thin films described herein have a thickness of less than 20 μm. In still other examples The thin films described herein have a thickness of less than 35 μm. In some examples, The thin films described in this specification have a thickness of less than 30 μm. In some other examples, this specification The thin films described in this document have a thickness of less than 25 μm. In one example, as described herein The thin film is less than 20 μm thick. In other examples, the thin film described herein is , with a thickness of less than 15 μm. In some examples, the thin films described herein have a thickness The thickness is less than 10 μm. In some other examples, the thin films described herein have a thickness of 5 It is less than μm. In one example, the thin film described herein has a thickness of less than 0.5 μm. In other examples, the thin films described herein have a thickness of less than 0.1 μm.

[0238] In some examples, provided herein are film thicknesses of approximately 100 nm to approximately 100 μm. This composition is formulated as a thin film. In one example, the thickness is less than 50 μm. In other examples, the thickness is less than 40 μm. In some examples, the thickness is less than 30 μm. In other examples, the thickness is less than 20 μm. In one example, the thickness is less than 10 μm. In other examples, the thickness is less than 5 μm. In some examples, the thickness is less than 1 μm. Furthermore, in another example, the thickness is 0.5 μm.

[0239] In some of these examples, the film has a length of 1 mm. In some other cases, the film is 5 mm in length. In yet another example, The membrane is 10 mm long. In another example, the membrane is 15 mm long. In one example, the film is 25 mm long. In another example, the film is 30 mm long. In that example, the film is 35 mm long. In some other examples, the film is, In another example, the film is 40 mm long. In yet another example, the film is 45 mm long. In one example, the length is 50 mm. In another example, the film is 30 mm long. In some examples, In some other examples, the film has a length of 55 mm. In another example, the film is 65 mm in length. In yet another example, the film is The length is 70 mm. In one example, the film is 75 mm long. In another example, the film The length is 80 mm. In some cases, the film is 85 mm long. In another example, the film has a length of 90 mm. In yet another example, the film has a length of 95 mm. In one example, the film has a length of 100 mm. In another example, the film has a length of 100 mm. It is 30mm.

[0240] In some examples, the membrane is 1 cm long. In some other examples, the membrane In one example, the length is 2 cm. In another example, the length of the film is 3 cm. In yet another example, The membrane is 4 cm long. In some examples, the membrane is 5 cm long. In one example, the membrane is 6 cm long. In yet another example, the membrane is 7 cm long. In some other examples, the membrane is 8 cm long. In yet another example, the The membrane is 9 cm long. In another example, the membrane is 10 cm long. In one example, the membrane is 11 cm long. In some other examples, the membrane is 12 cm long. It is cm. In another example, the membrane is 13 cm long. In yet another example, the membrane is , with a length of 14 cm. In some examples, the membrane is 15 cm long. In other examples, In one example, the membrane is 16 cm long. In yet another example, the membrane is 17 cm long. In some other examples, the membrane is 18 cm long. In yet another example, the membrane is The length is 19 cm. In another example, the film is 20 cm long. In several examples... In some other examples, the membrane is 21 cm long. In another example, the membrane is 23 cm long. In yet another example, the membrane is long It is 24 cm. In some examples, the membrane is 25 cm long. In other examples, the The membrane is 26 cm long. In yet another example, the membrane is 27 cm long. In another example, the membrane is 28 cm long. In yet another example, the membrane is It is 29 cm. In other examples, the film is 30 cm long. In some examples, The membrane is 31 cm long. In some other examples, the membrane is 32 cm long. In one example, the membrane is 33 cm long. In yet another example, the membrane is 34 cm long. In some examples, the membrane is 35 cm long. In other examples, the membrane is The length is 36 cm. In yet another example, the membrane is 37 cm long. In one example, the membrane is 38 cm long. In yet another example, the membrane is 39 cm long. Yes. In other examples, the membrane is 40 cm long. In some examples, the membrane is , with a length of 41 cm. In some other examples, the membrane is 42 cm long. In one example, the membrane is 43 cm long. In yet another example, the membrane is 44 cm long. In some examples, the membrane is 45 cm long. In other examples, the membrane is It is 46 cm. In another example, the membrane is 47 cm long. In several other examples... In one example, the membrane is 48 cm long. In yet another example, the membrane is 49 cm long. In another example, the membrane is 50 cm long. In some examples, the membrane is long It is 51 cm. In some other examples, the membrane is 52 cm long. In other examples In another example, the membrane is 53 cm long. In one example, the membrane is 55 cm long. In another example, the membrane is 56 cm long. Yes. In another example, the membrane is 57 cm long. In some other examples, The membrane is 58 cm long. In another example, the membrane is 59 cm long. In one example, the membrane is 60 cm long. In some examples, the membrane is 61 cm long. In some other examples, the membrane is 62 cm long. In one example, the length is 63 cm. In yet another example, the membrane is 64 cm long. In one example, the membrane is 65 cm long. In another example, the membrane is 66 cm long. In yet another example, the membrane is 67 cm long. In some other examples, the membrane is , with a length of 68 cm. In another example, the membrane has a length of 69 cm. In yet another example... In some cases, the membrane is 70 cm long. In some examples, the membrane is 71 cm long. In some other examples, the membrane is 72 cm long. In other examples, the membrane is long The length is 73 cm. In another example, the membrane is 74 cm long. In several examples... In one example, the membrane is 75 cm long. In another example, the membrane is 76 cm long. In other examples, the membrane is 77 cm long. In some other examples, the membrane is, In another example, the length of the membrane is 78 cm. The membrane is 80 cm long. In some examples, the membrane is 81 cm long. In a few other examples, the membrane is 82 cm long. In another example, the membrane is 83 cm long. It is cm. In another example, the film is 84 cm long. In some examples, The membrane is 85 cm long. In another example, the membrane is 86 cm long. Yet another example In this example, the membrane is 87 cm long. In some other examples, the membrane is 88 cm long. In another example, the membrane is 89 cm long. The length is 90 cm. In some cases, the membrane is 91 cm long. In another example, the membrane is 92 cm long. In yet another example, the membrane is 93 cm long. In other examples, the membrane is 94 cm long. In some examples, the membrane is In another example, the length is 95 cm. In yet another example, the length is 96 cm. In some other examples, the membrane is 97 cm long. In another example, the membrane is 99 cm long. In yet another example, the membrane is long The depth is 100 cm. In some examples, the membrane is 101 cm long. In one example, the membrane is 102 cm long. In another example, the membrane is 103 cm long. In another example, the membrane is 104 cm long. In some examples, the membrane is In another example, the length is 105 cm. In yet another example, In some other examples, the membrane is 107 cm long. There is. In another example, the membrane is 109 cm long. In yet another example, the membrane It is 110 cm long. In some cases, the membrane is 111 cm long. In another example, the membrane is 112 cm long. In another example, the membrane is 113 cm long. In another example, the membrane is 114 cm long. In some examples, The membrane is 115 cm long. In another example, the membrane is 116 cm long. In one example, the membrane is 117 cm long. In some other examples, the membrane is 1 It is 18 cm. In another example, the membrane is 119 cm long. In yet another example, The membrane is 120 cm long.

[0241] In some cases, garnet-based films are useful monoliths and in lithium secondary battery cells. They are manufactured as follows. In some of these cells, the shape elements of the garnet film are , about 10cm 2 It is a membrane with an upper surface area of ​​approximately 100 cm² in a given cell. 2 The upper surface area Shape elements of a garnet-based film.

[0242] In some examples, the films described herein have a Young's modulus of approximately 130–150 GPa. In some other examples, the films described herein have a Vickers hardness of approximately 5–7 GPa. So.

[0243] In some cases, the films described herein have a porosity of less than 20%. In the example described herein, the film has a porosity of less than 10%. Furthermore, the films described herein have a porosity of less than 5%. In other examples, The film described in the specification has a porosity of less than 3%.

[0244] (x. Composite materials) For Li-secondary battery applications, the energy density is determined by the presence of the electrolyte, catholite, and It is partially inversely proportional to the amount of anolite. Less electrolyte, catholite, or anolite material As the battery structure capacity increases, more cathode active material (e.g., FeF3, CoF2) is used. It is possible to incorporate NiF2, CoF2, and more negative electrode materials (e.g., Li-metal) into the same capacity. This allows for an increase in the battery's energy density, for example, energy per unit capacity. Therefore, in some cases, although less than 500 μm, exceeding 1 nm. or less than 450 μm but greater than 1 nm, or less than 400 μm but greater than 1 nm, is less than 350 μm but greater than 1 nm, or less than 300 μm but greater than 1 nm, or 250 Less than μm but greater than 1 nm, or less than 200 μm but greater than 1 nm, or less than 150 μm If it is less than 1 nm but exceeds 1 nm, or less than 100 μm but exceeds 1 nm, or less than 50 μm Some are larger than 1 nm, or less than 45 μm but still larger than 1 nm, or less than 40 μm but still 1 nm Greater than m, or less than 30 μm but greater than 1 nm, or less than 35 μm but greater than 1 nm or less than 25 μm but greater than 1 nm, or less than 20 μm but greater than 1 nm, Less than 15 μm but greater than 1 nm, or less than 10 μm but greater than 1 nm, or less than 9 μm However, if it is greater than 1 nm or less than 8 μm, however, if it is greater than 1 nm or less than 7 μm Larger than 1 nm, or less than 6 μm but larger than 1 nm, or less than 5 μm but larger than 1 nm or less than 4 μm but greater than 1 nm, or less than 3 μm but greater than 1 nm, or 2 Less than μm but greater than 1 nm, or less than 1 μm but greater than 1 nm, or less than 90 nm There are some that are greater than 1 nm, or less than 85 nm but greater than 1 nm, or less than 80 nm but 1 nm m or less than 75 nm but greater than 1 nm, or less than 70 nm but greater than 1 nm or less than 60nm but greater than 1nm, or less than 55nm but greater than 1nm, or 50 If it is less than nm but greater than 1 nm, or less than 45 nm but greater than 1 nm, or less than 40 nm Some are greater than 1 nm, or less than 35 nm but greater than 1 nm, or less than 30 nm but 1 nm If it exceeds 25 nm / μm, or if it is less than 25 nm / μm but exceeds 1 nm, or if it is less than 20 nm but exceeds 1 nm or less than 15nm but greater than 1nm, or less than 10nm but greater than 1nm, or 5nm It is less than m but greater than 1 nm, or less than 4 nm but greater than 1 nm, or less than 3 nm. This specification provides for a film thickness that is greater than 1 nm, or less than 2 nm but greater than 1 nm. It is preferable to use the method described.

[0245] In one example, the garnet material described herein is combined with a polymer. In these examples, the polymers are polyethylene oxide (PEO) and polypropylene. Polystyrene oxide (PPO), PEO-PPO block copolymer, styrene-butadiene, polystyrene (PS ), acrylate, diacrylate, methyl methacrylate, silicone, acrylamide t-butylacrylamide, styrenics, t-α-methylstyrene, acrylo Examples include, but are not limited to, nitriles and vinyl acetate.

[0246] Books listing binders (for example, in slurries or in unsintered thin films) In the example specification, the binder is made of polypropylene (PP) and polyvinyl butyral (PVB). Polyvinylpyrrolidone (PVP), Atactic polypropylene (aPP), Isotactic (iso tactive) Polypropylene ethylene propylene rubber (EPR), ethylene pentene copolymer (EP C) Polyisobutylene (PIB), ZEON (trademark), Styrene-butadiene rubber (SBR), Polyolefin Polyethylene-co-poly-1-octene (PE-co-PO); PE-co-poly (methylenecyclopentane) (PE-CO-PMCP); Stereoblock polypropylene, polypropylene polymethylpentene It can be selected from the group consisting of polymers and silicones.

[0247] (II. Lithium-ion batteries) In some cases, the disclosures herein refer to lithium-filled garnets described herein. The present invention describes a battery having a cassolite, an electrolyte, and / or anolite, which are composed of a set. Yes, they are.

[0248] (a. Battery structure) In some examples, the batteries described herein are coated on both sides of the current collector substrate. The positive electrode (e.g., cathode) includes an active material. In these examples, the garnet electrolyte is a It can also be applied to the surface or interior of the sword-activated material.

[0249] In some cases, the disclosures herein are manufactured by the methods described herein. This document describes a composite electrochemical device, where the device comprises: an active electrode material, lithium A group consisting of a garnet electrolyte or catholite filled with charcoal, conductive additives, and combinations thereof. It includes at least one layer containing a member selected from. In some examples, the device The device also includes at least one layer containing a garnet-type electrolyte.

[0250] In another embodiment, the present disclosure specifies the anode and anode current collector as described herein. A layer comprising at least one layer comprising garnet solid electrolyte (SSE); the garnet A layer comprising porous garnet in contact with a SSE; where the porous garnet The set may optionally contain carbon, lithium conductive polymers, active cathode materials, and combinations thereof. At least one member selected from the group consisting of is impregnated; and the porous garnet It includes at least one layer containing an aluminum cathode current collector in contact with the net, where, The porous garnet layer is porous by volume by at least 70%; the garnet is Li A La B M ' c M'' DZr E O F 、Li A La B M' C M'' D Ta E O F 、Li A La B M' C M'' D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4 , 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14, and M' and M'' are each, in each case independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2; 0 ≤ e < 2, 10 < f < 14, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb) is selected<0002五千三百八十selected material; and the active electrode material is NCA (lithium nickel cobalt aluminum oxide), LMNO (lithium manganese nickel oxide), NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide, i.e., LiCoO2), nickel fluoride (NiF x , where x is 0 to 2.5), copper fluoride (CuF y , where y is 0 to 2.5), or FeF z ( where z is selected from 0 to 3.5) is a cathode material selected from, an electrochemical device describes a layered material for use. In some examples, 10 < F < 13. In some examples, 0 < c ≤ 2.

[0251] (b. Battery components suitable for use with garnet cassolite, electrolyte, and cassolite) minutes) Suitable current collectors for use with the garnet materials described herein include gold Examples include metal foil, metal sheets, metal wires, and metal powders, where the metal is aluminum. Aluminum, copper, gold, nickel, cobalt, steel, stainless steel, lithium metal, and these alloys The member is selected from the group consisting of a mixture or combination. In some examples, this Provided in this specification is alumina-doped lithium as described in this application. This is an electrochemical device having an electrolyte composed of packed garnet. Some examples include: Provided herein is an alumina-doped material as described in this application. This is an electrochemical device having a catholite composed of lithium-filled garnet.

[0252] In some embodiments disclosed herein, the electrode is a conductive additive which is carbon. Includes. In one embodiment, carbon is Ketjenblack, VGCF, acetylene black. Calcium, graphite, graphene, nanotubes, nanofibers, and combinations thereof. It is a member selected from the group consisting of the following. In one embodiment, carbon is Ketschel. It is black. In one other embodiment, carbon is VGCF. In yet another embodiment, In this embodiment, carbon is acetylene black. In another embodiment, carbon is graphite. In some embodiments, carbon is graphene. In other embodiments... In one embodiment, carbon is in the form of nanotubes. In another embodiment, carbon is in the form of nanofibers.

[0253] (c. Cathode materials suitable for use with the garnet materials described herein) The garnet materials described herein are used with various cathode active materials or positive electrode active materials. They are suitable for use together. In particular, garnet has conversion chemical cathode activity. Materials, for example, but not limited to, an electrochemical conversion patent filed on June 19, 2013. Nanostructured materials for electrical chemical conversion reactions U.S. Non-Provisional Patent Application No. 13 / 922,214, entitled CTIONS; also filed on May 8, 2014, Protective coatings for conversion material cathodes U.S. Non-Provisional Patent Application No. 14 / 272,518, entitled AL CATHODES; also filed on 23 July 2014 Furthermore, a hybrid electrode (H) having both intercalation material and conversion material. A US-based provisional title titled "YBRID ELECTRODES WITH BOTH INTERCALATION AND CONVERSION MATERIALS" Patent application No. 62 / 027,908; and also, filed on November 26, 2013, for energy storage A US non-governmental researcher has published a paper titled "Iron Oxyfluoride Electrodes for Energy Storage." Provisional patent application No. 14 / 090,990; also, filed on October 25, 2013, for metals for self-forming batteries. A US publication titled "METAL FLUORIDE COMPOSITIONS FOR SELF-FORMED BATTERIES" Because it is chemically compatible with the active material described in National Non-Provisional Patent Application No. 14 / 063,966, Useful as a solite and electrolyte. The content of these patent applications is for all purposes. This is incorporated fully herein by reference.

[0254] The garnet materials described herein are other catholite and electrolyte materials, for example, limited It is not yet determined, but Li filed on May 15, 2014. A MP B S C (M = Si, Ge, and / or Sn) Solid catholyte or electrolyte for batteries ERY USING Li A MP B S C International PCT patent application PCT / US14 / 38283 titled (M = Si, Ge, and / or Sn) It is also suitable for use with the catholite and electrolyte materials described in the issue.

