SOLID ELECTROLYTES AND METHODS FOR MAKING THE SAME
20250171327 ยท 2025-05-29
Inventors
- Tej Prasad Poudel (Tallahassee, FL, US)
- Yan-Yan Hu (Tallahassee, FL, US)
- Ifeoluwa Peter Oyekunle (Tallahassee, FL, US)
Cpc classification
C01F7/78
CHEMISTRY; METALLURGY
C01P2002/76
CHEMISTRY; METALLURGY
C01P2002/72
CHEMISTRY; METALLURGY
C01P2002/77
CHEMISTRY; METALLURGY
C01G15/006
CHEMISTRY; METALLURGY
International classification
Abstract
In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to solid chalcohalide electrolytes and the efficient synthesis of solid chalcohalide electrolytes. The electrolytes have the general formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f and have relatively high ionic conductivity. The electrolytes can be a component of different types of batteries. The process of synthesizing the electrolytes can be done with cost-effective materials, which is useful for scaling-up production of batteries such as all-solid-state batteries.
Claims
1. A compound having the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, wherein A is Li, Na, K, or any combination thereof; M is Al, Ga, In, or any combination thereof; N is Mg, Ca, Zn, or any combination thereof; X and Y are, independently, F, Cl, Br, or I; S is sulfur; a is from about 1 to about 4; b is from about 0.5 to about 5.0; c is greater than or equal to 0 to about 1.5; d is from about 1 to about 5; e is greater than or equal to 0 to about 3; f is greater than 0 to about 3; and the sum (a+3b+2c) is equal to the sum (d+e+2f).
2. The compound of claim 1, wherein A is Li or Na, M is Al, and X is Cl.
3. The compound of claim 1, wherein A is Li, M is Al and Ga, X is Cl, and Y is F.
4. The compound of claim 1, where the compound has the formula A.sub.aAl.sub.bCl.sub.dS.sub.f, wherein A is Li or Na.
5. The compound of claim 4, wherein a is from about 2 to about 4, b is from about 0.5 to about 1.0, d is from about 2 to about 4, and f is from about 1 to about 3.
6. The compound of claim 1, wherein the compound has the formula Li.sub.aAl.sub.bN.sub.cCl.sub.dS.sub.f, wherein N is Ca or Zn.
7. The compound of claim 6, wherein a is from about 1 or to about 2, b is from about 0.5 to about 1.0, c is from about 0.1 to about 1.0, d is from about 2 to about 4, and f is from about 1 to about 3.
8. The compound of claim 1, where the compound has the formula Li.sub.aAl.sub.bCl.sub.dBr.sub.eS.sub.f.
9. The compound of claim 8, wherein a is from about 1 or to about 2, b is from about 0.5 to about 1, d is from about 2 to about 4, e is greater than zero to about 1, and f is from about 1 to about 3.
10. The compound of claim 1, wherein the compound has the formula Li.sub.2AlCl.sub.3S, Li.sub.4AlCl.sub.3S2, Na.sub.2AlCl.sub.3S, or K.sub.2AlCl.sub.3S.
11. The compound of claim 1, wherein the compound has the formula Li.sub.2Al.sub.bGa.sub.b2Cl.sub.dF.sub.eS, wherein (b1+b2)=b.
12. The compound of claim 11, wherein b1 is from about 0.5 to about 0.9, b2 is from about 0.1 to about 0.5, d is from about 2.1 to about 2.9, and e is from about 0.1 to about 0.9.
13. The compound of claim 1, wherein the compound has the formula Li.sub.aAlCl.sub.dS.sub.f, wherein a is from about 1.0 to about 2.0, d is from about 3.0 to about 4.0, and f is from about 0.1 to about 1.0.
14. The compound of claim 1, wherein the compound has the formula Li.sub.2Al.sub.0.9Ga.sub.0.1Cl.sub.2.7F.sub.0.3S, Li.sub.2Al.sub.0.3Ga.sub.0.2Cl.sub.2.4F.sub.0.6S, Li.sub.2Al.sub.0.7Ga.sub.0.3Cl.sub.2.1F.sub.0.9S, or Li.sub.1.6AlCl.sub.3.4S0.6.
15. The compound of claim 1, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 23.5 and 38.90.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 .
16. The compound of claim 1, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 28.4 and 40.60.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 .
17. The compound of claim 1, wherein the compound has a capacity of about 150 mAh/g to about 200 mAh/g at a discharge rate of 2 C.
18. A compound having the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, wherein A is Li, Na, K, or any combination thereof; M is Al, Ga, In, or any combination thereof; N is Mg, Ca, Zn, or any combination thereof; X and Y are, independently, F, Cl, Br, or I; S is sulfur; a is from about 1 to about 4; b is from about 0.5 to about 5.0; c is greater than or equal to 0 to about 1.5; d is from about 1 to about 5; e is greater than or equal to 0 to about 3; f is greater than 0 to about 3; and the sum (a+3b+2c) is equal to the sum (d+e+2f), wherein the compound is produced by the method comprising: mixing in the solid state the following components: (i) A.sub.2S; (ii) AX, AY, or a combination thereof; (iii) MX.sub.3, MY.sub.3, or a combination thereof; and (iv) NX.sub.2, NY.sub.2, or a combination thereof to produce a first mixture.
19. (canceled)
20. A battery comprising the compound of claim 1.
21. A battery comprising the compound of claim 18.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] 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.
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[0045] 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
[0046] 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.
[0047] Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
[0048] 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.
[0049] 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.
[0050] 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.
[0051] 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.
[0052] 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.
[0053] 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
[0054] 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.
[0055] 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.
[0056] 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.
[0057] 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.
[0058] 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.).
[0059] 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.
[0060] 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.
[0061] 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.
[0062] 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.
[0063] 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.
[0064] Unless otherwise specified, temperatures referred to herein are based on atmospheric pressure (i.e. one atmosphere).
Solid Electrolytes and Methods of Making and Using the Same
[0065] The present disclosure provides for chalcohalide solid electrolytes and the method of making and using chalcohalide solid electrolytes. The method of making can include using cost-effective precursors in the synthesis of chalcohalide solid electrolytes. The electrolytes have the general formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f and can have relatively high ionic conductivity. Additionally, the synthesis of these electrolytes with high ionic conductivity can be achieved via a one-step mechanochemical approach. The electrolytes can be included as a component of different types of batteries, such as solid-state batteries. In a particular aspect, Li- and Na-superionic solid electrolytes made with low-cost precursors work well for producing energy storage devices, such as batteries (e.g., solid-state batteries), on a large scale.
[0066] In one aspect, the electrolytes have the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, where A can be one of Li, Na, K, or any combination thereof; M can be Al, Ga, In, or any combination thereof; N can be Mg, Ca, Zn, or any combination thereof; X and Y can be, independently, F, Cl, Br, or I; and S is sulfur. Furthermore, a can be about 1 to about 4 or about 1.0, 2.0, 3.0, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 3.0 to 4.0); b can be about 0.5 to about 5.0 or about 0.5, 1.0, 2.0, 3.0, 4.0, or 5.0, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 3.0); c can be greater than or equal to 0 to about 1.5 or equal to 0.0, about 0.5, about 1.0, or about 1.5, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 1.0); d can be about 1 to about 5 or about 1.0, 2.0, 3.0, 4.0, or 5.0, where any value can be a lower and upper endpoint of a range (e.g., 4.0 to 5.0); e can be greater than or equal to 0 to about 3 or equal to 0.0, about 1.0, about 2.0, or about 3.0, where any value can be a lower and upper endpoint of a range (e.g., 2.0 to 3.0); and f can be greater than 0 to about 3 or about 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.5). Furthermore, a, b, c, d, e, and f can be assigned values such that (a+3b+2c) is equal to (d+e+2f). In some aspects, A is Li or Na, M is Al, and X is Cl. In other aspects, A is Li, M is Al and Ga, X is Cl, and Y is F.
[0067] In other aspects, a can be about 1 to about 2 or about 1.0, 1.5, or 2.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0). In other aspects, b can be about 0.5 to about 1.0 or about 0.50, 0.75, or 1.00, where any value can be a lower and upper endpoint of a range (e.g., 0.50 to 1.00). In other aspects, c can be about 0.1 to about 1.0 or about 0.1, 0.3, 0.7, or 1.0, where any value can be a lower and upper endpoint of a range (e.g., 0.3 to 1.0). In other aspects, d can be about 2 to about 4 or about 2.0, 2.5, 3.0, 3.5, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 2.5 to 3.0). In other aspects, e can be greater than 0 to about 1 or about 0.1, 0.3, 0.7, or 1.0, where any value can be a lower and upper endpoint of a range (e.g., 0.7 to 1.0).
[0068] In other aspects, the electrolytes can have the formula A.sub.aAl.sub.bCl.sub.dS.sub.f, where A can be Li or Na. In some aspects, a can be about 2 to about 4 or about 2.0, 2.5, 3.0, 3.5, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 2.5 to 3.0); b can be about 0.5 to about 1.0 or about 0.50, 0.75, or 1.00, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 1.0); d can be about 2 to about 4 or about 2.0, 2.5, 3.0, 3.5, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 2.5 to 3.0); and f can be about 1 to about 3 or about 1.0, 1.5, 2.0, 2.5, or 3.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0).
[0069] In other aspects, the electrolytes can have the formula Li.sub.aAl.sub.bN.sub.cCl.sub.dS.sub.f, where N is Ca or Zn. In some aspects, a can be about 1 to about 2 or about 1.0, 1.5, or 2.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0); b can be about 0.5 to about 1.0 or about 0.50, 0.75, or 1.00, where any value can be a lower and upper endpoint of a range (e.g., 0.50 to 1.00); c can be about 0.1 to about 1.0 or about 0.1, 0.3, 0.7, or 1.0, where any value can be a lower and upper endpoint of a range (e.g., 0.3 to 1.0); d can be about 2 to about 4 or about 2.0, 2.5, 3.0, 3.5, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 2.5 to 3.0); and f can be about 1 to about 3 or about 1.0, 1.5, 2.0, 2.5, or 3.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0).
