WO2024037397A1 - 一种卤化物全固态电池材料及其制备方法和应用 - Google Patents

一种卤化物全固态电池材料及其制备方法和应用 Download PDF

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WO2024037397A1
WO2024037397A1 PCT/CN2023/111920 CN2023111920W WO2024037397A1 WO 2024037397 A1 WO2024037397 A1 WO 2024037397A1 CN 2023111920 W CN2023111920 W CN 2023111920W WO 2024037397 A1 WO2024037397 A1 WO 2024037397A1
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solid
halide
state battery
ticl
battery material
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French (fr)
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马骋
王凯
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University of Science and Technology of China USTC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of all-solid-state battery materials, and in particular to a halide all-solid-state battery material and its preparation method and application.
  • all-solid-state batteries are expected to solve the safety issues of commercial lithium-ion batteries and further increase energy density.
  • the all-solid-state battery adopts a structure similar to that of commercial lithium-ion batteries, that is, materials with different functions serve as the positive electrode, negative electrode, and solid electrolyte.
  • the improvement of energy density and cycle stability of all-solid-state batteries depends largely on the cathode materials, but currently these cathode materials are extremely rigid oxides. When these oxides are used as cathode materials for all-solid-state batteries, they have to be combined with a large number of easily deformable solid electrolytes (such as halides, sulfides, etc.) to form composite electrodes to meet the needs of ion transport. This not only reduces the energy density of all-solid-state batteries, but also the side reactions between electrode materials and solid electrolyte materials in composite electrodes will further reduce their cycle stability.
  • the purpose of the present invention is to provide a halide all-solid-state battery material and its preparation method and application to solve the problem that the existing technology cannot simultaneously satisfy the requirements of high ion conductivity, good deformation ability and reversible non-lithium/sodium cations.
  • Technical issues of redox-capable multifunctional battery materials are considered.
  • the invention provides a halide all-solid-state battery material.
  • the general chemical formula of the halide all-solid-state battery material is A x My X z Y b , where A includes Li or Na; M includes Mg, Al, Si, One or more of P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr and Nb; X includes one or more of F, Cl, Br and I species; Y contains O and/or S; where 1 ⁇ x ⁇ 4, 0.5 ⁇ y ⁇ 1, 3 ⁇ z ⁇ 8, 0 ⁇ b ⁇ 3.
  • the chemical formula of the halide all-solid-state battery material is selected from one of the following chemical formulas:
  • the invention provides a method for preparing halide all-solid-state battery materials, which includes the following steps:
  • the halide all-solid-state battery material is obtained by mixing the raw materials in a stoichiometric ratio and performing ball milling.
  • the ball-to-material ratio of the ball mill is 10 to 15:1
  • the rotation speed of the ball mill is 500 to 600 rpm
  • the ball milling time is 20 to 50 hours.
  • annealing treatment is performed after ball milling.
  • the temperature of the annealing treatment is 300-500°C, and the time of the annealing treatment is 4-6 hours.
  • the invention provides an application of a halide all-solid-state battery material in preparing an all-solid-state battery.
  • the halide all-solid-state battery material obtained by the present invention not only has an ionic conductivity as high as 1 mS/cm, but also has good deformation ability.
  • the M element has reversible redox ability.
  • the good deformation ability ensures that the battery material can be made into an all-solid-state battery through simple cold pressing.
  • this battery material no longer needs to add easily deformable ion conductive agents that do not provide energy, and can increase the energy density of the battery.
  • the high lithium ion conductivity ensures that the battery has high rate performance.
  • the successful development of the halide all-solid-state battery material of the present invention will help optimize the structure of the all-solid-state battery, improve the energy density of the all-solid-state battery, and at the same time provide a new idea for the industrialization of the all-solid-state battery.
  • Figure 1 is the X-ray diffraction spectrum of the low crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 2 is the electrochemical impedance spectrum of the low crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 3 is the DC polarization spectrum of the low crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 4 is the X-ray diffraction spectrum of the highly crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 5 is the electrochemical impedance spectrum of the highly crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 6 is the DC polarization spectrum of the highly crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 7 is a charge and discharge curve of the highly crystalline Li 3 TiCl 6 material prepared in Example 1 as a cathode material;
  • Figure 8 is a charge and discharge curve of a single-material all-solid-state battery assembled from the highly crystalline Li 3 TiCl 6 material prepared in Example 1;
  • Figure 9 is the X-ray diffraction spectrum of the low crystalline Li 4 TiCl 6 material prepared in Example 2.
  • Figure 10 is the electrochemical impedance spectrum of the low crystalline Li 4 TiCl 6 material prepared in Example 2;
  • Figure 11 is the DC polarization spectrum of the low crystalline Li 4 TiCl 6 material prepared in Example 2;
  • Figure 12 is the X-ray diffraction spectrum of the low crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 13 is the electrochemical impedance spectrum of the low crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 14 is the DC polarization spectrum of the low crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 15 is the X-ray diffraction spectrum of the highly crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 16 is the electrochemical impedance spectrum of the highly crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 17 is the DC polarization spectrum of the highly crystalline Li 3 TiCl 5 O 0.5 material prepared in Example 3;
  • Figure 18 is the X-ray diffraction spectrum of the low crystalline Li 3 TiCl 5 F material prepared in Example 4;
  • Figure 19 is the electrochemical impedance spectrum of the low crystalline Li 3 TiCl 5 F material prepared in Example 4.
