INORGANIC SOLID ELECTROLYTES AND EFFICIENT METHODS FOR MAKING THE SAME

Abstract

In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to inorganic solid electrolytes and synthesis of inorganic solid electrolytes. The electrolytes have the general formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, exhibit superionic conductivity, and can be produced via a relatively fast synthesis route. The electrolytes can be a component of different types of batteries.

Claims

1. A compound having the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, wherein A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7.

2. The compound of claim 1, wherein A is Li or Na.

3. The compound of claim 1, wherein z is about 1.0 to about 2.0.

4. The compound of claim 1, wherein N is Ta.

5. The compound of claim 1, wherein v is about 1.00 to about 1.50.

6. The compound of claim 1, wherein y is from about 0.01 to about 0.99.

7. The compound of claim 1, wherein X is Cl or Br.

8. The compound of claim 1, wherein the compound is Li.sub.2TaS.sub.1-yO.sub.yCl.sub.5.

9. The compound of claim 8, wherein y is from about 0.10 to about 0.99.

10. The compound of claim 1, wherein the compound is Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5, Li.sub.2TaS.sub.0.4O.sub.0.6Cl.sub.5, or Li.sub.2TaS.sub.0.7O.sub.0.3Cl.sub.5.

11. The compound of claim 1, wherein the compound has an ionic conductivity of at least about 1.00 mS/cm to about 10.00 mS/cm.

12. The compound of claim 1, wherein the compound has an electronic conductivity of about 1.0010.sup.8 S/cm to about 1.0010.sup.10 S/cm.

13. The compound of claim 1, wherein the compound exhibits superionic conductivity over a temperature range of about 0 C. to about 80 C.

14. The compound of claim 1, wherein the compound has an activation energy for ion transport of from about 0.1 eV to about 0.5 eV.

15. A method for making a compound having the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, wherein A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; 1 z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7; the method comprising: (a) combining in the solid state the following components: (i) A.sub.2S, selected from the group consisting of Li.sub.2S, Na.sub.2S, K.sub.2S, and any combination thereof; (ii) A.sub.2O, selected from the group consisting of Li.sub.2O, Na.sub.2O, K.sub.2O, and any combination thereof; and (iii) NX.sub.5, selected from the group consisting of TaCl.sub.5, TaBr.sub.5, Tal.sub.5, NbCl.sub.5, NbBr.sub.5, Nbl.sub.5, and any combination thereof, to produce a precursor mixture; and (b) mixing the precursor mixture by mechanochemical milling.

16. The method of claim 15, wherein precursor mixture is mixed by mechanochemical milling for about 1 hour to about 4 hours, wherein the components are substantially anhydrous and mixed in an inert atmosphere.

17. The method of claim 15, wherein the components are combined in stoichiometric amounts.

18. A compound produced by the method of claim 15.

19. A battery comprising the compound of claim 1.

20. A sensor for ion detection, comprising the compound of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Many aspects of the present disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.

[0006] FIG. 1A shows a representative Nyquist plot and corresponding equivalent circuit fitting of Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 (LTSOC) and Li.sub.2TaSCl.sub.5 (LTSC) at 25 C.

[0007] FIG. 1B shows a representative Nyquist plot and corresponding equivalent circuit fitting of LTSOC at 20 C.

[0008] FIG. 1C shows variable-temperature Nyquist plots obtained for LTSOC.

[0009] FIG. 1D shows an Arrhenius-type plot of LTSOC.

[0010] FIG. 2A shows results of DC-Polarization on a symmetric SS|LTSOC|SS cell (SS: stainless steel) for determination of .sub.el.

[0011] FIG. 2B shows the respective I-V curves of the LTSOC under different DC voltages with the linear fit. The electric resistances were calculated based on Ohm's law. Taking the sample's geometric dimensions into account, the conductivity values were calculated.

[0012] FIG. 3 shows lab X-ray diffraction of highly disordered Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 and Li.sub.2TaSCl.sub.5.

[0013] FIGS. 4A-4B show the average and local structural data for Li.sub.2TaA.sub.1-xOxCl.sub.5 series. (a) Powder XRD patterns (b) .sup.6Li MAS NMR for Li.sub.2TaSCl.sub.5 and Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5.

[0014] FIGS. 5A-5F show Raman Spectra of LTSOC compared with related structure and local structural illustration.

[0015] FIG. 6 shows scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) mapping of as milled Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5.