[0255] Active electrodes suitable for use with the components, devices, and methods described herein. While not limited to specific materials, NCA (lithium nickel cobalt aluminum oxide) is one example. (Iridium), NMC (Lithium Nickel Manganese Cobalt Oxide), LMNO (Lithium Manganese Nickel Cobalt Oxide) (Lithium cobalt oxide), LCO (Lithium Cobalt Oxide, i.e., LiCoO2), Nickel Fluoride (NiFx, Here, x is between 0 and 2.5), copper fluoride (CuF y (where y is between 0 and 2.5), or FeF z (here (where z is selected from 0 to 3.5). In one embodiment, the active electrode material is , a material for the cathode. In one embodiment, the active cathode electrode material is NCA(L It is thium nickel cobalt aluminum oxide. In one other embodiment, the active The cathode electrode material is LMNO (lithium manganese nickel oxide). Further implementations In one embodiment, the active cathode electrode material is LCO (lithium cobalt oxide, i.e., Li It is CoO2). In yet another embodiment, the active cathode electrode material is NMC. In another embodiment, the active cathode electrode material is nickel fluoride (NiF x Here (where x is 0 to 2.5). In some other embodiments, the active cathode electrode material is copper fluoride (CuF y (where y is between 0 and 2.5). In one other embodiment, The active cathode electrode material is FeF z (Here, z is selected from 0 to 3.5).

[0256] (III. Methods for preparing the materials described herein) (a. Thin-film lithium-conducting powder material derived from deposition flux) In some examples, the ceramic electrolyte materials described herein (for example, A process for producing battery components containing lithium-filled garnet powder or film, wherein the process is performed at 400°C Using one or more flux materials having a lower melting point than the substrate, ceramics are applied to the substrate or its periphery. This is a process of mixing, dissolving, and / or densifying materials.

[0257] In some cases, ceramic electrolyte powder material, or its components, are used in two or more flats. The flux material is mixed with the other material at a temperature of less than 400°C to form a fluxed powder material. The fluxed powder material is molded and reheated at a temperature of less than 400°C to produce high-density lithium To form a conductive material.

[0258] The deposition methods described herein involve deposition materials, for example, garnet, etc. It is suitable for lithium-filled garnet, perovskite, NASICON, and LISICON structures.

[0259] In some examples, the deposition method involves a specified amount of lithium-conducting ceramic powder material. and providing by density. In one example, the powder has an average particle size of about 100 nm to 10 μm. Characterized by, or ground to the average particle size. In some examples, The average particle size is 800 nm to 2 μm. In some of these examples, the flux material The flux is provided in the second specified quantity and density. In one example, the second flux provided The material is less than 51% (w / w) of the first powder material. This flux material is typically used at approximately 500°C. This is a lithium-containing material that melts at ~800°C. Additional flux material is added to the reaction mixture. It can also be supplied. In some examples, various combinations of powder and flux materials are used. Mix to form a eutectic mixture. In some of these examples, the eutectic mixture It has a melting point of less than 500°C. In some further examples, the eutectic mixture is about 100-50 Heat to a temperature of 0°C. In some examples, the heated mixture is mixed. In the example, the mixture is then heated, and although not limited to sheets, thick films (thickness exceeding 100 μm) Thin films (less than 100 μm thick), rolls, spheres, disks, sheets, pellets, and cylinders. To form the desired shape. After the reaction time and / or further heating, the powder and flux material Cool as desired. In some examples, the flux is cooled with a solvent, for example, not limited to However, using water, acetone, ethanol, or a combination thereof, the product formed therein To separate or remove from a substance. In some cases, further heating is performed to a temperature below 500°C. Let's assume that by this method and its modification, high-density lithium-conducting ceramic powder This occurs, and in many cases, the density is 20% higher than the starting density of the reactants and / or flux. i. In one example, the powder and flux material is the formed garnet, for example ba, Li7La3Zr2O 12 , and oxides, for example, LiOH, La2O3, ZrO2, but these Not limited to. In one example, the garnet powder is a garnet precursor, for example, limited It is not specified, but LiOH, L2CO3, La2O3, ZrO2, Nb2O5, Ta2O5, Al nitrate, Al nitrate hydrate, or It is formed by mixing these combinations.

[0260] In some cases, the garnet materials described herein are used as garnet precursors. For example, but not limited to, LiOH, La2O3, ZrO2, Nb2O5, Ta2O5, Al nitrate, or these It is manufactured by mixing the combinations to form a mixture. Next, the mixture is heated at 600°C. 650℃, 700℃, 750℃, 800℃, 850℃, 900℃, 950℃, 1000℃, 1050℃, 1100℃, 1150 Calcined at temperatures of ℃, 1200℃, 1250℃, 1300℃, 1350℃, 1400℃, or 1450℃. In the example, the mixture is heated at 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, or 1100°C. Calcined. In some examples, the mixture is calcined at 800°C. The mixture is calcined at 850°C. In some examples, the mixture is calcined at 900°C. In some examples, the mixture is calcined at 950°C. In some examples, the mixture is 1 Calcined at 000°C. In some examples, the mixture is calcined at 1050°C. In this process, the mixture is calcined at 1100°C. In some of these examples, the mixture Calcinerate the material for 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 hours. In some examples, the mixture Calcinerate the material for 4, 5, 6, 7, or 8 hours. In some examples, calcinerate the mixture for 4 hours. In some examples, the mixture is calcined for 5 hours. Calcinerate for 6 hours. In some examples, calcinerate the mixture for 7 hours. The calcination temperature is achieved by a heating ramp rate of approximately 1°C / min, 5°C / min, or 10°C / min. In some of these examples, the calcined mixture was then crushed to form aggregates of the mixture. Dismantle it. In some of these examples, the calcined mixture is then crushed and flattened. To reduce uniform particle size. In one example, the pulverized calcined mixture was then heated at 600°C. 50℃, 700℃, 750℃, 800℃, 850℃, 900℃, 950℃, 1000℃, 1050℃, 1100℃, 1150℃, Sintering is performed at temperatures of 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, or 1450°C. Some examples: In this process, sintering is performed at 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, and 1350°C. The process is carried out at temperatures of 1400°C or 1450°C. In some examples, sintering is carried out at 1000°C, 1200°C, The process is carried out at a temperature of ℃ or 1400℃. In these examples, sintering is performed in steps 1, 2, 3, 4, 5, 6, and 7. , 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, It will last 28, 29, or 30 minutes.

[0261] In some cases, the flux is an inorganic salt, such as lithium, sodium, or potassium. Includes um and rubidium salts. For example, LiF, LiCl, LiBr, and / or LiI. Some examples In this, the flux contains inorganic oxides, such as LiOH and Li2CO3. The flux is This may also include metal hydroxides, chlorides, nitrates, sulfates, and combinations thereof. Useful specific combinations include LiOH, LiCl, LiBr, LiI, LiNO3, LiSO4, Li2O-SiO2, and Li2O -B2O3, Li2O-PbO, Li2O-Bi2O3, NaOH, NaCl, NaNO3, NaSO4, NaBr, Na2CO3, KOH, KCl, K A mixture of any one or more members selected from the group consisting of NO3, KSO4, KBr, and K2CO3. include.

[0262] The flux contains a eutectic mixture of materials, where the eutectic mixture is composed of the components of the mixture. It has a melting point lower than either of the following. For example, a mixture having LiOH at 0.3 and NaOH at 0.7. The mixture melts at around 250°C, which is lower than the melting point of either LiOH or NaOH.

[0263] In some examples, the powder, flux, and reaction mixture are used as current collectors, positive electrodes, and negative electrodes. Alternatively, deposit it in an electrolyte.

[0264] In some cases, to dissolve the synthesized powders of this specification in the flux components Next, the powder is mixed with the flux component. These fluxes, which have the dissolved powder, are used as a base. The material is cast onto a plate to form a film with a thickness of approximately 10 nm to approximately 250 μm. In some examples, The casting onto the substrate is done by slot casting, doctor blade casting, or by flattening the substrate. This is achieved by immersion coating in the material.

[0265] In some other examples, the compound specified herein is used to prepare slurries of these components. The resulting powder is mixed with the flux component and also with a liquid or solvent. Then the slurry - is cast onto a substrate to form a film with a thickness of approximately 10 nm to approximately 250 μm. Several examples In this process, casting onto the substrate is done by slot casting, doctor blade casting, or by substrate This is achieved by dipping and coating the flux. The slurry is then dried. Remove the solvent, and optionally melt and mix the flux components and powder. Some examples In this process, heating is performed at a rate of 1°C / min, to approximately 200°C, or approximately 250°C, or approximately 300°C, or approximately 350°C, Temperatures of approximately 350°C, 400°C, 450°C, or 500°C can be achieved. Some examples In order to completely dissolve the powder in the flux, more than the synthesized powder is used. Use flux. In other examples, not all of the powder in the flux dissolves. Therefore, use more synthesized powder than flux.

[0266] In some cases, the cathode active material is mixed with garnet powder, and the flux component is also mixed with garnet powder. Mix to form a mixture. Apply this mixture to one, two, or more current collectors. It can be deposited on the sides. The flux is treated as described herein, and optional When removed, the tight mixture of garnet material and active material is in direct contact with the current collector. To remain there.

[0267] In any of these examples, the substrate, for example, the current collector, is garnet, garnet front By immersion coating a flux containing a deterrent, an active material, or a combination thereof, A garnet material containing a positive electrode active material can be applied to the substrate. In any of the examples, the substrate, for example, the current collector, contains garnet, garnet precursor, active By casting a flux containing a material, or a combination thereof, a positive electrode is formed on the substrate. Garnet materials containing any active material can be coated. In these examples, flow En can be Dr. Blade Ryuen. In these examples, Ryuen is Slot It can be a casting process. In these examples, the casting can be a dip coating process. .

[0268] In some examples, the methods described herein involve using a lithium-conducting ceramic powder material of 1 or more To provide the above flux material in a eutectic mixture; the mixture at a temperature of about 400°C to about 800°C. To heat; optionally, to cast the flux material; and high-density lithium conductive gas - Includes forming a net material. In some examples, the formed material is It is more than 20% denser than the precursor. In some cases, the first flux is LiO One or more materials selected from H, LiCl, LiBr, LiNO3, LiSO4, or combinations thereof. The second flux is NaOH, NaCl, NaNO3, NaSO3, NaSO4, NaBr, Na2CO3, or a combination thereof. Two flux materials are used, which are one or more materials selected from the combination. In one example, the powder material is lithium-filled garnet. In some examples, the The powder material optionally includes a perovskite material. In some examples, the powder material is Includes NASICON, LISICON, or tungsten / bronze material. In some examples, the third F Lux is provided in this manner, selected from KOH, KCl, KNO3, KSO4, KBr, and / or K2CO3. It is one or more materials.

[0269] Further details, examples, and embodiments of these methods for producing garnet material can be found, for example, The contents thereof are incorporated fully herein by reference for all purposes, 2013. A patent application filed on October 7th concerns a method for forming garnet material using a sintering process and a cis Titled "Method and System for Forming Garnet Materials with Sintering Process" This is found in U.S. Provisional Patent Application No. 61 / 887,451.

[0270] As shown in Figure 1, in some examples, the precursor material is optionally pulverized and mixed with the flux. The mixture is combined (step a) and heated to dissolve the precursor in the flux (step b). The flux containing the substance is cast (step c), calcined (step d), and the precursor is reacted to further The particles are made larger and more crystalline (step e), and then densified with flux. In that example, the flux is removed (step f).

[0271] (b. Solutions and slurries) In some examples, the methods herein involve casting or depositing a solution and a saturates onto a substrate. This includes the use of rallies. In one example, the garnet precursor is the powder described herein. The materials are ground according to the grinding method. In some examples, these precursors are formulated into a slurry. To formulate. In some cases, these pulverized precursors are formulated into a slurry. After grinding, in some examples, the precursor is used in a coating formulation, such as a binder and a solvent. Formulation into a slurry containing these. These slurries and formulations, solvent, binder, dispersant, and surfactants. In some examples, the binder is polyvinyl butyral (PVB). The solvent is toluene and / or ethanol and / or diacetone alcohol. In some examples, PVB acts as both a binder and a dispersant. As binders, PVB, PVP, ethylcellulose, cellulose, PVA, and PVDF are also used. Examples include surfactants, fish oil, and fluorinated interfaces used as dispersants. Examples include activators, Triton, PVB, and PVP. In some slurries, 10% to 60% are used. The slurry is a solid precursor in a quantity of % (w / w). The binder and dispersant are each several In the slurry, the solvent can account for 50% w / w of the slurry, and the remaining weight percent Includes vintage.

[0272] In some examples disclosed herein, the slurry contains a conductive additive which is carbon. Includes. In one embodiment, carbon is Ketjenblack, VGCF, acetylene black. , graphite, graphene, nanotubes, nanofibers, and combinations thereof It is a member selected from the group consisting of the following. In one embodiment, carbon is Ketchembr It is a rack. In one other embodiment, carbon is VGCF. In yet another embodiment, In one embodiment, carbon is acetylene black. In another embodiment, carbon is graphite. Yes. In some embodiments, carbon is graphene. In other embodiments, In another embodiment, carbon is in the form of nanotubes.

[0273] In some examples, the solvent is toluene, ethanol, toluene:ethanol, or A selection is made from these combinations. In one embodiment disclosed herein, the binder - is polyvinyl butyral (PVB). In one embodiment disclosed herein, The binder is polypropylene carbonate. In one embodiment disclosed herein In this case, the binder is polymethyl methacrylate.

[0274] In some examples, the solvent is toluene, ethanol, toluene:ethanol, or These are the combinations. In some cases, the binder is polyvinyl butyral (PVB). ) In other examples, the binder is polypropylene carbonate. In this example, the binder is polymethyl methacrylate.

[0275] In some embodiments disclosed herein, removing the solvent involves vaporizing the solvent. This includes causing emission. In some of these embodiments, the solvent is removed. This includes heating the film. In some embodiments, removing the reducing atmosphere This includes using air. In other embodiments, removal is done using a vacuum. This includes expelling the solvent. In yet another embodiment, removal involves heating the film. This includes using a vacuum to expel the solvent.

[0276] (c. Cassolite) As shown in Figure 25, one method for producing an embodiment of the invention disclosed herein is A This includes depositing a high-density solid separator electrolyte for the node and optionally sintering the electrolyte. In some embodiments, the method involves depositing porous garnet castholite, This also includes sintering the catholite to achieve a porosity of more than 70%. In some embodiments... In this method, the method is selected from chemical vapor deposition (CVD), pyrolysis, or related technologies. This includes filling porous castholite with less than 10% by volume of carbon. In this method, a porous catholite is subjected to ion transfer of a liquid, gel, or polymer. This also includes filling with conductive fluid material. In some embodiments, the method involves an active material This also includes filling with material. In one embodiment, the method involves loading more than 40 volume percent of active material. Achieves quantity. In some embodiments, the method involves stacking cathode current collectors or steaming. This includes dressing them.

[0277] In some embodiments, the following are disclosed herein: A method for manufacturing, comprising the following steps: providing an anode layer including an anode current collector; and A garnet-type solid electrolyte (SSE) layer is provided in contact with at least one side of the node layer, The process involves sintering the SSE; providing a porous garnet layer in contact with the SSE layer; optionally, A step of sintering the porous garnet layer; optionally, carbon, lithium A small number of conductive polymers, active cathode materials, and combinations thereof, selected from the group. A process of impregnating at least one component; and a cathode collection in contact with the porous garnet layer. A method comprising the steps of providing an electrochemical layer in any order. In some examples, these The steps are carried out sequentially in the order they are listed.

[0278] In some examples, the methods described herein involve garnet-type solid electrolytes (SSEs). The further includes providing the layer to two independent sides of the anode current collector layer.

[0279] In some cases, sintering includes thermal sintering or electric field-assisted sintering (FAST). Here, heat sintering involves heating the garnet at a temperature range of approximately 800°C to 1200°C for approximately 1 to 600 minutes. The process involves heating and fast sintering the garnet in the range of approximately 600°C to approximately 800°C. This includes heating and applying a DC or AC electric field to the garnet.

[0280] In some cases, impregnating porous garnet layers with carbon is a chemical vapor deposition method. This includes using (CVD) or thermal decomposition.

[0281] In some cases, impregnating a porous garnet layer with an active material involves vapor / liquid This includes using body deposition or electrophoretic deposition.

[0282] In some examples, to provide a cathode current collector in contact with a porous garnet layer. This involves laminating the current collector onto a porous garnet layer, electroplating it, or vapor-depositing it. include.

[0283] In some cases, the porous garnet layer, after it is sintered, is less than [a certain amount] by volume. It is also 70% porous.

[0284] In some examples, the porous garnet layer exhibits a Li conductivity of 1e-3S / cm or higher at 60°C. In some cases, lithium-conducting polymers exhibit a Li conductivity of 1e-4 S / cm or higher at 60°C. The material described herein is characterized by a Li conductivity of 1e-4 S / cm or higher at 60°C. In the example, the conductivity is a measured value of bulk conductivity. In this case, the conductivity is such that conduction occurs in the material but is not affected by the porosity of the material. It is measured in this way.

[0285] In some examples, the porous garnet layer has an average pore diameter of approximately 5 nm to 1 μm. It has a hole for doing so.

[0286] In some cases, the polymer is stable at voltages above approximately 3.8V.

