Solid state batteries and methods of making and use thereof

Abstract

The disclosed subject matter relates to solid state batteries, such as pseudo solid state and all solid state batteries, and methods of making and use thereof. The solid state batteries comprise: an interfacial layer; a halide solid state electrolyte layer; and a composite cathode. The halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode. The interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window, and the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer. In some examples, the solid state batteries further comprise an anode disposed on the interfacial layer, wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode.

Description

[0001] SOLID STATE BATTERIES

[0002] AND METHODS OF MAKING AND USE THEREOF

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims the benefit of priority to U.S. Provisional Application No. 63 / 530,145 filed August 1, 2023, which is hereby incorporated herein by reference in its entirety.

[0005] BACKGROUND

[0006] Traditional lithium-ion batteries have reached their theoretical limit and have been found wanting in terms of the performance they enable in products such as electric vehicles. An explosion in electric vehicle demand has spurred the requirement of battery technology that can enable longer driving distances, faster charging times, and above all enhanced safety for the end consumer. The devices, methods, and systems discussed herein address these and other needs.

[0007] SUMMARY

[0008] In accordance with the purposes of the disclosed devices, methods, and systems as embodied and broadly described herein, the disclosed subject matter relates to solid state batteries, such as pseudo solid state and all solid state batteries, and methods of making and use thereof.

[0009] For example, disclosed herein are solid state batteries comprising: an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode. The interfacial layer is disposed on and in contact with the halide solid state electrolyte layer. The halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode. The interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window, and the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer. The composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte. In some examples, the solid state batteries further comprise an anode, wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer, and wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode.

[0010] Also disclosed herein are solid state batteries comprising: an anode; an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode. The interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer. The halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode. The anode, the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window, and the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode. The composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0011] In some examples, the anode is formed in situ.

[0012] In some examples, the anode has a high capacity and / or a high energy density. In some examples, the anode has a specific capacity of from 100 to 4000 mAh / g.

[0013] In some examples, the anode has a low intercalation voltage. In some examples, the anode has an intercalation voltage of as 1 V or less versus Li+ / Li°.

[0014] In some examples, the anode comprises a metal, an alloy, an intercalation material, or a combination thereof. In some examples, the anode comprises lithium, potassium, sodium, silicon, indium, graphite, hard carbon, or a combination thereof.

[0015] In some examples, the anode comprises lithium (e.g., lithium metal and / or a lithium alloy). In some examples, the anode comprises lithium metal. In some examples, the anode comprises a lithium alloy. In some examples, the anode comprises a lithium-indium alloy, a lithium-magnesium alloy, a lithium-aluminum alloy, a lithium-iron alloy, or a combination thereof. In some examples, the anode comprises a lithium-indium alloy.

[0016] In some examples, the anode comprises silicon or a silicon composite. In some examples, the anode is a composite (e.g., a composite anode). In some examples, the composite anode further includes a binder. In some examples, the binder comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0017] In some examples, the composite anode further includes a conductive additive. In some examples, the conductive additive comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof. In some examples, the conductive additive comprises carbon black.

[0018] In some examples, the anode comprises a prelithiated host structure (e.g., a prelithiated silicon anode, a prelithiated silicon-graphite composite anode, a prelithiated graphite, a prelithiated hard carbon, etc.), a silicon-graphite composite anode, or a combination thereof.

[0019] In some examples, the interfacial layer is formed in situ.

[0020] In some examples, the interfacial layer has an average thickness of from 1 nanometer (nm) to 100 micrometers (microns, pm).

[0021] In some examples, the interfacial layer has an ionic conductivity of lithium of from 1 x 10"8Scm1to 0.1 Scm1.

[0022] In some examples, the interfacial material comprises an alkali metal nitride, an alkali metal phosphide, or a combination thereof. In some examples, the interfacial material comprises LhN, LirP, Na-,P, Na^N, KjN, or a combination thereof. In some examples, the interfacial material comprises LisN, Li iP, or a combination thereof. In some examples, the interfacial material comprises LisN.

[0023] In some examples, the interfacial layer comprises a plurality of particles of the interfacial material. In some examples, the plurality of particles of the interfacial material have an average particle size of from 1 nanometers (nm) to 25 micrometers (microns, pm). In some examples, the plurality of particles of the interfacial material have an average particle size of from 1 to 10 micrometers (microns, pm).

[0024] In some examples, the halide solid state electrolyte layer has an average thickness of from 1 to 100 micrometers (microns, pm).

[0025] In some examples, the first halide solid state electrolyte has an ionic conductivity of lithium of from 1 x 10'5Scm1to 0.1 Scm1.

[0026] In some examples, the first halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof. In some examples, the first halide solid state electrolyte comprises a lithium halide. In some examples, the first halide solid state electrolyte comprises Li zM|III+z|X6, where X is one or more halides, z is an integer from -2 to 2, and [III+z] represents the valence of the M-ion(s) in the compound. In some examples, the first halide solid state electrolyte comprises LF YXr>, where X is F, Cl, Br, I, or a combination thereof. In some examples, the first halide solid state electrolyte comprises Li2ZrXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, the first halide solid state electrolyte comprises LCYC'le, LizZrCle, or a combination thereof. In some examples, the halide solid state electrolyte layer comprises a plurality of particles of the first halide solid state electrolyte. In some examples, the plurality of particles of the first halide solid state electrolyte have an average particle size of from 1 nanometer to 100 micrometers.

[0027] In some examples, the electrochemical stability window of the halide solid state electrolyte is compatible with the electrochemical stability window of the composite cathode.

[0028] In some examples, the cathode active material comprises a high density nickel-rich layered transition metal oxide (e.g., Li[NixMnyCoz]O2 (x+y+z = 1)), LiFei-xMnxPO4 (LMFP), a lithium iron phosphate (LFP, LiFePC ), lithium manganese oxide (LiMmCh), nickel -doped lithium manganese oxide (LitNio.5Mn1.5JO4), LiCoO , LiNiO2, or a combination thereof. In some examples, the cathode active material comprises Li[NixMnyCoz]O2 where x+y+z - 1, LiFePO4, or a combination thereof. In some examples, the cathode active material comprises LiNi- o.sMno.iCoojCh.

[0029] In some examples, the conductive additive in the composite cathode comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof. In some examples, the conductive additive in the composite cathode comprises carbon black.

[0030] In some examples, the composite cathode further comprises a binder. In some examples, the binder comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0031] In some examples, the solid state battery is an all solid state battery. In some examples, the electrolyte of the composite cathode is a plurality of particles comprising a second halide solid state electrolyte.

[0032] In some examples, the second halide solid state electrolyte has an ionic conductivity of lithium of from 1 x 10'6Scm-1to 1 Scm1.

[0033] In some examples, the second halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof. In some examples, the second halide solid state electrolyte comprises a lithium halide. In some examples, the second halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides, z is an integer from -2 to 2, and [III+z] represents the valence of the M-ion(s) in the compound. In some examples, the second halide solid state electrolyte comprises L YX , where X is F, Cl, Br, I, or a combination thereof. In some examples, the second halide solid state electrolyte comprises Li2ZrXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, wherein the second halide solid state electrolyte comprises LFYCle, LijZrCle, or a combination thereof. In some examples, the second halide solid state electrolyte and the first halide solid state electrolyte are the same. In some examples, the second halide solid state electrolyte and the first halide solid state electrolyte are different.

[0034] In some examples, the plurality of particles of second halide solid state electrolyte have an average particle size of from 1 nanometers to 50 micrometers. In some examples, the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are the same. In some examples, the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are different.

[0035] In some examples, the solid state battery is a pseudo solid state battery. In some examples, the electrolyte of the composite cathode is a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0036] In some examples, the solid state battery further comprises a first current collector, wherein the anode is sandwiched between and in contact with the first current collector and the interfacial layer. In some examples, the solid state battery further comprises a second current collector, wherein the cathode is sandwiched between and in contact with the second current collector and the halide solid state electrolyte layer. In some examples, the first current collector and / or the second current collector (when present) independently comprise a metal, a carbon material, or a combination thereof.

[0037] In some examples, the solid state battery further includes a casing that at least partially surrounds and / or encloses a cell comprising the anode (when present), the interfacial layer, the halide solid state electrolyte layer, the composite cathode, the first current collector (when present), and the second current collector (when present). In some examples, the casing comprises a polymer, a metal, an alloy, a polymer coated metal foil, or a combination thereof.

[0038] In some examples, the anode is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0039] In some examples, the interfacial layer is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0040] In some examples, the solid state battery exhibits an energy density of from 75 Wh / kg to 600 Wh / kg. In some examples, the solid state battery exhibits a specific discharge capacity of from 100 mA h / g to 400 mA h / g when discharged at a rate of from 0.1 C to 10 C.

[0041] In some examples, the solid state battery is rechargeable.

[0042] In some examples, the solid state battery exhibits a coulombic efficiency of 80% or more for 100 cycles or more. In some examples, the solid state battery exhibits a coulombic efficiency of 99% or more for 100 cycles or more.

[0043] In some examples, the solid state battery exhibits a capacity retention of 80% or more for 100 cycles or more. In some examples, the solid state battery exhibits a capacity retention of 90% or more for 100 cycles or more.

[0044] Also disclosed herein are methods of making any of the solid state batteries disclosed herein. In some examples, the methods comprise: making the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode; and stacking the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode together to form the solid state battery. In some examples, the methods comprise disposing the halide solid state electrolyte layer on the composite cathode, disposing the interfacial layer on the halide solid state electrolyte layer, and disposing the anode on the interfacial layer, such that the interfacial layer is between the anode and the halide solid state electrolyte layer, and the halide solid state electrolyte layer is between the interfacial layer and the composite cathode. In some examples, the methods further comprise disposing the composite cathode on the second current collector before disposing the halide solid state electrolyte on the composite cathode. In some examples, the methods further comprise disposing the first current collector on the anode.

[0045] Also disclosed herein are systems comprising one or more of the solid state batteries disclosed herein. In some examples, the system is an energy storage system.

[0046] Also disclosed herein are articles comprising one or more of the solid state batteries disclosed herein. In some examples, the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle. In some examples, the article comprises an electronic device, such as a portable electronic device, a laptop, a watch, or a cell phone.

[0047] Additional advantages of the disclosed devices, systems, and methods will be set forth in part in the description which follows, and in part will be obvious from the description. The advantages of the disclosed devices, systems, and methods will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosed devices, systems, and methods, as claimed.

[0048] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

[0049] BRIEF DESCRIPTION OF THE FIGURES

[0050] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects of the disclosure, and together with the description, serve to explain the principles of the disclosure.

[0051] Figure 1. X-Ray diffraction patterns of two example halide solid electrolytes, LizZrClo, and Li3YC16.

[0052] Figure 2. Electrochemical impedance spectrum of LEYCE example halide solid electrolyte fit with an equivalent circuit to determine the resistance of the material, which was used to calculate its Li+conductivity of 3.5 x 10'4Scm-1.

[0053] Figure 3. Electrochemical impedance spectrum of LizZrCle example halide solid electrolyte fit with an equivalent circuit to determine the resistance of the material, which was used to calculate its Li+conductivity of 2.9 x IO-4Scm1.

[0054] Figure 4. Electrochemical impedance spectrum of Li3N interfacial layer material fit with an equivalent circuit to determine the resistance of the material, which was used to calculate its Li+conductivity of 5 x 10"6Scm1

[0055] Figure 5. Equivalent circuit used to fit the electrochemical impedance spectra in Figure 2 - Figure 4.

[0056] Figure 6A. Schematic of an example pseudo solid-state battery.

[0057] Figure 6B. Schematic of an example all-solid-state battery.

[0058] Figure 7. Periodic galvanostatic cycling curves at 50°C of an all-solid-state battery comprising an LiNio.8Mno.1Coo.1O2, carbon black, and Li3YCle composite cathode, an Li3YCle solid electrolyte, and Li3N interfacial layer and an Li-In anode cycled at a 0.1 C rate for charge and discharge.

[0059] Figure 8. Capacity versus cycle number for the first 100 cycles at 50°C of the same cell shown in Figure 7.

[0060] Figure 9. Periodic galvanostatic cycling curves at 50°C of an all-solid-state battery comprising an LiNio.3Mno.1Coo.1O2, carbon black, and Li2ZrCle composite cathode, an Li2ZrCle solid electrolyte, and Li3N interfacial layer and an Li-In anode cycled at a 0.1 C rate for charge and discharge. Figure 10. Capacity versus cycle number for the first 100 cycles at 50°C of the same cell shown in Figure 9.

[0061] Figure 11. The first five galvanostatic cycling curves at room-temperature of an all-solid- state battery comprising single crystal LiNio.8Mno.1Coo.1O2, carbon black, and LisYCk composite cathode, an LLYCk, solid electrolyte, and Li iN interfacial layer and a lithium metal anode cycled at a 0.05 C rate for charge and discharge.

[0062] DETAILED DESCRIPTION

[0063] The devices, methods, and systems described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein.

[0064] Before the present devices, methods, and systems are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0065] Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.

[0066] General Definitions

[0067] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.

[0068] Throughout the description and claims of this specification the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps. As used in the specification and in the claims, the term “comprising” can include the aspects “consisting of’ and “consisting essentially of.”

[0069] As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the component” includes mixtures of two or more such components, and the like. “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

[0070] Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. By “about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect, ft will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0071] Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1 , 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.

[0072] When the specific values are disclosed between two end values, it is understood that these end values can also be included.

