A multifunctional halide material, its preparation method and application

By preparing multifunctional halide materials Li2-xM1-xAxCl4, Li2-xM'1-xAxCl4, or Li2-xM''1-xAxCl4-3xE3x, the problem of insufficient ionic conductivity in lithium replenishment materials in solid-state batteries was solved, achieving high energy density and stable ionic conductivity, thus improving battery performance.

CN122079240APending Publication Date: 2026-05-26SHENZHEN INST OF ADVANCED TECH CHINESE ACAD OF SCI
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Patent Information

Application Number
CN202610305130.9
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2026-03-12
Publication Date
2026-05-26

AI Technical Summary

Technical Problem

The ionic conductivity of lithium replenishment materials in existing solid-state batteries is weak and cannot meet the conductivity requirements. Furthermore, the decomposition products may hinder ion transport. Existing solid electrolytes cannot play a lithium replenishment role, which limits the improvement of energy density of all-solid-state batteries.

Method used

Multifunctional halide materials Li2-xM1-xAxCl4, Li2-xM'1-xAxCl4, or Li2-xM''1-xAxCl4-3xE3x are used, where M, M', and M'' are specific metals and A is a transition metal. They are prepared by ball milling to ensure the balance between lithium vacancies and lithium concentration, and have both ionic conductivity and lithium replenishment functions.

Benefits of technology

It achieves high ionic conductivity and lithium replenishment effect, improves the energy density of solid-state batteries, solves the capacity decay problem caused by lithium loss, and provides an additional lithium source during the first charge and plays the role of ionic conductivity as a solid electrolyte.

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Abstract

This invention provides a multifunctional halide material, its preparation method, and its application; the multifunctional halide material includes at least one of the following: (I) Li 2‑x M 1‑x A x Cl4;(II) Li 2‑x M' 1‑ x A x Cl4;(II)Li 2‑x M'' 1‑x A x Cl 4‑3x E 3x The multifunctional halide material of this invention possesses both high ionic conductivity and partially reversible delithiation capability, providing additional lithium ions to achieve a lithium replenishment effect.
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Description

Technical Field

[0001] This invention relates to the field of energy materials technology, and in particular to a multifunctional halide material, its preparation method, and its application. Background Technology

[0002] Lithium-ion batteries, as high-energy-density batteries, are widely used in electric vehicles, electric aircraft, and energy storage systems. However, traditional liquid lithium-ion batteries suffer from energy density bottlenecks and safety hazards, severely limiting their further development. Solid-state batteries, with their higher energy density and better safety, can effectively promote the development of new energy vehicles and other fields, accelerating the global energy transition from traditional fossil fuels to clean energy. Because the active lithium content in both the positive and negative electrodes decreases due to their own reactions during the typical lithium-ion battery formation stage, lithium replenishment technology, which uses materials capable of extracting and extracting high-capacity lithium sources, can effectively compensate for the loss of active lithium in both electrodes, thereby improving the battery's design capacity density. However, in solid-state batteries, the use of lithium replenishment materials will occupy a portion of the positive electrode active material and electrolyte material, indirectly reducing the positive electrode's load. Although lithium replenishment technology is key to improving battery capacity density, its use in all-solid-state batteries will be limited if the competition between lithium replenishment materials and electrolyte materials cannot be resolved. To further improve the energy density of solid-state batteries, solid electrolytes that combine ionic conductivity and lithium replenishment have become a research hotspot. These solid electrolytes with lithium replenishment not only have a high ionic conductivity, but also contribute to capacity while ensuring interface stability, suppressing capacity decay caused by lithium loss, and can effectively improve the energy density of solid-state batteries.

[0003] Currently, the only method to achieve this dual role is Jiang et al.'s design of a Li₂S-rich Li₆PS₅Cl mixed carbon black conductive agent as the positive electrode layer. During the first charge, the Li₂S decomposes to release lithium ions, both replenishing the lithium supply to the entire battery and generating the active material S. The dispersed solid electrolyte particles ensure rapid ion transport, but essentially, both roles are being played. Current lithium replenishing agents have weak ion conductivity, failing to meet the conductivity requirements for electrolytes in all-solid-state batteries; moreover, the decomposition products may hinder ion transport. Existing solid electrolytes also cannot effectively replenish lithium. Summary of the Invention

[0004] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide a multifunctional halide material, its preparation method, and its applications.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A first aspect of the present invention provides a multifunctional halide material comprising at least one of the following: (I)Li 2-x M 1-x A x Cl4; where M is Mn; A is selected from at least one of Fe, In, Ru, Rh, Ir, Ga, and Y; 0 <x<1; (II) Li 2-x M' 1-x A x Cl4; wherein M' is selected from at least one of Fe, Ti, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; 0 <x<1; (II)Li 2-x M'' 1-x A x Cl 4-3x E 3x Wherein, M'' is selected from at least one of Fe, Ti, Mn, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; E is selected from at least one of F, Br, I, and O; O <x<1。

[0006] In some implementations, 0.1 <x<0.4。

[0007] In some implementations, the molar ratio of A to M ( / M' / M'') satisfies 0.