  • Figure 20 is the DC polarization spectrum of the low crystalline Li 3 TiCl 5 F material prepared in Example 4.
  • Figure 21 is the X-ray diffraction spectrum of the low crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 22 is the electrochemical impedance spectrum of the low crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 23 is the DC polarization spectrum of the low crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 24 is the X-ray diffraction spectrum of the highly crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 25 is the electrochemical impedance spectrum of the highly crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 26 is the DC polarization spectrum of the highly crystalline Li 3 Ti 0.75 Al 0.25 Cl 6 material prepared in Example 5;
  • Figure 27 is the X-ray diffraction spectrum of the low crystalline Li 4 NiCl 6 material prepared in Example 6;
  • Figure 28 is the electrochemical impedance spectrum of the low crystalline Li 4 NiCl 6 material prepared in Example 6;
  • Figure 29 is the DC polarization spectrum of the low crystalline Li 4 NiCl 6 material prepared in Example 6;
  • Figure 30 is a charging curve diagram of the low crystalline Li 4 NiCl 6 material prepared in Example 6 as an electrode material in the 3.16-5V vs. Li/Li+ voltage range;
  • Figure 31 is a charge and discharge curve of the low crystalline Li 4 NiCl 6 material prepared in Example 6 as an electrode material in the voltage range of 1 to 3 V vs. Li/Li+;
  • Figure 32 is the X-ray diffraction spectrum of the low crystalline Li 3 ZrCl 6 material prepared in Example 7;
  • Figure 33 is the electrochemical impedance spectrum of the low crystalline Li 3 ZrCl 6 material prepared in Example 7;
  • Figure 34 is the DC polarization spectrum of the low crystalline Li 3 ZrCl 6 material prepared in Example 7;
  • Figure 35 is the X-ray diffraction spectrum of the low crystalline Li 3 Zr 0.75 Ti 0.25 Cl 6 material prepared in Example 8;
  • Figure 36 is the electrochemical impedance spectrum of the low crystalline Li 3 Zr 0.75 Ti 0.25 Cl 6 material prepared in Example 8;
  • Figure 37 is the DC polarization spectrum of the low crystalline Li 3 Zr 0.75 Ti 0.25 Cl 6 material prepared in Example 8;
  • Figure 38 is the X-ray diffraction spectrum of the low crystalline Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material prepared in Example 9;
  • Figure 39 is the electrochemical impedance spectrum of the low crystalline Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material prepared in Example 9;
  • Figure 40 is the DC polarization spectrum of the low crystalline Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material prepared in Example 9;
  • Figure 41 is the X-ray diffraction spectrum of the low crystalline Li 2.5 Zr 0.75 Ca 0.25 Cl 6 material prepared in Example 10;
  • Figure 42 is the electrochemical impedance spectrum of the low crystalline Li 2.5 Zr 0.75 Ca 0.25 Cl 6 material prepared in Example 10;
  • Figure 43 is the DC polarization spectrum of the low crystalline Li 2.5 Zr 0.75 Ca 0.25 Cl 6 material prepared in Example 10.
  • the invention provides a halide all-solid-state battery material.
  • the general chemical formula of the halide all-solid-state battery material is A x My X z Y b , where A includes Li or Na; M includes Mg, Al, Si, One or more of P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr and Nb; X includes one or more of F, Cl, Br and I species; Y contains O and/or S; where 1 ⁇ x ⁇ 4, 0.5 ⁇ y ⁇ 1, 3 ⁇ z ⁇ 8, 0 ⁇ b ⁇ 3.
  • x, y, z and b preferably, 2 ⁇ x ⁇ 3, 0.6 ⁇ y ⁇ 0.9, 4 ⁇ z ⁇ 7, 1 ⁇ b ⁇ 2; further preferably, 2.1 ⁇ x ⁇ 2.6, 0.7 ⁇ y ⁇ 0.8, 5 ⁇ z ⁇ 6, 1.2 ⁇ b ⁇ 1.8.
  • the chemical formula of the halide all-solid-state battery material is preferably the following chemical formula: A kind of:
  • the invention provides a method for preparing halide all-solid-state battery materials, which includes the following steps:
  • the halide all-solid-state battery material is obtained by mixing the raw materials in a stoichiometric ratio and performing ball milling.
  • the ball-to-material ratio of the ball mill is 10-15:1, the rotation speed of the ball mill is 500-600rpm, and the ball-milling time is 20-50h; preferably, the ball-to-material ratio of the ball mill is 11-14:1.
  • the rotation speed of the ball mill is 520-580 rpm, and the ball milling time is 24-45 hours; further preferably, the ball-to-material ratio of the ball mill is 12-13:1, the rotation speed of the ball mill is 550 rpm, and the ball milling time is 30-40 hours.
