Solid electrolyte and manufacturing method

Abstract

A process for preparing a solid electrolyte, comprising: mixing a lithium source with a sulfur source and a compound containing phosphorus and sulfur to form a complex; and then heating the complex to the melting point of the compound containing phosphorus and sulfur to form a solid electrolyte material. The solid electrolyte material prepared by the process, wherein formula I:Li (7-y-z) PS (6-y-z) X (y) W (z) A solid electrolyte material (wherein X and W are individually selected from F, Cl, Br, and I, y and z are individually in the range of 0 to 2, and y + z is in the range of 0 to 2).

Description

[Technical Field]

[0001] Cross-reference of related applications This application has priority under 35 U.S.C. 119(e) (35 U.S.C. 119(e)) of U.S. Patent Application No. 63 / 457,087, filed on April 4, 2023, with the entirety of which is incorporated herein by reference for all purposes.

[0002] This disclosure relates to a method for producing electrolyte materials and therefore encompasses the fields of chemistry, chemical engineering, and electrical engineering. [Background technology]

[0003] Background and Introduction Advancing battery technology is crucial to addressing the increasing adoption of mobile devices and electric vehicles, as well as the development of IoT (Internet of Things) devices; therefore, the need for battery technology with improved reliability, capacity (Ah), thermal properties, lifespan, and recharge performance is greater than ever. Solid-state battery cells utilize non-flammable solid electrolytes, in contrast to the flammable liquid electrolytes used in conventional batteries. As a result, solid-state battery cells are safer to use compared to conventional batteries. However, currently available solid-state battery cells have challenges such as cell short circuits, increased cell resistance, and low specific cell capacity. In addition, solid-state battery cells can be costly to manufacture due to the high cost of raw materials, and the manufacturing process is time-consuming and requires a considerable amount of energy to complete. To overcome these problems, a novel method for synthesizing solid electrolytes used in solid-state battery cells has been developed, which is described herein. [Overview of the Initiative]

[0004] Equation (I): Li (7-z-w) A β PS (6-z-w)X z+β Y w (I) (where X and Y are independently selected from the group consisting of F, Cl, Br, and I, A is selected from the group consisting of Na, K, Cs, Fr, and combinations thereof, 0 ≦ z ≦ 2 and 0 ≦ w ≦ 2, provided that z + w ≦ 2, and 0 < β ≦ 0.100.) A solid composition is provided herein. In some embodiments, the composition comprises a thiargyrite crystal structure.

[0005] In some embodiments, 0 < β ≦ 0.070, or 0 < β ≦ 0.050, or 0 < β ≦ 0.045, or 0 < β ≦ 0.035, or 0 < β ≦ 0.030, or 0 < β ≦ 0.020, or 0 < β ≦ 0.010, or 0.010 ≦ β ≦ 0.070, or 0.020 ≦ β ≦ 0.090, or 0.050 ≦ β ≦ 0.100.

[0006] Li3Na y PS4Cl y、 Li7Na y PS6Cl y、 Li7Na y P3S 11 Cl y , Li4Na y PS4XCl y , Li6Na y PS5XCl y , Li7Na y P2S8XCl y or a solid composition comprising a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≦ 0.100, is further provided herein. In some aspects, the composition comprises a thiargyrite crystal structure.

[0007] Formula (II): Li (3β+7-z-w) PS (6-z-w) O β Cl (β+z) Y w (II) (Where Y is at least one halogen selected from the group consisting of F, Cl, Br, I, and combinations thereof; 0 ≦ z ≦ 2, 0 ≦ w ≦ 2, z + w ≦ 2, and 0 < β ≦ 0.100.) A solid composition is further provided herein. In some embodiments, the composition comprises a thiogermanite crystal structure.

[0008] In some embodiments, 0 < β ≦ 0.070, or 0 < β ≦ 0.050, or 0 < β ≦ 0.045, or 0 < β ≦ 0.035, or 0 < β ≦ 0.030, or 0 < β ≦ 0.020, or 0 < β ≦ 0.010, or 0.010 ≦ β ≦ 0.070, or 0.020 ≦ β ≦ 0.090, or 0.050 ≦ β ≦ 0.100.

[0009] Li (3+3y) PS4O y Cl y , Li (7+3y) PS6O y Cl y , Li (7+3y) P3S 11 O y Cl y , Li (4+3y) PS4O y XCl y , Li (6+3y) PS5O y XCl y , Li (7+3y) P2S8O y XCl y Or a solid composition comprising a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≦ 0.100, is further provided herein. In some embodiments, the composition comprises a thiogermanite crystal structure.

[0010] A method for preparing the solid composition, the method comprising forming a solid composition by contacting Li2S, P2S5, LiCl, and an alkali metal salt (AY), and heat-treating the solid composition, wherein the composition comprises a thiogermanite crystal structure, is further provided herein.

[0011] A method for preparing a solid composition is further provided herein, comprising: forming the solid composition by contacting Li2S, P2S5, LiCl and Li3OCl; and heat-treating the solid composition, wherein the composition comprises a silver-germanium ore crystal structure.

[0012] Electrochemical cells comprising one or more compositions of formula (I) or formula (II) described herein are further provided herein. The electrochemical cell comprises a positive electrode (i.e., cathode) current collector; a positive electrode layer (i.e., cathode layer) having a first side operably in contact with the cathode current collector and a second side opposite to the first side; a separator layer having a first side operably in contact with the second side of the cathode layer and a second side opposite to the first side; a negative electrode layer (i.e., anode layer) having a first side operably in contact with the second side of the separator layer and a second side opposite to the first side; and a negative electrode (i.e., anode) current collector operably in contact with the second side of the anode layer. One or more of the positive electrode layer, separator layer, and negative electrode layer may contain one or more compositions of formula (I) or formula (II).

[0013] This disclosure can be understood by referring to the following detailed description in conjunction with the figures briefly described below. Note that for illustrative purposes, certain elements in the figures may not be depicted to scale. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 shows the X-ray diffraction pattern of the composition of this disclosure. [Modes for carrying out the invention]

[0015] The following description provides specific details to give a thorough understanding of the various embodiments of this disclosure. However, as a person skilled in the art reads and understands the specification, claims, and drawings, he will understand that some embodiments of this disclosure may be carried out without adhering to some of the specific details described herein. Furthermore, in order to avoid obscuring this disclosure, several well-known methods, processes, devices, and systems that find applications in the various embodiments described herein are not disclosed in detail.

[0016] The present invention is characterized by a process for preparing a solid electrolyte material. The process may include: a) mixing one or more lithium sources with an alkali metal salt having formula AY (wherein A is selected from the group consisting of Na, K, Cs, Fr, and combinations thereof, and Y is selected from F, Cl, Br, I, and combinations thereof), as well as a compound containing phosphorus and sulfur, to form a solid composition; and b) heat-treating the solid composition to form a solid electrolyte material. The lithium sources, alkali metal salts, and compounds containing phosphorus and sulfur may be referred to individually or collectively as “precursors” or “precursor materials” herein. The solid electrolyte material may include a silver-germanium ore crystal structure. In one embodiment, the process may further include simultaneously mixing the complexes while heating. Preferably, the process described herein can be carried out in less than 5 hours to prepare a solid electrolyte material.

[0017] In some embodiments, the mixing in step a) forms a homogeneous composite. As used herein, “homogeneous composite” is understood to mean a composite material in which all or substantially all of the components of the composite material (i.e., precursors) are distributed substantially uniformly throughout the composite material. Mixing the materials to form a homogeneous composite ensures the uniform distribution of all materials and allows the materials to react in appropriate ratios. Mixing during the heating step can also help ensure a uniform reaction. In addition, mixing during the reaction can prevent gas buildup. For example, materials such as Li2CO3 produce CO2. In other embodiments, the gas may include SO2, H2S, and other gases. Mixing can allow all gases to escape before reacting with any of the materials by helping to break any surface tension in the molten flux mixture.

[0018] The mixing in step a) can be accomplished by methods generally known in the art. In some embodiments, agitators, including agitated media mills, twin-screw compounders, and other high-shear equipment, may be used to mix the materials to form a homogeneous composite.

