Solid electrolyte and solid-state electrochemical cell having solid electrolyte

Abstract

A solid-state electrochemical cell containing a solid electrolyte, the solid electrolyte containing one or more dendrites formed on and / or in a solid electrolyte material, the dendrites of the solid electrolyte containing metal-containing compounds that further contain oxygen and / or sulfur.

Description

[Technical field]

[0001] Technical Field This disclosure relates generally to batteries, and more specifically to solid-state batteries containing a solid electrolyte, where the solid electrolyte contains a plurality of dendritic structures. [Background technology]

[0002] background Batteries, or electrochemical cells, are ubiquitous in modern technology and are used in a wide range of applications, from small electrochemical systems for industrial and medical devices, to larger electrochemical systems for electric vehicles and grid energy storage systems.

[0003] Perhaps the most well-known and widely used battery technology today is the lithium-ion battery, which generally comprises one or more electrochemical cells, each of which comprises two electrodes (e.g., a positive electrode, a negative electrode), typically a liquid electrolyte, and often a separator between the electrodes.

[0004] Alternative battery technologies include lithium metal batteries. Lithium metal batteries are similar to lithium ion batteries, but with a negative electrode and active electrode material of lithium metal. Unfortunately, the use of lithium metal as the negative electrode can result in the formation of lithium metal dendrites that grow as lithium ions are reduced to lithium metal and deposit on the ends of the forming dendrites. The conductive lithium metal dendrites continue to grow until the ends of the dendrites form an electrical connection with the surface of the positive electrode material, resulting in a short circuit of the battery.

[0005] What is needed are alternative batteries that offer improved performance as well as increased safety. Summary of the Invention [Problem to be solved by the invention]

[0006] overview The solid-state batteries of the present disclosure provide low interfacial charge transfer resistance and / or low grain boundary resistance that are similar to those of lithium-ion batteries formed using conventional liquid electrolytes. However, the use of a solid electrolyte, rather than a liquid, reduces safety issues associated with the use or storage of lithium batteries. The use of the disclosed solid electrolyte can further result in batteries that exhibit one or more of higher energy density, higher power density, longer cycle life, reduced cost, and enhanced temperature performance compared to other lithium-ion batteries, particularly other solid-state lithium-ion batteries. [Means for solving the problem]

[0007] The present disclosure can include a solid electrolyte containing a solid electrolyte material having one or more dendrites formed on and / or in the solid electrolyte material, where the one or more dendrites include a metal-containing dendritic material, and the metal-containing dendritic material further contains oxygen and / or sulfur.

[0008] This disclosure relates to -8 Ionic conductivity of 10 S / cm or more -3 The solid electrolyte can include a solid electrolyte that includes a solid electrolyte material that is a metal-containing material having an electrical conductivity of S / cm or less, where the solid electrolyte further includes one or more dendrites formed on and / or in the solid electrolyte material, the one or more dendrites including an alkali metal, alkaline earth metal, or amphoteric metal-containing dendritic material further containing at least one of oxygen and sulfur.

[0009] The present disclosure can include a solid-state electrochemical cell comprising an electrode including an electrode active material and a solid dendritic electrolyte containing a solid electrolyte material and one or more dendrites formed on and / or in the solid electrolyte material, where the one or more dendrites contain a metal-containing compound further containing at least one of oxygen and sulfur, and the solid dendritic electrolyte is in contact with the electrode.

[0010] The disclosed features, functions, and advantages of the disclosed apparatus, systems, and methods can be achieved independently in various embodiments of the present disclosure or can be combined in yet other embodiments, further details of which can be found in the following description and with reference to the drawings.

[0011] BRIEF DESCRIPTION OF THE DRAWINGS The drawings are not necessarily drawn to scale. The dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram of an exemplary solid-state battery comprising an exemplary electrochemical cell according to the present disclosure. [Figure 2A] 1 illustrates various exemplary dendrite morphologies according to the present disclosure. [Figure 2B] 1 illustrates various exemplary dendrite morphologies according to the present disclosure. [Figure 2C] 1 illustrates various exemplary dendrite morphologies according to the present disclosure. [Diagram 3] 1 is a flow chart of an exemplary method for manufacturing an electrochemical cell according to the present disclosure. [Figure 4] 4 is a flow chart of an alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure. [Diagram 5] 4 is a flow chart of an alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure. [Figure 6] 4 is a flow chart of an alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure. [Figure 7] 1 is a plot showing the stable cycling performance of a typical symmetric electrochemical cell with a solid electrolyte according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Detailed Description The solid-state batteries of the present disclosure include one or more electrochemical cells containing a solid-state dendritic electrolyte, which can exhibit several advantageous properties compared to lithium-ion batteries, particularly compared to other solid-state lithium-ion batteries, such as higher energy density, higher power density, longer cycle life, reduced cost, and enhanced temperature capability.

[0014] Unless otherwise stated, the following definitions are used herein.

[0015] "Electrode active material" means the portion or component of an electrode that participates in a reaction by transporting ions through an electrolyte and / or by transporting electrons through an external circuit.

[0016] "Current collector" means a component adjacent to an electrode that is configured to carry electrical current from a fixed portion to a moving portion of a circuit in an electrochemical cell, or vice versa.

[0017] "Electrolyte" means a material that provides ion transport in an electrochemical cell. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes.

[0018] "Full life cycle of an electrochemical cell" is intended to mean that the life of an electrochemical cell is considered to exceed its normal useful life, which is estimated herein to be the point at which the electrochemical cell exhibits 80% of its original capacity during the first hour.

[0019] "Electrospraying", also known as electrospinning, is a thin film manufacturing method in which electrically charged threads of an organic solution or melt are drawn and applied using electrical forces.

[0020] "Substantially" means more or less conforming to a particular size, area, shape, concept, or other aspect that is modified by the term, and does not require an exact conformance of features or components. For example, a "substantially cylindrical" object means that the object resembles a cylinder, but may have one or more deviations from a true cylinder.

[0021] "Comprising," "including," and "having" (and combinations thereof) are open-ended terms that are used interchangeably to mean the inclusion, but not necessarily limitation, of additional, unrecited elements or method steps and are not intended to be exclusive.

[0022] Terms such as "first," "second," and "third" may be used to distinguish or identify various elements of a group or the like and are not intended to denote sequential or quantitative limitations.

[0023] Unless relating to specific examples, all recitations of amounts and parts, particularly those intended to define the scope of the invention, indicate a tolerance of ±10%, for example: 11% means 9.9% to 12.1%. With respect to terms such as "a solvent," the word "a" should not be regarded as a numerical term, but rather as an indefinite article or pronoun, unless the context dictates otherwise.

