Centerless sintering setter

Abstract

SUMMARY OF THE INVENTION Materials, systems and methods are described herein for sintering a bilayer comprising a metallic layer and a ceramic layer.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 484,924, filed February 14, 2023, the entire disclosures of which are incorporated herein by reference for all purposes.

[0002] The present disclosure relates to methods for sintering oxides and related materials, and systems and materials used therein. [Background technology]

[0003] Ions in solid-state electrolytes (e.g., Li + ) is typically lower than the ion mobility in conventionally used, flammable liquid electrolytes. To compensate for this lower ion mobility, solid-state electrolytes are fabricated as thin films. In thin films, the distance that ions must travel through the solid-state electrolyte is reduced to the thickness of the film. The ion conduction distance in thin-film solid-state electrolytes is shorter than that in liquid electrolytes. As a result, when used in rechargeable battery cells, solid-state electrolytes can provide energy delivery rates (i.e., power) that are comparable to or better than those of batteries using liquid electrolytes.

[0004] However, fabricating solid-state electrolytes thinner than approximately 100 microns (μm) presents challenges. For example, cracks, voids, and other inhomogeneities can occur during fabrication. Such cracks, voids, and other inhomogeneities can adversely affect the performance of thin solid-state electrolytes in battery cells.

[0005] Solutions to the problems associated with fabricating solid-state electrolytes and other problems in the field to which this disclosure pertains are described herein. Summary of the Invention

[0006] The present disclosure relates generally to the fabrication of components for lithium rechargeable batteries. Specifically, the present disclosure relates to the fabrication of setter plates for sintering solid-state electrolytes and bilayers containing solid-state electrolytes. In some embodiments, the setter plates described herein are suitable for sintering high Li + It is useful for fabricating thin dense bilayers comprising a layer of a metal and a layer of a solid-state electrolyte with ionic conductivity and low area specific resistance (ASR).

[0007] In one embodiment, described herein is a stack comprising a lower setter comprising at least one or more refractory materials, a bilayer disposed on the lower setter, the bilayer including a layer comprising an oxide and a layer comprising a metal, and an upper setter disposed on the bilayer, the upper setter having a periphery but no center.

[0008] In another embodiment, described herein is a stack comprising a lower setter, a bilayer disposed on the lower setter, the bilayer including an oxide-containing layer and a metal-containing layer, and a metal mesh disposed on the electrolyte bilayer.

[0009] In yet another embodiment, described herein is a stack comprising a lower setter, a bilayer disposed on the lower setter, the bilayer including an oxide-containing layer and a metal-containing layer, and at least one or more shims disposed above the bilayer, the shims including a refractory material.

[0010] In yet another embodiment, described herein is a stack comprising a lower setter, a bilayer disposed on the lower setter, the bilayer including an oxide-containing layer and a metal-containing layer, and at least one shim disposed around the bilayer, the shim including a refractory material. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 illustrates certain forces present when sintering tape cast ceramic between setter plates. [Figure 2] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. [Figure 3] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. [Figure 4] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. [Figure 5] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. [Figure 6] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. [Figure 7] FIG. 1 illustrates one embodiment of a setter stack as disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0012] Described herein are apparatus and processes useful for achieving high-quality, rapidly processed ceramic electrolyte membranes. Described herein are high-throughput, continuous processes for sintering thin-film ceramics. Ceramics include lithium aluminum titanium phosphate (LATP), lithium-filled garnet oxides (e.g., Li7La3Zr2O), and other ceramics. 12 and Li7La3Zr2O 12Examples of suitable ceramic materials include, but are not limited to, Al2O3 (also known as LLZO), lithium lanthanum titanate, and lithium aluminum germanium phosphate (LAGP). In certain embodiments, the process includes a sintering step in which a portion of the sintered film (i.e., the center portion of the green film or green body on a bilayer in the process of becoming a sintered film or sintered bilayer) does not contact any surface during sintering. In some embodiments, when a bilayer is used, the metal layer may contact a surface, but the center portion of the green body does not contact the surface of the processing equipment, such as a setter. By sintering without contact with a setter during sintering, the portion of the sintered ceramic film produced by this process has unexpectedly advantageous properties, such as low flatness. For lithium-filled garnets, the processing equipment has unexpectedly advantageous properties that allow for the retention of lithium stoichiometry for a given LLZO formula and advantageous LLZO microstructure (e.g., high density, small grain size, and combinations thereof). In some embodiments, using the setters and stacks disclosed herein, the materials produced are free of surface scratches. In some embodiments, by using the setters and stacks disclosed herein, the bilayers produced herein have no surface scratches on the ceramic side of the bilayer.

[0013] A process for sequentially fabricating the bilayer is described herein, which includes step 1) binder burn-out (BBO) performed between room temperature and moderately elevated temperatures to remove organic material from the bilayer, and step 2) sintering at very high temperatures to convert the ceramic powder into a dense solid.

[0014] During both stages and the subsequent cooling to room temperature, the temperature profile and gas environment are controlled.

[0015] In some processes herein, both processing steps (BBO and sintering) are performed in a single tool. In other embodiments, separate tools are used for each step, i.e., one tool for BBO and one tool for sintering. For example, a dual-layer green body can be fired and sintered using a single setter stack.

[0016] definition The following description is presented to enable one skilled in the art to make and use the invention and to incorporate it into the context of a particular application. Various modifications and variations on different applications will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to a wide variety of embodiments. Thus, the present disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0017] In the following detailed description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. However, it will be apparent to those skilled in the art that the present disclosure may be practiced without necessarily being limited to these specific details. In other instances, well-known structures and devices are shown in block diagram form, rather than in detail, in order to avoid obscuring the present invention.

[0018] All features disclosed in this specification (including any accompanying claims, abstracts, and drawings), unless expressly stated otherwise, may be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only an example of a generic series of equivalent or similar features.

[0019] As used herein, the term "about" when used to modify a numerical value, e.g., about 15% (w / w), refers to the modified numerical value and, optionally, to a range of values ​​around the modified numerical value, including ±10% of the numerical value. For example, about 15% (w / w) includes not only 15% (w / w), but also 13.5% (w / w), 14% (w / w), 14.5% (w / w), 15.5% (w / w), 16% (w / w), or 16.5% (w / w). For example, "about 75°C" includes not only 75°C, but also 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, or 83°C.

[0020] As used herein, "selected from the group consisting of" refers to a single member of the group, two or more members of the group, or a combination of members of the group. A member selected from the group consisting of A, B, and C includes, for example, A alone, B alone, or C alone, as well as A and B, A and C, B and C, and A, B, and C.

[0021] As used herein, the term "solid separator" refers to a material that is substantially insulating to electrons (e.g., lithium ion conductivity is at least 10 times that of electronic conductivity). 3 times, often 10 6 times higher), which acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell, Li + Refers to ion-conducting materials.

[0022] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin, Maccor, or Biologic instrument unless otherwise specified.

[0023] As used herein, ionic conductivity is measured by electrical impedance spectroscopy, as known in the art.

[0024] As used herein, the term "electrolyte" refers to an ionically conductive and electrically insulating material. The electrolyte electrically insulates the positive and negative electrodes of a rechargeable battery while allowing ions, such as Li + is useful for enabling the electrolyte to conduct.

[0025] As used herein, the terms "solid state electrolyte separator" or "solid state separator" or "solid state separator" are used interchangeably with the term "solid separator" and refer to a separator that does not contain carbon and is free of atomic ions (e.g., Li +A solid-state electrolyte separator is a solid material suitable for electrically insulating the positive and negative electrodes of a lithium secondary battery while providing a conductive path for lithium ions. Examples of inorganic solid-state electrolytes include oxide electrolytes and sulfide electrolytes, which are further defined below. Non-limiting examples of sulfide electrolytes can be found, for example, in U.S. Patent No. 9,172,114, issued October 27, 2015, and U.S. Patent Application Publication No. 2017-0162901, published June 8, 2017, the entire contents of which are incorporated herein by reference in their entirety for all purposes. Non-limiting examples of oxide electrolytes can be found, for example, in U.S. Patent Application Publication No. 2015-0200420, published July 16, 2015, the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some instances, inorganic solid-state electrolytes also include polymers, referred to as composite electrolytes, as found, for example, in U.S. Patent No. 9,666,870, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0026] As used herein, the term "film thickness" refers to the distance or median measured distance between the top and bottom surfaces of the film. As used herein, the top and bottom surfaces refer to the sides of the film having the largest geometric surface area, which is calculated by multiplying the length of the surface by its width. As used herein, thickness is measured by cross-sectional scanning electron microscopy.

[0027] As used herein, the term "film" or "thin film" refers to a thin film less than 0.5 mm thick and greater than 10 nm thick. A film can have a lateral dimension greater than 5 mm. A "film" or "thin film" can be produced by a continuous process such as tape casting, slip casting, or screen printing. A thin film has a thickness of 1 μm to 100 μm unless otherwise specified.

[0028] As used herein, "thin" means, when modifying a solid-state electrolyte, a thickness dimension of less than 200 μm, sometimes less than 100 μm, in some cases 0.1 μm to 60 μm, in other cases about 10 μm to about 100 μm, and in other cases about 1 μm, 10 μm, or 50 μm.

[0029] As used herein, a "sintered thin film" refers to a thin film that has been sintered, e.g., heated to above 1000°C, to densify the structure without changing the chemical composition.

[0030] As used herein, "binder" refers to a polymer capable of enhancing the adhesion and / or cohesion of materials, such as solids in a green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene α-olefin copolymers. "Binder" refers to a material that aids in the adhesion of another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders may include polycarbonates. Other binders may include polyacrylates and polymethacrylates. These examples of binders are not limiting with respect to the full range of binders contemplated herein, but are merely illustrative.Binders useful in the present disclosure include polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (PMMA), acrylics, polyvinyl acetal resins, polyvinyl butyral resins (PVB), stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, silicones, polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyvinylpyrrolidone (PP), and the like. Examples of suitable polymers include, but are not limited to, polyethylene oxide (PVP), polyethylene oxide poly(allyl glycidyl ether) (PEO-AGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene fluoride (PVDF-HFP), nitrile rubber (NPR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, α-polyolefin, ethylene α-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA).