[0019] The mixing in step a) may further include grinding the homogeneous composite to a desired particle size. Grinding may include wet grinding or dry grinding. The homogeneous composite can be ground at a predetermined temperature for a predetermined period of time to achieve the desired particle size. Grinding can be achieved using a grinder mill, self-grinding mill, ball mill, planetary ball mill, stone mill, pebble mill, rod mill, semi-self-grinding mill, tower mill, longitudinal impactor mill, or other grinding equipment known in the art. Preferably, grinding is achieved in a planetary ball mill or grinder mill.

[0020] The mixing time and grinding time are not particularly limited, as long as they allow for proper homogenization and reaction of the precursor to produce a solid electrolyte material. The mixing temperature is not particularly limited, as long as it allows for proper mixing and is not too high, so that the precursor enters a gaseous state or quickly forms a molten reactive flux, as further described herein. Mixing and grinding can be carried out in an inert atmosphere, a moisture-free atmosphere, or an ambient atmosphere.

[0021] Mixing and / or grinding can be accomplished without the use of a solvent; that is, mixing and / or grinding can be solvent-free. Alternatively, mixing and / or grinding can be carried out in the presence of a solvent. The solvent may include alkanes, blends of alkanes, xylene (including para-, meta-, and ortho-xylene), toluene, benzene, heptane, octane, decalin, 1,2,3,4-tetrahydronaphthalene, or combinations thereof.

[0022] In another embodiment, the composite may be heated to a temperature of about 150°C to about 600°C in step b). The composite may be heated to a temperature of about 150°C to about 200°C, about 150°C to about 250°C, about 150°C to about 300°C, about 150°C to about 350°C, about 150°C to about 400°C, about 150°C to about 450°C, about 150°C to about 500°C, about 150°C to about 550°C, about 150°C to about 600°C, and about 200°C to about 600°C in step b). It can be heated to temperatures of approximately 250°C to 600°C, approximately 300°C to 600°C, approximately 350°C to 600°C, approximately 400°C to 600°C, approximately 450°C to 600°C, approximately 500°C to 600°C, approximately 550°C to 600°C, approximately 200°C to 400°C, approximately 200°C to 350°C, or approximately 250°C to 350°C. For example, the composite may be heated in step b) to a temperature of approximately 150°C, approximately 175°C, approximately 200°C, approximately 225°C, approximately 250°C, approximately 275°C, approximately 300°C, approximately 325°C, approximately 350°C, approximately 375°C, approximately 400°C, approximately 425°C, approximately 450°C, approximately 475°C, approximately 500°C, approximately 525°C, approximately 550°C, approximately 575°C, or approximately 600°C. In some examples, the composite may be heated in step b) to approximately 172°C, approximately 288°C, or approximately 408°C.

[0023] The alkali metal salts of this disclosure may generally have the formula AY, where A is selected from the group consisting of sodium (Na), potassium (K), cesium (Cs), francium (Fr), and combinations thereof, and Y is selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof.

[0024] An exemplary lithium source may include one or more of Li2S, Li2CO3, lithium halides, pseudolithium halides, Li2O, Li3PO4, LiBO2, Li2B4O7, Li2ZrO3, LiAlO2, Li2TiO3, LiNbO3, and Li2SiO3, or mixtures thereof. An exemplary lithium halide may include one or more of LiF, LiCl, LiBr, and LiI, while an exemplary pseudolithium halide may include LiNO3, LiOH, Li2SO3, Li2SO4, Li3N, Li2NH, LiNH2, LiBF4, and LiBH4.

[0025] Exemplary compounds containing phosphorus and sulfur include, for example, P4S X (x is in the range of 3 to 40) and may contain P2S5. In embodiments, phosphorus sulfide (P4S x ) is P4S x It contains a mixture of P4S3, P4S4, P4S5, P4S6, P4S7, P4S8, P4S9, and P4S 10 , and P4S x It may be a combination of the above, and x is a non-integer. In another embodiment, phosphorus sulfide (P4S x ) is P4S x The mixture comprises a mixture of the following, where x is in the range of 11 to 14. Compounds containing phosphorus and sulfur may have a low melting temperature. As used herein, a low melting temperature is defined as a melting temperature of less than 300°C, for example, 250°C or less, 200°C or less, or 150°C or less.

[0026] The method may further comprise mixing one or more sulfur sources with one or more lithium sources, a compound containing phosphorus and sulfur, and an alkali metal salt. Examples of sulfur sources include, for example, elemental sulfur, sulfur vapor (i.e., elemental sulfur that has sublimated or been heated above its boiling point), polysulfides, (NH4)2S, or H2S gas. Non-limiting examples of polysulfides that can be used as sulfur sources include lithium polysulfide, sodium polysulfide, and potassium polysulfide. In embodiments, the sulfur source is lithium polysulfide, for example, Li2S x The equation is such that x is between 2 and 10. In embodiments in which the sulfur source includes sulfur vapor or H2S gas, the sulfur vapor or H2S gas may be bubbled through or over the complex when heat is applied and the reaction takes place. Alternatively, in embodiments in which the sulfur source includes elemental sulfur, the elemental sulfur may be added directly to the complex mixture as a dry powder, slurry, solution, or a combination thereof.

[0027] The molar ratio of phosphorus to lithium to sulfur (P:Li:S) may be selected so that the reaction produces the desired solid electrolyte material. The molar amount of phosphorus in the molar ratio may be selected from about 1 to about 4, for example, about 1 to about 2, about 1 to about 3, about 2 to about 3, about 2 to about 4, or about 3 to about 4. In some examples, the molar amount of phosphorus in the molar ratio may be 1, 1.5, 2, 2.5, 3, 3.5, or 4. The molar amount of lithium in the molar ratio may be selected from about 1 to about 9, for example, about 1 to about 3, about 1 to about 5, about 1 to about 7, about 3 to about 5, about 3 to about 7, about 3 to about 9, about 5 to about 7, about 5 to about 9, or about 7 to about 9. In some examples, the molar amount of lithium in the molar ratio may be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9. The molar amount of sulfur in the molar ratio may be selected from about 3 to about 12, for example, about 3 to about 6, about 3 to about 9, about 3 to about 12, about 6 to about 9, about 6 to about 12, or about 9 to about 12. In some examples, the molar amount of sulfur in the molar ratio may be 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, or 13. Therefore, the molar ratio of phosphorus to lithium to sulfur may be 1 to 4:1 to 9:3 to 12.

[0028] In some preferred embodiments, the method includes preparing a solid composition by contacting Li2S, P2S5, LiCl, and an alkali metal salt (AY) to form a solid composition, followed by heat treatment of the solid composition.

[0029] In another preferred embodiment, the method includes preparing a solid composition by contacting Li2S, P2S5, LiCl, and Li3OCl to form a solid composition, and then heat-treating the solid composition.

[0030] The process described herein is based on formula I: Li (7-z-w) A β PS (6-z-w) X z+β Y w(I) X and Y are individually selected from F, Cl, Br, and I, respectively; A is selected from the group consisting of Na, K, Cs, Fr, and combinations thereof; w and z are in the range of 0 to 2, respectively; w + z is in the range of 0 to 2; and β is in the range of 0 to 0.100; which can be used to prepare a solid electrolyte material. An exemplary solid electrolyte material prepared by the process described herein is, for example, Li6PS5Cl, Li6PS5Cl 0.5 Br 0.5 Li 5.5 PS 4.5 Cl 1.5 Li 5.5 PS 4.5 ClBr 0.5 Li6Na 0.0608 PS5Cl 1.0608 Li 3.0858 PS4O 0.0286 Cl 0.0286 It may also contain Li5PS4Cl2. The solid electrolyte material may be crystalline, glassy, ​​or glassy ceramic.

[0031] In some embodiments, z may be in the range of 0 to 2. For example, z may be about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0. In some embodiments, z may be about 0 to about 0.5, about 0 to about 1, about 0 to about 1.5, about 0 to about 2, about 0.5 to about 2, about 1 to about 2, or about 1.5 to about 2.

[0032] In some embodiments, w may be in the range of 0 to 2. For example, w may be about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0. In some embodiments, w may be about 0 to about 0.5, about 0 to about 1, about 0 to about 1.5, about 0 to about 2, about 0.5 to about 2, about 1 to about 2, or about 1.5 to about 2.

