WO2019067675A1

WO2019067675A1 - Electrochemical compositions and preparation thereof

Info

Publication number: WO2019067675A1
Application number: PCT/US2018/053049
Authority: WO
Inventors: Bo Wang
Original assignee: Imerys Usa, Inc.
Priority date: 2017-09-27
Filing date: 2018-09-27
Publication date: 2019-04-04

Abstract

Materials useful in electrochemical applications are discussed as well as methods of producing and using such materials. For example, the materials may be formed by combining one or more of an aluminosilicate, a lithium compound, a gallium compound, a titanium compound, and a phosphate compound to form a mixture; and heating the mixture to form the material. The materials may be used as electrolytes, e.g., in a battery or a supercapacitor.

Description

ELECTROCHEMICAL COMPOSITIONS AND PREPARATION THEREOF

CLAIM FOR PRIORITY

[0001] This PCT International Application claims the benefit of priority of U.S. Provisional Application No. 62/564,042, filed September 27, 2017, the subject matter of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] Embodiments of the present disclosure relate generally to materials which can be used in electrochemical applications, for example as electrolyte materials, including the preparation of such materials and use thereof.

BACKGROUND

[0003] Materials having electrolyte properties are useful in variety of electrochemical applications, including batteries and supercapacitors. With the increasing demand for efficient sources of energy for devices such as laptops, mobile phones, and electric vehicles, there is a need for safe, inexpensive electrolyte materials that deliver high conductivity. Many materials currently used to power such devices having high energy demands have significant drawbacks, however. For example, traditional electrolytes such as liquid hydroxides and chlorides can have poor efficiency and low volumetric energy density, which limits their utility. Further, corrosive or caustic materials can leak and pose risks to users and/or the environment Organic-based electrolytes, such as those used in lithium-ion batteries, are typically volatile and flammable, which can result in thermal runaway due to overheating, overcharging, or mechanical damage.

[0004] Thus, developing cost effective electrolyte materials that demonstrate high conductivity while maintaining thermal and electrochemical stability remains a challenge. SUMMARY OF THE DISCLOSURE

[0005] The present disclosure includes electrochemical materials, preparation of such materials, compositions comprising such materials, and uses thereof. For example, disclosed herein is a method of forming an electrochemical material (e.g., an electrolyte material), the method comprising combining an aluminosilicate compound with a lithium compound, a gallium compound, a titanium compound, and a phosphate compound to form a mixture; and heating the mixture to form the electrochemical material. The electrochemical material may have a chemical formula Lii+2x+yAlxGa_yTi2-x-ySixP3-xOi2, wherein 0 < x < 0.3 and 0 < y < 0.4.

[0006] According to some aspects, the mixture may have a molar ratio of gallium to silicon ranging from 0.25 to 4.0. In additional or alternative aspects, the mixture may have a molar ratio of gallium to aluminum ranging from 0.25 to 4.0. Additionally or alternatively, the mixture may have a molar ratio of gallium to titanium ranging from 0.06 to 0.60.

Additionally or alternatively, the mixture may have a molar ratio of silicon to phosphorus ranging from 0.03 to 0.1 1. In additional or alternative examples, the mixture may have a molar ratio of the total of gallium and aluminum to titanium ranging from 0.11 to 1.0.

Additionally or alternatively, the mixture may have a molar ratio of the total of gallium, aluminum, and silicon to the total of titanium and phosphorus ranging from 0.06 to 0.25. Additionally or alternatively, the mixture may have a molar ratio of lithium to silicon ranging from 4 to 20 and/or a molar ratio of lithium to aluminum ranging from 4 to 20. In additional or alternative aspects, the mixture may have a molar ratio of lithium to gallium ranging from 4 to 20. Additionally or alternatively, the mixture may have a molar ratio of lithium to titanium ranging from 0.5 to 2. Additionally or alternatively, the mixture may have a molar ratio of lithium to phosphorus ranging from 0.4 to 0.8.

[0007] The aluminosilicate may have a molar ratio of aluminum to silicon of ranging from about 0.8 to about 1.2. According to some aspects, the aluminosilicate compound may have a particle size distribution with a median particle size (dso) less than 10 μιη. In additional aspects, the aluminosilicate compound may have a top particle size (d9₀) less than 30 μιη; for example, a dw less than 30 μιη. The aluminosilicate compound may comprise a clay or a zeolite. For example, the aluminosilicate may comprise kaolin. In at least one example, the kaolin may comprise less than 2.0% by weight of K₂0. Further, for example, kaolin may comprise less than 1.5% by weight of Na₂0.

[0008] The gallium compound may comprise, e.g., gallium (III) oxide or gallium hydroxide or a gallium salt. According to some examples, the titanium compound may comprise titanium oxide or a titanium salt. According to some aspects, the phosphate compound may comprise monoammonium phosphate or phosphoric acid. In further aspects, the phosphate compound is not monoammonium phosphate. In at least one example, the lithium salt may be lithium carbonate,

[0009] The method may comprise heating the mixture at temperature ranging from about 1000°C to about 1200°C. The method may further comprise heating the mixture at more than one temperature. For example, the mixture may be heated at a first temperature, and then at a second temperature higher than the first temperature. According to some examples, the mixture may be heated at first temperature ranging from about 150°C to about 200°C, and then at a second temperature ranging from about 1000°C to about 1200°C. In further examples, the mixture may be heated at a first temperature ranging from about 150°C to about 200°C, then heated at a second temperature ranging from about 600°C to about 800°C, and then heated at a third temperature ranging from about 1000°C to about 1200°C.

[0010] A further aspect of the disclosure includes the electrochemical material (e.g., electrolyte material) obtainable by any one of the methods described herein. The

electrochemical material may have an ionic conductivity of at least lxlO^"5 S/cm at a temperature of 21°C. In further aspects, the electrochemical material may have a lattice parameter a greater than 8.476 A.

[0011] The electrochemical materials disclosed herein may be used in a variety of electrical/electrochemical applications including, but not limited, batteries or supercapacitors. For example, the electrochemical material may be used in or as a coin cell, a pouch cell, a thin film battery, a cylindrical cell, a prismatic cell, a lithium air battery or a composite electrolyte. In some examples of the disclosure, the electrochemical material is used in a battery (e.g., as an electrolyte) wherein the anode may comprise lithium, lithium carbonate, graphite, silicon, or a combination thereof. In additional or alternative examples of the disclosure, the electrochemical material may be used in a battery (e.g., as an electrolyte) wherein the cathode may comprise lithium compounds such as lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, or a combination thereof. In additional or alternative examples, the cathode may contain vanadium oxide.