[0031] As used herein, the terms "electrochemical cell" or "battery cell" refer to a single cell containing a positive electrode and a negative electrode in ionic communication with each other using an electrolyte. In some embodiments, the same battery cell contains multiple positive electrodes and / or multiple negative electrodes enclosed in a single container.

[0032] As used herein, the term "electrochemical stack" refers to a stack of electrodes each containing at least a negative electrode (e.g., Li, LiC), a positive electrode (e.g., FeF, NiF), and a negative electrode (e.g., Li, LiC). x (where x is 2 or 3), nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), LiNi x Mn y Co z O2[NMC] or LiNi x Al y Co z O2[NCA] (where x+y+z=1, and 0≦x≦1, 0≦y≦1, and 0≦z≦1), optionally in combination with a solid-state electrolyte or a gel electrolyte), and a solid-state electrolyte (e.g., an oxide electrolyte described herein, such as lithium-filled garnet (Li7La3Zr2O 12 )). In some examples, there is an additional layer between the solid-state electrolyte and the positive electrode that includes a compatible material (e.g., a gel electrolyte). An electrochemical stack may include one of these aforementioned components. An electrochemical stack may include several of these aforementioned components arranged in electrical communication (e.g., electrical connection in series or parallel). In some embodiments, when an electrochemical stack includes several components, the components are stacked or laminated in a column. In some embodiments, when an electrochemical stack includes several components, the components are stacked or laminated in an array. In some embodiments, when an electrochemical stack includes several components, the stack is arranged so that two or more positive electrodes share one negative electrode. Alternatively, in some embodiments, when an electrochemical stack includes several components, the stack is arranged so that two or more negative electrodes share one positive electrode. Unless otherwise specified, an electrochemical stack includes one positive electrode, one solid-state electrolyte, and one negative electrode, and optionally includes an adhesion layer between the positive electrode and the solid electrolyte.

[0033] As used herein, the term "positive electrode" refers to a secondary battery that contains cations, such as Li, during battery discharge. +refers to an electrode towards which electrical current conducts, flows, or moves.

[0034] As used herein, the term "negative electrode" refers to a secondary battery that contains cations, such as Li, during battery discharge. + A negative electrode that includes lithium metal is referred to herein as a lithium metal negative electrode.

[0035] In a battery constructed with a Li metal electrode and an electrode (i.e., cathode active material) containing a conversion chemistry, an intercalation chemistry, or a combination of conversion / intercalation chemistry, the electrode having the conversion chemistry, intercalation chemistry, or combined conversion / intercalation chemistry material is referred to as the positive electrode. In some common usages, the cathode is used in place of the positive electrode and the anode is used in place of the negative electrode. When a Li secondary battery is charged, Li ions are transported to the positive electrode (e.g., NiF x , NMC, NCA) to the negative electrode (e.g., Li metal). When a Li secondary battery is discharged, Li ions migrate from the negative electrode to the positive electrode.

[0036] Unless expressly stated otherwise, the separators used herein are stable when in contact with lithium metal.

[0037] As used herein, the expression "lithium-filled garnet" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Lithium-filled garnets include oxides of the formula Li A La B Zr C O F , Li A La B M' C M'' D Ta E O F Or Li A La B M' C M'' D Nb E O F(where 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2, 0 < E < 2.5, 10 < F < 13, and M’ and M’’ are each independently selected from Al, Mo, W, Nb, Ga, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta in any case), or Li a La b Zr c Al d M’’ e O f (where 5 < a < 7.7, 2 < b < 4, 0 < c ≤ 2.5, 0 < d < 2, 0 < e < 2, 10 < f < 13, and Me’’ is a metal selected from Nb, V, W, Mo, Ta, Ga, and Sb) is included. Garnets used in this specification also include the above garnets doped with Al or Al2O3. Also, as garnets used in this specification, Li A La B Zr C O F +yAl2O3 (where x can be 5.8 - 7.0, y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, and 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2, 10 < F < 13) can be mentioned, but are not limited thereto. Also, as garnets used in this specification, Li x La3Zr2O 12 +yAl2O3 (where x can be 5.8 - 7.0 and y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0) can be mentioned, but are not limited thereto. When used in this specification, garnets include YAG garnet (that is, yttrium aluminum garnet, or for example Y3Al5O 12) As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite or cinnamon, tsavorite, uvarovite, and andradite, as well as pyrope-almandine-spessarite and uvarovite-grossular-andradite solid solutions. Garnet herein does not include nesosilicates having the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn, and Y is Al, Fe, and / or Cr.

[0038] As used herein, the phrase "lithium-filled garnet" refers to an oxide characterized by a crystalline structure related to the garnet crystalline structure. Examples of lithium-filled garnet electrolytes include those described in U.S. Patent Application Publication No. 2015 / 0099190, filed October 7, 2014, published April 9, 2015, entitled "GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS," the entire contents of which are incorporated herein by reference. Li-filled garnets generally comprise Li A La B M' C M'' D Zr E O F , Li A La B M' C M'' D Ta E O F Or Li A La B M' C M'' D Nb E O F(where 4 < A < 8.5, 1.5 < B < 4, 0 ≦ C ≦ 2.5, 0 ≦ D ≦ 2.5, 0 ≦ E < 2.3, 10 < F < 13, and M’ and M’’ are each independently selected from Al, Mo, W, Ga, Gd, Y, 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 < 8.5, 2 < b < 4, 0 < c ≤ 2.5, 0 ≤ d < 2, 0 ≤ e < 2, and 10 < f < 13, and Me’’ is a metal selected from Nb, Ta, V, W, Mo, or Sb), as described separately in US Patent Application Publication No. 2015 / 0099190. In some embodiments, A can be about 6.0 or about 6.1 or about 6.2 or about 6.3 or about 6.4 or about 6.5 or about 6.6 or about 6.7 or about 6.8 or about 6.9 or about 7.0 or about 7.1 or about 7.2 or about 7.3 or about 7.4. In some embodiments, B can be about 2.8 or about 2.9 or about 3.0 or about 3.1 or about 3.2. In some embodiments, C can be about 0 or about 0.1 or about 0.2 or about 0.3 or about 0.4 or about 0.5 or about 0.6 or about 0.7 or about 0.8 or about 0.9 or about 1.0 or about 1.1 or about 1.2 or about 1.3 or about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0. In some embodiments, D can be about 0 or about 0.1 or about 0.2 or about 0.3 or about 0.4 or about 0.5 or about 0.6 or about 0.7 or about 0.8 or about 0.9 or about 1.0 or about 1.1 or about 1.2 or about 1.3 or about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0. In some embodiments, E can be about 1.4 or about 1.5 or about 1.6 or about 1.7 or about 1.8 or about 1.9 or about 2.0 or about 2.1 or about 2.2. In some embodiments, F can be about 11.0 or about 11.1 or about 11.2 or about 11.3 or about 11.4 or about 11.5 or about 11.6 or about 11.7 or about 11.8 or about 11.9 or about 12.0 or about 12.1 or about 12.2 or about 12.3 or about 12.4 or about 12.5 or about 12.6 or about 12.7 or about

END

[0039] As used herein, lithium-filled garnets and / or garnets include YAG garnets (i.e., yttrium aluminum garnets, or, for example, YAlO 12 ) As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite or cinnamon, tsavorite, uvarovite, and andradite, as well as pyrope-almandine-spessarite and uvarovite-grossular-andradite solid solutions. Garnet herein does not include nesosilicates having the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn, and Y is Al, Fe, and / or Cr.

[0040] As used herein, the expressions "garnet precursor chemicals," "garnet-type electrolyte chemical precursors," "garnet precursors," and "garnet precursor materials" refer to chemicals that react to form the lithium-filled garnet materials described herein. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., LiO), lithium carbonate (e.g., LiCO), zirconium oxide (e.g., ZrO), zirconium hydroxide, zirconium acetate, zirconium nitrate, zirconium acetylacetonate, zirconium nitrate x-hydrate, lanthanum oxide (e.g., LaO), lanthanum hydroxide (e.g., La(OH)), lanthanum nitrate, lanthanum acetate, lanthanum acetylacetonate, aluminum oxide (e.g., AlO), aluminum hydroxide (e.g., Al(OH)), aluminum (e.g., Al), aluminum nitrate (e.g., Al(NO)), aluminum nitrate nonahydrate, boehmite, gibbsite, corundum, aluminum oxyhydroxide, niobium oxide (e.g., NbO), gallium oxide (GaO), and tantalum oxide (e.g., TaO). Other precursors of garnet materials may be suitable for use in the methods described herein.

[0041] As used herein, the expression "garnet-type electrolyte" refers to the lithium-loaded garnet materials described herein. + Refers to an electrolyte that contains an ionic conductor.

[0042] As used herein, the term "alumina-doped" refers to the substitution of another material, such as a particular component of a garnet, for Al2O3. Al2O3-doped lithium-filled garnet refers to a garnet in which aluminum (Al) replaces an element in the lithium-filled garnet's chemical formula, which may be, for example, Li or Zr.

[0043] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin or Biologic instrument unless otherwise specified.

[0044] As used herein, the "flatness" of a surface refers to the greatest perpendicular distance between the lowest point of the surface and the plane containing the three highest points of the surface, or alternatively, the greatest perpendicular distance between the highest point of the surface and the plane containing the three lowest points of the surface, which can be measured using an AFM, a high-precision optical microscope, or laser interferometry height mapping of the surface.

[0045] As used herein, the "porosity" of an object is the volume fraction not occupied by material. It can be measured by mercury porosimetry or by cutting a cross section of the object and optically determining the two-dimensional area fraction of porosity of the cross section.

