Solid-state batteries

Abstract

This patent discloses a solid-state battery structure including 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.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to provisional patent application number 62 / 681,576, filed June 6, 2018, entitled “HYBRIDSOLID-STATE BATTERY,” the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The present invention relates to solid-state rechargeable batteries, also known as secondary batteries. Background Art

[0004] A battery cell with a solid electrolyte separator between its positive and negative electrodes is called a solid-state battery. Solid-state electrolytes do not contain flammable organic solvents and, considering safety considerations, have promising applications.

[0005] Compared to liquid electrolyte batteries, solid-state batteries can operate in a wider range of temperature, voltage, and pressure. Solid-state batteries can also include solid-state positive and negative electrodes. For example, a solid-state battery can include a lithium metal negative electrode. The lithium metal negative electrode can maximize the voltage difference between the positive and negative electrodes, thereby making Li + Maximizing energy density in batteries. Solid-state rechargeable batteries are expected to be safer (e.g., less flammable) and have higher energy and power densities than currently commercially available liquid electrolyte batteries. However, a series of unresolved difficulties remain, hindering the commercialization of solid-state batteries.

[0006] Some solid-state battery researchers have employed monolithically integrated single-ion conductors as the electrolyte separator between the positive and negative electrodes. This approach presents numerous challenges. For example, to date, no single-ion conducting solid-state electrolyte has both high enough ionic conductivity and mechanical strength, while also being commercially cost-effective, lightweight enough for certain applications, and stable to Li in the 0-5 V voltage range. To date, addressing these challenges in solid-state batteries has inevitably led to design trade-offs.

[0007] Some researchers have attempted to incorporate more than one type of solid electrolyte into solid-state electrochemical cells. For example, some researchers have prepared an oxide-sulfide composite material for a lithium superion conductor. See J. Mater. Chem. A, 2014, 2, 4111-4116, DOI: 10.1039 / C3TA15223E, which proposes an oxide-sulfide composite comprising a mixture of lithium-filled garnet powder and lithium phosphide sulfide (LPS) powder. See also the abstract at http: / / ma.ecsdl.org / content / MA2016-01 / 2 / 264, which describes the effects of an electrochemical cell with a lithium metal anode, a solid oxide electrolyte (LLZO), and a composite cathode composed of a 75Li2S:25P2S5 sulfide electrolyte and TiS2. See also Y.Kato et al., DOI: 10.1038 / NENERGY.2016.30, which reported LiCoO2 cathode active materials with LiNbO3 coating and certain sulfide solid electrolytes (Li 9.6 P3S 12 、Li 10 GeP2S 12 、Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ) electrochemical cycling data of a single electrochemical cell. See also Suzuki et al., Journal of Power Sources 359 (2017) 97-103, which proposed a solid-state battery. The results of these reports have various drawbacks, including low capacity and capacity decay over time.

[0008] Since the above problems and other problems in related fields still have a series of unresolved difficulties, it is necessary to propose corresponding solutions. This patent provides compositions, processes and methods that overcome various difficulties and problems. Summary of the Invention

[0009] In one embodiment, a solid-state electrochemical cell (SSEC) is provided, comprising (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; (b) a solid buffer that conducts a single ion; (c) a borohydride binding layer; and (d) a lithium-filled garnet layer. The buffer is mixed within the positive electrode layer, or as a layer in contact with the positive electrode layer, or the buffer is mixed within the positive electrode layer and as a layer in contact with the positive electrode layer. The borohydride binding layer is between and in contact with the lithium-filled garnet layer and (i) the positive electrode layer in which the buffer is mixed, or (ii) the buffer layer in contact with the positive electrode.

[0010] In a second embodiment, a method for manufacturing an electrochemical cell is provided, the method comprising the following steps: (a) providing a first slurry comprising an active material, a cathode electrolyte and a solvent; (b) depositing the first slurry onto a current collector; (c) drying the first slurry; (e) providing a second slurry comprising a solid buffer that conducts a single ion; (f) depositing the second slurry onto a substrate; (g) drying the deposited second slurry to form a buffer layer; (h) transferring the buffer layer after drying to the first slurry to form a stack; (i) pressurizing and heating the stack; (j) providing a solid separator; (k) depositing a borohydride layer onto the solid separator; (l) combining the stack with the solid separator having the borohydride layer thereon to form an electrochemical cell stack; and (m) pressurizing and heating the electrochemical cell stack.

[0011] In one aspect, a solid-state electrochemical stack is provided, comprising: (a) a positive electrode layer comprising a positive electrode active material, a binder, and a sulfide cathode electrolyte, the positive electrode layer having a porosity of less than 15% v / v; (b) a buffer layer comprising a sulfide electrolyte in contact with the positive electrode layer, the buffer layer having a porosity of less than 15% v / v; (c) a separator layer comprising a material selected from the group consisting of lithium-filled garnet and LPSX, the separator layer having a porosity of less than 10% v / v; and the buffer layer being between the positive electrode layer and the separator layer.

[0012] On the other hand, a method for manufacturing a solid-state electrochemical stack is provided, comprising: (a) pouring a first slurry containing a sulfide solid electrolyte powder onto a first substrate to form a first layer; (b) pouring a second slurry containing a sulfide solid electrolyte powder and a positive electrode active powder onto a second substrate to form a second layer; (c) calendering the first layer and the second layer, wherein the first layer and the second layer are in direct contact with each other. On the other hand, the present patent provides a double-layer stack, comprising: (a) a positive electrode layer containing an active material and a sulfide cathode electrolyte; and (b) a solid buffer that conducts a single ion, wherein the buffer is mixed in the positive electrode layer, or is a layer in contact with the positive electrode layer, or is mixed in the positive electrode layer and in contact with the positive electrode layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 Schematic diagram of an electrochemical cell.

[0014] Figure 2 A cross-sectional scanning electron microscope image (cross-section generated by a focused ion beam) of a solid-state cathode (SSC), a buffer layer, an adhesive layer, and a garnet film in the electrochemical cell fabricated in Example 1 is shown. Figure 2The scale bar in the figure is 50 μm. Imaging conditions were: working distance 4.4 mm, high voltage 5.00 kV, high frequency resistance welded pipe (HFW) 207 μm, magnification 2000x, function TLD, tilt 52°, BSE mode.

[0015] Figure 3 This is a graph showing the change in voltage versus active mass specific capacity (mAh / g) over 50 cycles as described in Example 2.

[0016] Figure 4 This is a graph showing the change in active mass specific discharge capacity (mAh / g) as a function of cycle number described in Example 2.

[0017] Figure 5 3 is a graph showing the relationship between the ASR and the static voltage described in Example 2.

[0018] Figure 6 Schematic diagram of an electrochemical cell including a separator, a buffer layer, and a positive electrode layer.

[0019] Figure 7 is a schematic diagram of an electrochemical cell including a separator, an adhesive layer, and a positive electrode layer.

[0020] Figure 8 The lithium ion conductivity (Log (S / cm)) of a series of LBHI compositions and LBHI compositions doped with amide at 60° C. As shown, (A) is LiBH4:LiI (3:1), (B) is LiNH2:LiBH4:LiI (3:3:2), (C) is LiNH2:LiBH4:LiI (9:3:4), and (D) is LiNH2:LiBH4:LiI (9:3:2).

[0021] Figure 9 Cycling data is shown for a solid-state electrochemical cell in Example 13 comprising a lithium-filled garnet electrolyte membrane bonded to a solid-state cathode membrane with LPSI.

[0022] Detailed description

[0023] General Notes

[0024] In some examples, the patent describes a device that exhibits less than 50 Ω-cm at room temperature. 2An electrochemical cell of an ASR. The electrochemical cell disclosed in this patent includes an oxide electrolyte membrane and a sulfide electrolyte membrane. The electrochemical cell described in this patent includes a sulfide-oxide solid electrolyte interface. An adhesive layer comprising borohydride is used to bond the oxide electrolyte membrane and the sulfide electrolyte membrane. The oxide electrolyte membrane is kinetically stable to metallic Li and has suitable mechanical strength to conduct Li ions at a high current density. The sulfide cathode electrolyte in the solid cathode and / or the sulfide buffer layer adjacent to the solid cathode provides a conductive path for lithium ions and is suitable for use when the positive electrode is loaded with a highly active substance. In some embodiments, the sulfide cathode electrolyte is kinetically stable to the coated active material (e.g., LZO-coated NCA or LZO-coated NMC). In some instances, the sulfide cathode electrolyte is kinetically stable to the coated active material (e.g., LZO-coated NCA) at a voltage window of 2.7-4.2V relative to Li. The borohydride bonding layer bonds the oxide electrolyte membrane and the sulfide (buffer) electrolyte membrane and provides an ion-conducting path between the two electrolyte membranes.

[0025] In some embodiments, the electrochemical cell disclosed in this patent includes an oxide solid separator in contact with the negative electrode side of the electrochemical cell and a sulfide solid separator in contact with the positive electrode side of the electrochemical cell. In some embodiments, both the sulfide and oxide solid separators have high lithium ion conductivity, for example, greater than 1*10 -3 S / cm 2 In some embodiments, a borohydride bonding layer is provided between the oxide solid-state separator and the sulfide solid-state separator. In some embodiments, a lithium metal negative electrode is provided on the side of the oxide solid-state separator opposite the borohydride bonding layer. In some embodiments, a positive electrode is provided on the side of the sulfide solid-state separator opposite the borohydride bonding layer.

[0026] definition

[0027] If there is a conflict in a definition in any material incorporated by reference into this patent and a definition in this patent, the definition in this patent shall control.

[0028] As used herein, the term "about" when used to qualify a number, such as about 15% w / w, refers to the stated value and optionally includes values ​​within a range of ±10% of the stated value. For example, about 15% w / w includes 15% w / w and 13.5% w / w, 14% w / w, 14.5% w / w, 15.5% w / w, 16% w / w, or 16.5% w / w. For example, "about 75°C" includes 75°C and 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.

[0029] As used herein, the term "active material" refers to a material that intercalates or converts to lithium in a reversible reaction, making the active material suitable for use in rechargeable batteries. Active materials may include intercalating materials, such as NCA or NMC. Active materials may include, for example, chemical materials that convert to FeF3. For example, active materials may include, but are not limited to, all active materials described in U.S. Patent No. US20160211517A1, entitled "LITHIUM RICH NICKEL MANGANESE COBALT OXIDE," published on July 21, 2016.

[0030] The term "amorphous" as used in this patent refers to a material that is non-crystalline or does not contain a crystalline phase as the main phase. "Amorphous" refers to a material that does not exhibit crystalline characteristics, for example, clear X-ray diffraction peaks measured by X-ray diffraction. Amorphous materials are at least mainly amorphous and are characterized by having more amorphous components than crystalline components. Substantially amorphous refers to a material that does not include clear X-ray diffraction peaks or an X-ray diffraction pattern characterized by broad reflections, which are interpreted by those skilled in the art as a material whose main component is an amorphous phase. In fact, an amorphous material can have nanoscale crystalline domains, but is still characterized by an X-ray diffraction image as being mainly an amorphous phase. In an amorphous material, some transmission electron microscopy (TEM) area diffraction patterns (SADPs) can show crystalline domains, but the main component of the material is still shown as an amorphous body.

[0031] The terms "semi-amorphous" or "semi-crystalline" as used in this patent refer to compositions having both crystalline and amorphous domains. In addition to an amorphous component, a semi-crystalline material also includes a nanocrystalline and / or microcrystalline component. A semi-crystalline material is a partially crystalline material, or a material that includes some crystalline blocks and some amorphous blocks. For example, a material that is heated to a crystallization temperature but then cooled before all of the material is completely crystallized is a semi-crystalline material as described in this patent. An XRD powder pattern can characterize a semi-crystalline material as described in this patent, wherein the main peak of highest intensity has a full width at half maximum at at least 1° (2θ) or at least 2° (2θ), or at least 3° (2θ).

[0032] The term "anolyte" as used in this patent refers to an ionically conductive material that is mixed, layered, or laminated to the anode material or anode current collector.

[0033] The term "applying pressure" as used in this patent refers to the process by which an external device, such as a calender, applies pressure to another material.

[0034] The term "at least one selected from the group" as used in this patent includes selecting one or more items or combinations thereof from the group. Selected from the group consisting of A, B, and C includes, for example, only A, only B, or only C, as well as any combination of A and B, A and C, B and C, and A, B, C, or A, B, and C.

[0035] The term "ASR" as used in this patent refers to area specific resistance. ASR is measured using electrochemical impedance spectroscopy (EIS). EIS can be measured on a VMP3 instrument produced by Biologic or its equivalent. In the ASR measurement, lithium contacts are deposited on both sides of the sample. While measuring the current, an AC voltage of 25mV rms is applied at a frequency of 300kHz-0.1mHz. EIS separates the ASR into bulk contribution and boundary ASR contribution by analyzing the two semicircular patterns in the Nyquist plot.

[0036] The term "borohydride bonding layer" as used in this patent refers to a layer comprising borohydride, and the layer bonds the lithium-filled garnet layer to the sulfide electrolyte layer or the sulfide containing the buffer. Non-limiting examples of borohydrides include, but are not limited to, 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2. Boron hydrides are described in the patent application entitled "ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE", International PCT Patent Application No. PCT / US2017 / 057735, published on April 26, 2018, and published as WO2018 / 075972, the entire contents of which are incorporated herein by reference in their entirety for all purposes. Boron hydrides are mentioned in the patent application entitled “BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID STATE BATTERY”, International PCT Patent Application No. PCT / US2017 / 057739, filed on October 20, 2017, published on April 25, 2019, and published as WO2019078897A1, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0037] The term "binder" as used herein refers to a polymer having the ability to increase the adhesion and / or cohesion of an electrode. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene α-olefin copolymers.

[0038] The term "buffer" as used in this patent refers to a solid electrolyte that conducts a single ion and is thoroughly mixed within or combined with the positive electrode portion, or is a layer in direct contact with the positive electrode, for example, the solid electrolyte is an electrolyte layer laminated on the positive electrode layer. Conducting a single ion means that the material conducts only one type of ion, such as Li ions with a transference number greater than 0.9. Solid means that the buffer exists in a solid phase at ambient temperature and pressure.

[0039] The term "buffering agent mixed in the positive electrode layer" used in this patent means that the buffering material is ground, for example, milled, and then mixed with other positive electrode layer compounds such as active materials and conductive carbon when forming the positive electrode layer.

[0040] As used herein, the term "cast film" refers to the process of transferring a liquid or slurry into a mold or onto a substrate so that the liquid or slurry forms or becomes a thin film. Casting can be performed by doctor blade, metering rod, comma coater, gravure coater, micro gravure coating, reverse comma coater, coating die, slip mold, and / or tape casting, among other methods.

[0041] The term "characterized by a formula" as used in this patent refers to a description of the chemical composition of a compound.

[0042] The term "current collector" used in this patent refers to a component or layer in a secondary battery that is in direct contact with an electrode, through which electrons are conducted to or from the electrode to complete an external circuit. In some instances, the current collector is a metal (e.g., Al, Cu, or Ni, steel, and an alloy or combination thereof) layer laminated to the positive or negative electrode. In some instances, the current collector is Al. In some instances, the current collector is Cu. In some instances, the current collector is Ni. In some instances, the current collector is steel. In some instances, the current collector is an alloy of Al. In some instances, the current collector is an alloy of Cu. In some instances, the current collector is an alloy of steel. In some instances, the current collector is Al. In some instances, the current collector is coated with carbon. In some instances, the current collector includes a combination of the above metals. During charge and discharge, electrons are conducted in the direction opposite to the Li ion flow and pass through the current collector when entering or leaving the electrode.

[0043] The term "diameter (d 90 )” refers to the size distribution as measured by microscopy or other particle size analysis techniques, including but not limited to scanning electron microscopy or dynamic light scattering.90 Including a characteristic dimension, i.e., the particle size, means the total particle area (e.g., for 2D sampling methods such as microscopy) or volume (e.g., for 3D sampling methods such as light scattering) representing 90% of the particles is smaller than the stated dimension. In other words, in a particle mixture, d 90 Indicates that 90% of the particles in the mixture are smaller than the stated size. Similarly, the term "diameter (d 50 )” means the size that represents 50% of the total particle area (or volume) of the particles that is smaller than the stated size. Similarly, the term “diameter (d 10 )" means that 10% of the total particle area (or volume) of the particles is smaller than the stated size. These figures can be calculated per unit volume or per unit area. If not explicitly stated, the unit volume shall be the standard.

[0044] The term "adhesive" used in this patent refers to a material that helps to adhere to another material. For example, as used in this patent, polyvinyl butyral is an adhesive because it can be used to bond garnet materials. Other adhesives may include polycarbonate. Other adhesives may include polyacrylates and polymethacrylates. These examples of adhesives are not limited to the scope of the adhesive described in this patent and are only used as examples. Adhesives that can be used for 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-1-octene (PE-co-PO), polyethylene-co-(methylene cyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylic acid), acrylic acid, polyvinyl acetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, three-dimensional block polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, etc. In some examples, including any of the foregoing, the binder is selected from polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (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

[0014] The present invention also includes but is not limited to the following: polyimide, polyimide-1, polyimide-2, polyimide-3, polyimide-4, polyimide-5, polyimide-6, polyimide-7, polyimide-8, polyimide-9, polyimide-10, polyimide-11, polyimide-12, polyimide-13, polyimide-14, polyimide-15, polyimide-16, polyimide-17, polyimide-18, polyimide-19, polyimide-20, polyimide-21, polyimide-22, polyimide-23, polyimide-24, polyimide-25, polyimide-27, polyimide-28, polyimide-29, polyimide-30, polyimide-31, polyimide-32, polyimide-33, polyimide-34, polyimide-35, polyimide-36, polyimide-37, polyimide-38, polyimide-39, polyimide-40, polyimide-41, polyimide-42, polyimide-43, polyimide-44, polyimide-45, polyimide-46, polyimide-47, polyimide-48, polyimide-49, polyimide-50, polyimide-51, polyimide-52, polyimide-53, polyimide-54, polyimide-55, polyimide-56, polyimide-57, polyimide-58, polyimide-59, polyimide-60, polyimide-61, polyimide-62

[0045] Unless otherwise specified, the term "in contact" as used herein refers to direct contact. For conductive materials, contact means sufficient contact between the materials to allow electrical conduction. For ionically conductive materials, contact means sufficient contact between the materials to allow ion conduction. Direct contact between two materials means that there are no intervening layers between the two materials. The term "electrical contact" as used herein refers to sufficient contact between the materials to allow electrical conduction.

[0046] The term "direct contact" as used in this patent, for conductive materials or ion conductive materials, means that the physical contact between the two materials is sufficient to allow electronic or ionic current to be conducted between them; for materials where one of the materials is electrically insulating or ion insulating, direct contact between the two materials means that the two materials share an interface that can transmit external force or pressure.

[0047] The term "electrical contact" as used in this patent refers to two materials that are in direct contact and can conduct current through the direct contact point.

[0048] The terms "cathode" and "anode" used in this patent refer to the electrodes of a battery. During the charge cycle of a lithium secondary battery, lithium ions leave the cathode and move through the electrolyte to the anode. During the charge cycle, electrons leave the cathode and move through an external circuit to the anode. During the discharge cycle of a lithium secondary battery, lithium ions migrate from the anode to the cathode through the electrolyte. During the discharge cycle, electrons leave the anode and move through an external circuit to the cathode.

[0049] As used herein, the term "green film" or "green tape" refers to an unsintered tape or film comprising a lithium-filled garnet or a precursor of a lithium-filled garnet and at least one binder, plasticizer, carbon, dispersant, solvent, or a combination thereof. As used herein, "green film tape" refers to a cast roll, continuous layer, or cut portion of a dried or non-dried green film.

[0050] As used herein, the term "electrochemical cell" or "cell" refers to a single battery comprising a positive electrode and a negative electrode, ionically connected via an electrolyte. In some embodiments, the same cell comprises multiple positive electrodes and / or multiple negative electrodes enclosed in a single container.

[0051] The term "electrochemical device" as used in this patent refers to an energy storage device, such as but not limited to a lithium secondary battery that operates or generates electricity or current through an electrochemical reaction, for example, 3Li+FeF3 3LiF+Fe conversion chemical reaction.

[0052] The term "electrolyte" used in this patent refers to the electrolyte that allows ions (such as Li +) in it but does not allow electrons to conduct through it. The ionic conductivity is at least 1000 times greater than the electronic conductivity. The electrolyte can be used to electrically insulate between the cathode and anode of a secondary battery, but allows ions (such as Li + ) through the electrolyte. In some instances, solid electrolytes rely on ion hopping and / or diffusion through a rigid structure. Solid electrolytes may also be referred to as fast ion conductors or superionic conductors. In this case, the solid electrolyte layer may also be referred to as a solid electrolyte membrane or solid electrolyte membrane.

[0053] The term "energy storage electrode" as used in this patent refers to an electrode suitable for use in an energy storage device such as a lithium rechargeable battery or a lithium secondary battery. Such an electrode can conduct electrons and lithium ions required for charging and discharging a rechargeable battery.

[0054] As used herein, the term "film thickness" refers to the distance between the top and bottom surfaces of a film, or the median measured distance. The term "thickness," as used herein, refers to the distance between the top and bottom surfaces of each layer, or the median measured distance. As used herein, top and bottom refer to the sides of the film with the largest surface area. Unless otherwise specified, scanning electron microscopy was used to measure thickness.

[0055] The term "flat" as used in this patent refers to the maximum normal distance between the lowest point on a surface and a plane containing the three highest points on the surface, or the maximum normal distance between the highest point on a surface and a plane containing the three lowest points on the surface. This can be measured using an atomic force microscope (AFM), a high-precision optical microscope, or laser interferometry to measure the surface height map.

