All-solid-state batteries

Abstract

To provide solid-state battery architectures that include an oxide electrolyte in contact with an anode of an electrochemical cell and a sulfide electrolyte in contact with a cathode of the electrochemical cell.SOLUTION: A solid-state electrochemical cell (SSEC) comprises: (a) a positive electrode layer comprising an active material and a sulfide catholyte; (b) a single ion conducting, solid-state buffer; (c) a borohydride bonding layer; and (d) a lithium-stuffed garnet layer. The buffer is mixed in the positive electrode layer; the buffer is a layer in contact with the positive electrode layer; or the buffer is mixed in the positive electrode layer and the buffer is a layer in contact with the positive electrode layer. The borohydride bonding layer is between and in contact with the lithium-stuffed garnet layer and either (i) the positive electrode layer with the buffer mixed therein or (ii) the buffer layer in contact with the positive electrode.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 681,576, filed June 6, 2018, and entitled "HYBRID SOLID-STATE BATTERY," the entire contents of which are incorporated herein by reference in their entirety for all purposes. [Background technology]

[0002] Field FIELD OF THE DISCLOSURE

[0002] This disclosure relates to solid-state rechargeable batteries, also known as secondary batteries.

[0003] background

[0003] Batteries are described as all-solid-state batteries if they contain a solid-state electrolyte separator between the positive and negative electrodes of the battery cell. Solid-state electrolytes do not contain flammable organic solvents and are therefore attractive for safety reasons.

[0004]

[0004] All-solid-state batteries operate over a relatively wider temperature, voltage, and pressure range than liquid electrolyte-based batteries. All-solid-state batteries may also include solid-state anodes and cathodes. All-solid-state batteries may include, for example, metallic lithium (Li) cathodes. Li metal cathodes are preferred because they maximize the anode and cathode voltage difference. + Maximizing energy density in ion batteries. All-solid-state rechargeable batteries are predicted to be safer (e.g., less flammable) and have higher energy and power densities than currently commercially available liquid electrolyte-based batteries. However, a series of unmet challenges remain that prevent commercially viable all-solid-state batteries from being realized.

[0005]

[0005] Some solid-state battery researchers have utilized a single, monolithic, single-ion conductor to act as the electrolyte separator between the anode and cathode. There are many challenges associated with this approach. For example, to date, there are no single-ion conducting solid electrolytes that have both sufficiently high ionic conductivity and sufficient mechanical strength while being commercially available for processing, lightweight enough for certain applications, and stable in the voltage range of 0 to 5 V vs. Li. All-solid-state batteries to date have necessarily involved design tradeoffs to address each of these challenges.

[0006]

[0006] Some researchers have attempted to incorporate more than one type of solid electrolyte into an all-solid-state electrochemical cell. For example, some have prepared oxide-sulfide composites of lithium superionic conductors. See, for example, J. Mater. Chem. A, 2014,2, 4111-4116 DOI: 10.1039 / C3TA15223E, which reports an oxide-sulfide composite containing a mixture of lithium-loaded garnet powder and lithium phosphorus sulfide (LPS) powder. Also see http: / / ma.ecsdl.org / content / MA2016-01 / 2 / 264.abstract, which presents results for an electrochemical cell with a metallic Li anode, a solid oxide electrolyte (LLZO), and a composite cathode consisting of 75Li2S:25P2S5 sulfide electrolyte and TiS2. In addition, LiNbO3-coated LiCoO2 anode active material and specific sulfide solid electrolyte (Li 9.6 P3S 12 , Li 10 GeP2S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3See also Y. Kato, et al. DOI: 10.1038 / NENERGY.2016.30, which reports cycling data for electrochemical cells with ZnO, ZnO, and ZnO. See also Suzuki, et al., Journal of Power Sources 359 (2017) 97-103, which describes all-solid-state cells. These reported results suffer from various imperfections, including low capacity and capacity fade over time. Summary of the Invention [Problem to be solved by the invention]

[0007]

[0007] Solutions to the above and other problems in related fields are needed because a series of unmet problems remain. The present disclosure provides compositions, processes, and methods for solving these and other challenges and problems. [Means for solving the problem]

[0008] overview

[0008] In one embodiment, described herein is an all-solid-state electrochemical cell (SSEC) comprising: (a) an anode layer comprising an active material and a sulfide catholyte; (b) a single-ion conductive solid buffer; (c) a borohydride binder layer; and (d) a lithium-stuffed garnet layer. The buffer is mixed into the anode layer, the buffer is present as a layer in contact with the anode layer, or the buffer is mixed into the anode layer and the buffer is present as a layer in contact with the anode layer. The borohydride binder layer is between and in contact with the lithium-stuffed garnet layer and either (i) the anode layer in which the buffer is mixed, or (ii) the buffer layer in contact with the anode.

[0009]

[0009] In a second embodiment, a method for manufacturing an electrochemical cell is described herein, comprising the following steps: (a) providing a slurry comprising an active material, a catholyte, and a solvent; (b) depositing the slurry onto a current collector; (c) drying the slurry; (e) providing a second slurry comprising a single-ion conductive solid buffer; (f) depositing the second slurry onto a substrate; (g) drying the deposited second slurry to form a buffer layer; (h) transferring the buffer layer onto the first slurry so as to form a stack upon drying; (i) applying pressure and heat to the stack; (j) providing a solid separator; (k) depositing a borohydride layer onto the solid separator; (l) overlapping the stack and the solid separator having the borohydride layer to form an electrochemical cell stack; and (m) applying pressure and heat to the electrochemical cell stack.

[0010]

[0010] In one aspect, provided herein is a solid electrochemical stack comprising: (a) an anode layer comprising an anode active material, a binder, and a sulfide catholyte, and having a porosity of less than 15% by volume (v / v); (b) a buffer layer in contact with the anode layer, comprising a sulfide electrolyte, and having a porosity of less than 15% v / v; and (c) a separator layer comprising a member selected from the group consisting of lithium-filled garnet and LPSX, and having a porosity of less than 10% v / v, wherein the buffer layer is present between the anode layer and the separator layer.

[0011]

[0011] In another aspect, there is provided a method for making a solid electrochemical stack, comprising: (a) casting a first slurry comprising a sulfide solid electrolyte powder onto a first substrate to form a first layer; (b) casting a second slurry comprising the sulfide solid electrolyte powder and an anode active powder onto a second substrate to form a second layer; and (c) calendering the first and second layers, wherein the first and second layers are in direct contact with each other. In another aspect, there is provided herein a bilayer stack comprising: (a) an anode layer comprising an active material and a sulfide catholyte; and (b) a single-ion conductive solid buffer; wherein the buffer is mixed within the anode layer, is a layer in contact with the anode layer, or both. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 shows a schematic diagram of an example electrochemical cell. [Figure 2]

[0013] Figure 2 shows cross-sectional scanning electron microscopy images of the solid-state cathode (SSC), buffer layer, bonding layer, and garnet film of the electrochemical cell fabricated in Example 1 (cross-sections prepared by focused ion beam). The scale bar in Figure 2 is 50 μm. The imaging conditions were WD 4.4 mm, HV 5.00 kV, HFW, 207 μm, magnification 2000x, det TLD, tilt 52°, BSE mode. [Figure 3]

[0014] FIG. 3 is a plot of voltage as a function of active mass-specific capacity (mAh / g) over 50 cycles as described in Example 2. [Figure 4]

[0015] FIG. 4 is a plot of active mass specific discharge volume (mAh / g) as a function of cycle number as described in Example 2. [Figure 5]

[0016] FIG. 5 shows a plot of ASR as a function of rest voltage as described in Example 2. [Figure 6]

[0017] FIG. 6 shows a schematic diagram of an example electrochemical cell including a separator, a buffer layer, and an anode layer. [Figure 7]

[0018] FIG. 7 shows a schematic diagram of an example electrochemical cell including a separator, a bonding layer, and an anode layer. [Figure 8]

[0019] FIG. 8 shows plots of lithium ion conductivity (Log(S / cm)) at 60°C for several LBHI compositions and amide-doped LBHI compositions: (A) LiBH4:LiI (3:1), (B) LiNH2:LiBH4:LiI (3:3:2), (C) LiNH2:LiBH4:LiI (9:3:4), and (D) LiNH2:LiBH4:LiI (9:3:2). [Figure 9]

[0020] FIG. 9 shows cycling data for an all-solid-state electrochemical cell comprising a lithium-loaded garnet electrolyte membrane bonded to a solid cathode membrane comprising LPSI according to Example 13. DETAILED DESCRIPTION OF THE INVENTION

[0013] overview

[0021] In some embodiments, the present disclosure provides a dielectric constant of 50 Ω-cm at room temperature. 2 Electrochemical cells are disclosed that exhibit an ASR of less than 1000 kJ / cm 2 . The electrochemical cells disclosed herein include an oxide electrolyte separator and a sulfide electrolyte separator. The electrochemical cells herein include a sulfide-oxide solid electrolyte interface. A bonding layer comprising a borohydride is used to bond the oxide electrolyte separator and the sulfide electrolyte separator. The oxide electrolyte separator is kinetically stable to metallic Li and is compatible with Li +It has adequate mechanical strength to conduct high ionic current densities. The sulfide catholyte in the solid cathode and / or the sulfide buffer layer adjacent to the solid cathode provide a conductive pathway for lithium ions, making it suitable for use with high mass loadings of active material in the anode. In some embodiments, the sulfide catholyte is kinetically stable with coated active materials (e.g., LZO-coated NCA or LZO-coated NMC). In some embodiments, the sulfide catholyte is kinetically stable with coated active materials (e.g., LZO-coated NCA) in a voltage window of 2.7 to 4.2 V vs. Li. The borohydride bonding layer bonds the oxide electrolyte separator and the sulfide (buffer) electrolyte separator and also provides an ionic conduction pathway between the two electrolyte separators.

[0014]

[0022] The electrochemical cells disclosed herein, in certain embodiments, include an oxide solid separator in contact with the cathode side of the electrochemical cell and a sulfide solid separator in contact with the anode side of the electrochemical cell. In some embodiments, the sulfide and oxide solid separators are, for example, 1*10 -3 S / cm 2 In some embodiments, a bonding layer made from a borohydride is present between the oxide solid separator and the sulfide solid separator. In some embodiments, a lithium metal cathode is present on the side of the oxide solid separator opposite the borohydride bonding layer. In some embodiments, a cathode is present on the side of the sulfide solid separator opposite the borohydride bonding layer.

[0015] definition

[0023] To the extent that a definition provided in any document incorporated by reference herein differs from the definition provided herein, the definition provided herein shall control.

[0016]

[0024] As used herein, the term "about" when describing a number, e.g., about 15% w / w, refers to the number within the described number and, optionally, a range surrounding the described number, optionally including ±10% of that number. For example, about 15% w / w includes 15% w / w, as well as 13.5%, 14%, 14.5%, 15.5%, 16%, or 16.5% w / w. For example, "about 75°C" includes 75°C, as well as 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.

[0017]

[0025] As used herein, the phrase "active material" refers to a material that intercalates or converts lithium in a reversible reaction, making the active material suitable for use in a rechargeable battery. Active materials can include intercalation materials such as NCA or NMC. Active materials can include conversion chemistries such as FeF. For example, active materials can include, but are not limited to, any of the active materials set forth in U.S. Patent Application Publication No. 20160211517A1, entitled "LITHIUM RICH NICKEL MANGANESE COBALT OXIDE," published July 21, 2016.

[0018]

[0026] As used herein, the term "amorphous" refers to a material that is not crystalline or does not contain multiple crystalline phases. Amorphous refers to a material that does not exhibit crystalline characteristics, such as distinct X-ray diffraction peaks as measured by X-ray diffraction. An amorphous material is characterized as being at least primarily amorphous and having more amorphous components than crystalline components. Substantially amorphous refers to a material characterized by an X-ray diffraction pattern that does not contain distinct X-ray diffraction peaks or that contains broad reflections that would be recognized by those skilled in the art as having multiple constituent phases as amorphous phases. A substantially amorphous material may have crystalline nano-sized regions, but will still be characterized by an X-ray diffraction pattern as being primarily amorphous. In a substantially amorphous material, a transmission electron microscopy (TEM) selected area diffraction pattern (SADP) may reveal crystalline regions, but will also reveal that the majority of the volume of the material is amorphous.

[0019]

[0027] As used herein, the terms "semi-amorphous" or "semi-crystalline" refer to a composition having crystalline and amorphous regions. Semi-crystalline materials contain nanocrystalline and / or microcrystalline components in addition to amorphous components. Semi-crystalline materials are partially crystallized materials or materials containing some crystalline and some amorphous forms. For example, a material that is heated to its crystallization temperature but then cooled before all of the material can fully crystallize is described herein as a semi-crystalline material. As used herein, semi-crystalline materials can be characterized by an XRD powder pattern in which the main peak of highest intensity has a full width at half maximum of at least 1° (2θ), or at least 2° (2θ), or at least 3° (2θ).

[0020]

[0028] As used herein, the term "anolyte" refers to an ionically conductive material mixed with, layered on, or laminated to the anode material or anode current collector.

[0021]

[0029] As used herein, the phrase "applying pressure" refers to the process in which an external device, such as a calendar, applies pressure to another material.

[0022]

[0030] As used herein, the phrase "at least one member selected from a group" includes a single member from the group, two or more members from the group, or a combination of members from the group. At least one member selected from the group consisting of A, B, and C includes, for example, A alone, B alone, or C alone, as well as A and B, A and C, B and C, and A, B, and C, or any other combination of A, B, and C.

[0023]

[0031] As used herein, "ASR" refers to area-specific resistance. ASR is measured using electrochemical impedance spectroscopy (EIS). EIS can be performed on a Biologic VMP3 instrument or its equivalent. In ASR measurements, lithium contacts are deposited on two sides of the sample. An AC voltage of 25 mV RMS at a frequency between 300 kHz and 0.1 mHz is applied while the current is measured. By resolving the two semicircles of the Nyquist plot, EIS separates the ASR into a volumetric contribution and an interfacial ASR contribution.

[0024]

[0032] As used herein, the phrase "borohydride bonding layer" refers to a layer that includes a borohydride compound and adheres a lithium-loaded garnet layer to a sulfide electrolyte layer or sulfide-containing buffer. Non-limiting examples of borohydrides include, but are not limited to, 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2. The borohydride may be any of the compounds specified in International Publication No. WO 2018 / 075972, published April 26, 2018, and filed as International PCT Patent Application No. PCT / US2017 / 057735, and entitled "ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. The borohydride may be any compound specified in International Publication No. WO 2019078897A1, published April 25, 2019, and filed October 20, 2017 as International PCT Patent Application No. PCT / US2017 / 057739, and entitled "BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID STATE BATTERY." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes.

[0025]

[0033] As used herein, "binder" refers to a polymer capable of increasing the adhesive and / or cohesive strength of an electrode. Suitable binders may include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene alpha-olefin copolymers.

[0026]

[0034] As used herein, the term "buffer" refers to a single-ion conducting solid electrolyte that is finely mixed or combined with the anode components, or a layer in direct contact with the anode, e.g., an electrolyte layer laminated to the anode layer. Single-ion conducting means that the material can conduct only one type of ion, e.g., Li. + By solid, we mean that the buffer exists in a solid phase at ambient temperature and pressure.

[0027]

[0035] As used herein, the phrase "buffer is mixed into the anode layer" means that the buffer material is comminuted, e.g., milled, and then mixed with other anode layer compounds, e.g., active material and conductive carbon, when the anode layer is formed.

[0028]

[0036] As used herein, the phrase "casting a film" refers to the process of delivering or transporting a liquid or slurry into a mold or onto a substrate so that it forms or is formed into a film. Casting may be performed by doctor blade, Mayer rod, comma coater, gravure coater, microgravure, reverse comma coater, slot die, slip and / or tape casting, and other methods.

[0029]

[0037] As used herein, the phrase "characterized by the formula" refers to the description of a compound by its chemical formula.

[0030]

[0038] As used herein, the phrase "current collector" refers to a component or layer in a secondary battery in direct contact with an electrode through which electrons are conducted to or from the electrode to complete an external circuit and to which electrons are conducted. In some embodiments, the current collector is a metal (e.g., Al, Cu, or Ni, steel, alloys thereof, or combinations thereof) layer deposited on the anode or cathode. In some embodiments, the current collector is Al. In some embodiments, the current collector is Cu. In some embodiments, the current collector is Ni. In some embodiments, the current collector is steel. In some embodiments, the current collector is an alloy of Al. In some embodiments, the current collector is an alloy of Cu. In some embodiments, the current collector is an alloy of steel. In some embodiments, the current collector is Al. In some embodiments, the current collector is coated with carbon. In some embodiments, the current collector comprises a combination of the above metals. During charge and discharge, electrons move in the opposite direction to the flow of Li ions and pass through the current collector as they enter or exit the electrode.

[0031]

[0039] As used herein, "diameter (d 90 The term "particle size" refers to a size in a distribution of sizes as measured by microscopy or other particle size analysis techniques, including but not limited to scanning electron microscopy or dynamic light scattering. 90 includes the characteristic dimension, i.e., particle size, where 90% of the total particle area (for 2D sampling methods such as microscopy) or volume (for 3D sampling methods such as light scattering) represents particles smaller than the stated size. In other words, within a set of particle sizes, d 90 indicates the diameter at which 90% of the particles in the population have a diameter smaller than the stated diameter. 50 The term "diameter (d )" includes a characteristic dimension that describes particles where 50% of the total particle area (or volume) is smaller than the stated diameter. 10The term "diameter" includes characteristic dimensions that represent particles where 10% of the total particle area (or volume) is smaller than the stated diameter. These figures may be calculated on a volumetric or area basis. If not explicitly stated, a volumetric basis is assumed.

[0032]

[0040] As used herein, "binder" refers to a material that aids in adhering one material to another. 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 intended to be limiting as the entire scope of binders contemplated herein, but are merely useful as examples. Binders useful in the present disclosure include, but are not limited to, polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylics, polyvinyl acetoacetal resins, polyvinyl butyral resins, PVB, polyvinyl acetal resins, stereoblock polypropylene, polypropylene polymethylpentene copolymers, polyethylene oxide (PEO), PEO block copolymers, silicones, and the like.In some examples, including any of the above, the binder is selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, The polymer is selected from the group consisting of ethylenediamine fluoride (EPR), polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene polymer (EPR), nitrile rubber (NPR), styrene-butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA). As used herein, "selected from the group consisting of" refers to a single member from the group, two or more members from the group, or a combination of members from the group. Members selected from the group consisting of A, B, and C include, 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.

[0033]

[0041] As used herein, the term "contact" means direct contact unless otherwise specified. With respect to electrically conductive materials, contact means sufficient contact for electrical conduction to occur between the contacting materials. With respect to ionically conductive materials, contact means sufficient contact for ionic conduction to occur between the contacting materials. Two materials in direct contact are disposed without an interleaved layer between the two materials. As used herein, the phrase "electrical contact" means sufficient contact for electrical conduction to occur between the contacting materials.

[0034]

[0042] As used herein, "direct contact" means that two materials are in sufficient physical contact to conduct the flow of electrons or ions between them, if the materials are electrically or ionically conductive. Direct contact between two materials, one of which is electrically or ionically insulating, means that the two materials share an interface that conducts applied force or pressure.

[0035]

[0043] As used herein, the phrase electrical contact means that two materials are in direct contact and are capable of conducting electrical current through the point of direct contact.

[0036]

[0044] As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. During a charge cycle of a Li-secondary battery, Li ions leave the cathode, pass through the electrolyte, and migrate to the anode. During a charge cycle, electrons leave the cathode, pass through an external circuit, and migrate to the anode. During a discharge cycle of a Li-secondary battery, Li ions migrate from the anode to the cathode, pass through the electrolyte. During a discharge cycle, electrons leave the anode, pass through an external circuit, and migrate to the cathode.

[0037]

[0045] As used herein, the phrase "green film" or "green tape" refers to an unsintered tape or film comprising lithium-filled garnet or a precursor of lithium-filled garnet 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 of green film, either dried or undried, cast tape, or cut portions thereof.

[0038]

[0046] As used herein, the phrase "electrochemical cell" or "battery cell" refers to a single cell that includes an anode and a cathode with ionic communication between the two by an electrolyte. In some embodiments, the same battery cell includes multiple anodes and / or multiple cathodes enclosed in a single container.

[0039]

[0047] As used herein, the phrase "electrochemical device" refers to an energy storage device, such as, but not limited to, a Li-secondary battery, that operates or generates electricity or current via an electrochemical reaction, e.g., a conversion chemical reaction such as 3Li+FeF3⇔3LiF+Fe.

[0040]

[0048] As used herein, the term "electrolyte" refers to a compound containing ions, e.g., Li + An electrolyte is a material through which ions can move but electrons cannot be conducted. Ionic conductivity is at least 1000 times greater than electronic conductivity. An electrolyte is a material through which ions, e.g., Li, can move. + Solid electrolytes are useful for electrically insulating the cathode and anode of secondary batteries while allowing ions to be transported through the electrolyte. Solid electrolytes, in some embodiments, rely on ion hopping and / or diffusion through a rigid structure. Solid electrolytes may also be described as fast ion conductors or superionic conductors. In this case, the solid electrolyte layer may also be described as a solid electrolyte separator or solid electrolyte separator.

[0041]

[0049] As used herein, the phrase "energy storage electrode" refers to, for example, an electrode that is suitable for use in an energy storage device, such as a lithium rechargeable battery or a Li-secondary battery. As used herein, such an electrode is capable of conducting electrons and Li ions as needed for charging and discharging the rechargeable battery.

[0042]

[0050] As used herein, the phrase "film thickness" refers to the distance or median measured distance between the top and bottom surfaces of a film. As used herein, the term "thickness," when referring to a layer, refers to the distance or median measured distance between the top and bottom surfaces of the layer. As used herein, the top and bottom surfaces refer to the sides of the film having the largest surface area. Unless otherwise specified, thickness is measured using scanning electron microscopy.