[0070] In other aspects, the electrolytes can have the formula Li.sub.aAl.sub.bCl.sub.dBr.sub.eS.sub.f. In some aspects, a can be about 1 to about 2 or about 1.0, 1.5, or 2.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0); b can be about 0.5 to about 1.0 or about 0.50, 0.75, or 1.00, where any value can be a lower and upper endpoint of a range (e.g., 0.50 to 1.00); d can be about 2 to about 4 or about 2.0, 2.5, 3.0, 3.5, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 2.5 to 3.0); e can be greater than 0 to about 1 or about 0.1, 0.3, 0.7, or 1.0, where any value can be a lower and upper endpoint of a range (e.g., 0.7 to 1.0); and f can be about 1 to about 3 or about 1.0, 1.5, 2.0, 2.5, or 3.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.0).
[0071] In another aspect, the electrolytes can have the formula Li.sub.2Al.sub.b1Ga.sub.b2Cl.sub.dF.sub.eS. In some aspects, b1 can be about 0.5 to about 1.0 or about 0.50, 0.75, or 1.00, where any value can be a lower and upper endpoint of a range (e.g., 0.50 to 0.75); b2 can be about 0.1 to about 0.5 or about 0.1, 0.3, or 0.5, where any value can be a lower and upper endpoint of a range (e.g., 0.3 to 0.5); d can be from about 2.1 to about 2.9 or about 2.1, 2.3, 2.6, or 2.9, where any value can be a lower and upper endpoint of a range (e.g., 2.3 to 2.6); and e can be from about 0.1 to 0.9 or about 0.1, 0.3, 0.6, or 0.9, where any value can be a lower and upper endpoint of a range (e.g., 0.3 to 0.6). In further aspects, b1 and b2 can have values such that (b1+b2)=b.
[0072] In another aspect, the electrolytes can have the formula Li.sub.aAlCl.sub.dS.sub.f. In some aspects, a can be about 1.0 to about 2.0 or about 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., 1.5 to 1.7); d is from about 3.0 to about 4.0 or about 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 3.3 to 5.5); and f can be from about 0.1 to about 1.0 or about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 0.7).
[0073] In some aspects, the electrolytes can have the formula Li.sub.2AlCl.sub.3S, Li.sub.4AlCl.sub.3S.sub.2, Na.sub.2AlCl.sub.3S, or K.sub.2AlCl.sub.3S. In other aspects, the electrolytes can have the formula Li.sub.2AlCl.sub.3S, Li.sub.4AlCl.sub.3S.sub.2, or Na.sub.2AlCl.sub.3S. In other aspects, the electrolytes can have the formula Li.sub.2Al.sub.0.9Ga.sub.0.1Cl.sub.2.7F.sub.0.3S, Li.sub.2Al.sub.0.8Ga.sub.0.2Cl.sub.2.4F.sub.0.6S, Li.sub.2Al.sub.0.7Ga.sub.0.3Cl.sub.2.1F.sub.0.9S, or Li.sub.1.6AlCl.sub.3.4S.sub.0.6.
[0074] The electrolytes disclosed herein can be characterized by various properties. In one aspect, the electrolytes disclosed herein can have relatively high ionic conductivity. The electrolytes can have an ionic conductivity of at least about 0.10 mS/cm, 0.30 mS/cm, 0.50 mS/cm, 0.70 mS/cm, or 1.00 mS/cm. In other aspects, the electrolytes can have an ionic conductivity of about 0.10 mS/cm to about 1.00 mS/cm or about 0.10 mS/cm, 0.30 mS/cm, 0.50 mS/cm, 0.70 mS/cm, or 1.00 mS/cm, where any value can be a lower and upper endpoint of a range (e.g., 0.50 mS/cm to 0.70 mS/cm). In another aspect, the electrolytes can be conductive over a temperature range of about 20 C. to about 100 C. or about 20 C., 0 C., 20 C., 40 C., 60 C., 80 C., or 100 C., where any value can be a lower and upper endpoint of a range (e.g., 0 C. to 40 C.). In further aspects, the electrolytes can have an electronic conductivity of about 1.0010.sup.7 S/cm to about 1.0010.sup.10 S/cm or about 1.0010.sup.7 S/cm, 1.0010.sup.8 S/cm, 1.0010.sup.9 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.7 S/cm to 1.0010.sup.8 S/cm). Exemplary methods for determining ionic conductivity and electronic conductivity are provided in the Examples.
[0075] In some aspects, the electrolytes have a monoclinic structure type in the P2.sub.1/c space group. In other aspects, the electrolytes have an orthorhombic structure type in the P2.sub.12.sub.12.sub.1 space group. In other aspects, the electrolytes have a cubic structure type belonging to the Fm-3m space group.
[0076] The electrolytes described herein have unique X-ray diffraction (XRD) patterns. In some aspects, the X-ray powder diffractions can be performed using an X-ray wavelength of 1.5406 .
[0077] In some aspects, the electrolytes can have an X-ray powder diffraction pattern including peaks at 26.9, 31.2, and 44.80.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 . In further aspects, the electrolytes with this XRD pattern can include Li.sub.2AlCl.sub.3S and/or Li.sub.4AlCl.sub.3S.sub.2. In other aspects, the electrolytes can have an X-ray powder diffraction pattern including peaks at 24.6 and 26.90.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 . In further aspects, the electrolytes with this XRD pattern can include Li.sub.2Al.sub.0.9Ga.sub.0.1Cl.sub.2.7F.sub.0.3S, Li.sub.2Al.sub.0.8Ga.sub.0.2Cl.sub.2.4F.sub.0.6S, and/or Li.sub.2Al.sub.0.7Ga.sub.0.3Cl.sub.2.4F.sub.0.9S. In other aspects, the electrolytes can have an X-ray powder diffraction pattern including peaks at 23.5 and 38.90.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 . In further aspects, the electrolytes with this XRD pattern can include Na.sub.2AlCl.sub.3S. In still other aspects, the electrolytes can have an X-ray powder diffraction pattern including peaks at 28.4 and 40.60.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 . In further aspects, the electrolytes with this XRD pattern can include K.sub.2AlCl.sub.3S.
[0078] The electrolytes described herein possess unique solid-state NMR spectra. The Li-containing electrolytes can have peaks at about 0.98 ppm, 0.15 ppm, 1.60 ppm and 2.43 ppm as determined by .sup.6Li solid-state NMR spectroscopy. In further aspects, the Li-containing electrolytes can have peaks at about 0.98 ppm, 0.15 ppm, and 1.60 ppm as determined by .sup.6Li solid-state NMR spectroscopy. The Na-containing electrolytes can have peaks at about 42.66 ppm as determined by .sup.23Na solid-state NMR spectroscopy. In other aspects, the Na-containing electrolytes can have peaks at about 15.04 ppm, 16.63 ppm, 19.17 ppm, 21.75 ppm, 23.21 ppm, 24.83 ppm, and 42.66 ppm as determined by .sup.23Na solid-state NMR spectroscopy. In other aspects, the Na-containing electrolytes can have peaks at about 15.04 ppm, 16.63 ppm, 21.75 ppm, and 42.66 ppm as determined by .sup.23Na solid-state NMR spectroscopy. Exemplary methods for performing XRD and NMR measurements are provided in the Examples.
[0079] The electrolytes described herein possess good long-term cycling stability and rate performance, which makes the electrolytes described herein excellent candidates as electrolytes for all solid-state batteries (ASSBs). In one aspect, electrolytes described herein have a specific capacity of about 150 mAh/g to about 200 mAh/g at a discharge rate of 2 coulombs (C) in a battery cell. Exemplary methods for determining the capacity of the electrolytes described herein are provided in the Examples.
[0080] Also disclosed is a method for making chalcohalide solid electrolytes having the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, where A can be one of Li, Na, K, or any combination thereof; M can be Al, Ga, In, or any combination thereof; N can be Mg, Ca, Zn, or any combination thereof; and X and Y can be, independently, F, Cl, Br, or I; and S is sulfur. a can be about 1 to about 4 or about 1.0, 2.0, 3.0, or 4.0, where any value can be a lower and upper endpoint of a range (e.g., 3.0 to 4.0); b can be about 0.5 to about 5.0 or about 0.5, 1.0, 2.0, 3.0, 4.0, or 5.0, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 3.0); c can be greater than or equal to 0 to about 1.5 or equal to 0.0, about 0.5, about 1.0, or about 1.5, where any value can be a lower and upper endpoint of a range (e.g., 0.5 to 1.0); d can be about 1 to about 5 or about 1.0, 2.0, 3.0, 4.0, or 5.0, where any value can be a lower and upper endpoint of a range (e.g., 4.0 to 5.0); e can be greater than or equal to 0 to about 3 or equal to 0.0, about 1.0, about 2.0, or about 3.0, where any value can be a lower and upper endpoint of a range (e.g., 2.0 to 3.0); and f can be greater than 0 to about 3 or about 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, or 3.0, where any value can be a lower and upper endpoint of a range (e.g., 1.5 to 2.5). Furthermore, a, b, c, d, e, and f can be assigned values such that (a+3b+2c) is equal to (d+e+2f). The method includes mixing a plurality of precursor compounds, such as salts, in various amounts in the solid state. In one aspect, the compounds are mixed together in stoichiometric amounts. In further aspects, the mixing can include grinding stoichiometric amounts of the compounds in different molar ratios. The compounds mixed together can include A.sub.2S; AX, AY, or a combination thereof; MX.sub.3, MY.sub.3, or a combination thereof; and NX.sub.2, NY.sub.2, or a combination thereof. A, X, Y, M, and N are as defined previously.