[0056] As used herein, the term "film" refers to a film containing the components, components, or materials described herein, having an average thickness of about 10 nm to about 100 μm. In some embodiments, "film" refers to a film having a thickness of less than about 1 μm, 10 μm, or 50 μm.

[0057] The "lithium interface resistance" used here refers to the interface resistance of the material to the incorporation of Li ions. The lithium interface ASR (ASR) is calculated from the interface resistance (Rinterface) by the following formula: interface ), ASR interface =R interface *A / 2, where A represents the contact area between the electrode and the separator, the coefficient 2 represents the two interfaces (in a symmetrical single cell), and R interface =R total -R bulk , where R total is the total impedance, R bulk is the volume impedance.

[0058] As used in this patent, the term "lithium-filled garnet" refers to an oxide having crystal structure characteristics related to the garnet crystal structure. The entire content of the U.S. patent application with a filing date of October 7, 2014, a publication date of April 9, 2015, a patent application publication number of 2015 / 0099190, and a patent application number of 14 / 509,029 is incorporated herein by reference. This application describes lithium-filled garnet solid electrolytes for solid-state lithium rechargeable batteries. These lithium-filled garnets generally contain the components represented by the following formula: Li A La B M′ C M″ D Zr E O F 、Li A La B M′ C M″ D Ta E O F 或Li A La B M′ C M″ D Nb E O F , where 4 < A < 8.5, 1.5 < B < 4, 0 ≤ C ≤ 2, 0 ≤ D ≤ 2, 0 ≤ E < 2.5, 10 < F < 13, and M′ and M″ are each independently selected from Ga, Al, Mo, W, Nb, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta in each case; or Li a La b Zr c Al d Me” e O f , where 5 < a < 8.5, 2 < b < 4, 0 < c ≤ 2.5, 0 ≤ d < 2, 0 ≤ e < 2, 10 < f < 13, and Me” is a metal selected from Ga, Nb, Ta, V, W, Mo, and Sb; and other components as described in the patent with a U.S. patent application publication number of US 2015 / 0099190. The lithium-filled garnets and garnets described in this patent generally include, but are not limited to, Li 7.0 La3(Zr t1 +Nb t2 +Ta t3 )O 12+0.35Al2O3; wherein δ represents 0-3 and (t1+t2+t3=2), so 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 lithium-filled garnet contains Li 7±δ Li3Zr2O 12 In another embodiment, the lithium-filled garnet contains Li 7±δ Li3Zr2O 12 0.22Al2O3 composition. In other embodiments, the lithium-filled garnet contains Li 7±δ Li3Zr2O 12 0.35Al2O3 composition. In one embodiment, the lithium-filled garnet contains Li 7±δ Li3Zr2O 12 0.5Al2O3 composition. In another embodiment, the lithium-filled garnet contains Li 7±δ Li3Zr2O 12 ·0.75Al2O3 composition. Similarly, the garnet described in this patent includes but is 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 examples, the subscripts x, y, and F are selected so that the garnet is charge neutral. In some examples, x is 7 and y is 1.0. In some examples, x is 5 and y is 1.0. In some examples, x is 6 and y is 1.0. In some examples, x is 8 and y is 1.0. In some examples, x is 9 and y is 1.0. In some examples, x is 7 and y is 0.35. In some examples, x is 5 and y is 0.35. In some examples, x is 6 and y is 0.35. In some examples, x is 8 and y is 0.35. In some examples, x is 9 and y is 0.35. In some examples, x is 7 and y is 0.7. In some examples, x is 5 and y is 0.7. In some instances, x is 6 and y is 0.7. In some instances, x is 8 and y is 0.7. In some instances, x is 9 and y is 0.7. In some instances, x is 7 and y is 0.75. In some instances, x is 5 and y is 0.75. In some instances, x is 6 and y is 0.75. In some instances, x is 8 and y is 0.75. In some instances, x is 9 and y is 0.75. In some instances, x is 7 and y is 0.8. In some instances, x is 5 and y is 0.8. In some instances, x is 6 and y is 0.8. In some instances, x is 8 and y is 0.8. In some instances, x is 9 and y is 0.8. In some instances, x is 7 and y is 0.5. In some instances, x is 5 and y is 0.5. In some instances, x is 6 and y is 0.5. In some instances, x is 8 and y is 0.5. In some instances, x is 9 and y is 0.5. In some instances, x is 7 and y is 0.4. In some instances, x is 5 and y is 0.4. In some instances, x is 6 and y is 0.4. In some instances, x is 8 and y is 0.4. In some instances, x is 9 and y is 0.4. In some instances, x is 7 and y is 0.3. In some instances, x is 5 and y is 0.3. In some instances, x is 6 and y is 0.3. In some instances, x is 8 and y is 0.3. In some instances, x is 9 and y is 0.3. In some instances, x is 7 and y is 0.22. In some instances, x is 5 and y is 0.22. In some instances, x is 6 and y is 0.22. In some instances, x is 8 and y is 0.22. In some examples, x is 9 and y is 0.22. The lithium-filled garnets described in this patent also include but are not limited to Li x La3Zr2O 12 +yAl2O3, wherein y ranges from 0 to 1, including 0 and 1. In one embodiment, the lithium-filled garnet contains Li7Li3Zr2O 12 ingredients.

[0059] The garnet described in this patent does not include YAG garnet (i.e. yttrium aluminum garnet, or Y3Al5O 12 The garnet used in this patent does not include silicate-based garnets, such as pyrope, almandine, spessartine, grossular, cinnamonite or cinnabarite, tsavorite, grossular, andradite, pyrope-almandine-sponsartine solid solution, and grossular-grossular-andradite solid solution. The garnet used in this patent does not include island silicates of the general formula X3Y2(SiO4)3, wherein X is Ca, Mg, Fe and / or Mn; and Y is Al, Fe or Cr.

[0060] As used herein, the terms "garnet chemical precursor," "garnet-type electrolyte chemical precursor," "garnet precursor," and "garnet precursor material" refer to chemical substances capable of reacting to form lithium-filled garnet materials. Chemical precursors described herein include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., Li2O), lithium carbonate (e.g., LiCO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), lanthanum hydroxide (e.g., La(OH)3), aluminum oxide (e.g., Al2O3), aluminum hydroxide (e.g., Al(OH)3), AlOOH, aluminum (e.g., Al), boehmite, magnesite, corundum, aluminum nitrate (e.g., Al(NO3)3), aluminum nitrate nonahydrate, niobium oxide (e.g., Nb2O5), gallium oxide (Ga2O3), and tantalum oxide (e.g., Ta2O5). Other garnet precursors may be prepared using the methods described herein.

[0061] The term "garnet-type electrolyte," as used in this patent, refers to an electrolyte containing the lithium-filled garnet material described in this patent as a lithium-ion conductor. Solid-state, lithium-filled garnet electrolytes offer numerous advantages and can replace the liquid, flammable electrolytes commonly used in lithium-ion rechargeable batteries.

[0062] The term "LIRAP" as used in this patent refers to a lithium-rich antiperovskite, synonymous with "LOC" or "Li3OCl." The composition of LIRAP is aLi2O+bLiX+cLiOH+dAl2O3, where X = Cl, Br, and / or I, a / b = 7-9, c / a = 0.01-1, and d / a = 0.001-0.1.

[0063] The term "LXPS" or "LPS+X" used in this patent refers to a lithium-conducting electrolyte comprising Li, P, S, and X, wherein X = Cl, Br, and / or I. For example, "LSPI" refers to a lithium-conducting electrolyte comprising Li, P, S, and I. In general, it should be understood to include aLi2S+bP2S y+cLiX, where X = Cl, Br, and / or I, and y = 3 - 5 and where a / b = 2.5 - 4.5, where (a + b) / c = 0.5 - 15.

[0064] As used in this patent, the term "LBHPS" refers to a lithium-conducting electrolyte having Li, B, H, P, and S, such as A(LiBH4)(1 - A)(P2S5), where 0.05 ≤ A ≤ 0.95.

[0065] As used in this patent, the term "LSS" refers to a lithium-silicon sulfide that can be described as Li2S - SiS2, Li - SiS2, Li - S - Si and / or a cathode electrolyte mainly composed of Li, S, and Si. LSS refers to an electrolyte material represented by 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 may contain up to 10 at% oxygen. LSS also refers to an electrolyte material containing Li, Si, and S. In some examples, LSS is a mixture of Li2S and SiS2. In some examples, the molar ratio of Li2 S :SiS2 is 90:10, 85:15, 80:20, 75:25, 70:30, 2:1, 65:35, 60:4, 55:45, or 50:50. LSS can be doped with, for example, Li x PO y , LixBO y , Li4SiO4, Li3MO4, Li3MO3, PS x (where 0 < x ≤ 5 and 0 < y ≤ 5) and / or lithium halides such as, but not limited to, for example, LiI, LiC, LiF, or LiBr.

[0066] Unless otherwise specified, the "SLOPS" described in this patent contains Li2S:SiS2 in a molar ratio of 60:40 and 0.1 - 10 mol% of Li3PO4. In some examples, "SLOPS" contains Li 10 Si4S 13 (50:50 Li2S:SiS2) and 0.1 - 10 mol% Li3PO4. In some examples, "SLOPS" contains Li 26 Si7S 27 (65:35 Li2S:SiS2) and 0.1 - 10 mol% Li3PO, In some examples, "SLOPS" contains Li4SiS4 (67:33 Li2S:SiS2) and 0.1 - 5 mol% Li3PO4. In some examples, "SLOPS" contains Li 14 Si3S13 (70:30Li2S:SiS2) and 0.1-5mol% Li3PO4. In some examples, "SLOPS" is represented by the formula (1-x)(60:40Li2S:SiS2)*(x)(Li3PO4), where x is 0.01 to 0.99. The "LBS-POX" described in this patent refers to an electrolyte with a composition of Li2S:B2S3:Li3PO4:LiX, where X is a halogen ((X=F, Cl, Br, I). The composition may include Li3BS3 or Li5B7S doped with 0-30% lithium halide 13 , for example, the lithium halide is LiI and / or 0-10% Li3PO4.

[0067] The term "LSTPS" as used in this patent refers to an electrolyte material having the chemical composition of Li, Si, P, Sn, and S. As used in this patent, "LSPSO" refers to an LSPS doped with or having O. In some embodiments, "LSPSO" is an LSPS material with an oxygen content between 0.01 and 10 at%. "LATP" as used in this patent refers to an electrolyte material having the chemical composition of Li, As, Sn, and P. "LAGP" as used in this patent refers to an electrolyte material having the chemical composition of Li, As, Ge, and P. "LXPSO" as used in this patent refers to an electrolyte material having the formula Li a MP b S c O d The cathode electrolyte material represented by wherein M represents Si, Ge, Sn and / or Al, wherein 2≤a≤8, 0.5≤b≤2.5, 4≤c≤12, d<3. LXPSO refers to LXPS as defined above and doped with 0.1 to about 10 at% oxygen. LPSO refers to LPS as defined above and doped with 0.1 to about 10 at% oxygen. In some examples, "SLOPS" contains Li 10 Si4S 13 (50:50Li2S:SiS2) and 0.1-10mol%Li3PO4. In some examples, "SLOPS" contains Li 26 Si7S 27 (65:35Li2S:SiS2) and 0.1-10mol.% Li3PO4. In some examples, "SLOPS" contains Li4SiS4 (67:33Li2S:SiS2) and 0.1-5mol% Li3PO4. In some examples, "SLOPS" contains Li 14 Si3S 13(70:30Li2S:SiS2) and 0.1-5mol% Li3PO4. In some examples, "SLOPS" is represented by the formula (1-x)(60:40Li2S:SiS2)*(x)(Li3PO4), where x is 0.01 to 0.99. The "LBS-POX" described in this patent refers to an electrolyte with a composition of Li2S:B2S3:Li3PO4:LiX, where X is a halogen ((X=F, Cl, Br, I). The composition may include Li3BS3 or Li5B7S doped with 0-30% lithium halide 13 , for example, the lithium halide is LiI and / or 0-10% Li3PO4.

[0068] As used herein, the term "LPSC1" refers to an electrolyte material having a chemical composition of LiPS and Cl. As used herein, the term "LPSBr" refers to an electrolyte material having a chemical composition of LiPS and Br. As used herein, the term "LPSI" refers to an electrolyte material having a chemical composition of LiPS and I. LXPSO refers to LXPS as defined above, doped with 0.1 at% to about 10 at% oxygen. LPSO refers to LPS as defined above, doped with 0.1 at% to about 10 at% oxygen.

[0069] The term "LAPS" as used in this patent refers to an electrolyte material having a chemical composition of Li, As, P, and S. "LPSCl" refers to an electrolyte material having a chemical composition of Li, P, S, and Cl. The term "LTPS" as used in this patent refers to an electrolyte material having a chemical composition of Li, P, Sn, and S. The term "LSPS" as used in this patent refers to an electrolyte material having a chemical composition of Li, P, Si, and S. The term "LGPS" as used in this patent refers to an electrolyte material having a chemical composition of Li, P, Ge, and S. The term "LPS" as used in this patent refers to an electrolyte material having a chemical composition of Li, P, and S. The term "LSTPSCl" as used in this patent refers to an electrolyte material having a chemical composition of Li, Si, P, Sn, S, and Cl. The term "LSPSCl" as used in this patent refers to an electrolyte material having a chemical composition of Li, Si, P, S, and Cl. The term "LSPSBr" as used in this patent refers to an electrolyte material having a chemical composition of Li, Si, P, S, and Br. The term "LTS" used in this patent refers to lithium tin sulfide compounds, which can be described as Li2S:SnS2:As2S5, Li2S-SnS2, Li2S-SnS, Li-S-Sn and / or cathode electrolytes mainly composed of Li, S and Sn. Its composition can be Li x Sn y S z, where 0.25 ≤ x ≤ 0.65, 0.05 ≤ y ≤ 0.2, and 0.25 ≤ z ≤ 0.65. In some examples, the LTS is a mixture of Li2S and SnS2 in a molar ratio of 80:20, 75:25, 70:30, 2:1, or 1:1. The LTS may contain up to 10 at% oxygen. The LTS may be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and / or indium and / or lithium halides, such as, but not limited to, LiI, LiCl, LiF, or LiBr.

[0070] The term "LATS" used in this patent refers to LTS further comprising arsenic: As2S5, Li2S-SnS2, Li2S-SnS, Li-S-Sn and / or cathode electrolytes consisting mainly of Li, S and Sn. Its composition can be Li x Sn y S z , where 0.25 ≤ x ≤ 0.65, 0.05 ≤ y ≤ 0.2, and 0.25 ≤ z ≤ 0.65. In some examples, the LTS is a mixture of Li2S and SnS2 in a molar ratio of 80:20, 75:25, 70:30, 2:1, or 1:1. The LTS may contain up to 10 at% oxygen. The LTS may be doped with Bi, Sb, As, P, B, Al, Ge, Ga, and / or indium and / or lithium halides, such as, but not limited to, LiI, LiCl, LiF, or LiBr.

[0071] The term "LBHI" or "LiBHI" as used herein refers to a lithium-conducting electrolyte comprising Li, B, H, and I. Typically, it is understood to comprise aLiBH4+bLiX, where X = Cl, Br, and / or I, and where a:b = 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or within the range of a / b = 2-4. LBHI may also contain nitrogen in the form of aLiBH4+bLiX+cLiNH2, where (a+c) / b = 2-4 and c / a = 0-10.

[0072] The term "LBHXN" as used in this patent refers to a compound characterized by A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is fluorine (F), bromine (Br), chlorine (Cl), iodine (I), or a combination thereof, wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9. The term "LBHFN" as used in this patent refers to a compound characterized by A·(LiBH4)·B·(LiF)·C·(LiNH2), wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9. The term "LBHBrN" as used in this patent refers to a compound characterized by A·(LiBH4)·B·(LiBr)·C·(LiNH2), wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9. The term "LBHClN" as used in this patent refers to a compound characterized as A·(LiBH4)·B·(LiCl)·C·(LiNH2), where 3≤A≤6, 2≤B≤5, and 0≤C≤9. The term "LBHIN" as used in this patent refers to a compound characterized as A·(LiBH4)·B·(LiI)·C·(LiNH2), where 3≤A≤6, 2≤B≤5, and 0≤C≤9.

[0073] Unless otherwise specified, the "SLOBS" described in this patent contains Li2S:SiS2 with a molar ratio of 60:40 and 0.1-10 mol% LiBH4. In some examples, the "SLOBS" contains Li 10 Si4S 13 (50:50Li2S:SiS2) and 0.1-10mol% LiBH4. In some examples, "SLOBS" contain Li 26 Si7S 27 (65:35Li2S:SiS2) and 0.1-10mol.%LiBH4. In some examples, "SLOBS" contains Li4SiS4 (67:33Li2S:SiS2) and 0.1-5mol%LiBH4. In some examples, "SLOBS" contains Li 14 Si3S 13 (70:30Li2S:SiS2) and 0.1-5mol% LiBH4. In some examples, "SLOBS" is represented by the formula (1-x)(60:40Li2S:SiS2)*(x)(Li3BO4), where x is 0.01 to 0.99. The "LBS-BOX" described in this patent refers to an electrolyte with a composition of Li2S:B2S3:LiBH4:LiX, where X is a halogen ((X=F, Cl, Br, I). The composition may include Li3BS3 or Li5B7S doped with 0-30% lithium halide such as LiI and / or 0-10% LiPO4. 13 .

[0074] As used herein, the term "made of the same type of material" refers to two or more different physical forms of a material, but containing the same composition. For example, lithium-filled garnet powder and lithium-filled garnet film are made of the same type of material. For example, LSTPS powder and LSTPS film are made of the same type of material.

[0075] As used herein, the term "manufacturing" refers to the process or method of forming or causing to be formed the object being manufactured. For example, manufacturing an energy storage electrode includes a process, process operation, process step, or method of forming or causing to be formed an electrode of an energy storage device. The end result of the operations of manufacturing an energy storage electrode is the production of a material that functions as an electrode.

[0076] The term "positive electrode" as used in this patent refers to an electrode in a secondary battery that releases positive ions such as Li during battery discharge. + The term "negative electrode" as used in this patent refers to an electrode in a secondary battery where positive ions such as Li + Flow out of or leave the electrode. In a cathode active material composed of a lithium metal electrode and a conversion chemistry, an intercalation chemistry, or a combination of conversion / intercalation chemistry (i.e., a cathode active material; e.g., NiF x 、NCA、LiNi x Mn y Co z O2[NMC] or LiNi x Al y Co z In a battery composed of electrodes (electrodes such as NiF[NCA], where x+y+z=1), the electrode with conversion chemistry, intercalation chemistry, or combined conversion / intercalation chemistry is called the positive electrode. In some common practices, the cathode replaces the positive electrode and the anode replaces the negative electrode. When charging a lithium secondary battery, lithium ions are transferred from the positive electrode (e.g. NiF) to the negative electrode. x When a lithium secondary battery is discharged, lithium ions move from the negative electrode to the positive electrode.

[0077] As used herein, the term "organic content (10%)" refers to the weight percentage of organic matter in a host. For example, if a buffer layer includes LSTPS and a polymer, but contains an organic content (10%), this means that the total weight percentage of the polymer in the LSTPS and polymer mixture is 10%, and the remaining 90% is inorganic, such as LSTPS.

[0078] The term "porosity determined by SEM" as used in this patent refers to a density measurement obtained by analyzing scanning electron micrographs using image analysis software. For example, the user or the software first assigns porosity to pixels and / or areas of the image. The area fractions of those areas are then summed. Finally, the porosity determined by SEM is equal to the area fraction of the porous area in the image.

[0079] The term "providing" as used in this patent refers to the provision, generation, presentation or delivery of a provided object.

[0080] Unless otherwise specified, the terms "diaphragm" and "Li-ion conductive diaphragm" used in this patent are used interchangeably, where diaphragm is an abbreviation for Li-ion conductive diaphragm. A diaphragm refers to a solid electrolyte that can conduct Li ions and is essentially insulated from electrons and is suitable for use as a physical barrier or separator between the positive and negative electrodes in an electrochemical cell or rechargeable battery. When the lithium ion conductivity of the diaphragm is at least 10 greater than the electronic conductivity of the diaphragm, the diaphragm is used as a separator. 3 times (usually 10 6 The separators used in this patent are essentially insulating when the concentration of lithium metal is greater than 100 times. The separators can be thin films, monoliths, or particles. Unless otherwise explicitly stated, the separators used in this patent are stable in contact with lithium metal.

[0081] The term "sintered lithium-filled garnet film" as used in this patent refers to a film formed by sintering and compacting a green film containing lithium-filled garnet.

[0082] The terms "solid-state cathode" or "solid-state positive electrode" as used in this patent refer to a type of "positive electrode" as defined in this patent. In some instances, all components of the solid-state cathode film are in solid form. The solid-state cathode includes an active cathode material as defined in this patent, a solid cathode electrolyte as defined in this patent, optionally a conductive additive, and optionally a binder. In some instances, the solid-state cathode is a compacted film.

[0083] The term "solid electrolyte" used in this patent is interchangeable with the term "solid separator" and refers to a solid electrolyte that does not contain carbon and conducts ions (such as Li +) but does not conduct electrons. Inorganic solid electrolytes are solid materials that are suitable for electrical isolation between the positive and negative electrodes of lithium secondary batteries while providing a lithium ion conduction path. Exemplary inorganic solid electrolytes include oxide electrolytes and sulfide electrolytes, which will be further described below. Non-limiting example sulfide electrolytes can be found in, for example, U.S. Patent No. 9,172,114, issued on October 27, 2015, and U.S. Patent Application No. 2017-0162901A1, published on June 8, 2017, and U.S. Patent Application No. 15 / 367,103, filed on December 1, 2016, the entire contents of which are incorporated herein by reference for all purposes. Non-limiting example oxide electrolytes can be found in U.S. Patent Application No. 2015-0200420A1, published on July 16, 2015, the entire contents of which are incorporated herein by reference for all purposes. In some examples, the inorganic solid electrolyte further includes a polymer.