[0073] For the terms “for example” and “such as,” and grammatical equivalences thereof, the phrase “and without limitation” is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used not used in a restrictive sense, but for explanatory purposes. “Exemplary” means “an example of’ and is not intended to convey an indication of a preferred or ideal embodiment.

[0074] It is understood that throughout this specification the identifiers “first” and “second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms.

[0075] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper," “bottom,” “top,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the term "below" can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly.

[0076] It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element, or intervening elements may be present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationship between elements or layers should be interpreted in a like fashion (e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," "on" versus "directly on").

[0077] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0078] As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.

[0079] Still further, the term “substantially” can, in some aspects, refer to at least about 80 %, at least about 85 %, at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about 100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount.

[0080] In other aspects, as used herein, the term “substantially free,” when used in the context of a composition or component of a composition that is substantially absent, is intended to refer to an amount that is then about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition.

[0081] The expressions “ambient temperature” and “room temperature” as used herein are understood in the art and refer generally to a temperature from about 20°C to about 35 °C.

[0082] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight, components Y, X, and Y are present at a weight ratio of 2:5 and are present in such a ratio regardless of whether additional components are contained in the mixture.

[0083] A weight percent (wt.%) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0084] It is understood that the term “salt,” as used herein, refers to a chemical compound that can be formed form a reaction between an acid and a base. It is understood that the term “salt,” as used herein, encompasses both inorganic and organic salts capable of providing the desired properties to the composition. In still further aspects, a cation of the disclosed herein salts is a metal cation.

[0085] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of ordinary skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0086] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0087] The organic moieties mentioned when defining variable positions within the general formulae described herein (e.g., the term “halogen”) are collective terms for the individual substituents encompassed by the organic moiety. The prefix Cn-Cmpreceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows.

[0088] The term “ion,” as used herein, refers to any molecule, portion of a molecule, cluster of molecules, molecular complex, moiety, or atom that contains a charge (positive, negative, or both at the same time within one molecule, cluster of molecules, molecular complex, or moiety (e.g., zwitterions)) or that can be made to contain a charge. Methods for producing a charge in a molecule, portion of a molecule, cluster of molecules, molecular complex, moiety, or atom are disclosed herein and can be accomplished by methods known in the art, e.g., protonation, deprotonation, oxidation, reduction, alkylation, acetylation, esterification, de-esterification, hydrolysis, etc.

[0089] The term “anion” is a type of ion and is included within the meaning of the term “ion.” An “anion” is any molecule, portion of a molecule (e.g., zwitterion), cluster of molecules, molecular complex, moiety, or atom that contains a net negative charge or that can be made to contain a net negative charge. The term “anion precursor” is used herein to specifically refer to a molecule that can be converted to an anion via a chemical reaction (e.g., deprotonation).

[0090] The term “cation” is a type of ion and is included within the meaning of the term “ion.” A “cation” is any molecule, portion of a molecule (e.g., zwitterion), cluster of molecules, molecular complex, moiety, or atom, that contains a net positive charge or that can be made to contain a net positive charge. The term “cation precursor” is used herein to specifically refer to a molecule that can be converted to a cation via a chemical reaction (e.g., protonation or alkylation).

[0091] The term “halide” or “halogen” or “halo” as used herein refers to fluorine, chlorine, bromine, and iodine.

[0092] Solid State Batteries

[0093] Disclosed herein are solid state batteries, such as pseudo solid state and all solid state batteries.

[0094] For example, disclosed herein are solid state batteries comprising: an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer (e.g., a layer comprising a first halide solid state electrolyte); and a composite cathode. The interfacial layer is disposed on and in contact with the halide solid state electrolyte layer. The halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode. The interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window, and the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer.

[0095] In some examples, the solid state battery further comprises an anode, wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer. In some examples, the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode. In some examples, the anode is formed in situ (e.g. the anode is plated in situ during cycling).

[0096] For example, disclosed herein are solid state batteries comprising: an anode; an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer (e.g., a layer comprising a first halide solid state electrolyte); and a composite cathode. The interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer. The halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode. The anode, the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window, and the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode.

[0097] Without wishing to be bound by theory, the inclusion of the interfacial layer can overcome the instability of the halide solid state electrolyte layer with the anode (e.g., lithium metal anode) to enable an all-solid-state battery with a halide solid state electrolyte. For example, the integration of the interfacial layer between the halide solid state electrolyte and the anode can stabilize the interface for extended duration and plating / stripping of the anode.

[0098] Anode

[0099] The solid state batteries disclosed herein comprise an anode. The anode can comprise any suitable material, such as those known in the art.

[0100] In some examples, the anode is formed in situ (e.g., the anode is plated in situ during cycling).

[0101] In some examples, the anode has a high capacity and / or a high energy density. For example, the anode has a specific capacity of 100 mAh / g or more (e.g., 125 mAh / g or more, 150 mAh / g or more, 175 mAh / g or more, 200 mAh / g or more, 225 mAh / g or more, 250 mAh / g or more, 300 mAh / g or more, 350 mAh / g or more, 400 mAh / g or more, 450 mAh / g or more, 500 mAh / g or more, 600 mAh / g or more, 700 mAh / g or more, 800 mAh / g or more, 900 mAh / g or more, 1000 mAh / g or more, 1250 mAh / g or more, 1500 mAh / g or more, 1750 mAh / g or more, 2000 mAh / g or more, 2250 mAh / g or more, 2500 mAh / g or more, 2750 mAh / g or more, 3000 mAh / g or more, 3250 mAh / g or more, 3500 mAh / g or more, or 3750 mAh / g or more). In some examples, the anode can have a specific capacity of 4000 mAh / g or less (e.g., 3750 mAh / g or less, 3500 mAh / g or less, 3250 mAh / g or less, 3000 mAh / g or less, 2750 mAh / g or less, 2500 mAh / g or less, 2250 mAh / g or less, 2000 mAh / g or less, 1750 mAh / g or less, 1500 mAh / g or less, 1250 mAh / g or less, 1000 mAh / g or less, 900 mAh / g or less, 800 mAh / g or less, 700 mAh / g or less, 600 mAh / g or less, 500 mAh / g or less, 450 mAh / g or less, 400 mAh / g or less, 350 mAh / g or less, 300 mAh / g or less, 250 mAh / g or less, 225 mAh / g or less, 200 mAh / g or less, 175 mAh / g or less, 150 mAh / g or less, or 125 mAh / g or less). The specific capacity of the anode can range from any of the minimum values described above to any of the maximum values described above. For example, the anode can have a specific capacity of from 100 to 4000 mAh / g (e.g., from 100 to 2000 mAh / g, from 2000 to 4000 mAh / g, from 100 to 1000 mAh / g, from 1000 to 2000 mAh / g, from 2000 to 3000 mAh / g, from 3000 to 4000 mAh / g, from 100 to 3500 mAh / g, from 100 to 3000 mAh / g, from 100 to 2500 mAh / g, from 100 to 1500 mAh / g, from 100 to 750 mAh / g, from 500 to 4000 mAh / g, from 750 to 4000 mAh / g, from 1000 to 4000 mAh / g, from 1500 to 4000 mAh / g, from 2500 to 4000 mAh / g, from 250 to 3750 mAh / g, from 500 to 3500 mAh / g, from 750 to 3250 mAh / g, or from 1000 to 3000 mAh / g). The specific capacity of the anode can be calculated and / or theoretical. The specific capacity of the anode can be measured using methods known in the art, such as in an electrochemical cell, similar to charge / discharge cycling of a battery, for example using Galvanostatic cycling.

[0102] In some examples, the anode has a low intercalation voltage. For example, the anode can have an intercalation voltage of 1 V or less versus Li+ / Li° (e.g., 0.95 V or less, 0.9 V or less, 0.85 V or less, 0.8 V or less, 0.75 V or less, 0.7 V or less, 0.65 V or less, 0.6 V or less, 0.55 V or less, 0.5 V or less, 0.45 V or less, 0.4 V or less, 0.35 V or less, 0.3 V or less, 0.25 V or less, 0.2 V or less, 0.15 V or less, 0.1 V or less, or 0.05 V or less).

[0103] In some examples, the anode comprises a metal, an alloy, an intercalation material, or a combination thereof. For example, the anode can comprise lithium, potassium, sodium, silicon, indium, graphite, hard carbon, or a combination thereof.

[0104] In some examples, the anode comprises lithium (e.g., lithium metal and / or a lithium alloy). In some examples, the anode comprises lithium metal. In some examples, the anode comprises a lithium alloy, such as a lithium-indium alloy, a lithium-magnesium alloy, a lithiumaluminum alloy, a lithium-iron alloy, or a combination thereof. In some examples, the anode comprises a lithium-indium alloy.

[0105] In some examples, the anode comprises silicon or a silicon composite.

[0106] In some examples, the anode is a composite (e.g., a composite anode).

[0107] In some examples, the composite anode further includes a binder. Examples of suitable binders are known in the art. For example, the binder can comprise a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene -butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0108] In some examples, the composite anode further includes a conductive additive. The conductive additive can comprise any suitable material, such as those known in the art. Examples of suitable conductive additives include, but are not limited to, carbon black, modified carbon black, graphene, multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, reduced graphene oxide, and combinations thereof. In some examples, the conductive additive comprises carbon black.

[0109] In some examples, the anode comprises a prelithiated host structure anode (e.g., a prelithiated silicon anode, a prelithiated silicon-graphite composite anode, a prelithiated graphite, a prelithiated hard carbon, etc.), a silicon-graphite composite anode, or a combination thereof.

[0110] Interfacial Layer

[0111] The solid state batteries disclosed herein further comprise an interfacial layer.

[0112] The interfacial layer can comprise any suitable material. For example, the interfacial layer can comprise any material such that the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode. In some examples, the interfacial layer can comprise a material that is compatible with the halide solid state electrolyte layer and the anode.

[0113] In some examples, the interfacial layer can be formed in situ from a precursor layer. For example, the precursor layer can comprise a material that reacts (e.g., with the anode) during cycling to form the interfacial layer.

[0114] Examples of suitable interfacial materials include, but are not limited to, alkali metal nitrides, alkali metal phosphides, and combinations thereof. In some examples, the interfacial material can comprise LisN, LijP, NasP, NaaN, K3N, or a combination thereof. In some examples, the interfacial material comprises LEN, LEP, or a combination thereof. In some examples, the interfacial material comprises LEN.

[0115] In some examples, the interfacial layer has an ionic conductivity of lithium of 1 x 108Scm'1or more (e.g., 5 x 10'8Scm'1or more, 1 x 10’7Scm'1or more, 5 x 10'7Scm'1or more, 1 x 10"6Scm1or more, 5 x 10'6Scm1or more, 1 x 10"5Scm1or more, 5 x 10"5Scm1or more, 1 x 10'4Scm1or more, 5 x 10'4Scm1or more, 1 x 10"3Scm-1or more, 5 x 10"3Scm1or more, 1 x 10'2Scm1or more, or 5 x 10'2Scm'1or more). In some examples, the interfacial layer has an ionic conductivity of lithium of 0.1 Scm'1or less (e.g., 5 x 10'2Scm'1or less, 1 x IO'2Scm'1or less, 5 x 10'3Scm'1or less, 1 x 10‘3Scm'1or less, 5 x 10"4Scm'1or less, 1 x 10'4Scm'1or less, 5 x 10'5Scm'1or less, 1 x 10'5Scm'1or less, 5 x 10'6Scm'1or less, 1 x 10'6Scm'1or less, 5 x 10'7Scm'1or less, 1 x 10'7Scm'1or less, or 5 x 10'8Scm'1or less). The ionic conductivity of lithium of the interfacial layer can range from any of the minimum values described above to any of the maximum values described above. For example, the interfacial layer can have an ionic conductivity of lithium of from 1 x 10'8Scm'1to 0.1 Scm'1(e.g., from 1 x 10'8to 5 x 10'4Scm'1, from 5 x 10'4to 0.1 Scm'1, from 1 x 10'8to 5 x 10'7Scm'1, from 5 x 10'7to 1 x 10'5Scm'1, from 1 x 10'5to 5 x 10'3Scm'1, from 5 x 10'3to 0.1 Scm'1, 1 x 10'7to 0.1 Scm'1, from 1 x 10'6to 0.1 Scm-1, from 1 x 10'5to 0.1 Scm-1, from 1 x 10"4to 0.1 Scm-1, from 1 x 10"3to 0.1 Scm-1, or from 1 x 10"2to 0. 1 Scm1). The ionic conductivity of the interfacial layer can be measured using methods known in the art, such as using Electrochemical Impedance Spectroscopy (EIS) and then calculated with an ionic conductivity equation.

