Solid-state electrolyte and solid-state electrochemical cell having the same

Abstract

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

Description

Technical Field

[0001] The present disclosure relates generally to batteries, and more particularly to solid-state batteries including a solid-state electrolyte, wherein the solid-state electrolyte includes a plurality of dendrite structures. Background Art

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

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

[0004] Another battery technology includes lithium metal batteries. Lithium metal batteries are similar to lithium-ion batteries, but include a negative electrode and an electrode active material of lithium metal. Unfortunately, using lithium metal as the negative electrode can lead to the formation of lithium metal dendrites, which grow as lithium ions are reduced to lithium metal and deposit at the ends of the forming dendrites. The conductive lithium metal dendrites will continue to extend until the ends of the dendrites make an electrical connection with the surface of the positive electrode material, causing the battery to short-circuit.

[0005] What are needed are alternative batteries that offer improved performance as well as enhanced safety. Summary of the Invention

[0006] The solid-state batteries disclosed herein provide low interfacial charge transfer resistance and / or low grain boundary resistance, which is similar to the interfacial charge transfer resistance and / or grain boundary resistance of lithium-ion batteries formed using conventional liquid electrolytes. However, the use of solid electrolytes rather than liquid electrolytes reduces the safety hazards associated with the use or storage of lithium batteries. Compared to other lithium-ion batteries, and particularly compared to other solid-state lithium-ion batteries, the use of the disclosed solid electrolytes can additionally result in the battery exhibiting one or more of higher energy density, higher power density, longer cycle life, reduced cost, and enhanced temperature performance.

[0007] The present disclosure may include a solid-state electrolyte comprising a solid-state electrolyte material having one or more dendrites formed on and / or in the solid-state electrolyte material, wherein the one or more dendrites comprise a metal-containing dendrite material, wherein the metal-containing dendrite material additionally comprises oxygen and / or sulfur.

[0008] The present disclosure may include a solid electrolyte comprising a solid electrolyte material having a -8S / cm / and the ionic conductivity is less than or equal to 10 -3 S / cm; wherein the solid-state electrolyte further includes one or more dendrites formed on the solid-state electrolyte material and / or in the solid electrolyte material; wherein the one or more dendrites include a dendrite material, the dendrite material includes an alkali metal, an alkaline earth metal or an amphoteric metal; and further includes at least one of oxygen and sulfur.

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

[0010] The disclosed features, functions, and advantages of the disclosed devices, systems, and methods can be achieved independently in various embodiments of the present disclosure, or may be combined in other embodiments, further details of which can be seen with reference to the following description and drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The accompanying drawings are not necessarily drawn to scale. The dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure.

[0012] Figure 1 is a semi-schematic diagram of an illustrative solid-state battery including an exemplary electrochemical cell according to the present disclosure.

[0013] Figure 2A-2C Various illustrative dendrite morphologies according to the present disclosure are depicted.

[0014] Figure 3 is a flow chart of an illustrative method of making an electrochemical cell according to the present disclosure.

[0015] Figure 4 is a flow chart of an alternative illustrative method of manufacturing an electrochemical cell according to the present disclosure.

[0016] Figure 5 is a flow chart of an alternative illustrative method of manufacturing an electrochemical cell according to the present disclosure.

[0017] Figure 6 is a flow chart of an alternative illustrative method of manufacturing an electrochemical cell according to the present disclosure.

[0018] Figure 7is a two-dimensional line graph illustrating the stable cycling performance of an exemplary symmetric electrochemical cell including a solid-state electrolyte according to the present disclosure. DETAILED DESCRIPTION

[0019] The solid-state battery of the present disclosure includes one or more electrochemical cells, one or more electrochemical cells include a solid dendrite electrolyte, and compared with lithium-ion batteries, especially compared with other solid-state lithium-ion batteries, the solid-state battery of the present disclosure can exhibit various advantageous properties, such as higher energy density, higher power density, longer cycle life, reduced cost and enhanced temperature performance.

[0020] Unless otherwise indicated, the following definitions apply herein.

[0021] "Electrode active material" refers to the portion or component of an electrode that participates in a reaction by transporting ions through an electrolyte and / or electrons through an external circuit.

[0022] "Current collector" refers to a component adjacent to an electrode that is configured to transfer electrical current from a fixed portion to a moving portion of an electrochemical cell circuit, or vice versa.

[0023] "Electrolyte" refers to the material that provides for ion transport in an electrochemical cell. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes.

[0024] By "full cycle life of an electrochemical cell" is meant the life of the electrochemical cell considered to exceed its normal useful life, where normal useful life is assumed to be the point at which the cell first exhibits 80% of its original capacity.

[0025] "Electrospraying," also known as electrospinning, is a thin film production method that uses electricity to draw and apply charged wires of an organic solution or melt.

[0026] "Substantially" means conforming more or less to the specific size, range, shape, concept, or other aspect to which the term modifies, such that a feature or component need not conform exactly. For example, a "substantially cylindrical" object means that the object resembles a cylinder but may have one or more deviations from a true cylinder.

[0027] "Comprise," "include," and "have" (and their conjugations) are used interchangeably to mean inclusion but not necessarily limitation, and are open-ended terms that are not intended to exclude additional, unrecited elements or method steps.

[0028] Terms such as "first," "second," and "third" may be used to distinguish or identify individual members of a group, etc., and are not intended to imply sequential or numerical limitations.

[0029] Unless they relate to specific examples, all specifications regarding quantities and parts, especially those used to define the present invention, indicate a tolerance of ±10%, for example: 11% means: from 9.9% to 12.1%. For terms such as "a solvent", the word "a" should not be considered a numeral, but rather a general term or pronoun, unless the context indicates otherwise.

[0030] The term "combination" or "combinations" refers to all types of combinations starting from two of the relevant components to multiple or all of the components, unless otherwise specified.