[0012] In additional or alternative examples, the electrochemical material may be used in a composite electrolyte. The composite electrolyte may comprise the electrochemical material disclosed herein and at least one other electrochemical material or electrolyte. For example, the composite electrolyte may comprise the electrochemical material and a liquid electrolyte, a gel electrolyte, a solid electrolyte, or combination thereof. In some aspects, the liquid electrolyte may be an ionic liquid, such as, e.g., N-butyl-N-ethyl pyrrolidinium bis(trifluoromethylsulfonylimide), ethylmethylimidazolium

bis(trifluoromethylsulfonylimide), N-m ethyl -N-propyl pyrrolidinium

bis(trifluoromethylsulfonylimide), N-m ethyl -N-propyl piperidinium

bis(trifluoromethylsulfonylimide), lithium salts, or a combination thereof. In at least one example the ionic liquid may be lithium bis(trifluorom ethane sulfonylimide). BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate various exemplary aspects of the disclosure, and together with the description, serve to explain the principles of the present disclosure.

[0014] Fig. 1 shows X-ray powder diffraction (XRD) patterns of Samples 1, 2, 7, and

12.

[0015] Figs. 2A, 2B, and 2C show charts of cell parameters measured for Samples 1, 2, and 7.

[0016] Fig. 3 shows a chart of ionic conductivity isotherms measured for Samples 1, 2, 7 and 12.

[0017] Fig. 4 shows Arrhenius plots of ionic conductivity measured for Samples 1, 2, 7, 12, and 17.

[0018] Fig. 5 shows XRD patterns measured for Samples 2-6.

[0019] Figs. 6A, 6B, and 6C show charts of cell parameters measured for Samples 2-5 and 7-10.

[0020] Fig. 7 shows a chart of ionic conductivity isotherms measured for Samples 2-

6.

[0021] Fig. 8 shows Arrhenius plots of ionic conductivity measured for Samples 2-6.

DETAILED DESCRIPTION

[0022] Particular aspects of the present disclosure are described in greater detail below. The terms and definitions provided herein control, if in conflict with terms and/or definitions incorporated by reference.

[0023] In the Summary above and in the Detailed Description, and the claims below, and in the accompanying drawings, reference is made to particular features (including method steps) of the disclosure. It is understood that the present disclosure includes all possible combinations of such particular features. For example; where a particular feature is disclosed in the context of a particular aspect or embodiment, or a particular claim, that feature can also be used, to the extent possible in combination with and additionally or alternatively in the context of other particular aspects or embodiments of the disclosure and, in the disclosure generally.

[0024] As used herein, the terms "comprises," "comprising," or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process, method, composition, article, or apparatus that comprises a list of elements does not include only those elements, but may include other elements not expressly listed or inherent to such process, method, composition, article, or apparatus. The term "exemplary" is used in the sense of "example" rather than "ideal."

[0025] As used herein, the singular forms "a," "an," and "the" include plural reference unless the context dictates otherwise. The terms "approximately" and "about" refer to being nearly the same as a referenced number or value. As used herein, the terms

"approximately" and "about" should be understood to encompass ± 5% of a specified amount or value.

[0026] When a range is used herein as "ranging from (a first number)" to (a second number)," "between (a first number) and (a second number)," or "(a first number)-(a second number)," this refers to a range whose lower limit is the first number, and whose upper limit is the second number. As used herein, the term "at least" followed by a number denotes the start of a range beginning with that number, which may be a range having an upper limit or no upper limit depending on the variable term being defined. For example, "at least 1" includes 1 and more than 1.

[0027] The present disclosure includes materials useful as electrolytes, e.g., in batteries, preparation of such materials, and use of the materials in a variety of electrochemical applications. For example, the present disclosure includes methods of forming an electrolyte material by combining an aluminosilicate with one or more of a lithium compound, a gallium compound, a titanium compound, and a phosphate compound to form a mixture; and heating the mixture to form the electrolyte material. While certain aspects of the present disclosure refer to the materials as "electrolyte materials," it is understood that the materials herein are not limited only to use as electrolytes. Further, the materials herein include chemical compounds and mixture of chemical compounds. Further, the electrolyte material can be a solid electrolyte.

[0028] The materials herein may have a NASICON (sodium (Na) Super Ionic CONductor)-type of structure. NASICON materials typically have a crystal lattice structure made up of tetrahedral and octahedral complexes of zirconium oxide and silicon/phosphate oxides. Sodium ions move among different interstitial sites throughout the crystal structure, providing for ionic conductivity. Compounds having similar crystal lattice structures based on isovalent elements (e.g., lithium in place of sodium, titanium in place of zirconium, etc.) may be described as having a NASICON-type structure. For example, lithium-titanium- phosphate NASICON compounds may comprise Ti₂(P04)3 units of Ti0₆ octahedra and P0₄ tetrahedra sharing corner oxygen ions. The Ti₂(P0₄)3 units create a framework crystal structure with channels between the units. Mobile lithium ions are then distributed throughout the crystal structure in the connected channels.

[0029] In some examples, the materials herein may comprise, consist of, or consist essentially of lithium, titanium, phosphorus, and oxygen, the material having a crystal lattice structure that provides for ionic conductivity. According to some aspects, the material may comprise, consist of, or consist essentially of lithium, titanium, phosphorus, oxygen, aluminum and silicon, and optionally gallium, the material having a crystal lattice structure that provides for ionic conductivity. Without intending to be bound by theory, it is believed that the sizes and spacing of the ionic radii in the crystal lattice structure, and hence the cell parameters of the crystal structure, may impact electrochemical properties of the material. The materials herein may be suitable for use as an electrolyte, e.g., in a solid-state battery.

[0030] According to some aspects of the present disclosure, the material may comprise a chemical compound having the chemical formula:

Lil+2x+yAlxGa_yTi2-x-ySixP3-xOl2

Compound 1

wherein 0 < x < 0.4 and 0 < y < 0.4. Without intending to be bound by theory, it is believed that such materials, e.g., electrolyte materials, may have a NASICON-type structure, wherein the molar ratios of elements may increase mobile lithium ion concentration and affect the channel size within the crystal structure, and thus the ionic conductivity of the material. The materials, methods of preparation thereof, and methods of use thereof are not limited to materials having the chemical composition of Compound 1, however.