[0081] The compounds used to produce the electrolytes described herein are generally highly pure materials. In one aspect, each of the compounds has a purity of greater than 99%, greater than 99.5%, or greater than 99.9%. In one aspect, each compound used to produce the electrolytes is substantially anhydrous, where each 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 compound has less than 0.5 ppm water, less than 0.25 ppm water, or less than 0.1 ppm water.
[0082] In another aspect, the compounds can be mixed by mechanochemical milling. Mixing of the 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 compounds are mixed with one another for at least three hours, at least two hours, less than two hours, or less than one hour. In another aspect, the compounds are mixed from about 45 minutes to about 135 minutes or about 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, or 135 minutes, where any value can be a lower and upper endpoint of a range (e.g., 60 minutes to 105 minutes). In one aspect, the compounds are mixed in an inert atmosphere such as, for example, nitrogen or argon. In one aspect, the inert atmosphere has less than 0.5 ppm oxygen, less than 0.25 ppm oxygen, or less than 0.1 ppm oxygen. After mixing, the mixture can be pelletized.
[0083] 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.
Aspects
[0084] Aspect 1. A compound having the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, wherein [0085] A is Li, Na, K, or any combination thereof; [0086] M is Al, Ga, In, or any combination thereof; [0087] N is Mg, Ca, Zn, or any combination thereof; [0088] X and Y are, independently, F, Cl, Br, or I; [0089] S is sulfur; [0090] a is from about 1 to about 4; [0091] b is from about 0.5 to about 5.0; [0092] c is greater than or equal to 0 to about 1.5; [0093] d is from about 1 to about 5; [0094] e is greater than or equal to 0 to about 3; [0095] f is greater than 0 to about 3; and [0096] the sum (a+3b+2c) is equal to the sum (d+e+2f).
[0097] Aspect 2. The compound of Aspect 1, wherein A is Li.
[0098] Aspect 3. The compound of Aspect 1, wherein A is Na.
[0099] Aspect 4. The compound of any one of Aspects 1-3, wherein a is from about 1 to about 2.
[0100] Aspect 5. The compound of any one of Aspects 1-4, wherein M is Al.
[0101] Aspect 6. The compound of any one of Aspects 1-4, wherein M is Ga.
[0102] Aspect 7. The compound of any one of Aspects 1-4, wherein M is In.
[0103] Aspect 8. The compound of any one of Aspects 1-7, wherein b is from about 0.5 to about 1.0.
[0104] Aspect 9. The compound of any one of Aspects 1-8, wherein N is Ca.
[0105] Aspect 10. The compound of any one of Aspects 1-8, wherein N is Zn.
[0106] Aspect 11. The compound of any one of Aspects 1-10, wherein c is zero.
[0107] Aspect 12. The compound of any one of Aspects 1-10, wherein c is from about 0.1 to about 1.0.
[0108] Aspect 13. The compound of any one of Aspects 1-12, wherein X is Cl
[0109] Aspect 14. The compound of Aspect 13, wherein d is from about 2 to about 4.
[0110] Aspect 15. The compound of any one of Aspects 1-14, wherein when e is greater than zero, Y is Br.
[0111] Aspect 16. The compound of Aspect 15, wherein e is greater than zero to about 1.
[0112] Aspect 17. The compound of Aspect 1, wherein A is Li or Na, M is Al, and X is Cl.
[0113] Aspect 18. The compound of Aspect 1, wherein A is Li, M is Al and Ga, X is Cl, and Y is F.
[0114] Aspect 19. The compound of Aspect 1, where the compound has the formula A.sub.aAl.sub.bCl.sub.dS.sub.f, wherein A is Li or Na.
[0115] Aspect 20. The compound of Aspect 19, wherein a is from about 2 to about 4, b is from about 0.5 to about 1.0, d is from about 2 to about 4, and f is from about 1 to about 3.
[0116] Aspect 21. The compound of Aspect 1, wherein the compound has the formula Li.sub.aAl.sub.bN.sub.cCl.sub.dS.sub.f, wherein N is Ca or Zn.
[0117] Aspect 22. The compound of Aspect 21, wherein a is from about 1 or to about 2, b is from about 0.5 to about 1.0, c is from about 0.1 to about 1.0, d is from about 2 to about 4, and f is from about 1 to about 3.
[0118] Aspect 23. The compound of Aspect 1, where the compound has the formula Li.sub.aAl.sub.bCl.sub.dBr.sub.eS.sub.f.
[0119] Aspect 24. The compound of Aspect 23, wherein a is from about 1 or to about 2, b is from about 0.5 to about 1, d is from about 2 to about 4, e is greater than zero to about 1, and f is from about 1 to about 3.
[0120] Aspect 25. The compound of Aspect 1, wherein the compound has the formula Li.sub.2AlCl.sub.3S, Li.sub.4AlCl.sub.3S.sub.2, Na.sub.2AlCl.sub.3S, or K.sub.2AlCl.sub.3S.
[0121] Aspect 26. The compound of Aspect 1, wherein the compound has the formula Li.sub.2Al.sub.b1Ga.sub.b2Cl.sub.dF.sub.eS, wherein (b1+b2)=b.
[0122] Aspect 27. The compound of Aspect 26, wherein b1 is from about 0.5 to about 0.9, b2 is from about 0.1 to about 0.5, d is from about 2.1 to about 2.9, and e is from about 0.1 to about 0.9.
[0123] Aspect 28. The compound of Aspect 1, wherein the compound has the formula Li.sub.aAlCl.sub.dS.sub.f, wherein a is from about 1.0 to about 2.0, d is from about 3.0 to about 4.0, and f is from about 0.1 to about 1.0.
[0124] Aspect 29. The compound of Aspect 1, wherein the compound has the formula Li.sub.2Al.sub.0.9Ga.sub.0.1Cl.sub.2.7F.sub.0.3S, Li.sub.2Al.sub.0.8Ga.sub.0.2Cl.sub.2.4F.sub.0.6S, Li.sub.2Al.sub.0.7Ga.sub.0.3Cl.sub.2.1F.sub.0.9S, or Li.sub.1.6AlCl.sub.3.4S.sub.0.6.
[0125] Aspect 30. The compound of any one of Aspects 1-29, wherein the compound has an ionic conductivity of at least 0.10 mS/cm.
[0126] Aspect 31. The compound of any one of Aspects 1-29, wherein the compound has an ionic conductivity of at least 0.10 mS/cm to about 1.00 mS/cm.
[0127] Aspect 32. The compound of any one of Aspects 1-31, wherein the compound has an electronic conductivity less than 1.0010.sup.7 S/cm.
[0128] Aspect 33. The compound of any one of Aspects 1-31, wherein the compound has an electronic conductivity of about 1.0010.sup.7 S/cm to about 1.0010.sup.10 S/cm.
[0129] Aspect 34. The compound of any one of Aspects 1-33, wherein the compound is conductive over a temperature range of about 20 C. to about 100 C.
[0130] Aspect 35. The compound of any one of Aspects 1-34, wherein the compound has a monoclinic structure type with the space group P2.sub.1/c.
[0131] Aspect 36. The compound of any one of Aspects 1-35, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 26.9, 31.2, and 44.80.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 .
[0132] Aspect 37. The compound of any one of Aspects 1-35, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 24.6 and 26.90.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 1.5406 .
[0133] Aspect 38. The compound of any one of Aspects 1-37, wherein the compound has peaks at about 0.98 ppm, 0.15 ppm, and 1.60 ppm, as determined by .sup.6Li solid-state NMR spectroscopy.
[0134] Aspect 39. The compound of any one of Aspects 1-34, wherein the compound has an orthorhombic structure type with the space group P2.sub.12.sub.12.sub.1.
[0135] Aspect 40. The compound of any one of Aspects 1-34 or 39, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 23.5 and 38.90.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 .
[0136] Aspect 41. The compound of any one of Aspects 1-34, 39, or 40, wherein the compound has a peak at about 42.66 ppm, as determined by .sup.23Na solid-state NMR spectroscopy.
[0137] Aspect 42. The compound of any one of Aspects 1-34, wherein the compound has a cubic structure type with the space group Fm-3m.
[0138] Aspect 43. The compound of any one of Aspects 1-34 or 42, wherein the compound has an X-ray powder diffraction pattern comprising peaks at 28.4 and 40.60.2 2 as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 .
[0139] Aspect 44. The compound of any one of Aspects 1-34 or 39, wherein the compound has a capacity of about 150 mAh/g to about 200 mAh/g at a discharge rate of 2 coulombs (C).
[0140] Aspect 45. A method for making a compound having the formula A.sub.aM.sub.bN.sub.cX.sub.dY.sub.eS.sub.f, wherein [0141] A is Li, Na, K, or any combination thereof; [0142] M is Al, Ga, In, or any combination thereof; [0143] N is Mg, Ca, Zn, or any combination thereof; [0144] X and Y are, independently, F, Cl, Br, or I; [0145] S is sulfur; [0146] a is from about 1 to about 4; [0147] b is from about 0.5 to about 5.0; [0148] c is greater than or equal to 0 to about 1.5; [0149] d is from about 1 to about 5; [0150] e is greater than or equal to 0 to about 3; [0151] f is greater than 0 to about 3; and [0152] the sum (a+3b+2c) is equal to the sum (d+e+2f), the method comprising: [0153] mixing in the solid state the following components: (i) A.sub.2S; (ii) AX, AY, or a combination thereof; (iii) MX.sub.3, MY.sub.3, or a combination thereof; and (iv) NX.sub.2, NY.sub.2, or a combination thereof to produce a first mixture.
[0154] Aspect 46. The method of Aspect 45, wherein the components are substantially anhydrous.