[0043]

[0051] As used herein, the "flatness" of a surface refers to the maximum normal distance between the lowest point on the surface and a plane containing the three highest points on the surface, or alternatively, the maximum normal distance between the highest point on the surface and a plane containing the three lowest points on the surface, which can be measured using surface height mapping by atomic force microscopy (AFM), high-precision optical microscopy, or laser interferometry.

[0044]

[0052] As used herein, the term "thin film" refers to a film having an average thickness dimension of about 10 nm to about 100 μm, comprising a component, composition, or material described herein. In some embodiments, thin film refers to a film having a thickness of less than about 1 μm, less than 10 μm, or less than 50 μm.

[0045]

[0053] As used herein, the phrase "lithium interface resistance" refers to the resistance of Li + ASR refers to the interfacial resistance of a material to ion uptake. interface ) is the interface resistance (R interface ) and is calculated from the equation ASR interface =R interface *A / 2 (where A is the area of ​​the electrode in contact with the separator, and the index 2 corresponds to the two interfaces when measured in a symmetrical cell, and R interface =R total -R bulk and R total is the total resistance, and R bulk is the bulk resistance).

[0046]

[0054] As used herein, the term "lithium-stuffed garnet" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Some examples of lithium-stuffed garnets are described in U.S. Patent Application Publication No. 2015 / 0099190, filed Oct. 7, 2014, and published Apr. 9, 2015 as U.S. Patent Application No. 14 / 509,029, which is incorporated herein by reference in its entirety for all purposes. This application describes solid electrolyte Li-filled garnets for use in all-solid-state lithium rechargeable batteries. These Li-filled garnets have the general composition of 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, 0 ≤ D ≤ 2; 0 ≤ E ≤ 3, 10 < F < 13, and M’ and M’’ are each independently selected from Ga, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta in each instance), 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 Ga, Nb, Ta, V, W, Mo, and Sb), and generally have other compositions described in U.S. Patent Application Publication No. 2015 / 0099190. As used herein, lithium-stuffed garnets and garnets generally, but not limited to, Li7.0 ± δ La3(Zr t1 +Nb t2 +Ta t3 )O 12 +0.35Al2O3, where δ is 0-3 and (t1+t2+t3=2) such that the La:(Zr / Nb / Ta) ratio is 3:2. For example, δ is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. In some embodiments, the Li-filled garnets herein are Li7± δ Li3Zr2O 12 In yet another embodiment, the Li-filled garnet herein has a composition of Li7± δ Li3Zr2O 12 In still other embodiments, the Li-filled garnets herein have a composition of Li7± δ Li3Zr2O 12 In certain other embodiments, the Li-filled garnets herein have a composition of Li7± δ Li3Zr2O 12 In another embodiment, the Li-filled garnet herein has a composition of Li7± δ Li3Zr2O 12 0.75Al2O3. Also, the L-filled garnets used herein include, but are not limited to, Li x La3Zr2O F+yAl2O3, where x is in the range of 5.5 to 9 and y is in the range of 0.05 to 1. In these embodiments, the subscripts x, y, and F are selected so that the Li-filled garnet is charge neutral. In some embodiments, x is 7 and y is 1.0. In some embodiments, x is 5 and y is 1.0. In some embodiments, x is 6 and y is 1.0. In some embodiments, x is 8 and y is 1.0. In some embodiments, x is 9 and y is 1.0. In some embodiments, x is 7 and y is 0.35. In some embodiments, x is 5 and y is 0.35. In some embodiments, x is 6 and y is 0.35. In some embodiments, x is 8 and y is 0.35. In some embodiments, x is 9 and y is 0.35. In some embodiments, x is 7 and y is 0.7. In some embodiments, x is 5 and y is 0.7. In some embodiments, x is 6 and y is 0.7. In some embodiments, x is 8 and y is 0.7. In some embodiments, x is 9 and y is 0.7. In some embodiments, x is 7 and y is 0.75. In some embodiments, x is 5 and y is 0.75. In some embodiments, x is 6 and y is 0.75. In some embodiments, x is 8 and y is 0.75. In some embodiments, x is 9 and y is 0.75. In some embodiments, x is 7 and y is 0.8. In some embodiments, x is 5 and y is 0.8. In some embodiments, x is 6 and y is 0.8. In some embodiments, x is 8 and y is 0.8. In some embodiments, x is 9 and y is 0.8. In some embodiments, x is 7 and y is 0.5. In some embodiments, x is 5 and y is 0.5. In some embodiments, x is 6 and y is 0.5.In some embodiments, x is 8 and y is 0.5. In some embodiments, x is 9 and y is 0.5. In some embodiments, x is 7 and y is 0.4. In some embodiments, x is 5 and y is 0.4. In some embodiments, x is 6 and y is 0.4. In some embodiments, x is 8 and y is 0.4. In some embodiments, x is 9 and y is 0.4. In some embodiments, x is 7 and y is 0.3. In some embodiments, x is 5 and y is 0.3. In some embodiments, x is 6 and y is 0.3. In some embodiments, x is 8 and y is 0.3. In some embodiments, x is 9 and y is 0.3. In some embodiments, x is 7 and y is 0.22. In some embodiments, x is 5 and y is 0.22. In some embodiments, x is 6 and y is 0.22. In some embodiments, x is 8 and y is 0.22. In some embodiments, x is 9 and y is 0.22. As used herein, Li-filled garnets also include, but are not limited to, Li. x La3Zr2O 12 +yAl2O3, where y is 0 to 1, inclusive. In one embodiment, the Li-filled garnet herein is Li7Li3Zr2O 12 It has the composition:

[0047]

[0055] As used herein, garnet or Li-filled garnet includes YAG-garnet (i.e., yttrium aluminum garnet or, e.g., YAlO 12) As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, essonite or cinnamonstone, tsavorite, uvarovite, and andradite, and the solid solutions pyrope-almandine-spessarite and uvarovite-grossular-andradite. As used herein, garnet 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.

[0048]

[0056] As used herein, the phrases “garnet precursor chemical,” “chemical precursor of a garnet-type electrolyte,” “garnet precursor,” and “garnet precursor substance” 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., 2O), lithium carbonate (e.g., LiCO), zirconium oxide (e.g., ZrO), lanthanum oxide (e.g., LaO), lanthanum hydroxide (e.g., La(OH)), aluminum oxide (e.g., AlO), aluminum hydroxide (e.g., Al(OH)), AlOOH, aluminum (e.g., Al), boehmite, gibbsite, corundum, aluminum nitrate (e.g., Al(NO)), aluminum nitrate nonahydrate, 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.

[0049]

[0057] As used herein, the phrase "garnet-type electrolyte" refers to a Li + "refers to an electrolyte comprising the lithium-filled garnet material described herein as an ionic conductor. The advantages of Li-filled garnet solid electrolytes are many, including as a replacement for the liquid, flammable electrolytes commonly used in lithium rechargeable batteries."

[0050]

[0058] As used herein, the term "LIRAP" refers to lithium-rich antiperovskite and is used synonymously with "LOC" or "LiOCl." LIRAP has the composition aLiO + bLiX + cLiOH + dAlO, where X = Cl, Br, and / or I, a / b = 0.7-9, c / a = 0.01-1, and d / a = 0.001-0.1.

[0051]

[0059] As used herein, the term "LXPS" or "LPS+X" refers to a lithium conducting electrolyte containing Li, P, S, and X, where X = Cl, Br, and / or I. For example, "LSPI" refers to a lithium conducting electrolyte containing Li, P, S, and I. More generally, aLiS+bPS y +cLiX (wherein X=Cl, Br and / or I, y=3 to 5, a / b=2.5 to 4.5, and (a+b) / c=0.5 to 15).

[0052]

[0060] As used herein, the term "LBHPS" refers to a lithium conducting electrolyte having Li, B, H, P, and S, for example, A(LiBH)(1-A)(P2S5), where 0.05≦A≦0.95.

[0053]

[0061] As used herein, "LSS" refers to lithium silicon sulfide, which can be described as LiS-SiS, Li-SiS, Li-S-Si, and / or a catholyte consisting essentially of Li, S, and Si. LSS has the formula Li x Si y S z(where 0.33 ≦ x ≦ 0.5, 0.1 ≦ y ≦ 0.2, 0.4 ≦ z ≦ 0.55), and refers to an electrolyte material that may contain up to 10 atomic % oxygen. LSS also refers to an electrolyte material containing Li, Si, and S. In some embodiments, LSS is a mixture of Li2S and SiS2. In some embodiments, the molar ratio of Li2S:SiS2 is 90:10, 85:15, 80:20, 75:25, 70:30, 2:1, 65:35, 60:40, 55:45, or 50:50. LSS is Li x PO y , Li x BO y , Li4SiO4, Li3MO4, Li3MO3, PS x and / or may be doped with compounds such as, but not limited to, lithium halides such as LiI, LiCl, LiF, or LiBr (where 0 < x ≦ 5 and 0 < y ≦ 5). [[ID=**12**]]

[0054]

[0062] As used herein, the term "SLOPS" refers to a 60:40 molar ratio of Li2S:SiS2 containing 0.1 to 10 mol % of Li3PO4, unless otherwise specified. In some embodiments, "SLOPS" contains 0.1 to 10 mol % of Li3PO4Li and Li 10 Si4S 13 (50:50 Li2S:SiS2). In some embodiments, "SLOPS" contains 0.1 to 10 mol % of Li3PO4MO (where M is a metal) and Li 26 Si7S 27 (65:35 Li2S:SiS2). In some embodiments, "SLOPS" contains 0.1 to 5 mol % of Li3PO4 (where 0 < x ≦ 5 and 0 < y ≦ 5) and Li4SiS4 (67:33 Li2S:SiS2). In some embodiments, "SLOPS" contains 0.1 to 5 mol % of Li3PO4 and Li 14 Si3S 13(70:30 LiS:SiS). In some embodiments, "SLOPS" is characterized by the formula (1-x)(60:40 LiS:SiS)*(x)(LiPO), where x is between 0.01 and 0.99. As used herein, "LBS-POX" refers to an electrolyte composition of LiS:B2S3:LiPO4:LiX, where X is a halogen (X = F, Cl, Br, I). The composition may be Li3BS3 or Li5B7S doped with 0-30% lithium halide, such as LiI, and / or 0-10% LiPO4. 13 may include:

[0055]

[0063] As used herein, the term "LSTPS" refers to an electrolyte material having Li, Si, P, Sn, and S chemical components. As used herein, "LSPSO" refers to an LSPS doped with or having O present. In some embodiments, "LSPSO" is an LSPS material having an oxygen content of 0.01 to 10 atomic %. As used herein, "LATP" refers to an electrolyte material having Li, As, Sn, and P chemical components. As used herein, "LAGP" refers to an electrolyte material having Li, As, Ge, and P chemical components. As used herein, "LXPSO" refers to an LSPS material having the formula Li a MP b S c O d (wherein M is Si, Ge, Sn and / or Al, and 2≦a≦8, 0.5≦b≦2.5, 4≦c≦12, and d<3). LXPSO refers to a catholyte material characterized by the above-defined LXPS doped with 0.1 to about 10 atomic % oxygen. LPSO refers to an LPS as defined above doped with 0.1 to about 10 atomic % oxygen. 0.1 to 10 mol % Li3PO4 13 (50:50 Li2S:SiS2). In some embodiments, "SLOPS" refers to Li containing 0.1-10 mol% Li3PO4. 26 Si7S 27In some embodiments, "SLOPS" includes Li4SiS4 (67:33 Li2S:SiS2) with 0.1-5 mol% Li3PO4. In some embodiments, "SLOPS" includes Li14Si3S with 0.1-5 mol% Li3PO4. 13 (70:30 LiS:SiS). In some embodiments, "SLOPS" is characterized by the formula (1-x)(60:40 LiS:SiS)*(x)(LiPO), where x is between 0.01 and 0.99. As used herein, "LBS-POX" refers to an electrolyte composition of LiS:B2S3:LiPO4:LiX, where X is a halogen (X = F, Cl, Br, I). The composition may be Li3BS3 or Li5B7S doped with 0-30% lithium halide, such as LiI, and / or 0-10% LiPO4. 13 may include:

[0056]

[0064] As used herein, the term "LPSCl" refers to an electrolyte material having Li, P, S, and Cl chemical components. As used herein, the term "LPSBr" refers to an electrolyte material having Li, P, S, and Br chemical components. As used herein, the term "LPSI" refers to an electrolyte material having Li, P, S, and I chemical components. LXPSO refers to LXPS, as defined above, with 0.1 to about 10 atomic % oxygen doping. LPSO refers to LPS, as defined above, with 0.1 to about 10 atomic % oxygen doping.

[0057]

[0065] As used herein, the term "LAPS" refers to an electrolyte material having Li, As, P, and S chemical components. As used herein, "LTPS" refers to an electrolyte material having Li, P, Sn, and S chemical components. As used herein, the term "LSPS" refers to an electrolyte material having Li, P, Si, and S chemical components. As used herein, the term "LGPS" refers to an electrolyte material having Li, P, Ge, and S chemical components. As used herein, the term "LPS" refers to an electrolyte material having Li, P, and S chemical components. As used herein, the term "LSTPSC1" refers to an electrolyte material having Li, Si, P, Sn, S, and Cl chemical components. As used herein, the term "LSPSSC1" refers to an electrolyte material having Li, Si, P, S, and Cl chemical components. As used herein, the term "LSPSBr" refers to an electrolyte material having Li, Si, P, S, and Br chemical components. As used herein, "LTS" refers to lithium tin sulfide compounds that can be described as Li2S:SnS2:As2S5, Li2S-SnS2, Li2S-SnS, Li-S-Sn and / or catholytes consisting essentially of Li, S and Sn. x Sn y S z where 0.25≦x≦0.65, 0.05≦y≦0.2, and 0.25≦z≦0.65. In some embodiments, the LTS is a mixture of LiS and SnS in a molar ratio of 80:20, 75:25, 70:30, 2:1, or 1:1. The LTS can contain up to 10 atomic % oxygen. The LTS can be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and / or In, and / or lithium halides such as LiI, LiCl, LiF, or LiBr.

[0058]

[0066] As used herein, the term "LATS" refers to LTS further containing arsenic (As), As2S5, Li2S-SnS2, Li2S-SnS, Li-S-Sn and / or catholytes consisting essentially of Li, S and Sn. x Sn y S z where 0.25≦x≦0.65, 0.05≦y≦0.2, and 0.25≦z≦0.65. In some embodiments, the LTS is a mixture of LiS and SnS in a molar ratio of 80:20, 75:25, 70:30, 2:1, or 1:1. The LTS can contain up to 10 atomic % oxygen. The LTS can be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and / or In, and / or lithium halides such as LiI, LiCl, LiF, or LiBr.

[0059]

[0067] As used herein, the term "LBHI" or "LiBHI" refers to a lithium-conducting electrolyte having Li, B, H, and I. It is more generally understood to include aLiBH4 + bLiX, where X = Cl, Br, and / or I, and a:b = 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or in the range a / b = 2-4. LBHI may further include nitrogen in the form of aLiBH4 + bLiX + cLiNH2, where (a + c) / b = 2-4 and c / a = 0-10.

[0060]

[0068] As used herein, the term "LBHXN" refers to a composition characterized as A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine (F), bromine (Br), chlorine (Cl), iodine (I), or a combination thereof, and 3≦A≦6, 2≦B≦5, and 0≦C≦9. As used herein, the term "LBHFN" refers to a composition characterized as A·(LiBH4)·B·(LiF)·C·(LiNH2), where 3≦A≦6, 2≦B≦5, and 0≦C≦9. As used herein, the term "LBHBrN" refers to a composition characterized as A·(LiBH4)·B·(LiBr)·C·(LiNH2), where 3≦A≦6, 2≦B≦5, and 0≦C≦9. As used herein, the term "LBHClN" refers to a composition characterized as A·(LiBH4)·B·(LiCl)·C·(LiNH2), where 3≦A≦6, 2≦B≦5, and 0≦C≦9. As used herein, the term "LBHIN" refers to a composition characterized as A·(LiBH4)·B·(LiI)·C·(LiNH2), where 3≦A≦6, 2≦B≦5, and 0≦C≦9.

[0061]

[0069] As used herein, "SLOBS" refers to a 60:40 molar ratio of LiS:SiS containing 0.1-10 mol% LiBH, unless otherwise specified. In some embodiments, "SLOBS" refers to a 60:40 molar ratio of LiS:SiS containing 0.1-10 mol% LiBH. 10 Si4S 13 (50:50 LiS:SiS). In some embodiments, "SLOBS" refers to Li, including 0.1-10 mol % LiBH. 26 Si7S 27 In some embodiments, "SLOBS" includes Li4SiS4 (67:33 Li2S:SiS2) with 0.1-5 mol% LiBH4. In some embodiments, "SLOBS" includes Li4SiS4 (67:33 Li2S:SiS2) with 0.1-5 mol% LiBH4. 14 Si3S 13(70:30 LiS:SiS). In some embodiments, "SLOBS" are characterized by the formula (1-x)(60:40 LiS:SiS)*(x)(LiBO), where x is between 0.01 and 0.99. As used herein, "LBS-BOX" refers to an electrolyte composition of LiS:B2S3:LiBH4:LiX, where X is a halogen (X = F, Cl, Br, I). The composition may be Li3BS3 or Li5B7S doped with 0-30% lithium halide, such as LiI, and / or 0-10% LiPO4. 13 may include:

[0062]

[0070] As used herein, the phrase "made from the same type of material" refers to two or more different physical forms of a material that have the same composition. For example, a lithium-filled garnet powder and a lithium-filled garnet thin film are made from the same type of material. For example, an LSTPS powder and an LSTPS thin film are made from the same type of material.

[0063]

[0071] As used herein, the term "fabrication" refers to a process or method that forms or causes to be formed an object being fabricated. For example, fabrication of an energy storage electrode includes processes, process steps, or methods by which an electrode for an energy storage device is formed. The end result of the steps that constitute fabrication of an energy storage electrode is the production of a material that is functional as an electrode.

[0064]

[0072] As used herein, the phrase "anode" refers to a battery that has cations, such as Li, towards it during discharge of the battery. + As used herein, the phrase "cathode" refers to the electrode in a secondary battery from which cations, such as Li, are transferred during discharge of the battery. + Refers to the electrodes in a secondary battery through which the current flows or moves. This includes Li metal electrodes and electrodes that contain conversion chemistry, intercalation chemistry, or a combination of conversion / intercalation chemistry (i.e., cathode active materials; e.g., NiF x, NCA, LiNi x Mn y Co z O2[NMC] or LiNi x Al y Co z In batteries constructed with O2[NCA] (where x+y+z=1), the electrode with conversion chemistry, intercalation chemistry, or combined conversion / intercalation chemistry is referred to as the positive electrode. In some common uses, a cathode is used in place of the positive electrode, and an 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 cathode (e.g., Li-metal). When a Li-secondary battery is discharged, Li ions migrate from the cathode to the anode.

[0065]

[0073] As used herein, the phrase "organic component (10%)" refers to the weight percent amount of organic species in the host. For example, if a buffer layer includes LSTPS and a polymer, but is organic component (10%), this means, for example, that the total amount of polymer in the combination of LSTPS and polymer is 10% by weight, with the remaining 90% being non-organic, e.g., LSTPS.

[0066]

[0074] As used herein, the phrase "porosity determined by SEM" refers to a density measurement using image analysis software to analyze a scanning electron micrograph. For example, first, a user or software assigns pixels and / or regions of the image as porous. Second, the area fractions of those regions are summed. Finally, the porosity determined by SEM is taken as the area fraction of the porous regions of the image.

[0067]

[0075] As used herein, the phrase "provide" refers to the supply, origination or contribution or delivery of what is provided.

[0068]

[0076] As used herein, "separator" and "Li+ The term "ion-conducting separator" refers to a separator that is Li-ion conductive, unless otherwise specified. + It can be said as an abbreviation of ion-conducting separator. The separator is Li + Separator, as used herein, refers to a solid electrolyte that conducts ions, is substantially insulating to electrons, and is suitable for use as a physical barrier or spacer between the anode and cathode in an electrochemical cell or rechargeable battery. Separator, as used herein, refers to a solid electrolyte that conducts ions, is substantially insulating to electrons, and is suitable for use as a physical barrier or spacer between the anode and cathode in an electrochemical cell or rechargeable battery. The lithium ion conductivity of the separator is at least 10 times higher than the electronic conductivity of the separator. 3 times, typically 10 6 A separator is substantially insulating when it is greater than 100 times the thickness of the separator. The separator can be a membrane, monolith, or pellet. Unless specified to the contrary, a separator, as used herein, is stable when in contact with lithium metal.

[0069]

[0077] As used herein, "sintered lithium-filled garnet thin film" refers to a green film comprising lithium-filled garnet that has been sintered and densified to form a thin film.

[0070]

[0078] As used herein, the phrases "solid cathode" or "solid anode" refer to the type of "anode" defined herein. In certain embodiments, all components of the solid cathode membrane are in a solid state. The solid cathode includes a cathode active material as defined herein, a solid catholyte as defined herein, optionally a conductive additive, and optionally a binder. The solid cathode is a dense membrane in some embodiments.

[0071]

[0079] As used herein, the phrase "solid electrolyte" is interchangeable with the phrase "solid separator" and refers to a solid electrolyte that does not contain carbon and does not contain atomic ions (e.g., Li +) but not electrons. Inorganic solid electrolytes are solid materials suitable for electrically insulating the anode and cathode of a lithium secondary battery while providing a conductive path for lithium ions. Example inorganic solid electrolytes include oxide electrolytes and sulfide electrolytes, as further defined below. Non-limiting example sulfide electrolytes can be found, for example, in U.S. Patent No. 9,172,114, issued October 27, 2015, and in U.S. Patent Application Publication No. 2017-0162901A1, filed December 1, 2016 as U.S. Patent Application No. 15 / 367,103, published June 8, 2017. The entire contents of the above patents are incorporated herein by reference in their entireties for all purposes. Non-limiting example oxide electrolytes can be found, for example, in U.S. Patent Application Publication No. 2015-0200420A1, published July 16, 2015. The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In some embodiments, the inorganic solid electrolyte also includes a polymer.