[0008] In some embodiments, the multifunctional halide material includes at least one of the following: Li 2-x Mn 1-x Ga x Cl4, Li 2-x Mn 1-x Fe x Cl4, Li 2-x Mn 1-x In x Cl4, Li 2-x Mn 1-x Ru x Cl4, Li 2-x Mn 1- x Rh x Cl4, Li 2-x Mn 1-x Ir x Cl4, Li 2-x Fe 1-x ​Ga x Cl4、Li 2-x Fe 1-x In x Cl4、Li 2-x Fe 1-x Ru x Cl4、Li 2-x Fe 1- x Rh x Cl4、Li 2-x Fe 1-x Ir x Cl4、Li 2-x Ti 1-x Nd x Cl4、Li 2-x Ti 1-x Ce x Cl4、Li 2-x Mn 1-x La x Cl 4-3x Br 3x 、Li 2- x Mn 1-x Ga x Cl 4-3x Br 3x 、Li 2-x Mn 1-x In x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ce x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ru x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Rh x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Y x Cl4- 3x Br 3x 、Li 2-x Mn 1-x Ir x Cl 4-3x Br 3x 、Li 2-x Mn 1-x La x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ga x Cl 4-3x F 3x 、Li 2-x Mn 1- x In x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ce x Cl 4-3x F 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x F 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x F 3x 、Li 2-x Mn 1- x Ru x Cl 4-3x F 3x 、Li 2-x Mn 1-x Rh x Cl 4-3x F 3x 、Li 2-x Mn 1-x Y x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ir x Cl 4-3x F 3x 、Li 2-x Mn 1- x Sb x Cl 4-3x I 3x 、Li 2-x Mn1-x La x Cl 4-3x AND 3x 、Li 2-x Mn 1-x In x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Yes x Cl 4-3x AND 3x 、Li 2-x Mn 1- x No x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Ru x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Rh x Cl 4-3x AND 3x 、Li 2-x Mn 1- x Ireland x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Him x Cl 4-3x AND 3x 、Li 2-x You 1-x Fe x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Ru x Cl 4-3x AND 3x 、Li 2-x Nor 1- x Rh x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Ireland x Cl 4-3x AND 3x 、Li2-x Ni 1-x Ga x Cl 4-3x I 3x .

[0009] In some embodiments, the multifunctional halide material includes at least one of the following: Li 1.9 Mn 0.9 Ga 0.1 Cl4, Li 1.9 Mn 0.9 Fe 0.1 Cl4, Li 1.9 Mn 0.9 In 0.1 Cl4, Li 1.9 Mn 0.9 Ru 0.1 Cl4, Li 1.9 Mn 0.9 Rh 0.1 Cl4, Li 1.9 Mn 0.9 Ir 0.9 Cl4, Li 1.9 Mn 0.9 Y 0.1 Cl4, Li 1.9 Mn 0.9 La 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 Ga 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 In 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 Ce 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 Nd 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 Fe 0.1 Cl 3.7 Br 0.3 Li 1.9 Mn 0.9 Ru 0.1 Cl 3.7 Br0.3 、Li 1.9 Mn 0.9 Rh 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Ir 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Y 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 La 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 In 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Ce 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Nd 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Fe 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Ru 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Rh 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Ir 0.1 Cl 3.7 F 0.3 、Li 1.9 Mn 0.9 Y 0.1 Cl 3.7 F 0.3 、Li 1.9Mr 0.9 Day 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 In 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Ce 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Nd 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Feb 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Ru 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Rh 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Ir 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Ga 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Y 0.1 Cl 3.7 I 0.3 、Li 1.9 Feb 0.9 Ce 0.1 Cl 3.7 I 0.3 、Li 1.9 Feb 0.9 Nd 0.1 Cl 3.7 I 0.3 、Li 1.9 Feb 0.9 Feb 0.1 Cl 3.7 I 0.3 、Li 1.9 Feb 0.9 Ru0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Rh 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Ireland 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Him 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Y 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Yes 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 No 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Fe 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Ru 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Rh 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Ireland 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Him 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Y 0.1 Cl 3.7 AND 0.3 、Li 1.9 You 0.9 Yes 0.1 Cl 3.7 AND0.3 Li 1.9 Ti 0.9 Nd 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Fe 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Ru 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Rh 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Ir 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Ga 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Y 0.1 Cl 3.7 I 0.3 .

[0010] A second aspect of the present invention provides a method for preparing the aforementioned multifunctional halide material, comprising the following steps: LiCl, the chloride salt of M or the halide salt of M', and the chloride salt of A are ball-milled to obtain Li 2-x M 1-x A x Cl4 or Li 2- x M' 1-x A x Cl4; Alternatively, LiCl and M'' chloride salts can be ball-milled with A halide salts or A oxides to obtain Li. 2-x M'' 1- x A x Cl 4-3x E 3x .

[0011] In some embodiments, the halide salt of M includes MnCl2.

[0012] In some embodiments, the chloride salt or halide salt of M' includes one of MnCl2, FeCl2, TiCl2, and NiCl2.

[0013] In some embodiments, the chloride salt of A includes one of FeCl3, GaCl3, InCl3, RuCl3, RhCl3, IrCl3, NdCl3, CeCl3, LaCl3, and YCl3. In some embodiments, the halide salt of A includes one of FeF3, GaF3, InF3, RuF3, RhF3, IrF3, NdF3, CeF3, LaF3, YF3, FeBr3, GaBr3, InBr3, RuBr3, RhBr3, IrBr3, NdBr3, CeBr3, LaBr3, YBr3, FeI3, GaI3, InI3, RuI3, RhI3, IrI3, NdI3, CeI3, LaI3, and YI3.

[0014] In some embodiments, the oxide of A includes one of Fe2O3, Ga2O3, In2O3, Ru2O3, Rh2O3, Ir2O3, and Nd2O3.

[0015] In some embodiments, the ball milling includes high-energy ball milling; the rotational speed of the ball milling is 200-800 rpm, such as 250-700 rpm; the ball milling time is 3-24 h, such as 5-20 h.

[0016] In some embodiments, the ball-to-material mass ratio of the ball mill is (20-80):1; such as 40:1.

[0017] A third aspect of the present invention provides a positive electrode active material, comprising a multifunctional halide material; said multifunctional halide material comprising (A) Li 2-x M' 1-x A x Cl4; and / or (B)Li 2-x M'' 1-x A x Cl 4-3x E 3x ; Wherein, M' and M'' are each independently selected from at least one of Fe, Ti, Mn, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; E is selected from at least one of F, Br, I, and O; 0 <x<1。

[0018] In some implementations, 0.1 <x<0.4。

[0019] In some implementations, the molar ratio of A to M' ( / M'') satisfies 0.