[0155] Aspect 47. The method of Aspect 45 or 46, wherein the components are mixed by mechanochemical milling.
[0156] Aspect 48. The method of any one of Aspects 45-47, wherein the components are mixed in an inert atmosphere.
[0157] Aspect 49. A compound produced by the method of any one of Aspects 45-48.
[0158] Aspect 50. A battery comprising the compound in any one of Aspects 1-44 or 49.
[0159] Aspect 51. The battery of Aspect 50, wherein the battery is a solid-state battery.
EXAMPLES
[0160] 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.
Example 1
Materials and Methods
[0161] LiCl (Sigma Aldrich), LiBr (Sigma Aldrich), and NaCl (Sigma Aldrich) were dried at 200 C. for 12 hours under a dynamic vacuum before being stored in an argon-filled glovebox. Anhydrous Li.sub.2S (Alfa Aesar), anhydrous Na.sub.2S (Alfa Aesar), anhydrous AlCl.sub.3 (Alfa Aesar), ZnCl.sub.2 (Thermo Scientific), CaCl.sub.2 (Thermo Scientific), and GaF.sub.3 (Alfa Aesar) were received (packed under argon) and used without further purification. Stoichiometric amounts of precursors were ground using a mortar/pestle in different molar ratios for 5 minutes inside an argon-filled glovebox. After grinding, the hand-milled powder was transferred into a ZrO.sub.2 jar containing two 10-mm balls as a grinding aid followed by evacuation to ensure the vacuum sealing of the jar to protect it from any external reaction. Mechanochemical mixing of the hand-milled powder in a ZrO.sub.2 jar sealed under a vacuum was performed using a SPEX8000M MIXER/MILL high energy ball mill (SPEX SamplePrep, USA) for 10 hours. Afterward, the ball-milled powder, typically 130 mg, was pressed into an 8-mm pellet under pressure of 400 MPa inside an Argon-filled MBROUN glovebox. The resulting pellet after pressing had a thickness of 1 mm and the pellet appeared shiny white.
[0162] Powder X-ray DiffractionThe as-milled samples were packed in a zero-background sample holder. KAPTON film (DUPONT, USA) was used to seal the samples to prevent exposure to humid air. XRD was performed using a RIGAKU Smartlab powder diffractometer with Bragg-Brentano geometry at a voltage of 45 kV and current of 40 mA with Cu-Ka radiation (a=1.5406 ). The data was collected from 10-80 2 at a step size of 0.03 for 30 minutes.
[0163] Synchrotron X-ray DiffractionSynchrotron X-ray diffraction (SXRD) measurement was carried out in capillary transmission mode at beamline APS ANL, 17-BM-B at the Argonne National Lab, Illinois (ANL). The exact X-ray wavelength was refined to 0.24117 . The sample was loaded inside a special glass capillary and the holder moved up and down during tests to ensure uniformity of measured results.
[0164] Rietveld RefinementRietveld refinement was carried out on powder lab XRD and synchrotron XRD data with the aid of GSAS-II software. Structural analysis from synchrotron PXRD of Li-ion conductor reveals a monoclinic phase belonging to the P2.sub.1/c space group of LiAlCl.sub.4 (ICSD-35275). The LiCl and LiAlCl.sub.4 phases were used to refine the structure of LiAlCl.sub.4, while Li.sub.2S, LiCl, and LiAlCl.sub.4 were used for structural refinement of the Li.sub.2AlCl.sub.3S electrolyte. Sulfur occupancy was tested on all the chlorine sites and the result is only considered accurate when its occupancy is greater than 1% on the tested site. Lithium and aluminum occupancy were tested for the counter-cation sites of each other to find the most probable structure for the sulfur-doped electrolytes. Lab PXRD was used to refine the Li-ion conductor with the GaF.sub.3 substitution. The possible anion cation combination occupancy on the doping strategy was tested. Structural analysis from lab PXRD of Na-ion conductor reveals an orthorhombic phase belonging to the P2.sub.12.sub.12.sub.1 space group of NaAlCl.sub.4 (ICSD-2307). The NaCl and NaAlCl.sub.4 phases were used to refine the structure of NaAlCl.sub.4, while Na.sub.2S, NaCl, and NaAlCl.sub.4 were used for structural refinement of the Na.sub.2AlCl.sub.3S electrolyte. Sulfur occupancy was tested on all the chlorine sites and the result is only considered accurate when its occupancy is greater than 1% on the tested site. Sodium and aluminum occupancy were tested for the counter-cation sites of each other to find the most probable structure for the sulfur-doped electrolytes. Site occupancies for the same site were constrained to 1 except for Na.sub.2-xS.sub.1-xCl.sub.x. Atomic parameters for the same site were fixed for the substituents (Na, Ga, S, Cl, F, etc.).
[0165] Solid-state NMR.sup.6Li, .sup.7Li, and .sup.23Na NMR experiments were performed using a Bruker Advance-Ill 500 spectrometer at Larmor frequencies of 73.6 MHz, 194.4 MHz, and 132.31 MHz, respectively. The MAS rate was 24 kHz. For .sup.6Li.sub.7Li, and .sup.23Na, single-pulse NMR experiments were performed using /2 pulse lengths of 3.30 s, 2.90 s and 3.7 s, respectively. The recycle delays were 500s s for .sup.6Li, 80 s for .sup.7Li, and 50 s for .sup.23Na. .sup.6.7Li NMR spectra were calibrated with LiCl.sub.(s) at 1.1 ppm and .sup.23Na NMR spectra was calibrated with NaCl.sub.(aq) at 0 ppm. .sup.7Li T.sub.1 and .sup.23Na relaxation time was measured with an inversion-recovery pulse sequence.
[0166] Electrochemical Impedance Spectroscopy (EIS)The sample prepared was pressed in a mold of 8 mm split cell to make an approximately 1 mm thick pellet and sandwiched between 0.1 mm thick indium foils (6 mm diameter) as blocking electrodes. The measurement of potentiostatic EIS was carried out on a Gamry electrochemical analyzer on a frequency range from 1 Hz to 5 MHz. The conductivities are calculated using impedance from Nyquist plots. Variable temperature EIS characterization was performed in the CSZ microclimate chamber from 20 C. to 70 C. using a Biologic SP-300. Conductivities at various temperatures were calculated using Nyquist plots and the Arrhenius-type plots were prepared to calculate the activation energy.
[0167] DC polarizationTo measure the electronic conductivity, the DC polarization method was used..sup.19 In-house built split cells (diameter=8 mm) using PEEK insulating cylinder and stainless-steel plungers as current collectors and indium as ion-blocking electrodes were used.
Results and Discussion
[0168] X-ray DiffractionFirst, structural disorder was induced while maintaining periodic structure by subjecting stoichiometric amounts of AlCl.sub.3 and Li.sub.2S to high mechanical stress via high-energy ball milling. Structure characterization using powder XRD (PXRD) reveals the presence of a monoclinic LiAlCl.sub.4 phase for the pristine LAC composition as shown in
[0169] The evolution of peaks corresponding to extra phases was observed even at low sintering temperatures. The weak and diffuse diffraction pattern of the annealed LACS suggests a decrease in the crystallinity of the material. Compared to the as-milled LACS, the annealed LACS has an intense peak of around 300 which is also present in the monoclinic LAC phase. Previous research has established the coexistence of dual phases for annealed samples..sup.21 The coexistence of the monoclinic phase suggests a distortion in the crystal structure of the material..sup.21 In addition, by simultaneously doping Ga in place of Al, and F in place of Cl, a decrease in crystallinity of the LACS phase was observed (
[0170] In the case of the Na analog, similar mixed-anion effects on the structure, like in LACS, are observed. Stoichiometric amounts of NaCl, AlCl.sub.3 and Na.sub.2S were high-energy ball milled to synthesize NaAlCl.sub.4 and Na.sub.2AlCl.sub.3S. Structure characterization using powder XRD (PXRD) reveals the presence of an orthorhombic NaAlCl.sub.4 (NAC) phase for the pristine NAC composition (
[0171] In addition, synthesis of the potassium analog of LASC and NASC was attempted. The PXRD patterns of K.sub.2AlCl.sub.3S (KACS) and KAlCl.sub.4 (KAC) and the precursors are presented in
[0172] Structure RefinementLi.sub.2AlCl.sub.3S crystallizes as a monoclinic structure type in the P21/c space group. Structural refinement was performed using GSAS-II on the synchrotron XRD data.
[0173] The complete refinement parameters for the pristine and sulfur-substituted analog are provided in Table 4 to Table 9. From Table 5, refinement results reveal site disorder at the Cl.sup./S.sup.2 site. This confirms that sulfur substitution via mechanochemical synthesis enforces local disorder made possible by the dynamic anion effect..sup.22 Notably, the refinement results show the presence of a trace amount of Li.sub.2S in the ball-milled sample. This result is consistent with the data from powder XRD and solid-state NMR (see below), thereby validating the accuracy of the structure refinement. In contrast to the Li site occupancies for LAC, a fraction of Li occupies the shared Al tetrahedral interstitial sites in LACScreating more interconnected pathways for lithium-ion mobility. The fractional occupancy of lithium in tetrahedral sites particularly helps facilitate lithium hopping from one octahedral site to another octahedral site via connected tetrahedral sites. This validates the hypothesis that mechanochemical synthesis of the sulfur-substituted LAC generates a tetrahedral site occupation as confirmed by the low-intensity resonance in high-resolution .sup.6Li NMR analysis (see below). Notably, the formation of edge-sharing tetrahedrally coordinated lithium sites creates a pathway with lower energy barriers and correlates with the enhancement in the ionic conductivity of LACS.