[0024] The term "combination" or "combinations" means all types of combinations, starting from two of the elements, up to a plurality or all of such elements, unless otherwise specified.

[0025] U.S. patent application Ser. No. 17 / 175,267, filed February 12, 2021, discloses a high energy cathode and a method for making the same; U.S. patent application Ser. No. 17 / 220,823, filed April 1, 2021, discloses a high energy cathode and a method for making the same; and U.S. patent application Ser. No. 17 / 306,457, filed May 3, 2021, discloses an electrochemical cell containing greenhouse gases, each of which is incorporated by reference in its entirety for all purposes.

[0026] The present disclosure is directed to solid-state batteries. A battery is a power source that includes one or more electrochemical cells combined with external connections to power electrical devices such as flashlights, cell phones, and electric vehicles. A solid-state battery is a battery that incorporates at least one solid-state electrochemical cell. A solid-state electrochemical cell is an electrochemical cell that incorporates a solid electrolyte.

[0027] Although the description of various embodiments in this disclosure will be described in terms of illustrating a single solid-state electrochemical cell, it should be understood that similar principles may be applied to assemblies including two or more solid-state electrochemical cells (e.g., electrochemical cell packs, etc.), and such multiple cell assemblies should be understood to be included within the scope of the present disclosure.

[0028] An exemplary solid-state electrochemical cell 10 for battery 12 is shown generally in Figure 1. Electrochemical cell 10 includes an electrode 14, which may be a positive or negative electrode, preferably a positive electrode, where electrode 14 may further contain an active electrode material 16. Electrochemical cell 10 may further include an additional electrode 18 containing an additional active electrode material 20.

[0029] If electrode 14 is a negative electrode, then additional electrode 18 can be a positive electrode, and vice versa. Either electrode 14 or additional electrode 18, or both, can include a current collector 22 in electrical contact with that electrode. The current collector in contact with the negative electrode is referred to as the negative current collector, while the current collector in contact with the positive electrode is referred to as the positive current collector.

[0030] The electrochemical cell 10 further contains a solid electrolyte 24 that contains a solid electrolyte material 26. The components of the solid-state electrochemical cell 10 are typically held within a housing (i.e., battery case) 28, which can enclose the battery components and hold them under a desired gas or liquid composition 30. The solid-state battery 12 can have the form of an alternating plate or jelly roll, a button cell, a pouch cell, a prismatic cell, a cylindrical cell, a flow cell, among others.

[0031] electrolyte An electrolyte is a material that provides ion transport within the electrochemical cell of a battery. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes. During charging of the battery, the electrolyte facilitates the movement of ions from the positive electrode to the negative electrode, whereas during discharging, the electrolyte facilitates the movement of ions from the negative electrode to the positive electrode. In rechargeable batteries, the electrolyte facilitates the circulation of ions between the negative and positive electrodes.

[0032] The solid electrolyte 24 includes a solid electrolyte material 26 that is a solid material at standard temperature and pressure (NTP). The solid electrolyte material 26 is ionically conductive, which means that the solid electrolyte material 26 is ionically conductive at 10 -10 Ionic conductivity of 10 S / cm or more -1 This means that the solid electrolyte material 26 (and thus the solid electrolyte 24) has an electrical conductivity of 10 S / cm or less. -8 Ionic conductivity of 10 S / cm or more -3 In one embodiment, the solid electrolyte 24 has an electrical conductivity of 10 -7 It has an ionic conductivity of S / cm or more.

[0033] The solid electrolyte 24 of the electrochemical cell 10 can have any form that enables the solid electrolyte 24 to function as an electrolyte in the cell. For example, the solid electrolyte 24 can have a generally planar form, such as, for example, a film, foil, tape, paper, sheet, or layer, among others.

[0034] In one embodiment of the present disclosure, the solid electrolyte 24 comprises an electrosprayed solid electrolyte film containing a desired solid electrolyte material 26 and a polymeric material, as described below. Such electrosprayed solid electrolyte films can contain greater than 70% by weight, preferably greater than 80% by weight, and more preferably greater than 90% by weight of the solid electrolyte materials described herein.

[0035] The solid electrolyte material 26 may be a polymer, a glass, a phosphate, a fluorophosphate, a carbonate, an amine, a borate, a fluoroborate, a halide, a halate, an oxohalide, an oxide (e.g., SiO2, TiO2, Al2O3, Y2O3, Mg2B2O5, Li2O, LiOH, Li2O2, Li2CO3, P2O5, GeO2, AlPO4, Li2Ti3O7), a perovskite, an antiperovskite (e.g., Li3OBr, Li3OCl, Li2OHBr, Li2OHCl), a LISICON type electrolyte (e.g., Li 1+x Al x Ti 2-x (PO4)3, Li 2+2x Zinc 1-x GeO4, Li (3+x) Ge x V (1-x) O4, Li (4-x) S (1-x) P x O4, Li 1+x+y Al x Ti 2-x S y P 3-y O 12 , Li 1+x Al x Ge y Ti 2-x-y P3O 12 , Li 1+x+3y Al x (Ge,Ti) 2-x (Siy PO4)3, Li 14 ZnGeO 16 , Li 4-x V x Ge x O4), garnets (e.g., Li7La3Zr2O 12 , Li 7-x La3Zr 2-x Nb x O 12 , Li7La 3-x Ca x Zr 2-x Nb x O 12 , Li 6+x La3Zr 1+x Ta 1-x O 12 ), sulfides (e.g., Li6PS5Cl, Li 9.54 S 1.74 P 1.44 S 11.7 Cl 0.3 , Li 10 GeP2S 12 , Li7PS6, Li7P3S 11 , Li 3.25 P 0.95 S4, Li 3+x Ge x P 1-x S4), thio-LISICON type electrolytes (e.g., Li (4-x) Ge (1-x) P x S4), oxynitride, or nitride, etc. (LISICON is an acronym for LIthium Super Ionic CONductor).

[0036] In one embodiment, the solid electrolyte material 26 comprises 10 -8 Ionic conductivity of 10 S / cm or more -3 In another embodiment, the solid electrolyte material 26 includes a metal-containing material having an electrical conductivity of 10 S / cm or less. -8 Ionic conductivity of 10 S / cm or more -3 Lithium-containing materials having electrical conductivity of less than or equal to 1.5 S / cm are included.