[0287] In some cases, the porous garnet layer is approximately σ at 60°C. i Conductivity of >1e-3S / cm To use as a sign.

[0288] In some cases, the porous garnet layer contains more than 40% by volume of activated cathode material. The material is impregnated. In some cases, more than 55% by volume of the porous garnet layer is impregnated. The activated cathode material is impregnated.

[0289] In some cases, the garnet is stable at voltages ranging from approximately 1.3V to approximately 4.5V.

[0290] In some cases, the garnet is Li A La B M' c M'' D Zr E O F Li A La B M' C M'' D Ta E O F , Li A La B M' C M'' D Nb E O F (Here, 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, in each case, independently Al, Mo, W, Nb, Sb, Ca, Ba, Sr (Selected from Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me'' e O f (Here, 5 <a<7 .7; 2 <b<4; 0<c≦2.5; 0≦d<2; 0≦e<2、10<f<13であり、Me''は、Nb、Ta、V、W The material is selected from metals selected from Mo or Sb.

[0291] In some examples, the active electrode material is NCA (Lithium Nickel Cobalt Aluminum). Lithium oxide, LMNO (lithium manganese nickel oxide), LCO (lithium cobalt oxide, In other words, LiCoO2, NMC, nickel fluoride (NiF x (where x is 0 to 2.5), copper fluoride (Cu F y (where y is between 0 and 2.5), or FeF z (Here, z is selected from 0 to 3.5) It is a cathode material.

[0292] In some cases, what is disclosed herein is by the method described herein. It is an electrochemical device manufactured by [unspecified method].

[0293] As shown in Figures 27 and 29, in this specification, the electrolyte particles are used before the sintering process. This describes the process for manufacturing composite electrodes for solid-state batteries, which are composed of active electrode materials with scattered particles. It is described. In some embodiments, the layer contains a conductive additive (e.g., carbon). It is also possible.

[0294] As shown in Figure 31, the electrolyte and electrode materials have improved interfacial contact after sintering. It has. In some embodiments, a self-supporting double or triple layer as described herein The garnet film is bonded to lithium. The Li-garnet interface in these examples is as expected. It has a low specific area resistance (ASR) externally. In some examples, the ASR is 5 ohms cm at 80°C. 2 Not yet It is full. In some cases, the ASR is 100 ohms / cm at 80°C. 2 Less than several. In the example, the ASR is approximately 1 ohm cm at 80°C. 2 In some cases, ASR is at 80°C. 6 ohms cm 2 It is less than.

[0295] In some embodiments, Li is used in a sintered garnet film (a self-supporting double or triple layer). It is deposited or laminated and has a low ASR. In some examples, the ASR is 5 ohms cm at 80°C. 2 It is less than . In some cases, the ASR is 100 ohms / cm at 80°C. 2 Less than. Several In this example, the ASR is approximately 1 ohm cm at 80°C. 2 In some cases, the ASR is 80°C. 6 ohms cm 2 It is less than.

[0296] As shown in Figures 15, 16, 17, 20, 21, and 28, using a setter plate, In some examples, AC current can be applied, and in some other examples, DC current can be applied. By using a power supply device, the particles can be sintered.

[0297] As shown in Figure 4, an electrochemical device is manufactured by the sintering method described herein. This is possible. In Figure 4, for example, electrolyte powder, cassolite particles (for example, garnet Tocasolite, and active electrode particles (e.g., cathode active particles) are layered and mixed, The material can then be sintered according to the novel method described herein.

[0298] In some examples, the films described herein are made using an organic binder-solvent system (e.g., Toluene:Polyvinyl butyral in ethanol) is used to create powdered ceramic components (multiple components are possible) ( For example, electrolyte: lithium-filled garnet, lithium lanthanum, zirconium oxide; electrode: By manufacturing a slurry of lithium-nickel-manganese-cobalt oxide, " It can be initially formed in a "lean" (unsintered) state. In some examples of composite electrodes... In addition to the electrolyte and active electrode material, conductive additives such as carbon black are added. This can also increase the electrical conductivity in the final product. The slurry is typically 10-100 μm thick. It can be cast as a thin layer of varying thickness. The solvent is evaporated, leaving a flexible film behind. This film is easy to handle and can be processed at a moderate temperature (80°C) and low pressure (<1000 psi). By doing so, it can be laminated onto other such layers. For example, Li conductive garnet Green composite thin films of electrolyte and high-voltage cathode material (NMC) are shown, for example, in Figure 27. Yes, they are.

[0299] Some of the examples of methods described herein include thermal sintering.

[0300] In some cases, after a binder burn-out process to remove the binder (e.g., PVB) The composite electrode, for example, the composite electrode shown in Figure 27, is heated to a high temperature (for example, 800-1200°C). By holding it for a certain period (1 to 600 minutes), the particles are sintered, resulting in a much higher density matrix. It is possible to form a compound. In some of these examples, the compound of individual components The crystal grains fuse together, significantly increasing their contact area, as shown in Figure 27, for example. In some cases, it is advantageous to use finely ground powder, especially as an electrolyte component. Yes, because this increases the sintering reaction rate, allowing for densification at lower temperatures. Therefore, in order to maintain the flatness of the thin film under this process, the film is made of porous zirconium. It can be sandwiched between inert setter plates such as Nia. This allows the film to be maintained in layers. Not only is it maintained, but a release pathway for binder degradation products is also provided. The microstructure of the sintered electrode composite material is shown, for example, in Figures 30 and 31.

[0301] Some of the examples of methods described herein are electric field-assisted sintering (i.e., FAST sintering). This includes concluding a relationship.

[0302] One drawback of conventional sintering processes is that they can produce several harmful phenomena at high temperatures. This requires a long dwell time. For example, lithium is a highly volatile species. It evaporates from the solid electrolyte material, thereby reducing its ionic conductivity and creating a surface with high resistance. This can induce a depleted layer or even cause material decomposition. In the case of composite layers, once the crystal grains are depleted... Once they fuse, the electrolyte and electrode components will continue to interact with each other, and they will become individual The components can interdiffuse to such an extent that their electrochemical properties are lost, that is, electrolytes can ionize The ability to lose conductivity, or the properties of electrodes to store active ions (e.g., lithium). This can lead to losses. Therefore, to overcome all these problems, the sintering process is made possible. It is advantageous to make it as fast as possible. In some cases, this involves using electric field-assisted sintering. It will be achieved.

[0303] Figures 16, 17, 18, 19, 20, 21, and 22 show conventional sintered prostheses disclosed herein. Temperatures lower than 1100°C (e.g., 600-800°C or less) or (400-1000°C) A schematic diagram of the arrangement for fast sintering the electrolyte film at °C is shown. The film is sintered between two conductive metal plates. While sandwiched between the plates, bake in the oven at a moderate temperature (800°C) where lithium evaporation is not significant. Hold it in place. Then, apply an electric field to the sample to induce fast sintering. The electric field is a DC electric field or This can be an AC electric field. In some cases, ion species are greatly separated under stimulation. Since a sufficiently high frequency can be selected to prevent separation, an AC electric field is advantageous. The power supply to the sample must be controlled to avoid excessive Joule heating of the material. In some cases, this is done by initially operating in constant voltage amplitude mode, and sintering begins, and the sample This can be achieved by switching to a constant current when the impedance drops. The dissolved film is sintered to achieve full density in a much shorter time and at a lower temperature than conventional processes. It can be sintered.

[0304] In some cases, FAST sintering also overcomes the problem of interdiffusion in the composite electrode layer. Figure 29 shows a schematic diagram of the arrangement of a complete solid-state battery configuration under FAST sintering. Before sintering, the electrolyte The layers are stacked onto the composite electrode layer. The advantage of the FAST sintering process is that the voltage drop (i.e., the electric field) is... It is preferred over the high-impedance region, which is always a region with poor contact (i.e., a non-burned region). The distribution is such that when two types of particles are sintered and joined together, the contact between the constituent particles The contact improves, and the resistance decreases. As a result, the electric field distribution shifts to adjacent unsintered particles. Thus, the driving force for sintering moves away from the already fused and joined crystal grains, and further phases Interdiffusion is restricted.

[0305] These sintering methods offer fast sintering times, limited interdiffusion between components in the composite electrode, and Furthermore, due to the ability to provide a complete solid-state battery configuration, solid-state batteries that do not contain liquid electrolytes and This is advantageous for the components of bison.

[0306] (d. Doped composition) In some examples, provided herein are aluminum-doped lithium A method for producing um-filled garnet, comprising providing garnet precursors in a predetermined combination. The method includes performing the combination for 5 to 10 hours. In some examples, the method involves performing the combination for 5 to 10 hours. The method further includes grinding. In other examples, the method involves heating the combination in a container at about 500°C. This further includes calcining at approximately 1200°C for approximately 4 to 10 hours to form garnet. In the example, the method involves d 50 Grind until the particle size is 200-400 nm. This further includes the following: In other examples, the method involves crushing the formed garnet into a This further includes mixing with an inder to form a slurry. In this method, before sintering the slurry, the slurry is cast as a film. The method includes providing a green film by means of the slurry. In other examples, the method includes the slurry The method further includes filtering the filtered slurry. In other examples, the method may optionally include filtering the slurry. Further includes providing Lee pellets. In some of these examples, Before sintering the slurry, the method involves casting the slurry to produce a green film. This includes providing. In other examples, the method involves sintering the filtered slurry. This further includes the following. In an example of sintering the slurry, sintering is performed by setting the Apply pressure to the slurry using a tweezers, and then heat the slurry under a flowing inert gas at 140°C. Heat at ~400°C for approximately 1 to 6 hours, and then heat sinter or electric field assisted sinter for approximately 10 minutes to 10 hours. This includes doing so.

[0307] In one example, the garnet precursor was derived from LiOH, La2O3, ZrO2, and Al(NO3)3.9H2O. Selected.

[0308] In some cases, the garnet precursor is calcined in a container at 900°C for 6 hours. In this example, the container is an alumina (i.e., Al2O3) container.

[0309] In one example, crushing the formed garnet is a way of... d 50 This process is carried out until the particle size reaches approximately 300 nm. In another example, the formed garnet is powdered Crushing the formed garnet 50 This process is carried out until the particle size reaches approximately 100 nm. In that example, crushing the formed garnet is the d5 of the formed garnet. This process is carried out until the particle size reaches approximately 200 nm. In one example, the formed garnet is crushed. This means that the formed garnet d 50 This process is carried out until the particle size reaches approximately 250 nm. In one example, Therefore, crushing the formed garnet is the d of the formed garnet 50 Particle size is approximately 350 This is done until the size reaches nm. In one example, crushing the garnet is done to form the garnet - Net's d 50 This process continues until the particle size reaches approximately 400 nm.

[0310] In some cases, the crushed garnet is mixed with a binder to form a slurry. Forming it contains approximately 4% w / w of binder. In some examples, the binder It is polyvinyl butyral.

[0311] In some cases, filtration of the slurry is performed using an 80-mesh sieve. This includes doing so.

[0312] In some cases, providing filtered slurry pellets is possible with a diameter of 13 mm. The invention includes providing pellets having 10 mm, It has a diameter of 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm, or 20mm.

[0313] In some cases, applying pressure to the slurry using a setting plate is , including applying a pressure of 3 metric tons. In some other examples, setting Applying pressure to a slurry using a plate means applying a pressure of 2 metric tons. Includes. In some cases, pressure is applied to the slurry using a setting plate. This includes applying a pressure of 1 metric ton. In some examples, setting Applying pressure to a slurry using a plate means applying a pressure of 3.5 metric tons. Includes.

[0314] In some examples, the setter plate is a Pt setter plate. In other examples... And the setter plate is a garnet setter plate. In one example, the setter plate The setter plate is a porous setter plate. In other examples, the setter plate The setter plate is a porous garnet setter plate. In yet another example, the setter plate The plate is a porous zirconia setter plate.

[0315] In some examples, the method involves the flow of argon gas at a flow rate of 315 sccm. Contains inert gas.

[0316] In some examples, the methods described herein involve a slurry under flowing inert gas. This involves heating, which is done separately under a humidified argon flow at 160°C and 330°C for 2 hours (hr), respectively. This includes all the Doel.

[0317] (e. Microcrystalline lithium-filled garnet) In some examples, provided herein are alumina-doped lithium This is a method for fabricating thin films using microcrystalline grains of packed garnet. In some examples... To produce these microcrystalline grains, the film described herein is heated at a maximum temperature of 1150°C. Sintering is performed. In some examples, to produce these microcrystalline grains, as described herein The film to be treated is thermally sintered at a maximum temperature of 1150°C for a time of 6 hours or less. In some examples, To produce these microcrystalline grains, the film described herein is heat-sintered at a maximum temperature of 1075°C. In some examples, to produce these microcrystalline grains, the methods described herein are used. The film is heat-sintered at a maximum temperature of 1075°C for a time of 6 hours or less. In one example, the film is sintered for 15 minutes. If sintering does not occur, a maximum thermal sintering temperature of 1200°C is used.

[0318] As the temperature rises, the crystal grains grow larger. Also, at a given temperature, As the plant grows larger, the dwell time at that temperature increases. Therefore, this specification The method described herein involves heat sintering at a temperature of less than 1200°C, less than 1150°C, or less than 1075°C. This includes the following. In some of these examples, the methods described herein are This includes thermal sintering at the specified temperature for a time of 6 hours or less. In some examples, this specification The described method includes heating and sintering for a time of 15 minutes or less. In some other examples... The methods described herein include thermal sintering at 1050°C. Several other examples include The methods described herein include thermal sintering at 1000°C. Some other examples In this specification, the method includes thermal sintering at 950°C. In the example, the method described herein includes thermal sintering at 900°C. In other examples, the methods described herein include thermal sintering at 850°C. In several other examples, the methods described herein include thermal sintering at 800°C. In some other examples, the methods described herein include thermal sintering at 750°C. In some other examples, the methods described herein involve heat sintering at 700°C. This includes, in some other examples, the methods described herein involve heat sintering at 650°C. This includes, in some other examples, the methods described herein involve thermal sintering at 600°C. This includes, in some other examples, the methods described herein involve heating at 550°C. This includes sintering. In some other examples, the methods described herein are performed at 500°C This includes thermal sintering. In some other examples, the methods described herein are 45 This includes thermal sintering at 0°C. In some other examples, the method described herein , including heat sintering at 400°C. In some other examples, as described herein. The method involves thermal sintering at 350°C. In several other examples described herein, The method includes thermal sintering at 300°C. Several other examples are described herein. The method involves thermal sintering at 250°C. In some other examples, as specified herein The method described includes thermal sintering at 200°C. In some other examples, this specification The method described in this document includes thermal sintering at 150°C.

[0319] In some examples, a smaller amount of Li in lithium-filled garnet is specified herein. This results in fewer crystal grains in the described film.

[0320] (f. Ryuen) In some examples, the slurry described herein is dispensed using a slot die, slot Drafting, doctor blade casting, mold casting, roll coating, gravure, microgravure A. Using casting techniques including screen printing, flexographic printing, and / or other related methods, It is deposited onto the substrate.

[0321] Another casting method is the sintering process used to produce garnet material, as filed on October 7, 2013. Method and system for forming garnet materials with U.S. Provisional Patent Application No. 61 / 887,451, entitled "SINTERING PROCESS," filed on January 13, 2014. A provisional U.S. patent application titled "Garnet Thin Film Electrolyte" was filed. Patent No. 61 / 926,910, filed on June 4, 2014, describes the formation of garnet material by reaction sintering. Methods and systems for forming garnet material with RE U.S. Provisional Patent Application No. 62 / 007,417, entitled ACTIVE SINTERING, filed on July 18, 2014 Fine-grained lithium-ion conductive thin film garnet ceramics U.S. Provisional Patent Application No. 62 / 026,271, entitled "IUM-ION CONDUCTING THIN FILM GARNET CERAMICS" The patent application, filed on July 18, 2014, for garnet catholite and solid-state electrochemical devices. Garnet CATHOLYTE AND SINTERING OF SOLID STATE ELECTROCHEMICAL D This is described in U.S. Provisional Patent Application No. 62 / 026,440, titled "EVICES AND COMPONENTS". Each of these provisional patent applications is incorporated fully herein by reference for any purpose. It can be done.

[0322] (g. Sintering method) Certain solid ion conductors are subjected to pressure on small pellets with a diameter of approximately 10 mm and a thickness of 2 mm. By doing so, sintering can be performed using conventional processes, but thin films of garnet-based materials The known fabrication method requires a film width of approximately 10 cm and a thickness of 100 nm to 50 μm for battery applications. It is insufficient for that purpose.

[0323] Using applied current and applied voltage, thin films, particularly garnet (e.g., lithium-filled garnet), are processed. Sintering films containing a net is inherently difficult. One reason is that the current is gar As it flows through the net material, resistance heating occurs within it, resulting in a sintering effect. Related. For example, sintering garnet using electricity, similar to how it is done in fast sintering. Electricity is used to resistively heat and sinter the garnet material, which has the highest impedance. As the garnet is sintered and its impedance decreases, the current passing through the garnet The associated resistive heat also decreases. The impedance decreases in certain parts of the garnet material. The current that flows is mainly through the path with the least resistance (i.e., the path with the least impedance). Therefore, the unsintered portion of the garnet, which has a significantly higher impedance, is not resistively heated. As more garnet sinters and the impedance decreases, the remaining garnet It becomes more difficult to sinter the unsintered parts, and at the location where the impedance is highest, The garnet portion, where impedance is minimized, makes it particularly difficult.