[0116] In some examples, the interfacial layer can have an average thickness of 1 nanometer (nm) or more (e.g., 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 225 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1 micrometer (micron, pm) or more, 1.25 pm or more, 1.5 pm or more, 1.75 pm or more, 2 pm or more, 2.25 pm or more, 2.5 pm or more, 3 pm or more, 3.5 pm or more, 4 pm or more, 4.5 pm or more, 5 pm or more, 6 pm or more, 7 pm or more, 8 pm or more, 9 pm or more, 10 pm or more, 15 pm or more, 20 pm or more, 25 pm or more, 30 pm or more, 35 pm or more, 40 pm or more, 45 pm or more, 50 pm or more, 60 pm or more, 70 pm or more, 80 pm or more, or 90 pm or more). In some examples, the interfacial layer can have an average thickness of 100 micrometers (microns, pm) or less (e.g., 90 pm or less, 80 pm or less, 70 pm or less, 60 pm or less, 50 pm or less, 45 pm or less, 40 pm or less, 35 pm or less, 30 pm or less, 25 pm or less, 20 pm or less, 15 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, 5 pm or less, 4.5 pm or less, 4 pm or less, 3.5 pm or less, 3 pm or less, 2.5 pm or less, 2.25 pm or less, 2 pm or less, 1.75 pm or less, 1.5 pm or less, 1.25 pm or less, 1 pm or less, 900 nanometers (nm) or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 225 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less). The average thickness of the interfacial layer can range from any of the minimum values described above to any of the maximum values described above. For example, the interfacial layer can have an average thickness of from 1 nanometer (nm) to 100 micrometers (microns, pm) (e.g., from 1 nm to 1 pm, from 1 pm to 100 pm, from 1 nm to 10 nm, from 10 nm to 100 nm, from 100 nm to 1 pm, from 1 pm to 10 pm, from 10 pm to 100 pm, from 1 nm to 75 pm, from 1 nm to 50 pm, from 1 nm to 25 pm, from 1 nm to 10 pm, from 1 nm to 1 pm, from 1 nm to 100 nm, from 1 nm to 50 nm, from 1 nm to 25 nm, from 10 nm to 100 pm, from 25 nm to 100 pm, from 50 nm to 100 pm, from 100 nm to 100 pm, from 1 pm to 100 pm, from 10 pm to 100 pm, from 25 pm to 100 pm, from 50 pm to 100 pm, from 5 nm to 95 pm, from 10 nm to 90 pm, from 25 nm to 75 pm, from 50 nm to 50 pm, from 75 nm to 25 pm, from 1 pm to 20 pm, or from 100 nm to 1 pm). The thickness of the interfacial layer can be measured using methods known in the art, such as evaluation by electron microscopy (e.g., scanning electron microscopy, transmission electron microscopy, or a combination thereof) and / or dynamic light scattering. As used herein, the average thickness of the interfacial layer is determined by scanning electron microscopy.

[0117] In some examples, the interfacial layer can comprises a plurality of particles of the interfacial material.

[0118] The plurality of particles of the interfacial material can comprise particles of any shape desired for the specific application (e.g., a sphere, a rod, a quadrilateral, an ellipse, a triangle, a polygon, etc.). In some examples, the plurality of particles of the interfacial material can have an irregular shape, a regular shape, an isotropic shape, an anisotropic shape, or a combination thereof. In some examples, the plurality of particles of the interfacial material can have an isotropic shape. In some examples, the plurality of particles of the interfacial material are substantially spherical.

[0119] The plurality of particles of the interfacial material can have an average particle size. “Average particle size” and “mean particle size” are used interchangeably herein, and generally refer to the statistical mean particle size of the particles in a population of particles. For example, the average particle size for a plurality of particles with a substantially spherical shape can comprise the average diameter of the plurality of particles. For a particle with a substantially spherical shape, the diameter of a particle can refer, for example, to the hydrodynamic diameter. As used herein, the hydrodynamic diameter of a particle can refer to the largest linear distance between two points on the surface of the particle. For an anisotropic particle, the average particle size can refer to, for example, the average maximum dimension of the particle (e.g., the length of a rod shaped particle, the diagonal of a cube shape particle, the bisector of a triangular shaped particle, etc.). For an anisotropic particle, the average particle size can refer to, for example, the hydrodynamic size of the particle. Mean particle size can be measured using methods known in the art, such as evaluation by electron microscopy (e.g., scanning electron microscopy, transmission electron microscopy, or a combination thereof) and / or dynamic light scattering. As used herein, the average particle size is determined by scanning electron microscopy.

[0120] In some examples, the plurality of particles of the interfacial material can have an average particle size of 1 nanometers (nm) or more (e.g., 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 225 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1 micrometer (micron, pm) or more, 1.25 pm or more, 1.5 pm or more, 1.75 pm or more, 2 pm or more, 2.25 pm or more, 2.5 pm or more, 3 pm or more, 3.5 pm or more, 4 pm or more, 4.5 pm or more, 5 pm or more, 6 pm or more, 7 pm or more, 8 pm or more, 9 pm or more, 10 pm or more, 15 pm or more, or 20 pm or more). In some examples, the plurality of particles of the interfacial material can have an average particle size of 25 micrometers (microns, pm) or less (e.g., 20 pm or less, 15 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, 5 pm or less, 4.5 pm or less, 4 pm or less, 3.5 pm or less, 3 pm or less, 2.5 pm or less, 2.25 pm or less, 2 pm or less, 1.75 pm or less, 1.5 pm or less, 1.25 pm or less, 1 pm or less, 900 nanometers (nm) or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 225 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less). The average particle size of the plurality of particles of the interfacia] material can range from any of the minimum values described above to any of the maximum values described above. For example, the plurality of particles of the interfacial material can have an average particle size of from 1 nanometers (nm) to 25 micrometers (microns, pm) (e.g., from 1 nm to 100 nm, from 100 nm to 25 pm, from 1 nm to 10 nm, from 10 nm to 100 nm, from 100 nm to 1 pm, from 1 pm to 10 pm, from 10 pm to 25 pm, from 1 nm to 20 pm, from 1 nm to 10 pm, from 1 nm to 1 pm, from 1 nm to 100 nm, from 1 nm to 50 nm, from 1 nm to 25 nm, from 10 nm to 25 pm, from 25 nm to 25 pm, from 50 nm to 25 pm, from 100 nm to 25 pm, from 1 pm to 25 pm, from 5 pm to 25 pm, from 10 pm to 25 pm, from 10 nm to 20 pm, from 50 nm to 15 pm, from 100 nm to 10 pm, or from 1 to 10 pm). In some examples, the plurality of particles of the interfacial material can have an average particle size of from 1 to 10 micrometers (microns, pm).

[0121] In some examples, the plurality of particles of the interfacial material can be substantially monodisperse. “Monodisperse” and “homogeneous size distribution,” as used herein, and generally describe a population of particles where all of the particles are the same or nearly the same size. As used herein, a monodisperse distribution refers to particle distributions in which 80% of the distribution (e.g., 85% of the distribution, 90% of the distribution, or 95% of the distribution) lies within 25% of the average particle size (e.g., within 20% of the average particle size, within 15% of the average particle size, within 10% of the average particle size, or within 5% of the average particle size).

[0122] In some examples, the plurality of particles of the interfacial material can comprise: a first population of particles having a first average particle size, a first particle shape, and a first composition; and a second population of particles having a second average particle size, a second particle shape, and a second composition; wherein the first average particle size and the second average particle size are different, the first particle shape and the second particle shape are different, the first composition and the second composition are different, or a combination thereof. In some examples, the plurality of particles of the interfacial material can comprise a mixture of a plurality of populations of particles, wherein each population of particles within the mixture is different with respect to average particle size, shape, composition, or a combination thereof.

[0123] Halide Solid State Electrolyte Layer

[0124] The solid state batteries further comprise a halide solid state electrolyte layer (e.g., a layer comprising a first halide solid state electrolyte).

[0125] The first halide solid state electrolyte can comprise any suitable material, such as those known in the art. Examples of suitable materials for the first halide solid state electrolyte include, hut are not limited to, lithium halides, sodium halides, or a combination thereof. In some examples, the first halide solid state electrolyte comprises a lithium halide. In some examples, the first halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides (e.g., F, Cl, Br, I, or a combination thereof), z is an integer from -2 to 2 (e.g., z is -2, -1, 0, 1, or 2), and [III+z] represents the valence of the M-ion(s) in the compound. In some examples, M can be a metal, such as a transition metal, a post transition metal, or a combination thereof. Examples of transition metals include, but are not limited to, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and combinations thereof. Examples of post transition metals include, but are not limited to, Al, Ga, In, Sn, Tl, Pb, Bi, Po, and combinations thereof. In some examples, M can be Y, Zr, In, or a combination thereof. In some examples, M can be Y and / or Zr. In some examples, the first halide solid state electrolyte can comprise LEYXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, the first halide solid state electrolyte can comprise Li2ZrXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, the first halide solid state electrolyte comprises LEYCIe. LiiZrCl 6, or a combination thereof.

[0126] In some examples, the first halide solid state electrolyte can have an ionic conductivity of lithium of 1 x 10'5Scm1or more (e.g., 5 x 10'5Scm-1or more, 1 x 10’4Scm1or more, 5 x 10'4 Scm1or more, 1 x 10"3Scm-1or more, 5 x 10'3Scm-1or more, 1 x 10"2Scm-1or more, or 5 x 10’2Scm1or more). In some examples, the first halide solid state electrolyte can have an ionic conductivity of lithium of 0.1 Scm-1or less (e.g., 5 x 10'2Scm1or less, 1 x 10'2Scm1or less, 5 x 10’3Scm1or less, 1 x 10'3Scm1or less, 5 x 10'4Scm-1or less, 1 x 10’4Scm1or less, or 5 x 10"5Scm1or less). The ionic conductivity of lithium of the first halide solid state electrolyte can range from any of the minimum values described above to any of the maximum values described above. For example, the first halide solid state electrolyte can have an ionic conductivity of lithium of from 1 x 10‘5Scm-1to 0.1 Scm1(e.g., from 1 x 10‘5to 5 x 10‘3Scm1, from 5 x 10'3to 0.1 Scm1, from 1 x IO-5to 1 x 10"4Scm1, from 1 x 10"4to 1 x 10’3Scm1, from 1 x 10'3to 1 x 10"2Scm1, from 1 x 10"2to 0.1 Scm1, from 1 x 10"4to 0.1 Scm1, from 1 x 10"3to 0.1 Scm1, or from 1 x 10"2to 0.1 Scm1). The ionic conductivity can be measured using methods known in the art, such as using Electrochemical Impedance Spectroscopy (EIS) and then calculated with an ionic conductivity equation.

[0127] In some examples, the halide solid state electrolyte layer has an average thickness of 1 micrometer (micron, pm) or more (e.g., 5 pm or more, 10 pm or more, 15 pm or more, 20 pm or more, 25 pm or more, 30 pm or more, 35 pm or more, 40 pm or more, 45 pm or more, 50 pm or more, 55 pm or more, 60 pm or more, 65 pm or more, 70 pm or more, 75 pm or more, 80 pm or more, 85 pm or more, 90 pm or more, or 95 pm or more). In some examples, the halide solid state electrolyte layer can have an average thickness of 100 micrometers (microns, pm) or less (e.g., 95 pm or less, 90 pm or less, 85 pm or less, 80 pm or less, 75 pm or less, 70 pm or less, 65 pm or less, 60 pm or less, 55 pm or less, 50 pm or less, 45 pm or less, 40 pm or less, 35 pm or less, 30 pm or less, 25 pm or less, 20 pm or less, 15 pm or less, 10 pm or less, or 5 pm or less). The average thickness of the halide solid state electrolyte layer can range from any of the minimum values described above to any of the maximum values described above. For example, the halide solid state electrolyte layer can have an average thickness of from 1 to 100 micrometers (microns, pm) (e.g., from 1 to 50 pm, from 50 to 100 pm, from 1 to 20 pm, from 20 to 40 pm, from 40 to 60 pm, from 60 to 80 pm, from 80 to 100 pm, from 1 to 80 pm, from 1 to 60 pm, from 1 to 40 pm, from 1 to 10 pm, from 5 to 100 pm, from 10 to 100 pm, from 20 to 100 pm, from 40 to 100 pm, from 60 to 100 pm, from 5 to 95 pm, from 10 to 90 pm, or from 20 to 80 pm). The thickness of the halide solid state electrolyte layer can be measured using methods known in the art, such as evaluation by electron microscopy (e.g., scanning electron microscopy, transmission electron microscopy, or a combination thereof) and / or dynamic light scattering. As used herein, the average thickness of the halide solid state electrolyte layer is determined by scanning electron microscopy. In some examples, the halide solid state electrolyte layer comprises a plurality of particles of the first halide solid state electrolyte.

[0128] The plurality of particles of the first halide solid state electrolyte can comprise particles of any shape desired for the specific application (e.g., a sphere, a rod, a quadrilateral, an ellipse, a triangle, a polygon, etc.). In some examples, the plurality of particles of the first halide solid state electrolyte can have an irregular shape, a regular shape, an isotropic shape, an anisotropic shape, or a combination thereof. In some examples, the plurality of particles of the first halide solid state electrolyte can have an isotropic shape. In some examples, the plurality of particles of the first halide solid state electrolyte are substantially spherical.