[0037] The solid electrolyte 24 is typically modified to contain one or more, or a plurality of, dendrites 32, where a dendrite is a branched, tree-like structure that grows on and / or into the solid electrolyte 24. The branched structure of dendrites 32 is typically formed by crystallization of a metal compound or metal complex on or into the solid electrolyte 24. The dendrite 32 structure may contain multiple single crystal domains that may contain the same or different metals, metal compounds, or metal complexes. Preferably, the growth of the dendrites 32 results in a branched, tree-like structure that contains at least one branch having an aspect ratio (length divided by diameter / thickness) of 0.1 or more, preferably 1 or more, and more preferably 10 or more.

[0038] The solid electrolyte 24 can contain multiple dendrites 32, where the dendrites can have any suitable dendritic morphology, or structure. A single dendrite 32 can exhibit a variety of dendritic structures while remaining generally branched and tree-like. For example, each of FIGS. 2A-2C provides a schematic illustration of the stages of growth of different dendritic morphologies extending from a surface 34, which may be, for example, the surface of the electrolyte 24. As shown in FIG. 2A, the dendrite 32 can exhibit a "cactus-type" dendritic structure, having a large central ridge, or trunk, with several much smaller, possibly needle-like branches extending from the central ridge. Alternatively, as shown in FIG. 2B, the dendrite 32 can exhibit a "moss-type" dendritic structure, having a more organic morphology and with more rounded branches without such a clearly identified central trunk. Alternatively, as shown in FIG. 2C, dendrite 32 may exhibit a "branched" dendritic structure that has the organic overall morphology of a "moss" dendrite, but has better defined, further extending branches, and may be relatively more pointed (needle-like) than a moss dendrite.

[0039] 2A-2C, dendrites 32 are shown at various stages of growth, from the formation of an initial dendritic structure (far left) to a mature dendritic structure (far right) that has extended outward from surface 34 sufficiently to create a bridge between surface 34 and a second surface 36, which may be the surface of an electrode, current collector, or other electrochemical cell component. In a typical lithium-based battery, if a metal dendrite were to extend across such a gap, the dendrite would form an electrical connection (or short) between those two surfaces. In the case of the solid electrolyte of the present disclosure, no such electrical connection is formed, even though dendrites 32 extend across the gap to form a bridge between the two surfaces.

[0040] The plurality of dendrites 32 on and / or in the solid electrolyte 24 can contain any of the dendritic structures shown, or combinations or mixtures thereof. The particular structure of the dendrites 32 present on / in the solid electrolyte of the present disclosure typically depends on the material used to form the dendrites, the gas or liquid composition surrounding the electrolyte material during dendrite formation, and the conditions (temperature, pressure, etc.) within the electrochemical cell during dendrite formation.

[0041] Although dendrites have been previously observed to form in conventional lithium ion or lithium metal batteries, in those cases the dendrites are composed of pure metal and their presence can be detrimental to various aspects of battery performance. In contrast, the dendrites of the present disclosure can contain metal compounds and metal complexes (e.g., metal oxides, metal sulfides, among others), such that when present on / in the solid electrolyte 24, the dendrites can have a beneficial effect on various aspects of battery performance.

[0042] The dendrites of the solid electrolyte 24 may contain metal-containing compounds (e.g., metal complexes) where the metal may include alkali metals (e.g., lithium, sodium, potassium), alkaline earth metals (e.g., magnesium, calcium), or amphoteric metals (e.g., beryllium, aluminum, zinc, tin, lead). The metal compounds may also contain either or both of oxygen or sulfur. If the metal compound contains oxygen, the resulting material may not be as reactive to the environment as the analogous sulfide compounds. The dendrites of the present disclosure are typically ionically conductive and electrically insulating. Typically, the dendrites are 10 -10 Ionic conductivity of 10 S / cm or more -1 The dendrites have an electrical conductivity of 10 S / cm or less. -8 Ionic conductivity of 10 S / cm or more -3 More preferably, the dendrites have an electrical conductivity of 10 -7 Ionic conductivity of 10 S / cm or more -4 It has an electrical conductivity of less than S / cm.

[0043] The dendrites of the present disclosure may be formed electrochemically and / or chemically on and / or in the solid electrolyte 24 using a suitably reactive gas. Without wishing to be bound by theory, it is believed that dendrites form and grow where there are relatively weak physical spots in the solid electrolyte and / or where there are physically open spots on the electrolyte. Each dendrite 32 may originate from the electrode active material 16 or 20 and may have at least one branch extending in a direction generally perpendicular to one or both of the negative and positive current collectors. Each dendrite 32 may be in contact with the electrode 14, the additional electrode 18, and / or the current collector 22.

[0044] The presence of dendrites 32 on and / or in the solid electrolyte 24 can reduce the interfacial charge transfer resistance and / or grain boundary resistance of an electrochemical cell incorporating the electrolyte. Alternatively, or in addition, the action of the reactive gas can add electroactive functional groups to the surface of the electrode material and / or redesign the chemical structure of the electrode material. Such redesign of the electrode material can contribute to the resulting electrochemical cell being able to store more energy per unit mass or area of ​​the electrode.

[0045] The solid electrolyte 24 can include a polymer material, where the polymer material can be electrically insulating and / or ionically insulating. -7 The solid electrolyte 24 may have an ionic conductivity of 0.01 S / cm or less and may form a portion of the electrolyte and / or one or both electrodes. The polymeric material may include, for example, one or more of polyethylene oxide, polyethylene oxide, polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinylpyrrolidone, and poly(4-vinylpyridine), in any combination. The solid electrolyte 24 may have a composition of about 0.01% to about 30% by weight of polymeric material, preferably about 0.1% to about 20% by weight of polymeric material, and more preferably about 1% to about 10% by weight of polymeric material.

[0046] The solid electrolyte material 26 may contain a composition of solid particles. When present, the average particle size of such a composition may vary from about 5 nm to about 30 μm and may exhibit an average pore size of about 0.1 nm to about 500 nm. Typically, the average particle size or diameter of the solid electrolyte material 20 is less than about 30 μm. Preferably, the average particle size of the solid electrolyte material 20 is greater than about 10 nm and less than about 20 μm. More preferably, the average particle size of the solid electrolyte material 20 is greater than about 20 nm and less than about 10 μm. When the solid electrolyte material 20 contains a composition of solid particles, the average pore size of the solid electrolyte material 20 may be less than about 500 nm. Preferably, the average pore size of the solid electrolyte material 20 is greater than about 0.5 nm and less than about 200 nm. More preferably, the average pore size of the solid electrolyte material 20 is greater than about 1 nm and less than about 100 nm.

[0047] In some embodiments, in addition to the solid electrolyte material 26, the electrochemical cell 10 can further contain a non-solid electrolyte that is a liquid, a gel, or a liquefied gas.