[0031] U.S. application serial number 17 / 175267, filed on February 12, 2021, discloses a high-energy cathode and a method for manufacturing the same; U.S. application serial number 17 / 220823, filed on April 1, 2021, discloses a high-energy cathode and a method for manufacturing the same; and U.S. application serial number 17 / 306457, filed on May 3, 2021, discloses an electrochemical cell including a greenhouse gas; each application is incorporated herein by reference in its entirety for all purposes.

[0032] The present disclosure relates to solid-state batteries. A battery is a power source that includes one or more electrochemical cells in combination with external connections and is used to power electrical devices such as flashlights, cell phones, and electric vehicles. A solid-state battery is a battery that includes at least one solid-state electrochemical cell. A solid-state electrochemical cell is an electrochemical cell that includes a solid-state electrolyte.

[0033] It should be understood that although the description of various embodiments in the present disclosure is written based on describing a single solid-state electrochemical cell, similar principles can be applied to assemblies including more than one solid-state electrochemical cell (e.g., such as electrochemical cell packs, etc.). Such multi-cell assemblies should be understood to fall within the scope of the present disclosure.

[0034] Figure 1 An illustrative solid-state electrochemical cell 10 for a battery 12 is semi-schematically depicted. The electrochemical cell 10 includes an electrode 14, which may be a positive electrode or a negative electrode, preferably a positive electrode, wherein the electrode 14 may further include an electrode active material 16. The electrochemical cell 10 may further include an additional electrode 18 including an additional electrode active material 20.

[0035] If electrode 14 is a negative electrode, additional electrode 18 can be a positive electrode, and vice versa. Either or both of electrode 14 or additional electrode 18 can include a current collector 22 in electrical contact with the electrode. The current collector in contact with the negative electrode is referred to as the negative electrode current collector, while the current collector in contact with the positive electrode is referred to as the positive electrode current collector.

[0036] The electrochemical cell 10 also includes a solid electrolyte 24 comprising a solid electrolyte material 26. The components of the solid-state electrochemical cell 10 are typically held within an enclosure (i.e., battery housing) 28, which surrounds the battery components and can maintain the battery components under a desired gas composition or liquid composition 30. The solid-state battery 12 can have the form of a button cell, a pouch cell, a prismatic cell, a cylindrical cell, a flow cell, an alternating plate, or a jelly roll, among others.

[0037] electrolytes

[0038] An electrolyte is a material that facilitates ion transport within a battery's electrochemical cells. The electrolyte acts as a conduit for ion transport through its interaction with the electrodes. During battery charging, the electrolyte facilitates the movement of ions from the positive electrode to the negative electrode, while during discharge, the electrolyte facilitates the movement of ions from the negative electrode to the positive electrode. In rechargeable batteries, the electrolyte facilitates ion circulation between the negative and positive electrodes.

[0039] The solid electrolyte 24 includes a solid electrolyte material 26, which is a solid material at normal temperature and pressure (NTP). The solid electrolyte material 26 is ionically conductive, which means that the solid electrolyte material 26 has a conductivity greater than or equal to 10 -10 S / cm and the ionic conductivity is less than or equal to 10 -1 Preferably, the solid electrolyte material 26 (and therefore the solid electrolyte 24) has an electronic conductivity greater than or equal to 10 -8 S / cm and the ionic conductivity is less than or equal to 10 -3 In one embodiment, the solid electrolyte 24 has a conductivity greater than or equal to 10 -7 S / cm ionic conductivity.

[0040] The solid electrolyte 24 of the electrochemical cell 10 can have any configuration that allows the solid electrolyte 24 to function as an electrolyte within the cell. For example, the solid electrolyte 24 can have a substantially planar configuration, such as a film, foil, tape, paper, sheet, or layer.

[0041] In one embodiment of the present disclosure, the solid electrolyte 24 comprises an electrosprayed solid electrolyte membrane as described below, which includes the desired solid electrolyte material 26 and a polymer material. Such an electrosprayed solid electrolyte membrane may include greater than 70 weight percent, preferably greater than 80 weight percent, and more preferably greater than 90 weight percent of the solid electrolyte material described herein.

[0042] The solid electrolyte material 26 may include a polymer, glass, phosphate, fluorophosphate, carbonate, amine, borate, fluoroborate, halide, phthalate, oxyhalide, oxide (e.g., SiO2, TiO2, Al2O3, Y2O3, Mg2B2O5, Li2O, LiOH, Li2O2, Li2CO3, P2O5, GeO2, AIPO4, Li2Ti3O7), perovskite, antiperovskite (e.g., Li3OBr, Li3OCl, Li2OHBr, Li2OHCl), LISICON type electrolyte (e.g., Li 1+x Al x Ti 2-x (PO4)3、Li 2+2x Zn 1-x GeO4、Li (3+x) Ge x V (1-x) O4、Li (4-x) Si (1-x) P x O4、Li 1+x+y Al x Ti 2-x Si 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 (Si y PO4)3、Li 14 ZnGe4O 16 、Li 4-x V x Ge x O4), garnet (such as 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 Si1.74 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), sulfide LISICON type electrolyte (e.g., Li (4-x) Ge (1-x) P x S4), one or more of oxynitride, nitride, etc. (LISICON is the abbreviation of lithium superion conductor).

[0043] In one embodiment, the solid electrolyte material 26 includes a -8 S / cm and the ionic conductivity is less than or equal to 10 -3 S / cm. In another embodiment, the solid electrolyte material 26 comprises a metal-containing material having an electrical conductivity greater than or equal to 10 -8 S / cm and the ionic conductivity is less than or equal to 10 -3 S / cm conductivity of lithium-containing materials.

[0044] The solid electrolyte 24 is typically modified to include one or more, or a plurality of, dendrites 32, wherein a dendrite is a branched, tree-like structure that grows on and / or in the solid electrolyte 24. The branched structure of the dendrite 32 is typically formed by crystallization of a metal compound or metal complex on or in the solid electrolyte 24. The structure of the dendrite 32 may include a plurality of individual crystalline domains, which may include the same or different metals, metal compounds, or metal complexes. Preferably, the growth of the dendrite 32 produces a branched, tree-like structure that includes at least one branch having an aspect ratio (length divided by diameter / thickness) greater than or equal to 0.1, preferably greater than or equal to 1, and more preferably greater than or equal to 10.