[0020] In some embodiments, the multifunctional halide material includes at least one of the following: Li 2-x Mn 1-x Ga x Cl4, Li 2-x Mn 1-x Fe x Cl4, Li 2-x Mn 1-x In x Cl4, Li 2-x Mn 1-x Ru x Cl4, Li 2-x Mn 1- x Rh x Cl4, Li 2-x Mn 1-x Ir x Cl4, Li 2-x Mn 1-x Nd x Cl4, Li 2-x Mn 1-x Ce x Cl4, Li 2-x Mn 1-x La x Cl4, Li 2-x Fe 1- x Ga x Cl4, Li 2-x Fe 1-x In x Cl4, Li 2-x Fe 1-x Ru x Cl4, Li 2-x Fe 1-x Rh x Cl4, Li 2-x Fe 1-x Ir x Cl4, Li 2-x Ti 1- x Nd x Cl4, Li 2-x Ti 1-x Ce x Cl4, Li 2-x Mn​1-x La x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ga x Cl 4-3x Br 3x 、Li 2-x Mn 1-x In x Cl 4- 3x Br 3x 、Li 2-x Mn 1-x Ce x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x Br 3x 、Li 2-x Mn 1- x Ru x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Rh x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Y x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ir x Cl 4-3x Br 3x 、Li 2- x Mn 1-x La x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ga x Cl 4-3x F 3x 、Li 2-x Mn 1-x In x Cl 4-3x F 3x、Li 2-x Mr 1-x Ce x Cl 4-3x F 3x 、Li 2- x Mr 1-x Nd x Cl 4-3x F 3x 、Li 2-x Mr 1-x Feb x Cl 4-3x F 3x 、Li 2-x Mr 1-x Ru x Cl 4-3x F 3x 、Li 2-x Mr 1-x Rh x Cl 4-3x F 3x 、Li 2- x Mr 1-x Y x Cl 4-3x F 3x 、Li 2-x Mr 1-x Ir x Cl 4-3x F 3x 、Li 2-x Mr 1-x Sb x Cl 4-3x I 3x 、Li 2-x Mr 1-x Day x Cl 4-3x I 3x 、Li 2- x Mr 1-x In x Cl 4-3x I 3x 、Li 2-x Mr 1-x Ce x Cl 4-3x I 3x 、Li 2-x Mr 1-x Nd x Cl 4-3x I 3x 、Li 2-x Mr 1-x Feb x Cl 4-3x I3x Li 2- x Mn 1-x Ru x Cl 4-3x I 3x Li 2-x Mn 1-x Rh x Cl 4-3x I 3x Li 2-x Mn 1-x Ir x Cl 4-3x I 3x Li 2-x Mn 1-x Ga x Cl 4-3x I 3x Li 2- x Ti 1-x Fe x Cl 4-3x I 3x Li 2-x Ni 1-x Ru x Cl 4-3x I 3x Li 2-x Ni 1-x Rh x Cl 4-3x I 3x Li 2-x Ni 1-x Ir x Cl 4-3x I 3x Li 2- x Ni 1-x Ga x Cl 4-3x I 3x .

[0021] In some embodiments, the multifunctional halide material includes at least one of the following: Li 1.9 Mn 0.9 Ga 0.1 Cl4, Li 1.9 Mn 0.9 Fe 0.1 Cl4, Li 1.9 Mn 0.9 In 0.1 Cl4, Li 1.9 Mn 0.9 Ru 0.1 Cl4, Li1.9 Mn 0.9 Rh 0.1 Cl4、Li 1.9 Mn 0.9 Ir 0.9 Cl4、Li 1.9 Mn 0.9 Nd 0.1 Cl4、Li 1.9 Mn 0.9 Ce 0.1 Cl4、Li 1.9 Mn 0.9 La 0.1 Cl4、Li 1.9 Mn 0.9 Y 0.1 Cl4、Li 1.9 Mn 0.9 La 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Ga 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 In 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Ce 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Nd 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Fe 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Ru 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Rh 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9 Ir 0.1 Cl 3.7 Br 0.3 、Li 1.9 Mn 0.9Y 0.1 Cl 3.7 Bro 0.3 、Li 1.9 Mr 0.9 Day 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Ga 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 In 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Ce 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Nd 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Feb 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Ru 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Rh 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Ir 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Y 0.1 Cl 3.7 F 0.3 、Li 1.9 Mr 0.9 Day 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 In 0.1 Cl 3.7 I 0.3 、Li 1.9 Mr 0.9 Ce 0.1 Cl3.7 AND 0.3 、Li 1.9 Mn 0.9 No 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Fe 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Ru 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Rh 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Ireland 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Him 0.1 Cl 3.7 AND 0.3 、Li 1.9 Mn 0.9 Y 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Yes 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 No 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Fe 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Ru 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Rh 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Ireland 0.1 Cl 3.7 AND 0.3、Li 1.9 Fe 0.9 Him 0.1 Cl 3.7 AND 0.3 、Li 1.9 Fe 0.9 Y 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Yes 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 No 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Fe 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Ru 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Rh 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Ireland 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Him 0.1 Cl 3.7 AND 0.3 、Li 1.9 Nor 0.9 Y 0.1 Cl 3.7 AND 0.3 、Li 1.9 You 0.9 Yes 0.1 Cl 3.7 AND 0.3 、Li 1.9 You 0.9 No 0.1 Cl 3.7 AND 0.3 、Li 1.9 You 0.9 Fe 0.1 Cl 3.7 AND 0.3 、Li 1.9 You0.9 Ru 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Rh 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Ir 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Ga 0.1 Cl 3.7 I 0.3 Li 1.9 Ti 0.9 Y 0.1 Cl 3.7 I 0.3 .

[0022] In a fourth aspect, the present invention provides a positive electrode material comprising the multifunctional halide material described in the third aspect of the present invention or the positive electrode active material and the electronic conductive agent described therein.

[0023] In some embodiments, the positive electrode material comprises 90 wt%-97 wt% of a multifunctional halide material or the aforementioned positive electrode active material and 3 wt%-10 wt% of an electronically conductive agent.

[0024] In some embodiments, the electronically conductive agent includes at least one of carbon black, acetylene black, Super-P, carbon nanotubes, graphene, etc.