  • annealing treatment is performed after ball milling.
  • the temperature of the annealing treatment is 300-500°C, and the time of the annealing treatment is 4-6 hours; preferably, the temperature of the annealing treatment is 350-450°C, and the time of the annealing treatment is 4-5 hours; further preferably , the annealing temperature is 400°C, and the annealing time is 5 hours.
  • the material after annealing treatment is a high crystalline material
  • the material without annealing treatment is a low crystalline material
  • the invention provides an application of a halide all-solid-state battery material in preparing an all-solid-state battery.
  • the halide all-solid-state battery material can be used as one or more of the positive electrode, negative electrode and solid electrolyte of the all-solid-state battery.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 3 TiCl 6 material has good deformation ability; and the fact that the ionic conductivity is three orders of magnitude higher than the electronic conductivity proves that Li 3 TiCl 6 materials are pure ionic conductors that can serve as solid electrolytes.
  • the transition metal element Ti generally has the combined state of Ti 2+ , Ti 3+ and Ti 4+ and has potential redox ability as a cathode material.
  • Li 3 TiCl 6 (LTC) and carbon black (C) with a mass ratio of 95:5 evenly as the composite positive electrode, Li 2 ZrCl 6 (LZC) and Li 6 PS 5 Cl (LPSCl) as the solid electrolyte, Li -In alloy is used as the negative electrode to assemble an all-solid-state battery, verifying the feasibility of Li 3 TiCl 6 as the cathode material, as shown in Figure 7.
  • the results show that the all-solid-state battery has a first-cycle Coulombic efficiency of no less than 97.3% and an initial discharge specific capacity of 92.5mAh ⁇ g –1 , proving that Li 3 TiCl 6 can be used as a 3V-level plug-in cathode material.
  • the results show that the space group of Li 4 TiCl 6 material is C2/m, the room temperature ion conductivity of low crystalline Li 4 TiCl 6 material is 7.67 ⁇ 10 -6 S/cm, and the room temperature electronic conductivity is 8.65 ⁇ 10 -7 S/ cm; ionic conductivity and electrons
  • the electrical conductivity was measured after simply cold-pressing the battery material into sheets, indicating that the Li 4 TiCl 6 material has good deformation ability.
  • the transition metal element Ti generally has the combined state of Ti 2+ , Ti 3+ and Ti 4+ and has potential redox ability as a cathode material.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 3 TiCl 5 O 0.5 material has good deformation ability; and the fact that the ionic conductivity is three orders of magnitude higher than the electronic conductivity proves that Li 3 TiCl 5 O 0.5 material is a pure ionic conductor that can be used as a solid electrolyte.
  • the transition metal element Ti generally has the combined state of Ti 2+ , Ti 3+ and Ti 4+ and has potential redox ability as a cathode material.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 3 TiCl 5 F material has Good deformation ability; and the fact that the ionic conductivity is four orders of magnitude higher than the electronic conductivity proves that the Li 3 TiCl 5 F material is a pure ionic conductor that can be used as a solid electrolyte.
  • the transition metal element Ti generally has the combined state of Ti 2+ , Ti 3+ and Ti 4+ and has potential redox ability as a cathode material.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 3 Ti 0.75 Al 0.25 Cl 6 material has good deformation ability; and the ionic conductivity is four orders of magnitude higher than the electronic conductivity. It turns out that the Li 3 Ti 0.75 Al 0.25 Cl 6 material is a pure ionic conductor that can be used as a solid electrolyte.
  • the transition metal element Ti generally has the combined state of Ti 2+ , Ti 3+ and Ti 4+ and has potential redox ability as a cathode material.
  • the results show that the space group of Li 4 NiCl 6 material is C2/m, the room temperature ion conductivity of low crystalline Li 4 NiCl 6 material is 6.94 ⁇ 10 -6 S/cm, and the room temperature electronic conductivity is 1.48 ⁇ 10 -8 S/ cm. Ionic conductivity and electronic conductivity The rate is measured after simply cold-pressing the battery material into sheets, indicating that the Li 4 NiCl 6 material has good deformation ability.
  • the transition metal element Ni generally has the combined state of Ni + , Ni 2+ and Ni 3+ , and has potential redox ability as a cathode material.
  • the feasibility of 6 as an electrode material is shown in Figures 30 and 31. The results show that the Li 4 NiCl 6 material can be charged and discharged in different voltage ranges and can be used as positive electrode, negative electrode and electrolyte materials.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 3 ZrCl 6 material has good deformation ability; and the fact that the ionic conductivity is four orders of magnitude higher than the electronic conductivity proves that Li 3 ZrCl 6 material is a pure ionic conductor that can be used as a solid electrolyte.
  • the transition metal element Zr has the combined state of Zr 3+ and Zr 4+ , and has potential redox ability as a cathode material.
  • the low crystalline Li 3 Zr 0.75 Ti 0.25 Cl 6 material has a room temperature ion conductivity of 5.17 ⁇ 10 -4 S/cm and a room temperature electronic conductivity of 5.63 ⁇ 10 -9 S/cm.