[0324] To overcome this difficulty, cylindrical shape elements, such as the elements shown in Figure 15, are used. Some people do this. They move the applied current between spaced electrodes located at the very ends of the cylinder in the longitudinal direction. By doing so, these people overcome the aforementioned difficulties. This is because electric current is sintered This is because it passes through the longest part of the material. However, in this specification and in this patent application For some of the applications being considered, thin-film shape elements are required. In some examples, this shape element is rectangular in its shape. In the example, this shape element is rectangular in its shape. These films, thin films, and Rectangular-shaped elements are difficult to sinter, partly because they are electrodes to which current is applied. However, this is because the longest part of the film sample does not conduct electricity. For thin films, the applied current is It follows the z-direction of the film, which is one of the shorter paths through the bulk material.

[0325] In addition to the aforementioned difficulties, for many applications, thin films are primarily oriented in the x-direction or y-direction, rather than in the x-direction or y-direction. It is preferable to densify in the z-direction (as shown in Figure 23). This is because the film shrinkage mainly occurs in the z-direction. This means that it is greater than what occurs in either the x-direction or the y-direction. Achieving densification and shrinkage is also a difficulty addressed by this application. This document describes several sintering methods that overcome these and other sintering difficulties.

[0326] As shown in Figure 24 or Figure 45, an example sintering method is such that the applied current passes through the z-direction of the film. This includes arranging electrodes on thin-film shape elements. In this regard, FAST sintering is described herein. It is used according to the sintering method described.

[0327] As shown in Figure 16, another example of a sintering method involves the use of a sintering plate. In the example, the applied current passes through the sintered plate. In some other examples, the applied current is While passing through the sintered plate, pressure is applied according to the pressure values ​​listed herein and above. In another example, while the applied current is directly applied to the thin film, the setter plate Independently, pressure is applied according to the pressure values ​​listed herein and above. In other examples, one or more metal foil layers are inserted between the setter plate and the thin film, and applied The current is applied to the inserted metal foil. Figure 20 shows the metal foil connecting the sintered film and the setter plate. This shows an example of something being placed in between.

[0328] In some cases, the metal powder is sintered with a setter plate to form a garnet film. It is inserted between them. In some of these examples, the garnet film is sintered Consequently, the metal powder also sinters with the film during sintering and adheres to it. Figure 21 shows the metal powder settling with the sintered film. This shows an example of placement between plates.

[0329] In some of these examples, the setter plate is a porous setter plate. In some of these examples, the setter plate is a garnet-based setter. It is a setter plate. In some of these examples, the setter plate is porous. These are setter plates of the garnet type. In some of these examples, the setter - The plate is a metal setter plate. Garnet As a setter plate, a setter plate containing the garnet material described herein One example is [this].

[0330] As shown in Figure 17, in some examples, pressure is applied to sinter and optionally to sinter. The plate used is designed so that the applied current is directed to a specific location on the film during sintering. It can have individually addressable contact points. As shown in Figure 17, multiple trapezoids The tapered ends of the (100) shape indicate these individually addressable contact points. As used herein, individually addressable means controllable to a different contact point. A single contact point that may differ from the applied current or voltage, with controllable and individual current or voltage. It refers to the ability to apply to each.

[0331] In some examples, a press used for sintering and optionally applying pressure The grid can have a grid structure. In some examples, this grid structure This means that it can be placed on the sintering film at various positions during the sintering process. The sea urchin is movable.

[0332] As shown in Figure 18, in some examples, the thin film shape element is that it is a calendar row It is sintered while moving through the roller. In these examples, the calendar roller is described in this specification Apply pressure according to the pressure value specified in the manual, and sinter, for example, the applied current required for fast sintering or It also provides a conduit for the applied voltage. In Figure 18, the large, uncircled area parallel to the x-direction of the film. The arrows indicate the direction of movement of the film as it moves through the calender roller during sintering. It is.

[0333] As shown in Figure 19, an example in which a thin film shape element is sintered while moving through a calender roller. In some of these, the calendar roller is subjected to current or voltage at various positions during sintering. Individually addressable contacts that can be applied to the film in a controllable and individual manner. It has a contact point (200).

[0334] As shown in Figure 19, an example in which a thin film shape element is sintered while moving through a calender roller. In some of these designs, one of the calendar rollers is the ground electrode.

[0335] As shown in Figure 22, an example in which a thin film shape element is sintered while moving through a calender roller. In some of these, one of the calendar rollers rotates around its vertical axis, This spiral design allows movement parallel to the vertical axis. This allows the applied current or voltage to be directed towards the film during sintering.

[0336] (i. Reaction sintering) In some examples, the method described herein is reaction sintering. In these examples, the garnet precursor is mixed in to form a mixture. Examples of precursors include the garnet precursors described in this patent application. In the example, the mixture is ground according to the grinding method described in this patent application. In this example, the mixture is formulated as a slurry of pulverized precursor materials, and the slurry is To form. In some cases, the slurry is then used, but not limited to, by a doctor. It is applied to the substrate by methods such as blade casting, slot casting, or immersion coating. In several other examples, the slurry is cast to a substrate according to the casting method described in this patent application. Cast onto the surface. In some of these examples, the slurry is then dried. Then, remove the solvent or liquid from it. In some examples, the dried slurry is treated with karene. Process the slurry. In some further examples, the dried slurry is applied to other layers of the battery components. Laminate. In some of these examples, pressure is applied to bond the laminated layers together. They are bonded. In one example, a dry slurry layer to which pressure is applied is described herein. Sintering is performed according to the method. Sintering is performed in the form of a slurry or dried slurry. In examples where a garnet precursor is used, sintering is a chemical reaction of the garnet precursor. This occurs simultaneously, leading to the formation of sintered garnet.

[0337] In some cases, reaction sintering transforms garnet precursors into pre-formed garnets. This includes mixing with powder and sintering the mixture using temperature and / or applied current. In some cases, the ratio of garnet precursor to garnet powder is 10:90. In some cases, the ratio of garnet precursor to garnet powder is 20:80. In some cases, the ratio of garnet precursor to garnet powder is 25:75. In some examples, the ratio of garnet precursor to garnet powder is 50:50. In one example, the ratio of garnet precursor to garnet powder is 60:40. In that example, the ratio of garnet precursor to garnet powder is 70:30. In this example, the ratio of garnet precursor to garnet powder is 75:25. In the example, the ratio of garnet precursor to garnet powder is 80:20. Several examples In this study, the ratio of garnet precursor to garnet powder is 90:10.

[0338] (ii. Tape leakage) In some examples, tape casting for producing thin films is described herein. This is the method. In these methods, ceramic powder is mixed with a dissolved binder and optionally separated The powder is dispersed in a liquid or solvent to form a homogeneous mixture. A fine mixture or "slip" is cast onto a substrate using a doctor blade casting method. In some cases, the substrate is, but is not limited to, a silicone-coated MYLAR or similar material. This is an anti-adhesion substrate. Afterwards, the liquid or solvent is evaporated to form a dried "green film". To accomplish. In some cases, the green film is peeled off from MYLAR and into a specific shape, for example. Then, cut into square, rectangular, circular, or oval shapes. In this method, the thickness is 0.1 to 200 μm. A film is manufactured. Metal powder is optionally incorporated into the film or adhered to one side of the film. This is possible. In these examples, the metal powder is a mixture of Ni, Cu, Ni-garnet, C A mixture of u-garnets, or a combination thereof, is selected. In some examples, Tape flow casting involves the use of an opening of approximately 1 to 100 μm, through which tape flow occurs during deposition. A postponement will be made.

[0339] (iii. Hot Press) In some examples, the following methods for producing thin garnet films are described herein. This is the top press method. In these examples, the green tape as described above is shown in Figure 4. The urchin is sintered by uniaxial pressure. In one example, after first removing the binder, the sintering is performed. In these specific examples, the binder is heated to a temperature of approximately 200, 300, 400, 500, or 600°C. By burning it at a certain temperature, the binder can be removed. In some cases... The film is heated to a sintering temperature of approximately 800°C to 1200°C under a uniaxial load pressure of approximately 10 to 100 MPa. Sintering is performed by doing so. In these examples, the applied pressure is such that the film deforms or reverses during sintering. To prevent this, and for sintering in the direction perpendicular to the film surface, and for producing high-density films. It provides the driving force.

[0340] In some cases, the green film is fired by first casting the film onto a metal foil. It can be bonded. In some cases, sintering is performed after burning off the binder. In some of these examples, sintering is the process of forming a film under pressure on a metal foil substrate. or includes heating to a temperature lower than the melting points of multiple metals. Therefore, using a Ni substrate When using this method, a higher sintering temperature can be used compared to when using a Cu substrate. can.

[0341] (iv. Constrained Sintering) In some cases, the green film is placed between the setter plates. Therefore, it can be sintered, but even applying a small amount of pressure will restrain the film and sinter it. By applying stress to the membrane between the processes, it is possible to prevent the heterogeneity that causes it to warp. These examples In some of these, setter plates are porous, such as porous yttria. It is beneficial to fabricate stabilized zirconia. These porous pre- The process diffuses the binder from the film during the burning or sintering process. Among these examples... In some cases, the burning process and the sintering process are performed, for example, on these porous setter plates It can be achieved simultaneously, indirectly. In some cases, a small amount of pressure is used for burning. During the bonding process, no further external pressure is applied, and the material is placed on top of the green film. This is the pressure applied by the weight of the setter plate. In some examples... Constrained sintering is carried out substantially as shown in Figures 4 and / or 5.

[0342] (v. Vacuum sintering) In some cases, sintering is performed as described above, however, during sintering in a vacuum chamber This is done using a film. In this example, a vacuum is provided to trap the material within the ceramics during sintering. The trapped gas is expelled. In some of these examples, trapped gas is trapped within the ceramics. The gas trapped inside can prevent the ceramics from densifying beyond a certain point during sintering, creating pore spaces. By applying pressure inside, further sintering of the ceramics is prevented. Using a vacuum system By removing the trapped gas, the pores that contained the gas are sintered, and the vacuum system To make it more granular than would be possible if the trapped gas were not expelled. It is possible.

[0343] (vi. Electric field-assisted sintering, flash sintering, and fast sintering) Electric field-assisted sintering (FAST) technology can increase the sintering reaction rate. As a result, electrons, holes, and / or ions move within the sintered material, and thereafter, the material The material is heated by Joule heating. Heating is performed at the point where the resistance is maximum (P=I 2 R, here, I (where R is the current and R is the resistance) is concentrated at this point in the particle-particle neck. There is a tendency for this to happen. These locations are precisely where sintering is desirable, so FAST sintering is particularly effective. It can be effective. The standard garnet sintering procedure, in some examples, is 1050-1200°C. This can take 6 to 36 hours. In contrast, FAST sintering of garnet takes less than 5 minutes at 600°C. It can be carried out. The advantages are lower-cost processing (higher throughput), lower reactivity ( at lower temperatures, garnet is less likely to react with other components), and less lithium loss (lithium evaporation is a major failure mode that hinders effective sintering). FAST sintering of garnet is most effective at low current and short time [inserted data]. Since garnet materials have high ionic conductivity, a low current is preferred, similar to AC current, so that bulk transport of ions does not occur. The parameters are: 1 minute < time < 1 hour, 500 < temperature < 1050 °C, 1 Hz < frequency < 1 MHz, 1 V < VAC rms < 20 V. In some examples, FAST sintering is combined with hot pressing that includes uniaxially pressing the film during sintering. In some examples, FAST sintering is combined with hot pressing onto a permanent substrate, such as a metal, such as a current collector. In some examples, FAST sintering is combined with constrained sintering that fixes or physically constrains the film without applying a significant amount of pressure. In some examples, FAST sintering is combined with two-layer sintering (and three-layer sintering, such as electrolyte-metal-electrolyte) to provide mechanical support and

[0344] simultaneously form the current collector in one step. In some examples, FAST sintering is combined with vacuum sintering where sintering is performed under a low absolute pressure to promote pore removal. In some embodiments, what is disclosed herein is a method of making a thin film, the method including providing an unsintered thin film; If present in an unsintered thin film, this further includes removing the solvent. In some examples... The method optionally includes laminating a film onto a surface. In some examples, the method is If present in the membrane, the method includes removing the binder. In some examples, the method This includes sintering the film, where sintering is either thermal sintering or electric field-assisted sintering (FAST). This includes the process of thermal sintering the film, which is about 70 In the range of 0°C to approximately 1200°C, for approximately 1 to approximately 600 minutes, and 1 * 10 -1 ~1 * 10 -15 Oxygen partial pressure within a range of atmospheric pressure This includes heating in an atmosphere containing [unspecified element]. In other examples, fast sintering is used to sinter a film of about 500 [units of time]. This includes heating in the range of °C to approximately 900°C and applying a DC or AC electric field to the thin film.

[0345] In some embodiments, a method for preparing a film is disclosed herein. A method comprising providing an unsintered thin film; wherein the unsintered thin film is garnet Electrolytes, active electrode (e.g., cathode) materials, conductive additives, solvents, binders, and It includes at least one member selected from the group consisting of these combinations. The method further includes removing the solvent if it is present in an unsintered thin film. In some examples, the method optionally includes laminating a film onto a surface. The method includes removing the binder if present in the membrane. Several examples In this method, the method includes sintering the film, where sintering is thermal sintering. This includes the following. In some of these examples, thermal sintering is performed to form a film at approximately 700°C~ At a temperature range of approximately 1200°C, for approximately 1 to approximately 600 minutes, and 1 * 10 -1 ~1 * 10 -15 It has an oxygen partial pressure within the range of atmospheric pressure. This includes heating in a certain atmosphere.

[0346] In some embodiments, a method for preparing a film is disclosed herein. A method comprising providing an unsintered thin film; wherein the unsintered thin film is garnet It consists of type electrolytes, active electrode materials, conductive additives, solvents, binders, and combinations thereof. It includes at least one member selected from the group. In some examples, the method is not If present in a sintered thin film, this further includes removing the solvent. In some examples, The method optionally includes laminating a film onto a surface. In some examples, the method involves a film This includes removing the binder if present inside. In some examples, the method This includes sintering the film, where sintering includes electric field-assisted sintering (FAST). In some of these examples, fast sintering is performed in the range of approximately 500°C to approximately 900°C. This includes heating and applying a DC or AC electric field to the thin film.

[0347] In any of the methods described herein, the unsintered thin film is lithium-filled garnet It may contain an electrolyte or its precursor. In any of the methods described herein, The unsintered thin film may contain alumina-doped lithium-filled garnet electrolyte.

[0348] In any of the methods described herein, thermal sintering is performed to heat the film to approximately 400°C~ Approximately 1200°C; or approximately 500°C to approximately 1200°C; or approximately 900°C to approximately 1200°C; or approximately 1000°C to approximately 1200°C; or This may include heating in the range of approximately 1100°C to approximately 1200°C.

[0349] In any of the methods described herein, the method involves heating the membrane for about 1 to about 600 minutes. This may include: In any of the methods described herein, the method involves making a film about 20 This may include heating for approximately 600 minutes. In any of the methods described herein, The method may include heating the membrane for about 30 to about 600 minutes. In either case, the method may include heating the membrane for about 40 to about 600 minutes. In any of the methods described, the method involves heating the membrane for about 50 to about 600 minutes. May include. In any of the methods described herein, the method involves applying a film to about 60 to about 600 This may include heating for minutes. In any of the methods described herein, the method This may include heating the membrane for approximately 70 to 600 minutes. Any of the methods described herein. In this specification, the method may include heating the membrane for about 80 to about 600 minutes. In any of the methods, the method may include heating the film for about 90 to about 600 minutes. In any of the methods described herein, the method involves heating the membrane for about 100 to about 600 minutes. This may include: In any of the methods described herein, the method involves making a film about This may include heating for 120 to approximately 600 minutes, in any of the methods described herein. The method may include heating the membrane for about 140 to about 600 minutes. In any of the above, the method may include heating the membrane for about 160 to about 600 minutes. In any of the methods described in the book, the method involves heating the membrane for approximately 180 to 600 minutes. This may include: In any of the methods described herein, the method involves the film being about 200 to about 6 This may include heating for 0 minutes. In any of the methods described herein, the method This may include heating the membrane for about 300 to about 600 minutes. Any of the methods described herein. In this case, the method may include heating the membrane for about 350 to about 600 minutes. In any of the methods, the method may include heating the membrane for about 400 to about 600 minutes. In any of the methods described herein, the method involves applying the film for about 450 to about 600 minutes. This may include heating. In any of the methods described herein, the method involves the film This may include heating for approximately 500 to 600 minutes. Any of the methods described herein may be used to remove odors. The method may include heating the membrane for about 1 to about 500 minutes. In any of the above, the method may include heating the membrane for about 1 to about 400 minutes. In any of the methods described herein, the method includes heating the membrane for about 1 to about 300 minutes. It may be visible. In any of the methods described herein, the method involves drying the film for about 1 to about 200 minutes. This may include heating. In any of the methods described herein, the method involves a membrane This may include heating for about 1 to about 100 minutes. Any of the methods described herein may be used to remove odors. The method may include heating the membrane for about 1 to about 50 minutes.