[0031] As mentioned above and further discussed below, the materials herein may be prepared by combining suitable compounds of the desired elements into a mixture, e.g., compounds of lithium, aluminum, silicon, phosphorus (e.g., as phosphate or other

phosphorus-containing compound), and/or gallium, and heating the mixture. Such

compounds may comprise, for example, oxides, salts, and/or other suitable compounds. The relative amounts of each compound may be selected to provide the desired molar ratios.

[0032] In some examples according to the present disclosure, the material may be prepared from a mixture having a molar ratio of gallium to silicon ranging from 0.25 to 6.0, such as from 0.33 to 5.0, from 0.50 to 4.0, from 0.75 to 3.0, from 1.0 to 2.5, or from 1.25 to 2.0. Additionally or alternatively, the mixture may have a molar ratio of gallium to aluminum ranging from 0.25 to 6.0, from 0.33 to 5.0, from 0.50 to 4.0, from 0.75 to 3.0, from 1.0 to 2.5, or from 1.25 to 2.0. According to some aspects of the present disclosure, the mixture may additionally or alternatively have a molar ratio of gallium to titanium ranging from 0.06 to 0.60, from 0.70 to 0.55, from 0.12 to 0.45, from 0.14 to 0.38, or from 0.20 to 0.33.

Additionally, or alternatively, the mixture may have a molar ratio of the total of gallium and aluminum to titanium (i.e. the molar ratio of (Ga + Al):Ti) ranging from 0.1 1 to 1.0, from 0.17 to 0.82, from 0.25 to 0.67, or from 0.33 to 0.54. Further, for example, the mixture may additionally or alternatively have a molar ratio of lithium to silicon ranging from 4 to 20, from 5 to 18, from 6 to 15, from 7 to 13, or from 7.3 to 10. Thus, the mixture used to prepare the material may have a molar ratio of gallium to silicon ranging from 0.25 to 6.0, a molar ratio of gallium to aluminum ranging from 0.25 to 6.0, a molar ratio of gallium to titanium ranging from 0.06 to 0.60, and/or a molar ratio of gallium+aluminum to titanium ranging from 0.11 to 1.0. Such materials may, for example, have a chemical composition according to Compound 1.

[0033] Aluminosilicates may be used as a source of both aluminum and silicon for at least some examples herein, and may be natural or synthetic. For example, aluminosilicates useful for the materials herein include, but are not limited to, clays and zeolites. Exemplary clays include, but are not limited to, clays comprising kaolinite (Al₂Si₂05(OH)4) such as kaolin, hydrous kaolin, metakaolin, and calcined kaolin. Kaolin is clay mineral that typically comprises silica and alumina (e.g., as kaolinite), and lesser amounts of other components such as Fe₂0₃, Ti0₂, CaO, MgO, K₂0, Na₂0, P₂0₅, and/or water.

[0034] According to some aspects of the present disclosure, the aluminosilicate may have a molar ratio of aluminum to silicon of ranging from 0.8 to 1.2; such as, from 0.9 to 1.1; or from 1 to 1. According to some aspects of the present disclosure, incorporating

aluminosilicates and/or clays comprising aluminosilicate compounds into the mixture may result in materials with higher conductivity. [0035] For example, without being bound by theory, it is believed that using aluminosilicate compounds to form the electrochemical material (e.g., rather than separate silica and alumina compounds) may lower the activation energy required, e.g., considering the simultaneous or near simultaneous contribution of Al³⁺ and Si⁴⁺ and the relatively weaker bond strength of aluminosilicates. This lower activation energy, in turn, may allow for a more complete reaction to form the crystal lattice structure of the material (including, e.g., materials of Compound 1) and increased mobility of lithium ions as compared to lithium- titanium-phosphate materials (e.g., LiTi₂(P04)3).

[0036] Further, the use of aluminosilicates rather than separate aluminum and silicon compounds, e.g., alumina (A1₂0₃) and silica (Si0₂), may provide certain advantages. Again, without intending to be bound by theory, it is believed that electrolyte materials prepared from an aluminosilicate may exhibit higher ionic conductivity than electrolyte materials prepared from alumina and silica compounds. For example, aluminosilicates may have a lower melting point than alumina. Kaolin clays typically have melting points around 1750°C, which is lower than the melting point of A1₂0₃ (~2040°C). Therefore, under the same conditions, using an aluminosilicate such as a kaolinite (e.g., from a kaolin clay) may provide for a more complete reaction as compared to using A1₂0₃. Further, aluminosilicates may require less energy for reaction.

[0037] According to some examples of the present disclosure, the mixture used to prepare the material comprises a kaolin clay with low to trace amounts of alkali metals such as sodium and potassium. For example, the kaolin may comprise less than 3.0% by weight of K₂0, such as less than 2.5%, less than 2.0%, less than 1.5%, less than 1.25%, less than 1.0%, less than 0.75%, less than 0.50%, less than 0.25%, or less than 0.15%. Such kaolin clays may comprise from about 0.01% by weight to 3.0% by weight K₂0, such as from about 0.05% to about 2.0%) by weight, from about 0.1% to about 1.5%, or from about 0.1% to about 0.5% by weight. In at least one example, the kaolin does not comprise K₂0. Additionally, or alternatively, the kaolin may comprise less than 3.0% by weight of Na₂0, e.g., less than 2.5%, less than 2.0%, less than 1.5%, less than 1.0%, less than 0.75%, less than 0.66%, less than 0.50%), less than 0.33%>, less than 0.25%, or less than 0.1%> by weight. Such kaolin clays may comprise from about 0.01%> by weight to 3.0% by weight Na₂0, such as from about 0.05%) to about 2.0% by weight, from about 0.1% to about 1.5%, or from about 0.1% to about 0.5%) by weight. In at least one example, the kaolin does not comprise Na₂0. Without intending to be bound by theory, it is generally believed that certain metals (including, e.g., alkali metals such as potassium or sodium) may interfere with the mobility of lithium ions and reduce the conductivity of the material.