[0129] The plurality of particles of the first halide solid state electrolyte can have an average particle size. For example, the plurality of particles of the first halide solid state electrolyte can have an average particle size of 1 nanometer (nm) or more (e.g., 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 225 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1 micrometer (micron, pm) or more, 1 .25 pm or more, 1 .5 pm or more, 1 .75 pm or more, 2 pm or more, 2.25 pm or more, 2.5 pm or more, 3 pm or more, 3.5 pm or more, 4 pm or more, 4.5 pm or more, 5 pm or more, 6 pm or more, 7 pm or more, 8 pm or more, 9 pm or more, 10 pm or more, 15 pm or more, 20 pm or more, 25 pm or more, 30 pm or more, 35 pm or more, 40 pm or more, 45 pm or more, 50 pm or more, 60 pm or more, 70 pm or more, 80 pm or more, or 90 pm or more ). In some examples, the plurality of particles of the first halide solid state electrolyte can have an average particle size of 100 micrometers (microns, pm) or less (e.g., 90 pm or less, 80 pm or less, 70 pm or less, 60 pm or less, 50 pm or less, 45 pm or less, 40 pm or less, 35 pm or less, 30 pm or less, 25 pm or less, 20 pm or less, 15 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, 5 pm or less, 4.5 pm or less, 4 pm or less, 3.5 pm or less, 3 pm or less, 2.5 pm or less, 2.25 pm or less, 2 pm or less, 1.75 pm or less, 1.5 pm or less, 1.25 pm or less, 1 pm or less, 900 nanometers (nm) or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 225 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less). The average particle size of the plurality of particles of the first halide solid state electrolyte can range from any of the minimum values described above to any of the maximum values described above. For example, the plurality of particles of the first halide solid state electrolyte can have an average particle size of from 1 nanometer to 100 micrometers (e.g., from 1 nm to 1 pm, from 1 pm to 100 pm, from 1 nm to 10 nm, from 10 nm to 100 nm, from 100 nm to 1 pm, from 1 pm to 10 pm, from 10 pm to 100 pm, from 1 nm to 75 pm, from 1 nm to 50 pm, from 1 nm to 25 pm, from 1 nm to 10 pm, from 1 nm to 1 pm, from 1 nm to 100 nm, from 1 nm to 50 nm, from 1 nm to 25 nm, from 10 nm to 100 pm, from 25 nm to 100 pm, from 50 nm to 100 pm, from 100 nm to 100 pm, from 1 pm to 100 pm, from 10 pm to 100 pm, from 25 pm to 100 pm, from 50 pm to 100 pm, from 5 nm to 95 pm, from 10 nm to 90 pm, from 25 nm to 75 pm, from 50 nm to 50 pm, from 75 nm to 25 pm, from 100 nm to 20 pm, or from 100 nm to 10 pm).

[0130] In some examples, the plurality of particles of the first halide solid state electrolyte can be substantially monodisperse.

[0131] In some examples, the plurality of particles of the first halide solid state electrolyte can comprise: a first population of particles having a first average particle size, a first particle shape, and a first composition; and a second population of particles having a second average particle size, a second particle shape, and a second composition; wherein the first average particle size and the second average particle size are different, the first particle shape and the second particle shape are different, the first composition and the second composition are different, or a combination thereof. In some examples, the plurality of particles of the first halide solid state electrolyte can comprise a mixture of a plurality of populations of particles, wherein each population of particles within the mixture is different with respect to average particle size, shape, composition, or a combination thereof.

[0132] In some examples, the electrochemical stability window of the halide solid state electrolyte layer is compatible with the electrochemical stability window of the composite cathode. In some examples, the electrochemical stability window of the halide solid state electrolyte layer overlaps with the electrochemical stability window of the interfacial layer and the electrochemical stability window of the composite cathode.

[0133] In some examples, the halide solid state electrolyte layer is high-voltage stable. For example, the halide solid state electrolyte layer can be stable at a voltage of -0. 1 V or more vs. Li+ / Li° (e.g., 0 V or more, 0.5 V or more, 1 V or more, 1.5 V or more, 2 V or more, 2.5 V or more, 3 V or more, 3.5 V or more, 4 V or more, 4.5 V or more, or 5 V or more). In some examples, the halide solid state electrolyte layer can be stable at a voltage of 5.5 V or less vs. Li+ / Li° (e.g., 5 V or less, 4.5 V or less, 4 V or less, 3.5 V or less, 3 V or less, 2.5 V or less, 2 V or less, 1.5 V or less, 1 V or less, 0.5 V or less, or 0 V or less). The voltage at which the halide solid state electrolyte layer is stable can range from any of the minimum values described above to any of the maximum values described above. For example, the halide solid state electrolyte layer can be stable at a voltage of from -0. 1 V to 5.5 V vs. Li+ / Li° (e.g., from -0. 1 to 2.5 V, from 2.5 to 5.5 V, from -0.1 to 5 V, from -0.1 to 4.5 V, from -0.1 to 4 V, from -0.1 to 3.5 V, from -0.1 to 3 V, from -0.1 to 2.5 V, from -0.1 to 2 V, from -0.1 to 1.5 V, from -0.1 to 1 V, from 0 to 5.5 V, from 0.5 to 5.5 V, from 1 to 5.5 V, from 1.5 to 5.5 V, from 2 to 5.5 V, from 2.5 to 5.5 V, from 3 to 5.5 V, from 3.5 to 5.5 V, from 4 to 5.5 V, from 0 to 5 V, or from 1 to 5 V). As used herein, “stable” means mean no reaction occur or a reaction occurs that is favorable for lithium-transport (e.g., Li-ion conducting reaction products).

[0134] Composite Cathode

[0135] The solid state batteries further comprise a composite cathode. The composite cathode comprises a cathode active material, a conductive additive, and an electrolyte. The electrolyte of the composite cathode comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0136] Cathode Active Material

[0137] The cathode active material can comprise any suitable material, such as those known in the art. Examples of suitable cathode active materials include, but are not limited to, high density nickel-rich layered transition metal oxides (e.g., Li[NixMnyCoz]O2 (x+y+z = 1)), LiFei.xMnxPO4 (LMFP), lithium iron phosphate (LFP, LiFePCL), lithium manganese oxide (LiMmCh). nickel- doped lithium manganese oxide (LitNio.5Mn1.5lO4), LiCoO2, LiNiO2, and combinations thereof. In some examples, the cathode active material comprises Li[NixMnyCoz]O2 where x+y+z = 1, LiFePO4, or a combination thereof. In some examples, the cathode active material comprises Li[NixMnyCoz]O2 where x+y+z = 1. In some examples, the cathode active material comprises LiNio.sMno.1 Coo.102.

[0138] Conductive Additive

[0139] The conductive additive can comprise any suitable material, such as those known in the art. Examples of suitable conductive additives include, but are not limited to, carbon black, modified carbon black, graphene, multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, reduced graphene oxide, and combinations thereof. In some examples, the conductive additive comprises carbon black.

[0140] Binder

[0141] In some examples, the composite cathode further comprises a binder. Examples of suitable binders are known in the art. For example, the binder can comprise a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0142] Cathode Electrolyte

[0143] In some examples, the solid state battery is a pseudo solid state battery. In some examples, the solid state battery is a pseudo solid state battery and the electrolyte of the composite cathode is a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0144] In some examples, the solid state battery is an all solid state battery. Tn some examples, the solid state battery is an all solid state battery and the electrolyte of the composite cathode is a plurality of particles comprising a second halide solid state electrolyte.

[0145] The second halide solid state electrolyte can comprise any suitable material, such as those known in the art. Examples of suitable materials for the second halide solid state electrolyte include, but are not limited to, lithium halides, sodium halides, or a combination thereof. In some examples, the second halide solid state electrolyte comprises a lithium halide. In some examples, the second halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides (e.g., F, Cl, Br, I, or a combination thereof), z is an integer from -2 to 2 (e.g., z is -2, -1 , 0, 1 , or 2), and [ITI+z] represents the valence of the M-ion(s) in the compound. In some examples, M can be a metal, such as a transition metal, a post transition metal, or a combination thereof. Examples of transition metals include, but are not limited to, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and combinations thereof. Examples of post transition metals include, but are not limited to, Al, Ga, In, Sn, Tl, Pb, Bi, Po, and combinations thereof. In some examples, M can be Y, Zr, In, or a combination thereof. In some examples, M can be Y and / or Zr. In some examples, the second halide solid state electrolyte can comprise LisYXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, the second halide solid state electrolyte can comprise LizZrXe, where X is F, Cl, Br, I, or a combination thereof. In some examples, the second halide solid state electrolyte comprises LisYCIe, LizZrCle, or a combination thereof.

[0146] The second halide solid state electrolyte and the first halide solid state electrolyte can be the same or different.

[0147] In some examples, the second halide solid state electrolyte can have an ionic conductivity of lithium of 1 x 10"6Scm-1or more (e.g., 5 x 10"6Scm1or more, 1 x 10"5Scm1or more, 5 x 10'5Scm1or more, 1 x 10"4Scm1or more, 5 x 10"4Scm1or more, 1 x 10'3Scm1or more, 5 x 10"3Scm1or more, 1 x 10'2Scm1or more, 5 x 10'2Scm1or more, 0.1 Scm-1or more, or 0.5 Scm1 or more). In some examples, the second halide solid state electrolyte can have an ionic conductivity of lithium of 1 Scm'1or less (e.g., 0.5 Scm'1or less, 0.1 Scm'1or less, 5 x 10'2Scm'1or less, 1 x 10'2Scm'1or less, 5 x 10'3Scm'1or less, 1 x 10'3Scm'1or less, 5 x 10'4Scm'1or less, 1 x 10'4Scm'1or less, 5 x 10‘5Scm'1or less, 1 x 10'5Scm'1or less, or 5 x 10'6Scm'1or less). The ionic conductivity of lithium of the second halide solid state electrolyte can range from any of the minimum values described above to any of the maximum values described above. For example, the second halide solid state electrolyte can have an ionic conductivity of lithium of from 1 x IO'6Scm'1to 1 Scm'1(e.g., from 1 x 10'6to 1 x 10‘3Scm'1, from 1 x 10'3to 1 Scm'1, from 1 x 10'6to 1 x 10'5Scm'1, from 1 x 10'5to 1 x 10'4Scm'1, from 1 x 10'4to 1 x 10'3Scm'1, from 1 x 10'3to 1 x 10'2Scm'1, from 1 x 10'2to 0.1 Scm'1, from 0.1 to 1 Scm'1, from 1 x 10'5to 1 Scm'1, from 1 x 10'4to 1 Scm'1, or from 1 x 10'2to 1 Scm'1). The ionic conductivity can be measured using methods known in the art, such as using Electrochemical Impedance Spectroscopy (EIS) and then calculated with an ionic conductivity equation.

[0148] The plurality of particles of the second halide solid state electrolyte can comprise particles of any shape (e.g., a sphere, a rod, a quadrilateral, an ellipse, a triangle, a polygon, etc.). In some examples, the plurality of particles of the second halide solid state electrolyte can have an irregular shape, a regular shape, an isotropic shape, an anisotropic shape, or a combination thereof. In some examples, the plurality of particles of the second halide solid state electrolyte can have an isotropic shape. In some examples, the plurality of particles of the second halide solid state electrolyte are substantially spherical. In some examples, the shape of the plurality of particles of the first halide solid state electrolyte and the shape of the plurality of particles of the second halide solid state electrolyte can be the same or different.

[0149] The plurality of particles of the second halide solid state electrolyte can have an average particle size. For example, the plurality of particles of the second halide solid state electrolyte can have an average particle size of 1 nanometer (nm) or more (e.g., 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 225 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1 micrometer (micron, pm) or more, 1 .25 pm or more, 1.5 pm or more, 1 .75 pm or more, 2 pm or more, 2.25 pm or more, 2.5 pm or more, 3 pm or more, 3.5 pm or more, 4 pm or more, 4.5 pm or more, 5 pm or more, 6 pm or more, 7 pm or more, 8 pm or more, 9 pm or more, 10 pm or more, 15 pm or more, 20 pm or more, 25 pm or more, 30 pm or more, 35 pm or more, 40 pm or more, or 45 pm or more). In some examples, the plurality of particles of the second halide solid state electrolyte can have an average particle size of 50 micrometers (microns, pm) or less (e.g., 45 pm or less, 40 pm or less, 35 pm or less, 30 pm or less, or 25 pm or less, 20 pm or less, 15 pm or less, 10 pm or less, 9 pm or less, 8 pm or less, 7 pm or less, 6 pm or less, 5 pm or less, 4.5 pm or less, 4 pm or less, 3.5 pm or less, 3 pm or less, 2.5 pm or less, 2.25 pm or less, 2 pm or less, 1.75 pm or less, 1.5 pm or less, 1.25 pm or less, 1 pm or less, 900 nanometers (nm) or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 450 nm or less, 400 nm or less,

[0150] 350 nm or less, 300 nm or less, 250 nm or less, 225 nm or less, 200 nm or less, 175 nm or less,

[0151] 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less). The average particle size of the plurality of particles of the second halide solid state electrolyte can range from any of the minimum values described above to any of the maximum values described above. For example, the plurality of particles of the second halide solid state electrolyte can have an average particle size of from 1 nanometer to 50 micrometers (e.g., from 1 nm to 1 pm, from 1 pm to 50 pm, from 1 nm to 10 nm, from 10 nm to 100 nm, from 100 nm to 1 pm, from 1 pm to 10 pm, from 10 pm to 50 pm, from 1 nm to 25 pm, from 1 nm to 10 pm, from 1 nm to 5 pm, from 1 nm to 750 nm, from 1 nm to 500 nm, from 1 nm to 250 nm, from 1 nm to 100 nm, from 1 nm to 50 nm, from 1 nm to 25 nm, from 5 nm to 50 pm, from 10 nm to 50 pm, from 25 nm to 50 pm, from 50 nm to 50 pm, from 100 nm to 50 pm, from 250 nm to 50 pm, from 500 nm to 50 pm, from 750 nm to 50 pm, from 5 pm to 50 pm, from 10 pm to 50 pm, from 25 pm to 50 pm, from 5 nm to 45 pm, from 10 nm to 40 pm, from 50 nm to 30 pm, from 100 nm to 20 pm, or from 100 nm to 10 pm).

[0152] In some examples, the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte can be the same or different.

[0153] In some examples, the plurality of particles of the second halide solid state electrolyte can be substantially monodisperse.