[0046] As used herein, a green body is a material deposited from a slurry, comprising a ceramic or ceramic precursor and at least one member selected from a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof. A green body is considered green before it is heated to either or both remove organic materials, such as a solvent, a binder, a dispersant, a plasticizer, a surfactant, or a combination thereof, or sinter the ceramic component of the green body. Green bodies are made by depositing a slurry onto a substrate and, optionally, drying the deposited slurry.

[0047] As used herein, the terms "green film" or "green tape" refer to an unsintered tape or film comprising lithium-filled garnet, a precursor of lithium-filled garnet, or a combination thereof, and at least one of a binder, a plasticizer, carbon, a dispersant, a solvent, or a combination thereof. As used herein, "green film tape" refers to a roll, continuous layer, or cut portion of either a dried or undried cast tape of green film. The term "green body" is used interchangeably herein with the terms "green film" or "green tape." Green tape may also include patches of green body deposited on a metal layer (i.e., patch coatings of a metal layer).

[0048] As used herein, a "sintered bilayer" refers to a bilayer structure comprising a sintered solid-state electrolyte and a metal foil. As used herein, a "green bilayer" refers to a bilayer structure comprising a green film and a metal foil. In some instances, the metal foil is a metal layer.

[0049] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin or Biologic instrument unless otherwise specified. ASR is calculated by measuring the voltage drop, ΔV, after 30 to 180 seconds in response to a current interrupt measurement (ASR=ΔV / J, where J is A / cm). 2 is the unit current density).

[0050] As used herein, ionic conductivity is measured by electrical impedance spectroscopy, as known in the art.

[0051] As used herein, the phrase "casting a film" refers to the process of dispensing or moving a liquid or slurry into a mold or onto a substrate so that it forms or is molded into a film. Casting can be done by doctor blade, Mayer rod, comma coater, gravure coater, microgravure, reverse comma coater, slot die, slip and / or tape casting, and other methods.

[0052] Embodiment Figure 1 shows a conventional setter stack. Figure 1 shows the top and bottom setters. Between the top and bottom setters is the cast tape. The top setter exerts a downward force due to gravity, as indicated by the arrows. This force manifests as pressure across the area of ​​the cast tape. As the cast tape is heated and ultimately sintered, it reduces in size. In directions parallel to the top and bottom setters, the cast tape shrinks laterally across the surfaces of the top and bottom setters. If friction exists between the sintered cast tape and the surfaces of the top and bottom setters, or both, adhesion forces due to the existing friction also result. This is shown in Figure 1. The cast tape also shrinks in directions perpendicular to the surfaces of the top and bottom setters.

[0053] FIG. 2 shows a setter stack according to one embodiment of the present disclosure. FIG. 2 shows an upper setter and a lower setter. Between the upper and lower setters is a bilayer including one layer comprising a metal and a second layer comprising a green or sintered film. In some embodiments, the sintered film is a lithium-filled garnet sintered film. In some embodiments, including any of the above, the metal-containing layer further comprises lithium-filled garnet. In some embodiments, including any of the above, the metal-containing layer includes nickel (Ni). In some embodiments, including any of the above, the metal-containing layer includes copper (Cu). In some embodiments, including any of the above, the metal-containing layer includes iron (Fe). FIG. 2 shows a shim separating the upper and lower setters. In some embodiments, the shim is taller than the thickness of the bilayer. In some other embodiments, the shim is the same height as the thickness of the bilayer. In some embodiments, the shim is shorter than the thickness of the bilayer. In some embodiments, the shim is shorter than the thickness of the bilayer before sintering the bilayer, but taller than the thickness of the bilayer after sintering.

[0054] FIG. 3 shows a setter stack according to one embodiment of the present disclosure. FIG. 3 shows an upper setter and a lower setter. Between the upper and lower setters is a bilayer including one layer comprising a metal and a second layer comprising a green or sintered film. In some embodiments, the sintered film is a lithium-loaded garnet sintered film. In some embodiments, including any of the above, the metal-containing layer further comprises lithium-loaded garnet. In some embodiments, including any of the above, the metal-containing layer includes nickel (Ni). In some embodiments, including any of the above, the metal-containing layer includes copper (Cu). In some embodiments, including any of the above, the metal-containing layer includes iron (Fe). FIG. 3 shows a shim separating the upper and lower setters. In some instances, the shim is taller than the thickness of the bilayer. In some other embodiments, the shim is the same height as the thickness of the bilayer. In some other embodiments, the shim is a foam cutout. In some embodiments, the upper setter and shim form a unitary upper setter.

[0055] FIG. 4 shows a top-down view of the upper setter, which has a periphery but no center. In FIG. 4, the upper setter is referred to as the frame. FIG. 4 shows the outline of a green film placed on a 136 mm x 115 mm setter. The green film has dimensions of approximately 121.8 mm x 98.0 mm. After sintering, the green film transforms into a sintered film and reduces in size. FIG. 4 shows the outline of a sintered film placed on the setter, which has dimensions of approximately 96.8 mm x 77.9 mm. The upper setter (i.e., frame) has dimensions such that the frame, or a portion thereof, covers both the green film or the periphery of the green film before sintering and the sintered film or the periphery of the sintered film after sintering, as shown in FIG. 4. In one embodiment, the frame has outer peripheral dimensions of 121.8 mm x 98.0 mm. In one embodiment, the frame has inner peripheral dimensions of 86.8 mm x 67.9 mm. In Figure 4, the frame has a margin of 7.1 mm on one side and 8.5 mm on the other side between the frame and the edge of the setter on which it rests. Other dimensions than those in Figure 4 are possible, as long as the frame does not extend to the edge of the green film before sintering and does not expose the edge of the sintered film after sintering.

[0056] FIG. 5 shows an embodiment in which a bilayer is sandwiched between a foam material and a lower setter. An upper setter, which may or may not be present, sits atop the foam material. In some embodiments, including any of the above, the bilayer comprises one layer comprising a metal and a second layer comprising a green or sintered film. In some embodiments, the sintered film is a lithium-loaded garnet sintered film. In some embodiments, including any of the above, the metal-loaded layer further comprises lithium-loaded garnet. In some embodiments, including any of the above, the metal-loaded layer comprises nickel (Ni). In some embodiments, including any of the above, the metal-loaded layer comprises copper (Cu). In some embodiments, including any of the above, the metal-loaded layer comprises iron (Fe). In some embodiments, including any of the above, the foam material is a metal foam. In some embodiments, including any of the above, the foam material is a porous nickel foam.

[0057] FIG. 6 shows an embodiment in which a bilayer is sandwiched between a non-rigid top cover and a bottom setter. In some embodiments, the top cover is the top setter. In some embodiments, the top cover is a foam material. In some embodiments, including any of the above, the bilayer includes one layer comprising a metal and a second layer comprising a green film or a sintered film. In some embodiments, the sintered film is a lithium-filled garnet sintered film. In some embodiments, including any of the above, the metal-containing layer further includes lithium-filled garnet. In some embodiments, including any of the above, the metal-containing layer includes nickel (Ni). In some embodiments, including any of the above, the metal-containing layer includes copper (Cu). In some embodiments, including any of the above, the metal-containing layer includes iron (Fe). In some embodiments, including any of the above, the foam material is a metal foam. In some embodiments, including any of the above, the foam material is a porous nickel foam.

[0058] FIG. 7 shows an embodiment in which bilayer B is sandwiched between coreless cover A and lower setter C. In some embodiments, coreless cover A is the upper setter. In some embodiments, coreless cover A is a foam material. In some embodiments, including any of the above, bilayer B includes one layer comprising a metal and a second layer comprising a green film or sintered film. In some embodiments, the sintered film of bilayer B is a lithium-loaded garnet sintered film. In some embodiments, including any of the above, the metal-loaded layer of bilayer B further includes lithium-loaded garnet. In some embodiments, including any of the above, the metal-loaded layer of bilayer B includes nickel (Ni). In some embodiments, including any of the above, the metal-loaded layer includes copper (Cu). In some embodiments, including any of the above, the metal-loaded layer includes iron (Fe). In some embodiments, including any of the above, the foam material is a metal foam. In some embodiments, including any of the above, the foam material is a porous nickel foam.

[0059] stack In one embodiment, described herein is a stack comprising a lower setter comprising at least one or more refractory materials, a bilayer disposed on the lower setter, the bilayer comprising an oxide-containing layer and a metal-containing layer, and an upper setter disposed on the bilayer, the upper setter having a periphery but no center.

[0060] In some embodiments, including any of the above, the oxide-containing layer does not include a metal in the oxide-containing layer.

[0061] In some embodiments, including any of the above, the oxide-containing layer consists of an oxide.

[0062] In some embodiments, including any of the above, the oxide-containing layer consists essentially of oxide.

[0063] In some embodiments, including any of the above, the oxide-containing layer comprises a lithium-filled garnet oxide.

[0064] In some embodiments, including any of the above, the oxide-containing layer further comprises a metal in the oxide-containing layer.

[0065] In some embodiments, including any of the above, the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0066] In some embodiments, including any of the above, the metal in the oxide-containing layer is Ni.

[0067] In some embodiments, including any of the above, the metal in the oxide-containing layer is Fe.

[0068] In some embodiments, including any of the above, the oxide-containing layer includes two or more metals in the oxide-containing layer.

[0069] In some embodiments, including any of the above, the layer comprising a metal comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0070] In some embodiments, including any of the above, the layer comprising a metal comprises Ni.

[0071] In some embodiments, including any of the above, the layer comprising a metal comprises Fe.

[0072] In some embodiments, including any of the above, the layer comprising a metal comprises Cu.

[0073] In some embodiments, including any of the above, the upper setter is a metal foam.

[0074] In some embodiments, including any of the above, the upper setter is nickel (Ni) foam.

[0075] In some embodiments, including any of the above, the refractory material is Al2O3, LiAlO2, Li7La3Zr2O 12 , Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, and combinations thereof.

[0076] In some embodiments, including any of the above, the upper setter is Al2O3, LiAlO2, Li7La3Zr2O 12 , Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, and combinations thereof.