[0072]

[0080] As used herein, unless otherwise specified, the phrase "empirical formula subscripts and molar coefficients are based on the amounts of raw materials initially batched to produce the described material" refers to the amount of the subscript (e.g., Li7La3Zr2O 12 coefficients of 7, 3, 2, 12, and 0.35 in Al2O3) are used for a given material (e.g., Li7La3Zr2O 12 The term "Al2O3" refers to the ratio of elements in the chemical precursors (e.g., LiOH, La2O3, ZrO2, Al2O3) used to prepare a crystalline solid (Al2O3).

[0073]

[0081] As used herein, the phrases "slot casting" or "slot die coating" refer to a deposition process in which a substrate is coated or deposited with a solution, liquid, slurry, etc., by flowing the solution, liquid, slurry, etc., through a slot or mold of fixed dimensions that is positioned adjacent to, in contact with, or above the substrate on which the deposition or coating occurs. In some embodiments, the slot casting includes a slot opening of about 1-100 μm.

[0074]

[0082] As used herein, the term "oxide" refers to a compound that includes at least one oxygen atom and one other element in the compound's chemical formula. For example, "oxide" can be interchangeably referred to as "oxide electrolyte." 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.

[0075]

[0083] As used herein, the term "sulfide" refers to a compound that contains at least one sulfur atom and one other element in the compound's chemical formula. For example, "sulfide" can be interchangeably referred to as "sulfide electrolyte." Non-limiting examples of sulfide electrolytes can be found, for example, in U.S. Pat. No. 9,172,114, issued October 27, 2015, and U.S. Patent Application Publication No. 2017-0162901A1, filed December 1, 2016 as U.S. Patent Application No. 15 / 367,103, and published June 8, 2017. The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. As used herein, a sulfide catholyte is a catholyte that includes or consists essentially of sulfide.

[0076]

[0084] As used herein, the phrase "sulfide electrolyte" or "lithium sulfide" includes, but is not limited to, electrolytes described herein as LSS, LTS, LXPS, or LXPSO, where X is Si, Ge, Sn, As, Al, or Li-Sn-Si-PS or Li-As-Sn-S. In these acronyms (LSS, LTS, LXPS, or LXPSO), S refers to the element S, Si, or a combination thereof, and T refers to the element Sn. Also, "sulfide electrolyte" includes electrolytes containing Li a P b S c X d , Li a B b S c X d , Li a Sn b S c X d or Li a Si b S c X d (where X=F, Cl, Br, I, and 10%≦a≦50%, 10%≦b≦44%, 24%≦c≦70%, 0≦d≦18%, and % are atomic %). Up to 10 atomic % oxygen may be present in the sulfide electrolyte, either intentionally or as a contaminating species.

[0077]

[0085] As used herein, the term "sulfide halide" refers to a compound that contains at least one sulfur atom, at least one halogen atom, and one other element in the chemical formula of the compound.

[0078]

[0086] As used herein, voltages are given with respect to lithium metal (ie, V vs. Li) unless otherwise specified.

[0079] electrochemical cell

[0087] An example electrochemical cell is shown in FIG. 1. In FIG. 1, layer 101 represents a deposited lithium metal anode. Layer 102 represents a lithium-filled garnet layer. Layer 103 represents a bonding layer. Layer 104 represents a buffer layer. Layer 105 represents an anode layer. In some embodiments, layer 102 is about 100 μm thick. In some embodiments, layer 101 is about 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 μm thick. In some embodiments, layer 102 is about 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, or 125 μm thick. In some embodiments, layer 103 is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 μm thick. In some embodiments, layer 104 is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 μm thick. In some embodiments, layer 105 is about 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169 or 170 μm.

[0080]

[0088] In some embodiments, an all-solid-state electrochemical cell (SSEC) is described herein, comprising: (a) an anode layer comprising an active material and a sulfide catholyte; (b) a single-ion conductive solid buffer; (c) a borohydride bonding layer; and (d) a lithium-loaded garnet layer. The buffer is mixed into the anode layer, or the buffer is present as a layer in contact with the anode layer, or in some embodiments, the buffer is mixed into the anode layer and the buffer is present as a layer in contact with the anode layer. The borohydride bonding layer is between and in contact with the lithium-loaded garnet layer and either (i) the anode layer in which the buffer is mixed, or (ii) the buffer layer in contact with the anode. In some embodiments, the borohydride bonding layer is between and in contact with the lithium-loaded garnet layer and the anode layer in which the buffer is mixed. In some embodiments, the buffer is mixed into the anode layer. In some embodiments, the buffer is present as a layer in contact with the anode layer. In some embodiments, the buffer is mixed into the anode layer and the buffer is present as a layer in contact with the anode layer, hi some embodiments, the borohydride binding layer is between and in contact with the lithium-filled garnet layer and the buffer layer in contact with the anode.

[0081]

[0089] In some embodiments, including any of the above, the active material comprises a coating. In some embodiments, the active material comprises a coating of a material selected from LLZO.

[0082]

[0090] In these examples, the Li ions are conducted through the inorganic single ion conductor rather than through the polymer or organic component (10%).

[0083]

[0091] In some embodiments, described herein are all-solid-state electrochemical cells (SSECs) that include: (a) an anode layer that includes an active material and a sulfide catholyte; (b) a single-ion conductive solid buffer; (c) a borohydride bonding layer; and (d) a lithium-loaded garnet layer, wherein the buffer is intermixed within the anode layer, or the buffer is a layer in contact with the anode layer, or both, and the borohydride bonding layer is between and in contact with the lithium-loaded garnet layer and either (i) the anode layer in which the buffer is intermixed, or (ii) the buffer layer in contact with the anode.

[0084]

[0092] In some embodiments, including any of the above, a single-ion conductive solid buffer is mixed into the anode layer. In some embodiments, the buffer is mixed into the anode layer in a manner such that a gradient of active material and buffer material is achieved.

[0085]

[0093] In some embodiments, including any of the above, the single-ion conducting solid buffer is a layer in contact with the anode layer.

[0086]

[0094] In some embodiments, including any of the above, the single-ion conductive solid buffer is present as a layer mixed within and in contact with the anode layer.

[0087]

[0095] In some embodiments, including any of the above, the single-ion conducting solid buffer layer prevents the borohydride bonding layer from contacting the anode layer. In some embodiments, the borohydride bonding layer bonds the lithium-filled garnet layer to the buffer layer. In some embodiments, the borohydride bonding layer bonds the lithium-filled garnet layer to the buffer component of the anode layer.

[0088]

[0096] In some embodiments, including any of the above, the cathode layer is between and in contact with the lithium-filled garnet layer and the cathode current collector layer. In some embodiments, including any of the above, the buffer layer potential is shielded from the Li metal cathode potential. In some embodiments, including any of the above, the borohydride binding layer potential is shielded from the anode potential. In some embodiments, including any of the above, the SSEC is 50 Ω cm 2 It has the following ASR:

[0089]

[0097] In some embodiments, described herein is an all-solid-state electrochemical cell (SSEC) that includes: (a) an anode layer that includes an active material and a sulfide catholyte; (b) a buffer that includes a single-ion conducting solid electrolyte and is mixed within or in direct contact with the anode layer; (c) a bonding layer that includes a borohydride; and (d) a layer that includes a lithium-filled garnet. In this embodiment, the borohydride bonding layer is between and in contact with the layer that includes the lithium-filled garnet and either the anode layer or the buffer that is in direct contact with the anode layer.

[0090]

[0098] In some embodiments, including any of the above, the solid electrochemical stack further includes (d) a cathode current collector in direct contact with the separator layer. In another example, any of the above solid electrochemical stacks further includes (e) an anode current collector in direct contact with the anode layer. In a further example, any of the above solid electrochemical stacks further includes (d) a cathode current collector and (e) a cathode, wherein the (e) cathode is between and in direct contact with the separator layer and the cathode current collector.

[0091]

[0099] In certain embodiments, provided herein is a composite having a lithium-filled garnet and LBHI, wherein the LBHI fills at least 90% of the through pores and / or surface pores of the lithium-filled garnet, and the LBHI can be a composition having the formula A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is a halide and 3≦A≦6, 2≦B≦5, and 0≦C≦9.

[0092] [000100] In some embodiments, the borohydride bonding layer herein is LBHI (lithium borohydride with lithium iodide). The buffer layer is LSTPS. The buffer layer blocks or protects the high voltage anode.

[0093] Buffer composition [000101] The sulfide in the buffer layer in some examples can be any of the sulfides identified in U.S. Patent Application Publication No. 2017-0005367A1, entitled "COMPOSITE ELECTROLYTES," published January 5, 2017. The entire contents of the above patent are incorporated herein by reference in their entirety for all purposes.

[0094] [000102] In some embodiments, the sulfide in the buffer layer may be any of the sulfides specified in International Publication No. WO 2017 / 096088 A1, published on June 8, 2017. The above patent was filed on December 1, 2016, and was filed as International PCT Patent Application No. PCT / US2016 / 064492, entitled "LITHIUM, PHOSPHORUS, SULFUR, AND IODINE CONTAINING ELECTROLYTE AND CATHOLYTE COMPOSITIONS, ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL DEVICES, AND ANNEALING METHODS OF MAKING THESE ELECTROLYTES AND CATHOLYTES", and was published as International Publication No. WO 2017 / 096088 on June 8, 2017. The entire content of the above patent is incorporated herein by reference in its entirety for all purposes.

[0095] [000103] In some embodiments including any of the above, the buffer layer, sulfide catholyte or single ion conductive solid buffer or all of them have the following formula: Li a Si b Sn c P d S e O f (where 2 ≤ a ≤ 8, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, b + c = 1, 0.5 ≤ d ≤ 2.5, 4 ≤ e ≤ 12 and 0 ≤ f ≤ 10); Li a Si b P c S d X e (where ⑧ < a < 12, 1 < b < 3, 1 < c < 3, ⑧ < d < 14 and 0 < e < 1, X is F, Cl, Br or I); Li g As h Sn j S k O l [[ID=​​​​​​​wherein 2≦m≦6, 0≦n≦1, 0≦p≦1, 2≦q≦6; a mixture of (LiS):(P2S5) and LiI having a molar ratio of LiS:P2S5 of about 10:1 to about 6:4, wherein the ratio of [(LiS):(P2S5)]:LiI is between 95:5 and 50:50; LPS+X, where X is selected from Cl, I, or Br; vLiS+wP2S5+yLiX; or vLiS+wSiS2+yLiX. In some embodiments, including any of the above, the sulfide catholyte comprises LSTPS.2S+wB2S3+yLiX.

[0096] [000104] In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 4≦e≦12. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 2≦a≦8, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦2.5, and 4≦e≦12. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 3≦a≦7, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦1.5, and 8≦e≦12. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 3≦a≦5, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦1, and 5≦e≦9. In some embodiments, the buffer comprises Li a Si b Sn c P d S ewhere 3≦a≦5, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦1, and 5≦e≦9. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 2≦a≦8, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦2.5, and 4≦e≦12. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 3≦a≦5, 0≦b≦0.5, 0≦c≦0.5, 0≦d≦2, and 2≦e≦10. In some embodiments, the buffer comprises Li a Si b Sn c P d S e where 3≦a≦5, 0≦b≦0.25, 0≦c≦1, 0≦d≦1, and 2≦e≦14. In some embodiments, the buffer comprises Li a Si b Sn c P d S e wherein 3≦a≦5, 0≦b≦0.25, 0≦c≦1, 0≦d≦1, and 2≦e≦8.

[0097] [000105] In some embodiments, including any of the above, the single-ion conducting solid buffer comprises LSTPS.

[0098] [000106] The buffer layer does not conduct electrons, thereby shielding the anodic potential from that felt by the borohydride binding layer.

[0099] [000107] The buffer layer does not conduct electrons, thereby shielding the anode potential from the potential experienced by the cathode.

[0100] [000108] In some embodiments, the buffer layer is easily deformed.

[0101] [000109] In some embodiments, the buffer layer is chemically stable when in contact with the sulfide catholytes disclosed herein and / or the coated active materials disclosed herein.

[0102] [000110] In some embodiments, the buffer layer comprises LSTPS.

[0103] [000111] In some embodiments, the buffer layer has a D of about 10 nm to 1000 nm, about 100 nm to 500 nm, or about 150 nm to 300 nm. 50 In some embodiments, the buffer layer comprises particles having a D of about 100 nm, about 200 nm, or about 300 nm. 50 In some embodiments, the buffer layer comprises particles having a D of about 500 nm to 2000 nm, 750 nm to 1000 nm, or about 1000 nm. 90 In some embodiments, the buffer layer comprises particles having a D of about 800 nm, 900 nm, 1000 nm, or 1100 nm. 90 In some embodiments, the buffer layer comprises particles having a D of at least about 750 nm. 90 In some embodiments, the buffer layer comprises particles having a D of at least about 900 nm. 90 The particles include particles having the formula:

[0104] [000112] In some embodiments, the buffer layer is made of particles that are 1 / 10 the thickness of the buffer layer. For example, if the buffer layer is 5 μm thick, in some embodiments, it contains 0.5 μm buffer particles. In some embodiments, if the buffer layer is 5 μm thick, the buffer layer contains 0.5 μm d 50 The LSTPS particles have a particle diameter.

[0105] [000113] In some embodiments, the buffer layer has negligible interfacial resistance to the anode.

[0106] [000114] In some embodiments, the buffer layer is non-polymeric, meaning it contains less than 5% by weight of polymer.

[0107] [000115] In some embodiments, the buffer layer is attached to the anode by a lamination and densification process, resulting in a buffered anode that blocks electron access and protects the other electrolyte layers from the anode potential.

[0108] [000116] In some embodiments, the buffer layer is attached to the anode by a lamination and densification process, resulting in a buffered anode that blocks electron access and protects the other electrolyte layers from the anode potential.

[0109] [000117] In some embodiments, the buffer layer has a porosity of less than about 20% v / v, less than 15% v / v, less than 12.5% ​​v / v, less than 10% v / v, less than 5% v / v, less than 1% v / v, or less than about 5% v / v to 20% v / v or about 10% v / v to 15% v / v.

[0110] tie layer composition [000118] In certain embodiments, the tie layer can include a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), where X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and where 3≦A≦6, 2≦B≦5, and 0≦C≦9. In some examples, the tie layer includes A·(LiBH4)·B·(LiX)·C·(LiNH2), where 3≦A≦6, 2≦B≦5, and 3≦C≦6. In some examples, the tie layer includes A·(LiBH4)·B·(LiX)·C·(LiNH2), where 3≦A≦5, 2≦B≦5, and 3≦C≦5. In some embodiments, the bonding layer comprises A·(LiBH4)·B·(LiX)·C·(LiNH2), where 3≦A≦4, 2≦B≦4, and 3≦C≦4. In some embodiments, the bonding layer comprises A·(LiBH4)·B·(LiX)·C·(LiNH2), where 4≦A≦5, 2≦B≦4, and 4≦C≦5. In some embodiments, the bonding layer comprises A·(LiBH4)·B·(LiX)·C·(LiNH2), where 4≦A≦5, 3≦B≦4, and 4≦C≦5.

[0111] [000119] In certain embodiments, the tie layer can include a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), where X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and 0.1≦A≦3, 0.1≦B≦4.5, and 0≦C≦9.

[0112] [000120] In one embodiment, X can be bromine, chlorine, iodine, or a combination thereof. In another embodiment, X can be iodine. In some embodiments, A is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. In some embodiments, B is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5. In some embodiments, C is 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9 or 9.0.

[0113] [000121] In some embodiments, the bonding layer comprises a borohydride composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where 2.5 < A < 4.5, 2.5 < B < 5.5, and 4 < C < 9. In some embodiments including any of the above, the borohydride bonding layer comprises a borohydride composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2). In some embodiments, 2.5 < A < 3.5, 3.5 < B < 4.5, and 5 < C < 9.

[0114] [000122] In some embodiments including any of the above, the borohydride bonding layer comprises a borohydride composition where the composition is 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·9LiNH2. In one embodiment, the composition can be 3LiBH4·2LiI·3LiNH2. In another embodiment, the composition can be 3LiBH4·4LiI·9LiNH2. In another embodiment, the composition can be 3LiBH4·2LiCl·3LiNH2. In another embodiment, the composition can be 3LiBH4·4LiCl·9LiNH2. In another embodiment, the composition can be 3LiBH4·2LiBr·3LiNH2. In another embodiment, the composition can be 3LiBH4·4LiBr·9LiNH2.

[0115] [000123] In some embodiments, including any of the above, the borohydride bonding layer comprises a borohydride composition having the composition 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·5LiNH2. In one embodiment, the composition can be 4LiBH4·2LiI·4LiNH2. In another embodiment, the composition can be 4LiBH4·3LiI·4LiNH2. In another embodiment, the composition can be 4LiBH4·5LiCl·4LiNH2. In another embodiment, the composition can be 4LiBH4·6LiCl·4LiNH2. In some embodiments, including any of the above, the borohydride bonding layer comprises a borohydride composition having the composition 3LiBH4·3LiCl·4LiNH2 or 3LiBH4·3LiCl·5LiNH2. In one embodiment, the composition can be 3LiBH4·3LiI·6LiNH2. In another embodiment, the composition can be 3LiBH4·3LiI·7LiNH2.

[0116] [000124] In some embodiments, including any of the above, the borohydride bonding layer comprises a borohydride composition selected from LBHIN and LBHN. In some embodiments, including any of the above, the borohydride bonding layer comprises KBH4 and LiNH2.

[0117] [000125] In some embodiments, the composition may exist in various physical states. For example, in one embodiment, the composition may be amorphous. As a further example, in one embodiment, the composition may be semi-crystalline. The composition can be made amorphous or semi-crystalline by controlling the sintering profile, for example, by adjusting the cooling rate after sintering.

[0118] [000126] In certain embodiments, the LBHI composition may be present as a film, a single entity, or a pellet. For example, in one embodiment, the composition is a thin film. As a further example, in one embodiment, the composition is a monolith. As a further example, in one embodiment, the composition is a pressed pellet.

[0119] [000127] In some embodiments, the LBHI composition may further comprise an oxide, a sulfide, a sulfide halide, or an electrolyte. For example, in one embodiment, the oxide may be selected from lithium-filled garnets 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). As a further example, in one embodiment, the composition comprises an oxide having a coating of LBHI, and the oxide may be selected from lithium-filled garnets 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). As a further example, in one embodiment, the oxide may be selected from lithium-filled garnets characterized by the formula 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, Ga, Ta, or a combination thereof). As a further example, in one embodiment, the composition comprises an oxide having a coating of LBHI, and the oxide may be selected from lithium-filled garnets characterized by the formula 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, Ga, Ta or a combination thereof) can be selected from lithium-filled garnets characterized thereby. As a further example, one of the above Li a La b Zr c Al d Me’’ e O f In the embodiment of, Me’’ is Nb. As a further example, one of the above Li a La b Zr c Al d Me’’ e O f In the embodiment of, Me’’ is Ga. As a further example, one of the above Li a La b Zr c Al d Me’’ e O f In the embodiment of, Me’’ is Ta. As a further example, one of the above Li a La b Zr c [[ID=四十二]]Al d Me’’ e O f In the embodiment of, Me’’ is Nb and Ga. As a further example, one of the above Li a La b Zr c Al d Me’’ e O f In the embodiment of, Me’’ is Nb and Ta. As a further example, one of the above Li a La b Zr c Al d Me’’ e O<000^{280}In the embodiment of, Me’’ is Ga and Ta.

[0120] [000128] The borohydride bonding layer, in some embodiments, is made from a borohydride compound. The borohydride compound can be any of the compounds set forth in International Publication No. WO 2018 / 075972, published April 26, 2018, and filed as International PCT Patent Application No. PCT / US2017 / 057735, and entitled "ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE." The borohydride can be any compound set forth in International Publication No. WO 2019 / 078897, published April 25, 2019, and filed October 20, 2017, as International PCT Patent Application No. PCT / US2017 / 057739, and entitled "BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID STATE BATTERY."

[0121] [000129] In some embodiments, including any of the above, the lithium salt is selected from LiTFSI, LiFSI, LiPF6, LiClO4, LiAsF6, LiBOB, LiBETI, LiBF4, and LiI, and combinations thereof. In particular embodiments, the lithium salt is selected from LiPF6, lithium bis(oxolato)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, or LiI. In particular embodiments, the lithium salt is LiPF6. In particular embodiments, the lithium salt is LiBOB. In particular embodiments, the lithium salt is LiTFSi. In particular embodiments, the lithium salt is LiBF4. In particular embodiments, the lithium salt is LiClO4. In particular embodiments, the lithium salt is LiAsF6. In particular embodiments, the lithium salt is LiI. In particular embodiments, the lithium salt is LiBF4. In certain embodiments, several lithium salts may be present simultaneously at various concentrations. In some embodiments, the concentration is about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 M. In certain embodiments, the bonding layer may include two salts selected from LiPF, LiBOB, LiTFSi, LiBF, LiClO, LiAsF, LiFSI, or LiI. In certain embodiments, the bonding layer may include three salts selected from LiPF, LiBOB, LiTFSi, LiBF, LiClO, LiAsF, LiFSI, or LiI. In certain embodiments, the lithium salt is a lithium salt selected from LiPF, LiBOB, and LFTSi. In certain embodiments, the lithium salt is LiPF6 at a concentration of 0.5 M to 2 M. In some embodiments, the concentration is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 M. In certain embodiments, the lithium salt is LiTFSI at a concentration of 0.5 M to 2 M.In some embodiments, the concentration is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0M.