[0350] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating to a temperature range of approximately 1200°C and applying a DC or AC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 400°C to 900°C. This includes applying a DC or AC electric field to the thin film. In some examples, FAST sintering This involves heating the film to a temperature range of approximately 600°C to 1150°C and applying a DC or AC electric field to the thin film. This includes applying a heat. In some examples, fast sintering involves heating the film to approximately 700°C to approximately 9°C. This includes heating in the range of 0°C and applying a DC or AC electric field to the thin film. In this example, FAST sintering involves heating the film in the range of approximately 800°C to 900°C and thin film This includes applying a DC or AC electric field to the film. In some examples, this involves fast sintering. This involves heating the film to a temperature range of approximately 500°C to 800°C and applying a DC or AC electric field to the thin film. This includes the following. In some cases, fast sintering is performed in the range of approximately 500°C to approximately 700°C. This includes heating and applying a DC or AC electric field to the thin film. In some examples, FAST sintering involves heating the film in the range of approximately 500°C to 600°C and applying DC or This includes applying an AC electric field.

[0351] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating in the range of approximately 1000°C and applying a DC electric field to the thin film. In this example, FAST sintering involves heating the film in the range of approximately 600°C to approximately 900°C and thin film This involves applying a DC electric field to the film. In some examples, fast sintering is performed on the film. This includes heating in the range of approximately 600°C to approximately 900°C and applying a DC electric field to the thin film. In the case of Tsuka, FAST sintering involves heating the film in the range of approximately 700°C to approximately 900°C. This includes applying a DC electric field to the thin film. In some examples, FAST sintering is performed This includes heating the film to a temperature range of approximately 800°C to 900°C and applying a DC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 500°C to 800°C. This includes applying a DC electric field to the thin film. In some examples, fast sintering is performed. This includes heating the film to a temperature range of approximately 500°C to 700°C and applying a DC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 500°C to 600°C. This includes applying a DC electric field to a thin film.

[0352] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating in the range of approximately 1000°C and applying an AC electric field to the thin film. In any of the methods described, FAST sintering is performed in the range of approximately 500°C to approximately 900°C. This may include heating in an enclosure and applying an AC electric field to the thin film. In some examples... Fast sintering involves heating the film to a temperature range of approximately 600°C to 900°C and applying an AC electric field to the thin film. This includes applying a heat. In some examples, fast sintering involves heating the film to approximately 700°C to approximately 9°C. This includes heating in the range of 0°C and applying an AC electric field to the thin film. In some examples... Fast sintering involves heating the film in the range of approximately 800°C to 900°C and applying AC to the thin film. This includes applying an electric field. In some examples, fast sintering is performed at approximately 500°C. This includes heating to a temperature range of approximately 800°C and applying an AC electric field to the thin film. In the example, FAST sintering involves heating the film in the range of approximately 500°C to approximately 700°C and thin film. This includes applying an AC electric field. In some examples, fast sintering is used to make the film approximately This includes heating in the range of 500°C to approximately 600°C and applying an AC electric field to the thin film.

[0353] In one example, the method described herein, in accordance with the casting method described herein. The method includes providing an unsintered thin film by casting the film.

[0354] In some of the methods disclosed herein, sintering is performed using an inert setter plate. It takes place between the plates. In some cases, sintering takes place between inert setter plates. In this case, pressure is applied to the film during sintering by the setter plate. The pressure ranges from 1 to 1000 pounds per square inch (PSI). In some examples, the pressure is 1 PSI. In another example, the pressure is 10 PSI. In yet another example, the pressure is 20 PSI. In some other examples, the pressure is 30 PSI. In one example, the pressure is 40 PSI. Furthermore, in other examples, the pressure is 50 PSI. In some examples, the pressure is 60 PSI. In another example, the pressure is 70 PSI. In one example, the pressure is 80 PSI. In another example, the pressure is 90 PSI. In yet another example, the pressure is 100 PSI. In some examples, the pressure is 110 PSI. In other examples, the pressure is 120 PSI. In other examples, the pressure is 130 PSI. In some other examples, the pressure is 140 PSI. In one example, the pressure is 150 PSI. In yet another example, the pressure is 160 PSI. In some examples, the pressure is 170 PSI. In yet another example, the pressure is 180 PSI. In one example, the pressure is 190 PSI. In another example, the pressure is 200 PSI. In another example, the pressure is 210 PSI.

[0355] In some of the examples above, the pressure is 220 PSI. In other examples, the pressure is 23 It is 0 PSI. In another example, the pressure is 240 PSI. In some other examples, the pressure The force is 250 PSI. In one example, the pressure is 260 PSI. In yet another example, the pressure It is 270 PSI. In some examples, the pressure is 280 PSI. In yet another example, The pressure is 290 PSI. In one example, the pressure is 300 PSI. In another example, the pressure is 31 It is 0 PSI. In another example, the pressure is 320 PSI. In some examples, the pressure In one example, the pressure is 330 PSI. In another example, the pressure is 340 PSI. In yet another example, the pressure is 35 It is 0 PSI. In some other examples, the pressure is 360 PSI. In one example, the pressure is It is 370 PSI. In another example, the pressure is 380 PSI. In some examples, the pressure The force is 390 PSI. In another example, the pressure is 400 PSI. In one example, the pressure In one example, the pressure is 410 PSI. In another example, the pressure is 420 PSI. In yet another example, the pressure is It is 430 PSI. In some other examples, the pressure is 440 PSI. In one example, the pressure It is 450 PSI. In another example, the pressure is 460 PSI. In some examples, The pressure is 470 PSI. In yet another example, the pressure is 480 PSI. In one example, the pressure The force is 490 PSI. In another example, the pressure is 500 PSI. In yet another example, the pressure It is 510 PSI.

[0356] In some of the examples above, the pressure is 520 PSI. In other examples, the pressure is 53 It is 0 PSI. In another example, the pressure is 540 PSI. In some other examples, the pressure The force is 550 PSI. In one example, the pressure is 560 PSI. In yet another example, the pressure It is 570 PSI. In some examples, the pressure is 580 PSI. In yet another example, The pressure is 590 PSI. In one example, the pressure is 600 PSI. In another example, the pressure is 61 It is 0 PSI. In another example, the pressure is 620 PSI. In some examples, the pressure In one example, the pressure is 630 PSI. In another example, the pressure is 640 PSI. In yet another example, the pressure is 65 It is 0 PSI. In some other examples, the pressure is 660 PSI. In one example, the pressure is It is 670 PSI. In another example, the pressure is 680 PSI. In some examples, the pressure The force is 690 PSI. In another example, the pressure is 700 PSI. In one example, the pressure In one example, the pressure is 710 PSI. In another example, the pressure is 720 PSI. In yet another example, the pressure is It is 730 PSI. In some other examples, the pressure is 740 PSI. In one example, the pressure It is 750 PSI. In another example, the pressure is 760 PSI. In some examples, The pressure is 770 PSI. In yet another example, the pressure is 780 PSI. In one example, the pressure The force is 790 PSI. In another example, the pressure is 800 PSI. In yet another example, the pressure It is 810 PSI.

[0357] In another example, the pressure is 820 PSI. In one of the aforementioned examples, the pressure is 830 PSI. In another example, the pressure is 840 PSI. In some other examples, the pressure is 850 PSI. Yes. In one example, the pressure is 860 PSI. In yet another example, the pressure is 870 PSI. In some examples, the pressure is 880 PSI. In yet another example, the pressure is 890 PSI. In one example, the pressure is 900 PSI. In another example, the pressure is 910 PSI. In another example, the pressure is 920 PSI. In some examples, the pressure is 930 PSI. In another example, the pressure is 940 PSI. In yet another example, the pressure is 950 PSI. In some other examples, the pressure is 960 PSI. In one example, the pressure is 970 PSI. In another example, the pressure is 980 PSI. In some examples, the pressure is 990 PSI. Yes, in another example, the pressure is 1000 PSI.

[0358] In some cases, the setter plate can be porous. In other examples, the setter plate is not porous. In some examples, the setter - The lithium activity in the plate is relatively high, that is, the lithium concentration is low in the setter. At least 10 atomic percent. In other examples, the setter plate is described herein. The setter plate may be made of the garnet material on which it is placed. This can be a porous garnet setter plate. In other examples, the setter The plate may be made of zirconia. In some cases, the setter plate This can be a porous zirconia setter plate. In other examples, the setter The plate may be made of a metallic material as described herein. In some examples... The setter plate can be a porous metal setter plate.

[0359] In some cases, garnet-based setter plates provide beneficial surface properties for sintered films. These are useful for imparting. These beneficial surface properties include flatness, which is useful for battery applications. Its conductivity is one of its beneficial properties. Another beneficial property is the prevention of lithium evaporation during sintering. These beneficial properties include a preference for specific garnet crystal structures. It is also possible. In one method disclosed herein, the inert setter plate is porous Selected from conductive zirconia, graphite, or conductive metal plates. In some of our other products, the inert setter plate is made of graphite. In yet another method, the inert setter plate is a conductive metal plate.

[0360] In some of the methods disclosed herein, FAST sintering is performed by constant voltage vibration Operate in width mode, and then, once the membrane impedance has decreased by at least one order of magnitude, use constant current vibration. This includes operating in width mode.

[0361] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the impedance of the sintered film decreases by an order of magnitude, switch to constant current amplitude mode. This includes operating with the D button.

[0362] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the impedance of the sintered film decreases by two orders of magnitude, switch to constant current amplitude mode. This includes operating with the D button.

[0363] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the impedance of the sintered film decreases by three orders of magnitude, switch to constant current amplitude mode. This includes operating with the D button.

[0364] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the impedance of the sintered film decreases by four orders of magnitude, switch to constant current amplitude mode. This includes operating with the D button.

[0365] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then the impedance of the sintered film changes from 1 to 100 megaohms-cm to approximately 1 to 10 This includes operating in constant current amplitude mode once the resistance decreases to 000 ohms-cm.

[0366] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with a constant voltage.

[0367] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with constant power.

[0368] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with a constant current.

[0369] In some of the methods disclosed herein, FAST sintering is performed by burning the film. Until this density is at least 20, 30, 40, or 50% greater than the membrane before the bonding was performed. This includes operating at a constant voltage. In some of the methods disclosed herein, FA ST sintering means that the film is at least 20, 30, 40, or 50% thicker than the film before sintering. This includes operating at constant power until a high density is achieved. Among the methods disclosed herein In some cases, fast sintering results in a film that is less thick than the film before sintering. This also includes operating with a constant current until the density is 20, 30, 40, or 50% greater.

[0370] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is at least one, two, three, or four orders of magnitude lower than the impedance the film has before the connection is made. This includes operating at a constant voltage until [some of the methods disclosed herein] Furthermore, FAST sintering ensures that the film is at least 1,2 more thick than the film had before sintering. This includes operating at constant power until the impedance is three or four orders of magnitude lower. In some of the methods disclosed, FAST sintering is performed on a film during sintering. Maintain constant voltage until the impedance is at least one, two, three, or four orders of magnitude lower than the previous film. This includes operating in a flow manner.

[0371] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is at least one order of magnitude lower, and at most ten orders of magnitude lower, than the impedance the film had before the connection was made. This includes operating at a constant voltage until it is obtained. Some of the methods disclosed herein In this process, FAST sintering ensures that the film is at least as thick as the film was before sintering. This includes operating at constant power until the impedance is one order of magnitude lower or at most ten orders of magnitude lower. In some of the methods disclosed in the specification, FAST sintering means that the film is sintered The impedance is at least one order of magnitude lower, and at most ten orders of magnitude lower, than the impedance the film had before the process was performed. This includes operating with a constant current until the desired result is reached.

[0372] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The film is operated at a constant voltage until it has an impedance approximately two orders of magnitude lower than the impedance it had before the connection was made. This includes performing FAST sintering in some of the methods disclosed herein. This means that the film has an impedance that is about two orders of magnitude lower than the film had before sintering. This includes operating at constant power. In some of the methods disclosed herein, FAST sintering results in a film with an impedance approximately two orders of magnitude lower than the film had before sintering. This includes operating with a constant current until a balance is achieved.

[0373] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The film is operated at a constant voltage until it has an impedance approximately six orders of magnitude lower than the impedance it had before the connection was made. This includes performing FAST sintering in some of the methods disclosed herein. This means that the film has an impedance that is approximately six orders of magnitude lower than the impedance it had before sintering. This includes operating at constant power. In some of the methods disclosed herein, Fast sintering allows the film to have an impedance approximately six orders of magnitude lower than the film had before sintering. This includes operating with a constant current until a balance is achieved.

[0374] In some of the methods disclosed herein, FAST sintering is performed at a constant voltage. This includes operating. In some of the methods disclosed herein, FAST sintering This includes operating with constant power. Some of the methods disclosed herein include In this context, FAST sintering includes operating with a constant current.

[0375] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the membrane impedance has decreased by at least one order of magnitude, use constant current vibration. This includes operating in width mode.

[0376] In some of the methods disclosed herein, FAST sintering is performed by garnet The t particles have a central dimension that is at least twice the central dimension of the garnet particles before sintering. This includes operating at ramp voltage until the law is established. In some cases, FAST sintering is performed on garnet particles before sintering. The device is operated with ramp power until it has a central dimension that is at least twice the central dimension of the particle. This includes the following. In some of the methods disclosed herein, FAST sintering is The garnet particles are at least twice the central dimension of the garnet particles before sintering. This includes operating the lamp with current until it has a central dimension.

[0377] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the film thickness. For example, In some examples, sintering is applied until the film reaches a thickness of 50 μm. In other examples, In other examples, sintering is applied until the film is 40 μm thick. The process is applied until the film reaches a certain thickness. In other examples, sintering is applied until the film reaches a thickness of 20 μm. It is used. In other examples, sintering is applied until the film is 10 μm thick. In this case, sintering is applied until the film is 5 μm thick. In another example, sintering is applied until the film is The process is applied until the film reaches a thickness of 1 μm. In other examples, sintering is applied until the film reaches a thickness of 0.5 μm. This is applied as follows. As used in this paragraph, thickness is the average dimension of the film in the z-direction (shown in Figure 23). It refers to (su).

[0378] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the conductivity of the film. For example, Sintering can be applied until the film has a conductivity of 1e-4 S / cm. In other examples, sintering The method can be applied until the film has a conductivity of 1e-5S / cm. In other examples, sintering This can be applied until the film has a conductivity of 1e-6 S / cm. In other examples, sintering is It can be applied until the film has a conductivity of 1e-7 S / cm. In other examples, sintering is performed. It can be applied until the film has a conductivity of 1e-8 S / cm.

[0379] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the impedance of the membrane. For example, sintering can be applied until the impedance of the film reaches 500 ohms-cm.

[0380] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the particle size within the membrane.

[0381] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. These values ​​are adjusted accordingly. In some examples, these values ​​include the density of the membrane.

[0382] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the optical density of the film.

[0383] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the temperature of the film. For example, baking Sintering can be applied until the film reaches a temperature of 50°C. In other examples, sintering is applied to the film. It can be applied until the temperature reaches 100°C. In other examples, sintering is performed until the film reaches 150°C. It can be applied until the film reaches a temperature of 200°C. In other examples, sintering is performed until the film reaches a temperature of 200°C. It can be applied until the film has reached a temperature of 250°C. In other examples, sintering is performed until the film has reached a temperature of 250°C. It can be applied until the film reaches a temperature of 300°C. In other examples, sintering is performed until the film reaches a temperature of 300°C. It can be applied. In other examples, sintering is applied until the film reaches a temperature of 350°C. It is possible. In other examples, sintering is applied until the film reaches a temperature of 400°C. This is possible. In other examples, sintering can be applied until the film reaches a temperature of 450°C. In other examples, sintering can be applied until the film reaches a temperature of 500°C. In this example, sintering can be applied until the film reaches a temperature of 550°C. In other examples... In other examples, sintering can be applied until the film reaches a temperature of 600°C. Sintering can be applied until the film reaches a temperature of 650°C. In other examples, sintering This can be applied until the film reaches a temperature of 700°C. In other examples, sintering is performed on the film. It can be applied up to a temperature of 750°C. In other examples, sintering is performed until the film reaches 800°C. It can be applied until the film reaches a temperature of 850°C. In other examples, sintering is performed until the film reaches a temperature of 850°C. It can be applied until the film has reached a temperature of 900°C. In other examples, sintering is performed until the film has reached a temperature of 900°C. It can be applied until the film reaches a temperature of 950°C. In other examples, sintering is performed until the film reaches a temperature of 950°C. It can be applied. In other examples, sintering is applied until the film reaches a temperature of 1000°C. It is possible. In other examples, sintering is applied until the film reaches a temperature of 1150°C. This is possible. In other examples, sintering can be applied until the film reaches a temperature of 1200°C. In other examples, sintering can be applied until the film reaches a temperature of 1250°C. In this example, sintering can be applied until the film reaches a temperature of 1300°C. In other examples... In this process, sintering can be applied until the film reaches a temperature of 1350°C.