[0154] In some examples, the plurality of particles of the second halide solid state electrolyte can comprise: a first population of particles having a first average particle size, a first particle shape, and a first composition; and a second population of particles having a second average particle size, a second particle shape, and a second composition; wherein the first average particle size and the second average particle size are different, the first particle shape and the second particle shape are different, the first composition and the second composition are different, or a combination thereof. In some examples, the plurality of particles of the second halide solid state electrolyte can comprise a mixture of a plurality of populations of particles, wherein each population of particles within the mixture is different with respect to average particle size, shape, composition, or a combination thereof.

[0155] In some examples, the plurality of particles of the first halide solid state electrolyte can comprise a first population of particles having a first average particle size, a first particle shape, and a first composition; and the plurality of particles of the second halide solid state electrolyte can comprise a second population of particles having a second average particle size, a second particle shape, and a second composition; wherein the first average particle size and the second average particle size can be the same or different, the first particle shape and the second particle shape can be the same or different, the first composition and the second composition can be the same or different, or a combination thereof.

[0156] Current Collector (s)

[0157] In some examples, the solid state battery further comprises a first current collector. When the anode is present, the anode is sandwiched between and in contact with the first current collector and the interfacial layer. When the anode is absent, the current collector is in contact with the interfacial layer.

[0158] In some examples, the solid state battery further comprises a second current collector, wherein the cathode is sandwiched between and in contact with the second current collector and the halide solid state electrolyte layer.

[0159] The first current collector and / or the second current collector (when present) can independently comprise any suitable material, such as those known in the art. For example, The first current collector and / or the second current collector (when present) can independently comprise a metal, a carbon material, or a combination thereof.

[0160] In some examples, the first current collector and / or the second current collector (when present) can independently comprise a metal foil and / or a metal foam. In some examples, the first current collector and / or the second current collector (when present) can independently comprise copper, nickel, aluminum, or a combination thereof. Examples of suitable carbonbased conductive materials include, but are not limited to graphitic carbon and graphites, including amorphous carbon, carbon black, graphene, and others known in the art.

[0161] Casing

[0162] In some examples, the solid state battery can further include a casing that at least partially surrounds and / or encloses a cell comprising the anode (when present), the interfacial layer, the halide solid state electrolyte layer, the composite cathode, the first current collector (when present), and the second current collector (when present). The casing can comprise any suitable material such as those known in the art. For example, the casing can comprise a polymer, a metal, an alloy, a polymer coated metal foil, or a combination thereof.

[0163] Solid State Battery Properties

[0164] In some examples, the anode is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0165] In some examples, the interfacial layer is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0166] In some examples, the solid state battery exhibits an energy density of 75 Wh / kg or more (e.g., 100 Wh / kg or more, 125 Wh / kg or more, 150 Wh / kg or more, 175 Wh / kg or more, 200 Wh / kg or more, 225 Wh / kg or more, 250 Wh / kg or more, 275 Wh / kg or more, 300 Wh / kg or more, 325 Wh / kg or more, 350 Wh / kg or more, 375 Wh / kg or more, 400 Wh / kg or more, 425 Wh / kg or more, 450 Wh / kg or more, 475 Wh / kg or more, 500 Wh / kg or more, 525 Wh / kg or more, 550 Wh / kg or more, or 575 Wh / kg or more). In some examples, the solid state battery exhibits an energy density of 600 Wh / kg or less (e.g., 575 Wh / kg or less, 550 Wh / kg or less, 525 Wh / kg or less, 500 Wh / kg or less, 475 Wh / kg or less, 450 Wh / kg or less, 425 Wh / kg or less, 400 Wh / kg or less, 375 Wh / kg or less, 350 Wh / kg or less, 325 Wh / kg or less, 300 Wh / kg or less, 275 Wh / kg or less, 250 Wh / kg or less, 225 Wh / kg or less, 200 Wh / kg or less, 175 Wh / kg or less, 150 Wh / kg or less, 125 Wh / kg or less, or 100 Wh / kg or less). The energy density of the solid state battery can range from any of the minimum values described above to any of the maximum values described above. For example, the solid state battery can exhibit an energy density of from 75 Wh / kg to 600 Wh / kg (e.g., from 75 to 325 Wh / kg, from 325 to 600 Wh / kg, from 75 to 200 Wh / kg, from 200 to 325 Wh / kg, from 325 to 450 Wh / kg, from 450 to 600 Wh / kg, from 100 to 600 Wh / kg, from 200 to 600 Wh / kg, from 300 to 600 Wh / kg, from 400 to 600 Wh / kg, or from 500 to 600 Wh / kg). The energy density of the solid state battery can be measured and / or calculated using methods known in the art. For example, the energy density of the battery can be determined from the energy the solid state battery can hold and the total weight of the solid state battery.

[0167] In some examples, the solid state battery exhibits a specific discharge capacity of 100 mA h / g or more when discharged at a rate of from 0. 1 C to 10 C (e.g., 125 mA h / g or more, 150 mA h / g or more, 175 mA h / g or more, 200 mA h / g or more, 225 mA h / g or more, 250 mA h / g or more, 275 mA h / g or more, 300 mA h / g or more, 325 mA h / g or more, 350 mA h / g or more, or 375 mA h / g or more). In some examples, the solid state battery exhibits a specific discharge capacity of 400 mA h / g or less when discharged at a rate of from 0.1 C to 10 C (e.g., 375 mA h / g or less, 350 mA h / g or less, 325 mA h / g or less, 300 mA h / g or less, 275 mA h / g or less, 250 mA h / g or less, 225 mA h / g or less, 200 mA h / g or less, 175 mA h / g or less, 150 mA h / g or less, or 125 mA h / g or less). The specific discharge capacity of the solid state battery can range from any of the minimum values described above to any of the maximum values described above. For example, the solid state battery can exhibit a specific discharge capacity of from 100 mA h / g to 400 mA h / g when discharged at a rate of from 0.1 C to 10 C (e.g., from 100 to 250 mA h / g, from 250 to 400 mA h / g, from 100 to 200 mA h / g, from 200 to 300 mA h / g, from 300 to 400 mA h / g, from 150 to 400 mA h / g, from 200 to 400 mA h / g, from 250 to 400 mA h / g, or from 350 to 400 mA h / g). The specific discharge capacity of the solid state battery can be calculated and / or theoretical. The specific discharge capacity of the solid state battery can be measured and / or calculated using methods known in the art. For example, the specific discharge capacity of the solid state battery can be measured using Galvanostatic cycling.

[0168] In some examples, the solid state battery is rechargeable.

[0169] In some examples, the solid state battery exhibits a coulombic efficiency of 80% or more (e.g., 85% or more, 90% or more, or 95% or more) for 100 cycles or more. In some examples, the solid state battery exhibits a coulombic efficiency of 99% or more for 100 cycles or more (e.g., 99.1% or more, 99.2% or more, 99.3% or more, 99.4% or more, 99.5% or more, 99.6% or more, 99.7% or more, 99.8% or more, or 99.9% or more). The coulombic efficiency of the solid state battery over 100 cycles or more can be calculated and / or measured using methods known in the art. For example, the coulombic efficiency of the solid state battery can be measured by comparing the capacity of the solid state battery at any given cycle against the first cycle. The cycle life of a battery is said to be when the measured capacity of the cell reaches 80% of its original value.

[0170] In some examples, the solid state battery exhibits a capacity retention of 80% or more (e.g., 85% or more, 90% or more, or 95% or more) for 100 cycles or more. In some examples, the solid state battery exhibits a capacity retention of 90% or more for 100 cycles or more (e.g., 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, 96% or more, 97% or more, 98% or more, or 99% or more). The capacity retention of the solid state battery over 100 cycles or more can be calculated and / or measured using methods known in the art. For example, the capacity retention of the solid state battery can be measured by comparing the capacity of the solid state battery at any given cycle against the first cycle.

[0171] Methods of Making and Use

[0172] Also disclosed herein are methods of making and use of any of the solid state batteries disclosed herein. For example, also disclosed herein are methods of making any of the solid state batteries disclosed herein. In some examples, the methods can comprise making the anode (when present), the interfacial layer, the halide solid state electrolyte layer, and the composite cathode, and stacking the anode (when present), the interfacial layer, the halide solid state electrolyte layer, and the composite cathode together to form the solid state battery.

[0173] In some examples, the methods can comprise disposing the halide solid state electrolyte layer on the composite cathode, disposing the interfacial layer on the halide solid state electrolyte layer, and disposing the anode on the interfacial layer, such that the interfacial layer is between the anode and the halide solid state electrolyte layer, and the halide solid state electrolyte layer is between the interfacial layer and the composite cathode.

[0174] Also disclosed herein are methods of use of any of the solid state batteries disclosed herein, for example in a system and / or an article.

[0175] Also disclosed herein are systems comprising one or more of the solid state batteries disclosed herein. For example, the system can be an energy storage system.

[0176] Also disclosed herein are articles (e.g., articles of manufacture) comprising one or more of the solid state batteries disclosed herein. For example, the article can be a vehicle, such as a hybrid electric vehicle or an all-electric vehicle. In some examples, the article can comprise an electronic device, such as a portable electronic device, a laptop, a watch, a cell phone, etc.

[0177] A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.

[0178] The examples below are intended to further illustrate certain aspects of the systems and methods described herein, and are not intended to limit the scope of the claims.

[0179] EXAMPLES

[0180] The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention which are apparent to one skilled in the art.

[0181] Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of measurement conditions, e.g., component concentrations, temperatures, pressures and other measurement ranges and conditions that can be used to optimize the described process.

[0182] Example 1

[0183] Described herein is a secondary all-solid-state lithium metal battery comprising a halide- based ceramic solid electrolyte material and an interfacial material, such as lithium nitride (Lr,N j, between the solid electrolyte and the lithium metal anode. The interfacial layer can stabilize the lithium metal anode interface against the halide solid electrolyte for extended duration and plating / stripping of the lithium metal anode. Alternative alloy anode materials can also be implemented, such as silicon.

[0184] Introduction. An explosion in electric vehicle demand has spurred the requirement of battery technology that can enable longer driving distances, faster charging times, and above all enhanced safety for the end consumer. Traditional lithium-ion batteries have reached their theoretical limit and have been found wanting in terms of the performance they enable in such products as electric vehicles. The limitations of the lithium-ion battery are intrinsic to its material constituents; in particular, the flammable organic electrolyte and graphite anode are two components that can be improved upon to realize superior lithium battery performance. When a lithium-ion battery is charged faster than it can handle, it becomes preferable for lithium to plate on the graphite anode particles rather than intercalate within it. This plating on the exterior of the graphite anode particle is problematic as the instability of lithium metal in the organic liquid electrolyte causes dendritic lithium nucleation and growth instead of the plating of a dense metal. These lithium dendrites can perpetuate and grow across the porous separator of the battery and come into physical contact with the cathode of the battery, causing a short circuit of the battery. Once the battery is short-circuited, a large amount of heat is generated that can ignite the flammable organic liquid solvent of the electrolyte, ultimately resulting in catastrophic failure that can be harmful to the end user of the product containing this battery.

[0185] All-solid-state batteries circumvent the shortcomings of the traditional lithium-ion battery by replacing the organic liquid electrolyte battery with an inorganic solid-state ceramic that is non-flammable. The material characteristics of the solid electrolyte can also allow the implementation of more advanced materials. Specifically, if the solid electrolyte has a sufficiently wide electrochemical stability window, it can be used against a lithium metal anode and a high-voltage oxide cathode. This battery architecture has the potential to drastically enhance the volumetric and gravimetric energy density of the battery, which can result in longer runtime of consumer electronic devices or longer driving range on a single charge of the battery. The solid electrolyte can also serve as a physical barrier if dendritic lithium is formed, although if the solid electrolyte is chemically stable against lithium metal then dendritic lithium will not form. This aspect of implementing a solid electrolyte is especially important when considering fast-charge performance of the battery; because, if the solid electrolyte has a high ionic conductivity, then the battery can be fast charged with a lithium metal anode without fear of dendritic lithium penetrating the solid electrolyte and shorting the battery.

[0186] The pursuit of lithium superionic conductors (materials with an ionic conductivity of lithium (oLi) greater than 10‘4Scm1) has yielded several classes of materials of interest in the past two decades. The most promising materials include the oxide-based garnets (base formula Li7LasZr20i2), several sulfide-based materials (LiioGeP2Si2 and LnPSsCI among others), and the halides (Li YCI<> and Li2ZrCle). The halides are the most recently reported materials and have significant advantages over the other classes of materials - they are easier to process than oxides, and have less expensive precursors than sulfides. However, the halides are generally not chemically or electrochemically stable against lithium metal. In literature, this instability against lithium metal is side-stepped by testing the halide materials in full cells with a lithium-indium alloy anode, which is less reactive than lithium metal but results in a lower overall full cell voltage and thus a lower overall energy density for the battery.

[0187] Synopsis. Described herein is a scheme and materials to overcome the instability of the halide electrolytes with lithium metal to enable an all-solid-state lithium metal battery with a halide solid-state electrolyte. For example, the integration of an interfacial layer between the halide electrolyte and lithium metal anode to stabilize the interface towards uniform dense plating / striping of lithium metal is described herein. This strategy can also be implemented towards alternative next-generation anode materials with a low intercalation voltage where the electrolyte may be chemically, mechanically, or electrochemically unstable during battery assembly and / or operation.