  • Ionic conductivity and electronic conductivity are the Measured after the cell material is simply cold pressed into sheets, it shows that the Li 3 Zr 0.75 Ti 0.25 Cl 6 material has good deformation ability; and the fact that the ionic conductivity is five orders of magnitude higher than the electronic conductivity proves that Li 3 Zr 0.75 Ti 0.25 Cl 6 materials are pure ionic conductors that can serve as solid electrolytes.
  • the transition metal element Zr has the combined state of Zr 3+ and Zr 4+
  • Ti has the combined state of Ti 2+ , Ti 3+ and Ti 4+ , and has potential redox ability as a cathode material.
  • the X-ray diffraction spectrum, electrochemical impedance spectrum and DC polarization spectrum of the low crystalline Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material after ball milling are shown in Figures 38 to 40 respectively.
  • the results show that the room temperature ion conductivity of the low crystalline Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material is 1.51 ⁇ 10 -4 S/cm, and the room temperature electronic conductivity is 1.07 ⁇ 10 -8 S/cm.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, which shows that the Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material has good deformation ability; and the ionic conductivity is four orders of magnitude higher than the electronic conductivity.
  • Li 3.25 Zr 0.75 Mg 0.25 Cl 6 material is a pure ionic conductor that can be used as a solid electrolyte.
  • the transition metal element Zr has the combined state of Zr 3+ and Zr 4+ , and has potential redox ability as a cathode material.
  • Li 2.5 Zr 0.75 Ca 0.25 Cl 6 material has a room temperature ion conductivity of 2.15 ⁇ 10 -4 S/cm and a room temperature electronic conductivity of 2.85 ⁇ 10 -9 S/cm.
  • the ionic conductivity and electronic conductivity were measured after simply cold-pressing the battery material into sheets, indicating that the Li 2.5 Zr 0.75 Ca 0.25 Cl 6 material has good deformation ability; and the ionic conductivity is five orders of magnitude higher than the electronic conductivity.
  • It turns out Li 2.5 Zr 0.75 Ca 0.25 Cl 6 materials are pure ionic conductors that can be used as solid electrolytes.
  • the transition metal element Zr has the combined state of Zr 3+ and Zr 4+ , and has potential redox ability as a cathode material.
  • the present invention provides a halide all-solid-state battery material and its preparation method and application.
  • the halide all-solid-state battery material obtained by the present invention not only has an ionic conductivity as high as 1 mS/cm, but also has good deformation ability.
  • the M element has reversible redox ability.
  • the good deformation ability ensures that the battery material can be made into an all-solid-state battery through simple cold pressing.
  • this battery material no longer needs to add easily deformable ion conductive agents that do not provide energy, and can increase the energy density of the battery.
