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EP-4738394-A1 - HALIDE SOLID ELECTROLYTE PRODUCTION METHOD, HALIDE SOLID ELECTROLYTE, POSITIVE ELECTRODE MATERIAL, AND BATTERY

EP4738394A1EP 4738394 A1EP4738394 A1EP 4738394A1EP-4738394-A1

Abstract

A production method for a solid electrolyte of the present disclosure is a production method for a halide solid electrolyte containing Li, Ti, M, and X. The M is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and metalloid elements, and the X is at least one selected from the group consisting of F, Cl, Br, and I. The production method includes: (A) performing halogenation treatment on at least one Li source selected from the group consisting of a simple oxide and a simple carbonate of Li, at least one Ti source selected from the group consisting of a simple oxide and a simple carbonate of Ti, and at least one M source selected from the group consisting of a simple oxide and a simple carbonate of M, to obtain a simple halide of Li, a simple halide of Ti, and a simple halide of M, respectively; and (B) synthesizing the halide solid electrolyte using the simple halide of Li, the simple halide of Ti, and the simple halide of M.

Inventors

  • KOGA, EIICHI

Assignees

  • Panasonic Intellectual Property Management Co., Ltd.

Dates

Publication Date
20260506
Application Date
20240606

Claims (20)

  1. A production method for a halide solid electrolyte containing Li, Ti, M, and X, wherein the M is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and metalloid elements and metal elements, the X is at least one selected from the group consisting of F, Cl, Br, and I, and the production method comprises: (A) performing halogenation treatment on at least one Li source selected from the group consisting of a simple oxide and a simple carbonate of Li, at least one Ti source selected from the group consisting of a simple oxide and a simple carbonate of Ti, and at least one M source selected from the group consisting of a simple oxide and a simple carbonate of M, to obtain a simple halide of Li, a simple halide of Ti, and a simple halide of M, respectively; and (B) synthesizing the halide solid electrolyte using the simple halide of Li, the simple halide of Ti, and the simple halide of M.
  2. The production method for the halide solid electrolyte according to claim 1, wherein the (A) includes: (A-0) pulverizing at least one selected from the group consisting of the Li source, the Ti source, and the M source; and (A-1) performing halogenation treatment on the Li source, the Ti source, and the M source after the (A-0), to obtain the simple halide of Li, the simple halide of Ti, and the simple halide of M, respectively.
  3. The production method for the halide solid electrolyte according to claim 1, wherein the halide solid electrolyte includes a first crystal phase represented by the following composition formula (1) and a second crystal phase represented by the following composition formula (2), composition formula (1): Li 2 TiX 6 , and composition formula (2): Li 3 MX 6 .
  4. The production method for the halide solid electrolyte according to claim 1, wherein the M includes Al.
  5. The production method for the halide solid electrolyte according to claim 1, wherein the X includes F.
  6. The production method for the halide solid electrolyte according to claim 1, wherein the Li source, the Ti source, and the M source are in particle form.
  7. The production method for the halide solid electrolyte according to claim 1, wherein in the (A), the halogenation treatment on the Li source, the Ti source, and the M source is performed by performing heat treatment on a halogen-containing substance having thermal decomposition properties.
  8. The production method for the halide solid electrolyte according to claim 7, wherein the halogen-containing substance is in particle form.
  9. The production method for the halide solid electrolyte according to claim 7, wherein the (A) includes: (A-1-1) mixing the Li source and a first halogen-containing substance, mixing the Ti source and a second halogen-containing substance, and mixing the M source and a third halogen-containing substance; and (A-1-2) performing halogenation treatment on the Li source, the Ti source, and the M source by respectively performing heat treatment on a first mixture including the Li source and the first halogen-containing substance, a second mixture including the Ti source and the second halogen-containing substance, and a third mixture including the M source and the third halogen-containing substance, which are obtained in the (A-1-1).
  10. The production method for the halide solid electrolyte according to claim 7, wherein in the (A), a halogen gas is generated by performing heat treatment on a halogen-containing substance, and the halogen gas is brought into contact with the Li source, the Ti source, and the M source, thereby performing the halogenation treatment on the Li source, the Ti source, and the M source.
  11. The production method for the halide solid electrolyte according to claim 7, wherein the halogen-containing substance includes an ammonium salt.
  12. The production method for the halide solid electrolyte according to claim 11, wherein the ammonium salt includes NH 4 F.
  13. The production method for the halide solid electrolyte according to claim 7, wherein the halogen-containing substance includes a resin.
  14. The production method for the halide solid electrolyte according to claim 13, wherein the resin includes a fluorine resin.
  15. The production method for the halide solid electrolyte according to claim 7, wherein the halogen-containing substance includes a substance from which inorganic components generated by thermal decomposition during the heat treatment in the (A), other than halogen elements, are substantially not incorporated into the halide solid electrolyte.
  16. The production method for the halide solid electrolyte according to claim 7, wherein the halogen-containing substance includes a plurality of types of halogen-containing compounds.
  17. The production method for the halide solid electrolyte according to claim 1, wherein in the (A), the halogenation treatment on the Li source, the Ti source, and the M source is performed at a temperature of 150°C or higher.
  18. A halide solid electrolyte comprising: Li; Ti; Al; F; and at least one selected from the group consisting of P and S.
  19. The halide solid electrolyte according to claim 18, wherein the halide solid electrolyte is in particle form, and each particle of the halide solid electrolyte comprises a first crystal phase represented by the following composition formula (4) and a second crystal phase represented by the following composition formula (5), composition formula (4): Li 2 TiX 6 , and composition formula (5): Li 3 AlX 6 .
  20. The halide solid electrolyte according to claim 19, wherein the halide solid electrolyte comprises an amorphous phase.