[0077] In some embodiments, including any of the above, the refractory material comprises LiAlO 2 .

[0078] In some embodiments, including any of the above, the stack comprises at least one shim disposed between the upper setter and the lower setter.

[0079] In some embodiments, including any of the above, the stack comprises a third setter disposed above the upper setter, the third setter comprising at least one or more refractory materials.

[0080] In some embodiments, including any of the above, the stack further comprises a layer including a shim disposed above the upper setter and disposed between the upper setter and a third setter including at least one or more refractory materials disposed above the upper setter.

[0081] In some embodiments, including any of the above, two or more stacks are stacked on top of each other.

[0082] In one embodiment, described herein is a stack comprising a lower setter, a bilayer disposed on the lower setter, the bilayer including an oxide-containing layer and a metal-containing layer, and a metal mesh disposed on the electrolyte bilayer.

[0083] In some embodiments, including any of the above, the metal mesh comprises Ni.

[0084] In some embodiments, including any of the above, the metal mesh is a metal foam.

[0085] In some embodiments, including any of the above, the oxide-containing layer does not include a metal in the oxide-containing layer.

[0086] In some embodiments, including any of the above, the oxide-containing layer consists of an oxide.

[0087] In some embodiments, including any of the above, the oxide-containing layer consists essentially of oxide.

[0088] In some embodiments, including any of the above, the oxide-containing layer comprises a lithium-filled garnet oxide.

[0089] In some embodiments, including any of the above, the oxide-containing layer further comprises a metal in the oxide-containing layer.

[0090] In some embodiments, including any of the above, the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0091] In some embodiments, including any of the above, the metal in the oxide-containing layer is Ni.

[0092] In some embodiments, including any of the above, the metal in the oxide-containing layer is Fe.

[0093] In some embodiments, including any of the above, the stack includes two or more metals in a layer that includes an oxide.

[0094] In some embodiments, including any of the above, the layer comprising a metal comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0095] In some embodiments, including any of the above, the layer comprising a metal comprises Ni.

[0096] In some embodiments, including any of the above, the layer comprising a metal comprises Fe.

[0097] In some embodiments, including any of the above, the layer comprising a metal comprises Cu.

[0098] In some embodiments, including any of the above, the lower setter comprises one or more refractory materials, and the refractory materials are Al2O3, LiAlO2, Li7La3Zr2O 12 , Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, and combinations thereof.

[0099] In some embodiments, including any of the above, the upper setter is Al2O3, LiAlO2, Li7La3Zr2O 12, Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, or a combination thereof.

[0100] In some embodiments, including any of the above, the refractory material comprises LiAlO 2 .

[0101] In some embodiments, including any of the above, the stack comprises at least one shim disposed between the metal mesh and the lower setter.

[0102] In some embodiments, including any of the above, the metal mesh contacts the bilayer.

[0103] In some embodiments, including any of the above, the stack comprises a setter disposed above the metal mesh and including at least one or more refractory materials.

[0104] In some embodiments, including any of the above, the stack comprises a layer including a shim disposed above the metal mesh and disposed between the metal mesh and a setter including at least one or more refractory materials disposed above the metal mesh.

[0105] In some embodiments, including any of the above, two or more stacks are stacked on top of each other.

[0106] In one embodiment, described herein is a stack comprising a lower setter, a bilayer disposed on the lower setter, the bilayer comprising an oxide-containing layer and a metal-containing layer, and at least one or more shims disposed above the bilayer, the shims comprising a refractory material.

[0107] In one embodiment, a stack is described herein that includes a lower setter, a bilayer disposed on the lower setter, the bilayer including an oxide-containing layer and a metal-containing layer, and at least one or more shims disposed around the bilayer, the shims including a refractory material.

[0108] In some embodiments, including any of the above, the oxide-containing layer does not include a metal in the oxide-containing layer.

[0109] In some embodiments, including any of the above, the oxide-containing layer consists of an oxide.

[0110] In some embodiments, including any of the above, the oxide-containing layer consists essentially of oxide.

[0111] In some embodiments, including any of the above, the oxide-containing layer comprises a lithium-filled garnet oxide.

[0112] In some embodiments, including any of the above, the oxide-containing layer further comprises a metal in the oxide-containing layer.

[0113] In some embodiments, including any of the above, the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0114] In some embodiments, including any of the above, the metal in the oxide-containing layer is Ni.

[0115] In some embodiments, including any of the above, the metal in the oxide-containing layer is Fe.

[0116] In some embodiments, including any of the above, the oxide-containing layer comprises two or more metals.

[0117] In some embodiments, including any of the above, the layer comprising a metal comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

[0118] In some embodiments, including any of the above, the layer comprising a metal comprises Ni.

[0119] In some embodiments, including any of the above, the layer comprising a metal comprises Fe.

[0120] In some embodiments, including any of the above, the layer comprising a metal comprises Cu.

[0121] The apparatus further includes an upper setter disposed above the at least one shim including a refractory material.

[0122] In some embodiments, including any of the above, the upper setter is a metal foam.

[0123] In some embodiments, including any of the above, the upper setter is nickel (Ni) foam.

[0124] In some embodiments, including any of the above, the refractory material is Al2O3, LiAlO2, Li7La3Zr2O 12 , Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, or a combination thereof.

[0125] In some embodiments, including any of the above, the upper setter is Al2O3, LiAlO2, Li7La3Zr2O 12, Li2ZrO3, xLi2O-(1-x)SiO2 (where x=0.01 to 0.99), aLi2O-bB2O3-cSiO2 (where a+b+c=1), LiLaO2, Li2O, Li3PO4, ZrO2, ZnO2, or a combination thereof.

[0126] In some embodiments, including any of the above, the refractory material comprises LiAlO 2 .

[0127] In some embodiments, including any of the above, the stack comprises a third setter disposed above the upper setter, the third setter comprising at least one or more refractory materials.

[0128] In some embodiments, including any of the above, the stack further comprises a layer including a shim disposed above the upper setter and disposed between the upper setter and an additional layer including at least one or more refractory materials disposed above the upper setter.

[0129] In some embodiments, including any of the above, two or more stacks are stacked on top of each other.

[0130] In some embodiments, including any of the above, the bilayer is oriented so that the oxide-containing layer is in contact with the lower setter.

[0131] In some embodiments, including any of the above, the bilayer is oriented so that the metal-containing layer contacts the lower setter.

[0132] In some embodiments, including any of the above, the bilayer herein comprises a green body deposited on a metal layer. In some instances, the green body is continuous, while in other instances, the green body is deposited in a patch coating format. After sintering, the bilayer can have a ceramic layer thickness of 10 μm to 40 μm, and the metal layer thickness is 2 μm to 20 μm thick. The bilayer can have a ceramic layer thickness of 20 μm to 30 μm, and the metal layer thickness is 3 μm to 10 μm thick.

[0133] In some examples, including any of the above, the metal layer of the bilayer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.

[0134] In some examples, including any of the above, the metal layer of the bilayer is an alloy of Fe and Ni.

[0135] In some embodiments, including any of the above, the metal layer of the bilayer is an alloy of Fe and Ni, with the Fe being 1% to 25% (w / w) and the remainder being Ni.

[0136] In some embodiments, including any of the above, the thickness of the metal layer of the bilayer is between 1 μm and 20 μm.

[0137] In some embodiments, including any of the above, the thickness of the metal layer of the bilayer is between 1 μm and 10 μm.

[0138] In some embodiments, including any of the above, the thickness of the metal layer of the bilayer is between 5 μm and 10 μm.

[0139] In some examples, including any of the above, the sintered bilayer comprises a sintered lithium-filled garnet.

[0140] In some examples, including any of the above, the green body includes a binder.

[0141] In some examples, including any of the above, the green body includes a dispersant.

[0142] In some examples, including any of the above, the green body includes a solvent or combination of solvents.

[0143] In some examples, the sintered bilayer may have a width of 1 cm. In some examples, the sintered bilayer may have a width of 1 cm to 25 cm. In some examples, the sintered bilayer may have a width of 2 cm to 22 cm. In some examples, the sintered bilayer may have a width of 4 cm to 22 cm. In some examples, the sintered bilayer may have a width of 6 cm to 22 cm. In some examples, the sintered bilayer may have a width of 8 cm to 22 cm. In some examples, the sintered bilayer may have a width of 10 cm to 22 cm. In some examples, the sintered bilayer may have a width of 12 cm to 22 cm. In some examples, the sintered bilayer may have a width of 14 cm to 22 cm. In some examples, the sintered bilayer may have a width of 16 cm to 22 cm.

[0144] In some examples, the sintered membrane may have a width of 2 cm to 25 cm. In some examples, the sintered membrane may have a width of 4 cm to 25 cm. In some examples, the sintered membrane may have a width of 6 cm to 25 cm. In some examples, the sintered membrane may have a width of 8 cm to 25 cm. In some examples, the sintered membrane may have a width of 10 cm to 25 cm. In some examples, the sintered membrane may have a width of 12 cm to 25 cm. In some examples, the sintered membrane may have a width of 14 cm to 25 cm. In some examples, the sintered membrane may have a width of 16 cm to 25 cm.

[0145] In some examples, the sintered bilayer may have a width of 2 cm to 25 cm. In some examples, the sintered bilayer may have a width of 4 cm to 25 cm. In some examples, the sintered bilayer may have a width of 6 cm to 25 cm. In some examples, the sintered bilayer may have a width of 8 cm to 25 cm. In some examples, the sintered bilayer may have a width of 10 cm to 25 cm. In some examples, the sintered bilayer may have a width of 12 cm to 25 cm. In some examples, the sintered bilayer may have a width of 14 cm to 25 cm. In some examples, the sintered bilayer may have a width of 16 cm to 25 cm.