  • the high lithium ion conductivity ensures that the battery has high rate performance.

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Abstract

一种卤化物全固态电池材料及其制备方法和应用，属于全固态电池材料技术领域。卤化物全固态电池材料的化学通式为A xM yX zY b，其中A包含Li或Na；M包含Mg、Al、Si、P、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr和Nb中的一种或几种；X包含F、Cl、Br和I中的一种或几种；Y包含O和/或S；其中1≤x≤4，0.5≤y≤1，3≤z≤8，0≤b≤3。该材料具有良好的离子电导率、M阳离子可变价性与易变形性，使得他们可以满足作为全固态电池的正极、负极与固态电解质的多种要求，且具有优异的电化学性能。

Description

一种卤化物全固态电池材料及其制备方法和应用 技术领域
本发明涉及全固态电池材料技术领域，尤其涉及一种卤化物全固态电池材料及其制备方法和应用。
背景技术
全固态电池作为下一代储能技术，有望解决商业化锂离子电池的安全性问题与进一步提高能量密度。全固态电池采用了与商业化锂离子电池相似的结构，即具有不同功能的材料分别作为正极、负极与固态电解质。全固态电池的能量密度与循环稳定性的提升很大程度上取决于正极材料，但目前这些正极材料都是极具刚性的氧化物。当这些氧化物用作全固态电池的正极材料时，不得不配合大量易变形的固态电解质(如卤化物、硫化物等)形成复合电极才能满足离子传输的需求。这不仅降低了全固态电池的能量密度，而且复合电极中电极材料与固态电解质材料的副反应会进一步降低其循环稳定性。
有鉴于此，优化和开发全新结构的全固态电池刻不容缓，这需要对电池材料功能进行进一步的开发。但是商业化锂离子电池材料的功能相对单一，正极、负极、电解质都由对应功能的材料担当，这极大的限制了对电池结构的优化。科学家们也曾尝试设计同时具有正极、负极与电解质多功能的电池材料，但至今尚未找到这种比较理想的多功能材料。难点在于这种新型多功能电池材料要同时满足较高的离子电导率、良好的形变能力与非锂/钠阳离子具有可逆的氧化还原能力，只有这样才可以同时充当全固态电池的正极、负极和电解质中的至少两种。
因此，如何得到一种同时具有正极、负极与电解质多功能的全固态电池材料是目前需要解决的技术问题。
发明内容
本发明的目的在于提供一种卤化物全固态电池材料及其制备方法和应用，以解决现有技术无法得到同时满足较高的离子电导率、良好的形变能力与非锂/钠阳离子具有可逆的氧化还原能力的多功能电池材料的技术问题。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种卤化物全固态电池材料，所述卤化物全固态电池材料的化学通式为AxMyXzYb，其中A包含Li或Na；M包含Mg、Al、Si、P、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr和Nb中的一种或几种；X包含F、Cl、Br和I中的一种或几种；Y包含O和/或S；其中1≤x≤4，0.5≤y≤1，3≤z≤8，0≤b≤3。
进一步的，所述卤化物全固态电池材料的化学式选自以下化学式中的一种：
Li3TiCl6、Li4TiCl6、Li3TiCl5O0.5、Li3TiCl5F、Li3Ti0.75Al0.25Cl6、Li4NiCl6、Li3ZrCl6、Li3Zr0.75Ti0.25Cl6、Li3.25Zr0.75Mg0.25Cl6、Li2.5Zr0.75Ca0.25Cl6。
本发明提供了一种卤化物全固态电池材料的制备方法，包括以下步骤：
取化学计量比的原料混合后进行球磨即得到卤化物全固态电池材料。
进一步的，所述球磨的球料比为10～15：1，球磨的转速为500～600rpm，球磨的时间为20～50h。
进一步的，球磨后进行退火处理。
进一步的，所述退火处理的温度为300～500℃，退火处理的时间为4～6h。
本发明提供了一种卤化物全固态电池材料在制备全固态电池中的应用。
本发明的有益效果：
本发明得到的卤化物全固态电池材料不仅具有高达1mS/cm的离子电导率，并且具有良好的形变能力，同时M元素具有可逆的氧化还原能力。良好的形变能力保证该电池材料可以通过简单冷压制成全固态电池。该电池材料作为正负极不再需要添加不提供能量的易变形离子导电剂，可以提升电池的能量密度。同时高的锂离子电导率保证了电池具有高的倍率性能。
本发明的卤化物全固态电池材料的成功开发有助于优化全固态电池的结构，提升全固态电池的能量密度，同时为全固态电池的产业化提供全新的思路。
附图说明
图1为实施例1所制备低结晶Li3TiCl6材料的X射线衍射谱图；
图2为实施例1所制备低结晶Li3TiCl6材料的电化学阻抗谱图；
图3为实施例1所制备低结晶Li3TiCl6材料的直流极化谱图；
图4为实施例1所制备高结晶Li3TiCl6材料的X射线衍射谱图；
图5为实施例1所制备高结晶Li3TiCl6材料的电化学阻抗谱图；
图6为实施例1所制备高结晶Li3TiCl6材料的直流极化谱图；
图7为实施例1所制备高结晶Li3TiCl6材料作为正极材料的充放电曲线图；
图8为实施例1所制备高结晶Li3TiCl6材料组装单一材料全固态电池的充放电曲线图；
图9为实施例2所制备低结晶Li4TiCl6材料的X射线衍射谱图；
图10为实施例2所制备低结晶Li4TiCl6材料的电化学阻抗谱图；
图11为实施例2所制备低结晶Li4TiCl6材料的直流极化谱图；
图12为实施例3所制备低结晶Li3TiCl5O0.5材料的X射线衍射谱图；
图13为实施例3所制备低结晶Li3TiCl5O0.5材料的电化学阻抗谱图；
图14为实施例3所制备低结晶Li3TiCl5O0.5材料的直流极化谱图；
图15为实施例3所制备高结晶Li3TiCl5O0.5材料的X射线衍射谱图；
图16为实施例3所制备高结晶Li3TiCl5O0.5材料的电化学阻抗谱图；
图17为实施例3所制备高结晶Li3TiCl5O0.5材料的直流极化谱图；
图18为实施例4所制备低结晶Li3TiCl5F材料的X射线衍射谱图；
图19为实施例4所制备低结晶Li3TiCl5F材料的电化学阻抗谱图；
图20为实施例4所制备低结晶Li3TiCl5F材料的直流极化谱图；
图21为实施例5所制备低结晶Li3Ti0.75Al0.25Cl6材料的X射线衍射谱图；
图22为实施例5所制备低结晶Li3Ti0.75Al0.25Cl6材料的电化学阻抗谱图；
图23为实施例5所制备低结晶Li3Ti0.75Al0.25Cl6材料的直流极化谱图；
图24为实施例5所制备高结晶Li3Ti0.75Al0.25Cl6材料的X射线衍射谱图；
图25为实施例5所制备高结晶Li3Ti0.75Al0.25Cl6材料的电化学阻抗谱图；