[0033] In some embodiments, β may be in the range of 0 to 0.100. For example, β may be about 0, 0.001, 0.005, 0.010, 0.015, 0.020, 0.0250, 0.030, 0.0350, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or about 0.100. In some aspects, β is approximately 0 to 0.001, approximately 0 to 0.005, approximately 0 to 0.010, approximately 0 to 0.015, approximately 0 to 0.020, approximately 0 to 0.0250, approximately 0 to 0.030, approximately 0 to 0.035, approximately 0 to 0.040, approximately 0 to 0.045, approximately 0 to 0.050, approximately 0 to 0.055, approximately 0 to 0.060, approximately 0 to 0.065, approximately 0 to 0.070, approximately 0 to 0.075, approximately 0 to 0.080, approximately 0 to 0.085, approximately 0 to 0.090, approximately 0 to 0.095, approximately 0 to 0. 0.100, approximately 0.001 to 0.100, approximately 0.005 to 0.100, approximately 0.010 to 0.100, approximately 0.015 to 0.100, approximately 0.020 to 0.100, approximately 0.025 to 0.100, approximately 0.030 to 0.100, approximately 0.035 to 0.100, approximately 0.040 to 0.100, approximately 0.045 to 0.100, approximately 0.050 to 0.100, approximately 0.055 to 0.100, approximately 0.060 to 0.100, approximately 0.065 to 0.100, approximately 0.070 to 0.100, approximately 0.075 β may be approximately 0.100, approximately 0.080 to approximately 0.100, approximately 0.085 to approximately 0.100, approximately 0.090 to approximately 0.100, or approximately 0.095 to approximately 0.100. In a preferred embodiment, β may be approximately 0.010 to approximately 0.070, approximately 0.020 to approximately 0.090, or approximately 0.050 to approximately 0.100. In another preferred embodiment, β may be greater than 0.

[0034] The solid composition is Li3Na. y PS4Cl y、 Li7Na y PS6 y、 Li7Na y P3S 11 Cl y Li4Na y PS4XCl y Li6Nay PS5XCl y 、 Li7Na y P2S8XCl y 、 or a solid electrolyte material having a combination thereof, wherein y is from 0 to 0.100 and X is a halogen (F, Cl, Br, or I). The solid electrolyte material may be included. For example, y may be about 0, 0.010, 0.020, 0.030, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090, or about 0.100. In some embodiments, y may be from about 0 to about 0.010, from about 0 to about 0.020, from about 0 to about 0.030, from about 0 to about 0.040, from about 0 to about 0.050, from about 0 to about 0.060, from about 0 to about 0.070, from about 0 to about 0.080, from about 0 to about 0.090, from about 0 to about 0.100, from about 0.010 to about 0.100, from about 0.020 to about 0.100, from about 0.030 to about 0.100, from about 0.040 to about 0.100, from about 0.050 to about 0.100, from about 0.060 to about 0.100, from about 0.070 to about 0.100, from about 0.080 to about 0.100, or from about 0.090 to about 0.100. Preferably, the solid composition of Formula I includes a thiargyrite crystal structure.

[0035] The solid composition of the present disclosure may be prepared according to the following reaction: Li2S + P2S5 → Li7PS6 → Li7PS 6+ yAY → Li7A y PS6Y y Li2S + P2S5 → Li7P3S 11 → → Li7P3S 11+ yAY → Li7A y P3S 11 Y y Li2S + P2S5 + LiX → Li4PS4X → Li4PS4X + yAY → Li4A y PS4XY y Li2S + P2S5 + LiX → Li6PS5X → Li6PS5X + yAY → Li6A y PS5XY y Li2S + P2S5 + LiX → Li7P2S8X → Li7P2S8X + yAY → Li7A y P2S8XY y

[0036] A method for preparing a solid composition, comprising mixing Li2S, P2S5, LiCl, and Li3OCl, forming a solid composition, and heating the solid composition; wherein Y is at least one halogen selected from the group consisting of F, Cl, Br, I, and combinations thereof, is further provided herein.

[0037] A solid composition of Formula II prepared by the method provided herein: Li (3β+7-z-w) PS (6-z-w) O β Cl (β+z) Y w (II) Wherein Y is a halogen selected from the group consisting of F, Cl, Br, I, and combinations thereof; z is from 0 to 2, w is from 0 to 2, and z + w is from 0 to 2; a solid composition is further provided herein. In a preferred embodiment, the solid composition of Formula II comprises a thiogermanate crystal structure.

[0038] In some embodiments, z may range from 0 to 2. For example, z may be about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0. In some aspects, z may be from about 0 to about 0.5, from about 0 to about 1, from about 0 to about 1.5, from about 0 to about 2, from about 0.5 to about 2, from about 1 to about 2, or from about 1.5 to about 2.

[0039] In some embodiments, w may be in the range of 0 to 2. For example, w may be about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or about 2.0. In some embodiments, w may be about 0 to about 0.5, about 0 to about 1, about 0 to about 1.5, about 0 to about 2, about 0.5 to about 2, about 1 to about 2, or about 1.5 to about 2.

[0040] In some embodiments, β may be in the range of 0 to 0.100. For example, β may be about 0, 0.001, 0.005, 0.010, 0.015, 0.020, 0.0250, 0.030, 0.0350, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or about 0.100. In some aspects, β is approximately 0 to 0.001, approximately 0 to 0.005, approximately 0 to 0.010, approximately 0 to 0.015, approximately 0 to 0.020, approximately 0 to 0.0250, approximately 0 to 0.030, approximately 0 to 0.035, approximately 0 to 0.040, approximately 0 to 0.045, approximately 0 to 0.050, approximately 0 to 0.055, approximately 0 to 0.060, approximately 0 to 0.065, approximately 0 to 0.070, approximately 0 to 0.075, approximately 0 to 0.080, approximately 0 to 0.085, approximately 0 to 0.090, approximately 0 to 0.095, approximately 0 to 0. 0.100, approximately 0.001 to 0.100, approximately 0.005 to 0.100, approximately 0.010 to 0.100, approximately 0.015 to 0.100, approximately 0.020 to 0.100, approximately 0.025 to 0.100, approximately 0.030 to 0.100, approximately 0.035 to 0.100, approximately 0.040 to 0.100, approximately 0.045 to 0.100, approximately 0.050 to 0.100, approximately 0.055 to 0.100, approximately 0.060 to 0.100, approximately 0.065 to 0.100, approximately 0.070 to 0.100, approximately 0.075 β may be approximately 0.100, approximately 0.080 to approximately 0.100, approximately 0.085 to approximately 0.100, approximately 0.090 to approximately 0.100, or approximately 0.095 to approximately 0.100. In a preferred embodiment, β may be approximately 0.010 to approximately 0.070, approximately 0.020 to approximately 0.090, or approximately 0.050 to approximately 0.100. In another preferred embodiment, β may be greater than 0.

[0041] The solid compositions of this disclosure may have X-ray diffraction patterns collected by Cu-Kα(1,2)=1.5418Å, with characteristic peaks at 2θ=15.7°±0.5°, 18.2°±0.5°, 25.8°±0.5°, 30.3°±0.5°, 31.6°±0.5°, and 31.8°±0.5°. In some embodiments, the peak intensity ratio of the peak at 31.6°±0.5° and the peak at 31.8°±0.5° may be greater than 5.

[0042] Electrochemical cells comprising one or more compositions of formula (I) or formula (II) described above are further provided herein. The electrochemical cell comprises a positive electrode (i.e., cathode) current collector; a positive electrode layer (i.e., cathode layer) having a first side operably in contact with the cathode current collector and a second side opposite to the first side; a separator layer having a first side operably in contact with the second side of the cathode layer and a second side opposite to the first side; a negative electrode layer (i.e., anode layer) having a first side operably in contact with the second side of the separator layer and a second side opposite to the first side; and a negative electrode (i.e., anode) current collector operably in contact with the second side of the anode layer.

[0043] The anode layer may contain one or more anode active materials. In one embodiment, the anode active material is one or more materials, for example, silicon (Si), tin (Sn), germanium (Ge), graphite, Li4Ti5O 12( It may contain LTO or other known anode active materials.