[0174] For the Na analog, Na.sub.2AlCl.sub.3S crystallizes as an orthorhombic structure type in the P2.sub.12.sub.12.sub.1 space group. Structural refinement was performed using GSAS-II on the lab PXRD data. The complete table of refinement parameters for the pristine and sulfur-substituted analog are provided in Table 7, Table 8, and Table 9. From Table 8, the refinement results reveal disorder at the Cl.sup./S.sup.2 sites, similar to the lithium analog. The structure of Na.sub.2AlCl.sub.3S consists of two different polyhedral oriented randomly within the structure. In the Na-only (Na1) polyhedral, six C atoms and one S atom are distributed along the vertices of the polyhedral to form a 7-coordinate geometry. Na2 and Al1 occupy the tetrahedral site and are coordinated to three C atoms and a vacancy-rich S atom. Utilizing two of the three C atoms and the S atom, Na2 in the tetrahedral interstitial is edge-sharing with Na-only (Na1) polyhedral.
[0175] Solid-state NMRTo advance understanding of the phases present and the local structure of LACS and Li.sub.4AlCl.sub.3S.sub.2(LACS2), .sup.6Li solid-state NMR was performed.
[0176] The ion diffusion mechanism in ternary halides which extends to normal-spinel type and inverse-spinel type structures has been described as that in which tetrahedral coordinated Li-ions migrate using octahedral interstitials..sup.25,26 As expected, the ionic conductivity of some SEs in this family such as Li.sub.2 ZnCl.sub.4 has been reported to be considerably low owing to the presence of only octahedrally coordinated sites for lithium ions..sup.25 This amplifies the need to explore routes that ensure the presence of tetrahedrally coordinated lithium sites where vacancies are preferentially generated to enhance Li.sup.+ mobility.
[0177] .sup.7Li spin-lattice relaxation time (T.sub.1) is a useful indicator of ion dynamics. Table 1 confirms that LACS has a shorter T.sub.i compared to LAC and LACS2, which suggests faster ion motion..sup.27
TABLE-US-00001 TABLE 1 .sup.7Li spin-lattice relaxation time (T.sub.1) of LAC, LACS, and LACS2 .sup.7Li T.sub.1 [s] Sample Li2 Li1 LiAlCl.sub.4 9.24 Li.sub.2AlCl.sub.3S 1.15 8.34 Li.sub.4AlCl.sub.3S.sub.2 1.19 8.73
[0178]
[0179] These resonances may depict different coordination environments that may not be prominent in the structural refinement of the diffraction data. Specifically, the significant site disorder in NACS, introduces a distribution of local environments for Na.sup.+ within the disordered region. The resonances at 15.04, 16.63, and 21.75 are therefore attributed to disordered Na.sub.1+xAlCl.sub.4-xS.sub.x from the NACS phase. Notably, the second-order quadrupolar line shape is not so prominent in NACS further corroborating the observation that the Na occupying the tetrahedral site may not be distinctly described by a perfect tetrahedral, but rather by a random distribution of S.sup.2 and Cl.sup...sup.24 The T.sub.1 of NACS is shown in Table 2.
TABLE-US-00002 TABLE 2 .sup.23Na spin-lattice relaxation time (T.sub.1) of Na.sub.2AlCl.sub.3S .sup.23Na T.sub.1 [s] Sample Na1 Na2 Na.sub.2AlCl.sub.3S 0.45 0.61
[0180] Electrochemical PropertiesTo probe the alkali-ion dynamics of all prepared materials electrochemical impedance spectroscopy (EIS) was performed and the corresponding Nyquist plots are presented in
[0181] For the composition of LACS the ionic conductivity was at least twenty-fold greater than pristine LiAlCl.sub.4 at room temperature. Based on fitted resistance from the Nyquist plot using equivalent circuit modeling (exemplary fit given in
[0182] LACS2 are shown in
[0183] Additionally, Na-ion diffusion was probed in the synthesized SEs using EIS. At an optimal composition of NACS, approximately a sixty-fold increase in ionic conductivity than pristine NAC is observed at room temperature. Based on the fitting of the Nyquist plot, an ionic conductivity of 0.15 mS cm.sup.1 is achieved for NACS (
[0184] Despite the futile attempt to synthesize KACS, the EIS analysis was performed on the prepared materials. Since there was no evident semicircle from the Nyquist plot, the activation energy and ionic conductivity were not determined.
[0185] The presence of octahedral and tetrahedral sites has been established for ternary metal halides such as Li.sub.2MgCl.sub.4 and LiAlCl.sub.4 where intrinsic tetrahedral and octahedral interstitial sites govern the ion conduction mechanism. As expected, these materials possess relatively higher conductivity owing to the modified structure that facilitates ion hopping from the 4e octahedral site to the 4e tetrahedral site..sup.1 This 2D conduction pathway from Li.sub.tetLi.sub.octLi.sub.tet has been poised as one that could be generated via mechanochemical synthesis..sup.1 Indeed, high-resolution .sup.6Li NMR of LACS and LACS2 in this present study reveals the two resonances at 0.98 and 0.15 ppm assigned as lithium octahedral and tetrahedral sites. It then becomes more plausible to relate the origin of the higher conductivity to the S.sup.2/Cl.sup. site disorder and the presence of edge-sharing tetrahedrally coordinated lithium sites.
TABLE-US-00003 TABLE 3 Different compositions of prepared A.sub.aM.sub.bNcX.sub.dY.sub.eS.sub.f SEs and their corresponding ionic conductivity, electronic conductivity, activation energy, and Arrhenius prefactor at room 25 C. Log(.sub.0) .sub.DC, 25 C. .sub.e, 25 C. E.sub.a [S cm.sup.1 Composition [S cm.sup.1] [S cm.sup.1] [eV] K] LiAlCl.sub.4 - BM 8.65 10.sup.6 3.49 10.sup.8 0.51 6.55 Li.sub.2AlCl.sub.3S - BM 1.80 10.sup.4 5.43 10.sup.8 0.44 6.07 Li.sub.4AlCl.sub.3S.sub.2 - BM 1.30 10.sup.4 7.73 10.sup.8 0.46 6.27 Li.sub.2Al.sub.0.9Ga.sub.0.1Cl.sub.2.7F.sub.0.3S - 1.70 10.sup.4 6.12 10.sup.8 0.49 7.04 BM Li.sub.2Al.sub.0.8Ga.sub.0.2Cl.sub.2.4F.sub.0.6S - 3.50 10.sup.4 4.75 10.sup.9 0.44 6.43 BM Li.sub.2Al.sub.0.7Ga.sub.0.3Cl.sub.2.1F.sub.0.9S - 1.50 10.sup.4 3.16 10.sup.9 0.46 6.51 BM NaAlCl.sub.4 - BM 3.10 10.sup.6 4.31 10.sup.9 0.46 4.86 Na.sub.2AlCl.sub.3S - BM 1.5 10.sup.4 4.07 10.sup.9 0.41 5.63
TABLE-US-00004 TABLE 4 Rietveld-refinement results of synchrotron diffraction data at room temperature for the mechanochemically synthesized LiAlCl.sub.4. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li1 Li 4e 0.176(3) 1.009(4) 0.380(2) 1 0.038(6) Al1 Al 4e 0.7098(8) 0.329(1) 0.9006(5) 1 0.039(2) Cl1 Cl 4e 0.6944(8) 0.1834(8) 0.0459(5) 1 0.045(2) Cl2 Cl 4e 0.8085(8) 0.6225(8) 0.9265(5) 1 0.036(2) Cl3 Cl 4e 0.9232(8) 0.1819(9) 0.8136(5) 1 0.038(2) Cl4 Cl 4e 0.4469(8) 0.3062(8) 0.8127(5) 1 0.035(2) LiAlCl.sub.4 - Ball milled for 20 h. Composition: LiAlCl.sub.4 Lattice parameter: a = 7.0035(7), b = 6.5088(6), c = 13.0008(8), a = g = 90.000, b = 93.34(7), Unit-cell volume = 591.62(8) .sup.3 Density of Li.sub.2AlCl.sub.4 = 1.973 g/cm.sup.3 R.sub.wp = 5.482%, Space group P2.sub.1/c, Impurity phases: 2.1 wt % of LiCl
TABLE-US-00005 TABLE 5 Rietveld-refinement results of synchrotron diffraction data at room temperature for the mechanochemically synthesized Li.sub.2AlCl.sub.4S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li1 Li 4e 0.17(1) 0.99(1) 0.364(6) 1 0.072(6) Li2 Li 4e 0.719 0.329 0.902 0.030(7) 0.023(3) Al2 Al 4e 0.719(2) 0.329(2) 0.902(1) 0.970(4) 0.026(3) Cl1 Cl 4e 0.677(2) 0.195(1) 0.0500(8) 1 0.039(3) Cl2 Cl 4e 0.945(2) 0.160(2) 0.811(1) 1 0.031(3) Cl3 Cl 4e 0.814(2) 0.619(1) 0.924(1) 1 0.016(2) Cl4 Cl 4e 0.464(2) 0.290(2) 0.806(1) 0.566(6) 0.015(4) S4 S 4e 0.464 0.290 0.806 0.434(6) 0.054(3) Li.sub.2AlCl.sub.3S - Ball milled for 20 h. Composition: Li.sub.1.03Al.sub.0.97Cl.sub.3.57S.sub.0.43 Lattice parameter: a = 7.0195(8), b = 6.5237(8), c = 13.003 (2), a = g = 90.0000, b = 93.47(1), Unit-cell volume = 594.38(8) .sup.3; Density of Li.sub.1.15Al.sub.0.85Cl.sub.3.68S.sub.0.32 = 1.941 g/cm.sup.3 R.sub.wp = 5.76%, Space group P2.sub.1/c Impurity phases: 23.2 wt % of Li.sub.2S and 3.3 wt % of Li.sub.2-xS.sub.1-xCl.sub.x