[0038] Kaolin clays used for preparation of the materials herein may comprise phosphorus (e.g., P2O5), iron (e.g., Fe₂0₃ and/or FeO), and/or titanium (e.g., T1O2). In some examples herein, the kaolin may comprise from about 0.01% to about 1.0% by weight P2O5, such as from about 0.1% to about 0.3% by weight, or less than 1.0% P2O5 by weight, such as less than 0.75%, less than 0.66%, less than 0.5%, less than 0.33%, less than 0.25%, or the kaolin may be free of P2O5. Additionally or alternatively, the kaolin may comprise from 0.01%) to about 1.0% by weight Fe₂0₃, such as from 0.1% to about 0.5% by weight, or less than 1.0% by weight, such as less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1% by weight. Further, for example, the kaolin may additionally or

alternatively comprise from about 0.01% to about 2.0% by weight T1O2, such as from about 0.5%) to about 1.5% by weight, or from about 1.5% to about 2.0% by weight, or less than 2.0%) by weight T1O2, such as less than 1.0% by weight. Further, for example, the kaolin may comprise less than 13% water by weight, such as less than 10%, less than 8%, less than 5%, less than 2%, less than 1%, or the kaolin may not comprise water. [0039] In some aspects of the present disclosure, the kaolin (or other aluminosilicate clay) may be subjected to one or more processes to reduce or enrich the concentration of certain components. Without intending to be bound by theory, it is generally believed that minimizing the amount of impurities (e.g., one or more components other than kaolinite) in the kaolin clay may improve the conductivity of the electrochemical material by minimizing the likelihood that the material will form multiple phases when synthesized. For example, a natural clay may undergo one or more beneficiation processes to remove select components of the clay, e.g., impurities in the kaolinite of a natural kaolin clay. In some examples, a natural kaolin clay may be treated to remove or reduce the amount of metals (e.g., one or more alkali metals, alkaline earth metals, and/or rare earth metals, etc.) and/or metalloids other than aluminum and silicon (e.g., iron, sodium, calcium, magnesium, and/or potassium), present in the clay. In additional or alternative examples, the kaolin clay may be treated with a bleaching agent.

[0040] The aluminosilicates may be characterized in terms of their particle size or particle size distribution. Particle sizes and other particle size properties referred to in the present disclosure may be measured by any appropriate measurement technique, such as, for example, a Sedi graph 5100 instrument, as supplied by Micromeritics Corporation, or a Microtrac Model X-100, as supplied by Leeds & Norththrup. Using such measuring devices, the size of a given particle is expressed in terms of the diameter of a sphere of equivalent diameter, sometimes referred to as equivalent spherical diameter or (ESD). The median particle size, or the dso value, is the diameter at which 50% by weight of the particles have an ESD less than the dso value. Similarly, the (d9₀) value is the diameter at which 90% by weight of the particles have an ESD less than the dw value, and the d₁₀ value is the diameter at which 10% by weight of the particles have an ESD less than the d₁₀ value. [0041] According to some aspects of the present disclosure, the aluminosilicate may have a median particle size (dso) of 10 μιη or less, such as ranging from about 1 μιη to about 8 μιη, from about 2 μιη to about 6 μιτι, or from about 3 μιη to about 5 μιη. Further, for example, the aluminosilicate may have a median particle size (dso) of less than 8 μιτι, such as ranging from about 0.5 μιη to 8 μιτι, or from about 0.5 μιη to about 5.0 μιτι, or less than 7.5 μιη, less than 5 μιτι, less than 2 μιτι, or less than 1 μιη. In some examples, the aluminosilicate compound has a dw less than 30 μιτι, such as ranging from about 5 μιη to 30 μιτι, or a dw less than 25 μιτι, less than 20 μιτι, less than 15 μιτι, less than 10 μιτι, less than 8 μιτι, less than 5 μιη, less than 2 μιτι, or less than 1 μιη.

[0042] Independently of any titanium and/or phosphorus that may be present in the aluminosilicate, the mixture may comprise one or more titanium compounds and/or one or more phosphorus/phosphate compounds. Suitable titanium compounds that may be useful for preparation of the materials disclosed herein include, but are not limited to, titanium oxide (T1O2) and titanium salts, such as titanium chloride (TiCb). Examples of phosphate compounds useful for the materials of the present disclosure, include, but are not limited to, monoammonium phosphate (also known as ammonium dihydrogen phosphate) (NH4H2PO4), lithium phosphate (L13PO4), and phosphoric acid (H2PO4). In some aspects of the present disclosure, the phosphate compound is not monoammonium phosphate (the mixture does not comprise monoammonium phosphate). Exemplary lithium compounds suitable for preparation of the materials herein may comprise lithium oxide (L12O) and lithium salts such as lithium carbonate (Li₂C0₃), lithium phosphate (L13PO4), lithium nitrate (L1NO3), or lithium chloride (LiCl).

[0043] According to some aspects of the present disclosure, the material may comprise gallium. Exemplary gallium compounds suitable for preparation of the materials herein include, but are not limited to, gallium(III) oxide (Ga2C"3) and gallium salts such as gallium chloride (GaCh) and gallium nitrate (Ga(N0₃)₃). Without intending to be bound by theory, it is generally believed that incorporating gallium into the crystal structure of the material (e.g., gallium doping) may provide several benefits. For example, Ga³⁺, with an ionic radius of 0.62 A, may replace elements having a smaller ionic radius, such as Ti⁴⁺ having an ionic radius of 0.605 A, at octahedral sites within the lattice crystal structure. The larger size of the Ga³⁺ ion may increase the channel size of the crystal structure available for lithium ion migration, e.g., resulting in increased conductivity. Further, substitution of Ga³⁺ for Ti⁴⁺ in some cases may improve the electrochemical stability of the material.

[0044] Exemplary properties that may be used to characterize or describe the materials herein include, but are not limited to, lattice parameters, ionic conductivity, and the activation energy associated with lithium conduction within the crystal structure.

[0045] The lattice parameters of the crystal unit cell (a, b, and c) as well as the total unit cell volume of the material may be determined using powder X-ray diffraction (XRD). The materials herein may have a rhombohedral crystal structure {a = b). In some examples, the material may have a lattice parameter a greater than 8.476 A, e.g., greater than 8.478 A, greater than 8.479 A, greater than 8.480 A, greater than 8.482 A, greater than 8.483 A, or greater than 8.484 A. For example, the material may have a lattice parameter a ranging from 8.476 A to 8.488 A, from 8.478 A to 8.486 A, or from 8.480 A to 8.484 A, e.g., a lattice parameter a of 8.476 A, 8.477 A, 8.478 A, 8.479 A, 8.480 A, 8.481 A, 8.482 A, 8.483 A, or 8.484 A. Additionally or alternatively, the material may have a lattice parameter c ranging from 20.72 A to 20.80 A, such as from 20.72 A to 20.78 A, or from 20.75 A to 20.77 A, e.g., a lattice parameter c of 20.74 A, 20.745 A, 20.75 A, 20.755 A, 20.76 A, 20.765 A, 20.77 A, 20.775 A, or 20.78 A.