图26为实施例5所制备高结晶Li3Ti0.75Al0.25Cl6材料的直流极化谱图；
图27为实施例6所制备低结晶Li4NiCl6材料的X射线衍射谱图；
图28为实施例6所制备低结晶Li4NiCl6材料的电化学阻抗谱图；
图29为实施例6所制备低结晶Li4NiCl6材料的直流极化谱图；
图30为实施例6所制备低结晶Li4NiCl6材料作为电极材料在3.16～5V vs.Li/Li+电压区间的充电曲线图；
图31为实施例6所制备低结晶Li4NiCl6材料作为电极材料在1～3V vs.Li/Li+电压区间的充放电曲线图；
图32为实施例7所制备低结晶Li3ZrCl6材料的X射线衍射谱图；
图33为实施例7所制备低结晶Li3ZrCl6材料的电化学阻抗谱图；
图34为实施例7所制备低结晶Li3ZrCl6材料的直流极化谱图；
图35为实施例8所制备低结晶Li3Zr0.75Ti0.25Cl6材料的X射线衍射谱图；
图36为实施例8所制备低结晶Li3Zr0.75Ti0.25Cl6材料的电化学阻抗谱图；
图37为实施例8所制备低结晶Li3Zr0.75Ti0.25Cl6材料的直流极化谱图；
图38为实施例9所制备低结晶Li3.25Zr0.75Mg0.25Cl6材料的X射线衍射谱图；
图39为实施例9所制备低结晶Li3.25Zr0.75Mg0.25Cl6材料的电化学阻抗谱图；
图40为实施例9所制备低结晶Li3.25Zr0.75Mg0.25Cl6材料的直流极化谱图；
图41为实施例10所制备低结晶Li2.5Zr0.75Ca0.25Cl6材料的X射线衍射谱图；
图42为实施例10所制备低结晶Li2.5Zr0.75Ca0.25Cl6材料的电化学阻抗谱图；
图43为实施例10所制备低结晶Li2.5Zr0.75Ca0.25Cl6材料的直流极化谱图。
具体实施方式
本发明提供了一种卤化物全固态电池材料，所述卤化物全固态电池材料的化学通式为AxMyXzYb，其中A包含Li或Na；M包含Mg、Al、Si、P、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr和Nb中的一种或几种；X包含F、Cl、Br和I中的一种或几种；Y包含O和/或S；其中1≤x≤4，0.5≤y≤1，3≤z≤8，0≤b≤3。
在本发明中，其中x、y、z和b优选的，2≤x≤3，0.6≤y≤0.9，4≤z≤7，1≤b≤2；进一步优选的，2.1≤x≤2.6，0.7≤y≤0.8，5≤z≤6，1.2≤b≤1.8。
在本发明中，所述卤化物全固态电池材料的化学式优选为以下化学式中 的一种：
Li3TiCl6、Li4TiCl6、Li3TiCl5O0.5、Li3TiCl5F、Li3Ti0.75Al0.25Cl6、Li4NiCl6、Li3ZrCl6、Li3Zr0.75Ti0.25Cl6、Li3.25Zr0.75Mg0.25Cl6、Li2.5Zr0.75Ca0.25Cl6。
本发明提供了一种卤化物全固态电池材料的制备方法，包括以下步骤：
取化学计量比的原料混合后进行球磨即得到卤化物全固态电池材料。
在本发明中，所述球磨的球料比为10～15：1，球磨的转速为500～600rpm，球磨的时间为20～50h；优选的，球磨的球料比为11～14：1，球磨的转速为520～580rpm，球磨的时间为24～45h；进一步优选的，球磨的球料比为12～13：1，球磨的转速为550rpm，球磨的时间为30～40h。
在本发明中，球磨后进行退火处理。
在本发明中，所述退火处理的温度为300～500℃，退火处理的时间为4～6h；优选的，退火处理的温度为350～450℃，退火处理的时间为4～5h；进一步优选的，退火处理的温度为400℃，退火处理的时间为5h。
在本发明中，退火处理后的材料为高结晶材料，未进行退火处理的材料为低结晶材料。
本发明提供了一种卤化物全固态电池材料在制备全固态电池中的应用。
在本发明中，所述卤化物全固态电池材料可作为全固态电池的正极、负极和固态电解质中的一种或几种。
下面结合实施例对本发明提供的技术方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
卤化物全固态Li3TiCl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl与TiCl3，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette7中在600r/min下球磨24小时。低结晶的样品为球磨后未退火的，高结晶的样品为密封于石英管中经过300℃高温退火5小时的，它们的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图1～6所示。结果显示，Li3TiCl6材料的空间群为C2/m，低结晶Li3TiCl6材料的室温离子电导率(σi)为 1.15×10-4S/cm，室温电子电导率(σe)为3.32×10-7S/cm；高结晶Li3TiCl6材料的室温离子电导率高达1.04×10-3S/cm，室温电子电导率为7.30×10-7S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3TiCl6材料具有良好的形变能力；并且离子电导率比电子电导率高三个数量级的事实证明Li3TiCl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Ti一般具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
将质量比为95：5的高结晶Li3TiCl6(LTC)与炭黑(C)混合均匀作为复合正极，Li2ZrCl6(LZC)与Li6PS5Cl(LPSCl)作为固态电解质，Li-In合金作为负极组装全固态电池，验证Li3TiCl6作为正极材料的可行性，如图7所示。结果显示，该全固态电池具有不低于97.3％的首圈库仑效率与92.5mAh·g–1的初始放电比容量，证明Li3TiCl6可以作为3V级插入式正极材料。
在氩气保护的手套箱中(水氧含量小于0.01ppm)，取质量比为95：5的高结晶Li3TiCl6(LTC)与炭黑(C)，然后混合均匀作为复合正极与复合负极。然后按Li3TiCl6+C│Li3TiCl6│Li3TiCl6+C的结构组装单一材料全固态电池，之后进行电化学测试，如图8所示。结果表明，其具有不低于86.1％的首圈库仑效率与80.5mAh·g–1的初始放电比容量，证明Li3TiCl6材料可以同时作为全固态电池的正极、负极与固态电解质。值得注意的是，Li3TiCl6可以替换为本发明中包含的多功能卤化物中的任意一种来组装单一材料全固态电池。
实施例2