[0084] Unless otherwise specified, the term "empirical formulas and molar coefficients are derived from the bulk of the raw materials used to prepare the examples" as used herein refers to formulas such as Li7La3Zr2O 12 The subscripts 7, 3, 2, 12 and the coefficient 0.35 in 0.35Al2O3 refer to the materials used to prepare certain materials (such as Li7La3Zr2O 12 ·0.35Al2O3) in chemical precursors (e.g. LiOH, La2O3, ZrO2, Al2O3).

[0085] As used herein, the term "slot casting" or "slot die coating" refers to a deposition process in which a solution, liquid, slurry, or the like is applied to or deposited on a substrate by passing the solution, liquid, slurry, or the like through a slot or die having fixed dimensions, the slot or die being adjacent to, in contact with, or positioned above the substrate. In some examples, the slot casting method includes a slot opening of approximately 1 to 100 μm.

[0086] As used herein, the term "oxide" refers to a compound that includes at least one oxygen atom and one other element in its chemical formula. For example, "oxide" may be used interchangeably with "oxide electrolyte." Non-limiting examples of oxide electrolytes can be found in U.S. Patent Application Publication No. 2015 / 0200420, published on July 16, 2015, the entire contents of which are incorporated herein by reference.

[0087] As used herein, the term "sulfide" refers to a compound that includes at least one sulfur atom and one other element in the compound's chemical formula. For example, "sulfide" may be used interchangeably with "sulfide electrolyte." Non-limiting examples of sulfide electrolytes can be found, for example, in U.S. Patent No. 9,172,114, issued on October 27, 2015, and U.S. Patent Application No. 2017-0162901A1, published on June 8, 2017, and U.S. Patent Application No. 15 / 367,103, filed on December 1, 2016, the entire contents of which are incorporated herein by reference for all purposes. A sulfide cathode electrolyte, as used herein, is a cathode electrolyte comprising or consisting essentially of a sulfide.

[0088] The term "sulfide electrolyte" or "lithium sulfide" used in this patent includes but is not limited to the electrolytes referred to in this patent 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 represents element S, Si or a combination thereof, and T represents element Sn. "Sulfide electrolyte" may also include 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%; the sulfide electrolyte may contain up to 10% oxygen, either intentionally added or present as impurities.

[0089] The term "sulfide-halide" as used in this patent refers to a compound that includes at least one sulfur atom, at least one halogen atom and one other element in the chemical formula of the compound.

[0090] Unless otherwise stated, the voltages used in this patent are relative to lithium metal (ie, voltage to lithium).

[0091] electrochemical cell

[0092] Figure 1 is a schematic diagram of an example of an electrochemical cell. Figure 1 As shown, layer 101 represents an evaporated lithium metal anode. Layer 102 represents a lithium-filled garnet layer. Layer 103 represents an adhesion layer. Layer 104 represents a buffer layer. Layer 105 represents a positive electrode layer. In some examples, layer 102 has a thickness of approximately 100 μm. In some examples, layer 101 has a thickness of approximately 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. In some examples, layer 102 has a thickness of 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. In some examples, layer 103 has a thickness of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 μm. In some examples, layer 104 has a thickness of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 μm. In some examples, layer 105 has a thickness of 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, 1 24, 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.

[0093] In some embodiments, the present patent discloses a solid-state electrochemical cell (SSEC) comprising (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; (b) a solid buffer that conducts a single ion; (c) a borohydride binding layer; and (d) a lithium-filled garnet layer. The buffer is mixed within the positive electrode layer, or the buffer is provided as a layer in contact with the positive electrode layer, or in some embodiments, the buffer is mixed within the positive electrode layer and is provided as a layer in contact with the positive electrode layer. The borohydride binding layer is between and in contact with the lithium-filled garnet layer and (i) the positive electrode layer mixed with the buffer or (ii) the buffer layer in contact with the positive electrode. In some embodiments, the borohydride binding layer is between and in contact with the lithium-filled garnet layer and the positive electrode layer mixed with the buffer. In some embodiments, the buffer is mixed within the positive electrode layer. In some embodiments, the buffer is provided as a layer in contact with the positive electrode layer. In some examples, the buffer is mixed within the positive electrode layer and also serves as a layer in contact with the positive electrode layer. In some examples, the borohydride bonding layer is between and in contact with the lithium-filled garnet layer and the buffer layer in contact with the positive electrode.

[0094] In some examples, including any of the above, the active material comprises a coating. In some examples, the active material comprises a coating selected from LLZO materials.

[0095] In these examples, lithium ions are conducted through the inorganic single ion conductor, rather than through the polymer or organic component (10%).

[0096] In some embodiments, the solid-state electrochemical cell (SSEC) described herein comprises: (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; (b) a solid buffer that conducts a single ion; (c) a borohydride binding layer; and (d) a lithium-filled garnet layer. The buffer is mixed within the positive electrode layer, is in contact with the positive electrode layer, or is a layer in contact with the positive electrode layer, or both. The borohydride binding layer is between and in contact with the lithium-filled garnet layer and (i) the positive electrode layer mixed with the buffer or (ii) the buffer layer in contact with the positive electrode.

[0097] In some examples, including any of the foregoing, a solid buffer that conducts a single ion is mixed into the positive electrode layer. In some embodiments, the buffer is mixed into the positive electrode layer in a gradient manner between the active material and the buffer material.

[0098] In some examples, including any of the foregoing, the single-ion conducting solid buffer is a layer in contact with the positive electrode layer.

[0099] In some examples, including any of the foregoing, a single ion conducting solid buffer is mixed within the positive electrode layer and serves as a layer in contact with the positive electrode layer.

[0100] In some examples, including any of the foregoing, a single ion conducting solid buffer layer prevents the borohydride adhesion layer from contacting the positive electrode layer. In some examples, the borohydride adhesion layer adheres the lithium-filled garnet layer to the buffer layer. In some examples, the borohydride adhesion layer adheres the lithium-filled garnet layer to the buffer as a component of the positive electrode layer.

[0101] In some examples, including any of the foregoing, the negative electrode layer is between and in contact with the lithium-filled garnet layer and the negative electrode current collector layer. In some examples, including any of the foregoing, the buffer layer potential is shielded from the potential of the Li metal negative electrode. In some examples, including any of the foregoing, the borohydride bonding layer potential is shielded from the potential of the positive electrode. In some examples, including any of the foregoing, the ASR of the SSEC is 50 Ω cm 2 or smaller.

[0102] In some embodiments, the present patent discloses a solid-state electrochemical cell (SSEC) comprising (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; (b) a buffer comprising a solid electrolyte that conducts a single ion and is mixed within the positive electrode layer or in direct contact with the positive electrode layer; (c) a binding layer comprising a borohydride; and (d) a layer comprising a lithium-filled garnet. In this embodiment, the borohydride binding layer is between and in contact with the layer containing the lithium-filled garnet and the positive electrode layer, or between the layer containing the lithium-filled garnet and the buffer layer, the buffer layer being in direct contact with the positive electrode.

[0103] In some examples, including any of the foregoing, the solid-state electrochemical stack further comprises (d) a negative electrode current collector in direct contact with the separator layer. In another example, any of the foregoing solid-state electrochemical stacks further comprises (e) a positive electrode current collector in direct contact with the positive electrode layer. In further examples, any of the foregoing solid-state electrochemical stacks further comprises (d) a negative electrode current collector and (e) a negative electrode, wherein (e) the negative electrode is between the separator layer and the negative electrode current collector and in direct contact with them.

[0104] In certain embodiments, the present patent discloses a composite material having a lithium-filled garnet and an LBHI, wherein the LBHI fills at least 90% of the through pores and / or surface pores of the lithium-filled garnet, and wherein the LBHI is a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X represents a halide, and 3≤A≤6, 2≤B≤5, and 0≤C≤9.

[0105] In some embodiments, the borohydride bonding layer described in this patent is LBHI (lithium borohydride and lithium iodide), and the buffer layer is LSTPS. The buffer layer seals (i.e., shields) the high-voltage positive electrode.

[0106] Buffer components

[0107] In some instances, the sulfide in the buffer layer can be any sulfide described in the U.S. patent application with a publication date of January 5, 2017, publication number 2017 - 0005367A1, and title "COMPOSITE ELECTROLYTES", the entire content of which is incorporated herein by reference for various purposes.

[0108] In some instances, the sulfide in the buffer layer can be any sulfide proposed in the patent WO2017096088A1, with a publication date of June 8, 2017, international PCT patent application number PCT / US2016 / 064492, filing date of December 1, 2016, and title "LITHIUM,PHOSPHORUS,SULFUR,AND IODINE CONTAINING ELECTROLYTEAND CATHOLYTE COMPOSITIONS,ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL DEVICES,AND ANNEALING METHODS OF MAKING THESE ELECTROLYTES AND CATHOLYTES", published as WO 2017 / 096088 on June 8, 2017, the entire content of which is incorporated herein by reference for various purposes.

[0109] In some instances, including any of the foregoing, the buffer layer, the sulfide cathode electrolyte, or the single - ion - conducting solid buffer, or all of them, can be characterized by one of the following formulas: 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, where 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; Li m [[ID=n S p I q , wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; a mixture of (Li2S):(P2S5) and LiI in a molar ratio of about 10:1 to about 6:4, wherein the ratio of [(Li2S):(P2S5)]:LiI is 95:5 to 50:50; LPS+X, wherein X is selected from Cl, I, or Br; vLi2S+wP2S5+yLiX or vLi2S+wSiS2+yLiX. In some examples, including any of the foregoing, the sulfide cathode electrolyte comprises LSTPS.2S+wB2S3+yLiX.

[0110] In some examples, the buffer comprises 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. In some examples, the buffer comprises Li a Si b Sn c P d S e , wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤2.5 and 4≤e≤12. In some examples, the buffer comprises Li a Si b Sn c P d S e , wherein 3≤a≤7, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤1.5 and 8≤e≤12. In some examples, the buffer comprises Li a Si b Sn c P d S e , wherein 3≤a≤5, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤1 and 5≤e≤9. In some examples, the buffer comprises Li a Si b Sn c P d S e , wherein 3≤a≤5, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤1 and 5≤e≤9. In some examples, the buffer comprises Li a Si b Sn c P d S e, wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, b+c=1, 0.5≤d≤2.5 and 4≤e≤12. In some examples, the buffer comprises Li a Si b Sn c P d S e , wherein 3≤a≤5, 0≤b≤0.5, 0≤c≤0.5, 0≤d≤2, and 2≤e≤10. In some examples, 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≤14. In some examples, 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≤8.

[0111] In some examples, including any of the foregoing, the single-ion conducting solid buffer comprises LSTPS.

[0112] The buffer layer does not conduct electrons, thereby isolating the potential of the positive electrode from that of the borohydride bonding layer.

[0113] The buffer layer does not conduct electrons, and thus the positive electrode potential is not affected by the negative electrode potential.

[0114] In some examples, the buffer layer is easily deformable.

[0115] In some examples, the buffer layer is chemically stable when in contact with the disclosed sulfide cathode electrolyte and / or the disclosed coated active material.

[0116] In some examples, the buffer layer includes LSTPS.

[0117] In some examples, the buffer layer includes D 50 The particles are about 10 nm to 1000 nm, about 100 nm to 500 nm, or about 150 nm to 300 nm. In some examples, the buffer layer includes D 50 are particles of about 100 nm, about 200 nm, or about 300 nm. In some examples, the buffer layer includes D 90The particles are about 500 nm to 2000 nm, 750 nm to 1000 nm or about 1000 nm. In some examples, the buffer layer includes D 90 are particles of about 800 nm, 900 nm, 1000 nm or 1100 nm. In some examples, the buffer layer includes D 90 In some embodiments, the buffer layer comprises D 90 The particles are at least about 900 nm.

[0118] In some examples, the buffer layer is made of particles that are 1 / 10 the thickness of the buffer layer. For example, in some examples, if the buffer layer is 5 μm thick, the buffer layer contains buffer particles that are 0.5 μm. In some examples, if the buffer layer is 5 μm thick, the buffer layer contains d 50 The particle size of LSTPS particles is 0.5 μm in diameter.

[0119] In some examples, the buffer layer has negligible interfacial resistance to the positive electrode.

[0120] In some examples, the buffer layer is non-polymeric, meaning that the buffer layer includes less than 5 wt % polymer.

[0121] In some examples, the buffer layer is adhered to the positive electrode through a lamination and compaction process. This creates a buffered positive electrode that blocks the entry of electrons, shielding the other electrolyte layers from the positive electrode potential.

[0122] In some examples, the buffer layer is adhered to the positive electrode through a lamination and compaction process. This creates a buffered positive electrode that blocks the entry of electrons, shielding the other electrolyte layers from the positive electrode potential.

[0123] In some examples, the porosity of the buffer layer is less than about 20% v / v, 15% v / v, 12.5% ​​v / v, 10% v / v, 5% v / v, 1% v / v, or less. In some examples, the porosity of the buffer layer is about 5% v / v to 20% v / v or about 10% v / v to 15% v / v.

[0124] Adhesive layer components

[0125] In certain embodiments, the bonding layer may include a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X may be fluorine, bromine, chlorine, iodine, or a combination thereof, 3≤A≤6, 2≤B≤5, and 0≤C≤9. In some instances, the bonding layer includes A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 3≤A≤6, 2≤B≤5, and 3≤C≤6. In some instances, the bonding layer includes A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 3≤A≤5, 2≤B≤5, and 3≤C≤5. In some instances, the bonding layer includes A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 3≤A≤4, 2≤B≤4, and 3≤C≤4. In some examples, the bonding layer comprises A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 4≤A≤5, 2≤B≤4, and 4≤C≤5. In some examples, the bonding layer comprises A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 4≤A≤5, 3≤B≤4, and 4≤C≤5.

[0126] In certain embodiments, the bonding layer may include a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X may be fluorine, bromine, chlorine, iodine, or a combination thereof, 0.1≤A≤3, 0.1≤B≤4.5, and 0≤C≤9.

[0127] 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.

[0128] In some instances, the adhesive 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 instances, including any of the foregoing, the borohydride adhesive layer comprises a borohydride composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2). In some instances, 2.5 < A < 3.5, 3.5 < B < 4.5, and 5 < C < 9.

[0129] In some examples, including any of the foregoing, the borohydride adhesion layer comprises a borohydride composition, the composition being 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·9LiNH2. In one embodiment, the composition may be 3LiBH4·2LiI·3LiNH2. In another embodiment, the composition may be 3LiBH4·4LiI·9LiNH2. In another embodiment, the composition may be 3LiBH4·2LiCl·3LiNH2. In another embodiment, the composition may be 3LiBH4·4LiCl·9LiNH2. In another embodiment, the composition may be 3LiBH4·2LiBr·3LiNH2. In another embodiment, the composition may be 3LiBH4·4LiBr·9LiNH2.

[0130] In some examples, including any of the foregoing, the borohydride bonding layer comprises a borohydride composition, wherein the composition is 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·5LiNH2. In one embodiment, the composition is 4LiBH4·2LiI·4LiNH2. In another embodiment, the composition is 4LiBH4·3LiI·4LiNH2. In another embodiment, the composition is 4LiBH4·5LiCl·4LiNH2. In another embodiment, the composition is 4LiBH4·6LiCl·4LiNH2. In some examples, including any of the foregoing, the borohydride bonding layer comprises a borohydride composition, wherein the composition is 3LiBH4·3LiCl·4LiNH2 or 3LiBH4·3LiCl·5LiNH2. In one embodiment, the composition is 3LiBH4·3LiI·6LiNH2. In another embodiment, the composition is 3LiBH4·3LiI·7LiNH2.

[0131] In some examples, including any of the foregoing, the borohydride adhesion layer comprises a borohydride composition selected from LBHIN and LBHN. In some examples, including any of the foregoing, the borohydride adhesion layer comprises KBH4 and LiNH2.

[0132] In some embodiments, the composition can exist in different physical states. For example, in one embodiment, the composition can be amorphous. As a further example, in one embodiment, the composition can be semi-crystalline. By controlling the sintering curve, for example, by adjusting the cooling rate after sintering, the composition can be made amorphous or semi-crystalline.

[0133] In some embodiments, the LBHI composition may exist in the form of a thin film, a monolithic material, 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 monolithic material. As a further example, in one embodiment, the composition is a pressed pellet.

[0134] In some embodiments, the LBHI composition may further include 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 as 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 another example, in one embodiment, the composition includes an oxide having an LBHI coating, and the oxide may be selected from lithium-filled garnets characterized as 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 another example, in one embodiment, the oxide may be selected from lithium-filled garnets characterized as 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, where Me” is a metal selected from Nb, Ga, Ta, or a combination thereof. As another example, in one embodiment, the composition includes an oxide having an LBHI coating, and the oxide may be selected from lithium-filled garnets characterized as 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, where Me” is a metal selected from Nb, Ga, Ta, or a combination thereof. As another example, in one of the foregoing Li a La b Zr c Al d Me” e O f embodiments, Me” is Nb. As another example, in one of the foregoing Lia La b Zr c Al d Me” e O f In the embodiment, Me" is Ga. As another example, in the aforementioned Li a La b Zr c Al d Me” e O f In the embodiment, Me" is Ta. As another example, in the aforementioned Li a La b Zr c Al d Me” e O f In the embodiment, Me" is Nb and Ga. As another example, in the aforementioned Li a La b Zr c Al d Me” e O f In the embodiment, Me" is Nb and Ta. As another example, in the aforementioned Li a La b Zr c Al d Me” e O f In the examples, "Me" is Ga and Ta.

[0135] In some examples, the borohydride bonding layer is made of a borohydride compound. The borohydride compound can be any compound described in the patent application with publication number WO2018 / 075972, published on April 26, 2018, and international PCT patent application number PCT / US2017 / 057735, entitled “ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE.” The borohydride can be any compound described in the patent application with a publication date of April 25, 2019, a publication number of WO 2019 / 078897, an application date of October 20, 2017, an international PCT patent application number of PCT / US2017 / 057739, and a title of "BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID STATEBATTERY".

[0136] In some examples, including any of the foregoing, the lithium salt is selected from LiTFSI, LiFSI, LiPF6, LiClO4, LiAsF6, LiBOB, LiBETI, LiBF4, and LiI, and combinations thereof. In some examples, the lithium salt is selected from LiPF6, lithium bis(oxalate)borate (LiBOB), lithium bis(perfluoroethanesulfonyl)imide (LIBETI), LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, or LiI. In some examples, the lithium salt is LiPF6. In some examples, the lithium salt is LiBOB. In some examples, the lithium salt is LiTFSi. In some examples, the lithium salt is LiBF4. In some examples, the lithium salt is LiClO4. In some examples, the lithium salt is LiAsF6. In some examples, the lithium salt is LiI. In some examples, the lithium salt is LiBF4. In some instances, several lithium salts can exist simultaneously at different concentrations. In some instances, 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 some instances, the bonding layer may include two salts selected from LiPF6, LiBOB, LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, or LiI. In some instances, the bonding layer may include three salts selected from LiPF6, LiBOB, LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, or LiI. In some instances, the lithium salt is a lithium salt selected from LiPF6, LiBOB, and LFTSi. In some instances, the lithium salt is LiPF6 at a concentration of 0.5 M to 2 M. In some examples, 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 some examples, the lithium salt is LiTFSI at a concentration of 0.5 M to 2 M. In some examples, 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.

[0137] In some examples, the lithium salt is present at a concentration of 0.01 M to 10 M. In some examples, the concentration 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, 3.3, 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, 3.2, 3.3, 3.4, 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 ,7.4,7.5,7.6,7.7,7.8,7.9,8.0,8.1,8.2,8.8,8.4,8.5,8.6,8.7,8.8,8.9,9.9,9.1,9.2,9.3,9.4,9.5,9.6,9.7,9.8,9.9,9.9,10.0M.

[0138] Other components

[0139] In some examples, including any of the foregoing, the buffer layer comprises a binder in an amount of 0.01% to 10% by weight. In some examples, the binder may comprise a polyolefin. The binder may comprise an ethylene α-olefin copolymer, an ethylene-octene copolymer, a polyolefin plastomer, a polyolefin elastomer, a styrene-butadiene rubber, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene), or the like.

[0140] In some examples, including any of the foregoing, the buffer layer comprises 10% or less by volume of the organic polymer.

[0141] In some examples, including any of the foregoing, the polymer is selected from polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (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 fluoride 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.

[0142] In some examples, including any of the foregoing, the buffer layer or buffer component does not include an organic polymer.

[0143] In some examples, including any of the foregoing, the positive electrode potential is shielded such that the potential of the lithium-filled garnet layer is not affected by the positive electrode potential.

[0144] In some examples, including any of the foregoing, the potential of the active material in the positive electrode is shielded such that the potential of the lithium-filled garnet layer is not affected by the potential of the active material in the positive electrode.

[0145] In some examples, the cathode includes an active material, wherein the active material is selected from LiNi x Mn y Co z O2(NMC) and LiNi x Al y Co z O2(NCA), where x+y+z=1.

[0146] In some examples, including any of the foregoing, the active material has a coating.

[0147] In some examples, including any of the foregoing, 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, hafnium oxide.

[0148] In some examples, including any of the foregoing, the active material is uncoated.