[0046] Further, in some examples according to the present disclosure, the material may have a unit cell volume between about 1290 A³ and about 1295 A³, such as between about 1291 A³ and about 1293 A³, or between about 1293 A³ and about 1295 A³. For example, the unit cell volume of the material may be between 1291.25 A³ and 1294.00 A³, between 1291.50 A³ and 1292.50 A³, between 1293.00 A³ and 1294.80 A³, between 1293.50 A³ and 1294.50 A³, or between 1293.20 A³ and 1294.00 A³.

[0047] Ionic conductivity of the material may be measured by a suitable impedance analyzer, e.g., using an AC complex impedance technique. An exemplary instrument that may be used to measure ionic conductivity is the SP-300 potentiostat/galvanostat/frequency response analyzer by Bio-Logic. The ionic conductivity of the material may increase with increasing temperature.

[0048] According to some aspects of the present disclosure, the material may have an ionic conductivity of at least lxlO^"5 S/cm at a temperature of 21°C (e.g., room temperature), such as at least 1.25xl0^-5 S/cm, at least 2xl0^-5 S/cm, at least 2.5xl0^-5 S/cm, at least 2.75xl0^-5 S/cm, at least 3xl0^"5 S/cm, at least 3.5xl0^"5 S/cm, at least 3.75xl0^"5 S/cm, at least 4xl0^"5 S/cm, at least 4.5xl0^"5 S/cm, at least 5xl0^"5 S/cm, at least 5.5xl0^"5 S/cm, at least 6.5xl0^"5 S/cm, at least 7.5xl0^"5 S/cm, at least 7.7 xlO^"5 S/cm, or at least 8.0xl0^"5 S/cm at a temperature of 21°C. For example, the material may have an ionic conductivity ranging from lxlO^"5 S/cm to about lxlO^"4 S/cm, such as from about 2xl0^"5 S/cm to about 9.0xl0^"5 S/cm, from about 5xl0^"5 S/cm to about 8.5xl0^"5 S/cm, or from about 6xl0^"5 S/cm to about 8xl0^"5 S/cm.

[0049] Further, for example, the material may have an ionic conductivity of at least 8xl0^"5 S/cm at a temperature of 50°C, such as at least lxlO^"4 S/cm or at least 2xl0^"4 S/cm. According to some aspects of the present disclosure, the ionic conductivity of the material at 50°C may range from about lxlO^"4 S/cm to about 5xl0^"4 S/cm, or from about 2xl0^"4 S/cm to about 3xl0^"4 S/cm. In some examples, the ionic conductivity of the material at 75°C may be at least 2xl0^"4 S/cm, such as at least 2xl0^"4 S/cm, or an ionic conductivity ranging from about 2xl0^"4 S/cm to about 8xl0^"4 S/cm. Additionally or alternatively, the material may have an ionic conductivity at a temperature of 100°C of at least 8xl0^"4 S/cm or at least lxlO^"3 S/cm. For example, the material may have an ionic conductivity ranging from about 9xl0^"4 S/cm to about 5xl0^"3 S/cm or from about lxlO^"4 S/cm to about 3xl0^"3 S/cm at a temperature of 100°C.

[0050] Ionic conductivity may be used to determine additional electrochemical characteristics of the material. For example, the activation energy for lithium ion migration though the material, e.g., when used as an electrolyte material, may be calculated from Arrhenius plots of the ionic conductivities of the electrolyte material at different

temperatures. In some examples, the electrolyte material may have an activation energy ranging from 0.30 eV to 0.50 eV. For example, the electrolyte material may have an activation energy ranging from 0.32 eV to 48 eV, from 0.34 eV to 0.46 eV, from 0.36 eV to 0.44 eV, or from 0.38 eV to 0.42 eV.

[0051] As mentioned above, according to some aspects of the present disclosure, the material may be prepared from a mixture of suitable compounds, e.g., in desired molar ratios. For example, the method of preparing the material may comprise combining an

aluminosilicate compound (such as, e.g., an aluminosilicate clay such as kaolin) with one or more of a lithium compound, a gallium compound, a titanium compound, and/or a phosphate compound to form a mixture; and then heating the mixture as a sufficient temperature to form the material. Heating of the mixture may be carried out in one heating step, e.g., at a single temperature for a period of time, or in multiple heating steps, e.g., each step performed at a different temperature than previous or subsequent steps. For example, heating the mixture may be carried out at a first temperature, and then at a second temperature higher than the first temperature. In some examples, heating the mixture may further include heating the mixture at a third temperature higher than the second temperature. The temperature of each step may range from about 150°C to aboutl200°C, and the duration of each step may range from about 30 minutes to 24 hours or more, depending on the composition of the mixture, for example, and/or the sequence of steps (if the method includes multiple heating steps).

[0052] In at least one example, the mixture may comprise a phosphate compound such as monoammonium phosphate, wherein heating the mixture may be carried out at a first temperature at which the phosphate decomposes without decomposition of one or more other components of the mixture, such as a lithium compound, e.g., L12CO3. In such examples, the mixture then may be heated at a second temperature higher than the first temperature. In some aspects, the first temperature may range from about 150°C to about 200°C, such as from about 160°C to about 190°C, or from about 170°C to about 180°C, and the second temperature may range from about 1000°C to about 1200°C, such as from about 1050°C to about 1150°C, or from about 1075°C to about 1125°C. In some examples, the mixture is heated at the first temperature for a period of time ranging from about 30 minutes to about 5 hours, such as from about 2 hours to about 4 hours. Further, in some examples, the mixture is heated at the second temperature for a period of time ranging from about 15 hours to about 30 hours; e.g. from about 17 hours to about 25 hours; or from about 18 to about 21 hours.

[0053] In some aspects of the disclosure, the mixture may be heated in three stages or steps. For example, the mixture may be heated at a first temperature, then at a second temperature higher than the first temperature, and then at a third temperature higher than the second temperature. For example, the mixture may be heated at a first temperature ranging from about 150°C to about 200°C, then heated at a second temperature ranging from about 600°C to about 800°C, and then heated at a third temperature ranging from about 1000°C to about 1200°C. In some aspects, the mixture is heated at the first temperature for a period of time ranging from about 30 minutes to about 5 hours, such as from about 2 hours to about 4 hours. Further, in some aspects, the mixture is heated at the second temperature for a period of time ranging from about 30 minutes to about 6 hours, such as from about 1 hour to about 5 hours, or from about 2 hours to about 4 hours. In additional or alternative aspects, the mixture is heated at a third temperature for a period of time ranging from about 15 hours to about 30 hours; e.g. from about 17 hours to about 25 hours; or from about 18 to about 21 hours.

