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CN-122025755-A - Halide electrolyte, battery and preparation method

CN122025755ACN 122025755 ACN122025755 ACN 122025755ACN-122025755-A

Abstract

The present disclosure provides a halide electrolyte, a battery, and a method of manufacturing. Specifically, the halide electrolyte comprises crystalline halide and a coating layer positioned on the surface of the crystalline halide, wherein the coating layer comprises amorphous sulfide. The halide electrolyte is coated on the harder crystalline halide by adopting amorphous sulfide with softer mechanical strength, so that gaps after electrolyte tabletting are effectively filled, the density is improved, the ion conductivity is increased, the amorphous halide coated by the amorphous sulfide is highly stable to lithium metal, the interface side reaction is inhibited, the chemical stability with a negative electrode plate is improved, and the cycling stability and the safety of a battery are improved.

Inventors

  • YU LE
  • QU XINXIN

Assignees

  • 远景动力技术(江苏)有限公司
  • 远景睿泰动力技术(上海)有限公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. The halide electrolyte is characterized by comprising a crystalline halide and a coating layer positioned on the surface of the crystalline halide, wherein the coating layer comprises amorphous sulfide.
  2. 2. The halide electrolyte of claim 1 wherein the crystalline halide has a composition of the formula Li a M b X c , wherein M is selected from at least one of Al, in, Y, zr, ti, ga, ge, X is halogen, 1≤a≤8, 1≤b≤4, 1≤c≤8, and/or The amorphous sulfide has a composition shown in a general formula of Li x A y S z , wherein A is at least one of P, si, sn, ge, B, ga, al, x is more than or equal to 2 and less than or equal to 7, y is more than or equal to 0.5 and less than or equal to 4, and z is more than or equal to 3 and less than or equal to 12.
  3. 3. The halide electrolyte of claim 2, wherein the amorphous sulfide further comprises a halogen doping.
  4. 4. A halide electrolyte as claimed in claim 2 or claim 3, wherein the halogen comprises at least one of F, cl, br, I.
  5. 5. The halide electrolyte of claim 1, wherein the crystalline form of the crystalline halide comprises at least one of a monoclinic, a cubic, a tetragonal, and a hexagonal form.
  6. 6. The halide electrolyte of claim 1, wherein the crystalline halide comprises at least one of Li 3 AlCl 4 、Li 3 YCl 6 、Li 2 ZrCl 6 、Li 3 InCl 6 、Li 3 YBr 6 , and/or The amorphous sulfide includes at least one of Li 2 S–P 2 S 5 、Li 2 S–SiS 2 、Li 2 S–SnS 2 、Li 2 S–GeS 2 、Li 2 S–B 2 S 3 、Li 2 S–Ga 2 S 3 、Li 2 S–Al 2 S 3 、Li 6 PS 5 Cl.
  7. 7. The halide electrolyte according to claim 1, wherein the coating layer has a thickness of 0.2nm to 100nm, optionally 2nm to 40nm, and/or The average grain diameter of the crystalline halide is 1-10 mu m.
  8. 8. The halide electrolyte according to claim 7, wherein the coating layer has a thickness of 8nm to 12nm, and/or The average grain diameter of the crystalline halide is 1-5 mu m.
  9. 9. The method for producing a halide electrolyte according to any one of claims 1 to 8, characterized in that the method comprises: providing particles of the crystalline halide; the amorphous sulfide is formed on the particles using an atomic layer deposition method.
  10. 10. A battery comprising a positive electrode sheet, a negative electrode sheet, and the halide electrolyte of any one of claims 1 to 8.

Description

Halide electrolyte, battery and preparation method Technical Field The disclosure relates to the technical field of batteries, in particular to a halide electrolyte, a battery and a preparation method. Background All-Solid-state lithium batteries (All-Solid-State Lithium Batteries, ASSLBs) based on halides are considered as important candidates for next generation high energy density energy storage systems by virtue of their wide electrochemical window of electrolyte and potential compatibility with high voltage positive electrodes. However, the progress in the practical use of halide solid-state batteries is still subject to complex interfacial chemical and mechanical failure problems. Disclosure of Invention In view of the above, the present disclosure is directed to a halide electrolyte, a battery and a preparation method thereof. In accordance with the above objects, a first aspect of the present disclosure provides a halide electrolyte comprising a crystalline halide and a coating layer on a surface of the crystalline halide, wherein the coating layer comprises an amorphous sulfide. In some embodiments, the crystalline halide has a composition represented by the general formula Li aMbXc, wherein M is selected from at least one of Al, in, Y, zr, ti, ga, ge, X is halogen, 1≤a≤8, 1≤b≤4, 1≤c≤8, and/or The amorphous sulfide has a composition shown in a general formula of Li xAySz, wherein A is at least one of P, si, sn, ge, B, ga, al, x is more than or equal to 2 and less than or equal to 7, y is more than or equal to 0.5 and less than or equal to 4, and z is more than or equal to 3 and less than or equal to 12. In some embodiments, the amorphous sulfide further comprises a halogen doping. In some embodiments, the halogen comprises at least one of F, cl, br, I. In some embodiments, the crystalline form of the crystalline halide comprises at least one of a monoclinic, a cubic, a tetragonal, and a hexagonal form. In some embodiments, the crystalline halide comprises at least one of Li3AlCl4、Li3YCl6、Li2ZrCl6、Li3InCl6、Li3YBr6, and/or The amorphous sulfide includes at least one of Li2S–P2S5、Li2S–SiS2、Li2S–SnS2、Li2S–GeS2、Li2S–B2S3、Li2S–Ga2S3、Li2S–Al2S3、Li6PS5Cl. In some embodiments, the thickness of the coating is 0.2nm to 100nm, optionally the thickness of the coating is 2nm to 40nm, and/or The average grain diameter of the crystalline halide is 1-10 mu m. In some embodiments, the coating layer has a thickness of 8nm to 12nm, and/or The average grain diameter of the crystalline halide is 1-5 mu m. Based on the same inventive concept, the second aspect of the present disclosure also provides a method for preparing any one of the aforementioned halide electrolytes, comprising: providing particles of the crystalline halide; the amorphous sulfide is formed on the particles using an atomic layer deposition method. Based on the same inventive concept, a third aspect of the present disclosure also provides a battery comprising a positive electrode tab, a negative electrode tab, and any one of the aforementioned halide electrolytes. As can be seen from the above, the present disclosure provides a halide electrolyte, a battery and a method of manufacturing the same, wherein the halide electrolyte includes a crystalline halide and a coating layer on a surface of the crystalline halide, and wherein the coating layer includes an amorphous sulfide. The halide electrolyte is coated on the harder crystalline halide by adopting amorphous sulfide with softer mechanical strength, so that gaps after electrolyte tabletting are effectively filled, the density is improved, the ion conductivity is increased, the amorphous halide coated by the amorphous sulfide is highly stable to lithium metal, the interface side reaction is inhibited, the chemical stability with a negative electrode plate is improved, and the cycling stability and the safety of a battery are improved. Detailed Description For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples. It should be noted that unless otherwise defined, technical or scientific terms used in the embodiments of the present disclosure should be given the ordinary meaning as understood by one of ordinary skill in the art to which the present disclosure pertains. As used in the embodiments of the present disclosure, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-130 and 70-120 are listed for a particular parameter, it is understood that ranges of 60-120 and 70-130 are also contemplated. Fu