TABLE-US-00006 TABLE 6 Na.sub.1.98.S.sub.0.92Cl.sub.0.07 phase from Rietveld-refinement results of XRD at room temperature for the mechanochemically synthesized Na.sub.2AlCl.sub.4S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li Li 8c 0.25 0.25 0.25 0.901(1) 0.014(5) S S 4a 0 0 0 0.801(1) 0.010(1) Cl Na 4a 0 0 0 0.199(3) 0.017(2) Refined composition: Li.sub.1.8.S.sub.0.8Cl.sub.0.2 Lattice parameter: a = 5.7138(7), a = b = g = 90.0000, Unit-cell volume = 186.54(5) .sup.3; Density of Na.sub.2AlCl.sub.3S = 1.867 g/cm.sup.3 Space group Fm-3m
TABLE-US-00007 TABLE 7 Rietveld-refinement results of X-ray diffraction data at room temperature for the mechanochemically synthesized NaAlCl.sub.4. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Na1 Na 4a 0.120(2) 0.218(1) 0.689(2) 1 0.063(6) Al1 Al 4a 0.0380(9) 0.483(2) 0.207(2) 1 0.033(4) Cl1 Cl 4a 0.0312(6) 0.492(1) 0.556(1) 1 0.048(3) Cl2 Cl 4a 0.145(1) 0.316(1) 0.113(2) 1 0.047(4) Cl3 Cl 4a 0.3475(7) 0.024(1) 0.923(1) 1 0.038(3) Cl4 Cl 4a 0.382(1) 0.336(1) 0.572(2) 1 0.049(4) NaAlCl.sub.4 - Ball milled for 20 h. Lattice parameter: a = 10.3406(2), b = 9.8956(2), c = 6.1723(6), a = b = g = 90.0000, Unit-cell volume = 631.59(8 .sup.3 Density of NaAlCl.sub.4 = 2.017 g/cm.sup.3 R.sub.wp = 4.190%, Space group P2.sub.12.sub.12.sub.1, Impurity phases: 2.9 wt % of NaCl
TABLE-US-00008 TABLE 8 Rietveld-refinement results of XRD at room temperature for the mechanochemically synthesized Na.sub.2AlCl.sub.4S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Na1 Na 4a 0.117(3) 0.211(3) 0.696(4) 1 0.036(7) Al1 Al 4a 0.039(2) 0.481(3) 0.215(3) 0.859(3) 0.015(6) Na2 Na 4a 0.039 0.481 0.215 0.141(4) 0.015 Cl1 Cl 4a 0.031(2) 0.493(4) 0.553(3) 1 0.041(9) Cl2 Cl 4a 0.141(7) 0.307(9) 0.111(7) 0.619(2) 0.04(2) Cl3 Cl 4a 0.344(2) 0.018(3) 0.921(4) 1 0.030(8) Cl4 Cl 4a 0.374(2) 0.333(2) 0.570(4) 1 0.012(8) S2 S 4a 0.144 0.314 0.105 0.381(2) 0.04 Refined composition: Na.sub.1.14Al.sub.0.86Cl.sub.3.62S.sub.0.38 Lattice parameter: a = 10.361(1), b = 9.890(1), c = 6.1765(6), a = b = g = 90.0000, Unit-cell volume = 632.85(8) .sup.3; Density of Na.sub.2AlCl.sub.3S = 1.993 g/cm.sup.3 R.sub.wp = 3.865%, Space group P2.sub.12.sub.12.sub.1
TABLE-US-00009 TABLE 9 Na.sub.1.98.S.sub.0.92Cl.sub.0.07 phase from Rietveld-refinement results of XRD at room temperature for the mechanochemically synthesized Na.sub.2AlCl.sub.4S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Na Na 8c 0.25 0.25 0.25 0.989(1) 0.011(1) S S 4a 0 0 0 0.920(1) 0.012(1) Cl Na 4b 0.5 0.5 0.5 0.073(3) 0.153(6) Refined composition: Na.sub.1.98.S.sub.0.92Cl.sub.0.07 Lattice parameter: a = 6.5389(7), a = b = g = 90.0000, Unit-cell volume = 279.59(3) .sup.3; Density of Na.sub.2AlCl.sub.3S = 1.867 g/cm.sup.3 Space group Fm-3m
TABLE-US-00010 TABLE 10 Different compositions of prepared A.sub.aM.sub.bNcX.sub.dY.sub.eS.sub.f SEs and their corresponding ionic conductivity at room 25 C. .sub.DC, 25 C. Composition [S/cm] LiAlCl.sub.4 - BM 8.65 10.sup.6 LiAl.sub.0.5Zn.sub.0.5Cl.sub.3.5 - BM 6.68 10.sup.7 Li.sub.1.5Al.sub.0.5Zn.sub.0.5Cl.sub.4 - BM 5.60 10.sup.6 Li.sub.1.5Al.sub.0.5Zn.sub.0.5Cl.sub.4 - 250 C. 4.90 10.sup.6 Li.sub.1.2Al.sub.0.8Ca.sub.0.2Cl.sub.4 - 200 C. 1.27 10.sup.7 Li.sub.1.6Al.sub.0.6Ca.sub.0.4Cl.sub.4 - 200 C. 1.68 10.sup.7 LiAlCl.sub.3.5Br.sub.0.5- BM 6.40 10.sup.6
Example 2
Material Synthesis
[0186] LiCl (Sigma Aldrich) was dried at 200 C. for 12 hours under a dynamic vacuum before being stored in an argon-filled glovebox. Anhydrous Li.sub.2S (Alfa Aesar) and ultra-dry AlCl.sub.3 (Alfa Aesar) were used as received and handled under argon. Stoichiometric amounts of precursors were ground using a mortar/pestle for 5 minutes inside an argon-filled glovebox. The hand-milled powder was transferred into a ZrO.sub.2 jar containing two 10-mm balls as milling media. After the jar was vacuum sealed, mechanochemical mixing was performed using a SPEX 8000M MIXER/MILL (SPEX SamplePrep, USA) for 20 hours. Afterward, the ball-milled powder, typically 130 mg, was pressed into a pellet of 8 mm in diameter under 400 MPa inside an argon-filled Mbraun glovebox. The resulting pellet had a thickness of 1.2 mm and appeared shiny white.
[0187] Powder X-ray DiffractionThe as-milled samples were packed in a zero-background sample holder. KAPTON film (DUPONT, USA) was used to seal the samples to prevent exposure to humid air. Powder X-ray Diffraction (PXRD) was performed using a RIGAKU Smartlab powder diffractometer with Bragg-Brentano geometry at a voltage of 45 kV and current of 40 mA with Cu-Ka radiation (a=1.540562 ). The data was collected in the 26 range of 10-80 at a step size of 0.03 for 30 minutes.
[0188] Synchrotron X-ray DiffractionSynchrotron X-ray diffraction (SXRD) measurements were carried out in the transmission mode at the 17-BM-B beamline, APS, at Argonne National Lab (ANL), Illinois. The exact X-ray wavelength was refined to 0.24117 . The sample was loaded inside a special glass capillary, and the holder was moved up and down during tests to ensure uniformity of the measured results.
[0189] Rietveld RefinementRietveld refinement of the lab and synchrotron PXRD data was performed using the GSAS-II software. Structural analysis of the synchrotron PXRD data on LiAlCl.sub.4 and Li.sub.2AlCl.sub.3S reveals a monoclinic phase belonging to the P2.sub.1/c space group of LiAlCl.sub.4 (ICSD-35275). Sulfur occupancy was tested on all the chlorine sites, and the result was only considered accurate when sulfur occupancy was greater than 1% on the tested site. Lithium and aluminum occupancy were tested for the counter-cation sites of each other to find the most probable structure. Atomic parameters for the site were fixed for the substituents (S, Cl, etc.).
[0190] Computational ApproachAll density functional theory (DFT) energy calculations and ab initio molecular dynamics (AIMD) simulations were carried out in the Vienna ab initio simulation package (VASP)..sup.18 The projector-augmented-wave (PAW) approach was used..sup.19 Perdew-Burke-Ernzerhof generalized-gradient approximation (GGA-PBE) was chosen as the exchange-correlation functional using the latest PAW potential files available in VASP..sup.20 Python Materials Genomics (Pymatgen) package.sup.21 was used to optimize the structures of Li.sub.2AlCl.sub.3S. 10 supercells with different local environments were generated based on the 221 supercell of the LACS obtained from the high-resolution XRD structure refinement. Geometry optimization of the generated supercells was carried out using DFT calculations. The AIMD simulations.sup.22 were based on the canonical ensemble for over 80 s with a time step of 2 fs. The temperature was initialized at 100 K and elevated to the target value for the simulations.
[0191] Solid-state NMR.sup.6Li and .sup.7Li NMR experiments were performed using a Bruker Advance-III 500 spectrometer at Larmor frequencies of 73.6 MHz and 194.4 MHz for .sup.6Li and .sup.7Li, respectively. The magic-angle-spinning (MAS) rate was 24 kHz. Single-pulse MAS .sup.6Li and .sup.7Li NMR experiments were performed using /2 pulse lengths of 3.30 s and 2.90 s, respectively. For Li.sub.2AlCl.sub.3S, the recycle delays were 500 s for .sup.6Li and 80 s for .sup.7Li, while a recycle delay of 500 s for .sup.6Li and 90 s for .sup.7Li was utilized for LiAlCl.sub.4.7Li NMR spectra were calibrated with LiCl(s) at 1.1 ppm, and .sup.7Li T.sub.1 relaxation time was measured with an inversion-recovery pulse sequence.
[0192] Variable-temperature .sup.7Li T.sub.1 relaxation NMR experiments were performed using a Bruker Avance-I 300 MHz Spectrometer from 25 to 70 C. An inversion recovery pulse sequence with a /2 pulse length of 2.63 s was utilized. The .sup.7Li Larmor frequency was 116.6 MHz. Sample powders were packed into 4 mm ZrO.sub.2 rotors under Argon and spun at a MAS rate of 10 kHz.