[0054] The materials, e.g., electrolyte materials, herein may be useful in a variety of applications. For example, the electrolyte materials may be used in batteries, e.g., solid-state batteries or ceramic batteries, and other electrochemical applications, including, but not limited to, supercapacitors, coin cells, pouch cells, and thin film batteries. Such thin-film batteries may have a total electrolyte thickness of about 1 μπι or less, for example. Thin-film batteries incorporating the materials may be formed by RF magnetron sputter deposition of the material on a substrate, for example, or other suitable methods for thin-film deposition.

[0055] Exemplary batteries may comprise an anode, a cathode, and the electrolyte material (which can be an electrochemical material of solid electrolyte) to separate the anode and cathode. In some examples, the anode may comprise lithium (e.g., lithium metal and/or a composite lithium materials such as Li₂Ti03 or Li₄Ti₅0₁₂ or the composite of Li₂Ti0₃ and Li₄Ti₅0₁₂), graphite, silicon, or a combination thereof. In at least one example, the anode may comprise Li₂Ti0₃, Li₄Ti₅0₁₂ or the composite of Li₂Ti0₃ and Li₄Ti₅0₁₂. In at least one example, the anode may comprise graphite and silicon. Additionally or alternatively, the cathode may comprise lithium compounds, such as lithium iron phosphate or a lithium-cobalt compound such as lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or a combination thereof.

[0056] Further, the materials herein may be useful in a composite electrolyte. For example, compositions according to the present disclosure may comprise the electrochemical material and at least one other solid electrolyte and/or at least one liquid and/or gel electrolyte to form a composite electrolyte. The materials disclosed herein (e.g., prepared from an aluminosilicate material) may provide benefits to the composite electrolyte, such as increased thermal stability and/or reduced leakage, as compared to a battery of similar composition without the material. In some examples, the composite electrolyte may comprise a liquid, a gel, at least one other solid, or a combination thereof.

[0057] Exemplary solids useful for the composite electrolyte in combination with the materials herein include, but are not limited to, ceramics, polymers, and glass. In at least one example, the materials herein may be used in combination with a polymer, e.g., the material serving as a filler in a polymer electrolyte. Such composite polymer electrolytes may have higher conductivity, greater mechanical strength, and/or higher thermal stability as compared to the polymer without the material disclosed herein.

[0058] Exemplary liquid electrolytes suitable for the composite electrolyte in combination with the materials herein include, but are not limited to, ionic liquids. For example, the ionic liquid may comprise a lithium salt, for example lithium

bis(trifluoromethane sulfonylimide). In some examples, the ionic liquid may comprise N- butyl-N-ethyl pyrrolidinium bis(trifluorom ethyl sulfonylimide), ethylmethylimidazolium bis(trifluoromethylsulfonylimide), N-m ethyl -N-propyl pyrrolidinium

bis(trifluoromethylsulfonylimide), N-m ethyl -N-propyl piperidinium

bis(trifluoromethylsulfonylimide), or a combination thereof.

[0059] Other aspects and embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the

embodiments disclosed herein.

EXAMPLES

[0060] The following examples are intended to illustrate the present disclosure without, however, being limiting in nature. It is understood that the present disclosure encompasses additional aspects and embodiments consistent with the foregoing description and following examples. [0061] Example 1

[0062] Studies were performed to prepare, characterize, and test the performance of various materials (Samples 1-17) for suitability as electrolytes, the materials having the chemical formula Lii+2_X+_y Al_xGa_yTi2-x-ySi_xP3-xOi2 (Compound 1) with values of x ranging from 0 to 0.3 and y values ranging from 0 to 0.4. The values of x and y and the corresponding chemical composition of each material are listed in Table 1.

Table 1

[0063] The following compounds were used in appropriate molar ratios to prepare Samples 1-17: [0064] Sample 1 : Lithium carbonate (Li₂C0₃) (Alfa Aesar, ACS, 99.0% min), titanium dioxide (Ti0₂) (ACROS, 98+%), and monoammonium phosphate ( H₄H₂P0₄) (ACROS, 99.9%).

[0065] Samples 2-16: Lithium carbonate (Li₂C0₃) (Alfa Aesar, ACS, 99.0% min), titanium dioxide (Ti0₂) (ACROS, 98+%), monoammonium phosphate ( H₄H₂P0₄) (ACROS, 99.9%), gallium(III) oxide (Ga₂0₃) (ACROS, 99.99+%), and kaolin (Imerys). The chemical composition of the kaolin was determined using a Thermo ARL ADVANT'XP XRF (X-Ray fluorescence) Spectrometer equipped with about a 60 kV rhodium target X-ray source . The XRF data of the kaolin used in Examples 2-16 is reported in Table 2.

Table 2. Chemical composition of kaolin (wt%)

[0066] Sample 17: Lithium carbonate (Li₂C0₃) (Alfa Aesar, ACS, 99.0% min), titanium dioxide (Ti0₂) (ACROS, 98+%), monoammonium phosphate ( H₄H₂P04) (ACROS, 99.9%), aluminum oxide (Al₂0₃)(Sigma-Aldrich, 99.6%), and silicon dioxide (Si0₂)(Alfa Aesar, 99.5%).

[0067] General preparation of the Example electrolyte materials: The x and y values of each Sample were used to determine the stoichiometric amounts of each reactant material necessary to synthesize an electrolyte material according to the chemical reaction of Equation 1.

(1+2+y) x y

[ ]Li₂C0₃+(₇)Al₄[Si₄O_in](OH ₈+(2-x-y)Ti0₂+ Ga₂0₃+(3-x) H₄H PO =

Li_1+2x+yAl_xGa_yTi₂._x._ySi_xP_3.xO_i2+[^f^ ]C0₂+(3-x) H +[^]H O Equation 1

[0068] Samples 1-17 were prepared by combining the appropriate molar ratios of the reactants in an agate mortar and mixing the reactant materials for about 5 minutes to form a well-distributed mixture. Each mixture was then heated in a platinum crucible at a temperature of 170°C for 4 hours, then heated at a temperature of 700°C for 4 hours, and then heated at a temperature of 1100°C for 20 hours to form an electrolyte material. After heating, each Sample material was milled in a SPEX^® 8000M Mixer/Mill^® High-Energy Ball Mill for 30 minutes, producing a median particle size (dso) of approximately 9 μιη as measured by Microtrac. The median particle size (dso) for each sample is shown in Table 3. Samples 1-16 had an average d₁₀ of 0.72 μιτι, an average dso of 9.31 μιτι, and an average dw of 57.64 μιη.