[0025] A fifth aspect of the present invention provides a solid-state battery comprising the multifunctional halide material described in the third aspect of the present invention, the positive electrode active material described therein, or the positive electrode material described in the fourth aspect of the present invention.

[0026] In some embodiments, the solid-state battery further includes a solid electrolyte and a negative electrode material.

[0027] In some embodiments, the solid electrolyte includes a sulfide solid electrolyte, the multifunctional halide material described in the third aspect of the present invention, or a layer consisting of a sulfide solid electrolyte and a layer consisting of the multifunctional halide material described in the third aspect of the present invention.

[0028] In some embodiments, the sulfide solid electrolyte includes Li3PS4 and Li7P3S. 11 Li 11 GeP2S 12 Li6PS5Cl, Li7P2S8I, Li 10SnP2S 12 Li 3 .25 Ge 0 .25 P 0 .75 One or more of S4.

[0029] In some embodiments, the negative electrode material includes at least one of Li, Li-In alloy, Si, graphite, and silicon-carbon composite materials.

[0030] A sixth aspect of the present invention provides an ionic conductivity agent comprising the multifunctional halide material and sulfide solid electrolyte described in the third aspect of the present invention.

[0031] In some embodiments, the mass ratio of the multifunctional halide material to the sulfide solid electrolyte is (1-20):(5-40).

[0032] In a seventh aspect, the present invention provides a positive electrode material, comprising a positive electrode active material, an ionic conductive agent and an electronic conductive agent as described in the sixth aspect of the present invention.

[0033] In some embodiments, the positive electrode material comprises 60wt%-80wt% positive electrode active material, 20wt%-40wt% of the ionic conductive agent and 1wt%-5wt% of the electronic conductive agent.

[0034] In some embodiments, the positive electrode active material includes at least one of layered oxide materials, polyanionic materials, or spinel structure materials.

[0035] In some embodiments, the layered oxide material includes at least one of lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel oxide, etc.

[0036] In some embodiments, the polyanionic material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, and lithium vanadium phosphate.

[0037] In some embodiments, the spinel structural material includes at least one of lithium manganese oxide, lithium nickel manganese oxide, etc.

[0038] In some embodiments, the electronically conductive agent includes at least one of carbon black, acetylene black, Super-P, carbon nanotubes, graphene, etc.

[0039] In an eighth aspect, the present invention provides a solid-state battery comprising the cathode material described in the seventh aspect of the present invention.

[0040] In some embodiments, the solid-state battery further includes a solid electrolyte and a negative electrode material.

[0041] In some embodiments, the solid electrolyte includes a sulfide solid electrolyte, the multifunctional halide material described in the third aspect of the present invention, or a layer consisting of a sulfide solid electrolyte and a layer consisting of the multifunctional halide material described in the third aspect of the present invention.

[0042] In some embodiments, the sulfide solid electrolyte includes Li3PS4 and Li7P3S. 11 Li 11 GeP2S 12 Li6PS5Cl, Li7P2S8I, Li 10 SnP2S 12 Li 3 .25 Ge 0 .25 P 0 .75 One or more of S4.

[0043] In some embodiments, the negative electrode material includes at least one of Li, Li-In alloy, Si, graphite, and silicon-carbon composite materials.

[0044] A ninth aspect of the present invention provides a positive electrode material, comprising a positive electrode active material, an ionic conductivity agent, and an electronic conductivity agent; wherein the ionic conductivity agent comprises a multifunctional halide material of the first aspect of the present invention.

[0045] In some embodiments, the positive electrode material comprises 60wt%-80wt% positive electrode active material, 20wt%-40wt% ionic conductivity agent and 1wt%-5wt% electronic conductivity agent.

[0046] In some embodiments, the positive electrode active material includes at least one of layered oxide materials, polyanionic materials, or spinel structure materials.

[0047] In some embodiments, the layered oxide material includes at least one of lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel oxide, etc.

[0048] In some embodiments, the polyanionic material includes at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, and lithium vanadium phosphate.

[0049] In some embodiments, the spinel structural material includes at least one of lithium manganese oxide, lithium nickel manganese oxide, etc.

[0050] In a tenth aspect of the present invention, a positive electrode material is provided, comprising a layered ternary oxide material, an ionic conductivity agent, and an electronic conductivity agent; wherein the ionic conductivity agent comprises a multifunctional halide material according to a third aspect of the present invention.

[0051] In some embodiments, the cathode material comprises 60wt%-80wt% layered ternary oxide material, 20wt%-40wt% ionic conductivity agent and 1wt%-5wt% electronic conductivity agent.

[0052] In some embodiments, the layered ternary oxide material includes at least one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, etc.

[0053] In an eleventh aspect of the present invention, a solid-state battery is provided, comprising the cathode material described in the ninth or tenth aspect of the present invention.

[0054] In some embodiments, the solid-state battery further includes a solid electrolyte and a negative electrode material.

[0055] In some embodiments, the solid electrolyte includes the multifunctional halide material described in the third aspect of the present invention, or a solid electrolyte consisting of one layer of sulfide and another layer of the multifunctional halide material described in the third aspect of the present invention.

[0056] In some embodiments, the sulfide solid electrolyte includes Li3PS4 and Li7P3S. 11 Li 11 GeP2S 12 Li6PS5Cl, Li7P2S8I, Li 10 SnP2S 12 Li 3 .25 Ge 0 .25 P 0 .75 One or more of S4.

[0057] In some embodiments, the negative electrode material includes at least one of Li, Li-In alloy, Si, graphite, and silicon-carbon composite materials.

[0058] A twelfth aspect of the present invention provides an electrical device comprising a solid-state battery as described in the fifth, eighth, or eleventh aspects of the present invention.

[0059] In some embodiments, the electrical equipment includes power equipment (such as electric vehicles, electric cars), electronic devices (such as mobile phones, tablets, laptops, digital cameras, etc.), wearable devices (such as watches, bracelets, VR glasses, etc.), energy storage power stations, etc.