卤化物全固态Li4TiCl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl与TiCl3与Ti粉，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在600r/min下球磨24小时。球磨后低结晶Li4TiCl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图9～11所示。结果显示，Li4TiCl6材料的空间群为C2/m，低结晶Li4TiCl6材料的室温离子电导率为7.67×10-6S/cm，室温电子电导率为8.65×10-7S/cm；离子电导率与电子 电导率是将电池材料简单冷压成片后测得的，说明Li4TiCl6材料具有良好的形变能力。过渡金属元素Ti一般具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例3
卤化物全固态Li3TiCl5O0.5材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、TiCl3与Li2O，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在600r/min下球磨24小时。低结晶的样品为球磨后未退火的，高结晶的样品为密封于石英管中经过300℃高温退火5小时的，它们的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图12～17所示。结果显示，Li3TiCl5O0.5材料的空间群为C2/m，低结晶Li3TiCl5O0.5材料的室温离子电导率为9.95×10-5S/cm，室温电子电导率为5.38×10-8S/cm；高结晶Li3TiCl5O0.5材料的室温离子电导率为2.64×10-4S/cm，室温电子电导率为1.22×10-7S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3TiCl5O0.5材料具有良好的形变能力；并且离子电导率比电子电导率高三个数量级的事实证明Li3TiCl5O0.5材料是可以作为固态电解质的纯离子导体。过渡金属元素Ti一般具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例4
卤化物全固态Li3TiCl5F材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、TiCl3与LiF，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在600r/min下球磨24小时。球磨后低结晶Li3TiCl5F材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图18～20所示。结果显示，Li3TiCl5F材料的空间群为C2/m，低结晶Li3TiCl5F材料的室温离子电导率为1.02×10-4S/cm，室温电子电导率为3.79×10-8S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3TiCl5F材料具有 良好的形变能力；并且离子电导率比电子电导率高四个数量级的事实证明Li3TiCl5F材料是可以作为固态电解质的纯离子导体。过渡金属元素Ti一般具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例5
卤化物全固态Li3Ti0.75Al0.25Cl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、TiCl3与AlCl3，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在600r/min下球磨24小时。低结晶的样品为球磨后未退火的，高结晶的样品为密封于石英管中经过300℃高温退火5小时的，它们的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图21～26所示。结果显示，Li3Ti0.75Al0.25Cl6材料的空间群为C2/m，低结晶Li3Ti0.75Al0.25Cl6材料的室温离子电导率为3.31×10-5S/cm，室温电子电导率为3.72×10-8S/cm；高结晶Li3Ti0.75Al0.25Cl6材料的室温晶内离子电导率为4.24×10-4S/cm、晶界离子电导率为1.63×10-4S/cm，室温电子电导率为1.50×10-8S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3Ti0.75Al0.25Cl6材料具有良好的形变能力；并且离子电导率比电子电导率高四个数量级的事实证明Li3Ti0.75Al0.25Cl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Ti一般具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例6
卤化物全固态Li4NiCl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl与NiCl2，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为12：1)，密封后在德国飞驰公司的高能球磨机Pulverisette7中在600r/min下球磨24小时。球磨后低结晶Li4NiCl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图27～29所示。结果显示，Li4NiCl6材料的空间群为C2/m，低结晶Li4NiCl6材料的室温离子电导率为6.94×10-6S/cm，室温电子电导率为1.48×10-8S/cm。离子电导率与电子电导 率是将电池材料简单冷压成片后测得的，说明Li4NiCl6材料具有良好的形变能力。过渡金属元素Ni一般具有Ni+、Ni2+与Ni3+的化合态，具有作为正极材料的潜在氧化还原能力。
将质量比为50：45：5的低结晶Li4NiCl6、LZC与炭黑(C)作为复合正极，LZC与LPSCl作为固态电解质，Li-In合金作为负极组装全固态电池，验证Li4NiCl6作为电极材料的可行性，如图30、31所示。结果显示，Li4NiCl6材料可以在不同的电压区间进行充放电，可以作为正极、负极与电解质材料。
实施例7
卤化物全固态Li3ZrCl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、ZrCl4与Zr粉，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为10：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在500r/min下球磨45小时。球磨后低结晶Li3ZrCl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图32～34所示。结果显示，低结晶Li3ZrCl6材料的室温离子电导率为2.62×10-4S/cm，室温电子电导率为4.47×10-8S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3ZrCl6材料具有良好的形变能力；并且离子电导率比电子电导率高四个数量级的事实证明Li3ZrCl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Zr具有Zr3+与Zr4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例8