[0149] In some examples, including any of the foregoing, the positive electrode includes a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

[0150] In some instances, the positive electrode has a porosity of less than about 20% v / v, 15% v / v, 12.5% ​​v / v, 10% v / v, 5% v / v, 1% v / v, or less. In some instances, the positive electrode has a porosity of about 5% v / v to 20% v / v or about 10% v / v to 15% v / v.

[0151] In some embodiments, including any of the foregoing, the intercalation material is selected from 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.

[0152] In some examples, including any of the foregoing, the lithium conversion material is selected from FeF2, NiF2, FeOxF 3-2x , FeF3, MnF3, CoF3, CuF2 materials, their alloys and their combinations.

[0153] In some examples, including any of the foregoing, the sulfide cathode electrolyte and the single-ion conducting solid buffer are made of the same type of material.

[0154] In some examples, including any of the foregoing, the sulfide cathode electrolyte and the single-ion conducting solid buffer, or both, are selected from LSS, SLOPS, LSTPS, LSTPSC1, SLOBS, LATS, and LPS+X, wherein X is selected from Cl, I, Br, and combinations thereof. In some examples, X is Cl. In some examples, X is I. In some examples, X is Br.

[0155] In some examples, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid buffer, or both, are selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSCl, LSPSCl, SLOBS, LATS, and LPS+X, wherein X is selected from Cl, I, Br, and combinations thereof. In some examples, X is Cl. In some examples, X is I. In some examples, X is Br.

[0156] In some instances, including any of the foregoing, the sulfide cathode electrolyte or the single-ion-conducting solid-state buffer or both are selected from LPSI, LXPS, LSTPS, LSPSCl, LPCS1, LSPSBr, and LPSBr.

[0157] In some instances, including any of the foregoing, the sulfide cathode electrolyte or the single-ion-conducting solid-state 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.

[0158] In some instances, including any of the foregoing, the sulfide cathode electrolyte or the single-ion-conducting solid-state buffer or both are selected from LSS, LGPS, LSTPS, and LSPS2S:ySiS2, where x and y are each independently a number from 0 to 1, and x + y = 1.

[0159] In some instances, including any of the foregoing, the borohydride adhesive layer includes lithium borohydride, sodium borohydride, or potassium borohydride.

[0160] In some instances, including any of the foregoing, the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiNH2.

[0161] In some instances, including any of the foregoing, any one or more of the lithium borohydride, sodium borohydride, or potassium borohydride are doped with LiI.

[0162] In some instances, including any of the foregoing, any one or more of the lithium borohydride, sodium borohydride, or potassium borohydride are doped with LiNH2 and LiI.

[0163] In some instances, including any of the foregoing, the borohydride adhesive layer includes a borohydride composition comprising A(LiBH4)(1 - A)(P2S5), where 0.05 ≤ A ≤ 0.95. In some instances, 0.5 < A < 0.95. In some instances, A is 0.85, 0.9, or 0.95.

[0164] In some instances, including any of the foregoing, the borohydride adhesive layer comprises 0.9(LiBH4)0.1(P2S5).

[0165] In some instances, including any of the foregoing, the borohydride adhesive layer is amorphous. In some instances, including any of the foregoing, the borohydride adhesive layer is semi-crystalline. In some instances, including any of the foregoing, the borohydride adhesive layer is polycrystalline.

[0166] In some instances, including any of the foregoing, the lithium-filled garnet layer includes a selection from Li x Lay Zr z O t Lithium-filled garnet of ·qAl2O3, where 4 < x < 10, 1 < y < 4, 1 < z < 3, 6 < t < 14 and 0 ≤ q ≤ 1.

[0167] In some instances, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet selected from Li7La3Zr2O 12 ·Al2O2O3 and Li7La3Zr2O 12 ·0.35Al2O3.

[0168] In some instances, including any of the foregoing, the lithium-filled garnet is doped with Nb, Ga, and / or Ta in Li7La3Zr2O 12 ·Al2O3 and Li7La3Zr2O 12 ·0.35Al2O3.

[0169] In some instances, including any of the foregoing, 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 Nb, Ga, Ta, and combinations thereof.

[0170] In some instances, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet 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 between 2 and 4; x is a rational number from 1 to 3; y is a rational number between 10 and 14; 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.

[0171] In some instances, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet characterized by the formula Li u La v Zr x O yA lithium-filled garnet oxide of zTa2O5, wherein u is a rational number from 4 to 10; 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 to 1; and u, v, x, y, and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0172] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of zNb2O5, wherein 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-filled garnet oxide is charge neutral.

[0173] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of zGa2O3, wherein u is a rational number from 4 to 10; 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 to 1; and u, v, x, y, and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0174] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of ·zTa2O5·bAl2O3, wherein u is a rational number from 4 to 10; 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; z is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected so that the lithium-filled garnet oxide is charge neutral.

[0175] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O yA lithium-filled garnet oxide of zNb2O5·bAl2O3, wherein u is a rational number from 4 to 10; 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; z is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected so that the lithium-filled garnet oxide is charge neutral.

[0176] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of ·zGa2O3·bAl2O3, wherein u is a rational number from 4 to 10; 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; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected so that the lithium-filled garnet oxide is charge neutral.

[0177] In some examples, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li 6.4 Ga 0.2 La3Zr2O 12.3 bAl2O3 lithium-filled garnet, wherein u is a rational number from 4 to 10; 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; y is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z + b ≤ 1; u, v, x, y and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0178] In some examples, including any of the foregoing, the SSEC further comprises a positive electrode current collector layer.

[0179] In some examples, including any of the foregoing, the SSEC further comprises a negative electrode current collector layer. In some examples, the negative electrode current collector layer is a sintered metal. In some examples, the sintered metal is selected from Al, Cu, Ni, Ag, Au, Pt, Pd, or Sn. In some examples, the metal is Ni.

[0180] In some examples, including any of the foregoing, the positive electrode layer further comprises a binder, carbon, or both a binder and carbon.

[0181] In some examples, including any of the foregoing, the lithium-filled garnet layer is between and in contact with the negative electrode current collector layer and the borohydride binding layer.

[0182] In some examples, including any of the foregoing, the borohydride adhesion layer is between and in contact with the lithium-filled garnet layer and the buffer layer.

[0183] In some examples, including any of the foregoing, the buffer layer is between and in contact with the borohydride adhesion layer and the positive electrode layer.

[0184] In some examples, including any of the foregoing, the positive electrode layer is between and in contact with the buffer layer and the positive electrode current collector layer.

[0185] In some examples, including any of the foregoing, the active material includes a coating or is coated. In some examples, the active material has a coating. In some examples, the active material is coated. In some examples, the active material includes a coating of a material selected from lithium lanthanum zirconium oxide (LLZO).

[0186] The lithium-filled garnet layer may include any of the lithium-filled garnets described in U.S. Patent No. 9,806,372 B2, entitled “Garnet Materials for Li Secondary Batteries and Methods of Making and Using Garnet Materials,” issued on October 31, 2017, and U.S. Patent No. 9,970,711, entitled “Lithium Stuffed Garnet Setterplates for Solid Electrolyte Fabrication,” issued on May 15, 2018. The entire contents of each of these patents are incorporated herein by reference for all purposes. The lithium-filled garnet layer is formed by forming a layer or film of the lithium-filled garnet layer described in this patent, for example, by using the method of U.S. Patent No. 9,806,372 B2. The lithium-filled garnet layer may include any of the lithium-filled garnets disclosed in U.S. Patent No. 9,966,630, published on May 8, 2018, entitled “ANNEALED GARNET ELECTROLYTE SEPARATORS,” which is hereby incorporated by reference in its entirety for all purposes. The lithium-filled garnet layer is formed by forming a layer or film of the lithium-filled garnet layer described in this patent, for example, by using the method of U.S. Patent No. 9,966,630 B2. The lithium-filled garnet layer may include any of the lithium-filled garnets disclosed in U.S. Patent Application No. 15 / 631,884, filed on June 23, 2017, entitled “LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS,” which is hereby incorporated by reference in its entirety for all purposes. The lithium-stuffed garnet layer is formed by forming a layer or film of the lithium-stuffed garnet layer described herein, for example, by using the methods of U.S. Patent Application No. 15 / 631,884. The lithium-stuffed garnet layer may include any of the lithium-stuffed garnets disclosed in International PCT Patent Application No. PCT / US2017 / 039069, entitled “LITHIUM-STUFFED GARNET ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS,” filed June 23, 2017, the entire contents of which are incorporated herein by reference for all purposes. The lithium-stuffed garnet layer is formed by forming a layer or film of the lithium-stuffed garnet layer described herein, for example, by using the methods of PCT / US2017 / 039069.

[0187] In some examples, the lithium-filled garnet layer is chemically stable when in contact with lithium metal. In some examples, the lithium-filled garnet layer is kinetically stable when in contact with lithium metal.

[0188] In some examples, the lithium-filled garnet includes lithium lanthanum zirconium oxide (LLZO), and has good electrochemical stability and mechanical strength, for example, greater than 500 MPa. In some examples, the LLZO is suitable for use with a lithium metal anode.

[0189] In any of the embodiments described herein, the lithium-filled garnet layer or LLZO can be used with a binder as disclosed in International PCT Patent Application No. PCT / US2017 / 032749, filed May 15, 2017, published November 16, 2017, and entitled “SOLID ELECTROLYTE SEPARATOR BONDING AGENT,” the entire contents of which are incorporated herein by reference for all purposes. In any of the embodiments described herein, the lithium-filled garnet is prepared according to the method described in 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 which are incorporated herein by reference for all purposes. In any of the examples described herein, the lithium-filled garnets are prepared according to the methods described in International PCT Patent Application No. PCT / US2016 / 027922, filed April 15, 2016, entitled “SETTERPLATES FOR SOLID ELECTROLYTE FABRICATION AND METHODS OF USING THE SAME TOPREPARE DENSE SOLID ELECTROLYTES,” which is hereby incorporated by reference in its entirety for all purposes. In any of the examples described herein, the lithium-filled garnets are prepared according to the methods described in International PCT Patent Application No. PCT / US2016 / 043428, filed July 21, 2016, entitled “PROCESSES AND MATERIALS FOR CASTING AND SINTERING GREEN GARNET THIN FILMS,” which is hereby incorporated by reference in its entirety for all purposes. In any of the examples described in this patent, the lithium-filled garnet is prepared according to the method described in U.S. Patent No. 9,970,711, entitled “LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION”, which is incorporated herein by reference in its entirety for all purposes.In any of the embodiments described herein, the lithium-filled garnet is prepared according to the method described in U.S. Patent No. 9,970,711, entitled “LITHIUM STUFFED GARNET SETTER PLATES FOR SOLIDELECTROLYTE FABRICATION,” issued on May 15, 2018, the entire contents of which are incorporated herein by reference for all purposes. In any of the embodiments described herein, the sulfide in the sulfide cathode electrolyte can be any sulfide described in U.S. Patent No. 9,172,114, entitled “SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES,” issued on October 27, 2015, the entire contents of which are incorporated herein by reference for all purposes. In any of the embodiments described in this patent, the sulfide in the sulfide cathode electrolyte can be any sulfide proposed in the patent application with an application date of February 1, 2016, an international PCT patent application number of PCT / US2016 / 015982, a publication number of WO 2016 / 126610, a publication date of August 11, 2016, and titled "METAL SULFIDE ANOLYTE FORELECTROCHEMICAL CELLS", the entire contents of which are incorporated by reference into this application for all purposes. In any of the examples described herein, the sulfide in the sulfide cathode electrolyte may be any sulfide described in the international PCT patent application number PCT / US2016 / 039424, entitled “COMPOSITE ELECTROLYTES,” filed on June 24, 2016, published on December 29, 2016, and with publication number WO 2016 / 210371, the entire contents of which are incorporated herein by reference for all purposes. In any of the examples described herein, the sulfide in the sulfide cathode electrolyte may be any sulfide described in U.S. patent application number 2017-0005367A1, entitled “COMPOSITE ELECTROLYTES,” filed on January 5, 2017, and with publication number 2017-0005367A1, the entire contents of which are incorporated herein by reference for all purposes.In any of the examples described in this patent, the sulfide in the sulfide cathode electrolyte can be any sulfide described in the patent application with an application date of December 1, 2016, a publication date of June 8, 2017, a publication number of WO 2017 / 096088, a PCT patent application number of PCT / US2016 / 064492, and a title of "LITHIUM, PHOSPHORUS, SULFUR, AND IODINE CONTAINING ELECTROLYTE AND CATHOLYTE COMPOSITIONS, ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL DEVICES, AND ANNEALING METHODS OF MAKING THESE ELECTROLYTES AND CATHOLYTES", the entire contents of which are incorporated by reference into this application for all purposes.

[0190] In some examples, the sulfide in the buffer layer can be any sulfide described in U.S. Patent No. 9,172,114, issued on October 27, 2015, entitled “SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES,” the entire contents of which are incorporated herein by reference for all purposes. In some examples, the sulfide in the buffer layer can be any sulfide described in WO 2016 / 126610, filed on February 1, 2016, published on August 11, 2016, and PCT Patent Application No. PCT / US2016 / 015982, or any sulfide described in patent application titled “METAL SULFIDE ANOLYTE FOR ELECTROCHEMICAL CELLS,” the entire contents of which are incorporated herein by reference for all purposes. In some instances, the sulfide in the buffer layer can be any sulfide described in patent application WO2016 / 210371, filed on June 24, 2016, published on December 29, 2016, entitled “COMPOSITE ELECTROLYTES,” and PCT patent application number PCT / US2016 / 039424, the entire contents of which are incorporated herein by reference for all purposes.

[0191] In some examples, the positive electrode includes about 85 wt % of LZO-coated NCA, about 13 wt % of LSTPS, and about 2 wt % of a binder.

[0192] In some examples, including any of the foregoing, the negative electrode is a lithium (Li) metal electrode layer. In some examples, including any of the foregoing, at least one current collector includes a material selected from the group consisting of nickel (Ni), nickel (Ni), copper (Cu), aluminum (Al) and stainless steel coated by carbon (C). In some examples, including any of the foregoing, the negative electrode current collector includes a material selected from the group consisting of nickel (Ni), nickel (Ni) and copper (Cu) coated by carbon (C). In some examples, including any of the foregoing, the positive electrode current collector layer includes a material selected from the group consisting of aluminum and aluminum coated by carbon (C). In some examples, including any of the foregoing, the negative electrode current collector layer is carbon-coated nickel. In some examples, including any of the foregoing, the positive electrode current collector layer is carbon-coated aluminum.

[0193] Buffer layer size

[0194] In some examples, including any of the foregoing, the thickness of the buffer layer is from about 1 μm to about 50 μm. In some examples, the thickness of the buffer layer is 1 μm. In some examples, the thickness of the buffer layer is 2 μm. In some examples, the thickness of the buffer layer is 3 μm. In some examples, the thickness of the buffer layer is 4 μm. In some examples, the thickness of the buffer layer is 5 μm. In some examples, the thickness of the buffer layer is 6 μm. In some examples, the thickness of the buffer layer is 7 μm. In some examples, the thickness of the buffer layer is 8 μm. In some examples, the thickness of the buffer layer is 9 μm. In some examples, the thickness of the buffer layer is 10 μm.

[0195] In some examples, including any of the foregoing, the solid-state buffer that conducts a single ion is mixed in the positive electrode layer, and its penetration depth in the positive electrode layer is about 1 μm to about 50 μm. The penetration depth is measured from the boundary edge of the positive electrode layer and the buffer layer or the borohydride bonding layer. In some examples, if the thickness of the positive electrode layer is 200 μm and the penetration depth in the positive electrode layer is about 1 μm to about 50 μm, it means that the buffer is closest to the side of the buffer layer (if present) or the side of the borohydride bonding layer (if no buffer layer is present) on the positive electrode. In some examples, if the thickness of the positive electrode layer is 200 μm and the penetration depth in the positive electrode layer is about 1 μm to about 50 μm, it means that there is no buffer component on the side of the positive electrode in contact with the positive electrode collector.

[0196] In some examples, including any of the foregoing, the solid-state buffer that conducts a single ion is mixed in the positive electrode layer, and its penetration depth in the positive electrode layer is about 1 μm to about 50 μm. The penetration depth is measured from the boundary edge of the positive electrode layer and the buffer layer or the borohydride bonding layer. In some examples, if the thickness of the positive electrode layer is 150 μm and the penetration depth in the positive electrode layer is about 1 μm to about 50 μm, it means that the buffer is closest to the side of the buffer layer (if present) or the side of the borohydride bonding layer (if no buffer layer is present) on the positive electrode. In some examples, if the positive electrode layer is 150 μm thick and the penetration depth in the positive electrode layer is about 1 μm to about 50 μm, it means that the positive electrode has no buffer component on the side in contact with the positive electrode collector.

[0197] In some examples, including any of the foregoing, the buffer layer is between the positive electrode layer and the separator layer and in direct contact with them. In some examples, the thickness of the buffer layer is about 1 μm to about 15 μm. In some examples, the thickness of the buffer layer is 1 μm. In some examples, the thickness of the buffer layer is 1 μm. In some examples, the thickness of the buffer layer is 2 μm. In some examples, the thickness of the buffer layer is 3 μm. In some examples, the thickness of the buffer layer is 4 μm. In some examples, the thickness of the buffer layer is 5 μm. In some examples, the thickness of the buffer layer is 6 μm. In some examples, the thickness of the buffer layer is 7 μm. In some examples, the thickness of the buffer layer is 8 μm. In some examples, the thickness of the buffer layer is 9 μm. In some examples, the thickness of the buffer layer is 10 μm. In some examples, the thickness of the buffer layer is 11 μm. In some examples, the thickness of the buffer layer is 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.

[0198] Adhesive layer size

[0199] In some examples, the bonding layer comprises lithium borohydride. In some examples, the bonding layer comprises lithium borohydride particles having an average diameter of at least about 1 μm. In some examples, 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.

[0200] In some examples, before assembling the battery, the bonding layer includes particles having an average diameter of at least about 1 μm. In some examples, the bonding 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.

[0201] In some examples, including any of the foregoing, the borohydride bonding layer has a thickness of about 1 μm to about 50 μm. In some examples, including any of the foregoing, the borohydride bonding layer has a thickness of about 1 μm to about 50 μm. In some examples, the borohydride bonding layer has a thickness of 1 μm. In some examples, the borohydride bonding layer has a thickness of 2 μm. In some examples, the borohydride bonding layer has a thickness of 3 μm. In some examples, the borohydride bonding layer has a thickness of 4 μm. In some examples, the borohydride bonding layer has a thickness of 5 μm. In some examples, the borohydride bonding layer has a thickness of 6 μm. In some examples, the borohydride bonding layer has a thickness of 7 μm. In some examples, the borohydride bonding layer has a thickness of 8 μm. In some examples, the borohydride bonding layer has a thickness of 9 μm. In some examples, the borohydride bonding layer has a thickness of 10 μm. In some examples, the borohydride bonding layer has a thickness of 11 μm. In some examples, the borohydride bonding layer has a thickness of 12 μm. In some examples, the borohydride bonding layer has a thickness of 13 μm. In some examples, the borohydride bonding layer has a thickness of 14 μm. In some examples, the borohydride bonding layer has a thickness of 15 μm. In some examples, the borohydride bonding layer has a thickness of 16 μm. In some examples, the borohydride bonding layer has a thickness of 17 μm. In some examples, the borohydride bonding layer has a thickness of 18 μm. In some examples, the borohydride bonding layer has a thickness of 19 μm. In some examples, the borohydride bonding layer has a thickness of 20 μm. In some examples, the borohydride bonding layer has a thickness of 31 μm. In some examples, the borohydride bonding layer has a thickness of 32 μm. In some examples, the borohydride bonding layer has a thickness of 33 μm. In some examples, the borohydride bonding layer has a thickness of 34 μm. In some examples, the borohydride bonding layer has a thickness of 35 μm. In some examples, the borohydride bonding layer has a thickness of 36 μm. In some examples, the borohydride bonding layer has a thickness of 37 μm. In some examples, the borohydride bonding layer has a thickness of 38 μm. In some examples, the borohydride bonding layer has a thickness of 39 μm. In some examples, the borohydride bonding layer has a thickness of 40 μm. In some examples, the borohydride bonding layer has a thickness of 41 μm. In some examples, the borohydride bonding layer has a thickness of 42 μm. In some examples, the borohydride bonding layer has a thickness of 43 μm. In some examples, the borohydride bonding layer has a thickness of 44 μm. In some examples, the borohydride bonding layer has a thickness of 45 μm. In some examples, the borohydride bonding layer has a thickness of 46 μm. In some examples, the borohydride bonding layer has a thickness of 47 μm.In some examples, the borohydride bonding layer has a thickness of 48 μm. In some examples, the borohydride bonding layer has a thickness of 49 μm. In some examples, the borohydride bonding layer has a thickness of 50 μm.

[0202] In some examples, including any of the foregoing, the borohydride adhesion layer penetrates into the buffer layer.

[0203] In some examples, including any of the foregoing, the borohydride adhesion layer infiltrates the lithium-filled garnet layer.

[0204] In some examples, including any of the foregoing, the borohydride adhesion layer penetrates into the buffer layer and the lithium-filled garnet layer.

[0205] In some examples, including any of the foregoing, the borohydride bonding layer has a density of 90% or greater of the raw material density as measured by quantitative analysis of cross-sectional SEM images, wherein the density is determined by analyzing porosity as a function of total area using SEM images and analysis software.

[0206] In some examples, including any of the foregoing, the borohydride bonding layer has a density that is 90% or greater of the density of the raw material as measured by quantitative analysis of cross-sectional SEM images.