[0146] In some examples, the sintered membrane may have a width of 1 cm. In some examples, the sintered membrane may have a width of 2 cm. In some examples, the sintered membrane may have a width of 1 cm. In some examples, the sintered membrane may have a width of 3 cm. In some examples, the sintered membrane may have a width of 4 cm. In some examples, the sintered membrane may have a width of 5 cm. In some examples, the sintered membrane may have a width of 6 cm. In some examples, the sintered membrane may have a width of 7 cm. In some examples, the sintered membrane may have a width of 8 cm. In some examples, the sintered membrane may have a width of 9 cm. In some examples, the sintered membrane may have a width of 10 cm. In some examples, the sintered membrane may have a width of 11 cm. In some examples, the sintered membrane may have a width of 12 cm. In some examples, the sintered membrane may have a width of 13 cm. In some examples, the sintered membrane may have a width of 14 cm. In some examples, the sintered membrane may have a width of 15 cm. In some examples, the sintered membrane may have a width of 16 cm. In some examples, the sintered membrane may have a width of 17 cm. In some examples, the sintered membrane may have a width of 18 cm. In some examples, the sintered membrane may have a width of 19 cm. In some examples, the sintered membrane may have a width of 20 cm. In some examples, the sintered membrane may have a width of 21 cm. In some examples, the sintered membrane may have a width of 22 cm. In some examples, the sintered membrane may have a width of 23 cm. In some examples, the sintered membrane may have a width of 24 cm. In some examples, the sintered membrane may have a width of 25 cm.

[0147] In some examples herein, the sintered film or sintered bilayer has a thickness of less than 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 50 μm.

[0148] In some examples herein, the sintered film or sintered bilayer has a thickness of about 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 90 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 40 μm.

[0149] In some examples herein, the sintered film or sintered bilayer has a thickness of 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 90 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 45 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 35 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 18 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 16 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some embodiments, including any of the above, the sintered membrane or bilayer after sintering has a thickness of between 20 μm and 40 μm.In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 80 μm.

[0150] In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 10 μm to about 50 μm. In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 20 μm to about 40 μm. In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 20 μm to about 30 μm.

[0151] In some examples herein, the sintered film or sintered bilayer has a thickness of less than 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of at least 50 μm.

[0152] In some examples herein, the sintered film or sintered bilayer has a thickness of about 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 90 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of about 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 40 μm.

[0153] In some examples herein, the sintered film or sintered bilayer has a thickness of 200 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 100 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 90 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 45 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 40 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 35 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 30 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 25 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 18 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 16 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of less than 15 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 5 μm to 50 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 40 μm. In some embodiments, including any of the above, the sintered membrane or bilayer after sintering has a thickness of between 20 μm and 40 μm.In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 10 μm to 80 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 60 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 70 μm. In some examples, including any of the above, the sintered film or sintered bilayer has a thickness of 20 μm to 80 μm.

[0154] In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 10 μm to about 50 μm. In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 20 μm to about 40 μm. In some of the methods disclosed herein, the thickness of the ceramic film in the bilayer after sintering is about 20 μm to about 30 μm.

[0155] In some examples, including any of the above, the sintered article comprises a bilayer. In examples, the bilayer comprises a metal foil and a ceramic film. In some examples, the sintered article comprises a triple layer. In some examples, the metal is Ni. In some examples, the Ni is 1 μm thick. In some examples, the Ni is 2 μm thick. In some examples, the Ni is 3 μm thick. In some examples, the Ni is 4 μm thick. In some examples, the Ni is 5 μm thick. In some examples, the Ni is 6 μm thick. In some examples, the Ni is 7 μm thick. In some examples, the Ni is 8 μm thick. In some examples, the Ni is 9 μm thick. In some examples, the Ni is 10 μm thick. In some examples, the Ni is 11 μm thick. In some examples, the Ni is 12 μm thick. In some examples, the Ni is 13 μm thick. In some examples, the Ni is 14 μm thick. In some examples, the Ni is 15 μm thick. In some examples, the Ni is 16 μm thick. In some examples, the Ni is 17 μm thick. In some examples, the Ni is 18 μm thick. In some examples, the Ni is 19 μm thick. In some examples, the Ni is 20 μm thick.

[0156] In some instances, the green film is a bilayer or trilayer.

[0157] In some examples, various layer structures are contemplated and can be sintered according to the sintering methods described herein: A) free-standing lithium-filled garnet material; B) free-standing lithium-filled garnet material, optionally including active material, binder, solvent, and / or carbon; C) bilayer having one layer of lithium-filled garnet and one layer of metal powder, foil, or sheet; D) bilayer having one layer of lithium-filled garnet and one layer including metal powder, foil, or sheet; E) bilayer having one layer of lithium-filled garnet material, optionally including active material, binder, solvent, and / or carbon, and one layer of metal powder, foil, or sheet; F) a bilayer having two layers of lithium-filled garnet and one layer of a metal powder, foil or sheet between and in contact with the garnet layers; G) a trilayer having two layers of lithium-filled garnet and one layer comprising a metal powder, foil or sheet between and in contact with the garnet layers; and H) a trilayer having two layers of lithium-filled garnet material, each garnet layer optionally including an active material, binder, solvent and / or carbon, and one layer of a metal powder, foil or sheet between and in contact with the garnet layers.

[0158] The triple layer may include a layer of lithium-filled garnet, a metal layer, and a second layer of lithium-filled garnet opposite the metal layer.

[0159] The bilayer may include a layer of lithium-filled garnet and a layer of metal foil. In some examples, the metal layer includes Ni, Fe, Cu, Al, Sn, In, Ag, Au, steel, an alloy, or a combination thereof. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 90% Ni and 10% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 91% Ni and 9% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 92% Ni and 8% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 93% Ni and 7% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 94% Ni and 6% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 95% Ni and 5% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 96% Ni and 4% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 97% Ni and 3% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 98% Ni and 2% Fe. For example, the metal layer may include Ni and Fe. For example, the metal layer may include 99% Ni and 1% Fe. In some examples, the metal layer is a metal sheet. In some examples, the metal layer is an aluminum sheet. In some examples, the metal layer is a nickel sheet. In some examples, the metal layer may be malleable. In some examples, the metal layer is 1 μm thick. In some examples, the metal layer is 2 μm thick. In some examples, the metal layer is 3 μm thick. In some examples, the metal layer is 4 μm thick. In some examples, the metal layer is 5 μm thick. In some examples, the metal layer is 6 μm thick. In some examples, the metal layer is 7 μm thick. In some examples, the metal layer is 8 μm thick. In some examples, the metal layer is 9 μm thick. In some examples, the metal layer is 10 μm thick. In some examples, the metal layer is 11 μm thick. In some examples, the metal layer is 12 μm thick. In some examples, the metal layer is 13 μm thick. In some examples, the metal layer is 14 μm thick.In some examples, the metal layer is 15 μm thick. In some examples, the metal layer is 16 μm thick. In some examples, the metal layer is 17 μm thick. In some examples, the metal layer is 18 μm thick. In some examples, the metal layer is 19 μm thick. In some examples, the metal layer is 20 μm thick.

[0160] In some examples, the lithium-filled garnet-metal sintered films herein are 1 μm to 100 μm thick. In certain examples, these films are co-sintered using mixed amounts of lithium-filled garnet and metal. The metal can be selected from the group consisting of Ni, Mg, Li, Fe, Al, Cu, Au, Ag, Pd, Pt, Ti, steel, alloys thereof, and combinations thereof. The lithium-filled garnet and metal are mixed as powders and then co-sintered to form the film. In some examples, the film comprises a homogeneous mixture of lithium-filled garnet and metal. The relative amounts of lithium-filled garnet and metal can vary by volume from 1% lithium-filled garnet to 99% lithium-filled garnet, with the remainder being metal.

[0161] In some examples, including any of the above, the lithium-filled garnet is sintered onto the ceramic-metal film.

[0162] These materials include, but are not limited to, a bilayer of a lithium-filled garnet film on a metal layer or a trilayer of a metal layer between two lithium-filled garnet films.The systems and methods described herein may be implemented in accordance with International Application Nos. PCT / US2016 / 043428, filed July 21, 2016, and published as WO 2017015511, entitled "Processes and materials for casting and sintering green garnet thin films," PCT / US2019 / 056584, filed October 16, 2019, and published as WO 2020081718, entitled "Sintering large area ceramic films," PCT / US2019 / 056584, filed January 27, 2016, and published as WO 2017131676, entitled "Annealed garnet electrolyte separators." International Application No. PCT / US2016 / 15209, filed January 23, 2017, and published as WO 2018236394, entitled "Lithium-stuffed garnet electrolytes with secondary phase inclusions," and International Application No. PCT / US2017 / 039069, filed October 1, 2019, and published as WO 2020072524, entitled "Methods of making and using an electrochemical cell comprising an intermediate layer." The present invention is useful for the production of lithium-loaded garnet films or composite materials, including, but not limited to, any of the sintered films or film-containing materials described in International Application PCT / US2019 / 54117, entitled "Lithium-Loaded Garnet Film Interlayer," U.S. Patent Nos. 10,403,931, 10,290,895, 9,966,630, 10,347,937, and 10,103,405, the entire contents of each of which are incorporated herein by reference in their entirety for all purposes.