[0188] For example, described herein is the use of lithium nitride (LisN) as an interfacial bridge between a halide-based solid electrolyte material and any anode material of a secondary battery with a low intercalation voltage - such as lithium metal. This strategy can also be described as a dual-layer solid electrolyte strategy for secondary lithium batteries. In the case where a non- metallic anode is used, the halide electrolyte can be considered a “catholyte” and the Li^N can be considered an “anolyte”.

[0189] Detailed description. The present disclosure features a dual-layer solid electrolyte for an all-solid-state battery with a high-capacity anode, such as lithium metal, for an energy dense lithium secondary battery. This dual-layer solid electrolyte comprises a halide-based ceramic material oriented towards the cathode side of the battery and Li iN oriented towards the anode side of the battery. For the cathode electrode, the halide electrolyte can also be integrated within the electrode matrix with a binder and conductive carbon additive. In the case of the anode electrode, if the anode is a metal (such as metallic lithium), the LisN can be an interfacial layer. If the anode is an alloy, or intercalation type material - such as silicon / indium or graphite, respectively - then the L13N can be incorporated into the anode electrode itself. In some examples, the LFN can serve as an interfacial layer with another anolyte or ionically conductive additive material being integrated into the anode electrode matrix.

[0190] Halide-based ceramic electrolyte materials have high ionic conductivity and high oxidation stability (are stable at high voltages) but suffer from low reduction stability (poor low voltage stability - can be reduced / decomposed against reducing agents). Thus, these materials can be paired with a high-voltage cathode material without having to make modifications to the cathode material, such as surface coating the cathode redox active particles to protect the electrolyte. This type of coating on cathode materials is required for other classes of solid electrolyte materials that are not stable at high voltages - such as the sulfide-based materials. However, when it comes to pairing the high-voltage cathode with a low voltage anode to produce a secondary battery of high energy density with a halide solid electrolyte, the choices for halides are limited. Although the halide solid electrolyte materials have a relatively wide electrochemical stability window, it is not wide enough to encompass anodes with a reaction voltage below 1 - 1.5 V versus Li+ / Li°. To overcome this shortcoming in enabling an all-solid- state battery of high energy density comprising a halide solid electrolyte, an interfacial material that “bridges” the electrochemical potential of the anode to be within the electrochemical stability window of the halide electrolyte can be used. The interfacial material has an electrochemical stability window that overlaps with the halide solid electrolyte and the low voltage anode.

[0191] Lithium nitride (LisN) is a well-known lithium fast-ion conductor that is stable against lithium metal. However, it has been limited in solid-state battery applications owing to its narrow electrochemical stability window -up to 1.5V versus Li+ / Li°. Herein, this narrow electrochemical stability window is overcome by pairing Lb,N with a halide-based solid electrolyte, wherein the halide-based solid electrolyte has a wide electrochemical stability window that overlaps with the upper bound of the LLN stability window, thus creating a dual- layer solid electrolyte with an ultra-wide electrochemical stability window that encompasses the redox potential of lithium metal and a high-voltage lithium transition-metal oxide cathode. Li+Conductivity of Constituent Materials. Figure 1 shows the X-ray diffraction (XRD) patterns of two halide-based electrolyte materials synthesized by high-energy and planetary ball milling, LiiZrCE and LFYCle. The XRD patterns show a single pure phase for each material that was further used to validate the scheme disclosed herein. Figure 2 shows the electrochemical impedance spectrum of the synthesized Li iYCIe material. Figure 3 shows the electrochemical impedance spectrum of the synthesized LiiZrCF material. Figure 4 shows the electrochemical impedance spectrum of the LFN used for the demonstration of the dual layer electrolyte technology disclosed herein. Each sample was compressed into a pellet for electrochemical impedance measurements and tested in a symmetric cell with stainless steel electrodes on both sides of the pellet. The impedance spectra were obtained in the frequency range of 1 MHz to 0.1 Hz with a perturbation voltage of 10 mV. The ionic conductivity values (o) shown for each material were determined by fitting each spectrum with the equivalent circuit shown in Figure 5. The R2 value obtained via the fitting was then input into the formula: where I is the thickness of the pellet sample, A is the cross-sectional area of the pellet sample, and R is the resistance value (R2 in Figure 5) obtained from the spectrum fitting for the respective material. No further modification was performed on the Li^N material used in the examples and testing disclosed herein, but particle size and morphology can affect material ionic conductivity and ensuing cell performance. Additionally, the particle size and morphology of the halide material can be tailored / optimized depending on the attributes of the cathode active material particle; for example, a device can include smaller sized halide electrolyte particles in the cathode and larger sized halide electrolyte particles in the bulk electrolyte.

[0192] All-Solid-State Batteries. The disclosed dual layer solid electrolyte strategy with an interlayer between a low-potential, highly reductive anode and a halide solid electrolyte can be used in applications in secondary all-solid-state and pseudo solid-state batteries where a liquid component can be used against the cathode. Figure 6A and Figure 6B show a schematic of a pseudo solid-state and all-solid-state battery, respectively. The cathode active material can vary depending on the final use case of the battery, which will dictate the required performance and cast metrics of the cell. Primary cathodes of industrial relevance are Li[NixMnyCoz]O2 (x+y+z= 1 ), LiFePCF, LiM^CX, LiCoCE, LiNiC , and combinations or variations thereof. The disclosed strategy can additionally be applied to alternative battery chemistries that incorporate lithium metal or a low-voltage cathode, such as a lithium sulfur (Li-S) battery. These devices are highly valuable in the energy storage space across a range of applications from large-scale grid storage to high-power, high-energy uses like hybrid electric and all-electric vehicles. Advantages of pseudo and all-solid-state batteries include that they provide a degree of safety with fastcharge capabilities and high energy density that, owing to intrinsic constituent materials limitations, which are not obtainable by current lithium-ion batteries. These differences stem from the use of a low- voltage, high-capacity anode, such as lithium metal or silicon (if silicon is used, it is encompassed in a composite matrix with a conductive additive and a binding agent, such as PVDF or PTFE if dry processed). Several batteries were assembled to demonstrate the all-solid-state concept.

[0193] Examples. In the following examples, the disclosed strategy was implemented in full cell lithium batteries with a lithium-indium alloy anode and pure lithium metal anode. Each of these examples demonstrates a purely all-solid-state battery without any liquid electrolyte, but the concept can be extended to pseudo all- solid-state batteries that comprise a liquid electrolyte on the cathode side of the electrochemical cell. The cathode composite in each of these examples does not contain a binder, but in larger cells and other cell architectures, a binder and current collector for each electrode can be used. In the coin cell format that the examples were prepared in, the spacer and cell casing acted as the current collectors.

[0194] Example A: All-Solid-State battery comprising a lithium-indium alloy anode, a Li YCE electrolyte, and a LisN interfacial anode layer. An example all-solid-state cell was constructed to demonstrate the disclosed concept, the cell comprising a composite cathode, an LLYCL electrolyte, an Li iN interfacial layer, and a Lio.sln alloy anode. The composite cathode comprises Li[Nio.8Mno.iCoo.i]02 (NMC811; 66.67 wt%) as the cathode active material, carbon black (4.76 wt%), and LhYCE (28.57 wt%). The overall active material mass loading of the cell was 5 mg / cm2. The cell was assembled and tested in a coin cell format.

[0195] Figure 7 shows the voltage (versus Lio.sln) and specific capacity of the cell (relative to the cathode material) obtained during galvanostatic charge / discharge cycling in the voltage range of 1.88-3.6 V versus Lio.sln at 50°C with a 0.1 C rate. Over the course of the first 100 cycles, the cycling curves show minimal degradation, implying that the interfacial layer (or dual-layer solid electrolyte) is mechanically stable against the Lio.sln anode. Additionally, the cell shows a low- overpotential and a relatively high first cycle efficiency, which demonstrates the chemical and electrochemical stability of the dual-layer solid electrolyte against the alloy anode and the high- voltage NMC811 cathode. Figure 8 shows the capacity retention and coulombic efficiency of this example cell. This curve further demonstrates the high stability of the cell as it maintains 94.4% of its capacity after the 100thcycle. Example B: All-Solid-State battery comprising a lithium-indium alloy anode, a Li ZrC electrolyte, and a Li N interfacial anode layer. Example B is an all-solid-state cell similar to Example A, but with a LiiZrCk, halide electrolyte used instead of the LLYCL halide material. Therefore, the cell comprises a composite cathode, an LisYCL electrolyte, an LisN interfacial layer, and a Lio.sln alloy anode. The composite cathode comprises NMC811 (66.67 wt%) as the cathode active material, carbon black (4.76 wt%), and LisZrCle (28.57 wt%). The overall active material mass loading of the cell was 5 mg / cm2. The cell was assembled and tested in a coin cell format.

[0196] Figure 9 shows the charge / discharge curves plotted in terms of the cell voltage (versus Lio.sln) and cell specific capacity (normalized to cathode active material). The cell was galvanostatically cycled in the voltage range of 1.88-3.6 V versus Lio.sln at 50°C with a 0.1 C rate. The cell shows slight decay over the first 100 cycles, but this degradation can be attributed to the use of slightly less solid electrolyte material within the cell causing the overall all-solid- state assembly within the coin cell to be thinner and thus operate under a lower internal cell pressure than in Example A. However, the overpotential of the cell is lower, indicating a greater chemical and electrochemical stability of the dual-layer electrolyte against both the cathode and the anode. Figure 10 shows the cycling and coulombic efficiency of the battery. Although the overall specific capacity of the cell is low, which can be attributed the reasons stated above, the cycling stability over the first 100 cycles is excellent. These results demonstrate the advantage of the interfacial layer in mechanically, chemically, and electrochemically stabilizing the interface between the halide solid electrolyte and a metallic / alloy anode.

[0197] Example C: All-Solid-State battery comprising a pure lithium metal anode, a LizZrCl6 electrolyte, and a LisN interfacial anode layer. Lithium metal is the best possible anode choice for a secondary lithium battery as it is the most efficient method of storing lithium within the cell - there is no wasted weight or volume on a host material / structure, nor is there a requirement for binder or a conductive agent that does not directly contribute to the lithium storage ability of the anode itself. Thus, an example cell was assembled with a full lithium metal anode. Additionally, the cell comprises a composite cathode, a Li iYC'E electrolyte, and an LisN interfacial layer between the halide solid electrolyte and the lithium metal anode. The composite cathode comprises NMC811 (66.67 wt%) as the cathode active material, carbon black (4.76 wt%), and LisYCL (28.57 wt%). The cathode active material loading in the cell is 2 mg / cm2. The cell was assembled and tested in a coin cell format.

[0198] Figure 11 shows the charge / discharge curves of the cell. The cell was galvanostatically cycled at a 0.05 C rate in the voltage range of 3.0-4.2 V versus Li+ / Li° at room temperature. Although the first cycle shows a slight irreversible capacity loss, indicating a passivation reaction at one of the electrodes, the ensuing four cycles show extremely stable cycling. Additionally, the low overpotential of the cell demonstrates the chemical and electrochemical stability of the halide electrolyte and interfacial layer against the cathode and anode, respectively. Thus, the strategy described herein shows promise of enabling an all-solid-state battery with a high voltage NMC811 cathode and a lithium metal anode which can be further engineered and optimized to enable a step-change in performance (energy density, safety, fast charge, etc.) over current lithium-ion technology.

[0199] EXEMPLARY ASPECTS

[0200] In view of the described solid state batteries, such as pseudo solid-state and all solid-state batteries, and methods of making and use thereof, herein below are described certain more particularly described aspects of the inventions. The particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulas literally used therein.

[0201] Example 1: A solid state battery comprising: an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode; wherein the interfacial layer is disposed on and in contact with the halide solid state electrolyte layer; wherein the halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode; wherein the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window; wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer; and wherein the composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0202] Example 2: The solid state battery of any examples herein, particularly example 1, further comprising an anode, wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer, and wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode. Example 3: A solid state battery comprising: an anode; an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode; wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer; wherein the halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode; wherein the anode, the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window; wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode; and wherein the composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0203] Example 4: The solid state battery of any examples herein, particularly example 2 or example 3, wherein the anode is formed in situ.

[0204] Example 5: The solid state battery of any examples herein, particularly examples 2-4, wherein the anode has a high capacity and / or a high energy density.

[0205] Example 6: The solid state battery of any examples herein, particularly examples 2-5, wherein the anode has a specific capacity of from 100 to 4000 mAh / g.

[0206] Example 7: The solid state battery of any examples herein, particularly examples 2-6, wherein the anode has a low intercalation voltage.

[0207] Example 8: The solid state battery of any examples herein, particularly examples 2-7, wherein the anode has an intercalation voltage of as 1 V or less versus Li+ / Li°.

[0208] Example 9: The solid state battery of any examples herein, particularly examples 2-8, wherein the anode comprises a metal, an alloy, an intercalation material, or a combination thereof.

[0209] Example 10: The solid state battery of any examples herein, particularly examples 2-9, wherein the anode comprises lithium, potassium, sodium, silicon, indium, graphite, hard carbon, or a combination thereof.

[0210] Example 11 : The solid state battery of any examples herein, particularly examples 2-10, wherein the anode comprises lithium (e.g., lithium metal and / or a lithium alloy).

[0211] Example 12: The solid state battery of any examples herein, particularly examples 2-11, wherein the anode comprises lithium metal.