[0016] FIGS. 7A-7B show lithium-ion dynamics of the Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 series from .sup.7Li NMR spin-lattice relaxation (T.sub.1) measurements showing (a) RT T.sub.1 changes with increasing oxygen content in Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 (b) VT T1 plots.

[0017] FIGS. 8A-8B show the electrochemical properties of Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 Arrhenius plots of the Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 series measured from 20 C. to 60 C. (A Comparison of the ionic conductivities and activation energies trend in the Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 series (B).

[0018] FIGS. 9A-9B show all-solid-state battery cycling performance of Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 (a) Rate capability plots (b) Voltage-capacity profiles showing the charge-discharge curves at 0.05, 0.1, 0.2, 0.5 and 1C.

[0019] Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

DETAILED DESCRIPTION

[0020] Many modifications and other embodiments disclosed herein will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. The skilled artisan will recognize many variants and adaptations of the aspects described herein. These variants and adaptations are intended to be included in the teachings of this disclosure and to be encompassed by the claims herein.

[0021] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0022] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure.

[0023] Any recited method can be carried out in the order of events recited or in any other order that is logically possible. That is, unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0024] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.

[0025] While aspects of the present disclosure can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present disclosure can be described and claimed in any statutory class.

[0026] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0027] Prior to describing the various aspects of the present disclosure, the following definitions are provided and should be used unless otherwise indicated. Additional terms may be defined elsewhere in the present disclosure.

Definitions

[0028] As used herein, comprising is to be interpreted as specifying the presence of the stated features, integers, steps, or components as referred to, but does not preclude the presence or addition of one or more features, integers, steps, or components, or groups thereof. Moreover, each of the terms by, comprising, comprises, comprised of, including, includes, included, involving, involves, involved, and such as are used in their open, non-limiting sense and may be used interchangeably. Further, the term comprising is intended to include examples and aspects encompassed by the terms consisting essentially of and consisting of. Similarly, the term consisting essentially of is intended to include examples encompassed by the term consisting of.

[0029] As used in the specification and the appended claims, the singular forms a, an and the include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an excipient include, but are not limited to, mixtures or combinations of two or more such excipients, and the like.

[0030] It should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as about that particular value in addition to the value itself. For example, if the value 10 is disclosed, then about 10 is also disclosed. Ranges can be expressed herein as from about one particular value, and/or to about another particular value. Similarly, when values are expressed as approximations, by use of the antecedent about, it will be understood that the particular value forms a further aspect. For example, if the value about 10 is disclosed, then 10 is also disclosed.

[0031] When a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase x to y includes the range from x to y as well as the range greater than x and less than y. The range can also be expressed as an upper limit, e.g. about x, y, z, or less and should be interpreted to include the specific ranges of about x, about y, and about z as well as the ranges of less than x, less than y, and less than z. Likewise, the phrase about x, y, z, or greater should be interpreted to include the specific ranges of about x, about y, and about z as well as the ranges of greater than x, greater than y, and greater than z. In addition, the phrase about x to y, where x and y are numerical values, includes about x to about y.

[0032] It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of about 0.1% to 5% should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range. Thus, for example, if a component is in an amount of about 1%, 2%, 3%, 4%, or 5%, where any value can be a lower and upper endpoint of a range, then any range is contemplated between 1% and 5% (e.g., 1% to 3%, 2% to 4%, etc.).

[0033] As used herein, the terms about, approximate, at or about, and substantially mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined. In such cases, it is generally understood, as used herein, that about and at or about mean the nominal value indicated +10% variation unless otherwise indicated or inferred. In general, an amount, size, formulation, parameter or other quantity or characteristic is about, approximate, or at or about whether or not expressly stated to be such. It is understood that where about, approximate, or at or about is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0034] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0035] Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.

[0036] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

[0037] As used herein, the terms optional or optionally means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0038] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e. one atmosphere).

Inorganic Solid Electrolytes and Methods of Making and Using the Same

[0039] The present disclosure provides for inorganic solid electrolytes and the method of making and using inorganic solid electrolytes. The electrolytes have the general formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, and exhibit superionic properties, even at low temperatures. With high ionic conductivity at low temperatures, the electrolytes have the potential to provide steady performance for electronic devices, such as electric vehicles, in cold environments. The electrolytes can be a component of different types of batteries, such as solid-state batteries. A relatively simple and fast synthesis route makes the production of the electrolytes efficient and feasible for scale-up.