[0384] In some of the methods disclosed herein, FAST sintering is performed by burning the film. Run until the film has a density at least 20, 30, 40, or 50% greater than the film before the bonding was performed. This includes operating with a voltage. In some of the methods disclosed herein, FA ST sintering means that the film is at least 20, 30, 40, or 50% thicker than the film before sintering. This includes operating with lamp power until a high density is achieved. In some of our cases, FAST sintering results in a film that is less thick than the film before sintering. This includes operating with a ramp current until the density is at least 20, 30, 40, or 50% greater. In some of the methods disclosed herein, FAST sintering is performed so that the film is sintered. The impedance is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower than what the film had before the process was performed. This includes operating with a ramp voltage until a balance is achieved. In some cases, fast sintering results in a film that is 1% thicker than the film had before sintering. Operates with ramp power until it has an impedance 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower. This includes performing FAST sintering in some of the methods disclosed herein. This means that the film is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times thicker than the film had before sintering. This includes operating with a ramp current until it has an impedance of an order of magnitude lower.

[0385] In some of the methods disclosed herein, FAST sintering is used for lamp electricity This includes operating under pressure. In some of the methods disclosed herein, FAST baking Connecting includes operating with lamp power. Among the methods disclosed herein In some cases, fast sintering involves operating with a ramp current.

[0386] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the membrane impedance has decreased by at least one order of magnitude, use constant current vibration. This includes operating in width mode. In some of the methods disclosed herein, FAST sintering is performed in constant voltage amplitude mode, and then the impedance of the sintered film is 1 If the magnitude decreases, the operation is performed in constant current amplitude mode. In some cases, FAST sintering is performed in constant voltage amplitude mode, and then sintering This specification includes operating in constant current amplitude mode when the membrane impedance decreases by two orders of magnitude. In some of the methods disclosed in this book, FAST sintering is performed in a constant voltage amplitude mode. Operate in this mode, and then, once the impedance of the sintered film has decreased by three orders of magnitude, operate in constant current amplitude mode. This includes performing FAST sintering in some of the methods disclosed herein. This means that the device is operated in constant voltage amplitude mode, and then, once the impedance of the sintered film decreases by four orders of magnitude, This includes operating in constant current amplitude mode.

[0387] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then the impedance of the sintered film changes from 1 to 100 megaohms-cm to approximately 1 to 10 This includes operating in constant current amplitude mode once the resistance decreases to 000 ohms-cm.

[0388] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with a constant voltage.

[0389] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with constant power.

[0390] In some of the methods disclosed herein, FAST sintering is performed by garnet The garnet particles have a central dimension that is twice as large as the garnet particles before sintering. This includes operating with a constant current.

[0391] In some of the methods disclosed herein, FAST sintering is performed by burning the film. Until this density is at least 20, 30, 40, or 50% greater than the membrane before the bonding was performed. This includes operating at a constant voltage. In some of the methods disclosed herein, FA ST sintering means that the film is at least 20, 30, 40, or 50% thicker than the film before sintering. This includes operating at constant power until a high density is achieved. Among the methods disclosed herein In some cases, fast sintering results in a film that is less thick than the film before sintering. This also includes operating with a constant current until the density is 20, 30, 40, or 50% greater.

[0392] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is at least one, two, three, or four orders of magnitude lower than the impedance the film has before the connection is made. This includes operating at a constant voltage until [some of the methods disclosed herein] Furthermore, FAST sintering ensures that the film is at least 1,2 more thick than the film had before sintering. This includes operating at constant power until the impedance is three or four orders of magnitude lower. In some of the methods disclosed, FAST sintering is performed on a film during sintering. Maintain constant voltage until the impedance is at least one, two, three, or four orders of magnitude lower than the previous film. This includes operating in a flow manner.

[0393] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is at least one order of magnitude lower, and at most ten orders of magnitude lower, than the impedance the film had before the connection was made. This includes operating at a constant voltage until it is obtained. Some of the methods disclosed herein In this process, FAST sintering ensures that the film is at least as thick as the film was before sintering. This includes operating at constant power until the impedance is one order of magnitude lower or at most ten orders of magnitude lower. In some of the methods disclosed in the specification, FAST sintering means that the film is sintered The impedance is at least one order of magnitude lower, and at most ten orders of magnitude lower, than the impedance the film had before the process was performed. This includes operating with a constant current until the desired result is reached.

[0394] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The film is operated at a constant voltage until it has an impedance approximately two orders of magnitude lower than the impedance it had before the connection was made. This includes performing FAST sintering in some of the methods disclosed herein. This means that the film has an impedance that is about two orders of magnitude lower than the film had before sintering. This includes operating at constant power. In some of the methods disclosed herein, FAST sintering results in a film with an impedance approximately two orders of magnitude lower than the film had before sintering. This includes operating with a constant current until a balance is achieved.

[0395] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The film is operated at a constant voltage until it has an impedance approximately six orders of magnitude lower than the impedance it had before the connection was made. This includes performing FAST sintering in some of the methods disclosed herein. This means that the film has an impedance that is approximately six orders of magnitude lower than the impedance it had before sintering. This includes operating at constant power. In some of the methods disclosed herein, Fast sintering allows the film to have an impedance approximately six orders of magnitude lower than the film had before sintering. This includes operating with a constant current until a balance is achieved.

[0396] In some of the methods disclosed herein, FAST sintering is performed at a constant voltage. This includes operating. In some of the methods disclosed herein, FAST sintering This includes operating with constant power. Some of the methods disclosed herein include In this context, FAST sintering includes operating with a constant current.

[0397] In some of the methods disclosed herein, FAST sintering is performed using constant voltage vibration Operate in width mode, and then, once the membrane impedance has decreased by at least one order of magnitude, use constant current vibration. This includes operating in width mode.

[0398] In some of the methods disclosed herein, FAST sintering is performed by garnet The t particles have a central dimension that is at least twice the central dimension of the garnet particles before sintering. This includes operating at ramp voltage until the law is established. In some cases, FAST sintering is performed on garnet particles before sintering. The device is operated with ramp power until it has a central dimension that is at least twice the central dimension of the particle. This includes the following. In some of the methods disclosed herein, FAST sintering is The garnet particles are at least twice the central dimension of the garnet particles before sintering. This includes operating the lamp with current until it has a central dimension.

[0399] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the film thickness. For example, In some examples, sintering is applied until the film reaches a thickness of 50 μm. In other examples, In other examples, sintering is applied until the film is 40 μm thick. The process is applied until the film reaches a certain thickness. In other examples, sintering is applied until the film reaches a thickness of 20 μm. It is used. In other examples, sintering is applied until the film is 10 μm thick. In this case, sintering is applied until the film is 5 μm thick. In another example, sintering is applied until the film is The process is applied until the film reaches a thickness of 1 μm. In other examples, sintering is applied until the film reaches a thickness of 0.5 μm. This is applied as follows. As used in this paragraph, thickness is the average dimension of the film in the z-direction (shown in Figure 23). It refers to (su).

[0400] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the conductivity of the film. For example, Sintering can be applied until the film has a conductivity of 1e-4 S / cm. In other examples, sintering The method can be applied until the film has a conductivity of 1e-5S / cm. In other examples, sintering This can be applied until the film has a conductivity of 1e-6 S / cm. In other examples, sintering is It can be applied until the film has a conductivity of 1e-7 S / cm. In other examples, sintering is performed. It can be applied until the film has a conductivity of 1e-8 S / cm.

[0401] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the impedance of the membrane. For example, sintering can be applied until the impedance of the film reaches 500 ohms-cm.

[0402] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the particle size within the membrane.

[0403] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. These values ​​are adjusted accordingly. In some examples, these values ​​include the density of the membrane.

[0404] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the optical density of the film.

[0405] In some embodiments, FAST sintering is operated by feedback control. Here, the applied voltage, applied power, or applied current satisfies a certain predetermined value during sintering. They are adjusted accordingly. In some examples, these values ​​include the temperature of the film. For example, baking Sintering can be applied until the film reaches a temperature of 50°C. In other examples, sintering is applied to the film. It can be applied until the temperature reaches 100°C. In other examples, sintering is performed until the film reaches 150°C. It can be applied until the film reaches a temperature of 200°C. In other examples, sintering is performed until the film reaches a temperature of 200°C. It can be applied until the film has reached a temperature of 250°C. In other examples, sintering is performed until the film has reached a temperature of 250°C. It can be applied until the film reaches a temperature of 300°C. In other examples, sintering is performed until the film reaches a temperature of 300°C. It can be applied. In other examples, sintering is applied until the film reaches a temperature of 350°C. It is possible. In other examples, sintering is applied until the film reaches a temperature of 400°C. This is possible. In other examples, sintering can be applied until the film reaches a temperature of 450°C. In other examples, sintering can be applied until the film reaches a temperature of 500°C. In this example, sintering can be applied until the film reaches a temperature of 550°C. In other examples... In other examples, sintering can be applied until the film reaches a temperature of 600°C. Sintering can be applied until the film reaches a temperature of 650°C. In other examples, sintering This can be applied until the film reaches a temperature of 700°C. In other examples, sintering is performed on the film. It can be applied up to a temperature of 750°C. In other examples, sintering is performed until the film reaches 800°C. It can be applied until the film reaches a temperature of 850°C. In other examples, sintering is performed until the film reaches a temperature of 850°C. It can be applied until the film has reached a temperature of 900°C. In other examples, sintering is performed until the film has reached a temperature of 900°C. It can be applied until the film reaches a temperature of 950°C. In other examples, sintering is performed until the film reaches a temperature of 950°C. It can be applied. In other examples, sintering is applied until the film reaches a temperature of 1000°C. It is possible. In other examples, sintering is applied until the film reaches a temperature of 1150°C. This is possible. In other examples, sintering can be applied until the film reaches a temperature of 1200°C. In other examples, sintering can be applied until the film reaches a temperature of 1250°C. In this example, sintering can be applied until the film reaches a temperature of 1300°C. In other examples... In this process, sintering can be applied until the film reaches a temperature of 1350°C.

[0406] In some of the methods disclosed herein, FAST sintering is performed by burning the film. Run until the film has a density at least 20, 30, 40, or 50% greater than the film before the bonding was performed. This includes operating with a voltage. In some of the methods disclosed herein, FA ST sintering means that the film is at least 20, 30, 40, or 50% thicker than the film before sintering. This includes operating with lamp power until a high density is achieved. In some of our cases, FAST sintering results in a film that is less thick than the film before sintering. This includes operating with a ramp current until the density is at least 20, 30, 40, or 50% greater.

[0407] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower than the impedance the membrane had before the knot was formed. This includes operating with a ramp voltage until a dance occurs. Among the methods disclosed herein In some cases, fast sintering makes the film thicker than the film had before sintering. The lamp power is operated until the impedance is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower. This includes the act of creating something.

[0408] In some of the methods disclosed herein, FAST sintering is performed by burning the film. The impedance is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 orders of magnitude lower than the impedance the membrane had before the knot was formed. This includes operating with a ramp current until a dance occurs.

[0409] In some of the methods disclosed herein, FAST sintering is used for lamp electricity This includes operating under pressure. In some of the methods disclosed herein, FAST baking Connecting includes operating with lamp power. Among the methods disclosed herein In some cases, fast sintering involves operating with a ramp current.

[0410] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating to a temperature range of approximately 1000°C and applying a DC or AC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 500°C to 900°C. This includes applying a DC or AC electric field to the thin film. In some examples, FAST sintering This involves heating the film to a temperature range of approximately 600°C to 900°C and applying a DC or AC electric field to the thin film. This includes applying heat. In some cases, fast sintering involves sintering the film at approximately 700°C to 900°C. This includes heating in a range of °C and applying a DC or AC electric field to the thin film. In the example, FAST sintering involves heating the film in the range of approximately 800°C to approximately 900°C and thin film. This includes applying a DC or AC electric field. In some examples, FAST sintering is performed This involves heating the film to a temperature range of approximately 500°C to 800°C and applying a DC or AC electric field to the thin film. This includes. In some cases, fast sintering is performed in the range of approximately 500°C to approximately 700°C. This includes heating and applying a DC or AC electric field to the thin film. In some examples... FAST sintering involves heating the film in the range of approximately 500°C to 600°C and applying DC or This includes applying an AC electric field.

[0411] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating in the range of approximately 1000°C and applying a DC electric field to the thin film. In this example, FAST sintering involves heating the film in the range of approximately 600°C to approximately 900°C and thin film This involves applying a DC electric field to the film. In some examples, fast sintering is performed on the film. This includes heating in the range of approximately 600°C to approximately 900°C and applying a DC electric field to the thin film. In the case of Tsuka, FAST sintering involves heating the film in the range of approximately 700°C to approximately 900°C. This includes applying a DC electric field to the thin film. In some examples, FAST sintering is performed This includes heating the film to a temperature range of approximately 800°C to 900°C and applying a DC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 500°C to 800°C. This includes applying a DC electric field to the thin film. In some examples, fast sintering is performed. This includes heating the film to a temperature range of approximately 500°C to 700°C and applying a DC electric field to the thin film. In some cases, fast sintering involves heating the film in the range of approximately 500°C to 600°C. This includes applying a DC electric field to a thin film.

[0412] In any of the methods described herein, FAST sintering is performed at approximately 400°C~ This may include heating in the range of approximately 1000°C and applying an AC electric field to the thin film. In any of the methods described, FAST sintering is performed in the range of approximately 500°C to approximately 900°C. This may include heating in an enclosure and applying an AC electric field to the thin film. In some examples... Fast sintering involves heating the film to a temperature range of approximately 600°C to 900°C and applying an AC electric field to the thin film. This includes applying a heat. In some examples, fast sintering involves heating the film to approximately 700°C to approximately 9°C. This includes heating in the range of 0°C and applying an AC electric field to the thin film. In some examples... Fast sintering involves heating the film in the range of approximately 800°C to 900°C and applying AC to the thin film. This includes applying an electric field. In some examples, fast sintering is performed at approximately 500°C. This includes heating to a temperature range of approximately 800°C and applying an AC electric field to the thin film. In the example, FAST sintering involves heating the film in the range of approximately 500°C to approximately 700°C and thin film. This includes applying an AC electric field. In some examples, fast sintering is used to make the film approximately This includes heating in the range of 500°C to approximately 600°C and applying an AC electric field to the thin film.

[0413] In one example, the method described herein involves casting a film to form an unsintered thin film. This includes providing.

[0414] (vii. Composite materials) In another embodiment, this disclosure relates to the fabrication of a composite electrochemical device. A method comprising the following steps: providing an anode layer including an anode current collector; and the anode A process for providing a garnet-type solid electrolyte (SSE) layer in contact with at least one side of a do layer. The process of optionally sintering the SSE; the process of providing a porous garnet layer in contact with the SSE layer; The process of optionally sintering the porous garnet layer; optionally, carbon in the porous garnet layer. A lithium conductive polymer, an active cathode material, and a combination thereof are selected from the group. A step of impregnating at least one member; and a casing in contact with the porous garnet layer This describes a method that includes the steps of providing a current collector layer in any order.

[0415] In some examples, the following are described herein: thin, self-supporting garnet films A sintering method comprising the following steps: casting a garnet slurry, A process of providing a tape; here, the slurry comprises a garnet precursor, garnet, and Selected from the group consisting of inders, solvents, plasticizers, dispersants, and combinations thereof, Each includes one component; the process of sintering the green tape between setter plates is optional. The method includes, in order; where the sintering is thermal sintering, discharge plasma sintering, or The process involves electric field-assisted sintering; and sintering is performed using the setter plate, and the film This optionally includes applying pressure to it.

[0416] In some of these aforementioned examples, the slurry is crushed and calcined gar Includes netting. In some cases, the solid filling amount of green tape is at least 30% It is w / w. In some examples, the solid filling amount of the green tape is at least 40% w / w. In some cases, the solid filling amount of the green tape is at least 50% w / w. Yes. In some cases, the solid filling amount of the green tape is at least 60% w / w. In some cases, the solid filling content of the green tape is at least 70% w / w. In some of these examples, the film is sintered directly onto the metal. In one example... The metal is either metal powder or metal foil. In some examples, the metal powder is green t It is located between one side of the loop and one setter plate, and is in contact with them. In this example, the metal powder layer is positioned between and in contact with the two green tapes. Here, the green tape is located between the setter plates, and these They are in contact. In some examples, the metal powder is Ni or Cu powder. In some cases, the source of Li is placed near the film being sintered during sintering. In physical examples, setter plates are made of YSZ, graphite, YSZ, Mg-SZ, and zirconia. Porous zirconia, SiO2, SiO2 sand, Al2O3, Al2O3 powder, Al2O3 paper, nickel, nickel Garnet powder, garnet, garnet powder, sacrificial garnet film, LiAlO2, LiLaO2, Li2ZrO Selected from 3. In some examples, two different setter plates are used. In some of these examples, the zirconia setter plate comes into contact with the metal powder. In some cases, the applied pressure ranges from 0.001 MPa to 200 MPa.