Table 3

[0069] Evaluation of Samples: After preparation, each material was evaluated by powder X-ray diffraction (XRD) to determine crystal structure and ionic conductivity was measured at different temperatures. The XRD measurements were carried out using a Philips X'Pert XRG-3100 diffractometer equipped with Cu K-a radiation using an accelerating voltage of 30 kV and a current of 20 mA. Data was collected in the 2Θ range of 10° to 70° with a 2Θ step size of 0.02° and a counting time of 60 s/step. The XRD patterns were indexed and the cell constants were refined by the program HighScore Plus.

[0070] Ionic conductivities were measured by an AC complex impedance technique using a BioLogic SP-300 frequency analyzer with an electrochemical interface at frequencies from 1 Hz to 7 MHz. In preparation for ionic conductivity measurement, each Sample was finely ground and cold pressed into a pellet. Then each pellet was sintered at 900°C for 10 hours. After sintering, gold contacts were deposited onto the faces of the pellets by sputtering. Next, the gold coated pellets were dried by heating the pellets in an oven at a temperature of 120°C oven and then storing the pellets in a vacuum desiccator. After drying, each pellet was sandwiched between platinum disks and pressed between Inconel flanges with two ceramic disks on top of the platinum disks to create a sample assembly. Each sample assembly was then placed in a sealed Thermolyne 21100 tube furnace with a thermocouple inserted in the tube furnace near the sample assembly. High purity argon was circulated through the furnace chamber and each sample assembly was heated from room temperature (21°C) to 100°C. Impedance measurements were taken at 21°C, 50°C, 75°C, and 100°C and used to determine ionic conductivity. Impedance measurements were also used to calculate the activation energy for lithium conduction using the Arrhenius equation.

[0071] Impact of aluminosilicate (Samples 2, 7, 12): Fig. 1 shows the XRD pattern of Sample 1 (LiTi₂(P04)₃) as well as the XRD pattern calculated for LiTi₂(P04)₃, and the XRD patterns of Samples 2, 7 and 12, prepared from kaolin. In Fig. 1, the diffraction peaks for the second crystal phase LiTiPOs are indicated by "*". As seen in Fig. 1, Sample 1, prepared without an aluminosilicate, is very similar to the reference LiTi₂(P04)₃ XRD pattern {Natl. Bur. Stand. (U.S.) Monogr. 25, 21, 79, 1984) with a rhombohedral R3c structure. For Samples 2, 7, and 12, Fig. 1 indicates a second phase of LiTiPOs starts to form as the amount of kaolin used to prepare the materials increases. For example, the XRD pattern of Sample 2 shows no indication of a second phase. But, for Samples 7 and 12, which contain greater amounts of aluminum and silicon, the XRD patterns begin to show the development of a second crystal phase of LiTiPOs.

[0072] Figs. 2A-2C show the unit cell parameters for the crystal structures of Samples 1, 2, and 7, wherein Fig. 2 A shows parameter a, Fig. 2B shows parameter c, and Fig. 2C shows the unit cell volume V. The results of Fig. 2A-2C demonstrate that the unit cell parameters of the materials decrease with increasing amounts of aluminum and silicon. This decrease of the unit cell parameters may indicate that octahedral site substitution within a NASICON-type structure has a greater impact than rhomboidal site substitution on unit cell dimensions.

[0073] Fig. 3 shows ionic conductivity isotherms for Samples 1, 2, 7 and 12. and Fig. 4 shows the corresponding Arrhenius plots (Sample 17 was prepared from silica and alumina compounds as opposed to kaolin). Table 4 lists the ionic conductivity measurements depicted in Fig. 3 and the activation energy as calculated from the Arrhenius plots.

Table 4

[0074] These results indicate that the NASICON-type materials prepared from aluminosilicates exhibited increased lithium ionic conductivity and lower activation energy as compared to Sample 1 (LiTi₂(P04)3). For example, Sample 2 exhibited superior conductivity at every temperature tested, and Samples 2 and 7 had lower calculated activation energy than Sample 1. Sample 2 also exhibited higher ionic conductivity and lower activation energy than Example 17, prepared from silica and alumina rather than kaolin. Accordingly, the results also indicate that electrolyte materials prepared from an aluminosilicate compound may have greater conductivity and lower activation energy as compared to similar materials prepared from individual AI2O3 and Si0₂.

[0075] Impact of aluminosilicate and gallium (Samples 3-6): Fig. 5 shows powder XRD patterns of Samples 2-6. The XRD patterns of Fig. 5 indicate a possible second crystal phase of LiTiPOs and third crystal phase GaPC"4 2H₂0 form with increased amounts of gallium in the NASICON-type structure. Diffraction peaks for second crystal phase LiTiPOs and third crystal phase GaPC"4 2H₂0 are indicated in Fig. 5 by "*" and "+", respectively.

[0076] Figures 6A-6C show the unit cell parameters and cell volumes for Samples 2-5 and 7-10. Figs. 6A, 6B, and 6C show the unit cell parameters a and c, and the unit cell volume for each example respectively. Figs. 6A and 6C show an increase in unit cell parameter a and cell volume corresponding with increased gallium in the crystal structure.

[0077] Table 5 lists the ionic conductivities for Samples 1-6 at various temperatures and the activation energy calculated for each Sample.

Table 5

[0078] The results in Table 5 show that ionic conductivity decreases initially with the inclusion of gallium in the crystal structure, see Samples 3 and 4. However, ionic conductivity increased significantly for Sample 5 (Li1.5Alo.1Gao.3Ti1.6Sio.1P2.9O12) before decreasing. Sample 5 exhibited the highest ionic conductivity at 50°C (2.9x10^"4 S/cm) and at 75°C (9.3xl0^"4 S/cm). Sample 5 also exhibited the highest overall conductivity of 2.4xl0^"3 S/cm at 100°C. Fig. 7 shows the ionic conductivity isotherms for Samples 2-6 as described in Table 5.