[0040] In one aspect, the electrolytes or compounds disclosed herein have the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, where A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7. In another aspect, the electrolytes or compounds can also have the formula Li.sub.2TaS.sub.1-yO.sub.yCl.sub.5. In another aspect, z can be from 0.01 to about 2.0, or about 0.01, 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 2.0, where any value can be a lower and upper endpoint of a range (e.g., 1.0 to 2.0). In another aspect, v can be from about 0.01 to about 1.5, or about 0.01, 0.05, 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, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 1.2). For any formula of electrolyte or compound disclosed herein, y can be from about 0.01 to about 0.99, or about 0.01, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 0.99, where any value can be a lower and upper endpoint of a range (e.g., 0.10 to 0.90). In a further aspect, the electrolyte or compound is Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5, Li.sub.2TaS.sub.0.4O.sub.0.6Cl.sub.5, or Li.sub.2TaS.sub.0.7O.sub.0.3Cl.sub.5.

[0041] The electrolytes disclosed herein have several desirable properties. In one aspect, the electrolytes can have good ionic conductivity. The electrolytes can have an ionic conductivity of at least about 1.00 mS/cm, at least about 2.00 mS/cm, at least about 2.50 mS/cm, at least about 3.00 mS/cm, or at least about 3.50 mS/cm. In another aspect, the ionic conductivity of the electrolytes can be from about 1.00 mS/cm to about 10.00 mS/cm, or about 1.00 mS/cm, 2.00 mS/cm, 3.00 mS/cm, 4.00 mS/cm, 5.00 mS/cm, 6.00 mS/cm, 7.00 mS/cm, 8.00 mS/cm, 9.00 mS/cm, or 10.00 mS/cm, where any value can be a lower and upper endpoint of a range (e.g., 2.00 mS/cm to 5.00 mS/cm). In a further aspect, the electrolytes ionic conductivity can be measured at about room temperature, about 18 C. to about 24 C., or about 20 C. to about 22 C. The electrolytes can be characterized as having superionic conductivity, which refers to ionic conductivity values that are greater than 1 mS/cm. In one aspect, the electrolytes remain conductive over a temperature range of about 0 C. to about 100 C., or about 0 C., 10 C., 20 C., 30 C., 40 C., 50 C., 60 C., 70 C., 80 C., 90 C., or 100 C., where any value can be a lower and upper endpoint of a range (e.g., 0 C. to 80 C.). In another aspect, the electrolytes exhibit superionic conductivity over the same temperature ranges. Exemplary methods for determining ionic conductivity are provided in the Examples.

[0042] In one aspect, the electrolytes disclosed herein can have low electronic conductivities. In one aspect, the electrolytes disclosed herein can have an electronic conductivity of less than about 1.00108 S/cm, less than about 5.0010.sup.9 S/cm, or less than about 2.0010.sup.9 S/cm. In another aspect, the electrolytes can have an electronic conductivity of from about 1.0010.sup.7 S/cm to about 1.0010.sup.10 S/cm, or about 1.0010.sup.7 S/cm, 5.0010.sup.8 S/cm, 1.0010.sup.8 S/cm, 5.0010.sup.9 S/cm, 1.0010.sup.9 S/cm, 5.0010.sup.10 S/cm, or 1.0010.sup.10 S/cm, where any value can be a lower and upper endpoint of a range (e.g., 1.0010.sup.8 S/cm to 1.0010.sup.10 S/cm). Exemplary methods for determining electronic conductivity are provided in the Examples.

[0043] In another aspect, the electrolytes disclosed herein can have relatively low activation energy barriers to ion transport. In one aspect, the electrolytes can have an activation energy of from about 0.1 eV to about 0.5 eV, or about 0.1 eV, 0.2 eV, 0.3 eV, 0.4 eV, or 0.5 eV, where any value can be a lower and upper endpoint of a range (e.g., 0.2 eV to 0.3 eV).

[0044] In one aspect, the electrolytes or compounds disclosed herein are disordered with a glassy or amorphous structure.

[0045] Additionally, the electrolytes described herein possess unique solid-state NMR spectra. In one aspect, the Li-containing electrolytes can have peaks at about 1.1 ppm, 0.68 ppm, and 2.8 ppm, and 1.1 ppm, and 2.8 ppm as determined by .sup.6Li solid-state NMR spectroscopy. Exemplary methods for performing NMR measurements are provided in the Examples.