[0122] [000130] In certain embodiments, the lithium salt is present in a concentration of 0.01M to 10M. In some embodiments, the concentrations are 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.3, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 2.0, 0.3, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 3.0, 3.1 ... 4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.8, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0M.

[0123] Other compositions [000131] In some embodiments, including any of the above, the buffer layer includes 0.01 to 10 wt. % of a binder. The binder, in some embodiments, can include a polyolefin. The binder can include an ethylene alpha-olefin copolymer, an ethylene octene copolymer, a polyolefin plastomer, a polyolefin elastomer, a styrene-butadiene rubber, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), and the like.

[0124] [000132] In some embodiments, including any of the above, the buffer layer comprises up to 10% by volume of an organic polymer.

[0125] [000133] In some embodiments, including any of the above, the polymer is polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxy)ethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxy)ethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE). ), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene-rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), polyvinylidene fluoride (PVDF) and polyethylene.

[0126] [000134] In some embodiments, including any of the above, the buffer layer or buffer component does not include an organic polymer.

[0127] [000135] In some embodiments, including any of the above, the anode potential is protected from the lithium-filled garnet layer potential.

[0128] [000136] In some embodiments, including any of the above, the active material potential of the positive electrode is protected from the lithium-filled garnet layer potential.

[0129] [000137] In some embodiments, the cathode is LiNi x Mn y Co z O2(NMC) and LiNi x Aly Co z O2(NCA) (where x+y+z=1).

[0130] [000138] In some embodiments, including any of the above, the active material is coated.

[0131] [000139] In some embodiments, including any of the above, the active material is coated or partially coated with a coating selected from the group consisting of lithium niobium oxide, lithium zirconium oxide, lithium aluminum oxide, lithium phosphate, lithium tantalum oxide, lithium hafnium oxide, niobium oxide, zirconium oxide, aluminum oxide, tantalum oxide, and hafnium oxide.

[0132] [000140] In some embodiments, including any of the above, the active material is uncoated.

[0133] [000141] In some embodiments, including any of the above, the anode includes a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

[0134] [000142] In some embodiments, the anode has a porosity of less than about 20% v / v, less than 15% v / v, less than 12.5% ​​v / v, less than 10% v / v, less than 5% v / v, less than 1% v / v, or less than 1% v / v, hi some embodiments, the anode has a porosity of between about 5% v / v and 20% v / v, or between about 10% v / v and 15% v / v.

[0135] [000143] In some embodiments, including any of the above, the intercalation material is nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O2, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), Li(NiCoMn)O2, LiMn2O4, LiCoO2, and LiMn 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, or Mn).

[0136] [000144] In some embodiments, including any of the above, the lithium conversion material is FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials, their alloys and combinations thereof 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, or Mn).

[0137] [000145] In some embodiments, including any of the above, the sulfide catholyte and the single-ion conducting solid buffer are made from the same material.

[0138] [000146] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, and LPS+X, where X is selected from the group consisting of Cl, I, Br, and combinations thereof. In some embodiments, X is Cl. In some embodiments, X is I. In some embodiments, X is Br.

[0139] [000147] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, LSPSCl, SLOBS, LATS, and LPS+X, where X is selected from the group consisting of Cl, I, Br, and combinations thereof. In some embodiments, X is Cl. In some embodiments, X is I. In some embodiments, X is Br.

[0140] [000148] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LPSI, LXPS, LSTPS, LSPSCl, LPSCl, LSPSBr, and LPSBr.

[0141] [000149] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conductive solid buffer, or both, are selected from x·Li2S:y·SiS2, where x and y are each independently a number from 0 to 1, and x + y = 1.

[0142] [000150] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, LGPS, LSTPS, and LSPS.2S:y·SiS2, where x and y are each independently a number from 0 to 1, and x + y = 1.

[0143] [000151] In some embodiments, including any of the above, the borohydride bonding layer comprises lithium borohydride, sodium borohydride, or potassium borohydride.

[0144] [000152] In some embodiments, including any of the above, the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiNH2.

[0145] [000153] In some embodiments including any of the above, any one or more of lithium borohydride, sodium borohydride or potassium borohydride is doped with LiI.

[0146] [000154] In some embodiments including any of the above, any one or more of lithium borohydride, sodium borohydride or potassium borohydride is doped with LiNH2 and LiI.

[0147] [000155] In some embodiments including any of the above, the borohydride bonding layer comprises a borohydride composition comprising A(LiBH4)(1 - A)(P2S5) (where 0.05 ≤ A ≤ 0.95). In some embodiments, 0.5 < A < 0.95. In some embodiments, A is 0.85, 0.9 or 0.95.

[0148] [000156] In some embodiments including any of the above, the borohydride bonding layer comprises 0.9(LiBH4)0.1(P2S5).

[0149] [000157] In some embodiments including any of the above, the borohydride bonding layer is amorphous. In some embodiments including any of the above, the borohydride bonding layer is semi - crystalline. In some embodiments including any of the above, the borohydride bonding layer is polycrystalline.

[0150] [000158] In some embodiments including any of the above, the lithium - filled garnet layer comprises 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 ≤ l) selected lithium - filled garnet.

[0151] [000159] In some embodiments including any of the above, the lithium-filled garnet layer is Li7La3Zr2O 12 ·Al2O2O3 and Li7La3Zr2O 12 ·0.35Al2O3.

[0152] [000160] In some embodiments including any of the above, the lithium-filled garnet is doped with Nb, Ga and / or Ta.7La3Zr2O 12 ·Al2O3 and Li7La3Zr2O 12 ·0.35Al2O3.

[0153] [000161] In some embodiments including any of the above, the lithium-filled garnet layer comprises a lithium-filled garnet characterized by the formula 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 the group consisting of Nb, Ga, Ta and combinations thereof).

[0154] [000162] In some embodiments including any of the above, the lithium-filled garnet layer comprises a lithium-filled garnet oxide characterized by the formula Li u La v Zr x O y ·zAl2O3 (where u is a rational number from 4 to 8; v is a rational number from 2 to 4; x is a rational number from 1 to 3; y is a rational number from 10 to 14; and z is a rational number from 0.05 to 1; u, v, x, y and z are selected such that the lithium-filled garnet oxide is charge-neutral).

[0155] [000163] In some embodiments including any of the above, the lithium-filled garnet layer is of the formula Li u Lav Zr x O y Lithium-filled garnet oxides characterized by zTa2O5, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0156] [000164] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y Lithium-filled garnet oxides characterized by zNb2O5, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0157] [000165] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y and zGa2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0158] [000166] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O yand lithium-filled garnet oxides characterized by zTa2O5 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; z is a rational number between 0 and 1; b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0159] [000167] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y and lithium-filled garnet oxides characterized by zNb2O5 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; z is a rational number between 0 and 1; b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet is charge-neutral.

[0160] [000168] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y and lithium-filled garnet oxides characterized by zGa2O3 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0161] [000169] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li 6.4 Ga 0.2 La3Zr2O 12.3bAlO, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet is charge-neutral.

[0162] [000170] In some embodiments, including any of the above, the SSEC further comprises an anode current collector layer.

[0163] [000171] In some embodiments, including any of the above, the SSEC further comprises a cathode current collector layer. In some embodiments, the cathode current collector layer is a sintered metal. In some embodiments, the sintered metal is selected from the group consisting of Al, Cu, Ni, Ag, Au, Pt, Pd, or Sn. In some embodiments, the metal is Ni.

[0164] [000172] In some embodiments, including any of the above, the anode layer further comprises a binder, carbon, or both a binder and carbon.

[0165] [000173] In some embodiments, including any of the above, the lithium-filled garnet layer is between and in contact with the cathode current collector layer and the borohydride bonding layer.

[0166] [000174] In some embodiments, including any of the above, the borohydride binding layer is between and in contact with the lithium-filled garnet layer and the buffer layer.

[0167] [000175] In some embodiments, including any of the above, the buffer layer is between and in contact with the borohydride binding layer and the anode layer.

[0168] [000176] In some embodiments, including any of the above, the anode layer is between and in contact with the buffer layer and the anode current collector layer.

[0169] [000177] In some embodiments, including any of the above, the active material includes a coating or the active material is coated. In some embodiments, the active material has a coating. In some embodiments, the active material is coated. In some embodiments, the active material includes a coating of a material selected from lithium-lanthanum-zirconium oxide (LLZO).

[0170] [000178] The lithium-filled garnet layer may include any of the lithium-filled garnets specified in U.S. Pat. No. 9,806,372 B2, issued October 31, 2017, and entitled "GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS," and U.S. Pat. No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. The lithium-filled garnet layer is fabricated by forming a layer or film of the lithium-filled garnet layer described herein, for example, by using the method of U.S. Pat. No. 9,806,372 B2. The lithium-filled garnet layer may include any of the lithium-filled garnets specified in U.S. Pat. No. 9,966,630, issued May 8, 2018, and entitled "ANNEALED GARNET ELECTROLYTE SEPARATORS." The entire contents of the above patent are incorporated herein by reference in their entirety for all purposes. The lithium-filled garnet layer may be fabricated by forming a layer or film of the lithium-filled garnet layer described herein, for example, by using the method of U.S. Pat. No. 9,966,630 B2. The lithium-filled garnet layer may include any of the lithium-filled garnets specified in U.S. Patent Application Publication No. 20180375149 A1, filed June 23, 2017, as U.S. Patent Application No. 15 / 631,884, and entitled "LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. Lithium-filled garnet layers are fabricated by forming layers or films of the lithium-filled garnet layers described herein, for example, by use of the methods of U.S. patent application Ser. No. 15 / 631,884.The lithium-filled garnet layer may include any of the lithium-filled garnets identified in International PCT Patent Application No. PCT / US2017 / 039069, filed June 23, 2017, and entitled "LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS," the entire contents of which are incorporated herein by reference in their entirety for all purposes. The lithium-filled garnet layer is fabricated by forming a layer or film of the lithium-filled garnet layer described herein, for example, by use of the methods of PCT / US2017 / 039069.

[0171] [000179] In some embodiments, the lithium-filled garnet layer is chemically stable when in contact with Li metal. In some embodiments, the lithium-filled garnet layer is kinetically stable when in contact with Li metal.

[0172] [000180] In some embodiments, the lithium-filled garnet comprises lithium lanthanum zirconium oxide (LLZO) and has good electrochemical stability and mechanical strength, e.g., greater than 500 MPa. In some embodiments, LLZO is suitable for use with Li metal anodes.

[0173] [000181] In any of the examples herein, the lithium-filled garnet layer or LLZO may be combined with a binder as set forth in International PCT Publication No. WO 2017197406A1, published November 16, 2017, and filed May 15, 2017 as International PCT Patent Application No. PCT / US2017 / 032749, entitled "SOLID ELECTROLYTE SEPARATOR BONDING AGENT." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In any of the examples herein, the lithium-filled garnet is fabricated according to the methods of International PCT Patent Application No. PCT / US2016 / 027886, filed April 15, 2016, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In any of the examples herein, the lithium-filled garnet is produced according to the methods of International PCT Patent Application No. PCT / US2016 / 027922, filed April 15, 2016, and entitled "SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION AND METHODS OF USING THE SAME TO PREPARE DENSE SOLID ELECTROLYTES." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In any of the examples herein, the lithium-filled garnet is produced according to the methods of International PCT Patent Application No. PCT / US2016 / 043428, filed July 21, 2016, and entitled "PROCESSES AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes.In any of the examples herein, the lithium-filled garnet is made according to the method of U.S. Pat. No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION," the entire contents of which are incorporated herein by reference in their entirety for all purposes. In any of the examples herein, the lithium-filled garnet is made according to the method of U.S. Pat. No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION," the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the sulfide catholyte may be any of the sulfides specified in U.S. Pat. No. 9,172,114, issued Oct. 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the sulfide catholyte may be any of the sulfides specified in International PCT Patent Application No. PCT / US2016 / 015982, filed Feb. 1, 2016, and entitled "METAL SULFIDE ANOLYTE FOR ELECTROCHEMICAL CELLS," published Aug. 11, 2016 as WO 2016 / 126610, the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the sulfide catholyte can be any sulfide specified in International PCT Patent Application No. PCT / US2016 / 039424, filed June 24, 2016, entitled "COMPOSITE ELECTROLYTES," and published December 29, 2016 as WO 2016 / 210371.The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the sulfide catholyte may be any of the sulfides specified in U.S. Patent Application Publication No. 2017-0005367A1, entitled "COMPOSITE ELECTROLYTES," published January 5, 2017. The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the sulfide catholyte can be any sulfide identified in International PCT Patent Application No. PCT / US2016 / 064492, filed December 1, 2016, entitled "LITHIUM, PHOSPHORUS, SULFUR, AND IODINE CONTAINING ELECTROLYTE AND CATHOLYTE COMPOSITIONS, ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL DEVICES, AND ANNEALING METHODS OF MAKING THESE ELECTROLYTES AND CATHOLYTES," and published June 8, 2017 as WO 2017 / 096088, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0174] [000182] In some embodiments, the sulfide in the buffer layer may be any of the sulfides specified in U.S. Pat. No. 9,172,114, issued Oct. 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some embodiments, the sulfide in the buffer layer may be any of the sulfides specified in International PCT Patent Application No. PCT / US2016 / 015982, filed Feb. 1, 2016, entitled "METAL SULFIDE ANOLYTE FOR ELECTROCHEMICAL CELLS," and published Aug. 11, 2016 as WO 2016 / 126610, the entire contents of which are incorporated herein by reference in their entirety for all purposes. In some examples, the sulfide in the buffer layer can be any sulfide identified in International PCT Patent Application No. PCT / US2016 / 039424, filed June 24, 2016, entitled "COMPOSITE ELECTROLYTES," and published December 29, 2016 as WO 2016 / 210371, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0175] [000183] In some embodiments, the anode comprises about 85 wt% LZO coated NCA, about 13 wt% LSTPS, and about 2 wt% binder.

[0176] [000184] In some embodiments, including any of the above, the cathode is a lithium (Li) metal electrode layer. In some embodiments, including any of the above, at least one current collector comprises a material selected from the group consisting of carbon (C)-coated nickel (Ni), nickel (Ni), copper (Cu), aluminum (Al), and stainless steel. In some embodiments, including any of the above, the cathode current collector comprises a material selected from the group consisting of carbon (C)-coated nickel (Ni), nickel (Ni), and copper (Cu). In some embodiments, including any of the above, the anode current collector layer comprises a material selected from the group consisting of carbon (C)-coated aluminum and aluminum. In some embodiments, including any of the above, the cathode current collector layer is C-coated Ni. In some embodiments, including any of the above, the anode current collector layer is C-coated Al.

[0177] Buffer layer dimensions [000185] In some embodiments, including any of the above, the buffer layer has a thickness of about 1 μm to about 50 μm. In some embodiments, the buffer layer has a thickness of 1 μm. In some embodiments, the buffer layer has a thickness of 2 μm. In some embodiments, the buffer layer has a thickness of 3 μm. In some embodiments, the buffer layer has a thickness of 4 μm. In some embodiments, the buffer layer has a thickness of 5 μm. In some embodiments, the buffer layer has a thickness of 6 μm. In some embodiments, the buffer layer has a thickness of 7 μm. In some embodiments, the buffer layer has a thickness of 8 μm. In some embodiments, the buffer layer has a thickness of 9 μm. In some embodiments, the buffer layer has a thickness of 10 μm.

[0178] [000186] In some embodiments, including any of the above, the single-ion conductive solid buffer is mixed into the anode layer to a penetration depth of about 1 μm to about 50 μm. Such penetration depth is measured from the edge where the anode layer connects to the buffer layer or the borohydride binding layer. In some embodiments, if the anode layer is 200 μm thick and the penetration depth into the anode layer is about 1 μm to about 50 μm, this means that the buffer is present in the anode on the side closest to the buffer layer, if present, or the borohydride binding layer, if no buffer layer is present. In some embodiments, if the anode layer is 200 μm thick and the penetration depth into the anode layer is about 1 μm to about 50 μm, this also means that the side of the anode in contact with the anode current collector does not have a buffer component.

[0179] [000187] In some embodiments, including any of the above, the single-ion conductive solid buffer is mixed into the anode layer to a penetration depth of about 1 μm to about 50 μm. Such penetration depth is measured from the edge where the anode layer connects to the buffer layer or the borohydride bonding layer. In some embodiments, if the anode layer is 150 μm thick and the penetration depth into the anode layer is about 1 μm to about 50 μm, this means that the buffer is present in the anode on the side closest to the buffer layer, if present, or the borohydride bonding layer, if not present. In some embodiments, if the anode layer is 150 μm thick and the penetration depth into the anode layer is about 1 μm to about 50 μm, this also means that the anode does not have a buffer component on the side in contact with the anode current collector.

[0180] [000188] In some embodiments, including any of the above, the buffer layer is between the anode layer and the separator layer and is in direct contact therewith. In some examples, the buffer layer has a thickness ranging from about 1 μm to about 15 μm. In some examples, the buffer layer has a thickness of 1 μm. In some examples, the buffer layer has a thickness of 1 μm. In some examples, the buffer layer has a thickness of 2 μm. In some examples, the buffer layer has a thickness of 3 μm. In some examples, the buffer layer has a thickness of 4 μm. In some examples, the buffer layer has a thickness of 5 μm. In some examples, the buffer layer has a thickness of 6 μm. In some examples, the buffer layer has a thickness of 7 μm. In some examples, the buffer layer has a thickness of 8 μm. In some examples, the buffer layer has a thickness of 9 μm. In some examples, the buffer layer has a thickness of 10 μm. In some examples, the buffer layer has a thickness of 11 μm. In some examples, the buffer layer has a thickness of 12 μm. In some examples, the buffer layer has a thickness of 13 μm. In some examples, the buffer layer has a thickness of 14 μm. In some examples, the buffer layer has a thickness of 15 μm.

[0181] Buffer layer dimensions [000189] In some embodiments, the bonding layer comprises lithium borohydride. In some embodiments, the bonding layer comprises lithium borohydride particles having an average diameter of at least about 1 μm. In some embodiments, the bonding layer comprises lithium borohydride particles having an average diameter of about 1 μm to about 50 μm, about 2 μm to about 20 μm, or about 1 μm to about 10 μm.

[0182] [000190] In some embodiments, prior to assembly of the battery cell, the tie layer includes particles having an average diameter of at least about 1 μm. In some embodiments, the tie layer particles have an average diameter of about 1 μm to about 50 μm, about 2 μm to about 20 μm, or about 1 μm to about 10 μm.

[0183] [000191] In some embodiments, including any of the above, the borohydride bonding layer has a thickness of about 1 μm to about 50 μm. In some embodiments, including any of the above, the borohydride bonding layer has a thickness of about 1 μm to about 50 μm. In some embodiments, including any of the above, the borohydride bonding layer has a thickness of 1 μm. In some embodiments, the borohydride bonding layer has a thickness of 2 μm. In some embodiments, the borohydride bonding layer has a thickness of 3 μm. In some embodiments, the borohydride bonding layer has a thickness of 4 μm. In some embodiments, the borohydride bonding layer has a thickness of 5 μm. In some embodiments, the borohydride bonding layer has a thickness of 6 μm. In some embodiments, the borohydride bonding layer has a thickness of 7 μm. In some embodiments, the borohydride bonding layer has a thickness of 8 μm. In some embodiments, the borohydride bonding layer has a thickness of 9 μm. In some embodiments, the borohydride bonding layer has a thickness of 10 μm. In some embodiments, the borohydride bonding layer is 11 μm thick. In some embodiments, the borohydride bonding layer is 12 μm thick. In some embodiments, the borohydride bonding layer is 13 μm thick. In some embodiments, the borohydride bonding layer is 14 μm thick. In some embodiments, the borohydride bonding layer is 15 μm thick. In some embodiments, the borohydride bonding layer is 16 μm thick. In some embodiments, the borohydride bonding layer is 17 μm thick. In some embodiments, the borohydride bonding layer is 18 μm thick. In some embodiments, the borohydride bonding layer is 19 μm thick. In some embodiments, the borohydride bonding layer is 20 μm thick. In some embodiments, the borohydride bonding layer is 31 μm thick. In some embodiments, the borohydride bonding layer is 32 μm thick. In some embodiments, the borohydride bonding layer is 33 μm thick. In some embodiments, the borohydride bonding layer is 34 μm thick.In some embodiments, the borohydride bonding layer is 35 μm thick. In some embodiments, the borohydride bonding layer is 36 μm thick. In some embodiments, the borohydride bonding layer is 37 μm thick. In some embodiments, the borohydride bonding layer is 38 μm thick. In some embodiments, the borohydride bonding layer is 39 μm thick. In some embodiments, the borohydride bonding layer is 40 μm thick. In some embodiments, the borohydride bonding layer is 41 μm thick. In some embodiments, the borohydride bonding layer is 42 μm thick. In some embodiments, the borohydride bonding layer is 43 μm thick. In some embodiments, the borohydride bonding layer is 44 μm thick. In some embodiments, the borohydride bonding layer is 45 μm thick. In some embodiments, the borohydride bonding layer is 46 μm thick. In some embodiments, the borohydride bonding layer is 47 μm thick. In some embodiments, the borohydride bonding layer is 48 μm thick. In some embodiments, the borohydride bonding layer is 49 μm thick. In some embodiments, the borohydride bonding layer is 50 μm thick.

[0184] [000192] In some embodiments, including any of the above, the borohydride binding layer permeates the buffer layer.

[0185] [000193] In some embodiments, including any of the above, the borohydride bonding layer infiltrates the lithium-filled garnet layer.

[0186] [000194] In some embodiments, including any of the above, the borohydride binding layer infiltrates the buffer layer and the lithium-filled garnet layer.

[0187] [000195] In some embodiments, including any of the above, the borohydride tie layer has a density of 90% or greater than the density of the starting material as measured by quantitative analysis of cross-sectional SEM images. Density is measured by analyzing porosity as a function of total area using SEM images and analysis software.