[0417] (viii. Two-layer and three-layer sintering) In some cases, the sintered film is a metal layer that later comes into contact with the garnet-electrolyte layer. It is provided as a garnet-electrolyte layer in contact with the electrolyte. Non-limiting examples are shown in Figure 4 or Figure 29. show.

[0418] (ix. Thermal sintering) In some embodiments, the following are disclosed herein: the fabrication of an energy storage electrode. A method comprising providing an unsintered thin film; wherein the unsintered thin film The membrane consists of a garnet-type electrolyte, an active electrode material, a conductive additive, a solvent, a binder, and this It includes at least one member selected from the group consisting of combinations of the above. The method further includes removing the solvent if present in the unsintered thin film. In some examples, the method optionally includes laminating the film onto a surface. In this method, the method includes removing the binder if present in the film. In that example, the method includes sintering the film, wherein sintering is a form of heating. This includes bonding. In some of these examples, thermal sintering is used to bond the film. It operates in a temperature range of approximately 700°C to 1200°C for approximately 1 to 600 minutes, and has an oxygen partial pressure of 1e-1 atmosphere to 1e-15 atmospheres. This includes heating in a certain atmosphere.

[0419] In some embodiments, the following are disclosed herein: the fabrication of an energy storage electrode. A method comprising providing an unsintered thin film; wherein the unsintered thin film The membrane consists of a garnet-type electrolyte, an active electrode material, a conductive additive, a solvent, a binder, and this It includes at least one member selected from the group consisting of combinations of the above. The method further includes removing the solvent if present in the unsintered thin film. In some examples, the method optionally includes laminating the film onto a surface. In this method, the method includes removing the binder if present in the film. In that example, the method includes sintering the film, wherein sintering is performed in an electric field This includes using assisted sintering (FAST). In some of these examples, FAST sintering is performed. This involves heating the film to a temperature range of approximately 500°C to 900°C and applying a DC or AC electric field to the thin film. This includes adding.

[0420] In any of the methods described herein, the unsintered thin film contains a garnet-type electrolyte. It may include. In other ways, the unsintered thin film may include the active electrode material. Further examples include In this process, the unsintered thin film may contain conductive additives. In one method, the unsintered thin film is dissolved It may contain a medium. In some cases, the unsintered thin film may contain a binder.

[0421] In any of the methods described herein, thermal sintering is performed to heat the film to approximately 700°C~ Approximately 1200°C; or approximately 800°C to approximately 1200°C; or approximately 900°C to approximately 1200°C; or approximately 1000°C to approximately 1200°C; or This may include heating in the range of approximately 1100°C to approximately 1200°C. In either case, the film is heat-sintered at approximately 700°C to 1100°C; or approximately 700°C to 1000°C; or This may include heating in the range of approximately 700°C to approximately 900°C; or approximately 700°C to approximately 800°C. In any of the methods described herein, thermal sintering is performed at approximately 700°C, approximately 7 50℃, approximately 850℃, approximately 800℃, approximately 900℃, approximately 950℃, approximately 1000℃, approximately 1050℃, approximately 1100℃, approximately 1150℃ This may include heating to approximately 1200°C, or any of the methods described herein. In this process, heat sintering is performed on the film at 700°C, 750°C, 850°C, 800°C, 900°C, 950°C, and 10°C. This may include heating to 00°C, 1050°C, 1100°C, 1150°C, or 1200°C. In any of the methods described in the book, thermal sintering means heating the film to 700°C. This may include: In any of the methods described herein, thermal sintering is This may include heating the film to 750°C. Any of the methods described herein. In this specification, thermal sintering may include heating the film to 850°C. In any of the methods described, heat sintering involves heating the film to 900°C. It may include. In any of the methods described herein, thermal sintering is This may include heating the film to 950°C. In this specification, thermal sintering may include heating the film to 1000°C. In any of the methods described, thermal sintering includes heating the film to 1050°C. It is possible to do so. In any of the methods described herein, thermal sintering is used to form a film. This may include heating to 1100°C. Furthermore, thermal sintering may include heating the film to 1150°C. In any of the methods described, thermal sintering includes heating the film to 1200°C. It is possible.

[0422] In any of the methods described herein, the method involves heating the membrane for about 1 to about 600 minutes. This may include: In any of the methods described herein, the method involves making a film about 20 This may include heating for approximately 600 minutes. In any of the methods described herein, The method may include heating the membrane for about 30 to about 600 minutes. In either case, the method may include heating the membrane for about 40 to about 600 minutes. In any of the methods described, the method involves heating the membrane for about 50 to about 600 minutes. May include. In any of the methods described herein, the method involves applying a film to about 60 to about 600 This may include heating for minutes. In any of the methods described herein, the method This may include heating the membrane for approximately 70 to 600 minutes. Any of the methods described herein. In this specification, the method may include heating the membrane for about 80 to about 600 minutes. In any of the methods, the method may include heating the film for about 90 to about 600 minutes. In any of the methods described herein, the method involves heating the membrane for about 100 to about 600 minutes. This may include: In any of the methods described herein, the method involves making a film about This may include heating for 120 to approximately 600 minutes, in any of the methods described herein. The method may include heating the membrane for about 140 to about 600 minutes. In any of the above, the method may include heating the membrane for about 160 to about 600 minutes. In any of the methods described in the book, the method involves heating the membrane for approximately 180 to 600 minutes. This may include: In any of the methods described herein, the method involves the film being about 200 to about 6 This may include heating for 0 minutes. In any of the methods described herein, the method This may include heating the membrane for about 300 to about 600 minutes. Any of the methods described herein. In this case, the method may include heating the membrane for about 350 to about 600 minutes. In any of the methods, the method may include heating the membrane for about 400 to about 600 minutes. In any of the methods described herein, the method involves applying the film for about 450 to about 600 minutes. This may include heating. In any of the methods described herein, the method involves the film This may include heating for approximately 500 to 600 minutes. Any of the methods described herein may be used to remove odors. The method may include heating the membrane for about 1 to about 500 minutes. In any of the above, the method may include heating the membrane for about 1 to about 400 minutes. In any of the methods described herein, the method includes heating the membrane for about 1 to about 300 minutes. It may be visible. In any of the methods described herein, the method involves drying the film for about 1 to about 200 minutes. This may include heating. In any of the methods described herein, the method involves a membrane This may include heating for about 1 to about 100 minutes. Any of the methods described herein may be used to remove odors. The method may include heating the membrane for about 1 to about 50 minutes.

[0423] (x. Lamination) In some of the methods described herein, lamination is performed at a rate of 1,000 pounds per square inch This includes applying a pressure of less than 1 / 2 (PSI) and heating the membrane. In other embodiments, Lamination involves applying a pressure of less than 750 pounds per square inch (PSI) and heating the film. In some other embodiments, the lamination is subjected to pressures of less than 700 pounds per square inch (PSI). This includes adding and heating the film. In another embodiment, the lamination is 650 pounds This includes applying pressure less than 1 square inch (PSI) and heating the membrane. In this embodiment, the lamination is subjected to a pressure of less than 600 pounds per square inch (PSI) and This includes heating the film. In other embodiments, the lamination is 550 pounds per square inch (PSI) This includes applying a pressure of less than a certain amount and heating the membrane. In some other embodiments, The lamination process involves applying a pressure of less than 500 pounds per square inch (PSI) and heating the film. In other embodiments, the lamination is subjected to a pressure of less than 450 pounds per square inch (PSI). This includes heating the film. In some other embodiments, the lamination is 400 pound This includes applying a pressure of less than dols per square inch (PSI) and heating the membrane. Other embodiments In this process, lamination is performed by applying a pressure of less than 350 pounds per square inch (PSI) and heating the film. This includes doing so. In some other embodiments, the lamination is 300 pounds per square inch (PS I) This includes applying a pressure of less than 1) and heating the film. In other embodiments, lamination is This includes applying a pressure of less than 250 pounds per square inch (PSI) and heating the membrane. In several other embodiments, the lamination is subjected to a pressure of less than 200 pounds per square inch (PSI). This includes heating the film. In another embodiment, the lamination is 150 pounds per square meter This includes applying pressure less than an inch (PSI) and heating the membrane.

[0424] In some other embodiments, the lamination is subjected to pressures less than 100 pounds per square inch (PSI). This includes adding and heating the film. In other embodiments, lamination is 50 pounds per square meter. This includes applying a pressure of less than one inch (PSI) and heating the membrane. In this embodiment, lamination is performed by applying a pressure of less than 10 pounds per square inch (PSI) and the film This includes heating. Some of the lamination methods described herein involve heating the film. This includes heating to approximately 80°C. Some of the lamination methods described herein involve This includes heating the film to be heated to approximately 25°C to approximately 180°C.

[0425] In some of the methods disclosed herein, the lamination step involves an unsintered thin film electrolyte. This includes stacking an electrolyte, an active electrode material, and a conductive material on a composite electrode; where the composite electrode comprises an electrolyte, an active electrode material, and a conductive material. It comprises at least one component selected from the group consisting of chemical additives and combinations thereof. In some of these embodiments, the composite electrode includes an electrolyte. In some other embodiments, the composite electrode includes an active electrode material. In some other types of composite electrodes, the composite electrode contains a conductive additive.

[0426] (xi. Setter Plate) In some of the methods disclosed herein, sintering is performed using an inert setter plate. It takes place between the plates. In some cases, sintering is performed between inert setter plates. In this case, pressure is applied to the film during sintering by the setter plate. In one example, Pressure ranges from 1 to 1000 pounds per square inch (PSI). In some examples, the pressure is 1 PSI. Yes. In another example, the pressure is 10 PSI. In yet another example, the pressure is 20 PSI. In some other examples, the pressure is 30 PSI. In one example, the pressure is 40 PSI. In other examples, the pressure is 50 PSI. In some examples, the pressure is 60 PSI. In another example, the pressure is 70 PSI. In another example, the pressure is 80 PSI. In this example, the pressure is 90 PSI. In yet another example, the pressure is 100 PSI. In one example, the pressure is 110 PSI. In another example, the pressure is 120 PSI. In this example, the pressure is 130 PSI. In some other examples, the pressure is 140 PSI. In one example, the pressure is 150 PSI. In yet another example, the pressure is 160 PSI. In some examples, the pressure is 170 PSI. In yet another example, the pressure is 180 PSI. In one example, the pressure is 190 PSI. In another example, the pressure is 200 PSI. Furthermore, In another example, the pressure is 210 PSI.

[0427] In some of the examples above, the pressure is 220 PSI. In other examples, the pressure is 23 It is 0 PSI. In another example, the pressure is 240 PSI. In some other examples, the pressure The force is 250 PSI. In one example, the pressure is 260 PSI. In yet another example, the pressure It is 270 PSI. In some examples, the pressure is 280 PSI. In yet another example, The pressure is 290 PSI. In one example, the pressure is 300 PSI. In another example, the pressure is 31 It is 0 PSI. In another example, the pressure is 320 PSI. In some examples, the pressure In one example, the pressure is 330 PSI. In another example, the pressure is 340 PSI. In yet another example, the pressure is 35 It is 0 PSI. In some other examples, the pressure is 360 PSI. In one example, the pressure is It is 370 PSI. In another example, the pressure is 380 PSI. In some examples, the pressure The force is 390 PSI. In another example, the pressure is 400 PSI. In one example, the pressure In one example, the pressure is 410 PSI. In another example, the pressure is 420 PSI. In yet another example, the pressure is It is 430 PSI. In some other examples, the pressure is 440 PSI. In one example, the pressure It is 450 PSI. In another example, the pressure is 460 PSI. In some examples, The pressure is 470 PSI. In yet another example, the pressure is 480 PSI. In one example, the pressure The force is 490 PSI. In another example, the pressure is 500 PSI. In yet another example, the pressure It is 510 PSI.

[0428] In some of the examples above, the pressure is 520 PSI. In other examples, the pressure is 53 It is 0 PSI. In another example, the pressure is 540 PSI. In some other examples, the pressure The force is 550 PSI. In one example, the pressure is 560 PSI. In yet another example, the pressure It is 570 PSI. In some examples, the pressure is 580 PSI. In yet another example, The pressure is 590 PSI. In one example, the pressure is 600 PSI. In another example, the pressure is 61 It is 0 PSI. In another example, the pressure is 620 PSI. In some examples, the pressure In one example, the pressure is 630 PSI. In another example, the pressure is 640 PSI. In yet another example, the pressure is 65 It is 0 PSI. In some other examples, the pressure is 660 PSI. In one example, the pressure is It is 670 PSI. In another example, the pressure is 680 PSI. In some examples, the pressure The force is 690 PSI. In another example, the pressure is 700 PSI. In one example, the pressure In one example, the pressure is 710 PSI. In another example, the pressure is 720 PSI. In yet another example, the pressure is It is 730 PSI. In some other examples, the pressure is 740 PSI. In one example, the pressure It is 750 PSI. In another example, the pressure is 760 PSI. In some examples, The pressure is 770 PSI. In yet another example, the pressure is 780 PSI. In one example, the pressure The force is 790 PSI. In another example, the pressure is 800 PSI. In yet another example, the pressure It is 810 PSI.

[0429] In another example, the pressure is 820 PSI. In one of the aforementioned examples, the pressure is 830 PSI. In another example, the pressure is 840 PSI. In some other examples, the pressure is 850 PSI. Yes. In one example, the pressure is 860 PSI. In yet another example, the pressure is 870 PSI. In some examples, the pressure is 880 PSI. In yet another example, the pressure is 890 PSI. In one example, the pressure is 900 PSI. In another example, the pressure is 910 PSI. In another example, the pressure is 920 PSI. In some examples, the pressure is 930 PSI. In another example, the pressure is 940 PSI. In yet another example, the pressure is 950 PSI. In some other examples, the pressure is 960 PSI. In one example, the pressure is 970 PSI. In another example, the pressure is 980 PSI. In some examples, the pressure is 990 PSI. Yes, in another example, the pressure is 1000 PSI.

[0430] In some cases, garnet-based setter plates provide beneficial surface properties for sintered films. These are useful for imparting. These beneficial surface properties include flatness, which is useful for battery applications. Its conductivity is one of its beneficial properties. Another beneficial property is the prevention of lithium evaporation during sintering. These beneficial properties include a preference for specific garnet crystal structures. It can also be done this way.

[0431] In a method disclosed herein, the inert setter plate is made of porous zirconia. A is selected from graphite or conductive metal plates. In this case, the inert setter plate is porous zirconia. In some other cases, the inert setter plate is graphite. In other methods, the inert setter plate is a conductive metal plate.

[0432] (h. Oxygen partial pressure) In some cases, the sintering method involves an acid in the atmosphere that comes into contact with the garnet material during sintering. This further includes controlling the elementary concentrations. In some examples, the partial pressure of oxygen is controlled by argon and water. By bringing a mixture of element and water (i.e., H2O) into contact with the garnet material during sintering and flowing it through... It is controlled. In some cases, the partial pressure of oxygen is controlled by the flow rate of argon, hydrogen, or water. Alternatively, it can be controlled by adjusting the flow rates of all three gases or any combination of these gases. In some cases, the partial pressure of oxygen is 2E-1 (i.e., 20% O2). In other examples, the partial pressure of oxygen is 1E-2. In some examples, the partial pressure of oxygen is 1E-3. In other examples, the partial pressure of oxygen is 1E-4. In some other examples, the partial pressure of oxygen is 1E It is -5. In some cases, the partial pressure of oxygen is 1E-6. In other cases, the partial pressure of oxygen is It is 1E-7. In some other examples, the partial pressure of oxygen is 1E-8. In some examples In one example, the partial pressure of oxygen is 1E-9. In another example, the partial pressure of oxygen is 1E-10. Some other examples In some cases, the partial pressure of oxygen is 1E-11. In some cases, the partial pressure of oxygen is 1E-3. In this example, the partial pressure of oxygen is 1E-12. In some other examples, the partial pressure of oxygen is 1E-13. Yes. In other examples, the partial pressure of oxygen is 1E-14. In some other examples, the partial pressure of oxygen It is 1E-15. In some cases, the partial pressure of oxygen is 1E-16. In other cases, oxygen The partial pressure is 1E-17. In some other examples, the partial pressure of oxygen is 1E-18. In this case, the partial pressure of oxygen is 1E-19. In other cases, the partial pressure of oxygen is 1E-20. In other examples, the partial pressure of oxygen is 1E-21. In some examples, the partial pressure of oxygen is 1E-22. Yes. In other examples, the partial pressure of oxygen is 1E-23. In some other examples, the partial pressure of oxygen It is 1E-24. In some cases, the partial pressure of oxygen is 1E-25.

[0433] (i. Grinding method) As described herein, several enumerated methods relate to mixing processes and The method includes processes relating to crushing or grinding. Grinding includes ball grinding. Grinding is not limited to However, ethanol, isopropanol, toluene, ethyl acetate, methyl acetate, acetone, This also includes grinding methods using inert solvents such as cetonitrile or combinations thereof. Depending on the material being used, the solvent does not necessarily have to be inert. Some of these examples are odor The pulverization is not limited to ethanol, isopropanol, toluene, ethyl acetate, Grinding using solvents such as methyl acetate, acetone, acetonitrile, or combinations thereof. include.