[0048] electrode The positive electrode is the electrode of a battery cell that receives electrons from an external circuit, is reduced during discharge, and transfers electrons to the external circuit by oxidation during charging. The positive electrode may be referred to as the cathode. The negative electrode is the electrode of a battery cell that transfers electrons to the external circuit by oxidation during discharge, and receives electrons from the external circuit and is reduced during charging. The negative electrode may be referred to as the anode.

[0049] If electrode 14 is a negative electrode, then additional electrode 18 is a positive electrode, and vice versa. Either electrode 14 or additional electrode 18, or both, may include a current collector 22 in electrical contact with that electrode. The current collector in contact with the negative electrode is referred to as the negative current collector, while the current collector in contact with the positive electrode is referred to as the positive current collector.

[0050] The electrode 14 and additional electrode 18, if present, typically contain one or more electrode active materials 16, 20, which may be the same or different. The electrode active materials 16, 20 comprise the portions or components of the electrode that participate in the electrochemical reaction by transporting ions through an electrolyte and / or transporting electrons through an external circuit, and that gain or lose electrons during the course of the electrochemical reaction. The electrode active materials 16, 20 can constitute the entirety of the associated electrode, but are typically components of, or coatings on, the electrode.

[0051] The electrode active materials 16, 20 can be starting materials, discharge products, or charge products. For example, in an electrochemical cell where graphite is used as the negative electrode active material, graphite (C6) is lithiated during charging to become LiC6. Then, during discharging, LiC6 is delithiated back to C6. Both C6 and LiC6 are considered to be electrode active materials. The starting materials, discharge products, and charge products can all be different from each other.

[0052] The electrode active materials 16, 20 can be generated in situ by selection of the appropriate components of the electrochemical cell 10, such as by selecting the composition of the solid electrolyte 24 and its additional components, optionally followed by application of a current collector to the electrochemical cell 10. The particular composition of the electrode active materials 16, 20 is not particularly critical, and any electrode active material capable of storing and releasing ions can be a suitable electrode active material for purposes of this disclosure.

[0053] For example, the electrode active materials 16, 20 can be, among others, alkali metals (e.g., lithium, sodium, potassium), alkaline earth metals (e.g., magnesium, calcium), amphoteric metals (e.g., beryllium, aluminum, zinc, tin, and lead), metalloids (e.g., silicon, silicon oxide, silicon carbide, silicides, arsenic, antimony, tin), inorganic carbon (e.g., graphite, graphene, graphene oxide, activated carbon, carbon nanotubes, carbon dots), sulfur, sulfur compounds (sulfides, e.g., lithium titanium disulfide (LTS), MV, ... 0.5 Ti0.5 S2 (wherein M is a metal), oxides (e.g., M x Ti5O 12 , TiO2, TiNb2O7, Nb2O5, M x VO4, H2Ti6O 13 , M x MnBO3, M x V2O5, M x MoO4, M x W2O 7、 M' 1-x M''O2, M' 1-w (M'' x M'' y )O2, M 1-w (M x Ni y Co z )O2, M 1-w (M x Ni y Co z Al w )O2, M 1-w (Ni x Co y Al z )O2, M' 1-w (Ni x Co y M'' z )O2, M' 1-w (Ni x Mn y M'' z )O2, M'M''M''2O4, M x V y O z ,M'M''PO4,M'M'' x M'' 1-x The material may be in the form of lithium phosphate (M'), lithium iron phosphate (LFP), lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium cobalt oxide (LCO), lithium nickel oxide (LNO), and lithium manganese oxide (LMO).

[0054] Alternatively, or in addition, the electrode active materials 16, 20 can contain organic materials (e.g., truxenone, truxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives, quinone, quinone derivatives, diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melamine, melamine derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, amide derivatives, amino acids, amino acid derivatives, viologen, viologen derivatives, nitroxide derivatives), halogens, halogen compounds (such as halides), or any combination thereof.

[0055] In some embodiments, the electrode active material 16, 20 can contain one or more organic moieties, where the organic moiety is a fragment or a substituent of a larger compound. When the electrode active material 16, 20 contains an organic moiety, it can be derived from an organic compound, as described above. Examples of organic moieties include alkyl, alkenyl, alkynyl, acyl, alkylamino, and aryl groups, among others. In one aspect, the electrode active material contains an organic compound containing heteroatoms such as boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and / or bromine, among others. Alternatively, or in addition, the electrode active material contains an organic compound containing one or more aromatic groups. When the electrode active material contains a metal or metal compound or complex, the metal is preferably an alkali metal or an alkaline earth metal. More preferably, the metal is an alkali metal, and such materials can provide the resulting electrochemical cell with the ability to provide high energy density.

[0056] In some cases, the electrochemical cell 10 can include an electrode or additional electrodes formed by applying an electrode active material to a substrate (e.g., current collector 22) that does not itself contain the electrode active material. The electrode active material can be applied to the substrate by depositing or intercalating into the substrate upon initial charging or discharging of the electrochemical cell. The electrode can further contain an electrolyte material. The electrode active material can be mixed with the electrolyte material. In these embodiments, a solid electrolyte 24 can be disposed with the electrode 14 or 18 and can be disposed between the current collector 22 and the electrode. In some embodiments, the current collector 22 corresponds to the housing 28 of the electrochemical cell 10.

[0057] The electrode active material 16, 20 can be present as a solid particle composition. Suitable electrode active materials can vary in average particle size from about 5 nm to about 50 μm and can exhibit an average pore size from about 0.1 nm to about 1 μm. Preferably, the average particle size of the electrode active material is greater than about 500 nm and less than about 50 μm. More preferably, the average particle size of the electrode active material is greater than about 1 μm and less than about 30 μm. When the electrode active material 16, 20 is present as a solid particle composition, the average pore size of the electrode active material can be less than about 1 μm. Preferably, the average pore size of the electrode active material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the electrode active material is greater than about 5 nm and less than about 200 nm.

[0058] The electrode 14 and the additional electrode 18, if present, can contain an electrically conductive material. The electrically conductive material can contain a porous carbon material containing one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, graphite, graphene, graphene oxide, and graphene nanoribbons. Carbon nanotubes, among others, are preferred for their high aspect ratio and durability. The porous carbon material can be doped with one or more heteroatoms selected from boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and bromine. Nitrogen or fluorine, among others, are preferred to enable lower charge transfer resistance. The electrically conductive material can also function as the electrode active material 16, 20, so long as it is capable of storing and releasing ions during operation of the electrochemical cell 10. In further aspects and embodiments, the porous carbon material can have the form of particles, powders, paper, foams, fibers, sheets, disks, rods, and / or foils.