[0188] [000196] In some embodiments, including any of the above, the borohydride tie layer has a density that is 90% or greater than the density of the starting material as measured by quantitative analysis of cross-sectional SEM images.

[0189] [000197] In some embodiments, including any of the above, the borohydride bonding layer has a melting point less than 250°C. In some embodiments, including any of the above, the borohydride bonding layer has a melting point greater than 250°C.

[0190] [000198] In some embodiments, including any of the above, the SSEC further comprises a cathode.

[0191] [000199] In some embodiments, including any of the above, the cathode is a lithium (Li) metal cathode.

[0192] [000200] In certain embodiments, including any of the above, the lithium-filled garnet layer is in contact with the cathode.

[0193] [000201] In certain embodiments, the composition may be a thin film and may include porosity as determined by SEM for the thin film. For example, in one embodiment, the composition defined herein may have a porosity of less than 5%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 6%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 7%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 8%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 4%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 3%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 2%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 1%. By way of further example, in one embodiment, the composition defined herein may have a porosity of less than 0.5%.

[0194] [000202] In some embodiments, the solid state electrochemical stack further comprises a tie layer between and in direct contact with the buffer layer and the separator layer.

[0195] [000203] In some embodiments, tie layers having a thickness of about 1 nm are provided herein. In some embodiments, tie layers having a thickness of about 5 nm to about 100 nm are provided herein.

[0196] [000204] In some embodiments, tie layers having a thickness of about 100 nm to about 1000 nm are provided herein. In some embodiments, tie layers have a thickness of about 200 nm to about 900 nm, about 300 nm to about 800 nm, or about 500 nm.

[0197] [000205] In some embodiments, a tie layer having a thickness of about 1 μm is defined herein. In some embodiments, a tie layer having a thickness of about 2 μm is defined herein. In some embodiments, a tie layer having a thickness of about 3 μm is defined herein. In some embodiments, a tie layer having a thickness of about 4 μm is defined herein. In some embodiments, a tie layer having a thickness of about 5 μm to about 100 μm is defined herein. In some embodiments, a tie layer having a thickness of about 10 μm to about 50 μm, about 15 μm to about 40 μm, or about 20 μm to about 40 μm is defined herein. In some embodiments, a tie layer having a thickness of about 1 μm is defined herein. In some embodiments, a tie layer having a thickness of about 2 μm is defined herein. In some embodiments, a tie layer having a thickness of about 3 μm is defined herein. In some embodiments, a tie layer having a thickness of about 4 μm is defined herein. In some embodiments, a tie layer having a thickness of about 5 μm is defined herein. In some embodiments, tie layers having a thickness of about 100 μm are provided herein, and in some embodiments, tie layers having a thickness of about 1 μm to about 100 μm, about 1 μm to about 50 μm, or about 5 μm to about 50 μm are provided herein.

[0198] [000206] In some embodiments, including any of the above, the median thickness of the tie layer is greater than 100 nm and less than 10 μm. In some embodiments, including any of the above, the polymer has a crosslink density, measured according to ASTM D2765, greater than 0.1% and less than 30%. In some embodiments, including any of the above, the tie layer reduces the interfacial impedance between the electrolyte separator and the anode compared to the absence of the tie layer. In some embodiments, the tie layer reduces the interfacial impedance between the electrolyte separator and the anode compared to the absence of the tie layer. In some embodiments, when the tie layer is located between and in direct contact with the oxide electrolyte separator and the anode, the interfacial impedance between the oxide electrolyte separator and the anode is greater than 50 Ω·cm at 50°C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 25 Ω cm at 50° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 10 Ω cm at 50° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 5 Ω cm at 50° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 5 Ω cm at 30° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 5 Ω cm at 20° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 5 Ω cm at 10° C. 2 In some embodiments, the interfacial impedance between the oxide electrolyte separator and the anode is less than 5 Ω cm at 0° C. 2 In some embodiments, including any of the above, the interfacial impedance between the electrolyte separator and the anode is less than 50 Ω cm at 50° C.2 In some embodiments, including any of the above, the interfacial impedance between the electrolyte separator and the anode is less than 25 Ω cm at 50° C. 2 In some embodiments, including any of the above, the interfacial impedance between the electrolyte separator and the anode is less than 10 Ω cm at 50° C. 2 In some embodiments, including any of the above, the interfacial impedance between the electrolyte separator and the anode is less than 5 Ω cm at 50° C. 2 In some embodiments, including any of the above, the anode comprises a lithium intercalation material, a lithium conversion material, or a combination thereof.

[0199] [000207] In some embodiments, the tie layer penetrates the anode. In other embodiments, the tie layer penetrates the anode through at least 10% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 9% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 8% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 7% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 6% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 5% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 4% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 3% of the thickness of the anode. In other embodiments, the tie layer penetrates the anode through at least 1% of the thickness of the anode.

[0200] [000208] In some embodiments, the tie layer contacts the catholyte at the anode. In some embodiments, the tie layer does not creep around the electrolyte separator. In some embodiments, the tie layer does not contain components that volatilize and diffuse around the electrolyte separator to contact the Li metal cathode.

[0201] [000209] In some embodiments, including any of the above, the tie layer penetrates the anode to a depth of at least 10% of the thickness of the anode.

[0202] [000210] In some embodiments, including any of the above, the tie layer contacts the solid catholyte at the anode.

[0203] [000211] In some embodiments, including any of the above, the diameter of the electrolyte separator is greater than the diameter of the anode.

[0204] [000212] In some embodiments, including any of the above, the width or diameter of the electrolyte separator is greater than the width or diameter, respectively, of the anode.

[0205] [000213] In some embodiments, including any of the above, the electrolyte separator has raised edges that prevent the tie layer or its components from creeping around the electrolyte separator.

[0206] [000214] In some embodiments, including any of the above, the coated end comprises a coating selected from parylene, polypropylene, polyethylene, alumina, Al2O3, ZrO2, TiO2, SiO2, a binary oxide, La2Zr2O7, a lithium carbonate species, or a glass selected from SiO2-B2O3 or Al2O3.

[0207] [000215] In some embodiments, the borohydride bonding layer comprises LBHI, LBHIN, [LBH-X], LBHPS, LiI, LPS, L[X]PS, or Li3PO4. In some embodiments, the borohydride bonding layer comprises a functionalized polymer such as PEO-LiTFSI, polypropylene carbonate (PPC)-LiTFSI, polyethylene carbonate (PEC)-LiTFSI, Li-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), Li-Nafion, Li-polyphenylene sulfide (PPS); or a solid organic salt couple such as ethylene carbonate (EC)-LiTFSI, dimethyl sulfide (DMS)-LiPF6, and succinonitrile (SCN)-LiBF4.

[0208] Dimensions of other components [000216] In some embodiments, including any of the above, the anode layer has a thickness of about 100 μm to about 1000 μm. In some embodiments, the anode layer has a thickness of 10 μm. In some embodiments, the anode layer has a thickness of 20 μm. In some embodiments, the anode layer has a thickness of 30 μm. In some embodiments, the anode layer has a thickness of 40 μm. In some embodiments, the anode layer has a thickness of 50 μm. In some embodiments, the anode layer has a thickness of 60 μm. In some embodiments, the anode layer has a thickness of 70 μm. In some embodiments, the anode layer has a thickness of 80 μm. In some embodiments, the anode layer has a thickness of 90 μm. In some embodiments, the anode layer has a thickness of 100 μm. In some embodiments, the anode layer has a thickness of 110 μm. In some embodiments, the anode layer has a thickness of 120 μm. In some embodiments, the anode layer has a thickness of 130 μm. In some embodiments, the anode layer has a thickness of 140 μm. In some embodiments, the anode layer has a thickness of 150 μm. In some embodiments, the anode layer has a thickness of 160 μm. In some embodiments, the anode layer has a thickness of 170 μm. In some embodiments, the anode layer has a thickness of 180 μm. In some embodiments, the anode layer has a thickness of 190 μm. In some embodiments, the anode layer has a thickness of 200 μm.

[0209] [000217] In some embodiments, including any of the above, the lithium-filled garnet layer has a thickness of about 1 μm to about 200 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 10 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 20 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 30 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 40 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 50 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 60 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 70 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 80 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 90 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 100 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 110 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 120 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 130 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 140 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 150 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 160 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 170 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 180 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 190 μm. In some embodiments, the lithium-filled garnet layer has a thickness of 200 μm.

[0210] [000218] In some embodiments, including any of the above, the separator layers of the solid electrochemical stacks described herein are rectangular. In other embodiments, the anode layers of the solid electrochemical stacks described herein are rectangular. In various embodiments, the separator layers of the solid electrochemical stacks described herein are circular. In embodiments, the anode layers of the solid electrochemical stacks described herein are circular.

[0211] [000219] In some embodiments, including any of the above, the geometric surface area of ​​the anode layer and the geometric surface area of ​​the separator layer are substantially the same.

[0212] [000220] In some embodiments, including any of the above, one side of the anode layer has a length of 2 cm to 30 cm. In some embodiments, one side of the anode layer has a length of 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, 11 cm, 12 cm, 13 cm, 14 cm, 15 cm, 16 cm, 17 cm, 18 cm, 19 cm, 20 cm, 21 cm, 22 cm, 23 cm, 24 cm, 25 cm, 26 cm, 27 cm, 28 cm, 29 cm, or 30 cm. In some embodiments, one side of the separator layer has a length of 2 cm to 30 cm. In some embodiments, one side of the separator layer is 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, 11 cm, 12 cm, 13 cm, 14 cm, 15 cm, 16 cm, 17 cm, 18 cm, 19 cm, 20 cm, 21 cm, 22 cm, 23 cm, 24 cm, 25 cm, 26 cm, 27 cm, 28 cm, 29 cm, or 30 cm in length.

[0213] [000221] In certain embodiments, a composite having a lithium-filled garnet and LBHI, wherein LBHI fills at least 90% of the through-holes and / or surface pores of the lithium-filled garnet, and the composite can be a composition having LBHI of A·(LiBH4)·B·(LiX)·C·(LiNH2) (where X is a halide, 3 ≦ A ≦ 6, 2 ≦ B ≦ 5, and 0 ≦ C ≦ 9) is provided herein.

[0214] [000222] In some examples including any of the above, the electrolyte separator is represented by the empirical formula Li x La A Zr B O h +yAl2O3 (where 3 ≦ x ≦ 8, 2 < A < 4, 1 < B < 3, 0 ≦ y ≦ 1, and 6 ≦ h ≦ 15; and the subscripts x and h and the coefficient y are selected such that the electrolyte separator is electrically neutral).

[0215] [000223] In some examples including any of the above, the electrolyte separator is doped with Ga, Nb, or Ta.

[0216] [000224] In some embodiments, including any of the above, the electrolyte separator has a surface roughness of about 0.01 μm to 10 μm on at least one surface. In some embodiments, including any of the above, the electrolyte separator has a surface roughness of about 0.01 μm to 5 μm on at least one surface. In some embodiments, including any of the above, the electrolyte separator has a surface roughness of about 0.01 μm to 2 μm on at least one surface. In some embodiments, including any of the above, the electrolyte separator has a density greater than 95% of its theoretical density. In some embodiments, including any of the above, the electrolyte separator has a density greater than 95% of its theoretical density as determined by scanning electron microscopy (SEM). In some embodiments, including any of the above, the electrolyte separator has a density greater than 95% of its theoretical density as measured by Archimedes' method. In some embodiments, including any of the above, the electrolyte separator has a surface roughness of 0.1 μm to about 50 μm.

[0217] [000225] In some embodiments, including any of the above, the lithium intercalation material is selected from the group consisting of nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), Li(NiCoMn)O, LiMnO, LiCoO, LiMn 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, and Mn).

[0218] [000226] In some embodiments, including any of the above, the lithium conversion material is FeF2, NiF2, FeO x F 3-2x, FeF3, MnF3, CoF3, CuF2 materials, alloys thereof and combinations thereof.

[0219] [000227] In some embodiments, including any of the above, the tie layer permeates the anode.

[0220] [000228] In some embodiments, electrochemical stacks are provided herein in which the electrolyte separator has a thickness of about 10 μm to 50 μm; the bonding layer has a thickness of about 1 μm to 20 μm; and the anode has a thickness of about 5 μm to 150 μm, excluding the current collector.

[0221] [000229] In some embodiments, the electrolyte separator has a surface roughness Ra or Rt of about 0.1 μm to 10 μm on at least one surface. In other embodiments, the electrolyte separator has a surface roughness of about 0.1 μm to 5 μm on at least one surface. In other embodiments, the electrolyte separator has a surface roughness of about 0.1 μm to 2 μm on at least one surface. In some embodiments, the electrolyte has a surface roughness of about 0.1 μm to 10 μm on the surface connecting the electrolyte separator and the Li metal cathode.

[0222] [000230] In some embodiments, the electrolyte separator has a density greater than 95% of its theoretical density. In other embodiments, the electrolyte separator has a density greater than 95% of its theoretical density as determined by scanning electron microscopy (SEM). In specific embodiments, the electrolyte separator has a density greater than 95% of its theoretical density as measured by Archimedes' method. In some embodiments, the electrolyte separator has a surface flatness of 0.1 μm to about 50 μm. In some embodiments, the lithium salt in the bonding layer is selected from LiPF6, LiBOB, LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, LiI, or LiBF4. In specific embodiments, the lithium salt in the bonding layer is selected from LiPF6, LiBOB, or LFTSi. In specific embodiments, the lithium salt in the bonding layer is LiPF6 at a concentration of 0.5M to 2M. In a specific embodiment, the lithium salt in the tie layer is LiTFSI at a concentration of 0.5 M to 2 M. In a specific embodiment, the lithium salt in the tie layer is present at a concentration of 0.01 M to 10 M.

[0223] [000231] In some embodiments, the anode comprises a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material. In some embodiments, the lithium intercalation material is selected from the group consisting of nickel manganese cobalt oxide, Li(NiCoMn)O2, (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O2, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), LiMn2O4, LiCoO2, LiMn 2-a Ni a In other embodiments, the lithium conversion material is selected from the group consisting of FeF, NiF, FeO, O4 (where a is 0-2), or LiMPO4 (where M is Fe, Ni, Co, and Mn). x F 3-2x, FeF3, MnF3, CoF3, CuF2 materials, alloys thereof, and combinations thereof. In other embodiments, the conversion material is doped with other transition metal fluorides or oxides.

[0224] [000232] In some embodiments, the anode comprises an electronically conductive source of carbon.

[0225] [000233] In some embodiments, the anode comprises a solid catholyte and a lithium intercalation or conversion material; the catholyte and the lithium intercalation or conversion material each independently have a d of about 0.1 μm to 5 μm. 50 In some embodiments, the anode comprises a solid catholyte and a lithium intercalation or conversion material; the catholyte and the lithium intercalation or conversion material each independently have a particle size of about 0.1 μm to 15 μm. 50 In some embodiments, the bonding layer is characterized by a thickness of about 1 nm to about 5 μm. In some embodiments, the Li cathode is characterized by a thickness of about 10 nm to about 50 μm. In some embodiments, the oxide separator is characterized by a thickness of about 0.1 μm to about 150 μm. In some embodiments, the oxide separator is characterized by a thickness of about 10 μm to about 50 μm.

[0226] [000234] In some embodiments, the coated edge comprises a coating selected from parylene, epoxy, polypropylene, polyethylene, alumina, Al2O3, ZrO2, TiO2, SiO2, binary oxides, lithium carbonate species, La2Zr2O7, or a glass selected from SiO2-BO3 or Al2O3. In some embodiments, the electrolyte separator has tapered edges that prevent the bonding layer from creeping around the electrolyte separator. In some embodiments, the separator electrolyte edge is selectively treated with heat (e.g., laser beam) or chemicals (e.g., plasma, water, acid, etc.).

[0227] [000235] In some embodiments, electrochemical stacks are provided herein having an electrolyte separator having a thickness of about 10-20 μm; a bonding layer having a thickness of about 1 μm-5 μm; and an anode having a thickness, excluding the current collector, of about 5 μm-150 μm. In some embodiments, electrochemical stacks are provided herein having an electrolyte separator having a thickness of about 10-50 μm; a bonding layer having a thickness of about 1 μm-5 μm; and an anode having a thickness, excluding the current collector, of about 5 μm-200 μm. In some embodiments, electrochemical stacks are provided herein having an electrolyte separator having a thickness of about 10-100 μm; a bonding layer having a thickness of about 1 μm-5 μm; and an anode having a thickness, excluding the current collector, of about 5 μm-200 μm.

[0228] method [000236] In some embodiments, disclosed herein is a method for manufacturing an electrochemical cell, the method including: providing a slurry including an active material, a catholyte, and a solvent; depositing the slurry onto a current collector; drying the slurry; providing a second slurry including a single-ion conductive solid buffer; depositing the second slurry onto a substrate; drying the second slurry; transferring the dried second slurry onto the dried first slurry to form a stack; applying pressure and heat to the stack; providing a solid separator; depositing a borohydride layer onto the solid separator; overlapping the stack with the solid separator having the borohydride layer thereon to form an electrochemical cell stack; and applying pressure and heat to the cell stack.

[0229] [000237] In some embodiments, including any of the above, the solids loading is at least 60% by weight.

[0230] [000238] In some embodiments, including any of the above, the buffer is an LSTPS.

[0231] [000239] In some embodiments, the buffer layer is produced by a calendering process in which the total force is at least about 100 psi, 500 psi, 1000 psi, 2000 psi, or more. In some embodiments, the buffer layer is produced at elevated temperatures, such as about 40°C, 50°C, 75°C, 100°C, 120°C, 140°C, or more. In some embodiments, the buffer layer is heated to a temperature greater than about 100°C.

[0232] [000240] In some embodiments, including any of the above, the pressure is applied uniaxially.

[0233] [000241] In certain embodiments, disclosed herein are methods for producing thin films comprising an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, the method comprising: a) preparing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition material; b) providing a molten mixture comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, chlorine, iodine, or a combination thereof, and 3≦A≦6, 2≦B≦5, and 0≦C≦9; c) dip-coating a substrate into the molten mixture; d) withdrawing the substrate; and e) cooling the substrate to room temperature. In some embodiments, the substrate is a current collector. In some embodiments, the substrate is a solid electrolyte. In some embodiments, the substrate is a lithium-loaded garnet.

[0234] [000242] In certain embodiments, provided herein is a method of coating a lithium ion conductive separator electrolyte, the method comprising: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and where 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. For example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is chlorine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, and chlorine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, chlorine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine, chlorine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.

[0235] [000243] In certain embodiments, provided herein is a method of coating a lithium ion conductive separator electrolyte, the method comprising: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and where 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. For example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is chlorine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, and chlorine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, or iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, chlorine, or iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.By way of further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte includes: a) providing a separator electrolyte; and b) pressing a composition of A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine, chlorine, or iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, onto at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI.

[0236] [000244] In certain embodiments, the temperature of the process is below the melting point (T m ) and is less than about 0.8T m (T m is expressed in Kelvin (K). In certain embodiments, the method further comprises c) maintaining pressure between the composition and the separator for 1 to 300 minutes.

[0237] [000245] In certain embodiments, the method further comprises d) cooling the coated lithium ion conductive separator electrolyte under pressure for 10 to 1000 minutes. In certain embodiments, the method further comprises d) cooling the coated lithium ion conductive separator electrolyte to room temperature under pressure for 10 to 1000 minutes. In certain embodiments, a method of coating a lithium ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH4)·B·(LiX)·C·(LiNH2) precursor; and c) depositing the mixture on a separator by spray coating, spin coating, dip coating, slot-die coating, gravure coating, or microgravure coating. For example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by spray coating. As a further example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by spin coating. As a further example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by dip coating.As a further example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by slot die coating. As a further example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by gravure coating. As a further example, in one embodiment, a method for coating a lithium-ion conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and an A·(LiBH)·B·(LiX)·C·(LiNH) precursor; and c) depositing the mixture on a separator by microgravure coating.

[0238] [000246] In certain embodiments, the solvent of the present process is selected from the group consisting of tetrahydrofuran, diethyl ether, methanol, and ethanol. For example, in one embodiment, the solvent of the present process is tetrahydrofuran. As a further example, in one embodiment, the solvent of the present process is diethyl ether. As a further example, in one embodiment, the solvent of the present process is ethanol. As a further example, in one embodiment, the solvent of the present process is methanol.

[0239] [000247] In certain embodiments, the lithium-stable separator of the present method has defects on its surface.

[0240] [000248] In certain embodiments, a composition is provided that includes A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, chlorine, iodine, or a combination thereof, and 3 < A < 6, 2 < B < 5, and 0 < C < 9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6° 2θ. For example, in one embodiment, a composition is provided that includes A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine and 3 < A < 6, 2 < B < 5, and 0 < C < 9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6° 2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is chlorine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is iodine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, and chlorine and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ.As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, chlorine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at about 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°2θ. As a further example, in one embodiment, there is provided a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is bromine, chlorine, and iodine, and 3≦A≦6, 2≦B≦5, and 0≦C≦9, having an XRD pattern characterized by peaks at approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6° 2θ.

[0241] [000249] In some embodiments, including any of the above, the polymer tie layer should be as thin as possible, for example, less than 5 μm, less than 2 μm, or less than 1 μm. The tie layer can be a thin film deposited from solution by spray coating, gravure coating, slot-die coating, dip coating, spin-casting, and similar techniques using solutions in DMF, NMP, THF, toluene, acetonitrile, or similar solvents. It can also be deposited from a melt above 50° C. A free-standing thin film can also be pressed against the cathode and separator at low temperatures (<120° C.) and pressures (<1000 psi).