[0060] The beneficial effects of this invention are: The multifunctional halide material of this invention has both high ionic conductivity and partially reversible delithiation function, and can provide additional lithium ions to achieve lithium replenishment.

[0061] The multifunctional halide material of this invention can provide an additional lithium source during the first charge, and after fulfilling its positive electrode lithium replenishment function during the first charge, it can also function as a solid electrolyte to play the role of ionic conductivity.

[0062] The multifunctional halide material of this invention provides additional capacity through the redox-active transition metal element, while the material itself has a relatively high ionic conductivity, which can provide lithium replenishment and ionic conductivity on the positive electrode side of solid-state batteries. Attached Figure Description

[0063] Figure 1 For the present invention Li 1.8 Mn 0.8 Ga 0.2 XRD pattern of Cl4-700rpm-20h.

[0064] Figure 2 For the present invention Li 1.9 Mn 0.9 Ga 0.1 XRD pattern of Cl4-700rpm-20h.

[0065] Figure 3 The XRD pattern of Li2MnCl4 at 700 rpm for 20 h is shown below.

[0066] Figure 4 Li in Embodiment 1 of the present invention 1.9 Mn 0.9 Ga 0.1 EIS chromatogram of Cl4-700rpm-20h.

[0067] Figure 5 Li in Embodiment 22 of the present invention 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 EIS graph of -700rpm-20h.

[0068] Figure 6 Li in Embodiment 65 of the present invention 1.9 Mn 0.9 Ga 0.1 The first charge capacity diagram of Cl4-700rpm-20h.

[0069] Figure 7 Li in Embodiment 123 of the present invention 1.8 Mn 0.8 Ga 0.2 The specific capacity diagram of the first charge-discharge cycle of Cl4-700rpm-20h.

[0070] Figure 8Li in Embodiment 85 of the present invention 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 The first charge capacity diagram from -700rpm to 20h.

[0071] Figure 9 Ni-Li in Example 181 of the present invention 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 The first-cycle charge-discharge specific capacity diagram of -Li6PS5Cl-Super P.

[0072] Figure 10 The first-cycle charge-discharge specific capacity curves of NCM-LMGFCl(02)-LPSCl-SP(6510205) in Example 197 of the present invention and NCM-LPSCl-SP(65305) in Comparative Example 5 are shown. Detailed Implementation

[0073] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0074] Example 1 This embodiment prepares a modified material, and the specific process is as follows: LiCl, MnCl2, and GaCl3 were weighed in a molar ratio of 1.9:0.9:0.1. The weighed raw material powders were placed in an agate mortar and mixed. After initial homogenization, the mixture was placed in a high-energy ball mill jar. Zirconium beads were added according to the total weighed mass, with a ball-to-material mass ratio of 40:1. The mixture was ball-milled at 700 rpm for 20 hours to obtain LiCl. 1.9 Mn 0.9 Ga 0.1 Cl4.

[0075] Example 2-64 The modified materials of Examples 2-64 were prepared by the same method as in Example 1, except that the raw materials in Table 1 were replaced.

[0076] Table 1

[0077] Comparative Example 1 A modified material was prepared in this comparative example, and the specific process is as follows: LiCl and MnCl2 were weighed in a molar ratio of 2:1. The weighed raw material powder was placed in an agate mortar and mixed. After initial mixing, it was placed in a high-energy ball mill jar. Zirconium beads were added according to the total weighed mass, with a ball-to-material mass ratio of 40:1. The milling speed was 700 rpm, and the milling time was 20 h to obtain Li2MnCl4 material.

[0078] Example 65 This embodiment demonstrates the fabrication of an all-solid-state battery, the specific process of which is as follows: The modified materials prepared in the examples and comparative examples were used in the fabrication of all-solid-state batteries. Specifically, 90 wt% of the prepared modified material Li was used... 1.9 Mn 0.9 Ga 0.1 Cl4 and 10wt% carbon black were mixed in an agate mortar and ground in a glove box under an inert gas atmosphere for half an hour to obtain the final cathode material. The obtained cathode material was then mixed with Li 1.9 Mn 0.9 Ga 0.1 The all-solid-state battery was assembled using Cl4 electrolyte and Li-In alloy anode. The preparation process of the all-solid-state battery was as follows: In a glove box protected by inert gas, 100 mg of solid electrolyte powder Li... 1.9 Mn 0.9 Ga 0.1 Cl4 is pressed into a sheet using a 10mm diameter solid-state battery mold at a pressure of 250MPa for 90 seconds. Then, 10mg of the prepared positive electrode material is weighed and evenly spread onto the pressed solid electrolyte sheet, and pressed into a sheet at a pressure of 380MPa for 2 minutes. The mold is then inverted, and the negative electrode material is placed on the other side of the electrolyte sheet and pressed at a pressure of 500MPa for 3 minutes. The mold containing the pressed positive and negative electrodes and the solid electrolyte is then placed into a solid-state battery fixture and subjected to a pressure of 250MPa to obtain an all-solid-state battery.

[0079] The steps to test EIS are as follows: Weigh 125 mg of Li 1.9 Mn 0.9 Ga 0.1 Cl4 powder was placed in a mold containing a 10mm diameter stainless steel sheet, and a pressure of 250 MPa was applied for 1 minute. Then, another stainless steel sheet was placed on top of the compressed powder, ensuring both sides of the powder were covered with stainless steel sheets as blocking electrodes. A pressure of 760 MPa was then applied for 1 minute to compact the powder. Finally, the powder was transferred to a pressure holding frame and held at 500 MPa for subsequent EIS testing. The EIS test mode was constant potential EIS testing, and the EIS test frequency was set to 0.1Hz-10 Hz. 6The conductivity at Hz is calculated using the formula σ = L / SR (where L is the thickness of the electrolyte tablet, S is the area of ​​the electrolyte tablet, and R is obtained from the Nyquist plot obtained by EIS testing). Examples 65-122, Comparative Example 2 The preparation method of the all-solid-state batteries in Comparative Examples 2, Examples 66-122, was the same as that in Example 65, except that the corresponding modified materials and electrolytes were replaced. The test results are shown in Table 2. Table 2

[0080] Figure 6 For Li 1.9 Mn 0.9 Ga 0.1 EIS chromatogram of Cl4-700rpm-20h. Figure 7 For Li 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 EIS graph of -700rpm-20h. Figure 8 For Li 1.9 Mn 0.9 Ga 0.1 The first charge capacity diagram of Cl4-700rpm-20h. Figure 9 For Li 1.8 Mn 0.8 Ga 0.2 The specific capacity diagram of the first charge-discharge cycle of Cl4-700rpm-20h. Figure 10 For Li 1.9 Mn 0.9 Ga 0.1 Cl 3.7 F 0.3 The first charge capacity diagram from -700rpm to 20h.