[0059] Electrically conductive materials useful for the electrodes 14, 18 can have an average particle size or diameter of about 5 nm to about 50 μm. Typically, the average particle size or diameter of the electrically conductive material is less than about 50 μm. Preferably, the average particle size of the electrically conductive material is greater than about 50 nm and less than about 40 μm. More preferably, the average particle size of the electrically conductive material is greater than about 500 nm and less than about 30 μm. The electrically conductive material can have an average pore size of less than about 1 μm. For example, the electrically conductive material can have an average pore size of about 0.1 nm to about 1 μm. Preferably, the average pore size of the electrically conductive material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the electrically conductive material is greater than about 5 nm and less than about 200 nm.

[0060] The average particle size or diameter of the particles making up the electrode active material 16, 20 and the particles of the electrically conductive material of the electrodes 14, 18 may be inversely correlated. For example, if the average particle size of the electrode active material is in the range of about 10 μm to about 50 μm, the average particle size of the electrically conductive material may be about 10 nm to about 500 nm, or vice versa. Typically, one or more of the electrode active material and the electrically conductive material contain particles having an average particle size or diameter greater than about 50 nm and less than about 50 μm, preferably greater than about 500 nm and less than about 40 μm, and more preferably greater than about 1 μm and less than about 30 μm.

[0061] The electrodes 14, 18 of the electrochemical cell 10 typically contain an electrically conductive material, either as a substrate or as an electrode body, on or within which the electrode active material and / or solid electrolyte are deposited or formed. Any suitable electrically conductive material, which may have the same or different formulation, can be used for the disclosed electrodes. The electrode active material 16, 20 and / or the electrically conductive material can be shaped into a planar surface and / or can be a granular solid. When the electrode active material, the electrically conductive material, and / or the solid electrolyte are granular, the single particles can have any suitable shape, such as a sphere, cube, rectangular prism, cone, pyramid, cylinder, square prism, hexagonal prism, hemisphere, triangular prism, pentagonal prism, octagonal prism, ring, octahedron, and dodecahedron, among others, or any combination thereof.

[0062] The electrodes 14, 18 and / or the solid electrolyte 24 may further include one or more of a polymer binder, a plasticizer, and a carboxylic acid. If the electrodes 14, 18 include a polymer binder, the polymer binder may be present to aid in forming a solid electrode from the electrode active material. Suitable polymer binders for this disclosure may include one or more of polycaprolactone, poly(acrylic acid), poly(methyl methacrylate), polytetrafluoroethylene, poly(vinylidene fluoride), polyacrylonitrile, poly(ethylene terephthalate), polyvinylpyrrolidone, poly(4-vinylpyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene-butadiene-rubber, sodium carboxymethyl cellulose, among others. In certain embodiments, the polymer binder includes one of poly(ethylene oxide) (PEO) or poly(vinylidene fluoride).

[0063] If the electrodes 14, 18 contain a carboxylic acid, the carboxylic acid may be present to facilitate transport of ions into and out of the electrode active material of the electrode. If present, the carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid. If the carboxylic acid is a polycarboxylic acid, it may be oxalic acid.

[0064] When the electrodes 14, 18 contain a plasticizer, the plasticizer comprises a material added to an organic or polymeric material to make it softer, more flexible, and / or to increase its plasticity. Exemplary plasticizers include, by way of non-limiting example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethylformamide, dimethylsulfoxide, gamma-butyrolactone, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitates, adipates, sebacates, maleates, or any combination thereof. In one embodiment, a suitable plasticizer may comprise succinonitrile.

[0065] The electrically conductive material of the electrode, along with any additional conductive material, polymeric binder, and plasticizer, if present, can be applied to the current collector using any suitable application technique, for example, the electrically conductive material can be cast as a film and then deposited onto the desired current collector.

[0066] Current collector Each current collector 22 functions as a bridging component to collect electrical current generated at the electrodes 14, 18 and is connected to an external circuit. Each current collector 22 is typically adjacent to its associated electrode. Typically, each current collector is or contains an electrically conductive material.

[0067] Each current collector 22, which may be the same or different, may contain any suitable and compatible electrically conductive material. The current collector 22 may contain one or more metals, such as alkaline earth metals, transition metals, rare earth metals, post-transition metals, and alkali metals, or any combination thereof. In particular, the current collector 22 may contain at least one of aluminum, aluminum alloys, copper, copper alloys, silver, silver alloys, nickel, nickel alloys, duplex stainless steels, or any combination thereof. Alternatively, or in addition, the current collector 22 may include a metal current collector containing one or more of molybdenum, titanium, and zirconium metals or metal alloys. The current collector 22 may be in contact with an electrically conductive material, for example, by being coated with the electrically conductive material. In this embodiment, the electrically conductive material can be a porous inorganic carbon material that is carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, microporous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, graphene nanoribbons, and mixtures and combinations thereof. In some embodiments, the porous inorganic carbon material can be in the form of particles, powders, rods, or any combination thereof. In particular, the current collector can contain free-standing carbon material in the form of paper, foam, felt, fiber, film, sheet, tape, cloth, disk, thread, foil, or any combination thereof.

[0068] Holes can be formed in the current collector 22, and the pore diameter can be about 500 nm or more (e.g., about 500 nm to about 5 mm, preferably about 500 nm to about 1 mm, and more preferably about 500 nm to about 200 μm), and the distance between the pores can be about 10 μm or more (e.g., about 10 μm to about 10 mm, preferably about 50 μm to about 10 mm, and more preferably about 200 μm to about 10 mm).

[0069] Separator In some embodiments, the solid electrolyte 24 can act as a separator 38 by separating the electrode 14 from the additional electrode 18 or from a current collector 22 associated with the additional electrode 18. Alternatively, the electrochemical cell 10 can include an additional separator 38 that is distinct from the solid electrolyte 24. The solid electrolyte 24 and / or separator 38 (if present) can be larger in their width and length than one or more current collectors 22 to avoid contact between the negative and positive electrodes.

[0070] The separator 38, if present, can be in contact with the electrode 14, or the separator 38 can be in contact with the solid electrolyte 24. If the electrochemical cell 10 includes an additional electrode 18, the separator 38 can be disposed between the electrode 14 and the additional electrode 18. To avoid contact between the electrode 14 and the additional electrode 18, contact between the individual current collectors 22, contact between the positive and negative current collectors, or contact between the negative and positive current collectors, the separator 38 can be larger in either or both of its width and length than the current collectors 22. The separator 38 can contain an electrolyte that provides ion transport within the electrochemical cell 10 and acts as a conduit for ion transport by its interaction with the electrode 14 and the additional electrode 18.