[0045] The solid electrolyte 24 may include a plurality of dendrites 32, wherein the dendrites may have any suitable dendrite morphology or structure. A single dendrite 32 may exhibit a variety of dendrite structures while still generally remaining branched and dendritic. For example, Figure 2A-2C Each of these provides a semi-schematic illustration of the growth stages of different dendrite morphologies extending from a surface 34, which may be, for example, the surface of the electrolyte 24. Figure 2AAs shown, dendrites 32 may exhibit a "cactus-type" dendrite structure having a large central protrusion or trunk from which several much smaller, possibly needle-like, branches extend. Figure 2B As shown, dendrites 32 may exhibit a "moss-type" dendrite structure having a more organic form and including more rounded branches without such a well-defined central trunk. Figure 2C As shown, dendrites 32 may exhibit a "branched" dendritic structure that includes the organic, monolithic form of "moss-type" dendrites, but with branches that are more defined, extend further, and may be relatively more pointed (needle-like) than moss-type dendrites.

[0046] exist Figure 2A-2C In each of the figures, a dendrite 32 is shown at different stages of growth, from the formation of an initial dendrite structure (on the far left) to a mature dendrite structure (on the far right) that extends outward from surface 34 far enough to form a bridge between surface 34 and a second surface 36, which can be the surface of an electrode, current collector, or other electrochemical cell component. In the case of a typical lithium-based battery, once a metal dendrite extends across such a gap, the dendrite forms an electrical connection (or short circuit) between the two surfaces. In the case of the solid-state electrolyte of the present disclosure, even if a dendrite 32 extends across such a gap and forms a bridge between the two surfaces, no electrical connection is formed.

[0047] The plurality of dendrites 32 on and / or in the solid electrolyte 24 may include any of the dendrite structures shown, or combinations or mixtures thereof. The specific structure of the dendrites 32 present on / in the solid electrolyte of the present disclosure generally depends on the material used to form the dendrites, the composition of the gas or liquid surrounding the electrolyte material during dendrite formation, and the conditions (temperature, pressure, etc.) within the electrochemical cell during dendrite formation.

[0048] While dendrites have been observed to form in conventional lithium-ion or lithium metal batteries, in these cases, the dendrites consist of pristine metal, and their presence can be detrimental to various aspects of battery performance. In contrast, the dendrites of the present disclosure can include metal compounds and metal complexes (e.g., metal oxides, metal sulfides, etc.), such that when present on / in the solid-state electrolyte 24, the dendrites can impart beneficial effects on various aspects of battery performance.

[0049] The dendrites of the solid electrolyte 24 may include metal-containing compounds (e.g., metal complexes), wherein the metal may include an alkali metal (e.g., lithium, sodium, potassium), an alkaline earth metal (e.g., magnesium, calcium), or an amphoteric metal (e.g., beryllium, aluminum, zinc, tin, lead). The metal compound may also include one or both of oxygen or sulfur. In the case where the metal compound includes oxygen, the reactivity of the resulting material with the environment may be lower than that of similar sulfur compounds. The dendrites of the present disclosure are generally ionically conductive and electrically insulating. Typically, the dendrites have a relative humidity greater than or equal to 10 -10 S / cm and the ionic conductivity is less than or equal to 10 -1 S / cm. Preferably, the dendrite has an electronic conductivity greater than or equal to 10 -8 S / cm and the ionic conductivity is less than or equal to 10 -3 More preferably, the dendrite has an electronic conductivity greater than or equal to 10 -7 S / cm ionic conductivity and less than or equal to 10 -4 The electronic conductivity is S / cm.

[0050] The dendrites of the present disclosure can be electrochemically and / or chemically formed on and / or in the solid electrolyte 24 using a suitable reactive gas. Without wishing to be bound by theory, it is believed that dendrites tend to form and grow where there are physically weaker points in the solid electrolyte and / or where there are physically vacant sites on the electrolyte. Each dendrite 32 can originate from the electrode active material 16 or 20 and can have at least one branch extending in a direction substantially perpendicular to one or both of the negative electrode current collector and the positive electrode current collector. Each dendrite 32 can be in contact with the electrode 14, the additional electrode 18 and / or the current collector 22.

[0051] 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 the electrochemical cell including the electrolyte. Alternatively or additionally, 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 help enable the resulting electrochemical cell to store more energy per unit mass or per electrode area.

[0052] The solid electrolyte 24 may include a polymer material, wherein the polymer material may be electrically insulating and / or ionically insulating. The polymer material may have a strength less than or equal to 10 -7S / cm ionic conductivity, and can form part of the electrolyte and / or one or both electrodes. The polymer material can include, for example, one or more of polyethylene oxide, polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, and poly(4-vinyl pyridine) in any combination. The solid electrolyte 24 can have a polymer material content in the range of about 0.01 weight percent and about 30 weight percent, preferably in the range of about 0.1 weight percent and about 20 weight percent, and more preferably in the range of about 1 weight percent and about 10 weight percent.

[0053] The solid electrolyte material 26 may include a solid particle component. When present, the average particle size of such a component may vary in the range of 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. In the case where the solid electrolyte material 20 includes a solid particle component, 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.

[0054] In some embodiments, in addition to the solid electrolyte material 26 , the electrochemical cell 10 may also include a non-solid electrolyte that is a liquid, gel, or liquefied gas.

[0055] electrode

[0056] The positive electrode is the electrode of the battery cell that receives electrons from the external circuit and is reduced during discharge, and transfers electrons to the external circuit through oxidation during charge. The positive electrode can be called the cathode. The negative electrode is the electrode of the battery cell that transfers electrons to the external circuit through oxidation during discharge, and receives electrons from the external circuit and is reduced during charge. The negative electrode can be called the anode.