[0193] A .sup.6Li| SE|.sup.6Li symmetrical cell was assembled in an argon-filled glovebox for the .sup.6Li .sup.7Li tracer exchange experiment. The cell was then subjected to galvanostatic cycling for 3 days at a current density of 5 A cm.sup.2 to drive the diffusion of .sup.6Li.sup.+ ions from the .sup.6Li foil into the Li.sub.2AlCl.sub.3S pellet. Following the galvanostatic cycling, .sup.6Li MAS NMR experiments were performed on the cycled Li.sub.2AlCl.sub.3S pellet using the Bruker Advance-Ill 500 spectrometer at a spinning rate of 24 kHz, using the same parameters as described above.
[0194] Electrochemical Impedance Spectroscopy (EIS)The samples were pressed in a mold of 8-mm diameter to make 1.3-mm thick pellets, which were sandwiched between Indium of diameter 6 mm (about 0.24 in) followed by stainless steel plungers as ion-blocking electrodes. The measurement of potentiostatic EIS was carried out on a Biologic SP-300 electrochemical analyzer within a frequency range from 7 MHz to 1 Hz using a voltage of 10 mV. The conductivities are calculated using resistance obtained by fitting the Nyquist plots using an equivalent circuit model. Variable-temperature EIS characterization was performed in the CSZ microclimate chamber from 20 C. to 70 C. using a Biologic SP-300, and Arrhenius-type plots were used to calculate the activation energies and Arrhenius prefactors.
[0195] DC PolarizationThe DC polarization method was used to measure the electronic conductivity..sup.23 In-house-built split cells (diameter=8 mm) using PEEK insulating cylinder and stainless-steel plungers as current collectors and indium foils (6 mm diameter) as ion-blocking electrodes were used.
[0196] Cyclic Voltammetry (CV) and Galvanostatic Cycling of ASSB Half-cellsASSB half-cells were assembled using pressure cells constructed in-house, using a PEEK casing of 10 mm diameter and stainless-steel plungers. For CV measurements, the initial steps involved pressing 100 mg of LiAlCl.sub.4 (or Li.sub.2AlCl.sub.3S) at 300 MPa for 10 s. Then, roughly 10 mg of the manually mixed 3SE:carbon black (C: Super P) composite was evenly spread and pressed at 300 MPa for 10 s. On the opposite side of the LiAlCl.sub.4 (or Li.sub.2AlCl.sub.3S) pellet, a piece of indium (In) foil measuring 5/16 inch in diameter and 0.1 mm in thickness, with an approximate weight of 32 mg was attached. Subsequently, lithium foil with a 3/16-inch diameter and weighing around 1 mg was pressed onto the In foil to form LiIn and used as the counter electrode, giving a final cell setup of LiIn|SE|3SE:C. With the cell sealed using vacuum grease, it was subjected to electrochemical cycling under an estimated stack pressure of approximately 30 MPa at 22 C. CV measurements were conducted with a scan rate of 0.2 mV s.sup.1 from 0 to 4 V vs. LiIn.
[0197] To prepare the composite cathode (or catholyte) for galvanostatic cycling, TiS.sub.2 (Sigma Aldrich, 99.9%) was initially dried at 200 C. for 12 hours, then subjected to ball milling for 5 hours at 300 rpm to reduce particle size. Subsequently, LiAlCl.sub.4 or Li.sub.2AlCl.sub.3S was combined with TiS.sub.2 at a TiS.sub.2:SE mass ratio of 1:2 and ground together using a mortar and pestle for 10 minutes. Li.sub.6PS.sub.5Cl, synthesized following the established method by Patel et al.,.sup.12 was pressed into pellets at 300 MPa for 10 seconds as the separator. For the half-cell assembly, 12 mg of the catholyte was evenly spread onto one side of the Li.sub.6PS.sub.5Cl pellet, achieving an aerial loading of approximately 1.25 mAh cm.sup.2, followed by further pressing at 300 MPa for 10 seconds. A LiIn alloy foil was affixed to the opposite side of the Li.sub.6PS.sub.5Cl pellet to assemble the LiIn|Li.sub.6PS.sub.5Cl|2SE:TiS.sub.2 (SE: LiAlCl.sub.4 or Li.sub.2AlCl.sub.3S) half cells. Finally, the cells were sealed with vacuum grease and subjected to controlled cycling conditions at 22 C. with a stack pressure of 30 MPa, within a voltage window of 1-2.5 V vs. LiIn. For rate performance evaluations, the cells underwent cycling for 5 cycles at each of the following rates: 0.1 C, 0.2 C, 0.5 C, 1 C, and 2 C, with C representing the charge-discharge rate. Correspondingly, these rates translate to current densities of 0.14 mA cm.sup.2, 0.28 mA cm.sup.2, 0.70 mA cm.sup.2, 1.40 mA cm.sup.2, and 2.80 mA cm-2, respectively. Subsequently, long-term stability testing was conducted over 175 cycles at 0.2 C.
Results and Discussion
X-Ray Diffraction and Structure
[0198] X-ray diffraction (XRD) was employed to investigate the long-range structure of the synthesized solid electrolytes. The powder XRD confirms the presence of a monoclinic LiAlCl.sub.4 phase. With sulfur substitution, the long-range monoclinic structure is maintained for Li.sub.2AlCl.sub.3S. However, the weak and diffuse diffraction pattern of the as-milled Li.sub.2AlCl.sub.3S suggests a decrease in the crystallinity of the material. Rietveld refinement was performed against high-resolution XRD data using GSAS-II.
[0199] Similarly, Li.sub.2AlCl.sub.3S crystallizes in the P2.sub.1/c space group. However, different from LiAlCl.sub.4, the unit cell consists of three octahedrally coordinated cation sitesLi1 at 4e, Li2 at 2a, and Li3 at the 2a Wyckoff position; and tetrahedrally coordinated Al at the 4e Wyckoff position. Sulfur and chlorine atoms co-occupy the 4e anionic site, yielding a disordered anion sublattice. Along the c-direction, the structure exhibits three distinct cation layers (
TABLE-US-00011 TABLE 11 Rietveld-refinement results of high-resolution X-ray diffraction data at room temperature for the mechanochemically synthesized LiAlCl.sub.4. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li1 Li 4e 0.176(3) 1.009(4) 0.380(2) 1 0.038(6) Al1 Al 4e 0.7098(8) 0.329(1) 0.9006(5) 1 0.039(2) Cl1 Cl 4e 0.6944(8) 0.1834(8) 0.0459(5) 1 0.045(2) Cl2 Cl 4e 0.8085(8) 0.6225(8) 0.9265(5) 1 0.036(2) Cl3 Cl 4e 0.9232(8) 0.1819(9) 0.8136(5) 1 0.038(2) Cl4 Cl 4e 0.4469(8) 0.3062(8) 0.8127(5) 1 0.035(2) LiAlCl.sub.4 - Ball milled for 20 h. Composition: LiAlCl.sub.4 Lattice parameter: a = 7.0035(7), b = 6.5088(6), c = 13.0008(8), a = g = 90.000, b = 93.34(7), Unit-cell volume = 591.62(8) .sup.3 Density of Li.sub.2AlCl.sub.4 = 1.973 g/cm.sup.3 R.sub.wp = 5.482%, Space group P2.sub.1/c, Impurity phases: 2.8 wt % of LiCl
TABLE-US-00012 TABLE 12 Rietveld-refinement results of the high-resolution X-ray diffraction data for the mechanochemically synthesized Li.sub.2AlCl.sub.3S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li1 Li 4e 0.198(1) 0.035(1) 0.349(6) 1 0.14(4) Li2 Li 2a 0 0 0 1(4) 0.08(2) Li3 Li 2a 0.5 0 0.5 0.17(3) 0.59(7) Al2 Al 4e 0.728(2) 0.335(2) 0.898(1) 1 0.057(3) Cl1 Cl 4e 0.685(2) 0.200(2) 0.043(1) 1 0.025(5) Cl2 Cl 4e 0.955(2) 0.164(2) 0.809(1) 1 0.032(3) Cl3 Cl 4e 0.812(2) 0.622(1) 0.925(1) 1 0.032(3) Cl4 Cl 4e 0.464(2) 0.296(2) 0.806(1) 0.519(6) 0.065(6) S4 S 4e 0.464(2) 0.296(2) 0.806(1) 0.481(6) 0.065(6) Refined composition: Li.sub.1.6AlCl.sub.3.4S.sub.0.6 Lattice parameter: a = 7.0207(8), b = 6.5206(8), c = 13.004(2), a = g = 90.0000, b = 93.43(1), Unit-cell volume = 594.26(8) .sup.3; Density of Li.sub.1.6AlCl.sub.3.4S.sub.0.6 = 1.984 g cm.sup.3 R.sub.wp = 2.85%, Space group P2.sub.1/c Impurity phases: 14 wt % of Li.sub.2S and 10 wt % of Li.sub.1.66S.sub.0.66Cl.sub.0.34
TABLE-US-00013 TABLE 13 Rietveld-refinement results of the Li.sub.1.66S.sub.0.66Cl.sub.0.34- phase present in Li.sub.2AlCl.sub.3S. Wycoff Atomic coordinates Name Atom position x y z Occupancy U.sub.iso Li Li 8c 0.25 0.25 0.25 0.83(1) 0.015(5) S S 4a 0 0 0 0.66(1) 0.012(1) Cl Cl 4a 0 0 0 0.34(2) 0.012(2) Refined composition: Li.sub.1.66S.sub.0.66Cl.sub.0.34 Lattice parameter: a = 5.7138(7), a = b = g = 90.0000, Unit-cell volume = 186.64(5) .sup.3; Density of Li.sub.1.66S.sub.0.66Cl.sub.0.34 = 1.592 g/cm.sup.3 Space group Fm-3m
[0200] To understand the local structures of LiAlCl.sub.4 and Li.sub.1.6AlCl.sub.3.4S.sub.0.6, .sup.6Li MAS NMR experiments were performed. As shown in
TABLE-US-00014 TABLE 14 Li (%) distribution in various components in LiAlCl.sub.4 and Li.sub.1.6AlCl.sub.3.4S.sub.0.6 from .sup.6Li NMR analysis. .sup.6Li (%) Sample Li.sub.1 Li.sub.2 Li.sub.3 Li.sub.2S LiCl Li.sub.1.66S.sub.0.66Cl.sub.0.34 LiAlCl.sub.4 92.5 7.5 Li.sub.1.6AlCl.sub.3.4S.sub.0.6 60.6 31.1 1.3 3.1 3.9
[0201] .sup.7Li spin-lattice relaxation time (T.sub.1) is a useful indicator of ion dynamics..sup.10,26 According to the Bloembergen, Purcell, and Pound (BPP) model, T.sub.1 relaxation time is a function of motional rate
where is the gyromagnetic ratio, is the reduced Planck's constant, r.sub.0 is the interatomic distance, .sub.0=B.sub.0 is the Larmor frequency, and B.sub.0 is the external magnetic field strength.