[0212] Example 13: The solid state battery of any examples herein, particularly examples 2-12, wherein the anode comprises a lithium alloy. Example 14: The solid state battery of any examples herein, particularly examples 2-13, wherein the anode comprises a lithium-indium alloy, a lithium-magnesium alloy, a lithiumaluminum alloy, a lithium-iron alloy, or a combination thereof.

[0213] Example 15: The solid state battery of any examples herein, particularly examples 2-14, wherein the anode comprises a lithium-indium alloy.

[0214] Example 16: The solid state battery of any examples herein, particularly examples 2-15, wherein the anode comprises silicon or a silicon composite.

[0215] Example 17: The solid state battery of any examples herein, particularly examples 2-16, wherein the anode is a composite (e.g., a composite anode).

[0216] Example 18: The solid state battery of any examples herein, particularly example 17, wherein the composite anode further includes a binder.

[0217] Example 19: The solid state battery of any examples herein, particularly example 18, wherein the binder comprises a polyethylene oxide (PEO), poly vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0218] Example 20: The solid state battery of any examples herein, particularly examples 17-19, wherein the composite anode further includes a conductive additive.

[0219] Example 21 : The solid state battery of any examples herein, particularly example 20, wherein the conductive additive comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof.

[0220] Example 22: The solid state battery of any examples herein, particularly example 20 or example 21, wherein the conductive additive comprises carbon black.

[0221] Example 23 : The solid state battery of any examples herein, particularly examples 2-22, wherein the anode comprises a prelithiated host structure (e.g., a prelithiated silicon anode, a prelithiated silicon-graphite composite anode, a prelithiated graphite, a prelithiated hard carbon, etc.), a silicon-graphite composite anode, or a combination thereof.

[0222] Example 24: The solid state battery of any examples herein, particularly examples 1-23, wherein the interfacial layer is formed in situ.

[0223] Example 25 : The solid state battery of any examples herein, particularly examples 1 -24, wherein the interfacial layer has an average thickness of from 1 nanometer (nm) to 100 micrometers (microns, pm). Example 26: The solid state battery of any examples herein, particularly examples 1-25, wherein the interfacial layer has an ionic conductivity of lithium of from 1 x 10"8Scm-1to 0.1 Scm1.

[0224] Example 27 : The solid state battery of any examples herein, particularly examples 1 -26, wherein the interfacial material comprises an alkali metal nitride, an alkali metal phosphide, or a combination thereof.

[0225] Example 28: The solid state battery of any examples herein, particularly examples 1-27, wherein the interfacial material comprises LisN, LisP, NaaP, NaaN, KaN, or a combination thereof.

[0226] Example 29: The solid state battery of any examples herein, particularly examples 1-28, wherein the interfacial material comprises Li tN, LiaP, or a combination thereof.

[0227] Example 30: The solid state battery of any examples herein, particularly examples 1-29, wherein the interfacial material comprises LEN.

[0228] Example 31 : The solid state battery of any examples herein, particularly examples 1-30, wherein the interfacial layer comprises a plurality of particles of the interfacial material.

[0229] Example 32: The solid state battery of any examples herein, particularly examples 1-31, wherein the plurality of particles of the interfacial material have an average particle size of from 1 nanometers (nm) to 25 micrometers (microns, pm).

[0230] Example 33: The solid state battery of any examples herein, particularly examples 1-32, wherein the plurality of particles of the interfacial material have an average particle size of from 1 to 10 micrometers (microns, pm).

[0231] Example 34: The solid state battery of any examples herein, particularly examples 1-33, wherein the halide solid state electrolyte layer has an average thickness of from 1 to 100 micrometers (microns, pm).

[0232] Example 35: The solid state battery of any examples herein, particularly examples 1-34, wherein the first halide solid state electrolyte has an ionic conductivity of lithium of from 1 x 105Scm1to 0.1 Scm1.

[0233] Example 36: The solid state battery of any examples herein, particularly examples 1-35, wherein the first halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof.

[0234] Example 37: The solid state battery of any examples herein, particularly examples 1-36, wherein the first halide solid state electrolyte comprises a lithium halide.

[0235] Example 38: The solid state battery of any examples herein, particularly examples 1-37, wherein the first halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides, z is an integer from -2 to 2, and [III+z] represents the valence of the M-ion(s) in the compound.

[0236] Example 39: The solid state battery of any examples herein, particularly examples 1-38, wherein the first halide solid state electrolyte comprises LiiYXr,. where X is F, Cl, Br, I, or a combination thereof.

[0237] Example 40: The solid state battery of any examples herein, particularly examples 1-39, wherein the first halide solid state electrolyte comprises LiiZrXs, where X is F, Cl, Br, I, or a combination thereof.

[0238] Example 41 : The solid state battery of any examples herein, particularly examples 1 -40, wherein the first halide solid state electrolyte comprises LEYCL, LizZrClo, or a combination thereof.

[0239] Example 42: The solid state battery of any examples herein, particularly examples 1-41, wherein the halide solid state electrolyte layer comprises a plurality of particles of the first halide solid state electrolyte.

[0240] Example 43: The solid state battery of any examples herein, particularly example 42, wherein the plurality of particles of the first halide solid state electrolyte have an average particle size of from 1 nanometer to 100 micrometers.

[0241] Example 44: The solid state battery of any examples herein, particularly examples 1 -43, wherein the electrochemical stability window of the halide solid state electrolyte is compatible with the electrochemical stability window of the composite cathode.

[0242] Example 45 : The solid state battery of any examples herein, particularly examples 1 -44, wherein the cathode active material comprises a high density nickel-rich layered transition metal oxide (e.g., Li[NixMnyCoz]O2 (x+y+z = 1)), LiFei- MnxPO4 (LMFP), a lithium iron phosphate (LFP, LiFePCh), lithium manganese oxide (LiMmCTO, nickel-doped lithium manganese oxide (LitNio.5Mn1.5JO4), LiCoO2, LiNiO . or a combination thereof.

[0243] Example 46: The solid state battery of any examples herein, particularly examples 1-45, wherein the cathode active material comprises Li[NixMnyCoz]O2 where x+y+z = 1, LiFePO4, or a combination thereof.

[0244] Example 47 : The solid state battery of any examples herein, particularly examples 1 -46, wherein the cathode active material comprises LiNio.8Mno.1Coo.1O2.

[0245] Example 48: The solid state battery of any examples herein, particularly examples 1-47, wherein the conductive additive comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof. Example 49: The solid state battery of any examples herein, particularly examples 1-48, wherein the conductive additive comprises carbon black.

[0246] Example 50: The solid state battery of any examples herein, particularly examples 1-49, wherein the composite cathode further comprises a binder.

[0247] Example 51 : The solid state battery of any examples herein, particularly example 50, wherein the binder comprises a polyethylene oxide (PEO), poly vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

[0248] Example 52: The solid state battery of any examples herein, particularly examples 1-51, wherein the solid state battery is an all solid state battery.

[0249] Example 53: The solid state battery of any examples herein, particularly example 52, wherein the electrolyte of the composite cathode is a plurality of particles comprising a second halide solid state electrolyte.

[0250] Example 54: The solid state battery of any examples herein, particularly example 53, wherein the second halide solid state electrolyte has an ionic conductivity of lithium of from 1 x 10’6Scm1to 1 Scm1.

[0251] Example 55: The solid state battery of any examples herein, particularly example 53 or example 54, wherein the second halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof.

[0252] Example 56: The solid state battery of any examples herein, particularly examples 53-55, wherein the second halide solid state electrolyte comprises a lithium halide.

[0253] Example 57: The solid state battery of any examples herein, particularly examples 53-56, wherein the second halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides, z is an integer from -2 to 2, and 1111+z | represents the valence of the M-ion(s) in the compound.

[0254] Example 58: The solid state battery of any examples herein, particularly examples 53-57, wherein the second halide solid state electrolyte comprises Li iYXo, where X is F, Cl, Br, I, or a combination thereof.

[0255] Example 59: The solid state battery of any examples herein, particularly examples 53-58, wherein the second halide solid state electrolyte comprises LiiZrXe, where X is F, Cl, Br, I, or a combination thereof. Example 60: The solid state battery of any examples herein, particularly examples 53-59, wherein the second halide solid state electrolyte comprises Li iYCk,, Li2ZrC16, or a combination thereof.

[0256] Example 61 : The solid state battery of any examples herein, particularly examples 53-60, wherein the second halide solid state electrolyte and the first halide solid state electrolyte are the same.

[0257] Example 62: The solid state battery of any examples herein, particularly examples 53-60, wherein the second halide solid state electrolyte and the first halide solid state electrolyte are different.

[0258] Example 63: The solid state battery of any examples herein, particularly examples 53-62, wherein the plurality of particles of second halide solid state electrolyte have an average particle size of from 1 nanometers to 50 micrometers.

[0259] Example 64: The solid state battery of any examples herein, particularly examples 53-63, wherein the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are the same.

[0260] Example 65: The solid state battery of any examples herein, particularly examples 53-63, wherein the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are different.

[0261] Example 66: The solid state battery of any examples herein, particularly examples 1-51, wherein the solid state battery is a pseudo solid state battery.

[0262] Example 67: The solid state battery of any examples herein, particularly example 66, wherein the electrolyte of the composite cathode is a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

[0263] Example 68: The solid state battery of any examples herein, particularly examples 1-67, wherein the solid state battery further comprises a first current collector, wherein the anode is sandwiched between and in contact with the first current collector and the interfacial layer.

[0264] Example 69: The solid state battery of any examples herein, particularly examples 1-68, wherein the solid state battery further comprises a second current collector, wherein the cathode is sandwiched between and in contact with the second current collector and the halide solid state electrolyte layer. Example 70: The solid state battery of any examples herein, particularly example 71 or example 69, wherein the first current collector and / or the second current collector (when present) independently comprise a metal, a carbon material, or a combination thereof.

[0265] Example 71 : The solid state battery of any examples herein, particularly examples 1-70, wherein the solid state battery further includes a casing that at least partially surrounds and / or encloses a cell comprising the anode (when present), the interfacial layer, the halide solid state electrolyte layer, the composite cathode, the first current collector (when present), and the second current collector (when present).

[0266] Example 72: The solid state battery of any examples herein, particularly example 71 , wherein the casing comprises a polymer, a metal, an alloy, a polymer coated metal foil, or a combination thereof.

[0267] Example 73: The solid state battery of any examples herein, particularly examples 1-72, wherein the anode is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0268] Example 74: The solid state battery of any examples herein, particularly examples 1-73, wherein the interfacial layer is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

[0269] Example 75: The solid state battery of any examples herein, particularly examples 1 -74, wherein the solid state battery exhibits an energy density of from 75 Wh / kg to 600 Wh / kg.

[0270] Example 76: The solid state battery of any examples herein, particularly examples 1-75, wherein the solid state battery exhibits a specific discharge capacity of from 100 mA h / g to 400 mA h / g when discharged at a rate of from 0.1 C to 10 C.

[0271] Example 77: The solid state battery of any examples herein, particularly examples 1-76, wherein the solid state battery is rechargeable.

[0272] Example 78: The solid state battery of any examples herein, particularly examples 1-77, wherein the solid state battery exhibits a coulombic efficiency of 80% or more for 100 cycles or more.

[0273] Example 79: The solid state battery of any examples herein, particularly examples 1-78, wherein the solid state battery exhibits a coulombic efficiency of 99% or more for 100 cycles or more.

[0274] Example 80: The solid state battery of any examples herein, particularly examples 1-79, wherein the solid state battery exhibits a capacity retention of 80% or more for 100 cycles or more. Example 81 : The solid state battery of any examples herein, particularly examples 1-80, wherein the solid state battery exhibits a capacity retention of 90% or more for 100 cycles or more.

[0275] Example 82: A method of making the solid state battery of any examples herein, particularly examples 1-81.

[0276] Example 83: The method of any examples herein, particularly example 82, wherein the method comprises: making the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode; and stacking the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode together to form the solid state battery.

[0277] Example 84: The method of any examples herein, particularly example 83, wherein the method comprises disposing the halide solid state electrolyte layer on the composite cathode, disposing the interfacial layer on the halide solid state electrolyte layer, and disposing the anode on the interfacial layer, such that the interfacial layer is between the anode and the halide solid state electrolyte layer, and the halide solid state electrolyte layer is between the interfacial layer and the composite cathode.

[0278] Example 85: The method of any examples herein, particularly example 84, further comprising disposing the composite cathode on the second current collector before disposing the halide solid state electrolyte on the composite cathode.

[0279] Example 86: The method of any examples herein, particularly example 84 or example 85, further comprising disposing the first current collector on the anode.

[0280] Example 87 : A system comprising one or more of the solid state batteries of any examples herein, particularly examples 1-81.

[0281] Example 88: The system of any examples herein, particularly example 87, wherein the system is an energy storage system.

[0282] Example 89: An article comprising one or more of the solid state batteries of any examples herein, particularly examples 1-81.

[0283] Example 90: The article of any examples herein, particularly example 89, wherein the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle.

[0284] Example 91 : The article of any examples herein, particularly example 89, wherein the article comprises an electronic device, such as a portable electronic device, a laptop, a watch, or a cell phone. Other advantages which are obvious and which are inherent to the invention will be evident to one skilled in the art. It will be understood that certain features and sub-combinations are of utility and may be employed without reference to other features and sub-combinations.

[0285] This is contemplated by and is within the scope of the claims. Since many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.