[0081] As can be seen, the EIS test data proves that the synthesized material has a fairly high ionic conductivity and can be used as an ionic conductive agent in the battery. The first charge-discharge specific capacity curve proves that the synthesized material has the capacity to provide additional lithium ions as a lithium replenishing agent.

[0082] Example 123 This embodiment demonstrates the fabrication of an all-solid-state battery, the specific process of which is as follows: The modified material Li prepared in Example 1 1.9 Mn 0.9 Ga 0.1Cl4 is used in the fabrication of all-solid-state batteries. The specific procedure involves adding 20 wt% of the prepared modified material Li... 1.9 Mn 0.9 Ga 0.1 Cl4 and 75wt% cathode material LiNi 0.8 Co 0.1 Mn 0.1 O2 cathode material and 5wt% carbon black were mixed in an agate mortar and ground in a glove box under an inert gas atmosphere for half an hour to obtain the final cathode material. The obtained cathode material was then mixed with Li 1.9 Mn 0.9 Ga 0.1 The all-solid-state battery was assembled using Cl4 solid electrolyte and Li-In alloy anode. The preparation process of the all-solid-state battery was as follows: In a glove box protected by inert gas, 100 mg of solid electrolyte powder Li... 1.9 Mn 0.9 Ga 0.1 Cl4 is pressed into a sheet using a 10mm solid-state battery mold at a pressure of 250MPa for 90 seconds. Then, 10mg of the prepared positive electrode is weighed and evenly spread onto the pressed solid electrolyte sheet, and pressed into a sheet at a pressure of 380MPa for 2 minutes. The mold is then inverted, and the negative electrode material is placed on the other side of the electrolyte sheet and pressed evenly at a pressure of 500MPa for 3 minutes. The pressed mold is then placed into a solid-state battery fixture and subjected to a pressure of 250MPa to obtain the all-solid-state battery.

[0083] The specific methods for testing all-solid-state batteries are as follows: The test mode is set to constant current mode, the activation rate is set to 0.05C, and the activation voltage range is 2.8V-4.3V. After activation, the activation rate is set to 0.5C, and the voltage range is 2V-4.4V.

[0084] Examples 124-165, Comparative Example 3 The all-solid-state batteries of Comparative Example 3 and Examples 124-165 were prepared in accordance with Example 123, except that the corresponding modified materials and solid electrolytes were replaced. The test results are shown in Table 3.

[0085] Table 3

[0086] Example 166 This embodiment demonstrates the fabrication of an all-solid-state battery, the specific process of which is as follows: The modified material Li prepared in Example 1 1.9 Mn 0.9 Ga 0.1Cl4 is used in the fabrication of all-solid-state batteries. The specific procedure involves preparing a 10wt% modified Li-based material... 1.9 Mn 0.9 Ga 0.1 Cl4, 20wt% sulfide solid electrolyte Li6PS5Cl, 65wt% cathode material LiNi 0.8 Co 0.1 Mn 0.1 The ratio of O2 cathode material and 5wt% carbon black was measured. The final cathode material obtained here was obtained by mixing in three steps: First, 65wt% LiNi... 0.8 Co 0.1 Mn 0.1 The O2 cathode material and 10wt% sulfide solid electrolyte were mixed in a mortar and ground for 30 minutes to obtain mixture 1. The second step is to add 10wt% Li 1.9 Mn 0.9 Ga 0.1 Cl4 was mixed with 5 wt% of sulfide solid electrolyte Li6PS5Cl and 5 wt% carbon black in a mortar and ground for 30 minutes to obtain mixture 2. The third step was to mix mixture 1 with mixture 2 and 5 wt% of sulfide solid electrolyte Li6PS5Cl in a mortar and grind for 30 minutes to obtain the final mixed positive electrode material. The obtained positive electrode material, sulfide solid electrolyte Li6PS5Cl, and Li-In alloy negative electrode were then assembled into an all-solid-state battery. The preparation process of the all-solid-state battery was as follows: In a glove box protected by inert gas, 100 mg of solid electrolyte powder was weighed and placed into a 10 mm solid-state battery mold to be pressed into a sheet at a pressure of 250 MPa for 90 seconds. Then, 10 mg of the prepared positive electrode was weighed and placed evenly on the pressed solid electrolyte sheet and pressed into a sheet at a pressure of 380 MPa for 2 minutes. The mold was then inverted and the negative electrode material was placed on the other side of the electrolyte sheet and pressed evenly at a pressure of 500 MPa for 3 minutes. The pressed mold is placed into the solid-state battery fixture housing and pressure of 250MPa is applied to obtain an all-solid-state battery.

[0087] The specific methods for testing all-solid-state batteries are as follows: The test mode is set to constant current mode, the activation rate is set to 0.05C, and the activation voltage range is 2.8V-4.3V. After activation, the activation rate is set to 0.5C, and the voltage range is 2V-4.4V.

[0088] Example 167 - Example 1, Comparative Example 4 The all-solid-state batteries of Comparative Example 4 and Examples 167-197 were prepared in accordance with Example 166, except that the corresponding modified materials and solid electrolytes were replaced. The test results are shown in Table 4.