[0044] In some embodiments, the anode active material may be present in the anode layer in an amount of about 30% to about 98% (by weight) of the anode layer. In some embodiments, the anode active material may be present in an amount of about 30% to about 35%, about 30% to about 40%, about 30% to about 45%, about 30% to about 50%, about 30% to about 55%, about 30% to about 60%, about 30% to about 65%, about 30% to about 70%, about 30% to about 75%, about 30% to about 80%, about 30% to about 85%, about 30% to about 90%, about 30% to about 95%, about 35% to about 98%, about 40% to about 98%, about 45% to about 98% It may be present in the anode layer in amounts of %, approximately 50% to 98%, approximately 55% to 98%, approximately 60% to 98%, approximately 65% ​​to 98%, approximately 70% to 98%, approximately 75% to 98%, approximately 80% to 98%, approximately 85% to 98%, approximately 90% to 98%, approximately 40% to 90%, approximately 40% to 80%, approximately 40% to 70%, approximately 40% to 60%, approximately 40% to 55%, approximately 40% to 50%, or approximately 40% to 45% (by weight) of the total.

[0045] In some embodiments, the anode layer may have a thickness of about 1 μm to about 100 μm. In some embodiments, the anode layer may have a thickness of about 1 μm to about 10 μm, about 1 μm to about 20 μm, about 1 μm to about 30 μm, about 1 μm to about 40 μm, about 1 μm to about 50 μm, about 1 μm to about 60 μm, about 1 μm to about 70 μm, about 1 μm to about 80 μm, about 1 μm to about 90 μm, about 10 μm to about 100 μm, or about 20 μm to about 100 μm. The anode layer may have a thickness of approximately 30 μm to 100 μm, approximately 40 μm to 100 μm, approximately 50 μm to 100 μm, approximately 60 μm to 100 μm, approximately 70 μm to 100 μm, approximately 80 μm to 100 μm, approximately 90 μm to 100 μm, approximately 10 μm to 50 μm, approximately 20 μm to 40 μm, or approximately 20 μm to 30 μm. In some additional embodiments, the anode layer may have a thickness of approximately 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or approximately 100 μm. In a preferred embodiment, the anode layer has a thickness of approximately 20 μm to 30 μm.

[0046] In some embodiments, the anode layer may optionally further contain one or more conductive additives. The conductive additives help to uniformly distribute the charge density across the entire anode. The conductive additives may include metal powders, fibers, filaments, or any other material known to conduct electrons. In some embodiments, the one or more conductive additives may include one or more conductive carbon materials, such as carbon fibers, graphite, graphene, carbon black, conductive carbon, amorphous carbon, vapor-grown carbon fibers (VGCF), activated carbon, and carbon nanotubes.

[0047] In some embodiments, the conductive additive may be present in the anode layer in an amount of about 0% to about 15% (weight %) of the anode layer. In some embodiments, the conductive additive may be present in the anode layer in an amount of about 0% to about 10%, or about 0% to about 5% (weight %) of the anode layer. In some additional embodiments, the conductive additive may be present in the anode layer in an amount of about 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or about 15% (weight %) of the anode layer. In a preferred embodiment, the conductive additive is present in the anode layer in an amount of about 0% to about 5% (weight %) of the anode layer.

[0048] In some embodiments, the average particle size of the conductive additive may be about 5 nm to about 100 nm. In some embodiments, the average particle size of the conductive additive may be about 5 nm to about 10 nm, about 5 nm to about 20 nm, about 5 nm to about 30 nm, about 5 nm to about 40 nm, about 5 nm to about 50 nm, about 5 nm to about 60 nm, about 5 nm to about 70 nm, about 5 nm to about 80 nm, about 5 nm to about 90 nm, about 10 nm to about 100 nm, about 20 nm to about 100 nm, about 30 nm to about 100 nm, about 40 nm to about 100 nm, about 50 nm to about 100 nm, about 60 nm to about 100 nm, about 70 nm to about 100 nm, about 80 nm to about 100 nm, about 90 nm to about 100 nm, about 10 nm to about 50 nm, or about 20 nm to about 40 nm. In some examples, the conductive additive may have a particle size of approximately 30 nm.

[0049] In some embodiments, the anode layer may optionally further comprise one or more solid electrolyte materials of the present disclosure; i.e., one or more compositions of formula (I) or formula (II) described herein. The solid electrolyte material, together with the conductive additive, helps to uniformly distribute the charge density throughout the anode. The one or more solid electrolyte materials may additionally or substitutedly comprise oxides, oxysulfides, sulfides, halides, nitrides, or any other solid electrolyte known in the art. In some preferred embodiments, the one or more solid electrolyte materials may comprise sulfide solid electrolyte materials, i.e., solid electrolytes having at least one sulfur component. In some embodiments, the one or more solid electrolytes may comprise a combination of one or more materials, e.g., Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2 S -P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-L iBr, Li2S-S-SiS2-LiCl, Li2S-S-SiS2-B2S3-LiI, Li2S-S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m and n are positive numbers, and Z is Ge, Zn, or Ga), Li2S-GeS2, Li2S-S-SiS2-Li3PO4, and Li2S-S-SiS2-Li x MO y (x and y are positive numbers, and M may be P, Si, Ge, B, Al, Ga, or In.)

[0050] In another embodiment, the solid electrolyte material is Li3PS4, Li4P2S6, Li7P3S 11 Li 10 GeP2S 12 Li 10 SnP2S 12may be one or more of them. In a further embodiment, the solid electrolyte may be one or more of thioargentogermanate electrolytes, such as Li6PS5Cl, Li6PS5Br, Li6PS5I, or may be represented by the formula Li 7-y PS 6-y X y : wherein, "X" represents at least one halogen and / or at least one pseudohalogen, 0 < y ≤ 2.0, the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN; In yet another embodiment, the solid electrolyte material is represented by the formula Li 8-y-z P2S 9-y-z X y W z (wherein, "X" and "W" represent at least one halogen and / or at least one pseudohalogen, 0 ≤ y ≤ 1 and 0 ≤ z ≤ 1), the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN. In an additional embodiment, the solid electrolyte material may be a halide electrolyte. The halide solid electrolyte may have a structure Li-M-X, where M is a metal element and X is a halogen. These are represented by the general formula Li α M 4+ β N 3+ (1-β) X Ω Y (6-Ω) , wherein: 0 ≤ β ≤ 1; 0 ≤ Ω ≤ 6; α = 6 - [(β * 4) + (1 - β) * 3]; X and Y are halogens, such as F, Cl, Br, I; M is an element having an oxidation state of 4+, such as Ti, Zr, Hf, and Rf; N is an element having an oxidation state of 3+, such as Ga, In, and Tl, Sc, Y, Fe, Ru, Os, Er; can be represented by. Examples of halide electrolytes include Li2ZrCl6, Li3InCl6, Li 2.25 Hf 0.75 Fe 0.25 Cl / sub>4Br2.

[0051] In some embodiments, the solid electrolyte material may be present in the anode layer 102 in an amount of about 0% to about 60% by weight of the anode layer; for example, the solid electrolyte may be present in the anode layer in an amount of about 0% to about 10%, about 0% to about 20%, about 0% to about 30%, about 0% to about 40%, about 0% to about 50%, about 10% to about 60%, about 20% to about 60%, about 30% to about 60%, about 40% to about 60%, or about 50% to about 60% by weight. In some embodiments, the solid electrolyte material may be present in the anode layer in an amount of about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% (by weight) of the anode layer. In a preferred embodiment, the solid electrolyte material is present in the anode layer in an amount of about 35% to about 45% (by weight) of the anode layer.

[0052] The anode layer may further contain a binder. The binder assists in the adhesion of the anode layer to the current collector and increases the structural integrity of the anode layer. In addition, the binder may enable improved aggregation between similar particles in different layers of the electrochemical cell (e.g., electrolyte). The binder also forms a flexible matrix when mixed with the solid electrolyte material. In some embodiments, the binder may contain fluoropolymers containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and derivatives thereof as structural units. In some additional embodiments, the binder may contain homopolymers, e.g., polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), and binary copolymers, e.g., copolymers of VdF and HFP, e.g., poly(vinylidene difluoride-hexafluoropropylene) copolymer (PVdF-HFP), etc. In another embodiment, the binder may be one or more thermoplastic elastomers, such as, but are not limited to, styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, and poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR).