[0202] In the fast-motion regime (.sub.0.sub.c<<1), T.sub.1 increases with increasing motional rate, while in the slow-motion regime (.sub.0.sub.c>>1), T.sub.1 decreases with increasing motional rate. In addition, a resonance can lie in the intermediate region where .sub.0.sub.e1..sup.27 Variable-temperature .sup.7Li NMR T.sub.1 relaxation data of Li.sub.1.6AlCl.sub.3.4S.sub.0.6 reveals a decrease in T.sub.1 relaxation time with increasing temperature and, thus, suggesting Li.sup.+ dynamics in Li.sub.1.6AlCl.sub.3.4S.sub.0.6 lie in the slow-motion regime (.sub.0.sub.c>>1). Therefore, a shorter T.sub.1 value will correlate with faster ion mobility. As presented in Table 15, the .sup.7Li T.sub.1 relaxation time significantly decreases from LiAlCl.sub.4 to Li.sub.1.6AlCl.sub.3.4S.sub.0.6, suggesting enhanced Li.sup.+ mobility.sup.28 with sulfur incorporation.
TABLE-US-00015 TABLE 15 .sup.7Li spin-lattice relaxation time (T.sub.1) of LiAlCl.sub.4 and Li.sub.1.6AlCl.sub.3.4S.sub.0.6 Sample .sup.7Li T.sub.1 [s] LiAlCl.sub.4 5.2 Li.sub.1.6AlCl.sub.3.4S.sub.0.6 3.1
Ion Transport Pathways Determined by Tracer-Exchange NMR
[0203] To directly probe the Li.sup.+ transport pathways in Li.sub.1.6AlCl.sub.3.4S.sub.0.6, tracer-exchange NMR is employed..sup.32 By identifying and quantifying .sup.6Li.sup.+ .sup.7Li.sup.+ exchange under an applied biased potential, the preferential pathway utilized by Li.sup.+ ions for migration is directly mapped outfacilitating the identification of active sites for Li.sup.+ transport..sup.29-32 The experimental configuration involves sandwiching Li.sub.1.6AlCl.sub.3.4S.sub.0.6 pellet between two .sup.6Li foils. An externally applied potential gradient establishes a driving force for .sup.6Li.sup.+ ions in the .sup.6Li foils to move toward and exchange with .sup.7Li.sup.+ in the Li.sub.1.6AlCl.sub.3.4S.sub.0.6 pellet. Consequently, the preferential Li.sup.+ transport pathways are selectively enriched with .sup.6Li.sup.+ ions. The .sup.6Li NMR spectra reveal changes in the relative intensities of resonances assigned to distinct Li.sup.+ environments. Notably, a significant increase in the intensity of the Li1 and Li2 resonances is observed, suggesting the major involvement of Li1 and Li2 in ion conduction. In addition, the Li3 resonance shows a small intensity enhancement after cycling. The enhancement of these resonances suggests that Li.sub.1, Li.sub.2, and Li3 all participate in Li.sup.+-ion transport within the Li.sub.1.6AlCl.sub.3.4S.sub.0.6 solid electrolyte.
AIMD Simulations
[0204] To further understand the effect of ClS anion mixing on the Li.sup.+ density distribution and diffusion, AIMD simulations are employed for LiAlCl.sub.4 and Li.sub.1.6AlCl.sub.3.4S.sub.0.6 in a 221 cell. The mean square displacements (MSD) of Li.sup.+ (
Electrochemical Properties
[0205] To examine ion transport properties of all prepared SEs, variable-temperature electrochemical impedance spectroscopy (EIS) was employed, and the corresponding Nyquist plots at 25 C. are presented in
TABLE-US-00016 TABLE 16 DC ionic conductivity at 25 C., electronic conductivity at 25 C., activation energy, and Arrhenius prefactor of LiAlCl.sub.4 and Li.sub.1.6AlCl.sub.3.4S.sub.0.6. .sub.DC, 25 C. .sub.e, 25 C. E.sub.a Log(.sub.0) Composition [S cm.sup.1] [S cm.sup.1] [eV] [S cm.sup.1 K] LiAlCl.sub.4 8.65 10.sup.6 3.49 10.sup.8 0.51 6.55 Li.sub.1.6AlCl.sub.3.4S.sub.0.6 1.80 10.sup.4 5.43 10.sup.8 0.44 6.07
Cyclic Voltammetry and Galvanostatic Cycling of ASSB Half-Cells
[0206] Conventionally, CV measurements were done using stainless steel as the blocking electrode, which fails to accurately measure the oxidation and reduction current of SEs due to the limited electrical contact area of the SE and the planar ion-blocking electrode..sup.10,34 To overcome this and estimate the oxidation-reduction reactions of the SE, we performed CV utilizing a 3SE:C (mass ratio) composite cathode in the LiIn|SE|3SE:C half-cell setup, according to the literature..sup.35-37 In this setup, carbon serves as an electronic conductive medium in the composite cathode, enabling increased SE surface area in electrical contact with the electrode and consequential detection of degradation current..sup.10,16,34-36,38-40
[0207] Titanium disulfide (TiS.sub.2) was employed as the cathode active material (CAM) in the half-cell configurations for electrochemical evaluation. LiIn|Li.sub.6PS.sub.5Cl|2(LiAlCl.sub.4):TiS.sub.2 and LiIn|Li.sub.6PS.sub.5Cl|2(Li.sub.1.6AlCl.sub.3.4S.sub.0.6):TiS.sub.2 cells were fabricated according to previous studies..sup.10,16 A LiIn anode was employed for enhanced stability against SEs and reduced dendrite formation through microporesreducing the risk of short circuits..sup.44 Li.sub.6PS.sub.5Cl was utilized as the separator due to its high ionic conductivity and stability against Li metal. The electrochemical performance of these half-cells was assessed through a series of rate capability tests, spanning charging/discharging currents from 0.1 C to 2 C conducted under galvanostatic conditions at 22 C. Each rate was applied over five cycles (0.1 C0.14 mA cm.sup.2, 0.2 C0.28 mA cm.sup.2, 0.5 C0.70 mA cm.sup.2, 1 C1.40 mA cm.sup.2, and 2 C2.80 mA cm.sup.2) followed by 125 cycles at 0.2 C. A theoretical capacity of 239 mAh g.sup.1 for TiS.sub.2 was used to calculate the charge-discharge rates.
[0208]
[0209] The Li.sub.1.6AlCl.sub.3.4S.sub.0.6-containing cell exhibited a capacity of 180 mAh g.sup.1 even at a high discharge rate of 2 C, indicative of exceptional rate performance in contrast to the significantly reduced capacity of 37 mAh g.sup.1 observed at a similar rate for the LiAlCl.sub.4-based cells. Upon returning to 0.2 C after 26 cycles, both cell configurations demonstrated remarkable stability over 200 cycles. Furthermore, these cells maintained a high coulombic efficiency exceeding 99% throughout this extended cycle period (
CONCLUSION
[0210] Developing inexpensive SEs using earth-abundant elements is imperative to reduce the cost of ASSBs for widespread applications in electric vehicles and consumer electronics. In this work, we synthesized a new lithium chalcohalide solid electrolyte, Li.sub.1.6AlCl.sub.3.4S.sub.0.6, with a room-temperature ionic conductivity of 0.18 mS cm.sup.1. Structural characterization reveals that the enhanced ionic conductivity of Li.sub.1.6AlCl.sub.3.4S.sub.0.6 strongly correlates with the formation of face- and edge-sharing octahedrally coordinated lithium sites. The face- and edge-shared octahedra create low-energy conduction pathways that promote 3D Li.sup.+ conduction, further confirmed by AIMD simulations using the refined structures. .sup.67Li MAS NMR combined with tracer exchange and relaxometry reveals increased ion mobility and participation of all Li.sup.+ sites in ion conduction. Li.sub.1.6AlCl.sub.3.4S.sub.0.6 demonstrates good long-term cycling stability and rate performance in ASSBs, achieving a specific capacity of 180 mAh g.sup.1 at a fast charging rate of 2 C in a LiIn|Li.sub.6PS.sub.5Cl|2(Li.sub.1.6AlCl.sub.3.4S.sub.0.6):TiS.sub.2 battery cell, compared to 37 mAh g.sup.1 in the LiAlCl.sub.4-containing cell. The cost-effectiveness, combined with the demonstrated high performance, makes Li.sub.1.6AlCl.sub.3.4S.sub.0.6 an excellent candidate as electrolytes for ASSBs.
[0211] 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.
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