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US-12623917-B2 - Solid electrolytes and methods for making the same

US12623917B2US 12623917 B2US12623917 B2US 12623917B2US-12623917-B2

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 a M b N c X d Y e S 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.

Inventors

  • Tej Prasad Poudel
  • Yan-Yan Hu
  • Ifeoluwa Peter Oyekunle

Assignees

  • FLORIDA STATE UNIVERSITY RESEARCH FOUNDATION, INC.

Dates

Publication Date
20260512
Application Date
20250814

Claims (11)

  1. 1 . A compound having the formula A a M b N c X d Y e S 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 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+20.
  2. 2 . The compound of claim 1 , wherein A is Li or Na, M is Al, and X is Cl.
  3. 3 . The compound of claim 1 , wherein A is Li, M is Al and Ga, X is Cl, and Y is F.
  4. 4 . The compound of claim 1 , wherein the compound has the formula Li a Al b N c Cl d S f , wherein N is Ca or Zn.
  5. 5 . The compound of claim 4 , 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.
  6. 6 . The compound of claim 1 , wherein the compound has an X-ray powder diffraction pattern comprising peaks at 23.5° and 38.9°±0.2° 2θ as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 Å.
  7. 7 . The compound of claim 1 , wherein the compound has an X-ray powder diffraction pattern comprising peaks at 28.4° and 40.6°±0.2° 2θ as measured by X-ray powder diffraction using an X-ray wavelength of 0.24 Å.
  8. 8 . 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 2C.
  9. 9 . A battery comprising the compound of claim 1 .
  10. 10 . A compound having the formula A a M b N c X d Y e S 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 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+20, wherein the compound is produced by the method comprising: mixing in the solid state the following components: (i) A 2 S; (ii) AX, AY, or a combination thereof; (iii) MX 3 , MY 3 , or a combination thereof; and (iv) NX 2 , NY 2 , or a combination thereof to produce a first mixture.
  11. 11 . A battery comprising the compound of claim 10 .

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation application of U.S. Nonprovisional patent application Ser. No. 18/959,854, filed on Nov. 26, 2024, which claims the benefit of and priority to U.S. Provisional Patent Application No. 63/603,404, filed on Nov. 28, 2023, the contents of which are incorporated by reference herein in their entireties. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT This invention was made with government support under DMR1847038, DMR1644779, and DMR2128556 awarded by the National Science Foundation. The government has certain rights in the invention. BACKGROUND As the demand for safe, affordable, sustainable, and renewable energy continues to rise, it has become more urgent to advance existing frontiers in the development of cost-effective energy storage. With the advent of superionic solid electrolytes (SEs), all-solid-state batteries (ASSBs) have emerged as next-generation high-performance secondary batteries. Both Li- and Na-superionic SEs can satisfy cost and performance metrics necessary for consumer electronics and large-scale energy storage. Over the past decades, ternary halides, e.g., LiAlCl4 (LAC) and NaAlCl4 (NAC), have gained popularity owing to their low cost and fast ion transport when in solution or as a melt. While this class of halide electrolytes demonstrates great potential in the liquid or molten state, there remains a need to overcome numerous safety issues associated with liquid electrolytes. One consideration in the development of SEs for practical applications is the cost of materials. Aluminum is the third most abundant element in the earth's crust, which makes its compounds desirable in both lithium and sodium SEs for ASSBs. The stability, electrochemical performance, and structure of alkali tetrahaloaluminates ZAlX4 (Z═Li, Na; X═Cl, Br, I) has been examined in previous studies. LiAlCl4, for example, has a good electrochemical stability window of 1.7 V-4.5 V vs Li/Li+. Computational predictions have suggested that doping LiAlCl4 with Zn may lead to some improvements in its ionic conductivity. However, the synthesis of computationally predicted materials requires a careful synthesis route which is often unachievable due to thermodynamic considerations. In the design of promising low melting point SEs, a one-step synthesis approach that uses mechanochemistry is beneficial as it can remove the extra heating step. Despite the efforts in the past years to provide structural insights to improve the Li+ dynamics within this material class, the ionic conductivity of this class of SE is still significantly low, consequently limiting the practical applications of this material. SUMMARY 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 AaMbNcXdYeSf 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. Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features, and advantages be included within this description, be within the scope of the present disclosure, and be protected by the accompanying claims. In addition, all optional and preferred features and modifications of the described embodiments are usable in all aspects of the disclosure taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with one another. BRIEF DESCRIPTION OF THE DRAWINGS 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. FIGS. 1A-1D show powder X-ray diffraction (XRD) pattern of as-milled LiAlCl4 (LAC), Li4AlCl3S2(LACS2), Li2AlCl3S (LACS), and Li2AlCl3S (heat treated at 150° C. for 2 hours) with the comparison of the ICSD patterns of precursor and LiAlCl4 monoclinic phase (P21/C space group) (FIG. 1A) and as-milled LiAlCl4, Li2Al0.9Ga0.1Cl2.7F0.3S, and Li2Al0.9Ga0.2Cl2.4F0.6S with the comparison of the ICSD patterns of precursor and LiAlCl4 monoclinic phase (P21/C space group) (FIG. 1C). FIG. 1B and FIG. 1D are magnifi