[0207] In some examples, including any of the foregoing, the borohydride bonding layer has a melting point below 250° C. In some examples, including any of the foregoing, the borohydride bonding layer has a melting point above 250° C.

[0208] In some examples, including any of the foregoing, the SSEC further comprises a negative electrode.

[0209] In some examples, including any of the foregoing, the negative electrode is a lithium (Li) metal negative electrode.

[0210] In some examples, including any of the foregoing, the lithium-filled garnet layer contacts the negative electrode.

[0211] In certain embodiments, the composition can be a film and includes a porosity of the film as determined by SEM. For example, in one embodiment, the composition described herein can have a porosity of less than 5%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 6%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 7%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 8%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 4%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 3%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 2%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 1%. As a further example, in one embodiment, the composition described herein can have a porosity of less than 0.5%.

[0212] In some examples, the solid-state electrochemical stack further includes an adhesion layer between and in direct contact with the buffer layer and the separator layer.

[0213] In some embodiments, the present invention discloses an adhesion layer having a thickness of about 1 nm. In some embodiments, the present invention discloses an adhesion layer having a thickness of about 5 nm to about 100 nm.

[0214] In some embodiments, the present invention provides an adhesive layer having a thickness of about 100 nm to about 1000 nm. In some embodiments, the adhesive layer has a thickness of about 200 nm to about 900 nm, about 300 nm to about 800 nm, or about 500 nm.

[0215] In some examples, the present invention describes an adhesive layer having a thickness of about 1 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 2 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 3 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 4 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 5 μm to about 100 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 10 μm to about 50 μm, about 15 μm to about 40 μm, or 20 μm to about 40 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 1 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 2 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 3 μm. In some examples, the present invention describes an adhesive layer having a thickness of about 4 μm. In some examples, the present invention discloses an adhesive layer having a thickness of about 5 μm. In some examples, the present invention discloses an adhesive layer having a thickness of about 100 μm. In some examples, the present invention discloses an adhesive layer 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.

[0216] In some instances, including any of the foregoing, the median thickness of the bonding layer is greater than 100 nm and less than 10 μm. In some instances, including any of the foregoing, the crosslink density of the polymer as measured by ASTM D2765 is greater than 0.1% and less than 30%. In some instances, including any of the foregoing, the bonding layer reduces the interfacial impedance between the electrolyte separator and the positive electrode compared to the case where the bonding layer is not present. In some instances, the bonding layer reduces the interfacial impedance between the electrolyte separator and the positive electrode compared to the case where the bonding layer is not present. In some instances, when the bonding layer is located between the oxide electrolyte separator and the positive electrode and is in direct contact with them, the interfacial impedance between the oxide electrolyte separator and the positive electrode is less than 50 Ω·cm at 50°C. 2 In some examples, the interfacial impedance between the oxide electrolyte membrane and the positive electrode is less than 25Ω·cm at 50°C. 2 In some examples, the interfacial impedance between the oxide electrolyte membrane and the positive electrode is less than 10Ω·cm at 50°C. 2 In some examples, the interface resistance between the oxide electrolyte membrane and the positive electrode is less than 5Ω·cm at 50°C. 2 In some examples, the interfacial impedance between the oxide electrolyte membrane and the positive electrode is less than 5Ω·cm at 30°C. 2 In some examples, the interfacial impedance between the oxide electrolyte membrane and the positive electrode is less than 5Ω·cm at 20°C. 2In some examples, the interface impedance between the oxide electrolyte membrane and the positive electrode is less than 5Ω·cm at 10°C. 2 In some examples, the interface impedance between the oxide electrolyte membrane and the positive electrode is less than 5Ω·cm at 0°C. 2 In some embodiments, including any of the foregoing, the interfacial impedance between the electrolyte separator and the positive electrode is less than 50Ω·cm at 50°C. 2 In some embodiments, including any of the foregoing, the interfacial impedance between the electrolyte separator and the positive electrode is less than 25Ω·cm at 50°C. 2 In some embodiments, including any of the foregoing, the interfacial impedance between the electrolyte separator and the positive electrode is less than 10Ω·cm at 50°C. 2 In some embodiments, including any of the foregoing, the interfacial impedance between the electrolyte separator and the positive electrode is less than 5Ω·cm at 50°C. 2 In some examples, including any of the foregoing, the positive electrode comprises a lithium intercalation material, a lithium conversion material, or a combination thereof.

[0217] In some examples, the adhesive layer penetrates into the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 10% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 9% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 8% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 7% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 6% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 5% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 4% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 3% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 2% of the thickness of the positive electrode. In other examples, the adhesive layer penetrates into the positive electrode to a thickness of at least 1% of the thickness of the positive electrode.

[0218] In some examples, the bonding layer contacts the cathode electrolyte in the positive electrode. In some examples, the bonding layer does not creep around the electrolyte separator. In some examples, the bonding layer does not include components that volatilize and diffuse around the electrolyte separator, thereby not contacting the Li metal negative electrode.

[0219] In some examples, including any of the foregoing, the thickness of the adhesive layer penetrating into the positive electrode is at least 10% of the thickness of the positive electrode.

[0220] In some examples, including any of the foregoing, the bonding layer contacts the solid cathode electrolyte in the positive electrode.

[0221] In some examples, including any of the foregoing, the diameter of the electrolyte separator is larger than the diameter of the positive electrode.

[0222] In some examples, including any of the foregoing, the width or diameter of the electrolyte separator is greater than the width or diameter of the positive electrode, respectively.

[0223] In some examples, including any of the foregoing, the electrolyte separator has a raised edge that protects the adhesive layer or its components from creeping around the electrolyte separator.

[0224] In some examples, including any of the foregoing, the coating edge comprises a material selected from parylene, polypropylene, polyethylene, alumina, Al2O3, ZrO2, TiO2, SiO2, binary oxides, La2Zr2O7, lithium carbonate or glass, and the glass is selected from SiO2-B2O3 or Al2O3.

[0225] In some examples, the borohydride adhesion layer includes LBHI, LBHIN, [LBH-X], LBHPS, LiI, LPS, L[X]PS, or Li3PO4. In some examples, the borohydride adhesion layer includes a functionalized polymer such as PEO-LiTFSI, polypropylene carbonate (PPC)-LiTFSI, polyethylene carbonate (PEC)-LiTFSI, lithium-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS), Li-Nafion, lithium-polyphenylene sulfide (PPS), or a solid organic salt association such as ethylene carbonate (EC)-LiTFSI, dimethyl sulfide (DMS)-LiPF6, and succinonitrile (SCN)-LiBF4.

[0226] Dimensions of other components

[0227] In some examples, including any of the foregoing, the thickness of the positive electrode layer is from about 100 μm to about 1000 μm. In some examples, the thickness of the positive electrode layer is 10 μm. In some examples, the thickness of the positive electrode layer is 20 μm. In some examples, the thickness of the positive electrode layer is 30 μm. In some examples, the thickness of the positive electrode layer is 40 μm. In some examples, the thickness of the positive electrode layer is 50 μm. In some examples, the thickness of the positive electrode layer is 60 μm. In some examples, the thickness of the positive electrode layer is 70 μm. In some examples, the thickness of the positive electrode layer is 80 μm. In some examples, the thickness of the positive electrode layer is 90 μm. In some examples, the thickness of the positive electrode layer is 100 μm. In some examples, the thickness of the positive electrode layer is 110 μm. In some examples, the thickness of the positive electrode layer is 120 μm. In some examples, the thickness of the positive electrode layer is 130 μm. In some examples, the thickness of the positive electrode layer is 140 μm. In some examples, the thickness of the positive electrode layer is 150 μm. In some examples, the thickness of the positive electrode layer is 160 μm. In some examples, the thickness of the positive electrode layer is 170 μm. In some examples, the thickness of the positive electrode layer is 180 μm. In some examples, the thickness of the positive electrode layer is 190 μm. In some examples, the thickness of the positive electrode layer is 200 μm.

[0228] In some examples, including any of the foregoing, the thickness of the lithium-filled garnet layer is from about 1 μm to about 200 μm. In some examples, the thickness of the lithium-filled garnet layer is 10 μm. In some examples, the thickness of the lithium-filled garnet layer is 20 μm. In some examples, the thickness of the lithium-filled garnet layer is 30 μm. In some examples, the thickness of the lithium-filled garnet layer is 40 μm. In some examples, the thickness of the lithium-filled garnet layer is 50 μm. In some examples, the thickness of the lithium-filled garnet layer is 60 μm. In some examples, the thickness of the lithium-filled garnet layer is 70 μm. In some examples, the thickness of the lithium-filled garnet layer is 80 μm. In some examples, the thickness of the lithium-filled garnet layer is 90 μm. In some examples, the thickness of the lithium-filled garnet layer is 100 μm. In some examples, the thickness of the lithium-filled garnet layer is 110 μm. In some examples, the thickness of the lithium-filled garnet layer is 120 μm. In some examples, the thickness of the lithium-filled garnet layer is 130 μm. In some examples, the thickness of the lithium-filled garnet layer is 140 μm. In some examples, the thickness of the lithium-filled garnet layer is 150 μm. In some examples, the thickness of the lithium-filled garnet layer is 160 μm. In some examples, the thickness of the lithium-filled garnet layer is 170 μm. In some examples, the thickness of the lithium-filled garnet layer is 180 μm. In some examples, the thickness of the lithium-filled garnet layer is 190 μm. In some examples, the thickness of the lithium-filled garnet layer is 200 μm.

[0229] In some embodiments, including any of the foregoing, the separator layer in the solid-state electrochemical stack described herein is rectangular. In another embodiment, the cathode layer in the solid-state electrochemical stack described herein is rectangular. In a different embodiment, the separator layer in the solid-state electrochemical stack described herein is circular. In one embodiment, the cathode layer in the solid-state electrochemical stack described herein is circular.

[0230] In some examples, including any of the foregoing, the geometric surface area of ​​the positive electrode layer and the geometric surface area of ​​the separator layer are substantially the same.

[0231] In some examples, including any of the foregoing, the length of one edge of the positive electrode layer is from 2 cm to 30 cm. In some examples, the length of one edge of the positive electrode 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 some examples, the length of one edge of the separator layer is from 2 cm to 30 cm. In some examples, the length of one edge 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.

[0232] In certain embodiments, the present patent provides a composite material containing lithium-filled garnet and LBHI, wherein the LBHI fills at least 90% of the through-holes and / or surface holes of the lithium-filled garnet, and wherein the LBHI can be a composition having A·(LiBH4)·B·(LiX)·C·(LiNH2), where 3 ≤ A ≤ 6, 2 ≤ B ≤ 5, and 0 ≤ C ≤ 9, and X is a halide.

[0233] In some examples, including any of the foregoing, the electrolyte separator is characterized 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, 6 ≤ h ≤ 15; and the subscripts x and h and the coefficient y are selected such that the electrolyte separator is charge-neutral.

[0234] In some examples, including any of the foregoing, the electrolyte separator is doped with Ga, Nb, or Ta.

[0235] In some examples, including any of the foregoing, the electrolyte membrane has a surface roughness of about 0.01 μm to 10 μm on at least one surface. In some examples, including any of the foregoing, the electrolyte membrane has a surface roughness of about 0.01 μm to 5 μm on at least one surface. In some examples, including any of the foregoing, the electrolyte membrane has a surface roughness of about 0.01 μm to 2 μm on at least one surface. In some examples, including any of the foregoing, the density of the electrolyte membrane is greater than 95% of its theoretical density. In some examples, including any of the foregoing, the density of the electrolyte membrane is greater than 95% of the theoretical density measured by scanning electron microscopy (SEM). In some examples, including any of the foregoing, the density of the electrolyte membrane is greater than 95% of the theoretical density measured by Archimedes' method. In some examples, including any of the foregoing, the surface flatness of the electrolyte membrane is 0.1 μm to about 50 μm.

[0236] In some examples, including any of the foregoing, the lithium intercalation material is selected from the group consisting of 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, LiMn 2- a Ni a O4, wherein a is 0 to 2, or LiMPO4, wherein M is Fe, Ni, Co and Mn.

[0237] In some examples, including any of the foregoing, the lithium conversion material is selected from the group consisting of FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials and their alloys and combinations.

[0238] In some examples, including any of the foregoing, the binding layer permeates the positive electrode.

[0239] In some examples, this patent discloses an electrochemical stack wherein the thickness of the electrolyte separator is between about 10 nm and 50 μm; the thickness of the bonding layer is between about 1 μm and 20 μm; and the thickness of the positive electrode excluding the current collector is between about 5 μm and 150 μm.

[0240] In some examples, 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 examples, the electrolyte separator has a surface roughness of about 0.1 μm to 5 μm on at least one surface. In other examples, the electrolyte separator has a surface roughness of about 0.1 μm to 2 μm on at least one surface. In some examples, the electrolyte has a surface roughness of about 0.1 μm to 10 μm at the surface interfacing with the electrolyte separator and the Li metal negative electrode.

[0241] In some instances, the density of the electrolyte separator is greater than 95% of its theoretical density. In other instances, the density of the electrolyte separator is greater than 95% of its theoretical density determined by scanning electron microscopy (SEM). In certain instances, the density of the electrolyte separator is greater than 95% of its theoretical density measured by the Archimedean method. In some instances, the surface flatness of the electrolyte separator is 0.1 μm to about 50 μm. In some instances, the lithium salt in the bonding layer is selected from LiPF6, LiBOB, LiTFSi, LiBF4, LiClO4, LiAsF6, LiFSI, LiI or LiBF4. In certain instances, the lithium salt in the bonding layer is selected from LiPF6, LiBOB or LFTSi. In certain instances, the lithium salt in the bonding layer is LiPF6 with a concentration of 0.5M to 2M. In certain instances, the lithium salt in the bonding layer is LiTFSI with a concentration of 0.5M to 2M. In certain examples, the concentration of the lithium salt in the bonding layer is 0.01M to 10M.

[0242] In some examples, the positive electrode includes a lithium intercalation material, a lithium conversion material, or both. In some examples, the lithium intercalation material is selected from lithium nickel cobalt manganese 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 O4 (wherein a is 0 to 2) or LiMPO4, where M is Fe, Ni, Co or Mn. In other cases, the lithium conversion material is selected from FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials and alloys thereof or combinations thereof. In other embodiments, the conversion material is doped with other transition metal fluorides or oxides.

[0243] In some examples, the positive electrode comprises an electronically conductive source of carbon.

[0244] In some examples, the positive electrode comprises a solid cathode electrolyte and a lithium insertion material or a lithium conversion material; wherein the cathode electrolyte and the lithium insertion material or the lithium conversion material each independently have a d 50 In some examples, the positive electrode comprises a solid cathode electrolyte and a lithium intercalation material or a lithium conversion material. The cathode electrolyte and the lithium intercalation material or the lithium conversion material each independently have a particle size of about 0.1 μm to 15 μm. 50 Particle size. In some examples, the bonding layer is characterized by a thickness of about 1 nm to about 5 μm. In some examples, the lithium negative electrode is characterized by a thickness of about 10 nm to about 50 μm. In some examples, the oxide separator is characterized by a thickness of about 0.1 μm to about 150 μm. In some examples, the oxide separator is characterized by a thickness of about 10 μm to about 50 μm.

[0245] In some examples, the coating edge comprises a coating selected from parylene, epoxy, polypropylene, polyethylene, alumina, Al2O3, ZrO2, TiO, SiO2, binary oxides, lithium carbonates, La2Zr2O7, or glass, wherein the glass is selected from SiO2-B2O3 or Al2O3. In some examples, the thickness of the electrolyte separator edge tapers to protect the adhesive layer from creeping around the electrolyte separator. In some examples, the separator electrolyte edge has been selectively treated with high temperature (e.g., laser beam) or chemicals (e.g., plasma, water, acid, etc.).

[0246] In some examples, the present invention provides an electrochemical stack having the following structure: an electrolyte separator having a thickness of about 10 to 20 μm; an adhesive layer having a thickness of about 1 μm to 5 μm; and a positive electrode, excluding the current collector, having a thickness of about 5 μm to 150 μm. In some embodiments, the present invention provides an electrochemical stack having the following structure: an electrolyte separator having a thickness of about 10 to 50 μm; an adhesive layer having a thickness of about 1 μm to 5 μm; and a positive electrode, excluding the current collector, having a thickness of about 5 μm to 200 μm. In some examples, the present invention provides an electrochemical stack having the following structure: an electrolyte separator having a thickness of about 10 to 100 μm; an adhesive layer having a thickness of about 1 μm to 5 μm; and a positive electrode, excluding the current collector, having a thickness of about 5 μm to 200 μm.

[0247] method

[0248] In some examples, the present patent provides a method for manufacturing an electrochemical cell, the method comprising: providing a first slurry comprising an active material, a cathode electrolyte, and a solvent; depositing the first slurry onto a current collector; drying the first slurry; providing a second slurry comprising a solid buffer that conducts a single ion; depositing the second slurry onto a substrate; drying the second slurry; transferring the dried second slurry onto the first slurry after drying to form a stack; applying pressure and heat to the stack; providing a solid separator; depositing a borohydride layer onto the solid separator; combining 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.

[0249] In some examples, including any of the foregoing, the solid loading is at least 60 wt%.

[0250] In some examples, including any of the foregoing, the buffer is LSTPS.

[0251] In some examples, the buffer layer is manufactured by a calendaring process, wherein the pressure is at least about 100 psi, 500 psi, 1000 psi, 2000 psi, or greater. In some examples, the buffer layer is manufactured under elevated temperature conditions, such as above about 40° C., 50° C., 75° C., 100° C., 120° C., 140° C., or greater. In some examples, the buffer layer is heated to a temperature greater than about 100° C.

[0252] In some examples, including any of the foregoing, the pressure is applied uniaxially.

[0253] In certain embodiments, this patent discloses a method for preparing a thin film comprising an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, the method comprising a) preparing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composite material, b) providing a molten mixture comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein 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 in the molten mixture; d) removing the substrate; and e) cooling the substrate to room temperature. In some examples, the substrate is a current collector. In some examples, the substrate is a solid electrolyte. In some examples, the substrate is a lithium-filled garnet.

[0254] In certain embodiments, the present patent provides a method for coating a conductive lithium ion separator electrolyte, the method comprising: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and 3≤A≤6, 2≤B≤5, and 0≤C≤9. For example, in one embodiment, the method for coating a conductive lithium ion separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is fluorine, and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte includes: a) providing a separator electrolyte; b) pressing a composition A·(LiBH4)·B·(LiX)·C·(LiNH2) on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is bromine and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte includes: a) providing a separator electrolyte; b) pressing a composition A·(LiBH4)·B·(LiX)·C·(LiNH2) on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is chlorine and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI, wherein X is iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI, wherein X is fluorine, bromine, and chlorine, and 3≤A≤6, 2≤B≤5, and 0≤C≤9.As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, wherein X is fluorine, bromine, and iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9, on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, wherein X is fluorine, chlorine, and iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9, on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. As a further example, in one embodiment, a method of coating a conductive lithium ion separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is bromine, chlorine, and iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9.

[0255] In certain embodiments, the present patent provides a method for coating a conductive lithium ion separator electrolyte, the method comprising: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X can be fluorine, bromine, chlorine, iodine, or a combination thereof, and 3≤A≤6, 2≤B≤5, and 0≤C≤9. For example, in one embodiment, the method for coating a conductive lithium ion separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is fluorine, and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte includes: a) providing a separator electrolyte; b) pressing a composition A·(LiBH4)·B·(LiX)·C·(LiNH2) on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is bromine and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte includes: a) providing a separator electrolyte; b) pressing a composition A·(LiBH4)·B·(LiX)·C·(LiNH2) on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is chlorine and 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI, wherein X is iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280° C. and a pressure of 10-2000 PSI, wherein X is fluorine, bromine, and chlorine, and 3≤A≤6, 2≤B≤5, and 0≤C≤9.As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, wherein X is fluorine, bromine, or iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9, on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. As a further example, in one embodiment, a method for coating a lithium ion conductive separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition, wherein X is fluorine, chlorine, or iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9, on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI. As a further example, in one embodiment, a method of coating a conductive lithium ion separator electrolyte comprises: a) providing a separator electrolyte; b) pressing an A·(LiBH4)·B·(LiX)·C·(LiNH2) composition on at least one surface of the separator at a temperature of 100-280°C and a pressure of 10-2000 PSI, wherein X is bromine, chlorine, or iodine, and wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9.

[0256] In certain embodiments, the temperature in the method is below the melting point (T m ), and is about 0.8T m , where T m Expressed in Kelvin (K). In certain embodiments, the method further comprises c) maintaining the pressure between the composition and the membrane for 1 to 300 minutes.

[0257] In certain embodiments, the method further includes d) cooling the coated conductive lithium ion separator electrolyte under pressure for 10-1000 minutes. In certain embodiments, the method further includes d) cooling the coated conductive lithium ion separator electrolyte under pressure for 10-1000 minutes to room temperature. In certain embodiments, a method for coating a conductive lithium ion separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and a precursor A·(LiBH4)·B·(LiX)·C·(LiNH2); c) depositing the mixture on the separator by spray coating, spin coating, dip coating, slot coating, gravure coating, or micro-gravure coating. For example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and a precursor A·(LiBH4)·B·(LiX)·C·(LiNH2); c) depositing the mixture on the separator by spray coating. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a solvent and a mixture of A·(LiBH4)·B·(LiX)·C·(LiNH2) precursors; c) depositing the mixture on the separator by spin coating. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a solvent and a mixture of A·(LiBH4)·B·(LiX)·C·(LiNH2) precursors; c) depositing the mixture on the separator by dip coating. As a further example, in one embodiment, a method for coating a conductive lithium ion separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a solvent and a mixture of A·(LiBH4)·B·(LiX)·C·(LiNH2) precursors; c) depositing the mixture on the separator by slot 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 a precursor A·(LiBH4)·B·(LiX)·C·(LiNH2); c) depositing the mixture on a separator by gravure coating. As a further example, in one embodiment, a method for coating a lithium-conductive separator electrolyte is provided, the method comprising: a) providing a lithium-stable separator electrolyte; b) providing a mixture of a solvent and a precursor A·(LiBH4)·B·(LiX)·C·(LiNH2); c) depositing the mixture on a separator by micro-gravure coating.