[0057] If electrode 14 is a negative electrode, additional electrode 18 is a positive electrode, and vice versa. Either or both of electrode 14 or additional electrode 18 may include a current collector 22 in electrical contact with the electrode. The current collector in contact with the negative electrode is referred to as the negative electrode current collector, while the current collector in contact with the positive electrode is referred to as the positive electrode current collector.

[0058] The electrode 14 and the additional electrode 18 (when present) typically include one or more electrode active materials 16, 20, which can be the same or different. The electrode active materials 16, 20 comprise portions or components of the electrodes that participate in electrochemical reactions by transporting ions through an electrolyte and / or electrons through an external circuit, thereby gaining or losing electrons during the electrochemical reaction. The electrode active materials 16, 20 can constitute the entirety of the associated electrode, but are typically components of the electrodes or coatings on the electrodes.

[0059] Electrode active materials 16, 20 can be starting materials, discharge products, or charge products. For example, in an electrochemical cell using graphite as the negative electrode active material, graphite (C6) is lithiated during charging and becomes LiC6. Then, during discharge, LiC6 is delithiated and returns to C6. Both C6 and LiC6 are considered electrode active materials. The starting materials, discharge products, and charge products can all be different.

[0060] The electrode active materials 16, 20 may be generated in situ by selecting appropriate components of the electrochemical cell 10, such as by selecting the composition of the solid-state electrolyte 24 and its additional components, optionally followed by application of a current collector to the electrochemical cell 10. The specific composition of the electrode active materials 16, 20 is not particularly critical, and any electrode active material capable of storing and releasing ions may be a suitable electrode active material for the purposes of the present disclosure.

[0061] For example, the electrode active materials 16, 20 may be 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, silicon compounds, arsenic, antimony, tin), inorganic carbon (e.g., graphite, graphene, graphene oxide, activated carbon, carbon nanotubes, carbon dots), sulfur, sulfur compounds (e.g., sulfides such as lithium titanium disulfide (LTS), MV 0.5 Ti 0.5 S2 (wherein M is a metal), oxides (e.g., in the form of M x Ti5O 12 、TiO2、TiNb2O7、Nb2O5、M x VO4, H2Ti6O 13 、M x MnBO3, M x V2O5、M x MoO4、M x W2O7、M′ 1-x M″O2、M′ 1-w (M″ x M″′ y )O2、M 1-w (Mn xNi y Co z )O2、M 1-w (Mn x Ni y Co z Al w )O2、M 1-w (Ni z 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 PO4 (wherein M′, M″ and M″′ are different metals), lithium titanate (LTO), lithium iron phosphate (LFP), nickel manganese cobalt lithium oxide (NMC), nickel cobalt aluminum lithium oxide (NCA), cobalt lithium oxide, nickel lithium oxide (LNO) and manganese lithium oxide (LMO)), etc.

[0062] Alternatively or additionally, the electrode active materials 16, 20 may include an organic material (e.g., indanone, an indanone derivative, phenoxazine, a phenoxazine derivative, phenothiazine, a phenothiazine derivative, quinone, a quinone derivative, a diamine derivative, phenazine, a phenazine derivative, quinoxaline, a quinoxaline derivative, pyrazine, a pyrazine derivative, cyclohexane, a cyclohexane derivative, triazine, a triazine derivative, melamine, a melamine derivative, dimethoxybenzene, a dimethoxybenzene derivative, a cyclopropene derivative, an amide derivative, an amino acid, an amino acid derivative, viologen, a viologen derivative, a nitrogen oxide derivative), a halogen, a halogen compound (e.g., a halide), or any combination thereof.

[0063] In some embodiments, the electrode active materials 16, 20 may include one or more organic moieties, wherein the organic moiety is a fragment or replacement portion of a larger compound. Where the electrode active materials 16, 20 include an organic moiety, it may be derived from an organic compound as described above. Examples of organic moieties include alkyl, alkenyl, alkynyl, acyl, alkylamino, and aryl groups, etc. In one aspect, the electrode active material includes an organic compound that includes heteroatoms such as boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and / or bromine, etc. Alternatively or additionally, the electrode active material includes an organic compound having one or more aromatic groups. When the electrode active material includes a metal or a metal compound or a metal complex, the metal is preferably an alkali metal or an alkaline earth metal. More preferably, the metal is an alkali metal because such a material can impart the resulting electrochemical cell with the ability to provide a high energy density.

[0064] In some cases, the electrochemical cell 10 may include an electrode or additional electrode formed by applying an electrode active material to a substrate (e.g., a current collector 22) that does not itself include an electrode active material. The electrode active material may be applied to the substrate by deposition or by forming an interlayer with the substrate during the initial charge or discharge of the electrochemical cell. The electrode may additionally include an electrolyte material. The electrode active material may be mixed with the electrolyte material. In these embodiments, a solid electrolyte 24 may be provided with the electrode 14 or 18 and arranged 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.

[0065] The electrode active materials 16, 20 may be present in the form of solid particle components. Suitable electrode active materials may have an average particle size ranging from about 5 nm to about 50 μm and may exhibit an average pore size ranging 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. In the case where the electrode active materials 16, 20 are present in the form of solid particle components, the average pore size of the electrode active material may 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.

[0066] The electrode 14 and the additional electrode 18 (when present) may include a conductive material. The conductive material may include a porous carbon material including one or more of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, graphite, graphene, graphene oxide, and graphene nanoribbons. Most importantly, carbon nanotubes are preferred due to their high aspect ratio and durability. The porous carbon material may be doped with one or more heteroatoms selected from boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and bromine. Most importantly, nitrogen or fluorine are preferred to allow for lower charge transfer resistance. Conductive materials may also be used as electrode active materials 16, 20, as long as the conductive material can store and release ions during operation of the electrochemical cell 10. In further aspects and embodiments, the porous carbon material may be in the form of particles, powder, paper, foam, fiber, sheet, disc, rod, and / or foil.