[0071] Separator 38 may be in contact with solid electrolyte 24 and may contain a polymeric material, such as, for example, a polymeric film. If present, the polymeric material may be polyethylene, polypropylene, poly(tetrafluoroethylene), or poly(vinyl chloride), among others. Typically, the polymeric film, if present, contains polypropylene and / or polyethylene. Alternatively, or in addition, separator 38 may contain non-woven fibers (such as nylon, polyester, and glass, among others), glass, ceramic, or any combination thereof. In some embodiments, separator 38 contains glass fibers. In some embodiments, separator 38 may contain a surfactant coating or treatment to enhance wettability of the liquid-based electrolyte.

[0072] Reactive Gases The electrochemical cell 10 can further contain a reactive gas, which is a gas at any given temperature or pressure that is a compound that reacts chemically or electrochemically with the solid electrolyte material 26 of the solid electrolyte 24 or the electrode active materials 16, 20 to form dendrites 32 on and / or in the solid electrolyte 24. In embodiments of the present disclosure, the reactive gas can contain compounds having at least one oxygen atom (e.g., CO, CO, O, N, O, NO, and SO) and / or compounds having at least one sulfur atom (e.g., S, COS, CS, SF, H, S, SO, CH, SH, (CH)S, and CHCHSH.

[0073] The solid electrolyte material 26 or dendrites 32 of the present disclosure may be formed or modified by a reactive gas, even if not in the gas phase. The reactive gas may optionally be liquefied under pressure and held within the housing 28 of the electrochemical cell 10. The liquefied gas may be in contact with and / or dissolved in the solid electrolyte 24. The reactive gas may be maintained in contact with either or both of the electrodes 14, 18, but the reactive gas is not intended to be used as an electrode active material.

[0074] Preparation of solid-state electrochemical cells The preparation of the solid-state electrochemical cell 10 necessarily involves the preparation of the solid electrolyte 24, and more specifically, the formation of dendrites 32 on the solid electrolyte 24. Although any method of combining the solid electrolyte material 26 with a reactive gas that results in the formation of dendrites on the solid electrolyte 24 is a suitable method of preparing the solid electrolyte of the present disclosure, it may be particularly convenient to form the improved solid electrolyte by applying a voltage or current in the presence of a reactive gas to an electrochemical cell that introduces the solid electrolyte 24. That is, the electrochemical cell 10 may be assembled, and then a reactive gas may be added to the electrochemical cell 10 such that subsequent application of a voltage or current results in the formation of dendrites on the solid electrolyte.

[0075] By introducing a reactive gas rich atmosphere into the cell housing 28, non-standard dendrites 32 for chemical and / or electrochemical reactions can be formed on the surfaces of the electrodes 14 and / or 18 and / or on the surface of the solid electrolyte material 26. The glass formed during the formation of the dendrites 32 can be purged with a selected reactive gas, an alternative (i.e., second) reactive gas, and / or an inert gas. Alternatively, instead of purging the existing gas, the partial pressure of the reactive gas within the housing can be reduced or the reactive gas can be removed by applying a vacuum to the electrochemical cell 10. It should be understood that any of the following methods can optionally further include one or more additional steps of applying a voltage or current to the electrochemical cell 10 that are performed after the purging step.

[0076] The solid-state electrochemical cells of the present disclosure can be made by providing an electrochemical cell housing, placing desired electrochemical cell components (e.g., desired electrodes, desired solid electrolyte) within the electrochemical cell housing, compressing the selected electrochemical cell components within the electrochemical cell housing, providing a desired reactive gas to the electrochemical cell housing to replace all or a portion of the ambient atmosphere within the electrochemical cell housing, and then sealing the electrochemical cell housing. Alternatively, instead of providing the desired reactive gas, the electrochemical cell housing can be sealed under a reactive gas atmosphere.

[0077] In one embodiment, placing the electrochemical cell components in the electrochemical cell housing can include placing the electrochemical cell components in the following order: i) anode current collector, ii) anode, iii) solid electrolyte (separator), iv) cathode, and v) cathode current collector. Alternatively, the order of the electrochemical cell components can be reversed. The step of compressing the electrochemical cell components should require careful control of the pressure applied to the electrochemical cell components so that the electrodes and the additional electrodes remain appreciably separated. The electrochemical cell components can be compressed, for example, using a press, with a stack pressure of 100 MPa or less (e.g., about 0.1 MPa to about 100 MPa, preferably about 0.5 MPa to about 70 MPa, more preferably about 1 MPa to about 50 MPa). Advantageously, the pressure applied during similar steps described herein can be lower than the pressure typically applied to conventional solid-state electrochemical cells during electrochemical cell manufacturing (where such pressure can be greater than 500 MPa).

[0078] As mentioned above, the solid-state electrochemical cell 10 of the present disclosure optionally comprises an electrosprayed solid electrolyte film containing a solid electrolyte material 26 and / or a polymeric material. Also, one or both electrodes 14, 18 can optionally contain such electrosprayed materials. One or more electrospraying parameters, such as flow rate, applied voltage, applied current, nozzle size, nozzle type, and distance between the nozzle tip and the current collector, among others, can be adjusted to optimize the electrospraying process. Electrospraying can advantageously allow for stretching and thinning of the polymeric material, which can not only strongly consolidate the electrolyte material to produce crack-free micron-thick free-standing films (e.g., >5 μm), but also allow a relatively small amount of polymeric material to cover the surface of the solid electrolyte material 26 compared to conventional application techniques.

[0079] An exemplary and illustrative method for manufacturing an electrochemical cell according to the present disclosure is shown in flow chart 40 of Figure 3. The method of flow chart 40 includes placing the desired electrochemical cell components in a desired order within an electrochemical cell housing at step 42, compressing the electrochemical cell components so that the solid electrolyte is in intimate contact with the electrode materials at step 44, sealing the electrochemical cell housing under a reactive gas rich atmosphere at step 46, applying a voltage or current to the electrochemical cell under the reactive gas rich atmosphere to form the desired dendritic structure at step 48, and purging the electrochemical cell housing of forming gas generated during application of voltage or current with the reactive gas at step 50.

[0080] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is shown in flow chart 52 of Figure 4. Figure 4 is a flow chart of an alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure. The method of flow chart 52 includes placing the desired electrochemical cell components in a desired order into an electrochemical cell housing in step 54, compressing the electrochemical cell components so that the solid electrolyte is in intimate contact with the electrode materials in step 56, sealing the electrochemical cell housing in step 58, introducing a reactive gas into the electrochemical cell housing in step 60 to displace ambient gas from the electrochemical cell housing, applying a voltage or current to the electrochemical cell under the reactive gas atmosphere in step 62, and purging the electrochemical cell housing of any forming gas generated during application of the voltage or current in step 64.