[0258] In certain embodiments, the solvent in the method is selected from tetrahydrofuran, diethyl ether, methanol, and ethanol. For example, in one embodiment, the solvent in the method is tetrahydrofuran. As another example, in one embodiment, the solvent in the method is diethyl ether. As another example, in one embodiment, the solvent in the method is ethanol. As another example, in one embodiment, the solvent in the method is methanol.

[0259] In certain embodiments, the lithium-stable separator of the method has defects on the surface.

[0260] In certain embodiments, a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, 3≤A≤6, 2≤B≤5, 0≤C≤9, and the XRD pattern thereof has characteristic peaks at approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6° 2θ. For example, in one embodiment, a composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is fluorine, 3≤A≤6, 2≤B≤5, 0≤C≤9, and the XRD pattern thereof has characteristic peaks at approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6° 2θ. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is bromine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is chlorine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is iodine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is fluorine, bromine, and chlorine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is fluorine, bromine and iodine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3° and 29.6°.As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is fluorine, chlorine, and iodine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°. As a further example, in one embodiment, a composition containing A·(LiBH4)·B·(LiX)·C·(LiNH2) is provided, wherein X is bromine, chlorine, and iodine, and 3≤A≤6, 2≤B≤5, 0≤C≤9, and its XRD pattern has characteristic peaks at 2θ of approximately 14.5°, 15.5°, 16.4°, 19.3°, and 29.6°.

[0261] In some embodiments, including any of the foregoing, the polymer adhesive layer should be as thin as possible, for example, less than 5 μm, less than 2 μm or less than 1 μm. The adhesive layer can be a film deposited from a solution in DMF, NMP, THF, toluene, acetonitrile or a similar solvent using spraying, gravure coating, slot coating, dip coating, spin coating and similar techniques. The adhesive layer can also be deposited from a melt at a temperature above 50°C. Free-standing films can also be pressed onto the cathode and separator at low temperatures (less than 120°C) and low pressure (less than 1000 psi).

[0262] In certain embodiments, the molten LBHXN is applied by spin coating. This embodiment uses a spin coater with heating capabilities. The powder is first applied to the substrate to be coated. The spin coater is heated to a temperature equal to or above the melting point of the LBHXN. After melting, the substrate is rotated at a speed of 100-5000 rpm while heating. It should be understood that the rotation speed is closely related to the thickness of the coating. After the rotation is stopped, the second layer can be laminated under a pressure of 10-2000 pounds per square inch (PSI), and the second layer is a solid cathode film or another conductive lithium ion separator (the same or different Li ion conductor as the first substrate). Whether to heat is optional. After the laminated material is cooled to room temperature, the substrate, LBHXN and top layer will be firmly bonded together and will not fall apart or crack unless damaged.

[0263] In some examples, the substrate can be spin coated at a speed of at least about 100 rpm, 500 rpm, 1000 rpm, 2000 rpm, 3000 rpm, or more.

[0264] In some examples, the present patent provides a method for manufacturing an electrochemical device, comprising the following steps: providing a positive electrode comprising an electrochemically active material and a solid cathode electrolyte; providing a solid cathode electrolyte comprising a sulfide single ion conductor; providing an electrolyte separator comprising a lithium-filled 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 the lithium metal negative electrode and the bonding layer; the bonding layer is between and in contact with the electrolyte separator and the positive electrode; and pressing the stack at low temperature and low pressure to bond, adhere or laminate the bonding layer to the positive electrode and the electrolyte separator.

[0265] In some examples, the pressure used during the formation of the bonding layer, the buffer layer, the positive electrode 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 examples, the pressure used during the formation of the bonding layer, the buffer layer, the positive electrode layer, or any combination thereof is at least 1000 kPa, 10,000 kPa, 100,000 kPa, 1 MPa, 10 MPa, or 100 MPa.

[0266] In some examples, the pressure used during cycling of the electrochemical cells described herein is greater than atmospheric pressure and is 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.

[0267] In some examples, including any of the foregoing, the pressure is less than 1000 PSI. In some examples, including any of the foregoing, the pressure is less than 300 PSI. In some examples, including any of the foregoing, the temperature is less than 180°C. In some examples, including any of the foregoing, the temperature is less than 120°C. In some examples, including any of the foregoing, the process is performed in a clean room. In some examples, including any of the foregoing, the dew point of the clean room is less than -20°C or less than -40°C. In some examples, including any of the foregoing, the clean room is a Class 10,000 clean room.

[0268] In some embodiments, the present patent describes a method for making an electrochemical device, comprising: providing a positive electrode comprising an electrochemically active material and a solid cathode electrolyte; providing a solid cathode electrolyte comprising a sulfide single ion conductor; providing an electrolyte separator comprising a lithium-filled garnet; providing a bonding layer comprising a polymer and a lithium salt; providing a stack wherein the electrolyte separator is in contact with the bonding layer; the bonding layer is located between and in contact with the electrolyte separator and the positive electrode; and pressing the stack at low temperature and low pressure to bond, adhere, or laminate the bonding layer to the positive electrode and the electrolyte separator.

[0269] In some examples, including any of the foregoing, the pressure is less than 1000 PSI. In some examples, including any of the foregoing, the pressure is less than 300 PSI.

[0270] In some examples, including any of the foregoing, the temperature is less than 180° C. In some examples, including any of the foregoing, the temperature is less than 120° C.

[0271] In some examples, including any of the foregoing, the process is performed in a cleanroom. In some examples, including any of the foregoing, the dew point of the cleanroom is less than -20°C or less than -40°C. In some examples, including any of the foregoing, the cleanroom is rated Class 10,000 or higher.

[0272] In some examples, during processing, the borohydride bonding layer is heated to a temperature at which it melts or partially melts to form intimate contact with the lithium-filled garnet layer and the buffer layer in contact with the positive electrode.

[0273] In some examples, during processing, the borohydride bonding layer melts or partially melts to come into intimate contact with the lithium-filled garnet layer and the positive electrode mixed with the buffer.

[0274] In some embodiments, this patent proposes a multilayer adhesive layer structure. In some embodiments, this patent proposes a multilayer "oxide-sulfide interface layer" structure, i.e., a multilayer adhesive layer. In some embodiments, the adhesive layer is kinetically stable to both the oxide and the sulfide. In some embodiments, the adhesive layer promotes or maintains interfacial contact between the oxide and the sulfide. In some embodiments, the adhesive layer fills the gap between the oxide and the sulfide, improving ionic conductivity therebetween.

[0275] In some examples, the borohydride adhesion layer is spin-coated onto a lithium-filled garnet layer, i.e., shielding the high-voltage positive electrode. In some examples, the borohydride adhesion layer is melt-cast onto a lithium-filled garnet layer. In some examples, the borohydride adhesion layer is melt-cast onto a lithium-filled garnet layer.

[0276] In some examples, the present patent provides a method for producing a solid-state electrochemical stack, the method comprising: (a) pouring a first slurry containing a sulfide solid electrolyte powder onto a first substrate to form a first layer; (b) pouring a second slurry containing a sulfide solid electrolyte powder and a positive electrode active powder onto a second substrate to form a second layer; and (c) calendering the first layer and the second layer, wherein the first layer and the second layer are in contact with each other.

[0277] In one set of embodiments, prior to step (a), the method includes providing a first substrate. In this case, prior to step (a), the method includes providing a first slurry containing sulfide solid electrolyte powder. In this case, prior to step (b), the method includes providing a second substrate. In this case, prior to step (b), the method includes providing a second slurry containing sulfide solid electrolyte powder and positive electrode active powder. In some cases, the method includes step (f) of contacting the second layer with the first layer.

[0278] Additional embodiments

[0279] In one embodiment, the present patent provides a solid-state electrochemical stack comprising: (a) a positive electrode layer comprising a positive electrode active material and a sulfide cathode electrolyte, wherein the volume porosity of the positive electrode layer is less than 15%; (b) a buffer layer comprising a sulfide electrolyte in contact with the positive electrode layer, the volume porosity of the buffer layer being less than 15%; (c) a separator layer comprising lithium-filled garnet and LPSX, the volume porosity of the separator layer being less than 10%; the buffer layer being between the positive electrode layer and the separator layer.

[0280] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte and sulfide electrolyte are solid.

[0281] In some embodiments, including any of the foregoing, the buffer layer substantially covers the positive electrode layer.

[0282] In some embodiments, including any of the foregoing, the buffer layer covers the positive electrode layer.

[0283] In some embodiments, including any of the foregoing, the buffer layer is uniform and dense.

[0284] In some embodiments, including any of the foregoing, the buffer layer has a uniform thickness.

[0285] In some embodiments, including any of the foregoing, the buffer layer is in direct contact with the positive electrode layer and the separator layer.

[0286] In some embodiments, including any of the foregoing, the adhesive layer is between and in direct contact with the buffer layer and the separator layer.

[0287] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is a sulfide single ion conductor.

[0288] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is an electrolyte comprising lithium (Li), phosphorus (P), and sulfur (S).

[0289] In some embodiments, including any of the foregoing, the cathode electrolyte comprises iodine (I).

[0290] In some embodiments, including any of the foregoing, the cathode electrolyte comprises chlorine (Cl), bromine (Br), iodine (I), or a combination thereof.

[0291] In some embodiments, including any of the foregoing, the cathode electrolyte comprises a member selected from the group consisting of tin (Sn), germanium (Ge), arsenic (As), silicon (Si), and combinations thereof.

[0292] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is selected from LPSI, LSTPS, LSPSC1, LBHI, and LPS.

[0293] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is LSTPS.

[0294] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is LPSI.

[0295] In some embodiments, including any of the foregoing, the sulfide electrolyte is a sulfide single ion conductor.

[0296] In some embodiments, including any of the foregoing, the positive electrode layer comprises a positive electrode active material having a mass loading of about 75% to about 90%.

[0297] In some embodiments, including any of the foregoing, the positive electrode active material comprises a lithium insertion material, a lithium conversion material, or both.

[0298] In some embodiments, including any of the foregoing, the positive electrode active material comprises a lithium intercalation material; wherein the intercalation material is selected from 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-aNi a O4, wherein a is 0 to 2 or LiMPO4, wherein M is Fe, Ni, Co or Mn.

[0299] In some embodiments, including any of the foregoing, the positive electrode active material comprises a lithium conversion material; the lithium conversion material is selected from FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2 materials and their alloys or combinations.

[0300] In some embodiments, including any of the foregoing, the embedding material is NCA.

[0301] In some embodiments, including any of the foregoing, the embedding material is NMC.

[0302] In some embodiments, including any of the foregoing, the solid-state electrochemical stack further comprises an adhesion layer.

[0303] In some embodiments, including any of the foregoing, the adhesion layer comprises a borohydride composition.

[0304] In some embodiments, including any of the foregoing, the buffer layer is between and in direct contact with the positive electrode layer and the borohydride layer, and the borohydride layer is between and in direct contact with the buffer layer and the separator layer.

[0305] In some embodiments, including any of the foregoing, the borohydride composition is represented by the formula:

[0306] A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is selected from fluorine (F), bromine (Br), chloride (Cl), iodine (I) and combinations thereof, wherein 3≤A≤6, 2≤B≤5 and 0≤C≤9.

[0307] In some embodiments, including any of the foregoing, the borohydride composition is represented by the formula A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is selected from fluorine (F), bromine (Br), chlorine (Cl), iodine (I) and combinations thereof, wherein 3≤A≤6, 2≤B≤5 and 3≤C≤9.

[0308] In some embodiments, including any of the foregoing, the borohydride composition is represented by the formula: A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is selected from fluorine (F), bromine (Br), chlorine (Cl), iodine (I) and combinations thereof, wherein 3≤A≤6, 2≤B≤5 and 3≤C≤6.

[0309] In some embodiments, including any of the foregoing, the borohydride composition is selected from one of the following formulas: 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2.

[0310] In some embodiments, including any of the foregoing, the adhesion layer further comprises LiI, LPS, LXPS, Li3PO4, or a combination thereof.

[0311] In some embodiments, including any of the foregoing, the solid-state electrochemical stack includes (d) a negative electrode current collector in direct contact with the separator layer.

[0312] In some embodiments, including any of the foregoing, the solid-state electrochemical stack includes (e) a positive electrode current collector in direct contact with the positive electrode layer.

[0313] In some embodiments, including any of the foregoing, the solid-state electrochemical stack includes (d) a negative electrode current collector and (e) a negative electrode, wherein the (e) negative electrode is between and in direct contact with the separator layer and the negative electrode current collector.

[0314] In some embodiments, including any of the foregoing, the negative electrode is a lithium (Li) metal electrode layer.

[0315] In some embodiments, including any of the foregoing, at least one current collector comprises an alloy selected from carbon (C) coated nickel (Ni), nickel (Ni), copper (Cu), aluminum (Al), stainless steel, and combinations thereof.

[0316] In some embodiments, including any of the foregoing, the negative electrode current collector comprises a material selected from the group consisting of carbon (C)-coated nickel (Ni), nickel (Ni), copper (Cu), alloys thereof, or combinations thereof.

[0317] In some embodiments, including any of the foregoing, the positive current collector layer comprises a material selected from the group consisting of carbon (C)-coated aluminum and aluminum.

[0318] In some embodiments, including any of the foregoing, the negative electrode current collector layer is carbon-coated Ni.

[0319] In some embodiments, including any of the foregoing, the membrane layer is rectangular.

[0320] In some embodiments, including any of the foregoing, the positive electrode layer is rectangular.

[0321] In some embodiments, including any of the foregoing, the diaphragm layer is circular.

[0322] In some embodiments, including any of the foregoing, the geometric surface area of ​​the positive electrode layer and the geometric surface area of ​​the separator layer are substantially the same.

[0323] In some embodiments, including any of the foregoing, a length of one edge of the positive electrode layer is 2 cm to 30 cm.

[0324] In some embodiments, including any of the foregoing items, the length of one edge of the diaphragm layer is 2 cm to 30 cm.

[0325] In some embodiments, including any of the foregoing, the positive electrode layer has a diameter of 10 cm.

[0326] In some embodiments, including any of the foregoing, the diameter of the diaphragm layer is 10 cm.

[0327] In some embodiments, including any of the foregoing, the positive electrode layer comprises a percolating network of ion conductors.

[0328] In some embodiments, including any of the foregoing, the separator layer comprises a percolating network of ion conductors.

[0329] In some embodiments, including any of the foregoing, the membrane layer comprises a polymer.

[0330] In some embodiments, including any of the foregoing, the positive electrode layer comprises carbon at a mass loading of about 0 to about 1%.

[0331] In some embodiments, including any of the foregoing, the carbon having a mass loading of about 0 to about 1% is C65 or vapor grown carbon fiber (VGCF).

[0332] In some embodiments, including any of the foregoing, the positive electrode layer comprises a binder having a mass loading of about 0 to about 2.5%.

[0333] In some embodiments, including any of the foregoing, the binder at a mass loading of about 0 to about 2.5% comprises a binder selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (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 fluoride hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, α-polyolefin, α-olefin, ethylene α-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.

[0334] In some embodiments, including any of the foregoing, the thickness of the positive electrode layer is from about 10 μm to about 500 μm.

[0335] In some embodiments, including any of the foregoing items, the thickness of the positive electrode layer is 100 μm to about 500 μm.

[0336] In some embodiments, including any of the foregoing, the isolation layer has a thickness of about 1 μm to about 200 μm.

[0337] In some embodiments, including any of the foregoing, the thickness of the positive electrode current collector layer is from about 3 μm to about 100 μm.

[0338] In some embodiments, including any of the foregoing, the thickness of the positive electrode current collector layer is about 15 μm.

[0339] In some embodiments, including any of the foregoing, the thickness of the negative electrode current collector layer is from about 3 μm to about 100 μm.

[0340] In some embodiments, including any of the foregoing, the thickness of the positive electrode current collector layer is about 15 μm.

[0341] In some embodiments, including any of the foregoing, the tab on the positive or negative current collector has a thickness of about 5 μm to about 100 μm.

[0342] In some embodiments, including any of the foregoing, the porosity of the positive electrode layer is less than 1% v / v.

[0343] In some embodiments, including any of the foregoing, the porosity of the buffer layer is less than 1% v / v.

[0344] In some embodiments, including any of the foregoing, the porosity of the positive electrode layer is at least 0.01% v / v.

[0345] In some embodiments, including any of the foregoing, the porosity of the buffer layer is at least 0.01% v / v.

[0346] In some embodiments, including any of the foregoing, the separator layer contains a lithium-filled garnet having the empirical formula Li7La3Zr2O 12 -xAl2O3, where x is a rational number and 0 ≤ x ≤ 1.

[0347] In some embodiments, including any of the foregoing, the separator 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 between 2 and 4; x is a rational number from 1 to 3; y is a rational number between 10 and 14; 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.

[0348] In some embodiments, including any of the foregoing, 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.

[0349] In some embodiments, including any of the foregoing, the separator layer comprises Li7La3Zr2O 12 ·Al2O3 or Li7La3Zr2O 12 ·0.35Al2O3.

[0350] In some embodiments, including any of the foregoing, the lithium-filled garnet is doped with Nb, Ga, and / or Ta.

[0351] In another embodiment, the present patent provides a solid-state electrochemical cell (SSEC) comprising: (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; (b) a solid buffer that conducts a single ion; (c) a borohydride binding layer; and (d) a lithium-filled garnet layer. The buffer is mixed within the positive electrode layer, is in contact with the positive electrode layer, or is a layer comprising both; and the borohydride binding layer is between and in contact with the lithium-filled garnet layer and (i) the positive electrode layer in which the buffer is mixed, or (ii) the buffer layer in contact with the positive electrode.

[0352] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is mixed within the positive electrode layer.

[0353] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is a layer in contact with the positive electrode layer.

[0354] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is mixed within the positive electrode layer and serves as a layer in contact with the positive electrode layer.

[0355] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer layer can avoid direct contact between the borohydride bonding layer and the positive electrode layer.

[0356] In some embodiments, including any of the foregoing, the thickness of the positive electrode layer is from about 100 μm to about 1000 μm.

[0357] In some embodiments, including any of the foregoing, the buffer layer has a thickness of about 0.5 μm to about 50 μm.

[0358] In some embodiments, including any of the foregoing, a solid buffer mixture that conducts a single ion is infiltrated into the positive electrode layer, and the penetration depth is about 1 μm to about 50 μm from the edge within the positive electrode layer, wherein the edge is the edge at the junction of the positive electrode layer and the buffer layer or the borohydride bonding layer.

[0359] In some embodiments, including any of the foregoing, the lithium-filled garnet layer has a thickness of about 1 μm to about 200 μm.

[0360] In some embodiments, including any of the foregoing, the borohydride adhesion layer has a thickness of about 0.5 μm to about 50 μm.

[0361] In some embodiments, including any of the foregoing, the borohydride adhesion layer penetrates into the buffer layer.

[0362] In some embodiments, including any of the foregoing, the borohydride adhesion layer infiltrates into the lithium-filled garnet layer.

[0363] In some embodiments, including any of the foregoing, the density of the borohydride bonding layer is 90% or greater of the density of the feedstock.

[0364] In some embodiments, including any of the foregoing, the borohydride bonding layer has a volumetric porosity of less than 10%.

[0365] In some embodiments, including any of the foregoing, the borohydride adhesion layer has a melting point below 250°C.

[0366] In some embodiments, including any of the foregoing, the borohydride adhesion layer has a melting point greater than 250°C.

[0367] In some embodiments, including any of the foregoing, the solid-state electrochemical stack comprises a negative electrode.

[0368] In some embodiments, including any of the foregoing, the negative electrode is a lithium (Li) metal negative electrode.

[0369] In some embodiments, including any of the foregoing, the lithium-filled garnet layer is in contact with a negative electrode.

[0370] In some embodiments, including any of the foregoing, the buffer layer comprises 0.01 to 10% by weight of the binder.

[0371] Embodiment 120: The SSEC of embodiment 120, wherein the binder is a polymer and does not conduct electrons or Li ions.

[0372] In some embodiments, including any of the foregoing, the buffer layer comprises 10% or less of an organic polymer by volume.

[0373] In some embodiments, including any of the foregoing, the polymer is selected from polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (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 α-olefin copolymer, polyvinylidene fluoride 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.

[0374] In some embodiments, including any of the foregoing, the buffer layer or buffer component does not include an organic polymer.

[0375] In some embodiments, including any of the foregoing, the positive electrode potential is shielded from the potential of the lithium-filled garnet layer.

[0376] In some embodiments, including any of the foregoing, the potential of the active material in the positive electrode is shielded from the potential of the lithium-filled garnet layer.

[0377] In some embodiments, including any of the foregoing, the active material is coated.

[0378] In some embodiments, including any of the foregoing, the coated active material has 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.

[0379] In some embodiments, including any of the foregoing, the active material is uncoated.

[0380] In some embodiments, including any of the foregoing, the positive electrode comprises a lithium insertion material, a lithium conversion material, or both.

[0381] In some embodiments, including any of the foregoing, the intercalation material is selected from 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.

[0382] In some embodiments, including any of the foregoing, the lithium conversion material is selected from FeF2, NiF2, FeO x F 3-2x , FeF3, MnF3, CoF3, CuF2, alloys thereof or combinations thereof.