[0067] The conductive material that can be used for electrodes 14, 18 can have an average particle size or diameter in the range of about 5 nm to about 50 μm. Typically, the average particle size or diameter of the conductive material is less than about 50 μm. Preferably, the average particle size of the conductive material is greater than about 50 nm and less than about 40 μm. More preferably, the average particle size of the conductive material is greater than about 500 nm and less than about 30 μm. The average pore size of the conductive material can be less than about 1 μm. For example, the conductive material can have an average pore size in the range of about 0.1 nm to about 1 μm. Preferably, the average pore size of the conductive material is greater than about 1 nm and less than about 500 nm. More preferably, the average pore size of the conductive material is greater than about 5 nm and less than about 200 nm.

[0068] The average particle size or diameter of the particles comprising the electrode active material 16, 20 may be inversely related to the particles of the conductive material of the electrodes 14, 18. For example, where 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 conductive material may be in the range of about 10 nm to about 500 nm, and vice versa. Typically, one or more of the electrode active material and the conductive material comprises 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.

[0069] The electrodes 14, 18 of the electrochemical cell 10 typically include a conductive material as a substrate, or as an electrode body, on which or in which an electrode active material and / or a solid electrolyte is deposited or formed. Any suitable conductive material can be used for the disclosed electrodes, which can have the same or different formulations. The electrode active materials 16, 20 and / or the conductive material can be formed into a flat plane and / or a granular solid. In the case where the electrode active material, the conductive material and / or the solid electrolyte are particles, the individual particles can have any suitable shape, including a sphere, a cube, a cuboid, a cone, a pyramid, a cylinder, a quadrangular prism, a hexagonal prism, a hemisphere, a triangular prism, a pentagonal prism, an octagonal prism, a torus, an octahedron and a dodecahedron or any combination thereof.

[0070] Electrode 14,18 and / or solid electrolyte 24 can further include one or more of a polymer binder, a plasticizer and a carboxylic acid. In the case where electrode 14,18 includes a polymer binder, the polymer binder may be present to help form a solid electrode by an electrode active material. Suitable polymer binders for the purposes of this disclosure may include polycaprolactone, poly(acrylic acid), poly(methyl methacrylate), polytetrafluoroethylene, poly(vinylidene fluoride), polyacrylonitrile, poly(ethylene terephthalate), polyvinyl pyrrolidone, poly(4-vinyl pyridine), polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyethylene, polypropylene, polylactic acid, polyvinyl butyral, polystyrene, polyurethane, polycarbonate, styrene-butadiene-rubber, sodium carboxymethyl cellulose, etc. In a particular embodiment, the polymer binder includes one of poly(ethylene oxide) (PEO) or poly(vinylidene fluoride).

[0071] In the case where the electrodes 14, 18 include carboxylic acids, the carboxylic acid may be present to facilitate ion transport into and out of the electrode active material of the electrode. When present, the carboxylic acid may be a monocarboxylic acid or a polycarboxylic acid. When the carboxylic acid is a polycarboxylic acid, it may be oxalic acid.

[0072] In the case where electrode 14,18 comprises a plasticizer, the plasticizer comprises adding to an organic or polymeric material to make it softer, more flexible and / or increase its plastic material.Exemplary plasticizers include, as non-limiting examples, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethyl formamide, dimethyl sulfoxide, gamma-butyrolactone, cyclopentane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalate derivatives, trimellitic acid ester, adipic acid ester, sebacate, maleate or its any combination.In one embodiment, suitable plasticizer can comprise succinonitrile.

[0073] The conductive material of the electrode, as well as additional conductive material, polymer binder, and plasticizer (if present), can be applied to the current collector using any suitable application technique. For example, the conductive material can be cast as a film and then deposited on the desired current collector.

[0074] Current Collector

[0075] Each current collector 22 acts as a bridging member that collects the current generated at the electrodes 14, 18 and connects to an external circuit. Each current collector 22 is typically adjacent to its associated electrode. Typically, each current collector is or includes a conductive material.

[0076] Each current collector 22 may be the same or different and may include any suitable and compatible conductive material. The current collector 22 may include 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 include at least one of aluminum, aluminum alloys, copper, copper alloys, silver, silver alloys, nickel, nickel alloys, duplex steel, stainless steel, or any combination thereof. Alternatively or additionally, the current collector 22 may include a metal current collector comprising one or more of molybdenum, titanium, and zirconium metals or metal alloys. The current collector 22 may be in contact with a conductive material, for example by coating the conductive material. In this embodiment, the conductive material may be a porous inorganic carbon material, which 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 may be in the form of particles, powder, rods, or any combination thereof. In particular, the current collector may include a freestanding carbon material in the form of paper, foam, felt, fiber, film, sheet, tape, cloth, disc, wire, foil, or any combination thereof.

[0077] The current collector 22 can be perforated, wherein the pore size can be about 500 nm or more (e.g., about 500 nm to about 5 mm, preferably about 500 nm to about 1 mm, 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, more preferably about 200 μm to about 10 mm).

[0078] partition

[0079] In some embodiments, the solid-state electrolyte 24 can perform the function of the separator 38 by separating the electrode 14 from the additional electrode 18 or from the 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-state electrolyte 24. The solid-state electrolyte 24 and / or separator 38 (when present) can be greater in width and length than one or more current collectors 22 to avoid contact between the negative electrode and the positive electrode.

[0080] When separator 38 is present, separator 38 may be in contact with electrode 14, or separator 38 may be in contact with solid electrolyte 24. In the case where electrochemical cell 10 includes additional electrode 18, separator 38 may be disposed between electrode 14 and additional electrode 18. One or both of the width and length of separator 38 may be greater than current collector 22 to prevent contact between electrode 14 and additional electrode 18, contact between individual current collectors 22, contact between positive and negative current collectors, or contact between negative and positive current collectors. Separator 38 may include an electrolyte to provide ion transport within electrochemical cell 10 and act as a conduit for ion transport through its interaction with electrode 14 and additional electrode 18.