[0081] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is shown in flow chart 66 of Figure 5. The method of flow chart 66 includes placing the desired electrochemical cell components in a desired order within an electrochemical cell housing at step 68, compressing the electrochemical cell components so that the solid electrolyte is in intimate contact with the electrode materials at step 70, sealing the outer electrochemical cell housing under a reactive gas rich atmosphere at step 72, applying a voltage or current to the electrochemical cell under the reactive gas atmosphere at step 74, and reducing the partial pressure of the reactive gas in the electrochemical cell component stack or removing the reactive gas at step 76 by applying a vacuum or purging the electrochemical cell housing with an inert gas. In the context of the method of flow chart 66, the partial pressure of the reactive gas in the electrochemical cell component stack can be reduced to 0.9 atm or less, preferably to 0.5 atm or less, and more preferably to 0.1 atm or less.

[0082] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is shown in flow chart 78 of Figure 6. The method of flow chart 78 includes placing the desired electrochemical cell components in an electrochemical cell housing in a desired order at step 80, compressing the electrochemical cell components so that the solid electrolyte is in intimate contact with the electrode materials at step 82, sealing the electrochemical cell housing at step 84, introducing a reactive gas into the electrochemical cell housing to displace ambient gas from the electrochemical cell housing at step 86, applying a voltage or current to the external electrochemical cell housing under a reactive gas atmosphere at step 88, and reducing the partial pressure of the reactive gas in the electrochemical cell component stack or removing the reactive gas at step 90 by applying a vacuum or purging the electrochemical cell housing with an inert gas. In the context of the method of flow chart 78, the partial pressure of the reactive gas in the electrochemical cell component stack can be reduced to 0.9 atm or less, preferably to 0.5 atm or less, and more preferably to 0.1 atm or less.

[0083] 7 is a graph showing the advantageous and stable cycling performance of a typical symmetric electrochemical cell containing a solid electrolyte according to the present disclosure. The solid-state electrochemical cell comprises a lithium metal foil and a solid electrolyte formed according to the present disclosure, and is capable of cycling at room temperature at 5 mA / cm. 2 The solid electrolyte film was placed between two lithium metal foils. 1.3 Al 0.3 Ti 1.7(PO4)3 (LATP) was selected as the solid electrolyte material. The solid electrolyte film was freestanding and fabricated by electrospraying technique. The weight ratio of the electrolyte film containing LATP, polycaprolactone, and poly(ethylene oxide) was 95:1:4. The thickness of the electrolyte film was about 30 μm. The stack pressure of the electrochemical cell was measured to be about 8 MPa. In an attempt to coat the solid electrolyte and poly(ethylene oxide) blend with an ultrathin nanofilm containing polycaprolactone, polycaprolactone was electrosprayed on the outer region of the coaxial nozzle, and the blend of LATP and poly(ethylene oxide) was electrosprayed on the core region. The solid electrochemical cell was charged under a reactive gas (e.g., carbon dioxide) atmosphere to form dendrites in and on the electrolyte material, and then purged with an inert gas (e.g., argon) to replace the reactive gas.

[0084] For the methods of the present disclosure, although the figures and description may illustrate a particular order of steps of the method, it should be understood that the order of such steps may differ from that depicted and described, unless otherwise specified above. Also, two or more steps may be performed simultaneously or with partial concurrence, unless otherwise specified above. Furthermore, one or more steps may be repeated before the next step. EXAMPLES

[0085] Working Example This section describes further aspects and features of the disclosed electrolytes, electrochemical cells, and methods, presented without limitation as a series of paragraphs, some or all of which may be designated by alphanumeric characters for clarity and efficiency. Each of these paragraphs may be combined in any suitable manner with one or more of the other paragraphs and / or with disclosure from elsewhere in this application. Some of the paragraphs below explicitly refer to and further qualify other paragraphs, providing without limitation examples of some suitable combinations.

[0086] A1. A solid electrolyte comprising a solid electrolyte material containing one or more dendrites formed on and / or within the solid electrolyte material, wherein the one or more dendrites comprise a metal-containing dendritic material, the metal-containing dendritic material further containing oxygen and / or sulfur.

[0087] A2. The solid electrolyte of paragraph A1, wherein the one or more dendrites are electrochemically and / or chemically formed on and / or in the solid electrolyte material under a reactive gas.

[0088] A3. The solid electrolyte of paragraph A1, wherein the metal-containing dendritic material contains an alkali metal or an alkaline earth metal.

[0089] A4. The solid electrolyte of any of paragraphs A1-A3, wherein the solid electrolyte material contains a polymeric material at a concentration of less than about 30% by weight.

[0090] A5. One or more dendrites are 10 -10 Ionic conductivity of 10 S / cm or more -1 4. The solid electrolyte of any of paragraphs A1 to A3, exhibiting an electrical conductivity of no more than S / cm.

[0091] A6. The solid electrolyte of any of paragraphs A1-A3, wherein one or more dendrites have at least one branch exhibiting an aspect ratio of 0.1 or greater.

[0092] A7. A solid-state electrochemical cell comprising the solid electrolyte according to any one of paragraphs A1 to A3.

[0093] B1.10 -8 Ionic conductivity of 10 S / cm or more -31. A solid electrolyte comprising a solid electrolyte material that is a metal-containing material having an electrical conductivity of S / cm or less, the solid electrolyte further comprising one or more dendrites formed on and / or in the solid electrolyte material, the one or more dendrites comprising an alkali metal, alkaline earth metal, or amphoteric metal-containing dendritic material further containing at least one of oxygen and sulfur.

[0094] B2. A solid-state electrochemical cell containing the solid electrolyte described in paragraph A7. B1.

[0095] C1. A solid-state electrochemical cell comprising an electrode comprising an electrode active material and a solid dendritic electrolyte comprising a solid electrolyte material and one or more dendrites formed on and / or in the solid electrolyte material, wherein the one or more dendrites contain a metal-containing compound further comprising at least one of oxygen and sulfur, and the solid dendritic electrolyte is in contact with the electrode.

[0096] C2. The solid-state electrochemical cell of paragraph C1, wherein the one or more dendrites are formed from an electrode active material.

[0097] C3. The solid-state electrochemical cell of any one of paragraphs C1 and C2, wherein one or more dendrites have at least one branch extending perpendicular to the electrode and at least one branch having an aspect ratio of 0.1 or greater.

[0098] C4. The solid-state electrochemical cell of paragraph C1, wherein one or more dendrites of the solid electrolyte are in contact with an electrode, an additional electrode, and / or a current collector coupled to the electrode or the additional electrode.