[0046] Also disclosed is a method for making sulfide electrolytes having the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, where A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7. The method includes combining a plurality of precursor compounds, such as salts, in various amounts in the solid state and mixing them together by mechanochemical milling. In one aspect, the precursor compounds are mixed together in stoichiometric amounts. The precursor compounds mixed together can include A.sub.2S, A.sub.2O, NX.sub.5, and any combination thereof, to produce a precursor mixture. In a further aspect, the precursor compounds mixed together can include A.sub.2S, selected from the group consisting of Li.sub.2S, Na.sub.2S, K.sub.2S, and any combination thereof; A.sub.2O, selected from the group consisting of Li.sub.2O, Na.sub.2O, K.sub.2O, and any combination thereof; and NX.sub.5, selected from the group consisting of TaCl.sub.5, TaBr.sub.5, Tal.sub.5, NbCl.sub.5, NbBr.sub.5, Nbl.sub.5, and any combination thereof. The components of the precursor mixture can be hand-ground before mechanochemical milling to form a homogenous precursor mixture. In another aspect, forming the precursor mixture and/or forming the homogenous precursor mixture can be performed in an inert atmosphere, such as an argon or nitrogen atmosphere, with an O.sub.2 content of less than 20 ppm, less than 10 ppm, less than 1 ppm, less than 0.5 ppm, or less than 0.1 ppm.

[0047] The precursor compounds used to produce the electrolytes described herein are generally highly pure materials. In one aspect, each of the precursor compounds has a purity of greater than 99%, greater than 99.5%, or greater than 99.9%. In one aspect, each precursor compound used to produce the electrolytes are substantially anhydrous, where each precursor compound is at least 95% moisture free, at least 98% moisture free, at least 99% moisture free, at least 99.9% moisture free, or 100% moisture free. In another aspect, each precursor compound has less than 0.5 ppm water, less than 0.25 ppm water, or less than 0.1 ppm water.

[0048] The precursor compounds can be mixed by mechanochemical milling. Mixing of the precursor compounds can occur in a mixing jar or container using one or more balls to produce a complex motion that combines back-and-forth swings with short lateral movements. In one aspect, the precursor compounds are mixed with one another for less than seven hours, less than 5 hours, or less than 3 hours. In another aspect, the compounds are mixed from about 1 hour to about 5 hours or about 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, where any value can be a lower and upper endpoint of a range (e.g., 1 hour to 4 hours). In one aspect, the precursor compounds are mixed in an inert atmosphere such as, for example, nitrogen or argon. In one aspect,, the inert atmosphere has less than 20 ppm oxygen, less than 10 ppm oxygen, less than 1 ppm oxygen, less than 0.5 ppm oxygen, less than 0.25 ppm oxygen, or less than 0.1 ppm oxygen. In some aspects, the mixture is further dried after mixing. After mixing, the mixture can be pelletized. The pellets can be formed by pressing the mechanochemically milled mixture into a mold.

[0049] The compounds disclosed herein can be components of different types of batteries, such as solid-state batteries. The component of the battery including the compounds can be an electrolyte, a separator membrane, or a combination thereof. The compounds disclosed herein can also be components of different types of sensors, such as ion-selective electrodes, that are configured for ion detection (e.g., Li.sup.+ detection). Sensors can be used to measure or detect metal contamination in water sources or biofluids.

Aspects

[0050] Aspect 1. A compound having the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, wherein A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7.

[0051] Aspect 2. The compound of aspect 1, wherein A is Li.

[0052] Aspect 3. The compound of aspect 1, wherein A is Na.

[0053] Aspect 4. The compound of any one of aspects 1-3, wherein z is about 1.0 to about 2.0.

[0054] Aspect 5. The compound of any one of aspects 1-4, wherein N is Ta.

[0055] Aspect 6. The compound of any one of aspects 1-5, wherein v is about 1.00 to about 1.50.

[0056] Aspect 7. The compound of any one of aspects 1-6, wherein y is from about 0.01 to about 0.99.

[0057] Aspect 8. The compound of any one of aspects 1-6, wherein y is from about 0.10 to about 0.90.

[0058] Aspect 9. The compound of any one of aspects 1-8, wherein X is Cl.

[0059] Aspect 10. The compound of any one of aspects 1-8, wherein X is Br.

[0060] Aspect 11. The compound of aspect 1, wherein the compound is Li.sub.2TaS.sub.1-yO.sub.yCl.sub.5.

[0061] Aspect 12. The compound of aspect 11, wherein y is from about 0.10 to about 0.99.

[0062] Aspect 13. The compound of aspect 11, wherein y is greater than 0.8 to less than 1.0.