[0163] In some examples, including any of the above, the ceramic-metal film can be an oxide-metal film. In some examples, the film has one layer that is ceramic and one layer that is metal. In other examples, the film is a homogeneous mixture of ceramic and metal. In some examples, the ceramic-metal film includes ceramic and metal. In some examples, the volume percentage of ceramic is 10% and the volume percentage of metal is 90%. In some examples, the volume percentage of ceramic is 20% and the volume percentage of metal is 80%. In some examples, the volume percentage of ceramic is 30% and the volume percentage of metal is 70%. In some examples, the volume percentage of ceramic is 40% and the volume percentage of metal is 60%. In some examples, the volume percentage of ceramic is 50% and the volume percentage of metal is 50%. In some examples, the volume percentage of ceramic is 60% and the volume percentage of metal is 40%. In some examples, the volume percentage of ceramic is 70% and the volume percentage of metal is 30%. In some examples, the volume percentage of ceramic is 80% and the volume percentage of metal is 20%. In some examples, the volume percentage of ceramic is 90% and the volume percentage of metal is 10%. In some examples, the volume percentage of ceramic is 5% and the volume percentage of metal is 95%. In some examples, the volume percentage of ceramic is 15% and the volume percentage of metal is 85%. In some examples, the volume percentage of ceramic is 25% and the volume percentage of metal is 75%. In some examples, the volume percentage of ceramic is 35% and the volume percentage of metal is 65%. In some examples, the volume percentage of ceramic is 45% and the volume percentage of metal is 55%. In some examples, the volume percentage of ceramic is 55% and the volume percentage of metal is 45%. In some examples, the volume percentage of ceramic is 65% and the volume percentage of metal is 32%. In some examples, the volume percentage of ceramic is 75% and the volume percentage of metal is 25%. In some examples, the volume percentage of ceramic is 85% and the volume percentage of metal is 15%.In some examples, the volume percentage of ceramic is 95% and the volume percentage of metal is 5%.

[0164] In some examples, including any of the above, the ceramic-metal film comprises an oxide and a metal. In some examples, the volume percentage of the oxide is 10% and the volume percentage of the metal is 90%. In some examples, the volume percentage of the oxide is 20% and the volume percentage of the metal is 80%. In some examples, the volume percentage of the oxide is 30% and the volume percentage of the metal is 70%. In some examples, the volume percentage of the oxide is 40% and the volume percentage of the metal is 60%. In some examples, the volume percentage of the oxide is 50% and the volume percentage of the metal is 50%. In some examples, the volume percentage of the oxide is 60% and the volume percentage of the metal is 40%. In some examples, the volume percentage of the oxide is 70% and the volume percentage of the metal is 30%. In some examples, the volume percentage of the oxide is 80% and the volume percentage of the metal is 20%. In some examples, the volume percentage of oxide is 90% and the volume percentage of metal is 10%. In some examples, the volume percentage of oxide is 5% and the volume percentage of metal is 95%. In some examples, the volume percentage of oxide is 15% and the volume percentage of metal is 85%. In some examples, the volume percentage of oxide is 25% and the volume percentage of metal is 75%. In some examples, the volume percentage of oxide is 35% and the volume percentage of metal is 65%. In some examples, the volume percentage of oxide is 45% and the volume percentage of metal is 55%. In some examples, the volume percentage of oxide is 55% and the volume percentage of metal is 45%. In some examples, the volume percentage of oxide is 65% and the volume percentage of metal is 32%. In some examples, the volume percentage of oxide is 75% and the volume percentage of metal is 25%. In some examples, the volume percentage of oxide is 85% and the volume percentage of metal is 15%. In some examples, the volume percentage of oxide is 95% and the volume percentage of metal is 5%.

[0165] In some examples, including any of the above, the ceramic-metal film can be an oxide-metal film. In some examples, the ceramic-metal film includes a ceramic and a metal. In some examples, the weight percentage of the ceramic is 10% and the weight percentage of the metal is 90%. In some examples, the weight percentage of the ceramic is 20% and the weight percentage of the metal is 80%. In some examples, the weight percentage of the ceramic is 30% and the weight percentage of the metal is 70%. In some examples, the weight percentage of the ceramic is 40% and the weight percentage of the metal is 60%. In some examples, the weight percentage of the ceramic is 50% and the weight percentage of the metal is 50%. In some examples, the weight percentage of the ceramic is 60% and the weight percentage of the metal is 40%. In some examples, the weight percentage of the ceramic is 70% and the weight percentage of the metal is 30%. In some examples, the ceramic weight percentage is 80% and the metal weight percentage is 20%. In some examples, the ceramic weight percentage is 90% and the metal weight percentage is 10%. In some examples, the ceramic weight percentage is 5% and the metal weight percentage is 95%. In some examples, the ceramic weight percentage is 15% and the metal weight percentage is 85%. In some examples, the ceramic weight percentage is 25% and the metal weight percentage is 75%. In some examples, the ceramic weight percentage is 35% and the metal weight percentage is 65%. In some examples, the ceramic weight percentage is 45% and the metal weight percentage is 55%. In some examples, the ceramic weight percentage is 55% and the metal weight percentage is 45%. In some examples, the ceramic weight percentage is 65% and the metal weight percentage is 32%. In some examples, the ceramic weight percentage is 75% and the metal weight percentage is 25%. In some examples, the ceramic weight percentage is 85% and the metal weight percentage is 15%. In some examples, the ceramic weight percentage is 95% and the metal weight percentage is 5%.

[0166] In some examples, including any of the above, the ceramic in the ceramic-metal film can be selected from alumina, silica, titania, lithium-filled garnet, lithium aluminate, aluminum hydroxide, aluminosilicate, lithium zirconate, lanthanum aluminate, lanthanum zirconate, lanthanum oxide, lithium lanthanum oxide, zirconia, LiZrO, xLiO-(1-x)SiO (where x=0.01 to 0.99), aLiO-bBO-cSiO (where a+b+c=1), LiLaO, LiAlO, LiO, LiPO, or a combination thereof.

[0167] In examples, the triple layer includes a metal foil and a green ceramic film on both sides of the metal foil. The metal foil in the double or triple layer can have a thickness of 0.5 μm to 50 μm. The metal foil in the double or triple layer can have a thickness of 3 μm to 30 μm. In some examples, the metal foil in the double or triple layer can have a thickness of 5 μm to 20 μm. In other examples, the metal foil in the double or triple layer can have a thickness of 5 μm to 15 μm.

[0168] In some examples, including any of the above, the sintered article comprises LLZO.

[0169] In some instances, the sintered film has a D of less than 5 μm. 50 In some instances, the sintered film has a particle size D of less than 4 μm. 50 In some instances, the sintered film has a particle size D of less than 3 μm. 50 In some instances, the sintered film has a particle size D of less than 2 μm. 50 In some instances, the sintered film has a particle size D of less than 1 μm. 50 In some instances, the sintered film has a particle size D of less than 0.9 μm. 50 In some instances, the sintered film has a particle size D of less than 0.8 μm. 50 In some instances, the sintered film has a grain size D of less than 0.7 μm. 50 In some instances, the sintered film has a particle size D of less than 0.6 μm. 50In some instances, the sintered film has a particle size D of less than 0.5 μm. 50 In some instances, the sintered film has a particle size D of less than 0.4 μm. 50 In some instances, the sintered film has a particle size D of less than 0.3 μm. 50 In some instances, the sintered film has a grain size D of less than 0.2 μm. 50 In some instances, the sintered film has a particle size of less than 0.1 microns. 50 In some instances, the sintered film has a particle size D of less than 5 μm. 90 In some instances, the sintered film has a particle size D of less than 4 μm. 90 In some instances, the sintered film has a particle size D of less than 3 μm. 90 In some instances, the sintered film has a particle size D of less than 2 μm. 90 In some instances, the sintered film has a particle size D of less than 1 μm. 90 In some instances, the sintered film has a particle size D of less than 0.9 μm. 90 In some instances, the sintered film has a particle size D of less than 0.8 μm. 90 In some instances, the sintered film has a grain size D of less than 0.7 μm. 90 In some instances, the sintered film has a particle size D of less than 0.6 μm. 90 In some instances, the sintered film has a particle size D of less than 0.5 μm. 90 In some instances, the sintered film has a particle size D of less than 0.4 μm. 90 In some instances, the sintered film has a particle size D of less than 0.3 μm. 90 In some instances, the sintered film has a grain size D of less than 0.2 μm. 90 In some instances, the sintered film has a particle size of less than 0.1 microns. 90The sintered film has a particle size. In some cases, the sintered film has a porosity of less than 5%. In some cases, the sintered film has a porosity of less than 4%. In some cases, the sintered film has a porosity of less than 3%. In some cases, the sintered film has a porosity of less than 2%. In some cases, the sintered film has a porosity of less than 1%. In some cases, the sintered film has a porosity of less than 0.5%. In some cases, the sintered film has a porosity of less than 0.4%. In some cases, the sintered film has a porosity of less than 0.3%. In some cases, the sintered film has a porosity of less than 0.2%. In some cases, the sintered film has a density of greater than 95%. In some cases, the sintered film has a density of greater than 96%. In some cases, the sintered film has a density of greater than 97%. In some cases, the sintered film has a density of greater than 98%. In some examples, the sintered film has a density greater than 99%. In some examples, the sintered film has a density greater than 99.5%. In some examples, the sintered film has a density greater than 99.6%. In some examples, the sintered film has a density greater than 99.7%. In some examples, the sintered film has a density greater than 99.8%. In some examples, the sintered film has a density greater than 99.9%.

[0170] In some instances, the roll of sintered membrane may further include additional padding.

[0171] In some examples, including any of the above, the sintered film has a D of less than 5 microns (μm). 50 It has a particle size.

[0172] In some examples, including any of the above, the sintered film has a D of less than 5 μm. 90 It has a particle size.

[0173] In some examples, including any of the above, the sintered membrane has a porosity of less than 5% by volume.

[0174] In some examples, including any of the above, the sintered film has a defect density of less than 100 protrusions from the surface per square centimeter that have an aspect ratio (height / diameter) greater than 1.

[0175] In some examples, including any of the above, the sintered film has a defect density of less than 100 valleys per square centimeter from the surface that have an aspect ratio (height / diameter) greater than 1.

[0176] In some examples, including any of the above, the sintered film has a defect density of less than 100 protrusions per square centimeter at the interface between the lithium-filled garnet film and the metal layer, with an aspect ratio (height / diameter) greater than 1.

[0177] In some examples, including any of the above, the sintered film has a valley defect density of less than 100 defects per square centimeter at the interface between the lithium-filled garnet film and the metal layer, where the valley defect density has an aspect ratio (height / diameter) greater than 1.

[0178] In some instances, including any of the above, D 50 The particle size is at least 10 nm.

[0179] In some instances, including any of the above, D 50 The particle size is at least 50 nm.