[0099] C5. The solid-state electrochemical cell of one of paragraphs C1, C2, and C4, wherein the metal-containing compound contains an alkali or alkaline earth metal.

[0100] C6. The solid-state electrochemical cell of paragraph C1, wherein the electrode active material comprises a metal or metalloid.

[0101] C7. The solid-state electrochemical cell of paragraph C1, wherein the electrodes contain an electrically conductive material.

[0102] C8. The solid-state electrochemical cell of paragraph C7, wherein the electrically conductive material is doped with one or more heteroatoms selected from boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and bromine.

[0103] C9. The solid-state electrochemical cell of any one of paragraphs C1, C2, C4, and C6-C8, wherein the electrode contains one or more of a polymeric binder, a plasticizer, and a carboxylic acid.

[0104] C10. The solid-state electrochemical cell of any one of paragraphs C1, C2, C4, and C6-C8, wherein the solid electrolyte comprises an electrosprayed film of a polymeric material.

[0105] C11. The solid-state electrochemical cell of any one of paragraphs C1, C2, C4, C6-C8, and C10, further comprising a current collector coupled to the electrode or additional electrode, wherein the current collector is metallic and contains one or more of molybdenum, titanium, and zirconium.

[0106] C12. The solid-state electrochemical cell of any one of paragraphs C1, C2, C4, C6-C8, and C10, further comprising a reactive gas liquefied in contact with the solid electrolyte or dissolved in the solid electrolyte.

[0107] C13. The solid-state electrochemical cell of paragraph C12, wherein the reactive gas comprises oxygen and / or sulfur.

[0108] C14. Reactive gases are CO2, CO, O2, N2O, NO2, and SO 2、 The solid-state electrochemical cell of paragraph C12, containing one or more of S8, COS, CS2, SF6, H2S, SO2, CH3SH, (CH3)2S, and C2H5SH.

[0109] conclusion The disclosure disclosed above can encompass a number of different embodiments having independent utility. Although each of these has been disclosed in one or more exemplary forms, the specific embodiments disclosed and described herein should not be considered in a limiting sense, as numerous alternative forms are possible. To the extent that section headings are used within this disclosure, such headings are for organizational purposes only. The subject matter of the present disclosure includes all novel and unobvious combinations and subcombinations of the various elements, features, functions, and / or properties disclosed herein. The following claims specifically set forth certain combinations and subcombinations that are deemed novel and unobvious. Other combinations and subcombinations of features, functions, elements, and / or properties may be claimed in applications claiming priority from this or related applications. Such claims are also considered to be within the subject matter of the present disclosure, whether broader, narrower, equal, or different in scope than the original claims.

Claims

1. 1. A solid electrolyte comprising a solid electrolyte material containing one or more dendrites formed on and / or within the solid electrolyte material, the one or more dendrites comprising a metal-containing dendritic material, the metal-containing dendritic material further comprising oxygen and / or sulfur.

2. 10. The solid electrolyte of claim 1, wherein the one or more dendrites are formed electrochemically and / or chemically on and / or in the solid electrolyte material under a reactive gas.

3. 10. The solid electrolyte of claim 1, wherein the metal-containing dendritic material contains an alkali metal or an alkaline earth metal.

4. 10. The solid electrolyte of claim 1, wherein the solid electrolyte material contains a polymeric material at a concentration of less than about 30% by weight.

5. The one or more dendrites are －１０ Ionic conductivity of 10 S / cm or more －１ 2. The solid electrolyte of claim 1, exhibiting an electrical conductivity of less than or equal to 100 S / cm.

6. 10. The solid electrolyte of claim 1, wherein the one or more dendrites have at least one branch exhibiting an aspect ratio of 0.1 or greater.

7. 10 －８ Ionic conductivity of 10 S / cm or more －３ 1. A solid electrolyte comprising a solid electrolyte material that is a metal-containing material having an electrical conductivity of less than or equal to 100 S / cm, the solid electrolyte further comprising one or more dendrites formed on and / or within the solid electrolyte material; 11. A solid electrolyte, wherein the one or more dendrites comprise a dendritic material containing an alkali metal, an alkaline earth metal, or an amphoteric metal and further containing at least one of oxygen and sulfur.

8. An electrode including an electrode active material; a solid dendritic electrolyte comprising a solid electrolyte material and one or more dendrites formed on and / or within the solid electrolyte material, the one or more dendrites contain a metal-containing compound that further contains at least one of oxygen and sulfur; and The solid-state electrochemical cell, wherein the solid dendritic electrolyte is in contact with the electrodes.

9. 10. The solid-state electrochemical cell of claim 8, wherein the one or more dendrites are formed from the electrode active material.

10. 10. The solid-state electrochemical cell of claim 8, wherein the one or more dendrites have at least one branch extending perpendicular to the electrode and at least one branch having an aspect ratio of 0.1 or greater.

11. 10. The solid-state electrochemical cell of claim 8, wherein the one or more dendrites of the solid electrolyte are in contact with the electrode, an additional electrode, and / or a current collector coupled to the electrode or the additional electrode.

12. 9. The solid-state electrochemical cell of claim 8, wherein the metal-containing compound contains an alkali or alkaline earth metal.

13. 9. The solid-state electrochemical cell of claim 8, wherein the electrode active material comprises a metal or metalloid.

14. 10. The solid-state electrochemical cell of claim 8, wherein the electrodes comprise an electrically conductive material.

15. 15. The solid-state electrochemical cell of claim 14, wherein the electrically conductive material is doped with one or more heteroatoms selected from boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and bromine.

16. 10. The solid-state electrochemical cell of claim 8, wherein the electrode contains one or more of a polymeric binder, a plasticizer, and a carboxylic acid.

17. 10. The solid-state electrochemical cell of claim 8, wherein the solid electrolyte comprises an electrosprayed film of a polymeric material.

18. 10. The solid-state electrochemical cell of claim 8 further comprising a current collector coupled to the electrode or an additional electrode, the current collector being metallic and containing one or more of molybdenum, titanium, and zirconium.

19. 10. The solid-state electrochemical cell of claim 8 further comprising a reactive gas liquefied in contact with the solid electrolyte or dissolved in the solid electrolyte.

20. 20. The solid-state electrochemical cell of claim 19, wherein the reactive gas comprises oxygen and / or sulfur.

21. The reactive gas is CO ２ , C.O., O ２ , N ２ O, NO ２ , S.O. ２、 S ８ , C.O.S., C.S. ２ , S.F. ６ , H ２ S, SO ２ , C.H. ３ S.H., (C.H. ３ ) ２ S and C ２ H ５ 21. The solid-state electrochemical cell of claim 20 containing one or more of: SH.

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