[0063] Aspect 14. The compound of aspect 1, wherein the compound is Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5, Li.sub.2TaS.sub.0.4O.sub.0.6Cl.sub.5, or Li.sub.2TaS.sub.0.7O.sub.0.3Cl.sub.5.

[0064] Aspect 15. The compound of any one of aspects 1-14, wherein the compound has an ionic conductivity of at least about 1.00 mS/cm.

[0065] Aspect 16. The compound of any one of aspects 1-15, wherein the compound has an ionic conductivity of at least about 1.00 mS/cm to about 10.00 mS/cm.

[0066] Aspect 17. The compound of any one of aspects 1-16, wherein the compound has an electronic conductivity of less than 1.0010.sup.8 S/cm.

[0067] Aspect 18. The compound of any one of aspects 1-17, wherein the compound has an electronic conductivity of about 1.0010.sup.8 S/cm to about 1.0010.sup.10 S/cm.

[0068] Aspect 19. The compound of any one of aspects 1-18, wherein the compound is conductive over a temperature range of about 0 C. to about 100 C.

[0069] Aspect 20. The compound of any one of aspects 1-18, wherein the compound exhibits superionic conductivity over a temperature range of about 0 C. to about 80 C.

[0070] Aspect 21. The compound of any one of aspects 1-20, wherein the compound has an activation energy for ion transport of from about 0.1 eV to about 0.5 eV.

[0071] Aspect 22. The compound of any one of aspects 1-20, wherein the compound has an activation energy for ion transport of from about 0.2 eV to about 0.3 eV.

[0072] Aspect 23. The compound of any one of aspects 1-22, wherein the compound is amorphous.

[0073] Aspect 24. The compound of any one of aspects 1-23, wherein the compound has peaks at about 1.1 ppm, 0.68 ppm, and 2.8 ppm as determined by Li solid-state NMR spectroscopy.

[0074] Aspect 25. A method for making a compound having the formula A.sub.zN.sub.vS.sub.1-yO.sub.yX.sub.5, wherein A is Li, Na, K, or any combination thereof; N is Ta, Nb, or any combination thereof; X is Cl, Br, I, or any combination thereof; z is greater than zero to about 2; y is greater than or equal to zero to less than 1; and the sum (z+5v) is equal to 7; the method comprising (a) combining in the solid state the following components (i) A.sub.2S, selected from the group consisting of Li.sub.2S, Na.sub.2S, K.sub.2S, and any combination thereof; (ii) A.sub.2O, selected from the group consisting of Li.sub.2O, Na.sub.2O, K.sub.2O, and any combination thereof; and (iii) NX.sub.5, selected from the group consisting of TaCl.sub.5, TaBr.sub.5, Tal.sub.5, NbCl.sub.5, NbBr.sub.5, Nbl.sub.5, and any combination thereof, to produce a precursor mixture; and (b) mixing the precursor mixture by mechanochemical milling.

[0075] Aspect 26. The method of aspect 25, wherein precursor mixture is mixed by mechanochemical milling for about 1 hour to about 4 hours.

[0076] Aspect 27. The method of aspect 25, wherein precursor mixture is mixed by mechanochemical milling for about 2 hours.

[0077] Aspect 28. The method of any one of aspects 25-27, wherein the components are substantially anhydrous.

[0078] Aspect 29. The method of any one of aspects 25-28, wherein the components are mixed in an inert atmosphere.

[0079] Aspect 30. The method of any one of aspects 25-29, wherein the components are combined in stoichiometric amounts.

[0080] Aspect 31. A compound produced by the method of any one of aspects 25-30.

[0081] Aspect 32. A battery comprising the compound in any one of aspects 1-24 and 31.

[0082] Aspect 33. The battery of aspect 32, wherein the battery is a solid-state battery.

[0083] Aspect 34. A battery comprising the compound in any one of aspects 1-24 and 31.

[0084] Aspect 35. A sensor for ion detection, comprising the compound in any one of aspects 1-24 and 31.

[0085] Now having described the aspects of the present disclosure, in general, the following Examples describe some additional aspects of the present disclosure. While aspects of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit aspects of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of the present disclosure.

EXAMPLES

[0086] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated and are intended to be purely exemplary of the disclosure and are not intended to limit the scope of what the inventors regard as their disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in C. or is at ambient temperature, and pressure.

