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CN-122003721-A - Solid electrolyte, method for producing solid electrolyte, and battery

CN122003721ACN 122003721 ACN122003721 ACN 122003721ACN-122003721-A

Abstract

The solid electrolyte contains M1, M2, and X, M1 is an element having a cation of 1 valence, including at least 1 element selected from the group consisting of Li, na, and K, M2 is at least 1 element having a cation of 3 valence, X is at least 1 element selected from the group consisting of F, cl, br, and I, and the axis angles α, β, and γ in the unit cell of the crystalline structure are each 90 °. Thus, a solid electrolyte having high ion conductivity can be provided.

Inventors

  • YAGI SUSUMU
  • High Bridge Remote Person
  • YOSHIDA TOSHIKATSU
  • Harasaki Reina

Assignees

  • 日本碍子株式会社
  • 国立大学法人名古屋工业大学

Dates

Publication Date
20260508
Application Date
20240919
Priority Date
20240528

Claims (11)

  1. 1. A solid electrolyte, wherein, Comprising M1, M2 and X, M1 is an element having a cation of valence 1, comprising at least 1 element selected from the group consisting of Li, na and K, M2 is at least 1 element in the form of a 3-valent cation, X is at least 1 element selected from the group consisting of F, cl, br and I, The axis angles α, β, γ in the unit cell of the crystalline structure are each 90 °.
  2. 2. The solid electrolyte according to claim 1, wherein, In an X-ray diffraction pattern obtained by X-ray diffraction measurement using CuK alpha rays, peaks exist in a range of 19 to 23 DEG, a range of 40 to 44 DEG, a range of 52 to 56 DEG, and a range of 64 to 68 DEG, respectively.
  3. 3. The solid electrolyte according to claim 1, wherein, In an X-ray diffraction pattern obtained by X-ray diffraction measurement using the CuK alpha ray, when the intensity of the strongest peak in the range of the diffraction angle 2 theta is defined as I1 and the intensity of the strongest peak in the range of the diffraction angle 2 theta is defined as I2, I1/(I1+I2) is greater than 0.30.
  4. 4. The solid electrolyte according to claim 1, wherein, Also included is M3, the M3 being at least 1 element that is a 4-valent cation.
  5. 5. The solid electrolyte according to claim 4, wherein, The composition is represented by M1 a M2 b M3 c X 6 , Satisfy 2< a <3, 0< b < 1) and 0< c <1.
  6. 6. The solid electrolyte according to claim 4, wherein, M3 comprises Ge or Si.
  7. 7. The solid electrolyte according to claim 1, wherein, X includes F.
  8. 8. The solid electrolyte according to claim 1, wherein, M2 comprises Al.
  9. 9. The solid electrolyte according to claim 1, wherein, M1 comprises Rb or Cs.
  10. 10. A method for producing a solid electrolyte according to any one of claims 1 to 9, comprising the steps of: a) Setting M1 as an element having 1 valence and including at least 1 element selected from the group consisting of Li, na and K, setting M2 as at least 1 element having 3 valence and setting X as at least 1 element selected from the group consisting of F, cl, br and I, setting M3 as at least 1 element having 4 valence, mixing M1 3 M2X 6 and M1 2 M3X 6 to obtain a mixture, or mixing M1X, M X 3 、M1 2 M3X 6 to obtain a mixture, and B) And carrying out mechanical grinding treatment on the mixture.
  11. 11. A battery is provided with: A positive electrode; Negative electrode, and An electrolyte layer provided between the positive electrode and the negative electrode, The solid electrolyte of any one of claims 1 to 9 being included in at least 1 of the positive electrode, the negative electrode, and the electrolyte layer.