[0180] In some instances, including any of the above, D 50 The particle size is at least 1 μm.

[0181] Sintered lithium-filled garnets on metal foils. The methods disclosed herein can be used to sinter lithium-filled garnets onto metal foils. In some examples, the metal foil is a densified metal layer. In certain examples, the metal foil is a densified metal layer and also includes a ceramic. In some of these examples, the ceramic is a lithium-filled garnet.

[0182] In some examples, the metal foil or layer is nickel, steel, stainless steel, copper, aluminum, Kovar, Invar, ceramic, Haynes 216, or a combination thereof.

[0183] In certain examples, the LLZO is sintered onto a metal foil. In some of these examples, the metal foil is pure Ni. In some of these examples, the metal foil is a combination of Ni and Fe. In some of these examples, the metal foil is 93% / 7% Ni / Fe.

[0184] In certain examples, the LLZO is sintered onto a metal foil. In some of these examples, the metal foil is pure Cu. In some of these examples, the metal foil is 93% / 7% Cu / Fe. In some of these examples, the metal foil is a combination of Cu and Fe.

[0185] In some instances, CTE matching is used to prevent bowing in the sintered film. CTE matching involves matching the coefficient of thermal expansion (CTE) of two layers. The interface between the two layers is formed / set during sintering above 1000°C. When the film is subsequently cooled to room temperature, if the CTEs are not the same, one layer will shrink slightly more than the other, resulting in a bowed film on one side (the side that has contracted more), which is undesirable.

[0186] As used herein, "Invar" is a Ni / Fe material.

[0187] In some examples, the green tape described above as being deposited on Mylar foil is instead deposited on a metal layer. The metal can be nickel, steel, stainless steel, copper, aluminum, Kovar, Invar, ceramic, ceramic on metal, Haynes 216, LLZO, LLZO on Ni, or a combination thereof. In this example, the green tape does not need to be peeled from the Mylar, but can instead be sintered directly onto the metal. The green tape and metal can be rolled up together before the green tape passes through the CML. In some examples, a backing layer is applied to the metal that is rolled up with the green tape on the metal. In some examples, an interleaf layer is used when rolling up the metal with the green tape on the metal. The interleaf provides a pad between the rolled up layers.

[0188] Sintered lithium-filled garnet without an underlying substrate In some examples, the methods and systems herein sinter lithium-filled garnets without an underlying substrate.

[0189] Sintered lithium-filled garnet with co-sintered current collector In some examples, the present disclosure uses a sintered lithium-filled garnet layer adjacent to a co-sintered current collector (CSC). The CSC layer can contain 0.0001% to 25% by weight Ni, 1% to 25% by weight Fe, or a combination thereof. In some cases, the CSC layer contains 1% to 20% by weight Ni and 1% to 10% by weight Fe, with the remainder being lithium-filled garnet. In some cases, the CSC layer contains 5% to 15% by weight Ni and 1% to 5% by weight Fe, with the remainder being lithium-filled garnet. In some cases, the CSC layer contains 10% to 15% by weight Ni and 3% to 5% by weight Fe, with the remainder being lithium-filled garnet.

[0190] Other configurations are contemplated herein. For example, the bare film configuration can be: a sintered LLZO film with no other metal-containing layers.

[0191] For example, a CSC or co-sintered construction can include a bilayer of green LLZO and a green metal-ceramic layer, the latter being a powder of metal and ceramic maintained in a green state.

[0192] For example, foil construction can be as follows: This involves casting green LLZO onto a metal layer / foil. The metal layer is a dense layer, not a powder. The foil in this case does not contain ceramic, can be purchased, and is typically manufactured by a process other than sintering (e.g., electrodeposition or roll annealing). For example, foil construction can also be achieved using ceramic-metal foils. This involves using regular metal foils; because it starts with a metal-ceramic foil, the resulting end product is similar to a CSC.

[0193] Setter In some embodiments described herein, the setter plate may include a member selected from LiZrO, xLiO-(1-x)SiO (where x = 0.01 to 0.99), aLiO-bBO-cSiO (where a + b + c = 1), LiLaO, LiAlO, LiO, LiPO, a Li-filled garnet, or a combination thereof. In some embodiments, the setter plate includes LiZrO. In some embodiments, the setter plate includes LiSiO. In some embodiments, the setter plate includes LiLaO. In some embodiments, the setter plate includes LiAlO. In some embodiments, the setter plate includes LiO. In some embodiments, the setter plate includes LiPO. In some embodiments, the setter plate includes a Li-filled garnet. In some embodiments, the setter plates include at least two, three, four, or more of LiZrO, LiSiO, LiLaO, LiAlO, LiO, LiPO, and Li-filled garnets. Additionally, these setter plates should not induce a chemical potential in the sintered film that would cause Li to diffuse from the sintered film, e.g., into the setter plate.

[0194] In some embodiments, the present disclosure provides a setter plate suitable for use in fabricating a solid electrolyte of a rechargeable battery, the setter plate comprising a Li-filled garnet compound characterized by the formula Li x La y Zr z O t ·qAl2O3 (where 4 < x < 10, 1 < y < 4, 1 < z < 3, 6 < t < 14, and 0 ≦ q ≦ 1). In some embodiments, the setter plate has a surface defined by a first lateral dimension of 2 cm to 30 cm and a second lateral dimension of 2 cm to 30 cm, and a thickness of 0.1 mm to 100 mm.

[0195] In some embodiments, the present disclosure provides a setter plate comprising any of the setter plates described in U.S. Patent No. 10,563,918 (which is incorporated herein by reference in its entirety for all purposes).

[0196] Method of Use In some embodiments comprising any of the above, a method of sintering a bilayer is described herein, which comprises preparing or having prepared the stack disclosed herein and sintering the bilayer.

[0197] The embodiments and examples described above are merely illustrative and are not intended to be limiting. One of ordinary skill in the art can recognize or confirm many equivalents of specific compounds, materials, and procedures using only routine experimentation. All such equivalents are considered to be within the scope and are encompassed by the appended claims.

Claims

1. a lower setter including at least one or more refractory materials; a bilayer disposed on the lower setter, a layer comprising an oxide; and a layer containing a metal; a bilayer comprising: an upper setter disposed on the bilayer, the upper setter having a periphery but no center; A stack comprising:

2. The stack of claim 1 , wherein the oxide-containing layer does not include a metal in the oxide-containing layer.

3. The stack of claim 2 , wherein the oxide-containing layer consists of an oxide.

4. 4. The stack of claim 2 or 3, wherein the oxide-containing layer consists essentially of oxide.

5. The stack of any one of claims 1 to 4, wherein the oxide-containing layer comprises a lithium-loaded garnet oxide.

6. 6. The stack of claim 1, 4 or 5, wherein the oxide-containing layer further comprises a metal in the oxide-containing layer.

7. 7. The stack of claim 6, wherein the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

8. 8. The stack of claim 6 or 7, wherein the metal in the oxide-containing layer is Ni.

9. 8. The stack of claim 6 or 7, wherein the metal in the oxide-containing layer is Fe.

10. 10. The stack according to claim 6, wherein the oxide-containing layer comprises two or more metals.

11. 11. The stack of any one of claims 1 to 10, wherein the metal-containing layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

12. The stack of claim 11 , wherein the metal-containing layer comprises Ni.

13. The stack of claim 11 , wherein the metal-containing layer comprises Fe.

14. The stack of claim 11 , wherein the metal-containing layer comprises Cu.

15. Stack according to any one of claims 1 to 14, wherein the upper setter is a metal foam.

16. The stack of any one of claims 1 to 15, wherein the upper setter is nickel (Ni) foam.

17. The refractory material is Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ The stack of any one of claims 1 to 16, selected from the group consisting of: and combinations thereof.

18. The upper setter is Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , LiAlO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ 18. The stack of any one of claims 1 to 17, comprising a refractory material selected from the group consisting of: and combinations thereof.

19. The refractory material is LiAlO ２ 19. The stack of claim 17 or 18, comprising:

20. The stack of any one of claims 1 to 19, further comprising at least one shim disposed between the upper setter and the lower setter.

21. The stack of any one of claims 1 to 20, further comprising a third setter disposed above the upper setter, the third setter comprising at least one or more refractory materials.

22. 22. The stack of claim 21, further comprising a layer including a shim disposed above the upper setter and disposed between the upper setter and a third setter including the at least one refractory material disposed above the upper setter.

23. Two or more stacks according to any one of claims 1 to 22, wherein two or more stacks are stacked on top of each other.

24. The lower setter and a bilayer disposed on the lower setter, a layer comprising an oxide; and a layer containing a metal; a bilayer comprising: a metal mesh disposed on the electrolyte double layer; A stack comprising:

25. 25. The stack of claim 24, wherein the metal mesh comprises Ni.

26. 26. The stack of claim 24 or 25, wherein the metal mesh is a metal foam.

27. The stack of any one of claims 24 to 26, wherein the oxide-containing layer does not include a metal in the oxide-containing layer.

28. The stack according to any one of claims 24 to 26, wherein the oxide-containing layer consists of an oxide.

29. Stack according to any one of claims 24 to 28, wherein the oxide-containing layer consists essentially of the oxide.

30. 30. The stack of any one of claims 24 to 29, wherein the oxide-containing layer comprises a lithium-loaded garnet oxide.

31. The stack of any one of claims 24 to 26 or 28 to 30, wherein the oxide-containing layer further comprises a metal in the oxide-containing layer.

32. 32. The stack of claim 31 , wherein the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

33. 33. The stack of claim 31 or 32, wherein the metal in the oxide-containing layer is Ni.

34. 33. The stack of claim 31 or 32, wherein the metal in the oxide-containing layer is Fe.

35. 33. The stack of claim 31 or 32, comprising two or more metals in the oxide-containing layer.

36. 36. The stack of any one of claims 24 to 35, wherein the metal-containing layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

37. 37. The stack of claim 36, wherein the metal-containing layer comprises Ni.

38. 37. The stack of claim 36, wherein the metal-containing layer comprises Fe.