[0053] In further embodiments, the binder may be an acrylic resin, for example, one or more of the following: polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, polybutyl (meth)acrylate, etc. In another embodiment, the binder may be a polycondensation polymer, for example, one or more of the following: polyurea, polyamide paper, polyimide, polyester, etc. In yet another embodiment, the binder may be a nitrile rubber, for example, one or more of the following: acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), etc.

[0054] In some embodiments, the binder may be present in the anode layer in an amount of about 0% to about 20% (by weight); for example, the binder may be present in the anode layer in an amount of about 0% to about 5%, about 0% to about 10%, about 0% to about 15%, about 5% to about 20%, about 10% to about 20%, or about 15% to about 20%. In a preferred embodiment, the binder is present in the anode layer in an amount of about 4% to about 5% (by weight).

[0055] The anode layer has a density of approximately 1.0 g / cm³. 3 ~Approx. 2.0g / cm 3 It may have a density of about 1.0 g / cm³. In some embodiments, the first anode layer has a density of about 1.0 g / cm³. 3 ~Approx. 1.1g / cm 3 , about 1.1g / cm 3 ~Approx. 1.2g / cm 3 , about 1.2g / cm 3 ~Approx. 1.3g / cm 3 , about 1.3g / cm 3 ~Approximately 1.4g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 1.5g / cm 3 , about 1.5g / cm 3 ~Approx. 1.6g / cm 3 , about 1.6g / cm 3 ~Approx. 1.7g / cm 3 , about 1.7g / cm3 ~Approx. 1.8g / cm 3 , about 1.8g / cm 3 ~Approx. 1.9g / cm 3 , about 1.9g / cm 3 ~Approx. 2.0g / cm 3 , about 1.0g / cm 3 ~Approx. 1.2g / cm 3 , about 1.0g / cm 3 ~Approx. 1.3g / cm 3 , about 1.0g / cm 3 ~Approximately 1.4g / cm 3 , about 1.0g / cm 3 ~Approx. 1.5g / cm 3 , about 1.0g / cm 3 ~Approx. 1.6g / cm 3 , about 1.0g / cm 3 ~Approx. 1.7g / cm 3 , about 1.0g / cm 3 ~Approx. 1.8g / cm 3 , about 1.0g / cm 3 ~Approx. 1.9g / cm 3 , about 1.1g / cm 3 ~Approx. 2.0g / cm 3 , about 1.2g / cm 3 ~Approx. 2.0g / cm 3 , about 1.3g / cm 3 ~Approx. 2.0g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 2.0g / cm 3 , about 1.5g / cm 3 ~Approx. 2.0g / cm 3 , about 1.6g / cm 3 ~Approx. 2.0g / cm 3 , about 1.7g / cm 3 ~Approx. 2.0g / cm 3 , about 1.8g / cm 3 ~Approx. 2.0g / cm 3 , or approximately 1.9 g / cm³ 3 ~Approx. 2.0g / cm 3 It may have a density of [this value].

[0056] The cathode layer is Li(Ni a Co b Mn c)It can be represented as O2(0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1) (referred to as "NMC") nickel-manganese-cobalt, or, for example, NMC111 (LiNi 0.33 Mn 0.33 Co 0.33 O2), NMC433 (LiNi 0.4 Mn 0.3 Co 0.3 O2), NMC532 (LiNi 0.5 Mn 0.3 Co 0.2 O2), NMC622 (LiNi 0.6 Mn 0.2 Co 0.2 O2), NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O2) or may contain a cathode active material such as a combination thereof. In another embodiment, the cathode active material is a coated or uncoated metal oxide, for example, but not limited to, V2O5, V6O 13 [[ID=3a]]、MoO3、LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiNi 1-Y Co Y O2、LiCo 1-Y Mn Y O2、LiNi 1-Y Mn Y O 2( 0 ≦ Y < 1), Li(Ni a Co b Mn c )O 4( 0 < a < 2, 0 < b < 2, 0 < c < 2, a + b + c = 2), LiMn 2-Z Ni Z O4、LiMn 2-Z Co Z O 4( 0 < Z < 2), LiCoPO4, LiFePO4, CuO, Li(Ni a Co b Al c )O 2( It should be noted that there seems to be an error in the original text where "V6O " and "LiCo " are incomplete expressions. This translation is based on the best understanding of the available text.One or more of 0 < a < 1, 0 < b < 1, 0 < c < 1, a + b + c = 1), or combinations thereof may be included. In another embodiment, the cathode active material may include one or more of a coated or uncoated metal sulfide, for example, but not limited to, titanium sulfide (TiS2), molybdenum sulfide (MoS2), iron sulfide (FeS, FeS2), copper sulfide (CuS), and nickel sulfide (Ni3S2), or combinations thereof. In a further embodiment, the cathode active material may include elemental sulfur (S). In an additional embodiment, the cathode active material may include a fluoride, for example, but not limited to, lithium fluoride (LiF), sodium fluoride (NaF), calcium fluoride (CaF2), magnesium fluoride (MgF2), nickel (II) fluoride (NiF2), iron (III) fluoride (FeF3), vanadium (III) fluoride (VF3), cobalt (III) fluoride (CoF3), chromium (III) fluoride (CrF3), manganese (III) fluoride (MnF3), aluminum fluoride (AlF3), and zirconium (IV) fluoride (ZrF4), or combinations thereof.

[0057] The cathode layer may further include one or more electron conductive additives. The electron conductive additive may include a metal powder, fiber, filament, or any other material known to conduct electrons. In some embodiments, the one or more electron conductive additives may include one or more electron conductive carbon materials, for example, carbon fiber, graphite, graphene, carbon black, conductive carbon, amorphous carbon, vapor grown carbon fiber (VGCF), activated carbon, and carbon nanotubes. In some embodiments, the electron conductive additive may be present in the cathode layer in an amount of about 1% to about 10%.

[0058] The cathode layer may further comprise one or more solid electrolytes of the present disclosure. The one or more solid electrolytes may additionally or alternatively comprise oxides, oxysulfides, sulfides, halides, nitrides, or any other solid electrolyte known in the art. In some preferred embodiments, the one or more solid electrolytes may comprise a sulfide solid electrolyte. In some embodiments, the solid electrolyte is a combination of one or more materials, for example, Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-S-SiS2-LiCl, Li2S-S-SiS2-B2S3-LiI, Li2S-S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m and n are positive numbers, and Z is Ge, Zn, or Ga), Li2S-GeS2, Li2S-S-SiS2-Li3PO4, and Li2S-S-SiS2-Li x MO y (x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In) In another embodiment, the solid electrolyte is Li3PS4, Li4P2S6, Li7P3S 11 Li 10 GeP2S 12 Li 10 SnP2S 12 It may be one or more of the following. In a further embodiment, the solid electrolyte may be one or more of silver-germanium sulfide mineral electrolytes, for example, Li6PS5Cl, Li6PS5Br, Li6PS5I, or the formula Li 7-y PS 6-y X y: Wherein, "X" represents at least one halogen and / or at least one pseudohalogen, 0 < y ≤ 2.0, at least one halogen may be one or more of F, Cl, Br, I, and at least one pseudohalogen may be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN; and may be represented by. In another embodiment, the solid electrolyte is of the formula Li 8-y-z P2S 9-y-z X y W z (wherein, "X" and "W" are at least one halogen element and / or pseudohalogen, 0 ≤ y ≤ 1 and 0 ≤ z ≤ 1), the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN. In an additional embodiment, the solid electrolyte material may be a halide electrolyte. The halide solid electrolyte may have a structure Li-M-X, where M is a metal element and X is a halogen. These may be represented by the general formula Li α M 4+ β N 3+ (1-β) X Ω Y (6-Ω) , wherein: 0 ≤ β ≤ 1; 0 ≤ Ω ≤ 6; α = 6 - [(β * 4) + (1 - β) * 3]; X and Y are halogens, for example, F, Cl, Br, I; M is an element having an oxidation state of 4+, for example, Ti, Zr, Hf, and Rf; N is an element having an oxidation state of 3+, for example, Ga, In, and Tl, Sc, Y, Fe, Ru, Os, Er; and may be represented by. Examples of halide electrolytes include Li2ZrCl6, Li3InCl6, Li 2.25 Hf 0.75 Fe 0.25 Cl4Br2. In some embodiments, the solid electrolyte may be present in the cathode layer in an amount of about 5% to about 20%.