[0286] The methods of the appended claims are not limited in scope by the specific methods described herein, which are intended as illustrations of a few aspects of the claims and any methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative method steps disclosed herein are specifically described, other combinations of the method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

Claims

CLAIMSWhat is claimed is:

1. A solid state battery comprising: an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode; wherein the interfaci l layer is disposed on and in contact with the halide solid state electrolyte layer; wherein the halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode; wherein the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window; wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer; and wherein the composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

2. The solid state battery of claim 1, further comprising an anode, wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer, and wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode.

3. A solid state battery comprising: an anode; an interfacial layer comprising an interfacial material; a halide solid state electrolyte layer, the halide solid state electrolyte layer being a layer comprising a first halide solid state electrolyte; and a composite cathode; wherein the interfacial layer is sandwiched between and in contact with the anode and the halide solid state electrolyte layer;wherein the halide solid state electrolyte layer is sandwiched between and in contact with the interfacial layer and the composite cathode; wherein the anode, the interfacial layer, the halide solid state electrolyte layer, and the composite cathode each has an electrochemical stability window; wherein the electrochemical stability window of the interfacial layer overlaps with that of the halide solid state electrolyte layer and the anode; and wherein the composite cathode comprises a cathode active material, a conductive additive, and an electrolyte; wherein the electrolyte comprises: a plurality of particles comprising a second halide solid state electrolyte; or a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

4. The solid state battery of claim 2 or claim 3, wherein the anode is formed in situ.

5. The solid state battery of any one of claims 2-4, wherein the anode has a high capacity and / or a high energy density.

6. The solid state battery of any one of claims 2-5, wherein the anode has a specific capacity of from 100 to 4000 mAh / g.

7. The solid state battery of any one of claims 2-6, wherein the anode has a low intercalation voltage.

8. The solid state battery of any one of claims 2-7, wherein the anode has an intercalation voltage of as 1 V or less versus Li+ / Li°.

9. The solid state battery of any one of claims 2-8, wherein the anode comprises a metal, an alloy, an intercalation material, or a combination thereof.

10. The solid state battery of any one of claims 2-9, wherein the anode comprises lithium, potassium, sodium, silicon, indium, graphite, hard carbon, or a combination thereof.

11. The solid state battery of any one of claims 2-10, wherein the anode comprises lithium (e.g., lithium metal and / or a lithium alloy).

12. The solid state battery of any one of claims 2-11, wherein the anode comprises lithium metal.

13. The solid state battery of any one of claims 2-12, wherein the anode comprises a lithium alloy.

14. The solid state battery of any one of claims 2-13, wherein the anode comprises a lithiumindium alloy, a lithium-magnesium alloy, a lithium- aluminum alloy, a lithium-iron alloy, or a combination thereof.

15. The solid state battery of any one of claims 2-14, wherein the anode comprises a lithiumindium alloy.

16. The solid state battery of any one of claims 2-15, wherein the anode comprises silicon or a silicon composite.

17. The solid state battery of any one of claims 2-16, wherein the anode is a composite (e.g., a composite anode).

18. The solid state battery of claim 17, wherein the composite anode further includes a binder.

19. The solid state battery of claim 18, wherein the binder comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

20. The solid state battery of any one of claims 17-19, wherein the composite anode further includes a conductive additive.21 . The solid state battery of claim 20, wherein the conductive additive comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof.

22. The solid state battery of claim 20 or claim 21 , wherein the conductive additive comprises carbon black.

23. The solid state battery of any one of claims 2-22, wherein the anode comprises a prelithiated host structure (e.g., a preli thiated silicon anode, a prelithiated silicon-graphite composite anode, a prelithiated graphite, a prelithiated hard carbon, etc.), a silicon-graphitecomposite anode, or a combination thereof.

24. The solid state battery of any one of claims 1-23, wherein the interfacial layer is formed in situ.

25. The solid state battery of any one of claims 1-24, wherein the interfacial layer has an average thickness of from 1 nanometer (nm) to 100 micrometers (microns, pm).

26. The solid state battery of any one of claims 1-25, wherein the interfacial layer has an ionic conductivity of lithium of from 1 x 10'8Scm1to 0.1 Scm1.

27. The solid state battery of any one of claims 1-26, wherein the interfacial material comprises an alkali metal nitride, an alkali metal phosphide, or a combination thereof.

28. The solid state battery of any one of claims 1-27, wherein the interfacial material comprises LisN, LisP, NasP, NasN, KjN, or a combination thereof.

29. The solid state battery of any one of claims 1-28, wherein the interfacial material comprises LiaN, Li ?P, or a combination thereof.

30. The solid state battery of any one of claims 1-29, wherein the interfacial material comprises LpN.

31. The solid state battery of any one of claims 1-30, wherein the interfacial layer comprises a plurality of particles of the interfacial material.

32. The solid state battery of any one of claims 1-31, wherein the plurality of particles of the interfacial material have an average particle size of from 1 nanometers (nm) to 25 micrometers (microns, pm).

33. The solid state battery of any one of claims 1-32, wherein the plurality of particles of the interfacial material have an average particle size of from 1 to 10 micrometers (microns, pm).

34. The solid state battery of any one of claims 1-33, wherein the halide solid state electrolyte layer has an average thickness of from 1 to 100 micrometers (microns, pm).

35. The solid state battery of any one of claims 1-34, wherein the first halide solid state electrolyte has an ionic conductivity of lithium of from 1 x 10"5Scm1to 0.1 Scm1.

36. The solid state battery of any one of claims 1-35, wherein the first halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof.

37. The solid state battery of any one of claims 1-36, wherein the first halide solid state electrolyte comprises a lithium halide.

38. The solid state battery of any one of claims 1-37, wherein the first halide solid state electrolyte comprises Li3-zM[in+z]Xe, where X is one or more halides, z is an integer from -2 to 2, and [III+z] represents the valence of the M-ion(s) in the compound.

39. The solid state battery of any one of claims 1-38, wherein the first halide solid state electrolyte comprises LisYXe. where X is F, Cl, Br, I, or a combination thereof.

40. The solid state battery of any one of claims 1-39, wherein the first halide solid state electrolyte comprises Li2ZrXe, where X is F, Cl, Br, I, or a combination thereof.

41. The solid state battery of any one of claims 1-40, wherein the first halide solid state electrolyte comprises LFYCIe, LizZrCle, or a combination thereof.

42. The solid state battery of any one of claims 1-41, wherein the halide solid state electrolyte layer comprises a plurality of particles of the first halide solid state electrolyte.

43. The solid state battery of claim 42, wherein the plurality of particles of the first halide solid state electrolyte have an average particle size of from 1 nanometer to 100 micrometers.

44. The solid state battery of any one of claims 1-43, wherein the electrochemical stability window of the first halide solid state electrolyte is compatible with the electrochemical stability window of the composite cathode.

45. The solid state battery of any one of claims 1-44, wherein the cathode active material comprises a high density nickel-rich layered transition metal oxide (e.g., Li[NixMnyCoz]O2 (x+y+z = 1)), LiFei-xMnxPO4 (LMFP), a lithium iron phosphate (LFP, LiFePCL), lithium manganese oxide (LiMmCh), nickel-doped lithium manganese oxide (LitNio.5Mn1.5JO4), LiCoO2, LiNiO2, or a combination thereof.

46. The solid state battery of any one of claims 1-45, wherein the cathode active material comprises Li[NixMnyCoz]O2 where x+y+z = 1, LiFePO4, or a combination thereof.

47. The solid state battery of any one of claims 1-46, wherein the cathode active material comprises LiNio.8Mno.1Coo.1O2.

48. The solid state battery of any one of claims 1-47, wherein the conductive additive comprises a carbon black, a modified carbon black, a graphene, a multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or a combination thereof.

49. The solid state battery of any one of claims 1-48, wherein the conductive additive comprises carbon black.

50. The solid state battery of any one of claims 1-49, wherein the composite cathode further comprises a binder.

51. The solid state battery of claim 50, wherein the binder comprises a polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, carboxymethylcellulose (CMC), styrene -butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, derivatives thereof, or a combination thereof.

52. The solid state battery of any one of claims 1 -51 , wherein the solid state battery is an all solid state battery.

53. The solid state battery of claim 52, wherein the electrolyte of the composite cathode is a plurality of particles comprising a second halide solid state electrolyte.

54. The solid state battery of claim 53, wherein the second halide solid state electrolyte has an ionic conductivity of lithium of from 1 x IO'6Scm1to 1 Scm'1.

55. The solid state battery of claim 53 or claim 54, wherein the second halide solid state electrolyte comprises a lithium halide, a sodium halide, or a combination thereof.

56. The solid state battery of any one of claims 53-55, wherein the second halide solid state electrolyte comprises a lithium halide.

57. The solid state battery of any one of claims 53-56, wherein the second halide solid state electrolyte comprises Li3-zM[III+z]X6, where X is one or more halides, z is an integer from -2 to 2, and [III+z] represents the valence of the M-ion(s) in the compound.

58. The solid state battery of any one of claims 53-57, wherein the second halide solid state electrolyte comprises LFYXG, where X is F, Cl, Br, I, or a combination thereof.

59. The solid state battery of any one of claims 53-58, wherein the second halide solid state electrolyte comprises Li2ZrXe, where X is F, Cl, Br, I, or a combination thereof.

60. The solid state battery of any one of claims 53-59, wherein the second halide solid state electrolyte comprises LhYCU, Li2ZrCle, or a combination thereof.

61. The solid state battery of any one of claims 53-60, wherein the second halide solid state electrolyte and the first halide solid state electrolyte are the same.

62. The solid state battery of any one of claims 53-60, wherein the second halide solid state electrolyte and the first halide solid state electrolyte are different.

63. The solid state battery of any one of claims 53-62, wherein the plurality of particles of second halide solid state electrolyte have an average particle size of from 1 nanometers to 50 micrometers.

64. The solid state battery of any one of claims 53-63, wherein the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are the same.

65. The solid state battery of any one of claims 53-63, wherein the average particle size of the plurality of particles of the first halide solid state electrolyte and the average particle size of the plurality of particles of the second halide solid state electrolyte are different.

66. The solid state battery of any one of claims 1-51, wherein the solid state battery is a pseudo solid state battery.

67. The solid state battery of claim 66, wherein the electrolyte of the composite cathode is a liquid electrolyte, a polymer electrolyte, and / or a gel electrolyte.

68. The solid state battery of any one of claims 1-67, wherein the solid state battery further comprises a first current collector, wherein the anode is sandwiched between and in contact with the first current collector and the interfacial layer.

69. The solid state battery of any one of claims 1-68, wherein the solid state battery further comprises a second current collector, wherein the cathode is sandwiched between and in contactwith the second current collector and the halide solid state electrolyte layer.

70. The solid state battery of claim 68 or claim 69, wherein the first current collector and / or the second current collector (when present) independently comprise a metal, a carbon material, or a combination thereof.

71. The solid state battery of any one of claims 1-70, wherein the solid state battery further includes a casing that at least partially surrounds and / or encloses a cell comprising the anode (when present), the interfacial layer, the halide solid state electrolyte layer, the composite cathode, the first current collector (when present), and the second current collector (when present).

72. The solid state battery of claim 71, wherein the casing comprises a polymer, a metal, an alloy, a polymer coated metal foil, or a combination thereof.

73. The solid state battery of any one of claims 1-72, wherein the anode is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

74. The solid state battery of any one of claims 1-73, wherein the interfacial layer is substantially free of dendrites during a plating / stripping cycle of operation of the solid state battery.

75. The solid state battery of any one of claims 1-74, wherein the solid state battery exhibits an energy density of from 75 Wh / kg to 600 Wh / kg.

76. The solid state battery of any one of claims 1-75, wherein the solid state battery exhibits a specific discharge capacity of from 100 mA h / g to 400 mA h / g when discharged at a rate of from 0.1 C to 10 C.

77. The solid state battery of any one of claims 1-76, wherein the solid state battery is rechargeable.

78. The solid state battery of any one of claims 1-77, wherein the solid state battery exhibits a coulombic efficiency of 80% or more for 100 cycles or more.

79. The solid state battery of any one of claims 1-78, wherein the solid state battery exhibits a coulombic efficiency of 99% or more for 100 cycles or more.

80. The solid state battery of any one of claims 1-79, wherein the solid state battery exhibits a capacity retention of 80% or more for 100 cycles or more.

81. The solid state battery of any one of claims 1-80, wherein the solid state battery exhibits a capacity retention of 90% or more for 100 cycles or more.

82. A method of making the solid state battery of any one of claims 1-81.

83. The method of claim 82, wherein the method comprises: making the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode; and stacking the anode (when present), the interfacial layer, the halide solid state electrolyte layer and the composite cathode together to form the solid state battery.

84. The method of claim 83, wherein the method comprises disposing the halide solid state electrolyte layer on the composite cathode, disposing the interfacial layer on the halide solid state electrolyte layer, and disposing the anode on the interfacial layer, such that the interfacial layer is between the anode and the halide solid state electrolyte layer, and the halide solid state electrolyte layer is between the interfacial layer and the composite cathode.

85. The method of claim 84, further comprising disposing the composite cathode on the second current collector before disposing the halide solid state electrolyte on the composite cathode.

86. The method of claim 84 or claim 85, further comprising disposing the first current collector on the anode.

87. A system comprising one or more of the solid state batteries of any one of claims 1-81.

88. The system of claim 87, wherein the system is an energy storage system.

89. An article comprising one or more of the solid state batteries of any one of claims 1-81.

90. The article of claim 89, wherein the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle.

91. The article of claim 89, wherein the article comprises an electronic device, such as a portable electronic device, a laptop, a watch, or a cell phone.

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