[0242] [000250] In certain embodiments, a film of molten LBHXN is formed by spin coating. A spin coater with heating capabilities is used for this embodiment. First, a powder is applied to the substrate to be coated. The spin coater is heated to above the melting point of LBHXN. After melting, the substrate is rotated at a speed of 100 to 5000 rpm while heat is applied. It should be understood that the rotation speed can be strongly correlated with the coating film thickness. After rotation is stopped, a second layer, which may be a solid cathode membrane, or another lithium-ion conductive separator (which may be the same or a different Li-ion conductor as the first substrate), is laminated at a pressure of 10 to 2000 pounds per square inch (PSI). Heat is optionally applied. After the laminate is cooled to room temperature, the substrate, LBHXN, and top layer are bonded so well that they cannot be separated without destruction.

[0243] [000251] In some embodiments, the substrate may be spin coated at a speed of at least about 100 rpm, 500 rpm, 1000 rpm, 2000 rpm, 3000 rpm or more.

[0244] [000252] In some embodiments, disclosed herein is a method for manufacturing an electrochemical device, the method including: providing an anode comprising an electrochemically active material and a solid catholyte; providing a solid catholyte comprising a sulfide single-ion conductor; providing an electrolyte separator comprising a lithium-loaded garnet; providing a bonding layer comprising a polymer and a lithium salt; providing a stack wherein the electrolyte separator is between and in contact with a lithium metal cathode and the bonding layer, and the bonding layer is between and in contact with the electrolyte separator and the anode; and bonding, adhering, or laminating the bonding layer to the anode and the electrolyte separator by pressing the stack at low temperature and pressure.

[0245] [000253] In some embodiments, the pressure used during the formation of the tie layer, buffer layer, anode layer, or any combination thereof is at least 5000 Pascals, 10 kiloPascals (kPa), 100 kPa, 500 kPa, 1000 kPa, 10,000 kPa, 100,000 kPa, 1 MPa, 10 MPa, or 100 MPa. In some embodiments, the pressure used during the formation of the tie layer, buffer layer, anode layer, or any combination thereof is at least 1000 kPa, 10,000 kPa, 100,000 kPa, 1 MPa, 10 MPa, or 100 MPa.

[0246] [000254] In some embodiments, the pressure used during cycling of the electrochemical cells described herein is greater than atmospheric pressure and is performed at a pressure of at least 100 Pascals, 1000 Pascals, 5000 Pascals, 10 kiloPascals (kPa), 100 kPa, 500 kPa, 1000 kPa, 10,000 kPa, 100,000 kPa, 1 MPa, 10 MPa, or 100 MPa.

[0247] [000255] In some embodiments, including any of the above, the pressure is less than 1000 PSI. In some embodiments, including any of the above, the pressure is less than 300 PSI. In some embodiments, including any of the above, the temperature is less than 180°C. In some embodiments, including any of the above, the temperature is less than 120°C. In some embodiments, including any of the above, the process is carried out in a clean room. In some embodiments, including any of the above, the clean room has a dew point of less than -20°C or less than -40°C. In some embodiments, including any of the above, the clean room is a Class 10,000 clean room.

[0248] [000256] In some embodiments, there is provided herein a method for manufacturing an electrochemical device, the method including providing an anode comprising an electrochemically active material and a solid catholyte; providing a solid catholyte comprising a sulfide single-ion conductor; providing an electrolyte separator comprising a lithium-loaded garnet; providing a bonding layer comprising a polymer and a lithium salt; providing a stack in which the electrolyte separator is in contact with the bonding layer, and the bonding layer is between and in contact with the electrolyte separator and the anode; and bonding, adhering, or laminating the bonding layer to the anode and the electrolyte separator by pressing the stack at low temperature and pressure.

[0249] [000257] In some embodiments, including any of the above, the pressure is less than 1000 PSI. In some embodiments, including any of the above, the pressure is less than 300 PSI.

[0250] [000258] In some embodiments, including any of the above, the temperature is less than 180°C. In some embodiments, including any of the above, the temperature is less than 120°C.

[0251] [000259] In certain embodiments, including any of the above, the process is carried out in a clean room. In certain embodiments, including any of the above, the clean room has a dew point of less than -20° C. or less than -40° C. In certain embodiments, including any of the above, the clean room is a Class 10,000 clean room or better.

[0252] [000260] In some embodiments, the borohydride bonding layer is heated to a temperature at which it melts or partially melts during the process to form intimate contact with both the lithium-filled garnet layer and the buffer layer in contact with the anode.

[0253] [000261] In some embodiments, the borohydride bonding layer melts or partially melts during the process to form intimate contact with both the lithium-filled garnet layer and the anode having the buffer mixed therein.

[0254] [000262] In some embodiments, multiple layers of bonding layers are specified herein. In some embodiments, multiple layers of "oxide-sulfide interfacial layers," i.e., multiple bonding layers, are specified herein. In some embodiments, these bonding layers are kinetically stable to both the oxide or sulfide. In some embodiments, these bonding layers promote or maintain oxide-sulfide interfacial contact. In some embodiments, these bonding layers fill the space between the oxide and sulfide, thereby improving ionic conductivity.

[0255] [000263] In some embodiments, the borohydride bonding layer is spin coated onto the lithium filled garnet layer, i.e., to protect the high voltage anode. In some embodiments, the borohydride bonding layer is melt cast onto the lithium filled garnet layer. In some embodiments, the borohydride bonding layer is melt cast onto the lithium filled garnet layer.

[0256] [000264] In some embodiments, disclosed herein is a method for manufacturing a solid electrochemical stack, the method comprising: (a) casting a first slurry comprising a sulfide solid electrolyte powder onto a first substrate to form a first layer; (b) casting a second slurry comprising a sulfide solid electrolyte powder and an anode active powder onto a second substrate to form a second layer; and (c) calendering the first layer and the second layer in contact with each other.

[0257] [000265] In one group of embodiments, prior to step (a), the process includes providing a first substrate. In such examples, prior to step (a), the process includes providing a first slurry including a sulfide solid electrolyte powder. In such examples, prior to step (b), the process includes providing a second substrate. In such examples, prior to step (b), the process includes providing a second slurry including a sulfide solid electrolyte powder and an anode active powder. In some examples, the process includes a step (f) of contacting the second layer and the first layer.

[0258] [000266] Further embodiments [000267] In one embodiment, provided herein is a solid electrochemical stack comprising: (a) an anode layer comprising an active anode material and a sulfide catholyte, the anode layer having a porosity of less than 15% by volume (v / v); (b) a buffer layer in contact with the anode layer, the buffer layer comprising a sulfide electrolyte, the buffer layer having a porosity of less than 15% v / v; and (c) a separator layer comprising a member selected from the group consisting of lithium-filled garnet and LPSX, the separator layer having a porosity of less than 10% v / v, wherein the buffer layer is between the anode layer and the separator layer.

[0259] [000268] In some embodiments, including any of the above, the sulfide catholyte and sulfide electrolyte are solid.

[0260] [000269] In some embodiments, including any of the above, the buffer layer substantially covers the anode layer.

[0261] [000270] In some embodiments, including any of the above, the buffer layer coats the anode layer.

[0262] [000271] In some embodiments, including any of the above, the buffer layer is uniformly dense.

[0263] [000272] In some embodiments, including any of the above, the buffer layer is uniformly thick.

[0264] [000273] In some embodiments, including any of the above, the buffer layer is in direct contact with the anode layer and the separator layer.

[0265] [000274] In some embodiments, including any of the above, the tie layer is between and in direct contact with the buffer layer and the separator layer.

[0266] [000275] In some embodiments, including any of the above, the sulfide catholyte is a sulfide single-ion conductor.

[0267] [000276] In some embodiments, including any of the above, the sulfide catholyte is an electrolyte that includes lithium (Li), phosphorus (P), and sulfur (S).

[0268] [000277] In some embodiments, including any of the above, the catholyte comprises iodine (I).

[0269] [000278] In some embodiments, including any of the above, the catholyte comprises chlorine (Cl), bromine (Br), iodine (I), or a combination thereof.

[0270] [000279] In some embodiments, including any of the above, the catholyte comprises a member selected from the group consisting of tin (Sn), germanium (Ge), arsenic (As), silicon (Si), and combinations thereof.

[0271] [000280] In some embodiments, including any of the above, the sulfide catholyte is selected from LPSI, LSTPS, LSPSCl, LBHI, and LPS.

[0272] [000281] In some embodiments, including any of the above, the sulfide catholyte is LSTPS.

[0273] [000282] In some embodiments, including any of the above, the sulfide catholyte is LPSI.

[0274] [000283] In some embodiments, including any of the above, the sulfide electrolyte is a sulfide single-ion conductor.

[0275] [000284] In some embodiments, including any of the above, the positive electrode layer comprises a positive electrode active material loading of about 75 to about 90 wt %.

[0276] [000285] In some embodiments, including any of the above, the positive electrode active material comprises a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

[0277] [000286] In some embodiments, including any of the above, the positive electrode active material comprises a lithium intercalation material; and the intercalation material is selected from the group consisting of nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), Li(NiCoMn)O, LiMnO, LiCoO, and LiMn 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, and Mn).

[0278] [000287] In some embodiments, including any of the above, the positive electrode active material comprises a lithium conversion material; and the lithium conversion material is selected from the group consisting of FeF, NiF, FeO xF 3-2x , FeF3, MnF3, CoF3, CuF2 materials, alloys thereof and combinations thereof.

[0279] [000288] In some embodiments, including any of the above, the intercalation material is an NCA.

[0280] [000289] In some embodiments, including any of the above, the intercalation material is NMC.

[0281] [000290] In some embodiments, including any of the above, the solid electrochemical stack further comprises a bonding layer.

[0282] [000291] In some embodiments, including any of the above, the tie layer comprises a borohydride composition.

[0283] [000292] In some embodiments, including any of the above, the buffer layer is between and in direct contact with the anode layer and the borohydride layer, and the borohydride layer is between and in direct contact with the buffer layer and the separator layer.

[0284] [000293] In some embodiments, including any of the above, the borohydride composition is represented by the formula:

[0285] [000294] A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is selected from fluorine (F), bromine (Br), chlorine (Cl), iodine (I), and combinations thereof, and 3≦A≦6, 2≦B≦5, and 0≦C≦9.

[0286] [000295] In some embodiments, including any of the above, the borohydride composition is represented by the formula: A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is selected from fluorine (F), bromine (Br), chlorine (Cl), iodine (I), and combinations thereof, and where 3≦A≦6, 2≦B≦5, and 3≦C≦9.

[0287] [000296] In some embodiments, including any of the above, the borohydride composition is represented by the formula: A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is selected from fluorine (F), bromine (Br), chlorine (Cl), iodine (I), and combinations thereof, and where 3≦A≦6, 2≦B≦5, and 3≦C≦6.

[0288] [000297] In some embodiments, including any of the above, the borohydride composition is selected from one of the following formulas: 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2.

[0289] [000298] In some embodiments, including any of the above, the bonding layer further comprises LiI, LPS, LXPS, Li3PO4, or a combination thereof.

[0290] [000299] In some embodiments, including any of the above, the solid electrochemical stack includes (d) a cathode current collector in direct contact with the separator layer.

[0291] [000300] In some embodiments, including any of the above, the solid electrochemical stack includes (e) an anode current collector in direct contact with the anode layer.

[0292] [000301] In some embodiments, including any of the above, the solid electrochemical stack includes (d) a cathode current collector and (e) a cathode, wherein the (e) cathode is between and in direct contact with the separator layer and the cathode current collector.

[0293] [000302] In some embodiments, including any of the above, the negative electrode is a lithium (Li) metal electrode layer.

[0294] [000303] In some embodiments, including any of the above, at least one current collector comprises a material selected from the group consisting of carbon (C) coated nickel (Ni), nickel (Ni), copper (Cu), aluminum (Al), stainless steel, alloys thereof, and combinations thereof.

[0295] [000304] In some embodiments, including any of the above, the cathode current collector comprises a material selected from the group consisting of carbon (C) coated nickel (Ni), nickel (Ni), copper (Cu), alloys thereof, and combinations thereof.

[0296] [000305] In some embodiments, including any of the above, the anode current collector layer comprises a material selected from the group consisting of carbon (C) coated aluminum and aluminum.

[0297] [000306] In some embodiments, including any of the above, the cathode current collector layer is C-coated Ni.

[0298] [000307] In some embodiments, including any of the above, the separator layer is rectangular.

[0299] [000308] In some embodiments, including any of the above, the anode layer is rectangular.

[0300] [000309] In some embodiments, including any of the above, the separator layer is circular.

[0301] [000310] In some embodiments, including any of the above, the geometric surface area of ​​the anode layer and the geometric surface area of ​​the separator layer are substantially the same.

[0302] [000311] In some embodiments, including any of the above, one side of the anode layer has a length of 2 cm to 30 cm.

[0303] [000312] In some embodiments, including any of the above, one side of the separator layer has a length of 2 cm to 30 cm.

[0304] [000313] In some embodiments, including any of the above, the anode layer has a diameter that is 10 cm in length.

[0305] [000314] In some embodiments, including any of the above, the separator layer has a diameter that is 10 cm in length.

[0306] [000315] In some embodiments, including any of the above, the anode layer comprises a percolating network of an ion conductor.

[0307] [000316] In some embodiments, including any of the above, the separator layer comprises a percolated network of an ion conductor.

[0308] [000317] In some embodiments, including any of the above, the separator layer comprises a polymer.

[0309] [000318] In some embodiments, including any of the above, the anode layer comprises carbon at a weight loading of about 0 to about 1%.

[0310] [000319] In some embodiments, including any of the above, about 0 to about 1% loading mass of carbon is C65 or steam grown carbon fiber (VGCF).

[0311] [000320] In some embodiments, including any of the above, the anode layer comprises a binder at a weight loading of from about 0 to about 2.5%.

[0312] [000321] In some embodiments, including any of the above, the binder at about 0 to about 2.5% loading mass is selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxy)ethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxy)ethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyfluoride, and the like. The binder may be selected from the group consisting of polyvinylidene fluoride hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene-rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, alpha-olefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), polyvinylidene fluoride (PVDF), polyethylene, POB3, polyolefin, rubber, or a combination thereof.

[0313] [000322] In some embodiments, including any of the above, the thickness of the anode layer is from about 10 μm to about 500 μm.

[0314] [000323] In some embodiments, including any of the above, the thickness of the anode layer is from 100 μm to about 500 μm.

[0315] [000324] In some embodiments, including any of the above, the thickness of the separator layer is from about 1 μm to about 200 μm.

[0316] [000325] In some embodiments, including any of the above, the thickness of the anode current collector layer is from about 3 μm to about 100 μm.

[0317] [000326] In some embodiments, including any of the above, the thickness of the anode current collector layer is about 15 μm.

[0318] [000327] In some embodiments, including any of the above, the thickness of the cathode current collector layer is from about 3 μm to about 100 μm.

[0319] [000328] In some embodiments, including any of the above, the thickness of the anode current collector layer is about 15 μm.

[0320] [000329] In some embodiments, including any of the above, the thickness of the tab on the anode current collector or the cathode current collector is from about 5 μm to about 100 μm.

[0321] [000330] In some embodiments, including any of the above, the anode layer has a porosity of less than 1% v / v.

[0322] [000331] In some embodiments, including any of the above, the buffer layer has a porosity of less than 1% v / v.

[0323] [000332] In some embodiments, including any of the above, the anode layer has a porosity of at least 0.01% v / v.

[0324] [000333] In some embodiments, including any of the above, the buffer layer has a porosity of at least 0.01% v / v.

[0325] [000334] In some embodiments, including any of the above, the separator layer has an empirical formula of LiLaZrO 12-x Lithium-filled garnets include those having Al2O3 (x is a rational number and 0≦x≦1).

[0326] [000335] In some embodiments including any of the above, the separator layer comprises a lithium-filled garnet oxide characterized by the formula LiuLavZrxOy·zAl2O3, where u is a rational number from 4 to 8; v is a rational number from 2 to 4; x is a rational number from 1 to 3; y is a rational number from 10 to 14; and z is a rational number from 0.05 to 1; u, v, x, y, and z are selected such that the lithium-filled garnet is charge-neutral.

[0327] [000336] In some embodiments including any of the above, the separator layer comprises 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.

[0328] [000337] In some embodiments including any of the above, the separator layer comprises Li7La3Zr2O 12 ·Al2O3 or Li7La3Zr2O 12 ·0.35Al2O3.

[0329] [000338] In some embodiments including any of the above, the lithium-filled garnet is doped with Nb, Ga, and / or Ta.

[0330] [000339] In another embodiment, a solid-state electrochemical cell (SSEC) comprising (a) an anode layer comprising an active material and a sulfide catholite; (b) a single-ion conductive solid buffer; (c) a borohydride bonding layer; and (d) a lithium-filled garnet layer, wherein the buffer is mixed within the anode layer or is a layer in contact with the anode layer or both; and the borohydride bonding layer is between and in contact with the lithium-filled garnet layer and (i) the anode layer having the buffer mixed therein or (ii) the buffer layer in contact with the anode, is disclosed herein.

[0331] [000340] In some embodiments, including any of the above, the single-ion conducting solid buffer is mixed within the anode layer.

[0332] [000341] In some embodiments, including any of the above, the single-ion conducting solid buffer is a layer in contact with the anode layer.

[0333] [000342] In some embodiments, including any of the above, the single-ion conductive solid buffer is present as a layer mixed within and in contact with the anode layer.

[0334] [000343] In some embodiments, including any of the above, the single-ion conducting solid buffer layer prevents direct contact between the borohydride binding layer and the anode layer.

[0335] [000344] In some embodiments, including any of the above, the thickness of the anode layer is from about 100 μm to about 1000 μm.

[0336] [000345] In some embodiments, including any of the above, the buffer layer has a thickness of about 0.5 μm to about 50 μm.

[0337] [000346] In some embodiments, including any of the above, the single-ion conductive solid buffer is mixed into the anode layer to a penetration depth within the anode layer of from about 1 μm to about 50 μm from the edge where the anode layer joins either the buffer layer or the borohydride binding layer.

[0338] [000347] In some embodiments, including any of the above, the lithium-filled garnet layer has a thickness of from about 1 μm to about 200 μm.

[0339] [000348] In some embodiments, including any of the above, the borohydride bonding layer has a thickness of from about 0.5 μm to about 50 μm.

[0340] [000349] In some embodiments, including any of the above, the borohydride binding layer permeates the buffer layer.

[0341] [000350] In some embodiments, including any of the above, the borohydride bonding layer infiltrates the lithium-filled garnet layer.

[0342] [000351] In some embodiments, including any of the above, the borohydride tie layer has a density that is 90% or greater than the density of the raw material.

[0343] [000352] In some embodiments, including any of the above, the borohydride tie layer has a porosity of less than 10% by volume.

[0344] [000353] In some embodiments, including any of the above, the borohydride tie layer has a melting point of less than 250°C.

[0345] [000354] In some embodiments, including any of the above, the borohydride tie layer has a melting point greater than 250°C.

[0346] [000355] In some embodiments, including any of the above, the solid-state electrochemical stack includes a cathode.

[0347] [000356] In some embodiments, including any of the above, the cathode is a lithium (Li) metal cathode.

[0348] [000357] In some embodiments, including any of the above, the lithium-filled garnet layer is in contact with the cathode.

[0349] [000358] In some embodiments, including any of the above, the buffer layer comprises 0.01 to 10 wt % of a binder.

[0350] [000359] The binder is a polymer and the electrons or Li + 121. The SSEC of embodiment 120, which does not conduct ions.

[0351] [000360] In some embodiments, including any of the above, the buffer layer comprises no more than 10% by volume of an organic polymer.

[0352] [000361] In some embodiments, including any of the above, the polymer is selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxy)ethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxy)ethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane , polyvinylidene fluoride (PVDF), ethylene alpha-olefin copolymer, polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene-rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), polyvinylidene fluoride (PVDF) and polyethylene.

[0353] [000362] In some embodiments, including any of the above, the buffer layer or buffer component does not include an organic polymer.

[0354] [000363] In some embodiments, including any of the above, the anode potential is protected from the lithium-filled garnet layer potential.

[0355] [000364] In some embodiments, including any of the above, the active material potential of the positive electrode is protected from the lithium-filled garnet layer potential.

[0356] [000365] In some embodiments, including any of the above, the active material is coated.

[0357] [000366] In some embodiments, including any of the above, the active material is coated with a coating selected from the group consisting of lithium niobium oxide, lithium zirconium oxide, lithium aluminum oxide, lithium tantalum oxide, lithium hafnium oxide, niobium oxide, zirconium oxide, aluminum oxide, tantalum oxide, and hafnium oxide.

[0358] [000367] In some embodiments, including any of the above, the active material is not coated.

[0359] [000368] In some embodiments, including any of the above, the anode comprises a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

[0360] [000369] In some embodiments, including any of the above, the intercalation material is selected from the group consisting of nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), Li(NiCoMn)O, LiMnO, LiCoO, and LiMn 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, or Mn).

[0361] [000370] In some embodiments, including any of the above, the lithium conversion material is FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials, alloys thereof and combinations thereof.

[0362] [000371] In some embodiments, including any of the above, the sulfide catholyte and the single-ion conductive solid buffer comprise the same type of material.

[0363] [000372] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, and LPS+X, where X is selected from the group consisting of Cl, I, Br, and combinations thereof.

[0364] [000373] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LPSI, LXPS, LSTPS, LSPSCl, LPSCl, LSPSBr, and LPSBr.

[0365] [000374] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conductive solid buffer, or both, are selected from x·LiS:y·SiS, where x and y are each independently a number from 0 to 1, and x+y=1.

[0366] [000375] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, LGPS, LSTPS, and LSPS.

[0367] [000376] In some embodiments including any of the above, the sulfide solid electrolyte or the single ion conductive solid buffer, or both, have the following formula: Li a Si b Sn c P d S e (where 2 ≤ a ≤ 8, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0.5 ≤ d ≤ 2.5, and 2 ≤ e ≤ 12); Li a Si b P c S d X e (where 8 < a < 12, 1 < b < 3, 1 < c < 3, 8 < d < 14, and 0 < e < , and X is F, Cl, Br, or I); Li g As h Sn j S k O l (where 2 ≤ g ≤ 6, 0 ≤ h ≤ 1, 0 ≤ j ≤ 1, 2 ≤ k ≤ 6, and 0 ≤ l ≤ 10); or Li m P n S p I<​​​​​​​​​​​​​​​​​​where 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 2≦e≦12.