Description

Solid electrolyte, method for producing solid electrolyte, and battery Technical Field The present invention relates to a solid electrolyte and a battery. [ Reference to related applications ] The present application claims the priority benefits of international patent application PCT/JP2023/35748 filed on 29 th 9 of 2023 and japanese patent application JP2024-86423 filed on 28 th 5 of 2024, the entire disclosures of which are incorporated herein. Background In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as power sources thereof has greatly increased. In a battery used for such applications, an organic electrolyte solution obtained by dissolving an electrolyte in a flammable organic solvent has been conventionally used as a medium for moving ions. In a battery including an organic electrolyte, there is a possibility that a problem relating to safety occurs. Accordingly, in order to intrinsically ensure safety, all-solid batteries using a solid electrolyte instead of an organic electrolyte have been developed. In all-solid batteries, the electrolyte is a nonflammable material, and therefore, an intrinsically safe lithium ion battery can be realized. For example, "All-Solid-State Lithium-Ion Batteries Using the Li3AlF6-Based Composite as the Solid Electrolyte"（ACS Applied Energy Materials, Volume 5, Issue 12, pp. 15365-15372）（ of Reona Miyazaki et al, patent publication No. 7, 1) discloses a solid electrolyte represented as Li 3AlF6－Li2SO4. Further, international publication No. 2023/13390 (document 2) discloses a solid electrolyte material including a crystal phase containing Li, zr, al, and F. From fig. 2 of document 2, it is considered that the crystal structure of the solid electrolyte material is monoclinic. In the solid electrolytes of documents 1 and 2, the ionic conductivity is insufficient, and therefore, a novel solid electrolyte having high ionic conductivity is required. Disclosure of Invention The present invention relates to a solid electrolyte, and an object thereof is to provide a solid electrolyte having high ion conductivity. The invention of claim 1 is a solid electrolyte comprising M1, M2, and X, M1 being an element having a cation of 1 valence, including at least 1 element selected from the group consisting of Li, na, and K, M2 being at least 1 element having a cation of 3 valence, X being at least 1 element selected from the group consisting of F, cl, br, and I, and the shaft angles α, β, and γ in the unit cell of the crystalline structure each being 90 °. According to the present invention, a solid electrolyte having high ion conductivity can be provided. The invention according to claim 2 is the solid electrolyte according to claim 1, wherein peaks exist in an X-ray diffraction pattern obtained by X-ray diffraction measurement using cukα rays in a range of 19 to 23 °, a range of 40 to 44 °, a range of 52 to 56 °, and a range of 64 to 68 ° respectively. The invention according to claim 3 is the solid electrolyte according to claim 1 or 2, wherein in the X-ray diffraction pattern obtained by the X-ray diffraction measurement using the cukα ray, when the intensity of the strongest peak in the range of the diffraction angle 2θ is I1 and the intensity of the strongest peak in the range of the diffraction angle 2θ is 19 to 23 ° is I2, I1/(i1+i2) is greater than 0.30. The invention of claim 4 further comprises M3, which is at least 1 element of a 4-valent cation, on the basis of the solid electrolyte of any one of claims 1 to 3. The invention of claim 5 is based on the solid electrolyte of claim 4, wherein the composition formula is represented by M1 aM2bM3cX6, and satisfies 2< a <3, 0< b <1, and 0< c <1. The invention of claim 6 is based on the solid electrolyte of claim 4 or 5, wherein M3 comprises Ge or Si. The invention of claim 7 is based on the solid electrolyte of any one of claims 1 to 6, wherein X includes F. The invention of claim 8 is the solid electrolyte of any one of claims 1 to 7, wherein M2 comprises Al. The invention of claim 9 is based on the solid electrolyte of any one of claims 1 to 8, M1 comprising Rb or Cs. The invention also relates to a method for manufacturing the solid electrolyte and a battery. The invention according to claim 10 is the method for producing a solid electrolyte according to any one of claims 1 to 9, comprising the steps of a) mixing M1 3M2X6 and M1 2M3X6 to obtain a mixture or mixing M1X, M X 3、M12M3X6 to obtain a mixture, wherein M1 is an element having a 1-valent cation and M2 is at least 1 element having a 3-valent cation, and M3 is at least 1 element selected from the group consisting of F, cl, br and I, and M1 3M2X6 and M1 2M3X6 are mixed to obtain a mixture, and b) subjecting the mixture to mechanical polishing. The invention of claim 11 is a battery provided with a positive electrode, a negative electrode, and an electrolyte layer provided between the positive e