[0081] Separator 38 can be in contact with solid electrolyte 24 and can comprise polymer material, such as polymer film. When present, polymer material can be polyethylene, polypropylene, polytetrafluoroethylene or polyvinyl chloride etc. Typically, polymer film (when present) comprises polypropylene and / or polyethylene. Alternatively or additionally, separator 38 can comprise non-woven fibers (such as nylon, polyester and glass etc.), glass, ceramic or any combination thereof. In some embodiments, separator 38 comprises glass fiber. In some embodiments, separator 38 can comprise a surface coating or treatment layer to enhance the wettability of liquid-based electrolyte.

[0082] Reactive gas

[0083] The electrochemical cell 10 may further include a reactive gas, which refers to a compound that is a gas at any given temperature or pressure and will chemically or electrochemically react with the solid electrolyte material 26 or the electrode active materials 16, 20 of the solid electrolyte 24 to form dendrites 32 on and / or in the solid electrolyte 24. In one embodiment of the present disclosure, the reactive gas may include a compound having at least one oxygen atom (e.g., CO2, CO, O2, N2O, NO2, and SO2) and / or at least one sulfur atom (e.g., S8, COS, CS2, SF6, H2S, SO2, CH3Sh, (CH3)2S, and CH3CH2SH).

[0084] The solid electrolyte material 26 or dendrites 32 of the present disclosure can be formed or modified by the reactive gas even when the reactive gas is not in the gas phase. The reactive gas can optionally be liquefied under pressure and contained within the housing 28 of the electrochemical cell 10. The liquefied gas can be in contact with and / or dissolved in the solid electrolyte 24. Although the reactive gas can remain in contact with one or both of the electrodes 14, 18, the reactive gas is not intended to serve as an electrode active material.

[0085] Preparation of solid-state electrochemical battery cells

[0086] The preparation of the solid-state electrochemical cell 10 necessarily includes the preparation of the solid-state electrolyte 24, and more specifically, the formation of dendrites 32 on the solid-state electrolyte 24. Although any method of combining the solid-state electrolyte material 26 with a reactive gas that causes the formation of dendrites on the solid-state electrolyte 24 is a suitable method for preparing the solid-state electrolyte of the present disclosure, it may be particularly convenient to form a modified solid-state electrolyte by applying a voltage or current in the presence of a reactive gas to an electrochemical cell including the solid-state electrolyte 24. That is, the electrochemical cell 10 can be assembled, and then the reactive gas can be added to the electrochemical cell 10 such that the subsequent application of a voltage or current causes the formation of dendrites on the solid-state electrolyte.

[0087] By including a reactive gas-rich atmosphere within the battery housing 28, unconventional dendrites 32 may be formed on the surface of the electrode 14 and / or electrode 18 and / or on the surface of the solid electrolyte material 26 due to chemical and / or electrochemical reactions. The gases formed during the formation of the dendrites 32 may 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 may be reduced by applying a vacuum to the electrochemical cell 10, or the reactive gas may be removed. It should be understood that any of the following methods may optionally further include one or more additional steps of applying a voltage or current to the electrochemical cell 10, performed after the purging step.

[0088] The solid-state electrochemical cell of the present disclosure can be prepared by providing an electrochemical cell housing, inserting desired electrochemical cell components (e.g., desired electrodes, desired solid electrolyte) into 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 displace all or part 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.

[0089] In one embodiment, inserting the electrochemical cell components into the electrochemical cell housing may include inserting the electrochemical cell components in the following order: i) negative electrode current collector, ii) negative electrode, iii) solid electrolyte (separator), iv) positive electrode, and v) positive electrode current collector. Alternatively, the order of the electrochemical cell components may 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 electrode remain clearly separated. The electrochemical cell components can be compressed using, for example, a press, using a stacking pressure of 100 MPa or less (e.g., from about 0.1 MPa to about 100 MPa, preferably from about 0.5 MPa to about 70 MPa, and more preferably from 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 the manufacture of the electrochemical cell, which may be greater than 500 MPa.

[0090] As described above, the solid-state electrochemical cell 10 of the present disclosure optionally includes an electrosprayed solid electrolyte membrane comprising a solid electrolyte material 26 and / or a polymer material. One or both electrodes 14, 18 may also optionally include such an electrosprayed material. One or more electrospraying parameters, such as flow rate, applied voltage, applied current, nozzle size, nozzle type, and the distance between the nozzle tip and the collector, may be adjusted to optimize the electrospraying process. Compared to conventional application techniques, electrospraying can advantageously allow elongation and thinning of the polymer material, which not only allows the electrolyte material to be firmly bonded to produce a micron-thick independent film (e.g., >5 μm) without breaking, but also allows the surface of the solid electrolyte material 26 to be covered with a relatively small amount of polymer material.

[0091] Exemplary and illustrative methods of manufacturing electrochemical cells according to the present disclosure are as follows Figure 3 The method of flowchart 40 includes: inserting desired electrochemical cell components into an electrochemical cell housing in a desired order at step 42; compressing the electrochemical cell components so that the solid electrolyte is in uniform contact with the electrode material 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 at step 48 to form a desired dendrite structure; and purging the electrochemical cell housing with a reactive gas to remove formed gases generated during the application of the voltage or current at step 50.

[0092] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is as follows Figure 4 As shown in the flow chart 52. Figure 4 is a flow chart of an alternative exemplary method for manufacturing an electrochemical cell according to the present disclosure. The method of flow chart 52 includes: at step 54, inserting the desired electrochemical cell components into an electrochemical cell housing in a desired order; at step 56, compressing the electrochemical cell components so that the solid electrolyte is in uniform contact with the electrode material; at step 58, sealing the electrochemical cell housing; at step 60, introducing a reactive gas into the electrochemical cell housing to displace ambient gas from the electrochemical cell housing; at step 62, applying a voltage or current to the electrochemical cell under the reactive gas atmosphere; and at step 64, purging the electrochemical cell housing to remove any formed gases generated during the application of the voltage or current.