Description

TECHNICAL FIELD The present disclosure relates to a production method for a halide solid electrolyte, a halide solid electrolyte, a positive electrode material, and a battery. BACKGROUND ART Patent Literature 1 discloses a halide-based solid electrolyte material. In addition, Patent Literature 2 discloses a halide-based solid electrolyte material as a solid electrolyte material that coats the surface of a positive electrode active material. CITATION LIST Patent Literature Patent Literature 1: WO 2021/186809Patent Literature 2: WO 2021/187391 SUMMARY OF INVENTION Technical Problem The present disclosure aims to provide a novel production method that allows a halide solid electrolyte, which has excellent ionic conductivity comparable to that of a halide solid electrolyte produced by a conventional production method, to be synthesized at a low cost. Solution to Problem A production method for a halide solid electrolyte of the present disclosure is a production method for a halide solid electrolyte containing Li, Ti, M, and X, wherein the M is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and metalloid elements,the X is at least one selected from the group consisting of F, Cl, Br, and I, andthe production method includes: (A) performing halogenation treatment on at least one Li source selected from the group consisting of a simple oxide and a simple carbonate of Li, at least one Ti source selected from the group consisting of a simple oxide and a simple carbonate of Ti, and at least one M source selected from the group consisting of a simple oxide and a simple carbonate of M, to obtain a simple halide of Li, a simple halide of Ti, and a simple halide of M, respectively; and(B) synthesizing the halide solid electrolyte using the simple halide of Li, the simple halide of Ti, and the simple halide of M. Advantageous Effects of Invention The present disclosure provides a novel production method that allows a halide solid electrolyte, which has excellent ionic conductivity comparable to that of a halide solid electrolyte produced by a conventional production method, to be synthesized at a low cost. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing an example of a production method for a halide solid electrolyte according to a first embodiment.FIG. 2 is a flowchart showing an example of a production method for a halide solid electrolyte according to a second embodiment.FIG. 3 is a flowchart showing a modification of the production method for a halide solid electrolyte according to the second embodiment.FIG. 4 is a flowchart showing an example of a production method for a halide solid electrolyte according to a third embodiment.FIG. 5 illustrates a cross-sectional view of a battery 1000 according to a fourth embodiment.FIG. 6A is a graph showing an X-ray diffraction pattern of a halide solid electrolyte after heat treatment and before pulverization treatment in a production method of Example 1.FIG. 6B is a graph showing X-ray diffraction patterns of a halide solid electrolyte after pulverization treatment obtained in Example 1 and a halide solid electrolyte obtained in Comparative Example 1. DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present disclosure will be specifically described with reference to the drawings. The embodiments described below are all comprehensive or specific examples. The numerical values, shapes, materials, components, etc., shown in the following embodiments are examples, and are not intended to limit the present disclosure. In addition, among the components in the following embodiments, the components that are not described in the independent claims that represent broadest concepts are described as discretionary components. [First Embodiment] Hereinafter, a production method for a halide solid electrolyte according to a first embodiment will be described. The production method according to the first embodiment is a production method for a halide solid electrolyte containing Li, Ti, M, and X. Here, M is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and metalloid elements, and X is at least one selected from the group consisting of F, Cl, Br, and I. The production method according to the first embodiment includes: (A) performing halogenation treatment on at least one Li source selected from the group consisting of a simple oxide and a simple carbonate of Li, at least one Ti source selected from the group consisting of a simple oxide and a simple carbonate of Ti, and at least one M source selected from the group consisting of a simple oxide and a simple carbonate of M, to obtain a simple halide of Li, a simple halide of Ti, and a simple halide of M, respectively; and(B) synthesizing the halide solid electrolyte using the simple halide of Li, the simple halide of Ti, and the simple halide of M. The "metalloid elements" are B, Si, Ge, As, Sb, and Te. The "metal elements"