[0089] Table 4

[0090] Comparative Example 5 This comparative example demonstrates the fabrication of an all-solid-state battery, the specific process of which is as follows: 30wt% sulfide solid electrolyte Li6PS5Cl and 65wt% cathode material LiNi 0.8 Co 0.1 Mn 0.1 O2 positive electrode material and 5wt% conductive carbon black Super-P were weighed in a specific ratio and ground in a mortar for 30 minutes to obtain a composite positive electrode material. The obtained positive electrode material, sulfide solid electrolyte Li6PS5Cl, and Li-In alloy negative electrode were then assembled into an all-solid-state battery. The preparation process of the all-solid-state battery is as follows: In a glove box under inert gas protection, 100mg of Li6PS5Cl powder was weighed and pressed into a sheet using a 10mm solid-state battery mold at a pressure of 250MPa for 90 seconds. Then, 10mg of the prepared positive electrode was weighed and evenly spread on the pressed solid electrolyte sheet, and pressed into a sheet at a pressure of 380MPa for 2 minutes. The mold was then inverted, and the negative electrode material was placed on the other side of the electrolyte sheet and pressed evenly at a pressure of 500MPa for 3 minutes. The pressed mold was then placed in a solid-state battery fixture shell and subjected to a pressure of 250MPa to obtain the all-solid-state battery.

[0091] The specific methods for testing all-solid-state batteries are as follows: The test mode is set to constant current mode, the activation rate is set to 0.05C, and the activation voltage range is 2.8V-4.3V. After activation, the activation rate is set to 0.5C, and the voltage range is 2V-4.4V.

[0092] The first-cycle charge-discharge specific capacity curves of NCM-LMGFCl(02)-LPSCl-SP(6510205) in Example 197 and NCM-LPSCl-SP(65305) in Comparative Example 5 are as follows: Figure 10 As shown, compared to conventional electrolytes without lithium replenishment function, the lithium-replenishing chloride electrolyte of Example 197 has a higher charge-discharge specific capacity, contributing approximately 20 mAh / g more to the charge specific capacity while maintaining the same mass of positive electrode active material. Furthermore, the electrolyte can still function as an ionic conductor in the battery after delithiation, which fully demonstrates that the halide electrolyte described in this invention possesses both ionic conductivity and partially reversible delithiation capability.

[0093] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A multifunctional halide material, characterized in that: Includes at least one of the following: (I)Li 2-x M 1-x A x Cl4; where M is Mn; A is selected from at least one of Fe, In, Ru, Rh, Ir, Ga, and Y; 0 <x<1; (II) Li 2-x M' 1-x A x Cl4; wherein M' is selected from at least one of Fe, Ti, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; 0 <x<1; (III)Li 2-x M'' 1-x A x Cl 4-3x E 3x Wherein, M'' is selected from at least one of Fe, Ti, Mn, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; E is selected from at least one of F, Br, I, and O; O <x<1。 2. The multifunctional halide material according to claim 1, characterized in that: The multifunctional halide material includes at least one of the following: Li 2-x Mr 1-x Ga x Cl4、Li 2-x Mr 1-x He x Cl4、Li 2-x Mr 1-x In x Cl4、Li 2-x Mr 1-x Ru x Cl4、Li 2-x Mr 1-x Rh x Cl4、Li 2-x Mr 1-x Ir x Cl4、Li 2-x He 1-x Ga x Cl4、Li 2-x He 1-x In x Cl4、Li 2-x He 1-x Ru x Cl4、Li 2-x He 1-x Rh x Cl4、Li 2- x He 1-x Ir x Cl4、Li 2-x You 1-x Nd x Cl4、Li 2-x You 1-x Ce x Cl4、Li 2-x Mr 1-x La x Cl 4-3x Br 3x 、Li 2-x Mr 1-x Ga x Cl 4- 3x Br 3x 、Li 2-x Mr 1-x In x Cl 4-3x Br 3x 、Li 2-x Mr 1-x Ce x Cl 4-3x Br 3x 、Li 2-x Mr 1-x Nd x Cl 4-3x Br 3x 、Li 2-x Mn 1- x Fe x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ru x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Rh x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Y x Cl 4-3x Br 3x 、Li 2- x Mn 1-x Ir x Cl 4-3x Br 3x 、Li 2-x Mn 1-x La x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ga x Cl 4-3x F 3x 、Li 2-x Mn 1-x In x Cl 4-3x F 3x 、Li 2- x Mn 1-x Ce x Cl 4-3x F 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x F 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ru x Cl 4-3x F 3x 、Li 2- x Mr 1-x Rh x Cl 4-3x F 3x 、Li 2-x Mr 1-x Y x Cl 4-3x F 3x 、Li 2-x Mr 1-x Ir x Cl 4-3x F 3x 、Li 2-x Mr 1-x Sb x Cl 4-3x I 3x 、Li 2- x Mr 1-x Day x Cl 4-3x I 3x 、Li 2-x Mr 1-x In x Cl 4-3x I 3x 、Li 2-x Mr 1-x Ce x Cl 4-3x I 3x 、Li 2-x Mr 1-x Nd x Cl 4-3x I 3x 、Li 2- x Mr 1-x Feb x Cl 4-3x I 3x 、Li 2-x Mr 1-x Ru x Cl 4-3x I 3x 、Li 2-x Mr 1-x Rh x Cl 4-3x I 3x 、Li 2-x Mr 1-x Ir x Cl 4-3x I 3x 、Li 2- x Mr 1-x Ga x Cl 4-3x I 3x 、Li 2-x You 1-x Fe x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Ru x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Rh x Cl 4-3x AND 3x 、Li 2- x Nor 1-x Ireland x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Him x Cl 4-3x AND 3x 。 3. A method for preparing the multifunctional halide material according to claim 1 or 2, characterized in that: Includes the following steps: LiCl, the chloride salt of M or the halide salt of M', and the chloride salt of A are ball-milled to obtain Li 2-x M 1-x A x Cl4 or Li 2-x M' 1- x A x Cl4; Alternatively, LiCl and M'' chloride salts can be ball-milled with A halide salts or A oxides to obtain Li. 2-x M'' 1-x A x Cl 4- 3x E 3x .