[0093] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is as follows Figure 5 66. The method of flowchart 66 includes: inserting the desired electrochemical cell components into an electrochemical cell housing in a desired order at step 68; compressing the electrochemical cell components so that the solid electrolyte is in uniform contact with the electrode material 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 within the stack of electrochemical cell components or removing the reactive gas by applying a vacuum or by purging the electrochemical cell housing with an inert gas at step 76. In the context of the method of flowchart 66, the partial pressure of the reactive gas within the stack of electrochemical cell components can be reduced to less than or equal to 0.9 atm, preferably to less than or equal to 0.5 atm, and more preferably to less than or equal to 0.1 atm.

[0094] An alternative exemplary method of manufacturing an electrochemical cell according to the present disclosure is as follows Figure 678. The method of flowchart 78 includes: at step 80, inserting the desired electrochemical cell components into an electrochemical cell housing in a desired order; at step 82, compressing the electrochemical cell components so that the solid electrolyte is in uniform contact with the electrode material; at step 84, sealing the electrochemical cell housing; at step 86, introducing a reactive gas into the electrochemical cell housing to displace ambient gas from the electrochemical cell housing; at step 88, applying a voltage or current to the outer electrochemical cell housing under an atmosphere of the reactive gas; and at step 90, reducing the partial pressure of the reactive gas within the stack of electrochemical cell components or removing the reactive gas by applying a vacuum or by purging the electrochemical cell housing with an inert gas. In the context of the method of flowchart 78, the partial pressure of the reactive gas within the stack of electrochemical cell components can be reduced to less than or equal to 0.9 atm, preferably to less than or equal to 0.5 atm, and more preferably to less than or equal to 0.1 atm.

[0095] Figure 7 is a graph illustrating advantageous stable cycling performance of an exemplary symmetrical electrochemical cell including a solid electrolyte according to the present disclosure. The solid electrochemical cell includes a lithium metal foil and a solid electrolyte formed according to the present disclosure at room temperature and at 5 mA / cm 2 The solid electrolyte shows excellent cycling performance at a current density of 3500 cycles and 900 hours. The solid electrolyte membrane is positioned between two lithium metal foils. 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP) is used as the solid electrolyte material. The solid electrolyte membrane is independent and prepared by electrospraying technology. The weight ratio of the electrolyte membrane including LATP, polycaprolactone and poly(ethylene oxide) is 95:1:4. The thickness of the electrolyte membrane is about 30 μm. The electrochemical cell stacking pressure is measured to be about 8 MPa. Polycaprolactone is electrosprayed in the outer area of ​​the coaxial nozzle, wherein LATP and poly(ethylene oxide) blend are electrosprayed in the core area in order to coat the solid electrolyte and poly(ethylene oxide) blend with an ultrathin nanofilm including polycaprolactone. The solid-state electrochemical cell is charged under an atmosphere of a reactive gas (e.g., carbon dioxide) to form dendrites in and on the electrolyte material, and then purged with an inert gas (e.g., argon) to displace the reactive gas.

[0096] With respect to the methods of the present disclosure, it should be understood that although the drawings and description may show a particular order of method steps, the order of these steps may differ from that depicted and described, unless otherwise stated above. In addition, two or more steps may be performed simultaneously or partially simultaneously, unless otherwise stated above. In addition, one or more steps may be repeated before the next step.

[0097] Example

[0098] This section describes additional aspects and features of the disclosed electrolytes, electrochemical cells, and methods, which are presented in the form of a series of paragraphs, some or all of which may be alphanumeric for clarity and efficiency. Each of these paragraphs can be combined with one or more other paragraphs in any suitable manner and / or with the disclosure elsewhere in this application. Some of the following paragraphs explicitly refer to and further qualify other paragraphs to provide examples of suitable combinations, but are not limited thereto.

[0099] A1. A solid electrolyte comprising a solid electrolyte material, the solid electrolyte material comprising one or more dendrites formed on and / or in the solid electrolyte material; wherein the one or more dendrites comprise a metal-containing dendrite material, wherein the metal-containing dendrite material further comprises oxygen and / or sulfur.

[0100] A2. A solid electrolyte according to paragraph A1, wherein the one or more dendrites are formed electrochemically and / or chemically on and / or in the solid electrolyte material under a reactive gas.

[0101] A3. A solid electrolyte according to paragraph A1, wherein the metal-containing dendrite material comprises an alkali metal or an alkaline earth metal.

[0102] A4. The solid electrolyte of any of paragraphs A1-A3, wherein the solid electrolyte material comprises a polymer material at a concentration of less than about 30 weight percent.

[0103] A5. A solid electrolyte according to any of paragraphs A1-A3, wherein the one or more dendrites exhibit a density greater than or equal to 10 -10 S / cm and the ionic conductivity is less than or equal to 10 -1 The electronic conductivity is S / cm.

[0104] A6. The solid-state electrolyte of any of paragraphs A1-A3, wherein the one or more dendrites have at least one branch exhibiting an aspect ratio greater than or equal to 0.1.

[0105] A7. A solid-state electrochemical cell comprising the solid-state electrolyte of any of paragraphs A1-A3.

[0106] B1. A solid electrolyte comprising a solid electrolyte material having a -8 S / cm and an ionic conductivity less than or equal to 10 -3 S / cm; wherein the solid-state electrolyte further comprises one or more dendrites formed on and / or in the solid-state electrolyte material; wherein the one or more dendrites comprise a dendrite material comprising an alkali metal, an alkaline earth metal, or an amphoteric metal; and further comprising at least one of oxygen and sulfur.

[0107] B2.A7. A solid-state electrochemical cell comprising a solid-state electrolyte according to paragraph B1.

[0108] C1. A solid-state electrochemical cell comprising: an electrode, the electrode comprising an electrode active material; and a solid dendrite electrolyte, the solid dendrite electrolyte comprising a solid electrolyte material and including one or more dendrites formed on and / or in the solid electrolyte material; wherein the one or more dendrites comprise a metal-containing compound, the metal-containing compound further comprising at least one of oxygen and sulfur; and the solid dendrite electrolyte is in contact with the electrode.