Materials and Methods

Synthesis

[0087] Lithium sulfide (99.9% Alfa Aesar), lithium oxide (99.5% Alfa Aesar), and tantalum chloride (99.99% Sigma Aldrich) were stored in an argon-filled glovebox, with moisture and O.sub.2 contents of <0.1 ppm each, to avoid moisture and ambient environment. A stoichiometric amount of the precursors was hand-ground and transferred into a 20-mL zirconia milling jar, with three 10 mm-sized zirconia balls, and vacuum sealed within the argon-filled glovebox. Mechanochemical milling was done using the 8000M Mixer/Mill High-Energy Ball Mill for 2 hours. The mechanically homogenized sample was stored in a glass vial inside the argon-filled glovebox (MBroun) for further characterization.

Characterization

[0088] Powder X-ray DiffractionThe prepared sample was sealed on a zero-background sample holder with Kapton film. The sample was analyzed in a Rigaku SmartLab X-ray diffractometer with a Cu source (wavelength of 0.154 nm). A step size of 0.03 and a scan rate of 2/min were used to collect the diffraction data for the 10 to 70 range of 2 values.

[0089] Electrochemical Impedance Spectroscopy (EIS)For impedance measurements, the sample was hand-ground and pressed in a 10 mm diameter mold to make a 0.8 mm thick pellet. The pellet was assembled in a split cell with steel as the blocking electrode. The measurement of potentiostatic EIS was carried out using a Gamry electrochemical analyzer and conductivities were calculated from the resulting Nyquist plots. Variable temperature EIS characterization was performed from 20 C. to 100 C. to calculate the activation energy via Arrhenius plots.

Results and Discussion

[0090] FIG. 1A shows the Nyquist plots of impedance values from EIS measurements. A bulk impedance of 400 ohms was observed for the pristine material Li.sub.2TaSCl.sub.5. This translates into an ionic conductivity value of 0.25 mS/cm. Upon substitution of the S.sup.2 with O.sup.2 a significant drop in the impedance values resulted.

[0091] Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 (LTSOC) displays an ionic conductivity of 3.69 mS/cm, an order-of-magnitude enhancement compared with Li.sub.2TaSCl.sub.5 (LTSC). This value is one of the highest ionic conductivities achieved so far in this class of oxo-sulfide SEs. The impedance spectra of LTSOC are composed of a single suppressed semicircle at high frequency and a sloped line at low frequency. The data has been modeled with the two (RQ)+Q equivalent circuit model to quantitatively understand these processes and their contributions to the impedance in LTSOC. A resistor (R) connected in parallel to a constant phase element (Q) is represented by the symbol (RQ). To account for heterogeneous surfaces between the steel electrode contacts and the pellet, a constant phase element was employed instead of a capacitor. The low-frequency tail is in line with capacitive build-up at steel-blocking electrodes. The high-frequency (RQ) semicircle can be attributed to a combination of bulk and grain-boundary impedances, as in other Li-ion conducting halide SEs. The incomplete (RQ) semicircle, which implies several overlapping processes at high frequencies, provides evidence for this. To differentiate between the contributions of the bulk (Rb) and grain-boundary (R.sub.gb) to the total resistivity (R.sub.t), a low temperature of 20 C., FIG. 1B, was selected rather than RT. The capacitance values extracted from the equivalent circuit fitting for LTSOC is 2.6810.sup.11 F. Even at very low temperatures, such as 20 C., bulk and grain boundary contributions cannot be reasonably deconvoluted. Therefore, the conductivities described here indicate total conductivities. A capacitance value of 5.2610.sup.6 F was extracted for the mid-frequency semicircle, which implies it's due to the electrode contribution..sup.11-13

[0092] Variable-temperature EIS experiments were conducted, as shown in FIG. 1C, to determine the material behavior at a wide temperature window and to determine the activation energy using the Arrhenius relationship. Notably, superionic Li conductivity (>1 mS/cm) was observed even at temperatures as low as 0 C. This is a game changer as it can potentially provide steady performance in harsh environments, such as cold climates, for electronic devices and electric vehicles.

[0093] A relatively low activation energy value of 0.27 eV was computed from the slope of the Arrhenius plot shown in FIG. 1D. This value falls within the range of that commonly reported for halide and sulfide fast-ion conductors 14 A linear relationship of the conductivity values versus temperature suggests that no phase change is occurring in the range of temperatures tested, 0-80 C. This hints at a thermally stable electrolyte.