卤化物全固态Li3Zr0.75Ti0.25Cl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、ZrCl4与Ti粉，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为10：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在500r/min下球磨45小时。球磨后低结晶Li3Zr0.75Ti0.25Cl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图35～37所示。结果显示，低结晶Li3Zr0.75Ti0.25Cl6材料的室温离子电导率为5.17×10-4S/cm，室温电子电导率为5.63×10-9S/cm。离子电导率与电子电导率是将电 池材料简单冷压成片后测得的，说明Li3Zr0.75Ti0.25Cl6材料具有良好的形变能力；并且离子电导率比电子电导率高五个数量级的事实证明Li3Zr0.75Ti0.25Cl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Zr具有Zr3+与Zr4+的化合态、Ti具有Ti2+、Ti3+与Ti4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例9
卤化物全固态Li3.25Zr0.75Mg0.25Cl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、ZrCl4、MgCl2与Zr粉，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为10：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在500r/min下球磨45小时。球磨后低结晶Li3.25Zr0.75Mg0.25Cl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图38～40所示。结果显示，低结晶Li3.25Zr0.75Mg0.25Cl6材料的室温离子电导率为1.51×10-4S/cm，室温电子电导率为1.07×10-8S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li3.25Zr0.75Mg0.25Cl6材料具有良好的形变能力；并且离子电导率比电子电导率高四个数量级的事实证明Li3.25Zr0.75Mg0.25Cl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Zr具有Zr3+与Zr4+的化合态，具有作为正极材料的潜在氧化还原能力。
实施例10
卤化物全固态Li2.5Zr0.75Ca0.25Cl6材料的制备：
在氩气保护的手套箱中(水氧含量小于0.01ppm)，分别按化学计量比称取LiCl、ZrCl4与CaCl2，置于装有5mm直径氧化锆球磨珠的80mL氮化硅球磨罐中(球料质量比为10：1)，密封后在德国飞驰公司的高能球磨机Pulverisette 7中在500r/min下球磨45小时。球磨后低结晶Li2.5Zr0.75Ca0.25Cl6材料的X射线衍射谱图、电化学阻抗谱图与直流极化谱图分别如图41～43所示。结果显示，低结晶Li2.5Zr0.75Ca0.25Cl6材料的室温离子电导率为2.15×10-4S/cm，室温电子电导率为2.85×10-9S/cm。离子电导率与电子电导率是将电池材料简单冷压成片后测得的，说明Li2.5Zr0.75Ca0.25Cl6材料具有良好的形变能力；并且离子电导率比电子电导率高五个数量级的事实证明 Li2.5Zr0.75Ca0.25Cl6材料是可以作为固态电解质的纯离子导体。过渡金属元素Zr具有Zr3+与Zr4+的化合态，具有作为正极材料的潜在氧化还原能力。
由以上实施例可知，本发明提供了一种卤化物全固态电池材料及其制备方法和应用。本发明得到的卤化物全固态电池材料不仅具有高达1mS/cm的离子电导率，并且具有良好的形变能力，同时M元素具有可逆的氧化还原能力。良好的形变能力保证该电池材料可以通过简单冷压制成全固态电池。该电池材料作为正负极不再需要添加不提供能量的易变形离子导电剂，可以提升电池的能量密度。同时高的锂离子电导率保证了电池具有高的倍率性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (7)

  1. 一种卤化物全固态电池材料，其特征在于，所述卤化物全固态电池材料的化学通式为AxMyXzYb，其中A包含Li或Na；M包含Mg、Al、Si、P、Ca、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Zr和Nb中的一种或几种；X包含F、Cl、Br和I中的一种或几种；Y包含O和/或S；其中1≤x≤4，0.5≤y≤1，3≤z≤8，0≤b≤3。
  2. 根据权利要求1所述的卤化物全固态电池材料，其特征在于，所述卤化物全固态电池材料的化学式选自以下化学式中的一种：
    Li3TiCl6、Li4TiCl6、Li3TiCl5O0.5、Li3TiCl5F、Li3Ti0.75Al0.25Cl6、Li4NiCl6、Li3ZrCl6、Li3Zr0.75Ti0.25Cl6、Li3.25Zr0.75Mg0.25Cl6、Li2.5Zr0.75Ca0.25Cl6。
  3. 权利要求1或2所述卤化物全固态电池材料的制备方法，其特征在于，包括以下步骤：
    取化学计量比的原料混合后进行球磨即得到卤化物全固态电池材料。
  4. 根据权利要求3所述的卤化物全固态电池材料的制备方法，其特征在于，所述球磨的球料比为10～15：1，球磨的转速为500～600rpm，球磨的时间为20～50h。
  5. 根据权利要求3或4所述的卤化物全固态电池材料的制备方法，其特征在于，球磨后进行退火处理。
  6. 根据权利要求5所述的卤化物全固态电池材料的制备方法，其特征在于，所述退火处理的温度为300～500℃，退火处理的时间为4～6h。
  7. 权利要求1或2所述卤化物全固态电池材料在制备全固态电池中的应用。
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