[0434] In some cases, crushing is ball crushing. In some cases, crushing is, It is horizontal grinding. In some cases, the grinding is attritor grinding. In this case, grinding is immersion grinding. In some examples, grinding is high-energy grinding. In some cases, the high-energy grinding process is d 50 This is a pulverized particle size of 100 nm. To produce cloth. In some cases, grinding is immersion grinding.

[0435] In some cases, a high-energy grinding process is used, 50 The particle size distribution is approximately 100 nm. This 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. In some cases, the solvent is diacetone alcohol. In the example, the solvent is listed as d 50 It is a suitable polar solvent for achieving the desired diameter.

[0436] In some cases, the grinding is performed using a 0.3 mm yttria-stabilized zirconium oxide grinding medium. This includes a high-energy wet grinding process using beads. In some examples, ball powder Crushing, horizontal grinding, attritor grinding, or immersion grinding can be used. Some examples include In this process, using a high-energy grinding process, approximately d 50 However, it has a particle size distribution of ~100 nm. Rasu. [Examples]

[0437] (IV. Examples) In the examples described herein, the product lithi formed by the method herein The subscript value of the um-filled garnet is used to produce the claimed composition. This represents the elemental molar ratio of the precursor chemicals.

[0438] (a. Example 1 - Flux deposition of Li-conducting ceramics) In one example, a pre-formed garnet material, i.e., a seed crystal, is used to create other garnets. A net material is manufactured. In this example, 100 grams (g) of Li7La3Zr2O 12 31.03g of Li2CO3 Mix with 58.65 g of La2O3 and 29.57 g of ZrO2. The resulting mixture is then mixed in isopropanol. The balls were crushed for 24 hours. Then the mixture was dried, and then calcined at 900°C for 12 hours. Then, it was sintered at 1100°C for 12 hours. The resulting product was then pulverized again in isopropanol. The average particle size was reduced to 1 μm.

[0439] (b. Example 2 - Flux deposition of Li-conducting ceramics) In this example, a thin film garnet electrolyte with a thickness of 3 μm to 50 μm is produced. The garnet precursor was determined to be LiOH / Li2CO3 / LiO2 / La2O3 / ZrO2. Yttria stabilization was performed on a 0.3 mm layer. The precursor material was pulverized using zirconium oxide pulverizing medium beads. The slurry formulation was dispersed, and the slurry was deposited onto a metal foil. The slurry was then dried. Then, pressure was applied to the film using a plate, and it was heated to sinter the components within it. AlNO3 and A doped composition was prepared using Al2O3 as the source of Al.Nb2O5 was used as the source of Nb, and Ta 2O5 was used as the source of Ta.

[0440] A garnet precursor slurry was deposited onto a metal foil substrate. A nickel piece approximately 0.5 mils thick was then used. The substrate was used as the base substrate. The substrate was manufactured using a cleaning method. In some cases, IPA solution was used. A medium was used to remove residual organic matter from the surface of the metal foil. UV ozone treatment, corona discharge treatment, large Plasma treatment and chemical treatment (light acids such as ammonium hydroxide or citric acid / acetic acid / To prepare a surface for slurry application using other surface cleaning methods such as a base solution. It is also possible to use a doctor blade and adjust the doctor blade gap to 3um~100 A film thickness of 100µm was achieved.

[0441] Next, the deposited film was dried. After drying the film, the deposited film was calendered and heated. High-density film was achieved before the process. Depending on the starting thickness, a thickness reduction of up to 50% was achieved through calendering. This was achieved after the previous step. The next step involved pressurizing the membrane. A maximum pressure of 20 MPa was applied.

[0442] Next, a sintering process was carried out. The size of the sintered crystal grains depends on the degree of sintering performed. It was decided that sintering would be carried out at a temperature range of approximately 900°C to 1200°C with a dwell time of only 15 to 90 minutes. provided.

[0443] The sintering process increases the density and uniformity of the garnet thin film. Figure 7 shows such a process. This is an XRD graph of a thin garnet film that has been processed as a material. The garnet phase can be confirmed in Figure 7. This is shown by the XRD.

[0444] (c. Example 3 - Densification with bismuth flux) In this example, the lithium-filled garnet powder is composed of a 1:1 mixture of Li2CO3 and B2O3. It was densified using flux.

[0445] Figure 52 shows the result of lithium-filled garnet films as a function of flux heating conditions. The obtained densities are shown: 900°C, 30 minutes (bottom curve); 950°C, 30 minutes (second curve from the bottom). Line); 950°C, 6 hours (third curve from the bottom); 100°C, 30 minutes (top curve).

[0446] (d. Example 4 - Fabrication of microcrystalline granular Li-ion conductive garnet ceramics) In this example, LiOH, La2O3, ZrO2, and Al(NO3)3.9H2O are combined in various ratios. The mixture was mixed for 8 hours by crushing dry balls. After that, the mixture was exposed to air in an alumina crucible. It was then pre-baked at 800-1000°C for 4-8 hours.

[0447] As described above, Li7La3Zr2O 12 • To produce the 0.35Al2O3 phase, use the molar ratio Li:La:Zr:Al2. The above reactants were mixed in a ratio of 7:3:2:0.35.

[0448] (Using yttria-stabilized zirconia grinding medium (approximately 2-10 hours) and an 80-mesh sieve) 64.6 grams (g) of dried and pulverized LiOH, 184.5 g of La2O3, 93.9 g of ZrO2, and 96.3 g of Al(NO3) Composition C (whose XRD is shown in Figure 49) was prepared by reacting it with 3·9H2O. The reactant powder was dried at 120°C for about 1 hour. This powder was then subjected to an alumina crucible in the air. It was pre-baked at 800-1000°C for 4-8 hours.

[0449] When the product is measured by light scattering, d 50 The material is friction-ground in a solvent until the particle size is ~300 nm, and then dried. The powder was dried to obtain a dry powder. This dry powder was then mixed with 4% w / w polyvinyl acetate in isopropanol. By mixing with thiral, removing isopropanol, and sieving through an 80-mesh sieve, Pellet formation was achieved.

[0450] This binder is used to create pellets with a diameter of 13 mm and a thickness of approximately 1.2 to 1.4 mm, at a rate of approximately 3 metric tons. Pressure was applied to the coated powder. The pellets were placed between setter places and dried aluminum. Sintering was performed in a tubular furnace into which gon (Ar; flow rate 315 sccm) was introduced. Sintering was performed at 150-180°C for 1-4 hours. After that, heat sintering at 300-350°C for 1-4 hours, then at 1000-1200°C for 3-9 hours, and then Cooling was included.

[0451] The mass and dimensions of the sintered pellets were measured to determine their geometric density, and scanning electron microscopy was performed. The grain size on the fracture surface was determined using this method.

[0452] Figure 9 shows a map of the compositional space under consideration. The compositional variables include lithium and aluminum. The lanthanum content was included. The ratio of lanthanum to zirconium was maintained at 3:2 throughout the study. Figure 9 shows the phase space under consideration with high conductivity (>10 -4 This indicates the existence of an area (S / cm). This area is larger at lower sintering temperatures (1075°C compared to 1150°C). Under conditions of high temperature and short dwell time (1200°C, 15 minutes), the test produced at lower temperatures will be less effective. The same level of conductivity as the material cannot be obtained. Some compositions disclosed in this study, for example Compositions A, B, C, and D exhibit high conductivity (as shown in Figure 9).

[0453] Composition A is Li 6.3 La3Zr2O 12 Characterized by 0.35Al2O3.

[0454] Composition B is Li 6.3 La3Zr2O 12 Characterized by 0.67Al2O3.

[0455] Composition C is Li7La3Zr2O 12 Characterized by 0.67Al2O3.

[0456] Composition D is Li7La3Zr2O 12 Characterized by Al2O3

[0457] Figure 10 shows a cross-section (Figure 9) through a phase space map, and also shows the relevant density and grain size. ru.

[0458] The processing and sintering of garnet ceramics described herein are comparable to other known techniques. In comparison, a relatively short reaction time and a moderate temperature were used. Figure 12 shows the given Al-doped reaction. Regarding Bell, below that point the garnet grain size remains relatively small (i.e., <10um), beyond that the crystal grain size becomes too large (i.e., >100um), lithium This indicates that a bell exists.

[0459] Figure 11 shows a comparative solution between known garnet compositions and the garnet compositions described herein. This shows the analysis. These other studies, for all the aluminum content examined, It is clear that it functions in the "high lithium" region. Furthermore, the known garnet sintering temperature Most were above 1200°C, and the processing time was long (for example, over 10 hours). This results in the growth of large crystal grains and is incompatible with the powders, films, and devices described in this application. This application relates to the production of a garnet film having a conductivity value suitable for use in secondary battery applications. This shows unexpectedly short processing dwell times and unexpectedly low processing conditions.

[0460] The examples described herein demonstrate how lithium can be controlled by limiting the Li content and sintering temperature. This demonstrates that small crystal grain sizes can be achieved with the moulanthanum-zirconia-alumina system. The specific composition (Composition B) with Li, Al = 6.3 and 0.67 is illustrative. This is because The composition is found to have small crystal grains after sintering at 1075°C, but after 1150°C... This is because it results in larger crystal grains. This is due to the selected processing conditions described herein and This demonstrates how specific the method is. A processing temperature of 1075°C was used. In this case, compositions A, B, C, and D in the current study have low grain size and high conductivity (>10). -4 S / cm) Please note that this results in a rather unique combination.

[0461] Figure 12 shows a material having the microcrystalline grains described herein and at a lower temperature, for example, 1075°C. This image shows an example of a scanning electron microscope image of a sintered lithium-filled garnet.

[0462] Figure 13 shows the bulk conductivity of 3 * 10 -4 Li exceeding S / cm x La3Zr2O 12 • Li:Al in yAl2O3 x:y It shows a ratio.

[0463] Figure 14 shows various compositions that can be prepared using the methods described herein. These compositions and their associated densities are shown.

[0464] Figure 49 shows the XRD of composition C.

[0465] (e. Example 5 - Impedance measuremen...

Claims

1. Lithium-filled garnet powder, and At least one member selected from the group consisting of binders, plasticizers, dispersants, and combinations thereof. A thin, unsintered film for solid lithium metal secondary batteries, including, The unsintered film has a thickness of less than 100 μm and more than 10 nm, and The lithium-filled garnet powder has a median grain size of 0.1 μm to 10 μm, and the thin, unsintered film is provided.

2. The thin, unsintered film according to claim 1, further comprising garnet precursor powder.

3. The thin, unsintered film according to claim 2, wherein the garnet precursor powder comprises one or more members selected from the group consisting of lithium hydroxide, lithium oxide, lithium carbonate, zirconium oxide, lanthanum oxide, aluminum oxide, aluminum, aluminum nitrate, aluminum nitrate nonahydrate, niobium oxide, tantalum oxide, and combinations thereof.

4. The thin, unsintered film according to claim 1, wherein the film further comprises a solvent.

5. The thin unsintered film according to claim 4, wherein the solid filling amount of the lithium-filled garnet powder is at least 30 volume% (v / v) based on the total volume of the unsintered film.

6. The thin unsintered film according to claim 4, wherein the solid filling amount of the lithium-filled garnet powder is 40 to 80 volume% (v / v) based on the total volume of the unsintered film.

7. The thin unsintered film according to claim 4, wherein the solid filling amount of the lithium-filled garnet powder is 40, 45, 50, 55, 60, 65, 70, 75, or 80 volume% (v / v) based on the total volume of the unsintered film.

8. The lithium-filled garnet powder is Li f La B M′ C M″ D Zr E O F 、Li A La B M′ C M″ D Ta E O F 、Li A La B M′ C M″ D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14, and M′ and M″ are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta in each case), or Li a La b Zr c Al d Me″ e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2 ≤ d < 2; 0 ≤ e < 2, 10 < f < 14, and Me″ is a metal selected from Nb, Ta, V, W, Mo, or Sb), the thin green film according to claim 1.

9. The lithium-filled garnet powder is Li x La 3 Zr 2 O 12 ・yAl 2 O 3 A thin, unsintered film according to claim 1, characterized by (where 5.5 ≤ x ≤ 9; and 0 < y ≤ 1).

10. The lithium-filled garnet powder is Al 2 O 3 :Li x La 3 Zr 2 O 12 (Here, Al 2 O 3 :Li x La 3 Zr 2 O 12 A thin, unsintered film according to claim 1, characterized by the ratio of 0.35, 0.5, 0.67, or 1.

0.

11. The lithium-filled garnet powder is Li 7 La 3 Zr 2 O 12 ・Al 2 O 3 A thin, unsintered film according to claim 1, characterized by...

12. The lithium-filled garnet powder is Li 7 La 3 Zr 2 O 12 0.35Al 2 O 3 A thin, unsintered film according to claim 1, characterized by...

13. The thin unsintered film according to claim 1, wherein the thickness of the unsintered film is less than 50 μm and greater than 10 nm.

14. The lithium-filled garnet powder has a particle size of less than 2 μm. 50 A thin, unsintered film according to claim 1, having crystal grains having a specific grain size.

15. The lithium-filled garnet powder has a particle size of less than 1 μm. 50 A thin, unsintered film according to claim 1, having crystal grains having a specific grain size.

16. A first layer comprising an unsintered lithium-filled garnet thin film, wherein the film comprises lithium-filled garnet powder and at least one member selected from the group consisting of a binder, a plasticizer, a dispersant, and a combination thereof, the first layer having a thickness of less than 100 μm and greater than 10 nm, and the lithium-filled garnet powder having a median grain size of 0.1 μm to 10 μm, and A second layer comprising a metal foil, wherein the second layer is in contact with the first layer, and the metal foil comprises a metal selected from the group consisting of aluminum (Al), nickel (Ni), copper (Cu), gold (Au), iron (Fe), steel, stainless steel, lithium (Li), alloys thereof, and combinations thereof. A multilayer for solid lithium metal secondary batteries, including a multilayer structure.

17. The multilayer according to claim 16, wherein the first layer further comprises garnet precursor powder.

18. The multilayer according to claim 17, wherein the garnet precursor powder comprises one or more members selected from the group consisting of lithium hydroxide, lithium oxide, lithium carbonate, zirconium oxide, lanthanum oxide, aluminum oxide, aluminum, aluminum nitrate, aluminum nitrate nonahydrate, niobium oxide, tantalum oxide, and combinations thereof.

19. The multilayer according to claim 16, wherein the first layer further comprises a solvent.

20. The multilayer according to claim 19, wherein the solid filling amount of the unsintered lithium-filled thin film is at least 30 volume% (v / v) based on the total volume of the unsintered film.

21. The multilayer according to claim 19, wherein the solid filling amount of the unsintered lithium-filled thin film is 40 to 80 volume% (v / v) based on the total volume of the unsintered film.

22. The multilayer according to claim 19, wherein the solid filling amount of the unsintered lithium-filled thin film is 40, 45, 50, 55, 60, 65, 70, 75, or 80 volume% (v / v) based on the total volume of the unsintered film.

23. The lithium-filled garnet powder is Li A La B M′ C M″ D Zr E O F Li A La B M′ C M″ D Ta E O F Li A La B M′ C M″ D Nb E O F (where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2; 0 ≤ E < 2, 10 < F < 14, and M' and M'' are each independently selected from Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, or Ta), or Li a La b Zr c Al d Me″ e O f The multilayer according to claim 16, characterized by (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 ≤ d < 2 ≤ d < 2; 0 ≤ e < 2, 10 < f < 14, and Me'' is a metal selected from Nb, Ta, V, W, Mo, or Sb).

24. The lithium-filled garnet powder is Li x La 3 Zr 2 O 12 ・yAl 2 O 3 The multilayer according to claim 16, characterized by (where 5.5 ≤ x ≤ 9; and 0 < y ≤ 1).

25. where the lithium-filled garnet powder is Al 2 O 3 :Li x La 3 Zr 2 O 12 (where the ratio of Al 2 O 3 :Li x La 3 Zr 2 O 12 is 0.35, 0.5, 0.67 or 1.0), the multilayer according to claim 16.

26. The lithium-filled garnet powder is Li 7 La 3 Zr 2 O 12 ・Al 2 O 3 The multilayer according to claim 16, characterized by...

27. The lithium-filled garnet powder is Li 7 La 3 Zr 2 O 12 0.35Al 2 O 3 The multilayer according to claim 16, characterized by...

28. The multilayer according to claim 16, wherein the thickness of the unsintered film is less than 50 μm and greater than 10 nm.

29. The lithium-filled garnet powder has a particle size of less than 2 μm. 50 A multilayer according to claim 16, having crystal grains having a crystal grain size.

30. The lithium-filled garnet powder has a particle size of less than 1 μm. 50 A multilayer according to claim 16, having crystal grains having a crystal grain size.

31. The multilayer according to claim 16, wherein the metal foil contains nickel (Ni).

32. The multilayer according to claim 16, wherein the metal foil contains copper (Cu).

33. The multilayer according to claim 16, wherein the metal foil contains iron (Fe).

34. The multilayer according to claim 16, wherein the metal foil comprises an alloy of nickel (Ni) and copper (Cu).

35. The multilayer according to claim 16, wherein the metal foil comprises an alloy of nickel (Ni) and iron (Fe).

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