[0094] For the experimental investigation of electronic contribution (.sub.el) to the total conductivity, the DC polarization technique was applied to the samples in a symmetric setup SS|LTSOC|SS. FIG. 2A shows results of DC-Polarization on a symmetric SS|LTSOC|SS cell (SS: stainless steel) for determination of .sub.el. Equilibrium currents were monitored at different voltages to increase the accuracy of DC polarization measurements. Then, using Ohm's rule (V=IR), the respective partial conductivities can be determined from the voltage vs. current plot. .sup.15 Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 exhibits a low electronic conductivity of 3.3310.sup.9 S/cm (FIG. 2B), which ensures a negligible contribution of electron transport to the measured total conductivity.

[0095] The XRD data in FIG. 3 shows no crystalline reflections for LTSC and LTSOC. This suggests that the material is amorphous with no long-range order, typical of glasses. This has an advantage for catholyte fabrication, as it improves the interfacial contact between the SEs and cathode active materials, and increased disorder facilitates faster Li-ion motion. A comprehensive local structure and ion dynamics study using advanced solid-state NMR techniques is ongoing.

[0096] Additional compounds described herein were further evaluated. To understand the structural properties of the Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 samples prepared via rapid 2-Hr BM synthesis, XRD and high-resolution NMR were conducted. The powder XRD patterns for the Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 series, FIG. 4A, exhibit broad diffraction peaks, characteristic of amorphous materials. This broadening indicates a lack of long-range order in the crystal structure, suggesting that the material does not form well-defined crystalline phases.

[0097] The deconvoluted NMR plots in FIG. 4B reveal the local structural environments in both LTSC and LTSOC. The isotropic peaks in both spectra resonate at approximately 0.64 and 0.67 ppm respectively, indicating nearly identical chemical environments for the observed nuclei. However, a significant difference is observed in the spectra widths. The linewidth for LTSC is about 34 Hz, which is more than 1.5 times broader than the 21 Hz linewidth of LTSOC. This broader linewidth in LTSC suggests a greater degree of local structural disorder with restricted ion dynamics compared to LTSOC..sup.+ In contrast, the narrower linewidth in LTSOC indicates that the lithium ions are in a more homogenous local environment, which could be linked to its enhanced ionic transport properties, as fewer interactions and less disorder can facilitate easier ion movement..sup.+ Both NMR and PXRD data revealed the presence of small amounts of LiCl, and Li.sub.2S impurities in LTSC and LiCl and Li.sub.2O impurities in LTSOC. The presence of LiCl phase suggests a multistep reaction of the precursors to the final product, of which the intermediate phase generates LiCl.

[0098] The Raman spectra presented in FIG. 5A compares different tantalum-based compounds, namely TaCl.sub.5, LiTaCl6, Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5, and Ta.sub.2O.sub.5. The black spectrum of TaCl.sub.5 exhibits strong characteristic peaks, particularly in the 200-500 cm.sup.1 region, which are attributed to TaCl vibrational modes. As Li is introduced in LiTaCl.sub.6 (green spectrum), peak intensity decreases, and there are slight spectral shifts, indicating modifications in the local structure around Ta atoms. The Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 spectrum (red curve) displays further peak broadening and shifts, suggesting significant structural alterations due to the partial substitution of sulfur (S) and oxygen (O) for chlorine (Cl) in the anionic framework.

[0099] FIG. 5C provides a detailed look at the Raman peaks and their assignments. The low-wavenumber peaks (200-400 cm.sup.1) correspond to TaCl and TaS vibrations, indicating the presence of mixed halide and chalcogenide coordination. A peak near 500 cm.sup.1 is labeled as a ClTaS vibrational mode, suggesting a direct interaction between chloride and sulfide ligands in the Ta-centered octahedra. The higher-wavenumber region (600-900 cm.sup.1, highlighted in blue) features broad Raman bands associated with oxygen incorporation, specifically linked to O-3Ta and O-2Ta stretching modes. These peaks confirm the presence of TaO bonds, reinforcing the notion of partial oxidation in the material. The spectral broadening in this region also suggests a degree of structural disorder, which could impact the material's ionic transport properties.

[0100] The coordination environments of tantalum in these materials are illustrated in FIG. 5B, showing Ta-centered octahedral units with varying ligand compositions. In LiTaCl.sub.6, tantalum is predominantly coordinated by chlorine (Cl), forming an ordered TaCl.sub.6 octahedral structure. However, in Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5, the replacement of some chloride ligands with sulfur (S) and oxygen (O) alters the Ta coordination geometry. This mixed-anion environment can impact the material's ionic conductivity and electrochemical stability, particularly if anion disorder facilitates Li-ion migration pathways.