[0059] The cathode layer may further contain one or more of the binders. In some embodiments, the binder may contain fluororesins containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and derivatives thereof as structural units. Specific examples of these include homopolymers, such as polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), and polytetrafluoroethylene (PTFE), and binary copolymers, such as copolymers of VdF and HFP, such as poly(vinylidene difluoride-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the binder may be one or more thermoplastic elastomers, such as, but not limited to, styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, and poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR). In yet another embodiment, the binder may be one or more acrylic resins, such as, but not limited to, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, and polybutyl (meth)acrylate. In yet another embodiment, the binder may be one or more polycondensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, and polyester. In further embodiments, the binder may be one or more nitrile rubbers, such as, but not limited to, acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), and mixtures thereof. In some embodiments, the binder may be present in the cathode layer in an amount of about 0% to about 5%.

[0060] The cathode layer has a density of approximately 1.0 g / cm³. 3 ~Approx. 2.0g / cm 3It may have a density of about 1.0 g / cm³. In some embodiments, the first anode layer has a density of about 1.0 g / cm³. 3 ~Approx. 1.1g / cm 3 , about 1.1g / cm 3 ~Approx. 1.2g / cm 3 , about 1.2g / cm 3 ~Approx. 1.3g / cm 3 , about 1.3g / cm 3 ~Approximately 1.4g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 1.5g / cm 3 , about 1.5g / cm 3 ~Approx. 1.6g / cm 3 , about 1.6g / cm 3 ~Approx. 1.7g / cm 3 , about 1.7g / cm 3 ~Approx. 1.8g / cm 3 , about 1.8g / cm 3 ~Approx. 1.9g / cm 3 , about 1.9g / cm 3 ~Approx. 2.0g / cm 3 , about 1.0g / cm 3 ~Approx. 1.2g / cm 3 , about 1.0g / cm 3 ~Approx. 1.3g / cm 3 , about 1.0g / cm 3 ~Approximately 1.4g / cm 3 , about 1.0g / cm 3~約 1.5 g / cm³ 3 , about 1.0g / cm 3 ~Approx. 1.6g / cm 3 , about 1.0g / cm 3 ~Approx. 1.7g / cm 3 , about 1.0g / cm 3 ~Approx. 1.8g / cm 3 , about 1.0g / cm 3 ~Approx. 1.9g / cm 3 , about 1.1g / cm 3 ~Approx. 2.0g / cm 3 , about 1.2g / cm 3 ~Approx. 2.0g / cm 3 , about 1.3g / cm 3 ~Approx. 2.0g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 2.0g / cm 3, about 1.5g / cm 3 ~Approx. 2.0g / cm 3 , about 1.6g / cm 3 ~Approx. 2.0g / cm 3 , about 1.7g / cm 3 ~Approx. 2.0g / cm 3 , about 1.8g / cm 3 ~Approx. 2.0g / cm 3 , or approximately 1.9 g / cm³ 3 ~Approx. 2.0g / cm 3 It may have a density of [this value].

[0061] The electrolyte layer (also referred to herein as the “separator layer”) may contain one or more solid electrolytes of the present disclosure. The one or more solid electrolytes may additionally or substitutedly contain oxides, oxysulfides, sulfides, halides, nitrides, or any other solid electrolyte known in the art. In some preferred embodiments, the one or more solid electrolytes may contain a sulfide solid electrolyte. In some embodiments, the solid electrolyte of one or more sulfides is a combination of one or more materials, for example, Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-GeS2, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-P2S5-LiI-LiBr, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-S-SiS2-LiCl, Li2S-S-SiS2-B2S3-LiI, Li2S-S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m and n are positive numbers, and Z is Ge, Zn, or Ga), Li2S-GeS2, Li2S-S-SiS2-Li3PO4, and Li2S-S-SiS2-Li x MO y (x and y are positive numbers, and M is P, Si, Ge, B, Al, Ga, or In) may be included. In some embodiments, one or more of the solid electrolyte materials are Li3PS4, Li4P2S6, Li7P3S 11 Li 10 GeP2S 12 Li 10SnP2S 12 may be. In another embodiment, one or more of the solid electrolyte materials may be a thioargentogermanate electrolyte, such as Li6PS5Cl, Li6PS5Br, Li6PS5I, or of the formula Li 7-y PS 6-y X y : wherein, "X" represents at least one halogen and / or at least one pseudohalogen, 0 < y ≦ 2.0, the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN; may be represented by. In another embodiment, one or more of the solid electrolyte materials is of the formula Li 8-y-z P2S 9-y-z X y W z (wherein, "X" and "W" represent at least one halogen and / or at least one pseudohalogen, 0 ≦ y ≦ 1 and 0 ≦ z ≦ 1), the halogen may be one or more of F, Cl, Br, I, and the pseudohalogen may be one or more of N, NH, NH2, NO, NO2, BF4, BH4, AlH4, CN, and SCN. In an additional embodiment, the solid electrolyte material may be a halide electrolyte. The halide solid electrolyte may have a structure Li-M-X, where M is a metal element and X is a halogen. These are of the general formula Li α M 4+ β N 3+ (1-β) X Ω Y (6-Ω) , wherein: 0 ≦ β ≦ 1; 0 ≦ Ω ≦ 6; α = 6 - [(β * 4) + (1 - β) * 3]; X and Y are halogens, such as F, Cl, Br, I; M is an element having an oxidation state of 4+, such as Ti, Zr, Hf, and Rf; N is an element having an oxidation state of 3+, such as Ga, In, and Tl, Sc, Y, Fe, Ru, Os, Er; may be represented by. Examples of halide electrolytes include Li2ZrCl6, Li3InCl6, Li 2.25 Hf 0.75 Fe 0.25 Cl4Br2.

[0062] The electrolyte layer may further contain one or more of the binders. In some embodiments, the binder may contain fluororesins containing vinylidene fluoride (VdF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and derivatives thereof as structural units. Specific examples of these include homopolymers, such as polyvinylidene fluoride (PVdF), polyhexafluoropropylene (PHFP), and polytetrafluoroethylene (PTFE), and binary copolymers, such as copolymers of VdF and HFP, such as poly(vinylidene difluoride-hexafluoropropylene) copolymer (PVdF-HFP). In another embodiment, the binder may be one or more thermoplastic elastomers, such as, but not limited to, styrene-butadiene rubber (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene block copolymer (SIS), styrene-ethylene-butylene-styrene (SEBS), polyacrylonitrile (PAN), nitrile-butylene rubber (NBR), polybutadiene, polyisoprene, and poly(methacrylate)nitrile-butadiene rubber (PMMA-NBR). In yet another embodiment, the binder may be one or more acrylic resins, such as, but not limited to, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polyisopropyl (meth)acrylate, polyisobutyl (meth)acrylate, and polybutyl (meth)acrylate. In yet another embodiment, the binder may be one or more polycondensation polymers, such as, but not limited to, polyurea, polyamide paper, polyimide, and polyester. In further embodiments, the binder may be nitrile rubber, for example, one or more of acrylonitrile-butadiene rubber (ABR), polystyrene-nitrile-butadiene rubber (PS-NBR), and mixtures thereof.

[0063] The binder may be present in the electrolyte layer in an amount of approximately 0% to approximately 40% (by weight). For example, the binder may be present in the electrolyte layer in an amount of approximately 0% to approximately 5%, approximately 0% to approximately 10%, approximately 0% to approximately 15%, approximately 0% to approximately 20%, approximately 0% to approximately 25%, approximately 0% to approximately 30%, approximately 0% to approximately 35%, approximately 0% to approximately 40%, approximately 5% to approximately 40%, approximately 10% to approximately 40%, approximately 15% to approximately 40%, approximately 20% to approximately 40%, approximately 25% to approximately 40%, approximately 30% to approximately 40%, approximately 35% to approximately 40%, approximately 5% to approximately 15%, approximately 5% to approximately 20%, approximately 10% to approximately 15%, approximately 10% to approximately 20%, or approximately 15% to approximately 20% (by weight).