[0079] Fig. 8 displays the Arrhenius plots of ionic conductivity of Samples 2-6 used to calculate the activation energies listed in Table 5. Table 6 lists the ionic conductivities measured at 21°C for Samples 7-11.

Table 6

[0080] Table 7 lists the ionic conductivities measured at 21°C for Samples 12-16.

Table 7

[0081] It is intended that the specification and examples therein be considered as exemplary only, with a true scope and spirit of the present disclosure being indicated by the following claims.

Claims

CLAIMS What is claimed is:

1. A method of forming an electrochemical material, the method comprising:

combining an aluminosilicate with a lithium compound, a gallium compound, a titanium compound, and a phosphate compound to form a mixture; and

heating the mixture to form the electrochemical material.

2. The method according to claim 1, wherein the mixture has at least one of the

following:

a molar ratio of gallium to silicon ranging from 0.25 to 4.0;

a molar ratio of gallium to aluminum ranging from 0.25 to 4.0;

a molar ratio of gallium to titanium ranging from 0.06 to 0.60;

a molar ratio of silicon to phosphorus ranging from 0.03 to 0.11;

a molar ratio of the total of gallium and aluminum to titanium ranging from 0.11 to

1.0; or

a molar ratio of the total of gallium, aluminum and silicon to the total of titanium and phosphorus ranging from 0.06 to 0.25.

3. The method according to claim 1 or 2, wherein the mixture has a molar ratio of lithium to silicon or a molar ratio of lithium to aluminum ranging from 4 to 20, a molar ratio of lithium to gallium ranging from 4 to 20, a molar ratio of lithium to titanium ranging from 0.5 to 2, and a molar ratio of lithium to phosphorus ranging from 0.4 to 0.8.

4. The method according to any of claims 1-3, wherein the aluminosilicate comprises a clay or a zeolite, the aluminosilicate has a molar ratio of aluminum to silicon of ranging from 0.8 to 1.2, or the aluminosilicate comprises a clay or a zeolite having a molar ratio of aluminum to silicon of ranging from 0.8 to 1.2.

5. The method according to any of claims 1-4, wherein the aluminosilicate comprises kaolin.

6. The method according to claim 5, wherein the kaolin comprises less than 1% by weight of K₂0 and less than 1% by weight of Na₂0.

7. The method according to any of claims 1-6, wherein the gallium compound comprises gallium oxide or a gallium salt, and the titanium compound comprises titanium oxide or a titanium salt.

8. The method according to any of claims 1-7, wherein the phosphate compound

comprises monoammonium phosphate.

9. The method according to any of claims 1-8, wherein heating the mixture is carried out at a first temperature that decomposes the phosphate compound without

decomposition of the lithium compound, and then at a second temperature higher than the first temperature;

optionally wherein the first temperature ranges from about 150°C to about 200°C, and the second temperature ranges from about 1000°C to about 1200°C.

10. The method according to any of claims 1-7, wherein the phosphate compound is not monoammonium phosphate, optionally wherein the heating is carried out at a temperature ranging from about 1000°C to about 1200°C.

11. The method according to any of claims 1-10, wherein the aluminosilicate has a

particle size distribution with a median particle size (dso) less than 10 μπι.

12. The method according to any of claims 1-11, wherein the aluminosilicate has a

particle size distribution with a 690 diameter less than 30 μπι.

13. The method according to any of claims 1-12, wherein the electrochemical material is solid electrolyte and has an ionic conductivity of at least lxlO^"5 S/cm at a temperature of 21°C.

14. The method according to any of claims 1-13, wherein the electrochemical material has a chemical formula Lii+2x+yAlxGa_yTi2-x-ySixP3-xOi2, wherein 0 < x < 0.4 and 0 < y < 0.4.

15. The method according to any of claims 1-14, wherein the electrochemical material has a lattice parameter a greater than 8.478 A.

16. A method of forming an electrochemical material, the method comprising:

combining kaolin with a lithium salt, titanium oxide, and a phosphate compound to form a mixture, wherein the kaolin comprises less than 1% by weight of K₂0 and Na₂0 combined; and

heating the mixture to form the electrochemical material;

wherein the electrochemical material has an ionic conductivity of at least 5xl0^"5 S/cm at a temperature of 21°C.

17. The method according to claim 16, wherein the mixture further comprises gallium oxide.

18. The method according to claim 17, wherein the lithium salt is lithium carbonate, the gallium oxide is gallium(III) oxide, and the phosphate compound is monoammonium phosphate.

19. The method according to any of claims 16-18, wherein the mixture is heated at a first temperature ranging from about 150°C to about 200°C, then heated at a second temperature ranging from about 600°C to about 800°C, and then heated at a third temperature ranging from about 1000°C to about 1200°C.

20. An electrochemical material comprising a compound of formula

Lii+2x+yAlxGayTi₂-x-ySixP3-xOi2,

wherein 0 < x < 0.4 and 0 < y < 0.4.

21. The electrochemical material of claim 20, wherein the electrochemical material has an ionic conductivity of at least lxlO^"5 S/cm at a temperature of 21°C.

22. The electrochemical material of claim 20 or 21, where the electrochemical material has a lattice parameter a greater than 8.478 A.

23. A composition comprising the electrochemical material of any of claims 20-22 or the electrochemical material prepared according to the method of any of claims 1-19.

24. A battery comprising the electrochemical material prepared according to the method of any of claims 1-19.

25. The battery according to claim 24, wherein the battery is a coin cell, a pouch cell, a cylindrical cell, a prismatic cell, a lithium air battery, or a thin-film battery.

26. A battery comprising at least one of:

an anode;

a cathode; and

the electrochemical material of solid electrolyte according to any of claims 20-22 to separate the anode and cathode.

The battery according to claim 26, wherein the anode comprises lithium, graphite, silicon, or a combination thereof, and wherein the cathode comprises lithium compounds, or vanadium oxide.

28. The battery according to claim 26 or 27, wherein the anode comprises Li₂Ti03 or Li₄Ti₅0₁₂ or the composite of Li₂Ti0₃ and Li₄Ti₅0₁₂

The battery according to any of claims 26-28, wherein the cathode comprises lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, vanadium oxide or a combination thereof.

30. A composite electrolyte comprising at least one of a liquid, a solid, or a gel and the electrochemical material of any of claims 20-22. The composite electrolyte according to claim 30, wherein the composite electrolyte comprises an ionic liquid.

A thin-film electrolyte system comprising the electrochemical material of any of claims 20-22.