39. 37. The stack of claim 36, wherein the metal-containing layer comprises Cu.

40. The lower setter comprises one or more refractory materials, and the refractory materials are Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ 40. The stack of any one of claims 24 to 39, selected from the group consisting of: and combinations thereof.

41. The upper setter is Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ 41. The stack of any one of claims 24 to 40, comprising one or more refractory materials selected from:

42. The refractory material is LiAlO ２ 42. The stack of claim 40 or 41, comprising:

43. The stack of any one of claims 24 to 42, further comprising at least one shim disposed between the metal mesh and the lower setter.

44. 43. The stack of any one of claims 24 to 42, further comprising the metal mesh in contact with the bilayer.

45. 45. The stack of any one of claims 24 to 44, further comprising a setter disposed above the metal mesh and including at least one refractory material.

46. 46. ​​The stack of claim 45, further comprising a layer including a shim disposed above the metal mesh and disposed between the metal mesh and the setter including the at least one refractory material disposed above the metal mesh.

47. Two or more stacks according to any one of claims 24 to 46, wherein two or more stacks are stacked on top of each other.

48. The lower setter and a bilayer disposed on the lower setter, a layer comprising an oxide; and a layer containing a metal; a bilayer comprising: at least one shim disposed above the bilayer, the shim comprising a fire-resistant material; A stack comprising:

49. The lower setter and a bilayer disposed on the lower setter, a layer comprising an oxide; and a layer containing a metal; a bilayer comprising at least one shim disposed around the bilayer, the shim comprising a fire-resistant material; A stack comprising:

50. 50. The stack of claim 48 or 49, wherein the oxide-containing layer does not include a metal in the oxide-containing layer.

51. 50. The stack of claim 48 or 49, wherein the oxide-containing layer consists of an oxide.

52. 50. The stack of claim 48 or 49, wherein the oxide-containing layer consists essentially of oxide.

53. 53. The stack of any one of claims 48 to 52, wherein the oxide-containing layer comprises a lithium-loaded garnet oxide.

54. 54. The stack of claim 48, 49 or 53, wherein the oxide-containing layer further comprises a metal in the oxide-containing layer.

55. 55. The stack of claim 54, wherein the metal in the oxide-containing layer is selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

56. 56. The stack of claim 54 or 55, wherein the metal in the oxide-containing layer is Ni.

57. 56. The stack of claim 54 or 55, wherein the metal in the oxide-containing layer is Fe.

58. 56. The stack of claim 54 or 55, comprising two or more metals in the oxide-containing layer.

59. 59. The stack of any one of claims 48 to 58, wherein the metal-containing layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), titanium (Ti), zirconium (Zr), and combinations thereof.

60. 60. The stack of claim 59, wherein the metal-containing layer comprises Ni.

61. 60. The stack of claim 59, wherein the metal-containing layer comprises Fe.

62. 60. The stack of claim 59, wherein the metal-containing layer comprises Cu.

63. 63. The stack of any one of claims 48 to 62, further comprising an upper setter disposed on top of at least one or more shims comprising the refractory material.

64. 64. The stack of claim 63, wherein the upper setter is a metal foam.

65. 65. The stack of claim 63 or 64, wherein the upper setter is nickel (Ni) foam.

66. The refractory material is Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ 66. The stack of any one of claims 48 to 65, selected from:

67. The upper setter is Al ２ O ３ , LiAlO ２ , Li ７ La ３ Zr ２ O １２ , Li ２ ZrO ３ , xLi ２ O-(1-x)SiO ２ (where x=0.01 to 0.99), aLi ２ O-bB ２ O ３ -cSiO ２ (where a+b+c=1), LiLaO ２ , Li ２ O, Li ３ P.O. ４ , ZrO ２ , ZnO ２ 67. The stack of any one of claims 48 to 66, comprising a refractory material selected from:

68. The refractory material is LiAlO ２ 68. The stack of claim 66 or 67, comprising:

69. 69. The stack of any one of claims 63 to 68, further comprising a third setter disposed above the upper setter, the third setter comprising at least one or more refractory materials.

70. 70. The stack of claim 69, further comprising a layer including a shim disposed above the upper setter and disposed between the upper setter and an additional layer including at least one or more refractory materials disposed above the upper setter.

71. Two or more stacks according to any one of claims 48 to 70, wherein two or more stacks are stacked on top of each other.

72. 72. The stack of any one of claims 1 to 71, wherein the bilayer is oriented such that the oxide-containing layer is in contact with the lower setter.

73. 72. The stack of any one of claims 1 to 71, wherein the bilayer is oriented such that the metal-containing layer is in contact with the lower setter.

74. 74. The stack of any one of the preceding claims, wherein the metal-containing layer comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), copper (Cu), platinum (Pt), gold (Au), silver, alloys thereof, or combinations thereof.

75. 75. The stack of any one of claims 1 to 74, wherein the metal-containing layer is an alloy of Fe and Ni.

76. 76. The stack of any one of claims 1 to 75, wherein the metal-containing layer is an alloy of Fe and Ni, the amount of Fe being 1% to 25% (w / w), the remainder being Ni.

77. 77. The stack of any one of the preceding claims, wherein the metal-containing layer has a thickness of 1 μm to 20 μm.

78. 78. The stack of any one of the preceding claims, wherein the metal-containing layer has a thickness of 1 μm to 10 μm.

79. Stack according to any one of the preceding claims, wherein the metal-containing layer has a thickness of 5 μm to 10 μm.

80. 80. The stack of any one of claims 1 to 79, wherein the bilayer is less than 200 μm thick.

81. 81. The stack of any one of claims 1 to 80, wherein the metal-containing layer comprises no more than 10% by weight (w / w) relative to the total weight of the bilayer.

82. The double layer has a resistance of 20 Ω cm at room temperature. ２ 82. The stack of any one of claims 1 to 81, having an area specific resistance of less than 1000 kJ / cm.

83. The double layer has a resistance of 20 Ω cm at 20°C. ２ 83. The stack of any one of claims 1 to 82, having an area specific resistance of less than 1000 kJ / cm.

84. 84. The stack of any one of claims 1 to 83, wherein the bilayer is about 30 μm to 50 μm thick.

85. 85. The stack of any one of claims 1 to 84, wherein the bilayer is about 30 μm, 40 μm or 50 μm thick.

86. Stack according to any one of the preceding claims, wherein the surface of the bilayer opposite the metal-containing layer is free of defects.

87. The bilayer has a D of about 50 μm ９０ The stack of any one of claims 1 to 86, having a ceramic grain size.

88. The bilayer has a D of about 25 μm ９０ 88. The stack of any one of claims 1 to 87, having a ceramic grain size.

89. The bilayer has a D of about 5 μm ９０ The stack of any one of the preceding claims, having a ceramic grain size.

90. 90. The stack of any one of claims 1 to 89, wherein the bilayer comprises a sintered lithium-filled garnet oxide.

91. 91. The stack of any one of claims 1 to 90, wherein the bilayer has a porosity of less than 5% by volume as determined by scanning electron microscopy (SEM).

92. 92. The stack of any one of claims 1 to 91, wherein the bilayer has a porosity of less than 0% as measured by BET surface area analysis.

93. 93. The stack of any one of the preceding claims, wherein the bilayer has a porosity of less than 0% by volume as measured by a helium leak test.

94. The oxide-containing layer includes lithium-filled garnet, and the oxide-containing layer is 100 mm ２ 94. The stack of any one of claims 1 to 93, wherein the stack is free of defects on the lithium-filled garnet over an area of ​​0.1 to 0.5 mm.

95. The oxide-containing layer comprises lithium-filled garnet, and the oxide-containing layer is 100 cm ２ 95. The stack of any one of claims 1 to 94, wherein the stack is free of defects on the lithium-filled garnet over an area of ​​0.1 to 0.5 mm.

96. The oxide-containing layer includes lithium-filled garnet, and the oxide-containing layer is 100 mm ２ 96. The stack of any one of claims 1 to 95, wherein the stack is free of defects on the lithium-filled garnet over an area of ​​.

97. The oxide-containing layer has a D of about 50 μm. ９０ 97. The stack of any one of claims 1 to 96, comprising a lithium-filled garnet having a grain size.

98. The oxide-containing layer has a D of about 25 μm. ９０ 98. The stack of any one of claims 1 to 97, comprising a lithium-filled garnet having a grain size.

99. The oxide-containing layer has a D of about 5 μm. ９０ 99. The stack of any one of claims 1 to 98, comprising a lithium-filled garnet having a grain size.

100. 100. The stack of any one of the preceding claims, wherein the bilayer comprises a lithium-loaded garnet oxide.

101. Stack according to any one of the preceding claims, wherein the bilayer has a porosity of less than 5% by volume as determined by scanning electron microscopy (SEM).

102. Stack according to any one of the preceding claims, wherein the bilayer has a porosity of 0% by volume as measured by BET surface area analysis.

103. Stack according to any one of the preceding claims, wherein the bilayer has a porosity of less than 0% by volume as measured by a helium leak test.

104. 104. The stack of any one of claims 1 to 103, wherein the oxide-containing layer comprises a lithium-filled garnet having a defect density of less than 100 protrusions per square centimeter from the surface with an aspect ratio (height / diameter) greater than 1.

105. 105. The stack of any one of claims 1 to 104, wherein the oxide-containing layer comprises a lithium-filled garnet having a defect density of less than 100 valleys per square centimeter from the surface, with an aspect ratio (height / diameter) greater than 1.

106. The oxide-containing layer has a D of at least 10 nm. ５０ 106. The stack of any one of claims 1 to 105, comprising a lithium-filled garnet having a grain size.

107. The oxide-containing layer has a D of at least 50 nm. ５０ 107. The stack of any one of claims 1 to 106, comprising a lithium-filled garnet having a grain size.

108. The oxide-containing layer has a D of at least 1 μm. ５０ 108. A stack according to any preceding claim, comprising a lithium-filled garnet having a grain size.

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