[0064] The electrolyte layer contains approximately 1.0 g / cm³ 3 ~Approx. 2.0g / cm 3 It may have a density of about 1.0 g / cm³. In some embodiments, the first anode layer has a density of about 1.0 g / cm³. 3 ~Approx. 1.1g / cm 3 , about 1.1g / cm 3 ~Approx. 1.2g / cm 3 , about 1.2g / cm 3 ~Approx. 1.3g / cm 3 , about 1.3g / cm 3 ~Approximately 1.4g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 1.5g / cm 3 , about 1.5g / cm 3 ~Approx. 1.6g / cm 3 , about 1.6g / cm 3 ~Approx. 1.7g / cm 3 , about 1.7g / cm 3 ~Approx. 1.8g / cm 3 , about 1.8g / cm 3 ~Approx. 1.9g / cm 3 , about 1.9g / cm 3 ~Approx. 2.0g / cm 3 , about 1.0g / cm 3 ~Approx. 1.2g / cm 3 , about 1.0g / cm 3 ~Approx. 1.3g / cm 3 , about 1.0g / cm 3 ~Approximately 1.4g / cm 3 , about 1.0g / cm 3~約 1.5 g / cm³ 3, about 1.0g / cm 3 ~Approx. 1.6g / cm 3 , about 1.0g / cm 3 ~Approx. 1.7g / cm 3 , about 1.0g / cm 3 ~Approx. 1.8g / cm 3 , about 1.0g / cm 3 ~Approx. 1.9g / cm 3 , about 1.1g / cm 3 ~Approx. 2.0g / cm 3 , about 1.2g / cm 3 ~Approx. 2.0g / cm 3 , about 1.3g / cm 3 ~Approx. 2.0g / cm 3 Approximately 1.4 g / cm³ 3 ~Approx. 2.0g / cm 3 , about 1.5g / cm 3 ~Approx. 2.0g / cm 3 , about 1.6g / cm 3 ~Approx. 2.0g / cm 3 , about 1.7g / cm 3 ~Approx. 2.0g / cm 3 , about 1.8g / cm 3 ~Approx. 2.0g / cm 3 , or approximately 1.9 g / cm³ 3 ~Approx. 2.0g / cm 3 It may have a density of [this value].

[0065] In some embodiments, the electrolyte layer may have a thickness of about 10 to about 40 μm. In some embodiments, the electrolyte layer may have a thickness of about 10 μm to about 20 μm, about 10 μm to about 30 μm, about 20 μm to about 30 μm, about 20 μm to about 40 μm, or about 30 μm to about 40 μm. In some additional embodiments, the electrolyte layer may have a thickness of approximately 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, or approximately 40 μm.

[0066] The negative electrode current collector may contain one or more of the following materials: copper, aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, or gold. In some embodiments, the negative electrode current collector may have a thickness of about 5 μm to about 10 μm. In some embodiments, the negative electrode current collector includes a carbon coating. In preferred embodiments, the negative electrode current collector contains copper, nickel, and / or steel.

[0067] The positive electrode current collector may contain one or more of the following materials: copper, aluminum, nickel, titanium, stainless steel, magnesium, iron, zinc, indium, germanium, silver, platinum, or gold. In some embodiments, the negative electrode current collector may have a thickness of about 5 μm to about 10 μm. In some embodiments, the negative electrode current collector includes a carbon coating. In preferred embodiments, the negative electrode current collector contains copper, nickel, and / or aluminum.

[0068] List of embodiments Embodiment 1: Formula (I): Li (7-z-w) A β PS (6-z-w) X z+β Y w (I) (In the formula, X and Y are independently selected from the group consisting of F, Cl, Br, and I.) A is selected from the group consisting of Na, K, Cs, Fr, and combinations thereof. 0 ≤ z ≤ 2 and 0 ≤ w ≤ 2, where z + w ≤ 2 and 0 < β ≤ 0.100. A solid composition.

[0069] Embodiment 2: The composition according to Embodiment 1, wherein the composition comprises a silver-germanium ore crystal structure.

[0070] Embodiment 3: The composition according to Embodiment 1 or 2, wherein 0 < β ≤ 0.070.

[0071] Embodiment 4: The composition according to any one of Embodiments 1 to 3, wherein 0 < β ≤ 0.050.

[0072] Embodiment 5: The composition according to any one of Embodiments 1 to 4, wherein 0 < β ≤ 0.045.

[0073] Embodiment 6: The composition according to any one of Embodiments 1 to 5, wherein 0 < β ≤ 0.035.

[0074] Embodiment 7: The composition according to any one of Embodiments 1 to 6, wherein 0 < β ≤ 0.030.

[0075] Embodiment 8: The composition according to any one of Embodiments 1 to 7, wherein 0 < β ≤ 0.020.

[0076] Embodiment 9: The composition according to any one of Embodiments 1 to 8, wherein 0 < β ≤ 0.010.

[0077] Embodiment 10: The composition according to Embodiment 1 or 2, wherein 0.010 ≤ β ≤ 0.070.

[0078] Embodiment 11: The composition according to Embodiment 1 or 2, wherein 0.020 ≤ β ≤ 0.090.

[0079] Embodiment 12: The composition according to Embodiment 1 or 2, wherein 0.050 ≤ β ≤ 0.100.

[0080] Embodiment 13: Li3Na y PS4Cl y、 Li7Na y PS6Cl y、 Li7Na y P3S 11 Cl y 、Li4Na y PS4XCl y 、Li6Na y PS5XCl y 、Li7Na y P2S8XCl y or a solid composition comprising a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≤ 0. This is a solid composition.

[0081] Embodiment 14: The composition of Embodiment 13, wherein the composition comprises a silver-germanium ore crystal structure.

[0082] Embodiment 15: Formula (II): Li (3β+7-z-w) PS (6-z-w) O β Cl (β+z) Y w (II) (In the formula, Y is at least one halogen selected from the group consisting of F, Cl, Br, I and combinations thereof.) 0≦z≦2, 0≦w≦2, z+w≦2, and 0 < β ≤ 0.100. A solid composition.

[0083] Embodiment 16: The composition according to Embodiment 15, wherein the composition comprises a silver-germanium ore crystal structure.

[0084] Embodiment 17: The composition according to Embodiment 15 or 16, wherein 0 < β ≤ 0.070.

[0085] Embodiment 18: The composition according to any one of Embodiments 15 to 17, wherein 0 < β ≤ 0.050.

[0086] Embodiment 19: The composition according to any one of Embodiments 15 to 18, wherein 0 < β ≤ 0.045.

[0087] Embodiment 20: The composition according to any one of Embodiments 15 to 19, wherein 0 < β ≤ 0.035.

[0088] Embodiment 21: The composition according to any one of Embodiments 15 to 20, wherein 0 < β ≤ 0.030.

[0089] Embodiment 22: The composition according to any one of Embodiments 15 to 21, wherein 0 < β ≤ 0.020.

[0090] Embodiment 23: The composition according to any one of Embodiments 15 to 22, wherein 0 < β ≤ 0.010.

[0091] Embodiment 24: The composition according to Embodiment 15 or 16, wherein 0.010 ≤ β ≤ 0.070.

[0092] Embodiment 25: The composition according to Embodiment 15 or 16, wherein 0.020 ≤ β ≤ 0.090.

[0093] Embodiment 26: The composition according to Embodiment 15 or 16, wherein 0.050 ≤ β ≤ 0.100.

[0094] Embodiment 27: Li (3+3y) PS4O y Cl y 、Li (7+3y) PS6O y Cl y 、Li (7+3y) P3S 11 O y Cl y 、Li (4+3y) PS4O y XCl y 、Li (6+3y) PS5O y XCl y 、Li (7+3y) P2S8O y XCl y Or a solid composition comprising a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≤ 0.100.

[0095] Embodiment 28: The composition according to Embodiment 27, wherein the composition comprises a thiargyrite crystal structure.

[0096] Embodiment 29: A method for preparing a solid composition, the method comprising forming a solid composition by contacting Li2S, P2S5, LiCl, and an alkali metal salt (AY), and heat-treating the solid composition, wherein the composition comprises a thiargyrite crystal structure.

[0097] Embodiment 30: A method for preparing a solid composition, the method comprising forming a solid composition by contacting Li2S, P2S5, LiCl and Li3OCl, and heat-treating the solid composition, wherein the composition comprises a silver-germanium ore crystal structure.

[0098] Embodiment 31: An electrochemical cell comprising the composition according to any one of claims 1 to 28.