[0370] [000379] In some embodiments, including any of the above, the sulfide catholyte has the formula: Li a Si b Sn c P d S e where 2≦a≦5, 0≦b≦0.5, 0≦c≦0.5, 0.5≦d≦2, and 2≦e≦12.

[0371] [000380] In some embodiments, including any of the above, the single-ion conducting solid buffer comprises LSTPS.

[0372] [000381] In some embodiments, including any of the above, the borohydride bonding layer comprises lithium borohydride, sodium borohydride, or potassium borohydride.

[0373] [000382] In some embodiments, including any of the above, the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiNH2.

[0374] [000383] In some embodiments, including any of the above, one or more of the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiI.

[0375] [000384] In some embodiments, including any of the above, one or more of lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiNH2 and LiI.

[0376] [000385] In some embodiments, including any of the above, the borohydride tie layer comprises a borohydride composition including A(LiBH4)(1-A)(P2S5), where 0.05≦A≦0.95.

[0377] [000386] In some embodiments, including any of the above, 0.5 <A<0.95である。

[0378] [000387] In some embodiments, including any of the above, A is 0.85, 0.9, or 9.95.

[0379] [000388] In some embodiments, including any of the above, the borohydride bonding layer comprises 0.9(LiBH4)0.1(P2S5).

[0380] [000389] In some embodiments, including any of the above, the borohydride bonding layer comprises a borohydride composition including A·(LiBH4)·B·(LiX)·C·(LiNH2), where X is fluorine, bromine, chlorine, iodine, or a combination thereof, and 3≦A≦6, 2≦B≦5, and 0≦C≦9.

[0381] [000390] In some embodiments, including any of the above, 3 < A < 6, 2 < B < 5, and 3 < C < 9.

[0382] [000391] In some embodiments, including any of the above, X is bromine, chlorine, iodine, or a combination thereof.

[0383] [000392] In some embodiments, including any of the above, X is chlorine.

[0384] [000393] In some embodiments, including any of the above, X is bromine.

[0385] [000394] In some embodiments, including any of the above, X is iodine.

[0386] [000395] In some embodiments, including any of the above, 3≦A≦6, 3≦B≦5, and 3≦C≦9.

[0387] [000396] In some embodiments, including any of the above, 4≦A≦6, 4≦B≦5, and 4≦C≦6.

[0388] [000397] In some embodiments, including any of the above, the borohydride tie layer includes a borohydride composition that is 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·9LiNH2.

[0389] [000398] In some embodiments, including any of the above, the borohydride tie layer includes a borohydride composition that is 3LiBH4·2LiBr·3LiNH2 or 3LiBH4·4LiBr·9LiNH2.

[0390] [000399] In some embodiments, including any of the above, the borohydride tie layer comprises a borohydride composition that is 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2.

[0391] [000400] In some embodiments, including any of the above, the borohydride tie layer comprises a borohydride composition selected from LBHIN and LBHN.

[0392] [000401] In some embodiments, including any of the above, the borohydride bonding layer comprises KBH4 + LiNH2.

[0393] [000402] In some embodiments, including any of the above, the borohydride bonding layer is amorphous.

[0394] [000403] In some embodiments including any of the above, the borohydride bonding layer is semi-crystalline.

[0395] [000404] In some embodiments including any of the above, the borohydride bonding layer is polycrystalline.

[0396] [000405] In some embodiments including any of the above, the lithium-filled garnet layer comprises a lithium-filled garnet selected from 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).

[0397] [000406] In some embodiments including any of the above, the lithium-filled garnet layer comprises a lithium-filled garnet selected from Li7La3Zr2O 12 ·Al2O3 and Li7La3Zr2O 12 ·0.35Al2O3.

[0398] [000407] In some embodiments including any of the above, the lithium-filled garnet is doped with Nb, Ga and / or Ta.

[0399] [000408] In some embodiments including any of the above, the lithium-filled garnet layer is characterized by the formula Li a [[ID=​​​​​​​​​​​​​[000409] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y In some embodiments, including any of the above, the lithium-filled garnet layer comprises a lithium-filled garnet oxide characterized by the formula LiAlO, where u is a rational number from 4 to 8; v is a rational number from 2 to 4; x is a rational number from 1 to 3; y is a rational number from 10 to 14; and z is a rational number from 0.05 to 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet is charge-neutral. u La v Zr x O y Lithium-filled garnet oxides characterized by zTa2O5, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0401] [000410] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y Lithium-filled garnet oxides characterized by zNb2O5, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0402] [000411] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O yand zGa2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0403] [000412] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y and lithium-filled garnet oxides characterized by zTa2O5 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; z is a rational number between 0 and 1; b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0404] [000413] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O y and lithium-filled garnet oxides characterized by zNb2O5 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; z is a rational number between 0 and 1; b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet is charge-neutral.

[0405] [000414] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li u La v Zr x O yand lithium-filled garnet oxides characterized by zGa2O3 bAl2O3, where u is a rational number between 4 and 10; v is a rational number between 2 and 4; x is a rational number between 1 and 3; y is a rational number between 10 and 14; and z is a rational number between 0 and 1; b is a rational number between 0 and 1; z+b≦1; and u, v, x, y, and z are selected such that the lithium oxide-filled garnet oxide is charge-neutral.

[0406] [000415] In some embodiments, including any of the above, the lithium-filled garnet layer has the formula Li 6.4 Ga 0.2 La3Zr2O 12 The present invention includes lithium-filled garnets characterized by:

[0407] [000416] In some embodiments, including any of the above, the SSEC comprises an anode current collector layer.

[0408] [000417] In some embodiments, including any of the above, the SSEC comprises a cathode current collector layer.

[0409] [000418] In some embodiments, including any of the above, the cathode current collector layer is a sintered metal.

[0410] [000419] In some embodiments, including any of the above, the sintered metal is selected from the group consisting of Al, Cu, Ni, Ag, Au, Pt, Pd, or Sn.

[0411] [000420] In some embodiments, including any of the above, the metal is Ni.

[0412] [000421] In some embodiments, including any of the above, the anode layer further comprises a binder, carbon, or both a binder and carbon.

[0413] [000422] In some embodiments, including any of the above, the lithium-filled garnet layer is between and in contact with the cathode current collector layer and the borohydride bonding layer.

[0414] [000423] In some embodiments, including any of the above, the borohydride bonding layer is between and in contact with the lithium-filled garnet layer and the buffer layer.

[0415] [000424] In some embodiments, including any of the above, the buffer layer is between and in contact with the borohydride binding layer and the anode layer.

[0416] [000425] In some embodiments, including any of the above, the anode layer is between and in contact with the buffer layer and the anode current collector layer.

[0417] [000426] In some embodiments, including any of the above, the cathode layer is between and in contact with the lithium-filled garnet layer and the cathode current collector layer.

[0418] [000427] In one embodiment, provided herein is a battery comprising a SSEC of any one of the embodiments provided herein.

[0419] [000428] In one embodiment, provided herein is an electric vehicle including a battery of any one of the embodiments provided herein.

[0420] [000429] In one embodiment, there is set forth herein a method for manufacturing an electrochemical cell, the method including providing a slurry including an active material, a catholyte, and a solvent; depositing the slurry onto a current collector; drying the slurry; providing a second slurry including a single-ion conductive solid buffer; depositing the second slurry onto a substrate; drying the second slurry; transferring the dried second slurry onto the dried first slurry to form a stack; applying pressure and heat to the stack; providing a solid separator; depositing a borohydride layer onto the solid separator; overlapping the stack with the solid separator having the borohydride layer thereon to form an electrochemical cell stack; and applying pressure and heat to the cell stack.

[0421] [000430] In some embodiments, including any of the above, the solids loading is at least 60% by weight.

[0422] [000431] In some embodiments, including any of the above, the buffer is an LSTPS.

[0423] [000432] In some embodiments, including any of the above, the pressure is applied uniaxially.

[0424] [000433] In one embodiment, provided herein is a bilayer stack comprising: (a) an anode layer comprising an active material and a sulfide catholyte; and (b) a single-ion conductive solid buffer, wherein the buffer is mixed within the anode layer, is a layer in contact with the anode layer, or both.

[0425] [000434] In some embodiments, including any of the above, the single-ion conducting solid buffer is mixed within the anode layer.

[0426] [000435] In some embodiments, including any of the above, the single-ion conducting solid buffer is a layer in contact with the anode layer.

[0427] [000436] In some embodiments, including any of the above, the single-ion conductive solid buffer is present as a layer mixed within and in contact with the anode layer.

[0428] [000437] In some embodiments, including any of the above, the buffer is mixed into the anode layer to a penetration depth within the anode layer of from about 1 μm to about 50 μm from the edge where the anode layer joins either the buffer layer or the borohydride binding layer.

[0429] [000438] In some embodiments, including any of the above, the lithium-filled garnet layer has a thickness of from about 1 μm to about 200 μm.

[0430] [000439] In some embodiments, including any of the above, the buffer layer comprises no more than 10% by volume of an organic polymer.

[0431] [000440] In some embodiments, including any of the above, the polymer is selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxy)ethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxy)ethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane , polyvinylidene fluoride (PVDF), ethylene alpha-olefin copolymer, polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene-rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), polyvinylidene fluoride (PVDF) and polyethylene.

[0432] [000441] In some embodiments, including any of the above, the active material is coated.

[0433] [000442] In some embodiments, including any of the above, the active material is coated with a coating selected from the group consisting of lithium niobium oxide, lithium zirconium oxide, lithium aluminum oxide, lithium tantalum oxide, lithium hafnium oxide, niobium oxide, zirconium oxide, aluminum oxide, tantalum oxide, and hafnium oxide.

[0434] [000443] In some embodiments, including any of the above, the active material is not coated.

[0435] [000444] In some embodiments, including any of the above, the anode comprises a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

[0436] [000445] In some embodiments, including any of the above, the intercalation material is selected from the group consisting of nickel manganese cobalt oxide (NMC), nickel cobalt aluminum oxide (NCA), Li(NiCoAl)O, lithium cobalt oxide (LCO), lithium manganese cobalt oxide (LMCO), lithium nickel manganese cobalt oxide (LMNCO), lithium nickel manganese oxide (LNMO), Li(NiCoMn)O, LiMnO, LiCoO, and LiMn 2-a Ni a O4 (wherein a is 0 to 2) or LiMPO4 (wherein M is Fe, Ni, Co, or Mn).

[0437] [000446] In some embodiments, including any of the above, the lithium conversion material is FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials, alloys thereof and combinations thereof.

[0438] [000447] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, and LPS+X, where X is selected from the group consisting of Cl, I, Br, and combinations thereof.

[0439] [000448] In some embodiments, including any of the above, the sulfide catholyte or the single-ion conducting solid buffer, or both, is selected from the group consisting of LPSI, LXPS, LSTPS, LSPSCl, LPSCl, LSPSBr, and LPSBr.

[0440] [000449] In some embodiments including any of the above, the sulfide catholite or the single-ion conductive solid buffer, or both, are selected from x·Li2S:y·SiS2 (where x and y are each independently a number from 0 to 1 and x + y = 1).

[0441] [000450] In some embodiments including any of the above, the sulfide catholite or the single-ion conductive solid buffer, or both, are selected from the group consisting of LSS, LGPS, LSTPS, and LSPS.

[0442] [000451] In some embodiments including any of the above, the sulfide catholite or the single-ion conductive solid buffer, or both, are of the following formula: Li a Si b Sn c P d S e (where 2 ≤ a ≤ 8, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0.5 ≤ d ≤ 2.5, and 2 ≤ e ≤ 12); Li a Si b P c S d X e (where 8 < a < 12, 1 < b < 3, 1 < c < 3, 8 < d < 14, and 0 < e < 1, and X is F, Cl, Br, or I); Li g As h Sn j S k O l (where 2 ≤ g ≤ 6, 0 ≤ h ≤ 1, 0 ≤ j ≤ 1, 2 ≤ k ≤ 6, and 0 ≤ l ≤ 10); or Li m P n S​​​wherein 2≦m≦6, 0≦n≦1, 0≦p≦1, 2≦q≦6; a mixture of (LiS):(P2S5) and LiI having a molar ratio of LiS:P2S5 of about 10:1 to about 6:4, wherein the ratio of [(LiS):(P2S5)]:LiI is between 95:5 and 50:50; LPS+X, where X is selected from Cl, I, or Br; vLiS+wP2S5+yLiX; vLiS+wSiS2+yLiX; or vLiS+wB2S3+yLiX. In these embodiments, x, w, and y can individually range from 0, inclusive, to 1, inclusive, in each instance.

[0443] [000452] In some embodiments, including any of the above, the sulfide catholyte comprises LSTPS.

[0444] [000453] In some embodiments, including any of the above, the sulfide catholyte has the formula: Li a Si b Sn c P d S e where 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 2≦e≦12.

[0445] [000454] In some embodiments, including any of the above, the sulfide catholyte has the formula: Li a Si b Sn c P d S e where 2≦a≦5, 0≦b≦0.5, 0≦c≦0.5, 0.5≦d≦2, and 2≦e≦12.

[0446] [000455] In some embodiments, including any of the above, the lithium-filled garnet layer may comprise 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), including a lithium-filled garnet selected therefrom.

[0447] [000456] Specific advantages have been listed above, but various embodiments may include some or all of the listed advantages, or may not include the listed advantages. Other technical advantages may be readily apparent to those skilled in the art upon consideration of the following drawings and description.

Example

[0448] Example [000457] Reagents, chemicals, and materials were purchased commercially unless otherwise specified. Chemical reagents and solvents were purchased commercially and used without purification unless otherwise specified. The pouch cell containers were purchased from Showa Denko. The electrochemical potentiostat used was an Arbin potentiostat. Electrochemical impedance spectroscopy (EIS) was performed with a Biologic VMP3, VSP, VSP-300, SP-150, or SP-200. Viscosity was measured using a Rheometer at a shear rate of 100 seconds -1 under the shear rate of. Milling was performed using a Retsch PM 400 Planetary ball mill. Mixing was performed using a Fischer Scientific vortex mixer, a Flaktek speed mixer, or a Primix filmix homogenizer. Casting was performed using a TQC draw-down table. Calendering was performed using an IMC calender. Light scattering was performed using a Horiba, model: Partica, model number: LA-950V2, general term: laser scattering particle size distribution analyzer.

[0449] [000458] Electron microscopy was performed on an FEI Quanta SEM, Helios 600i, or Helios 660 FIB-SEM, although equivalent tools may be substituted. XRD was performed on a Bruker D8 Advance ECO or Rigaku MiniFlex 2 using Cu K-α radiation, with a 6 mm slit width, a scan time of 76 ms per step or 0.4 s per step, and room temperature. Optical imaging was performed with an optical camera. DC cycling was performed on an Arbin BT-2043 or BT-G, although it is understood that equivalent tools may be substituted.

[0450] Example 1 [000459] Step 1(1): A solid anode layer was prepared. A slurry was prepared with a solids loading of 30-80 wt% in 20-70% toluene. The solids loading included 70-95 wt% lithiated nickel-cobalt-aluminum oxide (NCA) active material coated with lithiated lithium zirconium oxide (LZO), 13 wt% LSTPS, and 2 wt% binder. The LSTPS composition was Li a Si b Sn c P d S e wherein 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 4≦e≦12, further comprising greater than 0 atomic % to 15 atomic % oxygen, and prepared as described in U.S. Pat. No. 9,172,114, issued October 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0451] [000460] The slurry was cast onto a carbon-coated Al foil using a doctor blade. The resulting cast slurry was dried at room temperature to 120°C for 1 to 24 hours to form an anode layer film on the carbon-coated Al foil. This carbon-coated Al foil served as a current collector when the electrochemical cell was assembled in step 7(7). After drying, the anode layer adhered to this current collector.

[0452] [000461] Step 2(2): A buffer layer in contact with the solid anode layer was prepared. A slurry was prepared using 10 to 70 wt % LSTPS in toluene. The slurry was cast onto Ni foil using a doctor blade. The resulting cast slurry was dried at room temperature to 120°C for 1 to 24 hours to form a buffer layer film. In this example, the buffer layer contained LSTPS of the same chemical composition as that used in the anode layer. Without being bound by theory, it is proposed that this layer does not contain an electron conductor. This prevents electrons from accessing the borohydride binding layer. In this way, the buffer layer blocks the anode layer potential from the binding layer potential. This also allows the buffer layer to protect the cathode (anode) potential from the anode layer.

[0453] [000462] Step 3(3): The buffer layer film was peeled off, i.e., removed, from the Ni foil after drying in Step 2(2). The buffer layer was then transferred and placed on the anode layer prepared according to Step 1(1) to produce a stack (buffer layer-anode layer-current collector).

[0454] [000463] Step 4(4): A uniaxial pressure of approximately 300 MPa was applied to the stack fabricated in Step 3(3) at low temperature (room temperature). The stack was maintained at high temperature (150 to 180°C) while the pressure was applied.

[0455] [000464] Step 5(5): A lithium-filled garnet layer was fabricated according to the lithium-filled garnet layer or film formation method in U.S. Patent No. 9,806,372 B2, issued October 31, 2017, and entitled "GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS," and U.S. Patent No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION," the entire contents of each of which are incorporated herein by reference in their entirety for all purposes.

[0456] [000465] Step 6(6): A borohydride bonding layer was prepared. The borohydride composition used to form the borohydride bonding layer was described in accordance with International PCT Patent Application No. PCT / US2017 / 057735, filed October 20, 2017, and entitled "ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE"; and International PCT Patent Application No. PCT / US2017 / 057739, filed October 20, 2017, and entitled "BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID-STATE BATTERY." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. The composition 3LiBH4·2LiCl·3LiNH2 was melted and spin-coated onto the lithium-filled garnet film prepared in step 5(5). The borohydride bonding layer forms intimate contact with both the lithium-filled garnet and the buffer layer, which is in contact with the anode layer.

[0457] [000466] Step 7(7): The lithium-filled garnet film with the LBHIN spin-coated layer was placed on the stack from step 4(4), where the LBHIN borohydride binder layer was in direct contact with the buffer layer. The stack was then densified by applying a pressure of approximately 10,000 pounds per square inch (PSI) at the temperature at which LBHIN melts (250°C). The stack was then cooled to room temperature.

[0458] [000467] Step 8(8): For the stack resulting from Step 7(7), a current collector was attached to the side of the lithium-loaded garnet film that did not have the LBHIN spin-coated layer to form an electrochemical cell. Prior to attaching the current collector, lithium metal was evaporated onto the lithium-loaded garnet to form a lithium metal cathode. The electrochemical cell contained 30 μm of evaporated lithium.

[0459] [000468] Step nine(9): The stack resulting from step eight(8) was cycled to form a lithium metal anode between the adhered current collector and the lithium-loaded garnet film.

[0460] Example 2 [000469] An electrochemical cell was formed according to steps 1(1) through 8(8) of Example 1. The cell was electrochemically cycled between 3.0 V and 4.2 V at a C / 3 rate at 45°C after an initial formation cycle of C / 10. The electrochemical cell was pressurized to 300 pounds per square inch (psi).

[0461] [000470] The results are shown in Figures 3 to 5.

[0462] [000471] Figure 3 demonstrates that the electrochemical cell completed 50 cycles at a C / 3 rate at 45°C without significant volume loss. The first and 50th cycles are overlapped in Figure 3.

[0463] [000472] Figure 4 demonstrates that the electrochemical cell completed 200 cycles and retained greater than 80% of its energy at the 200th cycle. The coulombic efficiency was observed to be close to 1 (>0.999 during most cycles). The first (1st) cycle efficiency was greater than 90%. This is due to the use of a LiNbO3-coated LiCoO2 positive electrode active material and a sulfide solid electrolyte (Li 9.6 P3S 12 , Li 10 GeP2S 12 , Li 9.54 Si 1.74 P 1.44 S 11.7 C l0.3 It is worth comparing these unexpected results with those of Kato et al. (DOI:10.1038 / NENERGY.2016.30), which reports cycling data for electrochemical cells with ZnO, ZnS, and ZnO. Kato et al. report coulombic efficiencies of 90%, 61%, and 39%, respectively, in Figure 4. However, in Kato et al., only low-voltage (2.5 V) electrochemical cells were tested. These low-voltage (2.5 V) cells were expected to have high coulombic efficiencies. However, only the 2.5 V cells exhibited coulombic efficiencies of 93% at cycle 1 and 99% at cycles 10 and 100. In contrast to Kato et al., the electrochemical cells prepared in this example exhibited coulombic efficiencies of approximately 100% (greater than 99.9%) after 10 cycles, as shown in Figure 4 in this provisional patent application. Compared to the prior art, the demonstrated coulombic efficiencies are higher when tested under identical conditions. This indicates improved electrochemical stability on the sulfide cathode interface.

[0464] [000473] Figure 5 shows that the electrochemical cell exhibited a resistance of approximately 54 Ω-cm at 45°C. 2 LSTPS and lithium-filled garnets each individually have high area-specific resistivities (ASRs) at room temperature (e.g., 1000 Ω-cm). 2Therefore, it is unexpected that simply pressing LSTPS and a lithium-filled garnet together, as performed in Example 1, to form a heterointerface therebetween, can result in a low ASR in a cell containing both LSTPS and a lithium-filled garnet.

[0465] [000474] Figures 6 and 7 show schematic diagrams of the electrochemical cell tested. The electrochemical cell was prepared according to Example 1 and tested according to Example 2. The electrochemical cell represented by Figure 6 included layer 701, which represents a deposited lithium metal anode. Layer 702 represents a lithium-filled garnet layer. Layer 704 represents a buffer layer. Layer 705 represents an anode layer.