[0101] FIGS. 5D-5F provide further insights into the crystal structures. FIG. 5D likely represents Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5, showing a distorted framework where S, O, and Cl ligands interact in a complex coordination environment. The dashed lines represent potential Li.sup.+ migration pathways, which play a crucial role in ionic conductivity. The weak interaction between Li.sup.+ ions and anions, primarily Cl.sup., reduces energy barriers for migration, facilitating efficient Li+transport. FIG. 5E illustrates a possible structural arrangement in which the Ta-centered octahedra forms a linked, polymer-like chain, maintaining a symmetrical configuration of anion clusters. In contrast, FIG. 5F depicts a slightly distorted or branched arrangement, suggesting structural flexibility that could further influence ionic mobility and conductivity.

[0102] SEM and EDS images were obtained for ball-milled LTSOC powders to examine sample morphology (FIG. 6). The images reveal that LTSOC particles tend to aggregate. This aggregation likely enhances contact, reduces grain boundaries, and improves transport properties. The corresponding EDS images show a uniform distribution of the constituent elementsTa, S, O, and Clin the LTSOC sample.

[0103] FIG. 7A shows that variable temperature .sup.7Li T.sub.1 spin-lattice relaxation times is higher with oxygen incorporation, At room temperature, LTSOC reaches 1.1 s and LTSC around 0.25 s. This suggests faster Li-ion relaxation in LTSC compared to LTSOC, likely due to stronger Li.sup.+O interactions from the more electronegative oxygen anions. The relaxation behavior of both LTSC and LTSOC falls within the intermediate-motion region described by the Bloembergen-Purcell-Pound theory. A decrease in peak width with increased temperature is expected, as shown in FIG. 7B.

[0104] FIG. 8A displays Arrhenius plots obtained from variable temperature EIS measurements for the Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 series, the extracted activation energy and RT ionic conductivities are depicted in FIG. 8B. For the unsubstituted LTSC, a relatively higher activation energy of 0.36 eV was determined, and it also exhibited the lowest ionic conductivity, 0.28 mS cm.sup.1. It can be seen (FIG. 8B) that modifying the composition by replacing some Li.sub.2S with Li.sub.2O results in appreciably enhanced ionic conductivity. The increased ionic conductivities observed for the 2 hr BM Li.sub.2TaS.sub.1-xO.sub.xCl.sub.5 sample, when x is 0.3, 0.6. and 0.9 were 0.8, 3.1, and 3.7 mS cm.sup.1 respectively. An opposite trend was observed for the associated activation energies with the lowest value of 0.32 eV exhibited by Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5. Oxygen incorporation into the LTSOC structure likely helped stabilize the superionic conducting phase, as the transport property exhibited by Li.sub.2TaS.sub.0.1O.sub.0.9Cl.sub.5 is over 13 times greater than in the pristine Li.sub.2TaSCl5. The ionic conductivity of the 2-hour ball-milled LTSOC material surpasses most reported for lithium-conducting halides, which typically require energy-intensive solid-state reactions or wet-chemical synthesis methods taking dozens of hours, or days, to synthesize.

[0105] The all-solid-state battery (ASSB) with the set-up TiS.sub.2|LTSOCLi.sub.6PS.sub.5ClLiIn was cycled between 1.0V and 2.5V, where the TiS.sub.2 cathode active material (CAM) is electrochemically stable. At a cycling rate of 0.1C, the discharge capacity for the first cycle reached 258 mAh g.sup.1 with a high Coulombic efficiency (CE) of nearly 100% (FIG. 9A). This capacity significantly exceeds the theoretical capacity of the TiS.sub.2 cathode active material (239 mAh g.sup.1). This discrepancy is likely due to potential capacity-generating redox reactions involving unknown phases formed from the interactions between the solid electrolyte and TiS.sub.2, as observed in similar studies on TiS.sub.2 catholytes..sup.+ As the current density increased, the capacity decreased from 258 mAh/g (0.1C) to 211 mAh g.sup.1 (0.2C), 124 mAh g.sup.1 (0.5C), and 55 mAh g.sup.1 (1C), demonstrating good capacity retention at higher current densities (FIGS. 9A-9B). After 100 cycles at 0.1C, the capacity retained 196 mAh g.sup.1, corresponding to 78% of the initial capacity.

[0106] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

REFERENCES

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[0122] It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.