[0383] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte and the single-ion conducting solid buffer comprise the same type of material.

[0384] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid buffer, or both, are selected from LSS, SLOPS, LSTPS, LSTPSC1, SLOBS, LATS, and LPS+X, wherein X is selected from Cl, I, Br, and combinations thereof.

[0385] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid buffer, or both, are selected from LPSI, LXPS, LSTPS, LSPSCl, LPCS1, LSPSBr, and LPSBr.

[0386] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid buffer, or both, are selected from x.Li2S:y.SiS2, wherein x and y are each independently 0 to 1, wherein x+y=1.

[0387] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or single-ion conducting solid buffer, or both, is selected from the group consisting of LSS, LGPS, LSTPS, and LSPS.

[0388] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the solid buffer conducting a single ion, or both, are characterized by one of the following formulas: 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, where 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 q , where 2 ≤ m ≤ 6, 0 ≤ n ≤ 1, 0 ≤ p ≤ 1, 2 ≤ q ≤ 6; or a mixture of (Li2S):(P2S5) and LiI in a molar ratio of about 10:1 to about 6:4, where the ratio of [(Li2S):(P2S5)]:LiI is 95:5 to 50:50; LPS + X, where X is selected from Cl, I, or Br; vLi2S + wP2S5 + yLiX; vLi2S + wSiS2 + yLiX or vLi2S + wB2S3 + yLiX.

[0389] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte comprises LSTPS.

[0390] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is characterized by 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, 2 ≤ e ≤ 12.

[0391] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is characterized by the following 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, 2 ≤ e ≤ 12.

[0392] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer comprises LSTPS.

[0393] In some embodiments, including any of the foregoing, the borohydride adhesion layer comprises lithium borohydride, sodium borohydride, or potassium borohydride.

[0394] In some embodiments, including any of the foregoing, the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiNH2.

[0395] In some embodiments, including any of the foregoing, any one or more of the lithium borohydride, sodium borohydride, or potassium borohydride is doped with LiI.

[0396] In some embodiments, including any of the foregoing, any one or more of the lithium borohydride, sodium borohydride, or potassium borohydride are doped with LiNH2 and LiI.

[0397] In some embodiments, including any of the foregoing, the borohydride adhesion layer comprises a borohydride composition of A(LiBH4)(1-A)(P2S5), wherein 0.05≤A≤0.95.

[0398] In some embodiments, including any of the foregoing, 0.5 <A<0.95。

[0399] In some embodiments, including any of the foregoing, A is 0.85, 0.9, or 9.95.

[0400] In some embodiments, including any of the foregoing, the borohydride adhesion layer comprises 0.9(LiBH4)0.1(P2S5).

[0401] In some embodiments, including any of the foregoing, the borohydride adhesion layer comprises a borohydride composition comprising A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9.

[0402] In some embodiments, including any of the foregoing, 3≤A≤6, 2≤B≤5, and 3≤C≤9.

[0403] In some embodiments, including any of the foregoing, X is bromine, chlorine, iodine, or a combination thereof.

[0404] In some embodiments, including any of the foregoing, X is chloro.

[0405] In some embodiments, including any of the foregoing, X is bromo.

[0406] In some embodiments, including any of the foregoing, X is iodine.

[0407] In some embodiments, including any of the foregoing, 3≤A≤6, 3≤B≤5, and 3≤C≤9

[0408] In some embodiments, including any of the foregoing, 4 ≤ A ≤ 6, 4 ≤ B ≤ 5, and 4 ≤ C ≤ 6

[0409] In some embodiments, including any of the foregoing, the borohydride adhesive layer comprises a borohydride composition which is 3LiBH4·2LiCl·3LiNH2 or 3LiBH4·4LiCl·9LiNH2.

[0410] In some embodiments, including any of the foregoing, the borohydride adhesive layer comprises a borohydride composition which is 3LiBH4·2LiBr·3LiNH2 or 3LiBH4·4LiBr·9LiNH2..

[0411] In some embodiments, including any of the foregoing, the borohydride adhesive layer comprises a borohydride composition which is 3LiBH4·2LiI·3LiNH2 or 3LiBH4·4LiI·9LiNH2.

[0412] In some embodiments, including any of the foregoing, the borohydride adhesive layer comprises a borohydride composition selected from LBHIN and LBHN.

[0413] In some embodiments, including any of the foregoing, the borohydride adhesive layer comprises KBH4 + LiNH2.

[0414] In some embodiments, including any of the foregoing, the borohydride adhesive layer is amorphous.

[0415] In some embodiments, including any of the foregoing, the borohydride adhesive layer is semi-crystalline.

[0416] In some embodiments, including any of the foregoing, the borohydride adhesive layer is polycrystalline.

[0417] In some embodiments, including any of the foregoing, 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.

[0418] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet selected from Li7La3Zr2O x ·Al2O3 and Li7La3Zr2O 12 ·0.35Al2O¡¬3 of lithium-filled garnet.

[0419] In some embodiments, including any of the foregoing, the lithium-filled garnet is doped with Nb, Ga, and / or Ta.

[0420] In some embodiments, including any of the foregoing, 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, 0 < f < 13, and Me” is a metal selected from Nb, Ga, Ta, and combinations thereof.

[0421] In some embodiments, including any of the foregoing, 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 between 2 and 4; x is a rational number from 1 to 3; y is a rational number between 10 and 14; 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. In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet oxide characterized by the formula Li u La v Zr x O y ·zTa2O5, where u is a rational number from 4 to 10; v is a rational number between 2 and 4; x is a rational number from 1 to 3; y is a rational number between 10 and 14; z is a rational number from 0 to 1; u, v, x, y, and z are selected such that the lithium-filled garnet oxide is charge-neutral.

[0422] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet oxide characterized by the formula Li u La v Zr x O y ·zNb2O5, where u is a rational number from 4 to 10; v is a rational number between 2 and 4; x is a rational number from 1 to 3; y is a rational number between 10 and 14; z is a rational number from 0 to 1; u, v, x, y, and z are selected such that the lithium-filled garnet oxide is charge-neutral.

[0423] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet characterized by the formula Li u La v Zrx O y A lithium-filled garnet oxide of zGa2O3, wherein u is a rational number from 4 to 10; 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 to 1; and u, v, x, y, and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0424] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of ·zTa2O5·bAl2O3, wherein u is a rational number from 4 to 10; 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; z is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0425] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of zNb2O5·bAl2O3, wherein u is a rational number from 4 to 10; 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; z is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0426] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li u La v Zr x O y A lithium-filled garnet oxide of ·zGa2O3·bAl2O3, wherein u is a rational number from 4 to 10; 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; z is a rational number from 0 to 1; b is a rational number from 0 to 1; wherein z+b≤1; u, v, x, y and z are selected such that the lithium-filled garnet oxide is charge neutral.

[0427] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a lithium-filled garnet layer characterized by the formula Li 6.4 Ga 0.2 La3Zr2O 12 of lithium-filled garnets.

[0428] In some embodiments, including any of the foregoing, the SSEC comprises a positive current collector layer.

[0429] In some embodiments, including any of the foregoing, the SSEC comprises a negative current collector layer.

[0430] In some embodiments, including any of the foregoing, the negative electrode current collector layer is a sintered metal.

[0431] In some embodiments, including any of the foregoing, the sintered metal is selected from Al, Cu, Ni, Ag, Au, Pt, Pd, or Sn.

[0432] In some embodiments, including any of the foregoing, the metal is Ni.

[0433] In some embodiments, including any of the foregoing, the positive electrode layer further comprises a binder, carbon, or both.

[0434] In some embodiments, including any of the foregoing, the lithium-filled garnet layer is between and in contact with the negative electrode current collector layer and the borohydride bonding layer.

[0435] In some embodiments, including any of the foregoing, the borohydride adhesion layer is between and in contact with the lithium-filled garnet layer and the buffer layer.

[0436] In some embodiments, including any of the foregoing, the buffer layer is between and in contact with the borohydride adhesion layer and the positive electrode layer.

[0437] In some embodiments, including any of the foregoing, the positive electrode layer is between and in contact with the buffer layer and the positive electrode current collector layer.

[0438] In some embodiments, including any of the foregoing, the negative electrode layer is between and in contact with the lithium-filled garnet layer and the negative electrode current collector layer.

[0439] In one embodiment, the present patent provides a battery comprising the SSEC described in any one of the embodiments.

[0440] In one embodiment, this patent proposes an electric vehicle comprising the battery described in any embodiment.

[0441] In one embodiment, the present patent discloses a method for manufacturing an electrochemical cell: providing a first slurry comprising an active material, a cathode electrolyte, and a solvent; depositing the first slurry onto a current collector; drying the first slurry; providing a second slurry comprising a solid buffer that conducts a single ion; depositing the second slurry onto a substrate; drying the second slurry; transferring the dried second slurry onto the first slurry to form a stack; pressurizing and heating the stack; providing a solid separator; depositing a borohydride layer onto the solid separator; combining the stack with the solid separator having the borohydride layer thereon to form an electrochemical cell stack; and pressurizing and heating the cell stack.

[0442] In some embodiments, including any of the foregoing, the solid loading is at least 60 wt%.

[0443] In some embodiments, including any of the foregoing, the buffer is LSTPS.

[0444] In some embodiments, including any of the foregoing, pressurization is unidirectional.

[0445] In one embodiment, the present patent proposes a bilayer stack comprising: (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; and (b) a solid buffer that conducts a single ion, the buffer being mixed within the positive electrode layer, or being a layer in contact with the positive electrode layer, or both.

[0446] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is mixed into the positive electrode layer.

[0447] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is a layer in contact with the positive electrode layer.

[0448] In some embodiments, including any of the foregoing, the single-ion conducting solid buffer is mixed within the positive electrode layer and serves as a layer in contact with the positive electrode layer.

[0449] In some embodiments, including any of the foregoing, the buffer mixture penetrates into the positive electrode layer, and the penetration depth is about 1 μm to about 50 μm from the edge of the positive electrode layer, wherein the edge is the edge of the junction of the positive electrode layer and the buffer layer or the borohydride bonding layer.

[0450] In some embodiments, including any of the foregoing, the lithium-filled garnet layer has a thickness of about 1 μm to about 200 μm.

[0451] In some embodiments, including any of the foregoing, the buffer layer comprises 10% or less of an organic polymer by volume.

[0452] In some embodiments, including any of the foregoing, the polymer is selected from polyacrylonitrile (PAN), polypropylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (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-AG), E), polysiloxane, polyvinylidene fluoride (PVDF), ethylene α-olefin copolymer, polyvinylidene fluoride 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.

[0453] In some embodiments, including any of the foregoing, the active material is coated.

[0454] In some embodiments, including any of the foregoing, 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, hafnium oxide.

[0455] In some embodiments, including any of the foregoing, the active material is uncoated.

[0456] In some embodiments, including any of the foregoing, the positive electrode comprises a lithium insertion material, a lithium conversion material, or both.

[0457] In some embodiments, including any of the foregoing, the intercalation material is selected from 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 NiaO4, wherein a is 0 to 2, or LiMPO4, wherein M is Fe, Ni, Co or Mn.

[0458] In some embodiments, including any of the foregoing, the lithium conversion material is selected from FeF2, NiF2, FeOxF 3-2x , FeF3, MnF3, CoF3, alloys or combinations thereof.

[0459] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid-state buffer or both are selected from LSS, SLOPS, LSTPS, LSTPSC1, SLOBS, LATS, and LPS+X, where X is selected from Cl, I, Br, and combinations thereof.

[0460] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid-state buffer or both are selected from LPSI, LXPS, LSTPS, LSPSCl, LPSC1, LSPSBr, and LPSBr.

[0461] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid-state buffer or both are selected from x·Li2S:y·SiS2, where x and y are each independently a value from 0 to 1, and x + y = 1.

[0462] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid-state buffer or both are selected from LSS, LGPS, LSTPS, and LSPS.

[0463] In some embodiments including any of the foregoing, the sulfide cathode electrolyte or the single-ion conducting solid-state buffer or both are characterized by one of the following formulas: 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, where 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 q, wherein 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; or a mixture of (Li2S):(P2S5) and LiI in a molar ratio of about 10:1 to about 6:4, wherein the ratio of [(Li2S):(P2S5)]:LiI is 95:5 to 50:50; LPS+X, wherein X is selected from Cl, I or Br; vLi2S+wP2S5+yLiX; vLi2S+wSiS2+yLiX or vLi2S+wB2S3+yLiX. In these embodiments, the values ​​of x, w and y in each instance range from 0 to 1, inclusive.

[0464] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte comprises LSTPS.

[0465] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is characterized by 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, 2≤e≤12.

[0466] In some embodiments, including any of the foregoing, the sulfide cathode electrolyte is characterized by 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, 2≤e≤12.

[0467] In some embodiments, including any of the foregoing, the lithium-filled garnet layer comprises a selected from Li x La y Zr z O t qAl2O3 lithium-filled garnet, where 4 <x<10、1<y<4、1<z<3、6<t<14、0≤q≤1。

[0468] Although specific advantages are listed above, various embodiments may include all, some, or none of the listed advantages. Other technical advantages will be apparent to those skilled in the art based on the following drawings and description. Example

[0469] Unless otherwise stated, reagents, chemicals, and materials were purchased from commercial sources. Unless otherwise stated, chemical reagents and solvents were purchased from commercial sources and used without purification. The soft-pack battery container was purchased from Showa Denko. The electrochemical potentiostat used was an Arbin potentiostat. Electrical impedance spectroscopy (EIS) was measured using a Biologic VMP3, VSP, VSP-300, SP-150, or SP-200. A rheometer was used for 100 s -1 Viscosity was measured at a shear rate of 100 Å. Grinding was performed using a Retsch PM 400 planetary ball mill. Mixing was performed using a Fischer Scientific vortex mixer, a Flktek speed mixer, or a Primix filmix homogenizer. Casting was performed on a TQC casting table. Rolling was performed on an IMC calender. Light scattering was performed on a Horiba Partica LA-950V2 laser scattering particle size analyzer.

[0470] Electron microscopy was performed on a FEI Quanta SEM, Helios 600i, or Helios 660 FIB-SEM, or equivalent instruments. XRD was performed at room temperature on a Bruker D8Advance ECO or Rigaku MiniFlex 2 with CuK-α radiation and a 6 mm slit width, with a scan time of 76 ms / step or 0.4 s / step. Optical imaging was performed with an optical camera. DC cycling was performed using an Arbin BT-2043 or BT-G, or equivalent instruments.

[0471] Example 1

[0472] Step (1): Prepare a solid cathode layer. Prepare a slurry with a solid loading of 30-80 wt% using 20-70% toluene. The solid loading comprises 70-95 wt% of lithiated lithium zirconium oxide (LZO) coated with lithiated nickel cobalt aluminum oxide active material (NCA), 13 wt% of LSTPS and 2 wt% of a binder. The LSTPS composition is characterized by 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, and it further contains greater than 0 to 15at% oxygen, and is prepared according to the preparation method described in U.S. Patent No. 9,172,114, entitled "SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES", issued on October 27, 2015, the entire contents of which are incorporated by reference into this application for all purposes.

[0473] The slurry is cast onto a carbon-coated aluminum foil using a doctor blade. The resulting cast slurry is dried at room temperature to 120° C. for 1-24 hours to form a positive electrode layer thin film on the carbon-coated aluminum foil. When the electrochemical cell is assembled in step (7), the carbon-coated aluminum foil serves as a current collector. After drying, the positive electrode layer is adhered to the current collector.

[0474] Step (2): Prepare a buffer layer in contact with the solid positive electrode layer. Prepare a slurry with 10-70wt% LSTPS in toluene. Use a doctor blade to cast the slurry on a nickel foil. The resulting cast slurry is dried at room temperature to 120°C for 1-24 hours to form a buffer layer film. In this example, the buffer layer includes LSTPS with the same chemical composition as used in the positive electrode layer. Without being bound by theory, this patent believes that this layer does not contain an electron conductor. Therefore, the buffer layer prevents electrons from entering the borohydride bonding layer. In this way, the buffer layer shields the positive electrode layer potential from the bonding layer potential. The buffer layer can then protect the negative electrode (anode) potential from being affected by the positive electrode layer.

[0475] Step (3): After drying in step (2), the buffer layer film is peeled off from the nickel foil, i.e., the buffer layer film is removed. The buffer layer is then transferred and placed on top of the positive electrode layer prepared according to step (1) to form a stack (buffer layer-positive electrode layer-current collector).

[0476] Step (4): Applying a uniaxial pressure of about 300 MPa to the laminate formed in step (3) at low temperature (room temperature). Applying pressure to the laminate at high temperature (150-180°C).

[0477] Step (5): The lithium-filled garnet layer is made according to the method for forming a lithium-filled garnet layer or film in U.S. Patent No. 9,806,372B2, entitled “GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING AND USING GARNET MATERIALS,” which was granted on October 31, 2017, and U.S. Patent No. 9,970,711, entitled “LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION,” which are incorporated herein by reference in their entirety for all purposes.

[0478] Step (6): Prepare a borohydride bonding layer. The borohydride composition for forming the borohydride bonding layer can be found in a patent application filed on October 20, 2017, with International PCT Patent Application No. PCT / US2017 / 057735, entitled “ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE,” and a patent application filed on October 20, 2017, with International PCT Patent Application No. PCT / US2017 / 057739, entitled “BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID-STATE BATTERY,” the entire contents of which are incorporated herein by reference for all purposes. The composition 3LiBH4·2LiCl·3LiNH2 was melted and spin-coated onto the lithium-filled garnet film prepared in step (5). The borohydride adhesion layer formed an intimate contact with both the lithium-filled garnet and the buffer layer in contact with the positive electrode layer.

[0479] Step (7): A lithium-filled garnet film with a LBHIN spin-coated layer is placed on top of the stack formed in step (4), with the LBHIN borohydride adhesion layer in direct contact with the buffer layer. The stack is then compacted by applying a pressure of approximately 10,000 pounds per square inch (PSI) at a temperature that melts the LBHIN (250°C). The stack is then cooled to room temperature.

[0480] Step (8): A current collector is attached to the side of the lithium-filled garnet film on the stack formed in step (7) that does not have the LBHIN spin-coated layer to form an electrochemical cell. Prior to attaching the current collector, lithium metal is evaporated onto the lithium-filled garnet to form a lithium metal negative electrode. The electrochemical cell contains 30 μm of evaporated lithium.

[0481] Step (9): The stack obtained in step (8) is cycled to form a lithium metal anode between the adhered current collector and the lithium filled garnet film.

[0482] Example 2

[0483] An electrochemical cell was fabricated according to steps (1) to (8) of Example 1. The cell was subjected to an initial forming cycle at 45° C. at a C / 10 rate and electrochemical cycling at a C / 3 rate between 3.0 V and 4.2 V. The electrochemical cell was pressurized to 300 pounds per square inch (psi).

[0484] The results are as follows Figure 3-5 shown.

[0485] Figure 3 The electrochemical cell was shown to complete 50 cycles at a C / 3 rate at 45 °C without significant capacity loss. Figure 3 Cycles 1 and 50 are shown.

[0486] Figure 4 The electrochemical cell was shown to complete 200 cycles and retain more than 80% of its energy in the 200th cycle. Coulombic efficiencies close to 1 were observed (greater than 0.999 in most cycles). The first cycle efficiency was greater than 90%. It is necessary to compare these unexpected results with those in the paper by Kato et al. DOI: 10.1038 / NENERGY.2016.30, which reported a LiCoO2 cathode active material with a LiNbO3 coating 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 Cl 0.3 ) electrochemical cell. Figure 4reported coulombic efficiencies of 90%, 61%, and 39%, respectively. However, Kato et al. only tested low-voltage (2.5V) electrochemical cells. It is foreseeable that these low-voltage (2.5V) cells have high coulombic efficiencies. However, the 2.5V cell only showed a coulombic efficiency of 93% at the first cycle and only 99% at the 10th and 100th cycles. Unlike Kato et al., Figure 4 As shown, the electrochemical cell prepared in the embodiment of the present patent application has a coulombic efficiency of about 100% (greater than 99.9%) after 10 cycles. If tested under the same conditions, it has a higher coulombic efficiency than the prior art, which indicates that the electrochemical stability at the sulfide-cathode interface is improved.

[0487] Figure 5 Demonstrated electrochemical cell with approximately 54 Ω-cm at 45 °C 2 Both LSTPS and lithium-filled garnets may have high area specific resistance (ASR) (e.g., 1000 Ω-cm) at room temperature. 2 or higher). Therefore, surprisingly, by simply pressing LSTPS and lithium-filled garnet together to form a heterointerface therebetween as in Example 1, a single cell comprising LSTPS and lithium-filled garnet has a low ASR.

[0488] Figure 6 and Figure 7 Schematic diagram of the electrochemical cell under test. The electrochemical cell was prepared according to Example 1 and tested according to Example 2. Figure 6 The electrochemical cell shown includes: layer 701 representing an evaporated lithium metal anode; layer 702 representing a lithium filled garnet layer; layer 704 representing a buffer layer; and layer 705 representing a positive electrode layer.

[0489] like Figure 7 The electrochemical cell shown includes: layer 801 representing an evaporated lithium metal anode; layer 802 representing a lithium filled garnet layer; layer 803 representing an adhesive layer; and layer 805 representing a positive electrode layer.