[0466] [000475] The electrochemical cell represented by Figure 7 included layer 801, which represents a deposited lithium metal anode. Layer 802 represents a lithium-filled garnet layer. Layer 803 represents a bonding layer. Layer 805 represents an anode layer.

[0467] Example 3 - Fabrication of an electrochemical cell with a buffer layer [000476] Step 1(1): A solid anode layer (cathode layer, SSC) was prepared. A slurry was prepared with a solid loading of 30-80 wt% in 20-70% toluene. The solid loading included 70-95 wt% lithiated nickel-cobalt-aluminum oxide active material (NCA) coated with lithium zirconium oxide (LZO), 13 wt% LSTPS, and 2 wt% binder. The LSTPS composition consisted of Li a Si b Sn c P d S ewherein a is 4, b is 0.5, c is 0.5, d is 1, and e is 8, further comprising greater than 0 atomic % to 15 atomic % oxygen, and was prepared as described in U.S. Pat. No. 9,172,114, issued October 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0468] [000477] The slurry was cast onto a carbon-coated aluminum foil using a doctor blade. The resulting cast slurry was dried at room temperature to 120°C for 1 to 24 hours to form an anode layer film on the carbon-coated aluminum foil.

[0469] [000478] Step 2(2): A sulfide layer, which would later be placed in contact with the solid anode layer, was prepared. A slurry was prepared using 10 to 70 wt. % LSTPS in toluene. The slurry was cast onto Ni foil using a doctor blade casting method. The resulting cast slurry was dried for 1 to 24 hours at room temperature to 120°C to form a buffer layer film. In this example, the buffer layer contained LSTPS with the same chemical composition as that used in the anode layer. Without being bound by theory, it is proposed that this layer is not electrically conductive (having an electronic conductivity of less than 1E-6 S / cm). This buffer layer thereby shields the cathode (anode) potential from the anode layer.

[0470] [000479] Step 3(3): The two layers of step (1) and step (2) were placed on top of each other such that the sulfide layer and the cathode layer were in direct contact with each other to form a stack (nickel film-buffer layer-anode layer-aluminum film).

[0471] [000480] Step 4(4): The stack from step (3) is placed on an aluminum guide foil. The membrane is passed through a calender at 1.0 meter / min, 140°C, and a fluid pressure of approximately 100-110 bar (10-11 MPa) (applying 1100-1200 N / mm). A Saueressig GK 300 L or Ono Roll Type 12 calender was used. After calendering, the sulfide layer was transferred onto the cathode layer, and both layers were densified together in one step. The results are shown in the image in Figure 2. During calendering, a carbon-coated aluminum foil was also adhered to the aluminum guide foil to form the first current collector on the side of the SSC.

[0472] [000481] The stack from step (4) was assembled into an electrochemical cell containing a lithium-loaded garnet separator for testing.

[0473] [000482] The lithium-filled garnet layers were fabricated according to the methods for forming lithium-filled garnet layers or films in U.S. Patent No. 9,806,372 B2, issued October 31, 2017, and entitled "GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS," and U.S. Patent No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION," the entire contents of each of which are incorporated herein by reference in their entirety for all purposes.

[0474] [000483] Step 6(6): A lithium-filled garnet film was placed on the stack resulting from step 4(4) so ​​that the lithium-filled garnet film was in direct contact with the buffer layer. The stack was then densified by applying a pressure of about 500 pounds per square inch (PSI) at a temperature of 140°C. The stack was then cooled to room temperature.

[0475] [000484] Step 7(7): To create a lithium metal cathode in the stack resulting from Step 6(6), lithium metal was evaporated onto the lithium-filled garnet (30 μm of evaporated lithium), and the stack was bonded to a cathode current collector to form an electrochemical cell. In some cells, the cathode current collector was directly bonded onto the lithium-filled garnet film, and lithium from the anode was deposited between the lithium-filled garnet film and the cathode current collector.

[0476] Example 4 - Fabrication of an electrochemical cell with a buffer layer and a borohydride layer [000485] Step 1(1): A solid anode layer (cathode layer, SSC) was prepared. A slurry was prepared with a solid loading of 30-80 wt% in 20-70% toluene. The solid loading included 70-95 wt% lithiated nickel-cobalt-aluminum oxide active material (NCA) coated with lithium zirconium oxide (LZO), 13 wt% LSTPS, and 2 wt% binder. The LSTPS composition was Li a Si b Sn c P d S e wherein a is 5, b is 0.75, c is 0.25, d is 1, and e is 6, further comprising greater than 0 atomic % to 15 atomic % oxygen, and was prepared as described in U.S. Pat. No. 9,172,114, issued October 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0477] [000486] The slurry was cast onto a carbon-coated aluminum foil using a doctor blade. The resulting cast slurry was dried at room temperature to 120°C for 1 to 24 hours to form an anode layer film on the carbon-coated aluminum foil.

[0478] [000487] Step 2(2): A sulfide layer, which would later be placed in contact with the solid anode layer, was prepared. A slurry was prepared using 10 to 70 wt % LSTPS in toluene. The slurry was cast onto Ni foil using a doctor blade casting method. The resulting cast slurry was dried at room temperature to 120°C for 1 to 24 hours to form a buffer layer film. In this example, the buffer layer contained LSTPS with the same chemical composition as that used in the anode layer. Without being bound by theory, it is proposed that this layer was not electrically conductive (having an electronic conductivity of less than 1E-6 S / cm). This buffer layer thereby shielded the cathode (anode) potential from the anode layer.

[0479] [000488] Step 3(3): The two layers of step (1) and step (2) were placed on top of each other such that the sulfide layer and the cathode layer were in direct contact with each other to form a stack (nickel film-buffer layer-anode layer-aluminum film).

[0480] [000489] Step 4(4): The stack from step (3) was placed on an aluminum guide foil. The membrane was passed through a calender at 1.0 meter / min, 140°C, and a fluid pressure of approximately 100-110 bar (10-11 MPa) (applied 1100-1200 N / mm). A Saueressig GK 300 L or Ono Roll Type 12 calender was used. After calendering, the sulfide layer was transferred onto the cathode layer, and both layers were densified together in one step. During calendering, a carbon-coated aluminum foil was also adhered to the aluminum guide foil to form the first current collector on the side of the SSC.

[0481] [000490] The stack from step (4) was assembled into an electrochemical cell containing a garnet separator and a borohydride bonding layer for testing.

[0482] [000491] Step five (5): A lithium-filled garnet layer was fabricated according to the lithium-filled garnet layer or film formation method in U.S. Patent No. 9,806,372 B2, issued October 31, 2017, and entitled "GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS," and U.S. Patent No. 9,970,711, issued May 15, 2018, and entitled "LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION," the entire contents of each of which are incorporated herein by reference in their entirety for all purposes.

[0483] [000492] Step 6(6): A borohydride bonding layer was prepared. The borohydride composition used to form the borohydride bonding layer was described in accordance with International PCT Patent Application No. PCT / US2017 / 057735, filed October 20, 2017, and entitled "ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE"; and International PCT Patent Application No. PCT / US2017 / 057739, filed October 20, 2017, and entitled "BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID-STATE BATTERY." The entire contents of the above patents are incorporated herein by reference in their entirety for all purposes. The composition 3LiBH4·2LiCl·3LiNH2 was melted and spin-coated onto the lithium-filled garnet film prepared in step 5(5).

[0484] [000493] Step 7(7): The lithium-filled garnet film with the LBHIN spin-coated layer was placed on the stack resulting from step 4(4) so ​​that the LBHIN borohydride bonding layer was in direct contact with the buffer layer. The stack was then densified at 140°C by applying a pressure of approximately 1000 pounds per square inch (PSI). The stack was then cooled to room temperature. Figure 3 shows an SEM FIB image of the resulting stack.

[0485] [000494] Step 8(8): To create a lithium metal cathode in the stack resulting from Step 7(7), lithium metal was evaporated onto the lithium-loaded garnet (30 μm of evaporated lithium), and the stack was bonded to a cathode current collector to form an electrochemical cell. In some cells, the cathode current collector was bonded directly onto the lithium-loaded garnet film, and lithium from the anode was deposited between the lithium-loaded garnet film and the cathode current collector.

[0486] Example 5 [000495] LBHI powder was prepared by mixing three (3) molar parts LiBH with one (1) molar part LiI. The mixture was then milled twice (2) in a zirconia container at 300 rpm for eight hours, followed by annealing at 300°C in a closed container and cooling to room temperature to form a mixed and annealed LBHI powder.

[0487] [000496] Garnet thin film (almost Li 7-x La3Zr2O 12 Li-filled garnet (characterized as Al2O3) was prepared as follows. The garnet precursor was a mixture of LiOH, ZrO2, La2O3, and boehmite in a molar ratio of 6–7:1.5:2:0.1–1.5. The mixed precursor was ball milled and calcined at 700–1000°C for 1–10 hours to form a cubic garnet phase with a second phase. The powder was milled in a wet mill with a solvent, surfactant, and dispersant. A binder solution was prepared by dissolving the binder in the same solvent. The binder solution and powder slurry were mixed and tape-cast onto a Mylar substrate using a doctor blade with a gap height of 10–300 μm to form a cast green tape. The green tape was peeled from the substrate, cut to the desired size, and sintered between setters at 800–1200°C for 1–10 hours and then cooled to room temperature to form a sintered garnet thin film.

[0488] [000497] The mixed and annealed LBHI powder (1-4 g) was heated to 300-350°C under argon atmosphere in a boron nitride or alumina crucible placed in a stainless steel heating block equipped with a band heater for approximately 2 hours until the LBHI powder melted. Garnet thin films were dip-coated into the molten LBHI at 300-350°C under argon with a dwell time of 600 seconds. The garnet thin films were then applied by dip coating in 0.05-300 mm increments. -1 The LBHI garnet was then extracted from the melt at a rate of 0.1 s and cooled for 5 seconds to 5 minutes under argon to provide the dip-coated LBHI garnet.

[0489] Example 6 [000498] LBHI was prepared in the same manner as in Example 5 and heated to 300-350°C. A copper current collector thin foil was then dip-coated in the molten LBHI at 300-350°C under argon for a residence time of 600 seconds. Copper was then applied to the molten LBHI in a thickness of 0.05-300 mm. -1 The copper was then pulled out of the molten LBHI at a rate of 0.1 s and allowed to cool for 5 seconds to 5 minutes under argon to provide the dip-coated LBHI copper.

[0490] Example 7 [000499] Dip-coated LBHI-garnet was prepared as in Example 5. ASR and calendar life were tested as follows: Uncoated garnet and dip-coated LBHI-garnet were contacted on both sides with Li electrodes (8 mm contact area) and subjected to 0.5 mAcm2 at 80°C and 300 PSI using 30-second pulses twice daily. 2 Current densities were applied (forward and reverse).

[0491] Example 8 [000500] The separator (uncoated garnet film or LBHI-coated garnet film prepared according to Example 6) was placed in a symmetric electrochemical cell with Li-metal electrodes on both sides of the sample. A hydrostatic pressure of 5000 PSI was applied uniaxially to both sides of the cell under controlled temperature and argon. Then, 2 mA / cm at 80°C was applied. 2 20 planar microns of lithium (approximately 4 mAh / cm 2 ) was passed over an electrode contact area of ​​8 mm. For the surviving samples (those that did not short out), the current was 3 mAh / cm at 80°C. 2 For the surviving samples, the current was then increased to 4 mAh / cm at 80°C. 2 and then increased to 5 mAh / cm at 80°C for the surviving samples. 2 was increased to

[0492] Example 9 [000501] LBHClN was prepared by mixing three (3) molar parts LiBH, three (3) molar parts LiNH with one (1) molar part LiCl. The mixture was then milled twice (2) times in a zirconia container at 300 rpm for eight (8) hours, followed by annealing at 180°C in a closed container for two (2) hours and cooling to form LBHClN powder.

[0493] [000502] A lithium-filled garnet film was prepared as in Example 5, and lithium metal was applied to one side. LBHClN powder was then added dropwise to the other side of the lithium-filled garnet film. The lithium-filled garnet with the LBHClN powder on it was then heated to 80-140°C, where the LBHClN powder melted.

[0494] [000503] Sulfide-containing solid cathode membranes (SSC) were prepared. The SSC contained sulfide catholyte, LSTPS, and cathode active material (NCA) in volume ratios of approximately 1 / 3 and 2 / 3 LSTPS:NCA. Small amounts of carbon and binder, approximately 0-5 wt%, were added to the LSTPS and NCA. These resulting combinations of LSTPS / NCA / carbon / binder were suspended in toluene at a loading mass of 20% powder in toluene. The suspensions were then mixed for 15 and 6 minutes using a Flacktek and a Filmix, respectively. The mixture was then cast onto carbon-coated aluminum foil and dried under an argon atmosphere until the toluene evaporated. The membranes were punched to the desired size. The SSC membranes were densified at 180°C under a pressure of 300,000 PSI.

[0495] [000504] The SSC membrane was then placed on top of the molten LBHClN powder. The SSC membrane was then pressed at 10 to 2000 pounds per square inch (PSI) while cooling to room temperature. The cell was cycled at a C / 10 rate at 45°C.

[0496] Example 10 [000505] LBHXN powders, where X is Cl, Br, or I, or a mixture thereof, were prepared as described above. Spin casting was used to deposit a tie layer of LBHXN thin films onto the lithium-filled garnet. In this procedure, a small amount of LBHXN powder was applied to the center of the lithium-filled garnet on the chuck of a spin coater, which was heated to the LBHXN melting temperature (approximately 100–280°C). Upon reaching the melting temperature, the LBHXN melted. A flat spatula was used to cast the molten LBHXN onto the substrate to coat the surface. While the chuck was still at the temperature required to melt the LBHXN, the spin coater was turned on at speeds of 100 rpm–5000 rpm. After 1–10 min, the spin coater was turned off. After cooling to room temperature, a uniform coating of LBHXN was achieved on the substrate.

[0497] Example 11 [000506] An organic, non-aqueous, aprotic solvent is added to the LSTPS powder mixture to form a slurry at a loading weight of at least about 35%. The slurry is then cast and coated onto a metal foil using a coater. A buffer layer is then placed in contact with the layer of cathode material. This layer is densified at a force of at least about 1000 psi or greater.

[0498] Example 12 [000507] The composition LiNH:LiBH:LiI (3:3:2) was coated onto a solid cathode film by drop casting. Specifically, LBHIN powder was prepared and cast onto the densified solid cathode. An uncoated lithium-loaded film (prepared according to Example 5) was pressed onto the LBHIN layer at 20-2000 PSI and 20-350°C.

[0499] Example 13 [000508] A solid anode layer (cathode layer, SSC) was prepared. A slurry was prepared with a solids loading of 30-80 wt% in 20-70% toluene. The solids loading included 70-95 wt% lithiated nickel-cobalt-aluminum oxide active material (NCA) coated with lithium zirconium oxide (LZO), 13 wt% LSTPS, and 2 wt% binder. The LSTPS composition was Li a Si b Sn c P d S e wherein a is 5, b is 0.75, c is 0.25, d is 1, and e is 6, further comprising greater than 0 atomic % to 15 atomic % oxygen, and was prepared as described in U.S. Pat. No. 9,172,114, issued October 27, 2015, and entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES," the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0500] [000509] A lithium-filled garnet film was prepared as in Example 5, and lithium metal was applied to one side.

[0501] [000510] LPSI was cast onto the side of the lithium-filled garnet film opposite the side with the lithium metal.

[0502] [000511] The thickness of the lithium-filled garnet film was about 100 μm. The thickness of the cathode was about 150 μm. The thickness of the LPSI was about 10 μm.

[0503] [000512] The resulting electrochemical cell was cycled at 300 psi at 45°C at a C / 10 rate. The results are shown in Figure 9.

[0504] [000513] The above embodiments and examples are intended to be illustrative only and not limiting. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific compounds, materials, and procedures. All such equivalents are considered to be within the scope of, and encompassed by, the appended claims.

Claims

1. (a) an anode layer comprising an active material and a sulfide catholyte, the active material being LiNi ｘ Mn ｙ Co ｚ O ２ and LiNi ｘ Al ｙ Co ｚ O ２ wherein, independently in each of the preceding formulas, x+y+z=1; (b) a single-ion conducting solid buffer layer characterized by Li a Si b Sn c P d S e O f, where 2≦a≦8, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦2.5, 4≦e≦12, and 0≦f≦10; (c) A. (LiBH ４ )・B・(LiX)・C・(LiNH ２ wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, and 3≦A≦6, 2≦B≦5, and 0≦C≦9; (d) a lithium-filled garnet layer, wherein the lithium-filled garnet layer comprises 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 wherein 4<A<8.5, 1.5<B<4, 0≦C≦2, 0≦D≦2; 0≦E<3, 10<F<13, and M′ and M″ are each independently selected from Ga, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta, or Li ａ La ｂ Zr ｃ Al ｄ Me'' ｅ O ｆ wherein 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 Ga, Nb, Ta, V, W, Mo and Sb; and a lithium filled garnet layer comprising a lithium filled garnet selected from 1. An all-solid-state electrochemical cell (SSEC) comprising: the buffer layer is a layer in contact with the anode layer, An all-solid-state electrochemical cell (SSEC), wherein the borohydride bonding layer is between and in contact with the lithium-filled garnet layer and the buffer layer, which is in contact with the anode layer.

2. The SSEC of claim 1 , wherein the buffer layer has a thickness of 1 μm to 15 μm.

3. The buffer layer has a D of 10 nm to 1000 nm. ５０ 2. The SSEC of claim 1, comprising particles having:

4. 10. The SSEC of claim 1, wherein the buffer layer has a porosity of less than 20% v / v.

5. The SSEC of claim 1 , wherein the buffer layer comprises no more than 10% by volume of an organic polymer.

6. The lithium-filled garnet is Li ａ La ｂ Zr ｃ Al ｄ Me'' ｅ O ｆ 2. The SSEC of claim 1, wherein 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 Ga, Nb, Ta, V, W, Mo and Sb.

7. The borohydride bonding layer is LiBH ４ :LiI(3:1), LiNH ２ : LiBH ４ :LiI (3:3:2), LiNH ２ : LiBH ４ : LiI (9:3:4), or LiNH ２ : LiBH ４ 2. The SSEC of claim 1, comprising: LiI:LiI (9:3:2).

8. 10. The SSEC of claim 1, wherein the active material is coated or partially coated with a coating selected from the group consisting of lithium niobium oxide, lithium zirconium oxide, lithium aluminum oxide, lithium phosphate, lithium tantalum oxide, lithium hafnium oxide, niobium oxide, zirconium oxide, aluminum oxide, tantalum oxide, and hafnium oxide.

9. 10. The SSEC of claim 1, wherein the active material is coated or partially coated with a coating of lithium zirconium oxide.

10. 2. The SSEC of claim 1, wherein the sulfide catholyte is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, SLOBS, LATS, and LPS+X, where X is selected from the group consisting of Cl, I, Br, and combinations thereof.

11. The sulfide catholyte has the following formula: Li ａ Si ｂ Sn ｃ P ｄ S ｅ wherein 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 2≦e≦12; Li ａ Si ｂ P ｃ S ｄ X ｅ wherein 8<a<12, 1<b<3, 1<c<3, 8<d<14, and 0<e<1, and X is F, Cl, Br, or I; Li ｇ As ｈ Sn ｊ S ｋ O ｌ wherein 2≦g≦6, 0≦h≦1, 0≦j≦1, 2≦k≦6, and 0≦1≦10; or Li ｍ P ｎ S ｐ I ｑ (wherein 2≦m≦6, 0≦n≦1, 0≦p≦1, 2≦q≦6); Li 10:1 to 6:4 ２ S:P ２ S ５ (Li ２ S): (P ２ S ５ ) and LiI, a mixture of [(Li ２ S): (P ２ S ５ ) )]:LiI ratio of 95:5 to 50:50; LPS+X, where X is selected from Cl, I, or Br; vLi ２ S+wP ２ S ５ +yLiX; vLi ２ S+wSiS ２ +yLiX; or vLi ２ S+wB ２ S ３ +yLiX, where X is selected from Cl, I, or Br, and 0≦v≦1; 0≦w≦1; and 0≦y≦1.

2. The SSEC of claim 1, represented by one of:

12. The sulfide catholyte has the following formula: Li ａ Si ｂ Sn ｃ P ｄ S ｅ 12. The SSEC of claim 11, represented by the formula: wherein 2≦a≦8, 0≦b≦1, 0≦c≦1, 0.5≦d≦2.5, and 2≦e≦12.

13. 12. The SSEC of claim 11, wherein the sulfide catholyte comprises LPS+X, where X is selected from Cl, I, or Br.

14. 10. The SSEC of claim 1, wherein the SSEC retains more than 80% of its energy after cycling for 200 cycles.

15. The SSEC measured 54 Ω-cm at 45°C. ２ 10. The SSEC of claim 1 having a low area specific resistance (ASR) of 0.1 to 0.

5.

16. (a) an anode layer comprising an active material and a sulfide catholyte, the active material being LiNi ｘ Mn ｙ Co ｚ O ２ and LiNi ｘ Al ｙ Co ｚ O ２ wherein, independently in each of the preceding formulas, x+y+z=1; (b) a single-ion conducting solid buffer layer characterized by Li a Si b Sn c P d S e O f, where 2≦a≦8, 0≦b≦1, 0≦c≦1, b+c=1, 0.5≦d≦2.5, 4≦e≦12, and 0≦f≦10; A bilayer stack comprising: the buffer layer has a thickness of 1 μm to 15 μm; A bilayer stack wherein the buffer layer is the layer in contact with the anode layer.

17. The buffer layer has a D of 10 nm to 1000 nm. ５０ 17. The bilayer stack of claim 16, comprising particles having:

18. A bilayer stack as described in claim 16, wherein the buffer layer has a porosity of less than 20% v / v.

19. A bilayer stack as described in claim 16, wherein the buffer layer contains an organic polymer at 10% by volume or less.

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