4. A positive electrode active material, characterized in that: Including multifunctional halide materials; the multifunctional halide materials include (A) Li 2-x M' 1-x A x Cl4; and / or (B)Li 2-x M'' 1-x A x Cl 4-3x E 3x ; Wherein, M' and M'' are each independently selected from at least one of Fe, Ti, Mn, and Ni; A is selected from at least one of Fe, Ga, In, Ru, Rh, Ir, Nd, Ce, La, and Y; E is selected from at least one of F, Br, I, and O; 0 <x<1。 5. The positive electrode active material according to claim 4, characterized in that: The multifunctional halide material includes at least one of the following: Li 2-x Mn 1-x Ga x Cl4, Li 2-x Mn 1-x Fe x Cl4, Li 2-x Mn 1-x In x Cl4, Li 2-x Mn 1-x Ru x Cl4, Li 2-x Mn 1-x Rh x Cl4, Li 2-x Mn 1-x Ir x Cl4, Li 2-x Mn 1-x Nd x Cl4, Li 2-x Mn 1-x Ce x Cl4, Li 2-x Mn 1-x La x Cl4, Li 2-x Fe 1-x Ga x Cl4, Li 2- x Fe 1-x In x Cl4, Li 2-x Fe 1-x Ru x Cl4, Li 2-x Fe 1-x Rh x Cl4, Li 2-x Fe 1-x Ir x Cl4, Li 2-x Ti 1-x Nd x Cl4, Li 2-x Ti 1- x Ce x Cl4, Li 2-x Mn 1-x La x Cl 4-3x Br 3x Li 2-x Mn 1-x Ga x Cl 4-3x Br 3x Li 2-x Mn 1-x In x Cl 4-3x Br 3x 、Li 2-x Mn 1- x Ce x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Fe x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ru x Cl 4-3x Br 3x 、Li 2- x Mn 1-x Rh x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Y x Cl 4-3x Br 3x 、Li 2-x Mn 1-x Ir x Cl 4-3x Br 3x 、Li 2-x Mn 1-x La x Cl 4-3x F 3x 、Li 2- x Mn 1-x Ga x Cl 4-3x F 3x 、Li 2-x Mn 1-x In x Cl 4-3x F 3x 、Li 2-x Mn 1-x Ce x Cl 4-3x F 3x 、Li 2-x Mn 1-x Nd x Cl 4-3x F 3x 、Li 2- x Mr 1-x Feb x Cl 4-3x F 3x 、Li 2-x Mr 1-x Ru x Cl 4-3x F 3x 、Li 2-x Mr 1-x Rh x Cl 4-3x F 3x 、Li 2-x Mr 1-x Y x Cl 4-3x F 3x 、Li 2- x Mr 1-x Ir x Cl 4-3x F 3x 、Li 2-x Mr 1-x Sb x Cl 4-3x I 3x 、Li 2-x Mr 1-x Day x Cl 4-3x I 3x 、Li 2-x Mr 1-x In x Cl 4-3x I 3x 、Li 2- x Mr 1-x Ce x Cl 4-3x I 3x 、Li 2-x Mr 1-x Nd x Cl 4-3x I 3x 、Li 2-x Mr 1-x Feb x Cl 4-3x I 3x 、Li 2-x Mr 1-x Ru x Cl 4-3x I 3x 、Li 2- x Mr 1-x Rh x Cl 4-3x I 3x 、Li 2-x Mn 1-x Ireland x Cl 4-3x AND 3x 、Li 2-x Mn 1-x Him x Cl 4-3x AND 3x 、Li 2-x You 1-x Fe x Cl 4-3x AND 3x 、Li 2- x Nor 1-x Ru x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Rh x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Ireland x Cl 4-3x AND 3x 、Li 2-x Nor 1-x Him x Cl 4-3x AND 3x 。 6. A cathode material, characterized in that: It includes the multifunctional halide material or the positive electrode active material as described in claim 4 or 5, and the electronic conductive agent.

7. The cathode material according to claim 6, characterized in that: The cathode material comprises 90 wt%-97 wt% of a multifunctional halide material or the aforementioned cathode active material and 3 wt%-10 wt% of an electronically conductive agent.

8. A solid-state battery, characterized in that: This includes the multifunctional halide material as described in claim 4 or 5, the positive electrode active material as described, or the positive electrode material as described in claim 6 or 7.

9. An ionic conductivity agent, characterized in that: Includes the multifunctional halide material and sulfide solid electrolyte described in claim 4 or 5.

10. A cathode material, characterized in that: It includes the positive electrode active material, the ionic conductive agent and the electronic conductive agent as described in claim 9.

11. The cathode material according to claim 10, characterized in that: The positive electrode material comprises 60wt%-80wt% positive electrode active material, 6wt%-60wt% of the ionic conductivity agent and 1wt%-5wt% of the electronic conductivity agent.

12. A solid-state battery, characterized in that: Includes the cathode material as described in claim 10 or 11.

13. A cathode material, characterized in that: It includes a positive electrode active material, an ionic conductive agent, and an electronic conductive agent; the ionic conductive agent includes the multifunctional halide material of claim 1 or 2.

14. The cathode material according to claim 13, characterized in that: The cathode material comprises 60wt%-80wt% cathode active material, 20wt%-40wt% ionic conductivity agent and 1wt%-5wt% electronic conductivity agent.

15. A positive electrode material, characterized in that: It includes layered ternary oxide materials, ionic conductive agents, and electronic conductive agents; the ionic conductive agent includes the multifunctional halide material as described in claim 4 or 5.

16. The cathode material according to claim 15, characterized in that: The cathode material comprises 60wt%-80wt% layered ternary oxide material, 20wt%-40wt% ionic conductivity agent and 1wt%-5wt% electronic conductivity agent.

17. A solid-state battery, characterized in that: Includes the cathode material as described in any one of claims 13-16.

18. An electrical appliance, characterized in that: Includes the solid-state battery as described in any one of claims 8, 12, and 17.