[0099] Embodiment 32: Positive electrode current collector, A positive electrode layer having a first side that is operably in contact with the positive electrode current collector and a second side opposite the first side, A separator layer having a first side operably in contact with a second side of the cathode layer and a second side opposite the first side, comprising the composition described in any one of embodiments 1 to 28, A negative electrode layer having a first side operably in contact with a second side of a separator layer and a second side opposite the first side, and Negative electrode current collector in operable contact with the second side of the negative electrode layer An electrochemical cell containing [a specific component]. [Examples]

[0100] Comparative Example 1 A composite mixture was formed by combining Li2S, P2S5, and LiCl in a molar ratio of 5:1:2. This composite mixture was heated at 450°C for 1 hour. The resulting electrolyte material was a Li6PS5Cl material having a silver-germanium ore crystal structure. When measured by X-ray diffraction (XRD) collected from Cu-Kα(1,2)=1.5418Å, the material had peak positions at 2θ=15.7°, 18.2°, 25.8°, 30.3°, and 31.6°.

[0101] Example 1 Aliquots of the electrolyte material prepared in Comparative Example 1 were mixed with NaCl to form a composite of 95% by weight Li6PS5Cl and 5% NaCl. This composite is of the formula Li6Na 0.24 PS5Cl 1.24The material exhibits the following characteristics. When measured by X-ray diffraction (XRD) collected from Cu-Kα(1,2)=1.5418Å, the material had peak positions at 2θ=15.7°, 18.2°, 25.8°, 30.3°, 31.6°, and 31.8°. The intensity ratio between the peaks at 31.6° and 31.8° was greater than 5.

[0102] Example 2 Aliquots of the electrolyte material prepared in Comparative Example 1 were mixed with NaCl to form a composite of 90% by weight Li6PS5Cl and 10% NaCl. This composite is of the formula Li6Na 0.51 PS5Cl 1.51 It had.

[0103] When measured by X-ray diffraction (XRD) collected from Cu-Kα(1,2) = 1.5418 Å, the material had peak positions at 2θ = 15.7°, 18.2°, 25.8°, 30.3°, 31.6°, and 31.8°.

[0104] drying room exposure Aliquots of the materials prepared in Comparative Example 1, Example 1, and Example 2 were placed in separate open containers. These containers were then placed in a drying chamber for 1 hour. The drying chamber maintained an average dew point of -55°C throughout the test.

[0105] As shown in Table 1, the ionic conductivity of the marked electrolyte in Comparative Example 1 decreased by 14.95% after 1 hour of exposure in a drying chamber (DR). However, the ionic conductivity of the marked electrolyte complex in Example 1 decreased by 0.00% after 1 hour of exposure in a drying chamber (DR). This suggests that incorporating an alkali metal salt, such as NaCl, into the electrolyte complex may increase the drying chamber stability of the complex. [Table 1]

[0106] The features described above and the features of the claims below may be combined in various ways without departing from these scopes. Therefore, it should be noted that matters included in the above detailed description or shown in the accompanying figures should be interpreted as illustrative and not as restrictive.

Claims

1. Equation (I): Li （７－ｚ－ｗ） A β PS （６－ｚ－ｗ） X ｚ＋β Y ｗ (I) (In the formula, X and Y are independently selected from the group consisting of F, Cl, Br, and I.) A is selected from the group consisting of Na, K, Cs, Fr and combinations thereof. 0 ≤ z ≤ 2 and 0 ≤ w ≤ 2, where z + w ≤ 2 and 0 < β ≤ 0.

100. A solid composition.

2. The composition according to claim 1, wherein the composition comprises a silver-germanium ore crystal structure.

3. The composition according to claim 1, wherein 0 < β ≤ 0.

070.

4. The composition according to claim 1, wherein 0 < β ≤ 0.

050.

5. The composition according to claim 1, wherein 0 < β ≤ 0.

045.

6. The composition according to claim 1, wherein 0 < β ≤ 0.

035.

7. The composition according to claim 1, wherein 0 < β ≤ 0.

030.

8. The composition according to claim 1, wherein 0 < β ≤ 0.

020.

9. The composition according to claim 1, wherein 0 < β ≤ 0.

010.

10. The composition according to claim 1, wherein 0.010 ≤ β ≤ 0.

070.

11. The composition according to claim 1, wherein 0.020 ≤ β ≤ 0.

090.

12. The composition according to claim 1, wherein 0.050 ≤ β ≤ 0.

100.

13. Li ３ Na ｙ PS ４ Cl ｙ、 Li ７ Na ｙ PS ６ Cl ｙ、 Li ７ Na ｙ P ３ S １１ Cl ｙ 、 Li ４ Na ｙ PS ４ XCl ｙ 、 Li ６ Na ｙ PS ５ XCl ｙ 、 Li ７ Na ｙ P ２ S ８ XCl ｙ A solid composition comprising Li, Na, PS, Cl, Li, Na, PS, Cl, Li, Na, P, S, Cl, Li, Na, PS, XCl, Li, Na, PS, XCl, Li, Na, P, S, XCl, or a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≤ 0.

100.

14. The composition according to claim 13, wherein the composition comprises a silver-germanium ore crystal structure.

15. Formula (II): Li （３β＋７－ｚ－ｗ） PS （６－ｚ－ｗ） O β Cl （β＋ｚ） Y ｗ (II) (In the formula, Y is at least one halogen selected from the group consisting of F, Cl, Br, I and combinations thereof.) 0 ≤ z ≤ 2, 0 ≤ w ≤ 2, z + w ≤ 2, and (0 < β ≤ 0.100.) A solid composition.

16. The composition according to claim 15, wherein the composition comprises a silver-germanium ore crystal structure.

17. The composition according to claim 15, wherein 0 < β ≤ 0.

070.

18. The composition according to claim 15, wherein 0 < β ≤ 0.

050.

19. The composition according to claim 15, wherein 0 < β ≤ 0.

045.

20. The composition according to claim 15, wherein 0 < β ≤ 0.

035.

21. The composition according to claim 15, wherein 0 < β ≤ 0.

030.

22. The composition according to claim 15, wherein 0 < β ≤ 0.

020.

23. The composition according to claim 15, wherein 0 < β ≤ 0.

010.

24. The composition according to claim 15, wherein 0.010 ≤ β ≤ 0.

070.

25. The composition according to claim 15, wherein 0.020 ≤ β ≤ 0.

090.

26. The composition according to claim 15, wherein 0.050 ≤ β ≤ 0.

100.

27. Li （３＋３ｙ） PS ４ O ｙ Cl ｙ Li （７＋３ｙ） PS ６ O ｙ Cl ｙ Li （７＋３ｙ） P ３ S １１ O ｙ Cl ｙ Li （４＋３ｙ） PS ４ O ｙ XCl ｙ Li （６＋３ｙ） PS ５ O ｙ XCl ｙ Li （７＋３ｙ） P ２ S ８ O ｙ XCl ｙ Or a solid composition comprising a combination thereof, wherein X is at least one halogen selected from the group consisting of F, Cl, Br, and I, and 0 < y ≤ 0.

100.

28. The composition according to claim 27, wherein the composition comprises a silver-germanium ore crystal structure.

29. A method for preparing a solid composition, wherein the method comprises Li ２ S, P ２ S ５ A method comprising contacting LiCl and an alkali metal salt (AY) to form a solid composition, and heat-treating the solid composition, wherein the composition contains a silver-germanium ore crystal structure.

30. A method for preparing a solid composition, wherein the method comprises Li ２ S, P ２ S ５ , LiCl and Li ３ A method comprising forming a solid composition by contacting OCl, and heat-treating the solid composition, wherein the composition contains a silver-germanium ore crystal structure.

31. An electrochemical cell comprising the composition according to any one of claims 1 to 28.

32. positive electrode current collector, A positive electrode layer having a first side that is operably in contact with the positive electrode current collector and a second side opposite to the first side, A separator layer having a first side operably in contact with the second side of the cathode layer and a second side opposite the first side, comprising the composition according to any one of claims 1 to 28, A negative electrode layer having a first side that is operably in contact with the second side of the separator layer and a second side opposite to the first side, and Negative electrode current collector operably in contact with the second side of the negative electrode layer An electrochemical cell containing [a specific component].

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