[0109] C2. The solid-state electrochemical cell of paragraph C1, wherein the one or more dendrites are formed from electrode active material.

[0110] C3. A solid-state electrochemical cell according to any of paragraphs C1 and C2, 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 greater than or equal to 0.1.

[0111] C4. The solid-state electrochemical cell of paragraph C1, wherein one or more dendrites of the solid-state electrolyte are in contact with an electrode, an additional electrode, and / or a current collector connected to an electrode or an additional electrode.

[0112] C5. The solid-state electrochemical cell of one of paragraphs C1, C2, and C4, wherein the metal-containing compound comprises an alkali metal or an alkaline earth metal.

[0113] C6. The solid-state electrochemical cell of paragraph C1, wherein the electrode active material comprises a metal or metalloid.

[0114] C7. The solid-state electrochemical cell of paragraph C1, wherein the electrode comprises a conductive material.

[0115] C8. The solid-state electrochemical cell of paragraph C7, wherein the conductive material is doped with one or more heteroatoms selected from boron, nitrogen, oxygen, sulfur, phosphorus, fluorine, chlorine, and bromine.

[0116] C9. The solid-state electrochemical cell of any of paragraphs C1, C2, C4, and C6-C8, wherein the electrode comprises one or more of a polymer binder, a plasticizer, and a carboxylic acid.

[0117] C10. The solid-state electrochemical cell of any of paragraphs C1, C2, C4, and C6-C8, wherein the solid-state electrolyte comprises an electrosprayed film of a polymer material.

[0118] C11. The solid-state electrochemical cell of any of paragraphs C1, C2, C4, C6-C8, and C10, further comprising a current collector associated with the electrode or the additional electrode, wherein the current collector is metallic and comprises one or more of molybdenum, titanium, and zirconium.

[0119] C12. The solid-state electrochemical cell of any of paragraphs C1, C2, C4, C6-C8, and C10, further comprising a reactive gas that is liquefied, in contact with, or dissolved in the solid-state electrolyte.

[0120] C13. The solid-state electrochemical cell of paragraph C12, wherein the reactive gas comprises oxygen and / or sulfur.

[0121] C14. A solid-state electrochemical cell according to paragraph C12, wherein the reactive gas comprises one or more of CO2, CO, O2, N2O, NO2, SO2, S8, CoS, CS2, SF6, H2S, SO2, CH3SH, (CH3)2S and C2H5SH.

[0122] in conclusion

[0123] The above disclosure may include multiple different examples with independent utility. Although each of these examples has been disclosed in one or more illustrative forms, the specific embodiments thereof disclosed and described herein should not be considered restrictive, as many variations are possible. To the extent that section headings are used in this disclosure, such headings are used for organizational purposes only. The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of the various elements, features, functions and / or properties disclosed herein. The following claims specifically point out some combinations and sub-combinations that are considered novel and non-obvious. Other combinations and sub-combinations of features, functions, elements and / or properties may be claimed in applications claiming priority to this application or a related application. Such claims, whether broader, narrower, the same or different in scope than the original claims, are also deemed to be included in the subject matter of the present disclosure.

Claims

1. A solid electrolyte comprising a solid electrolyte material, the solid electrolyte material comprising one or more dendrites formed on and / or in the solid electrolyte material; wherein the one or more dendrites comprise a metal-containing dendrite material, wherein the metal-containing dendrite material further comprises oxygen and / or sulfur; the one or more dendrites are ionically conductive and electrically insulating.

2. A solid-state electrolyte according to claim 1, wherein the one or more dendrites are formed electrochemically and / or chemically on and / or in the solid-state electrolyte material under a reactive gas.

3. The solid-state electrolyte of claim 1, wherein the metal-containing dendrite material comprises an alkali metal or an alkaline earth metal.

4. The solid electrolyte according to claim 1, wherein the solid electrolyte material comprises a polymer material at a concentration of less than 30 weight percent.

5. The solid electrolyte of claim 1 , wherein the one or more dendrites exhibit a relative humidity greater than or equal to 10 -10 S / cm and the ionic conductivity is less than or equal to 10 -1 The electronic conductivity is S / cm.

6. The solid-state electrolyte of claim 1, wherein the one or more dendrites have at least one branch exhibiting an aspect ratio greater than or equal to 0.

1.

7. A solid electrolyte comprising a solid electrolyte material having a -8 S / cm and an ionic conductivity less than or equal to 10 -3 S / cm electronic conductivity of the metal-containing material; wherein the solid electrolyte further comprises one or more dendrites formed on and / or in the solid electrolyte material; Wherein the one or more dendrites comprise a dendrite material comprising an alkali metal, an alkaline earth metal, or an amphoteric metal; and further comprising at least one of oxygen and sulfur; the one or more dendrites are ionically conductive and electrically insulating.

8. A solid-state electrochemical cell comprising: an electrode, the electrode comprising an electrode active material; as well as a solid dendrite electrolyte comprising a solid electrolyte material and including one or more dendrites formed on and / or in the solid electrolyte material; wherein the one or more dendrites comprise a metal-containing compound further comprising at least one of oxygen and sulfur; the one or more dendrites are ionically conductive and electrically insulating; and A solid dendrite electrolyte is in contact with the electrodes.

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

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 greater than or equal to 0.

1.

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

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

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

14. The solid-state electrochemical cell of claim 8, wherein the electrode comprises a conductive material.

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

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

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

18. The solid-state electrochemical cell of claim 8, further comprising a current collector associated with the electrode or the additional electrode, wherein the current collector is metallic and comprises one or more of molybdenum, titanium, and zirconium.

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

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

21. The solid-state electrochemical cell of claim 20, wherein the reactive gas comprises one or more of CO2, CO, O2, N2O, SO2, COS, CS2, SF6, H2S, CH3SH, (CH3)2S, and C2H5SH.

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