[0490] Example 3 - Fabrication of an electrochemical cell with a buffer layer

[0491] Step (1): Preparation of solid positive electrode layer (cathode layer, SSC). Prepare a slurry with a solid loading of 30-80 wt% in 20-70% toluene. The solid loading includes 70-95 wt% of lithium zirconium oxide (LZO) coated lithiated nickel cobalt aluminum oxide active material (NCA), 13 wt% of LSTPS and 2 wt% of binder. The LSTPS composition is characterized by Lia Si b Sn c P d S e , wherein a is 4, b is 0.5, c is 0.5, d is 1, and e is 8, further comprising from greater than 0 to 15 at% oxygen, prepared according to the method described in U.S. Patent No. 9,172,114, entitled “SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES,” issued on October 27, 2015, the entire contents of which are incorporated herein by reference for all purposes.

[0492] The slurry was cast on a carbon-coated aluminum foil using a doctor blade and the resulting cast slurry was dried at room temperature to 120° C. for 1 to 24 hours to form a positive electrode layer film on the carbon-coated aluminum foil.

[0493] Step (2): Prepare a sulfide layer that will be in contact with the solid positive electrode layer. Prepare a slurry with 10-70wt% LSTPS in toluene. Cast the slurry on a nickel foil using a doctor blade casting method. The resulting cast slurry is dried at room temperature to 120°C for 1-24 hours to form a buffer layer film. In this example, the buffer layer includes the same chemical composition LSTPS as in the positive electrode layer. Without being bound by theory, this patent believes that this layer does not conduct electrons (the electron conductivity is less than 1E-6S / cm). Therefore, the buffer layer can prevent the negative electrode (anode) potential from being affected by the positive electrode layer.

[0494] Step (3): The two layers of step (1) and step (2) are placed on top of each other so that the sulfide layer and the cathode layer are in direct contact with each other to produce a stack (nickel film-buffer layer-positive electrode layer-aluminum film).

[0495] Step (4): The laminate from step (3) is placed on an aluminum guide foil. The film is passed through a calender at 140°C at a speed of 1.0 m / min and a hydraulic pressure of about 100-110 kg (10-11 MPa) (1100-1200 N / mm). The calender used is a Saueressig GK 300L or OnoRoll Type 12. After calendering, the sulfide layer is transferred to the cathode layer and the two layers are compacted together in one step. The result is shown in FIG. Figure 2 The carbon-coated aluminum foil is also bonded to the aluminum guide foil during the calendering process and forms the first current collector on the side of the SSC.

[0496] The stack of step (4) was incorporated into an electrochemical cell including a lithium-filled garnet separator for testing.

[0497] The lithium-filled garnet layer is made according to the method for forming a lithium-filled garnet layer or film in U.S. Patent No. 9,806,372B2, entitled “GARNET MATERIALS FOR LI SECONDARY BATTERIES AND METHODS OF MAKING and USING GARNET MATERIALS,” issued on October 31, 2017, and U.S. Patent No. 9,970,711, entitled “LITHIUM STUFFED GARNET SETTER PLATES FOR SOLID ELECTROLYTE FABRICATION,” issued on May 15, 2018, the entire contents of which are incorporated herein by reference for all purposes.

[0498] Step (6): A lithium-filled garnet film is placed on top of the stack produced in step (4) so ​​that the lithium-filled garnet film is in direct contact with the buffer layer. The stack is then compacted by applying a pressure of about 500 pounds per square inch (PSI) at a temperature of about 140°C. The stack is then cooled to room temperature.

[0499] Step (7): Lithium metal is evaporated onto the lithium-filled garnet (the evaporated lithium is 30 μm) to form a lithium metal negative electrode in the stack obtained in step (6), and the battery stack is adhered to the negative electrode collector to form an electrochemical cell. In some cells, the negative electrode collector is directly attached to the lithium-filled garnet film, and the lithium of the positive electrode is plated between the lithium-filled garnet film and the negative electrode collector.

[0500] Example 4 - Fabrication of an electrochemical cell having a buffer layer and a borohydride layer

[0501] Step (1): Preparation of solid positive electrode layer (cathode layer, SSC). Prepare a slurry with a solid loading of 30-80 wt% in 20-70% toluene. The solid loading includes 70-95 wt% of lithium zirconium oxide (LZO) coated lithiated nickel cobalt aluminum oxide active material (NCA), 13 wt% of LSTPS and 2 wt% of binder. The LSTPS composition is characterized as 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, and further comprises an oxygen content of greater than 0 to 15 at%, prepared according to U.S. Patent No. 9,172,114, entitled “SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES,” issued on October 27, 2015, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0502] The slurry was cast on a carbon-coated aluminum foil using a doctor blade and the resulting cast slurry was dried at room temperature to 120° C. for 1-24 hours to form a positive electrode layer thin film on the carbon-coated aluminum foil.

[0503] Step (2): Prepare a sulfide layer that is subsequently in contact with the solid positive electrode layer. Prepare a slurry with 10-70 wt% LSTPS in toluene. Cast the slurry on a nickel foil using a doctor blade casting method. The resulting cast slurry is dried at room temperature to 120°C for 1-24 hours to form a buffer layer film. In this example, the buffer layer includes the same chemical composition component LSTPS as in the positive electrode layer. Without being bound by theory, this patent believes that this layer does not conduct electrons (electronic conductivity is less than 1E-6S / cm). As a result, the buffer layer shields the negative electrode (anode) potential, leaving the positive electrode layer unaffected.

[0504] Step (3): The two layers of step (1) and step (2) are placed on top of each other so that the sulfide layer and the cathode layer are in direct contact with each other to produce a stack (nickel film-buffer layer-positive electrode layer-aluminum film).

[0505] Step (4): The stack from step (3) is placed on an aluminum guide foil. The film is passed through a calender at 140°C at a speed of 1.0 m / min and a hydraulic pressure of approximately 100-110 kg (10-11 MPa) (1100-1200 N / mm). The calender used is a Saueressig GK 300L or Ono Roll Type 12. After calendering, the sulfide layer is transferred to the cathode layer, and the two layers are compacted together in a single step. The carbon-coated aluminum foil is also bonded to the aluminum guide foil during the calendering process and forms the first current collector on the side of the SSC.

[0506] The stack of step (4) was incorporated into an electrochemical cell including a lithium-filled garnet separator for testing.

[0507] Step (5): The lithium-filled garnet layer is made according to the method for forming a lithium-filled garnet layer or film in U.S. Patent No. 9,806,372B2, entitled “GARNET MATERIALS FOR LISECONDARY BATTERIES AND METHODS OF MAKING and USING GARNET MATERIALS”, issued on October 31, 2017, and U.S. Patent No. 9,970,711, entitled “LITHIUM STUFFED GARNET SETTERPLATES FOR SOLID ELECTROLYTE FABRICATION”, issued on May 15, 2018, the entire contents of which are incorporated by reference into this application for all purposes.

[0508] Step (6): Preparing a borohydride bonding layer. The borohydride composition used to form the borohydride bonding layer is prepared according to patent application number PCT / US2017 / 057735, filed on October 20, 2017, entitled “ELECTROLYTE SEPARATORS INCLUDING LITHIUM BOROHYDRIDE AND COMPOSITE ELECTROLYTE SEPARATORS OF LITHIUM-STUFFED GARNET AND LITHIUM BOROHYDRIDE”; and patent application number PCT / US2017 / 057739, filed on October 20, 2017, entitled “BOROHYDRIDE-SULFIDE INTERFACIAL LAYER IN ALL SOLID-STATE BATTERY,” the entire contents of which are incorporated herein by reference for all purposes. The composition 3LiBH4·2LiCl·3LiNH2 was melted and spin-coated onto the lithium-filled garnet film prepared in step (5).

[0509] Step (7): The lithium-filled garnet film with the LBHIN spin-coated thereon is placed on top of the stack produced in step (4), so that the LBHIN borohydride adhesion layer is in direct contact with the buffer layer. The stack is then compacted by applying a pressure of approximately 1000 pounds per square inch (PSI) at a temperature of 140°C. The stack is then cooled to room temperature. Figure 3 A SEM FIB image of the resulting stack is shown.

[0510] Step (8): Lithium metal is evaporated onto the lithium-filled garnet (the evaporated lithium is 30 μm) to form a lithium metal negative electrode in the battery stack obtained in step (7), and the battery stack is adhered to the negative electrode collector to form an electrochemical cell. In some cells, the negative electrode collector is directly attached to the lithium-filled garnet film, and the lithium of the positive electrode is plated between the lithium-filled garnet film and the negative electrode collector.

[0511] Example 5

[0512] LBHI powder was prepared by mixing 3 mol of LiBH4 with 1 mol of LiI. The mixture was milled twice in a zirconia container at 300 rpm for 8 hours, then annealed in a sealed container at 300°C and cooled to room temperature to form annealed mixed LBHI powder.

[0513] Garnet film (roughly characterized by Li 7-x La3Zr2O 12 Lithium-filled garnet (Al2O3) is prepared as follows. Garnet precursors are mixed with LiOH, ZrO2, La2O3, and boehmite in a molar ratio of 6-7:1.5:2:0.1-1.5. The mixed precursors are ground in a ball mill and calcined at 700-1000°C for 1-10 hours to form a cubic garnet phase with a secondary phase. The powder is ground in a wet mill with a solvent, surfactant, and dispersant. A binder solution is prepared by dissolving a binder in the same solvent. The binder solution and powder slurry are mixed and cast onto a polyester film substrate using a doctor blade with a gap height of 10-300 μm to form a tape-shaped film, forming a cast green tape. The green tape is peeled from the substrate, cut into the desired size, sintered at 800-1200°C for 1-10 hours, and cooled to form a sintered garnet film.

[0514] Under argon atmosphere, the mixed and annealed LBHI powder (1-4g) was heated to 300-350°C in a boron nitride or alumina crucible. The crucible was placed in a stainless steel heating kettle equipped with a belt heater and heated for about 2 hours until the LBHI powder melted. Under argon conditions at 300-350°C, the garnet film was immersed in the molten LBHI once for 600s. The garnet film was then heated at 0.05-300mm min. -1 The LBHI-coated garnet was removed from the molten LBHI at a rate of 1000 nm and cooled under argon for 5 seconds to 5 minutes to form the LBHI-coated garnet.

[0515] Example 6

[0516] As shown in Example 5, LBHI was prepared and heated to 300-350°C. Then, a thin current collector copper foil was immersed in the molten LBHI at 300-350°C under argon atmosphere for 600 seconds. The copper was then heated at a rate of 0.05-300 mm min. -1 The copper foil is taken out from the molten LBHI at a rate of 1000 nm and cooled under argon for 5 seconds to 5 minutes to provide a LBHI-dip-coated copper foil.

[0517] Example 7

[0518] The ASR and service life of the LBHI-coated garnet prepared in Example 5 were tested as follows. The uncoated garnet and the LBHI-coated garnet were placed in contact with Li electrodes (contact area of ​​8 mm) on both sides and the electrodes were charged at 0.5 mA / cm2 at 80°C and 300 PSI. 2 The current density was applied twice a day (forward and reverse) for 30 seconds.

[0519] Example 8

[0520] The separator (the uncoated garnet membrane or the LBHI-coated garnet membrane prepared according to Example 6) was placed in a symmetrical electrochemical cell with Li-metal electrodes on both sides of the electrochemical cell sample. A hydrostatic pressure of 5000 PSI was applied unidirectionally to both sides of the cell under controlled temperature and argon atmosphere at 80°C and 2 mA / cm 2 Under the conditions of 20 micron lithium (about 4 mAh / cm 2 ) were cycled 5 times within an 8 mm electrode contact area. For samples that continued to cycle (non-short-circuited samples), the current was increased to 3 mAh / cm at 80 °C. 2 For samples that continued to cycle, the current was increased to 4 mAh / cm at 80 °C. 2 , and then the samples that can continue to cycle at 80 ° C increased to 5 mAh / cm 2 .

[0521] Example 9

[0522] LBHClN was prepared by mixing 3 mol of LiBH4, 3 mol of LiNH2, and 1 mol of LiCl. The mixture was then milled twice in a zirconia container at 300 rpm for 8 hours, annealed in a sealed container at 180°C for 2 hours, and cooled to form LBHClN powder.

[0523] A lithium-filled garnet film was prepared according to the method of Example 5 and coated with lithium metal on one side. LBHClN powder was then dropped onto the other side of the lithium-filled garnet film. The lithium-filled garnet film with the LBHClN powder was then heated to 80-140°C to melt the LBHClN powder.

[0524] A sulfide containing solid cathode membrane (SSC) was prepared. The SSC included a sulfide cathode electrolyte, LSTPS, and a cathode active material (NCA) having LSTPS, with the volume ratio of LSTPS:NCA being approximately 1 / 3 and 2 / 3. A small amount of carbon and a binder of approximately 0-5 wt% was added to the LSTPS and NCA. The resulting mixture of LSTPS / NCA / carbon / binder was suspended in toluene at a mass loading of 20% powder in toluene. The suspension was then mixed using Flacktek and Filmix for 15 minutes and 6 minutes, respectively. The mixture was then cast onto carbon-coated aluminum foil and dried in an argon atmosphere until the toluene evaporated. The membrane was punched out to the desired size. The SSC membrane was compacted at 180°C and a pressure of 300,000 PSI.

[0525] The SSC film was placed on top of the melted LBHClN powder. The SSC film was then pressed at a pressure of 10-2000 pounds per square inch (PSI) while cooling to room temperature. The cell was cycled at 45°C at a C / 10 rate.

[0526] Example 10

[0527] LBHXN powder, where X is Cl, Br, or I, or a mixture thereof, is prepared as described above. A bonding layer of LBHXN thin film is deposited onto a lithium-filled garnet by spin casting. In this process, a small amount of LBHXN powder is added to the center of a lithium-filled garnet, which is placed on the chuck of a spin coater and heated to the LBHXN melting temperature (approximately 100-280°C). Upon reaching the melting temperature, the LBHXN melts. Using a flat spatula, the molten LBHXN is poured onto the substrate, covering the area. While the chuck is still at the required temperature to melt the LBHXN, the spin coater is turned on to a speed of 100 to 5000 rpm. After 1-10 minutes, the spin coater is turned off. After cooling to room temperature, a uniform coating of LBHXN is obtained on the substrate.

[0528] Example 11

[0529] An organic, non-aqueous, aprotic solvent is added to the LSTPS powder mixture to form a slurry having a solids loading of at least about 35%. The slurry is then poured and coated onto a metal foil using a coater. A buffer layer is then placed in contact with the cathode material layer. The layers are compacted using a force of at least about 1000 psi or greater.

[0530] Example 12

[0531] A LiNH2:LiBH4:LiI (3:3:2) composition was applied to the solid cathode film via a drop casting method. Specifically, LBHIN powder was prepared and cast onto the compacted solid cathode. An uncoated lithium-filled thin film (prepared according to Example 5) was pressed onto the LBHIN layer at 20-2000 PSI and 20-350°C.

[0532] Example 13

[0533] A solid-state cathode layer (cathode layer, SSC) was prepared. A slurry with a solid loading of 30-80 wt% in 20-70% toluene was prepared. The solid loading included 70-95 wt% of lithium zirconium oxide (LZO) coated lithiated nickel cobalt aluminum oxide active material (NCA), 13 wt% of LSTPS, and 2 wt% of a binder. The LSTPS composition was characterized as 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, and further comprises from greater than 0 to 15 at% oxygen, prepared according to the method described in U.S. Patent No. 9,172,114, entitled “SOLID STATE CATHOLYTES AND ELECTROLYTES FOR ENERGY STORAGE DEVICES,” issued on October 27, 2015, the entire contents of which are incorporated herein by reference for all purposes.

[0534] Lithium metal was added to one side of the lithium-filled garnet film prepared in Example 5.

[0535] LPSI is cast onto the lithium-filled garnet film on the side opposite to the side with lithium metal.

[0536] The thickness of the lithium-filled garnet film is about 100 μm, the thickness of the cathode is about 150 μm, and the thickness of the LPSI is about 10 μm.

[0537] The obtained electrochemical cell was cycled at a rate of C / 10 at 45°C and 30 psi. Figure 9 shown.

[0538] The above embodiments and examples are illustrative and non-restrictive. Those skilled in the art will recognize or determine many equivalent specific compounds, materials and procedures using only routine experimentation. All such equivalent forms are considered to be within the scope of the appended claims.

Claims

1. A solid-state electrochemical cell SSEC, comprising: (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte, wherein the active material is selected from LiNi x Mn y Co z O2 and LiNi x Al y Co z O2, where x+y+z equals 1; (b) a solid buffer layer that conducts a single ion, wherein the solid buffer layer comprises LSTPS, wherein LSTPS refers to a solid having chemical compositions of Li, Si, P, Sn and S and conforming to the chemical formula Li a Si b Sn c P d S e An electrolyte material, wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, 0.5≤d≤2.5, 2≤e≤12, and the thickness of the solid buffer layer is greater than 1 μm and less than or equal to 15 μm; (c) a borohydride bonding layer, the borohydride bonding layer comprising a borohydride composition comprising: A.(LiBH4)-B.(LiX)-C.(LiNH2), wherein X is fluorine, bromine, chlorine, iodine, or a combination thereof, wherein 3≤A≤6, 2≤B≤5, and 0≤C≤9; and (d) A lithium-filled garnet layer, the lithium-filled garnet layer comprising 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; The solid buffer layer is in contact with the positive electrode layer; and the borohydride bonding layer is between the lithium-filled garnet layer and the buffer layer in contact with the positive electrode and in contact with them.

2. The SSEC according to claim 1, wherein: The solid buffer layer prevents the borohydride bonding layer from directly contacting the positive electrode layer. The SSEC according to claim 1 , further comprising a negative electrode.

4. The SSEC according to claim 3, wherein: The negative electrode is a lithium (Li) metal negative electrode.

5. The SSEC according to claim 4 or 3, wherein: The lithium filled garnet layer contacts the negative electrode.

6. The SSEC according to any one of claims 1 to 5, wherein The solid buffer layer includes an organic polymer in an amount of 10% by volume or less.

7. The SSEC according to any one of claims 1-6, wherein the active material is coated.

8. The SSEC according to any one of claims 1-6, wherein the active material is uncoated.

9. The SSEC according to any one of claims 1 to 8, wherein The positive electrode includes a lithium intercalation material, a lithium conversion material, or both a lithium intercalation material and a lithium conversion material.

10. The SSEC according to any one of claims 1-9, wherein the sulfide cathode electrolyte is selected from the group consisting of LSS, SLOPS, LSTPS, LSTPSC1, SLOBS, LATS and LPS+X, wherein X is selected from Cl, I, Br and combinations thereof.

11. The SSEC of any one of claims 1-10, wherein the sulfide cathode electrolyte is characterized by one of the following formulas: 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, where 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 q , where 2≤m≤6, 0≤n≤1, 0≤p≤1, 2≤q≤6; A mixture of (Li2S):(P2S5) and LiI in a molar ratio of about 10:1 to about 6:4, wherein The ratio of [(Li2S):(P2S5)]:LiI is 95:5 to 50:50; LPS+X, wherein X is selected from Cl, I or Br; vLi2S+wP2S5+yLiX; vLi2S+wSi2S5+yLiX; or vLi2S+wB2S3+yLiX, wherein X is selected from Cl, I or Br, wherein 0≤v≤1, 0≤w≤1, 0≤y≤1.

12. The SSEC of any one of claims 1-11, wherein the sulfide cathode electrolyte comprises LSTPS.

13. The SSEC of claim 11 or 12, wherein the sulfide cathode electrolyte is characterized by 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.

14. The SSEC according to any one of claims 1 to 13, further comprising a positive current collector.

15. The SSEC according to any one of claims 1 to 14, further comprising a negative electrode current collector.

16. A battery comprising the SSEC according to any one of claims 1 to 15.

17. An electric vehicle comprising the battery according to claim 16.

18. A method for manufacturing an electrochemical cell: providing a first slurry comprising an active material, a sulfide cathode electrolyte, and a solvent; depositing the first slurry onto a current collector; drying the first slurry; providing a second slurry comprising a single ion conducting solid buffer layer; depositing the second slurry onto a substrate; drying the second slurry; transferring the dried second slurry onto the first slurry to form a laminate; applying pressure and heat to the stack; Providing a solid diaphragm; Depositing a borohydride layer onto the solid diaphragm to prepare a solid diaphragm having a borohydride layer; combining the stack with a solid separator having a borohydride layer to form an electrochemical cell stack; and applying pressure and heat to the cell stack Wherein: the active material is selected from LiNi x Mn y Co z O2 and LiNi x Al y Co z O2, where x+y+z equals 1; The solid buffer layer includes LSTPS, wherein LSTPS refers to a solid having chemical compositions of Li, Si, P, Sn and S and conforming to the chemical formula Li a Si b Sn c P d S e An electrolyte material, wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, 0.5≤d≤2.5, 2≤e≤12, and the thickness of the solid buffer layer is greater than 1 μm and less than 15 μm; The borohydride layer includes a borohydride composition, which includes: A·(LiBH4)·B·(LiX)·C·(LiNH2), wherein X is fluorine, bromine, chlorine, iodine or a combination thereof, wherein 3≤A≤6, 2≤B≤5 and 0≤C≤9.

19. A double-layer laminate comprising: (a) a positive electrode layer comprising an active material and a sulfide cathode electrolyte; and (b) Solid buffer layer conducting a single ion Wherein: the active material is selected from LiNi x Mn y Co z O2 and LiNi x Al y Co z O2, where x+y+z equals 1; The solid buffer layer includes LSTPS, wherein LSTPS refers to a solid having chemical compositions of Li, Si, P, Sn and S and conforming to the chemical formula Li a Si b Sn c P d S e An electrolyte material, wherein 2≤a≤8, 0≤b≤1, 0≤c≤1, 0.5≤d≤2.5, 2≤e≤12, and the thickness of the solid buffer layer is greater than 1 μm and less than 15 μm; Wherein, the solid buffer layer is in contact with the positive electrode layer.

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