Lithium-sodium universal halide glass ceramic phase solid-state electrolyte and application

Abstract

The application discloses a lithium and sodium universal halide glass ceramic phase solid electrolyte and application. x MN y Cl x+3+z*y ; the solid electrolyte comprises a ceramic phase A a MCl 3+a and a glass phase A b N y Cl b+z*y (wherein a+b=x), wherein A is one selected from Li and Na, M is one selected from La, Ce, Eu, Sm, Gd and Y or a combination thereof, and N is one selected from Al, Ga, Mg, Ca, Sr, Zn, Zr, Ta, Nb and Hf or a combination thereof. The application designs the components of the glass ceramic composite phase halide solid electrolyte by the mechanical chemical method, and the components include the selection of the ceramic phase A a MCl 3+a and the glass phase A b N y Cl b+z*y The lithium and sodium universal halide glass ceramic phase solid electrolyte has high ion conductivity, and can be applied to lithium and sodium ion batteries and is expected to widen the application field of all-solid-state ion batteries.

Description

Technical Field

[0001] This invention relates to the field of lithium battery technology, and more specifically, to a solid electrolyte material, its preparation method, and its application. Background Technology

[0002] Since Sony introduced lithium-ion batteries in 1991, they have been widely used in various portable electronic products (such as laptops, mobile phones, and digital cameras) and electric vehicles. However, recent frequent safety incidents involving new energy vehicles are mainly due to the fact that traditional lithium-ion batteries require flammable organic solvents as electrolytes, posing a risk of flammability and explosion that cannot be fundamentally addressed through conventional means. Therefore, solid-state lithium-ion batteries using solid electrolytes offer significant safety advantages. Using solid electrolytes not only fundamentally solves the safety problems of lithium-ion batteries but also promises to greatly simplify manufacturing and packaging processes, improving battery energy density, reliability, and design freedom. Among various new battery systems, solid-state batteries are the next-generation technology closest to industrialization, a consensus reached by both industry and the scientific community. On the other hand, with the increasing demand and intensified competition in the lithium-ion battery market, the price of lithium-based raw materials continues to rise. Due to the use of more prevalent sodium and potassium ions, sodium-based and potassium-based solid-state batteries offer a significant cost advantage over lithium-ion solid-state batteries.

[0003] For solid-state electrolytes, a fundamental requirement is high ionic conductivity. Studies have shown that materials with certain specific crystal structures facilitate faster lithium-ion transport. Therefore, recent research on solid-state electrolytes has primarily focused on inorganic materials, especially sulfides, oxides, and halides. Specifically, sulfide materials, particularly those with a body-centered cubic (bcc) anionic framework, such as Li7P3S... 11 and Li 10 GeP2S 12 Materials, etc., presenting 10 -2 Lithium-ion conductivity at the S / cm level ( Energy Environ. Sci. 13, 1429-1461 (2020); Nature Materials 10, 682-686 (2011); Nature Energy 1, 16030 (2016); ACS Appl. Mater. Interfaces 8, 7843-7853 (2016)). Na3PS4 and Na in sodium-based systems. 10 SnP2S 12 It also has 10 -4 -10 -3Ion conductivity in the S / cm range. However, sulfide-based materials suffer from poor air stability and a narrow electrochemical window, making them difficult to apply directly to all-solid-state batteries. Oxide-based electrolytes, on the other hand, exhibit superior chemical and electrochemical stability compared to sulfide-based materials, thus holding greater application potential. However, their ionic conductivity is generally low, only around 10. -3 The conductivity is in the S / cm range, similar to that of lithium-ion electrolytes in traditional electrolytes. Although oxide-based solid electrolytes exhibit good chemical and electrochemical stability, their high hardness, rigidity, and numerous grain boundaries pose significant drawbacks for practical battery applications.

[0004] In recent years, halide-based solid electrolytes have once again attracted attention. Similar to oxide-based electrolyte materials, lithium halide-based materials (such as Li3InCl6, Li-Y-Cl, Li-Sc-Cl, and Li-Ho-Cl) exhibit good electrochemical stability and can be directly used with unmodified lithium cobalt oxide or nickel-cobalt-manganese cathode materials. Adv. Mater. 2018, 30, 1803075; Angew. Chem., 2019, 131, 16579-16584; J. Am. Chem. Soc. (2020, 142, 7012-7022.). Most reported halide-based materials are crystalline materials with anionic frameworks; the highest reported conductivity in lithium-based systems to date is 3 × 10⁻⁶. -3 S / cm, approximately 4 × 10⁻⁶ for sodium-based systems. -5 S / cm, there are few reports on potassium ion conductivity. Although halide solid electrolyte materials have achieved relatively fast lithium-ion transport capabilities in lithium-based systems, there are still no good methods or systems to achieve high ionic conductivity in the sodium and potassium ion fields.

[0005] In summary, this paper provides a simple method for preparing a halide solid electrolyte and demonstrates that the solid electrolyte has high lithium and sodium ion conductivity, which meets the needs of more diverse solid-state batteries and has important research significance. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a type of glass-ceramic phase halide solid electrolyte. This type of solid electrolyte exhibits high lithium-ion and sodium-ion ionic conductivity at room temperature, reaching up to 3 × 10⁻⁶. -3 S / cm (room temperature). This type of electrolyte can be used in lithium and sodium-ion batteries, and is expected to broaden the application fields of all-solid-state ion batteries.

[0007] Another object of the present invention is to provide a method for preparing the solid electrolyte material described above, which is mild and simple to implement.

[0008] To achieve the above objectives, the present invention discloses the following technical contents: A type of glass-ceramic phase solid electrolyte material, the composition of which is expressed as follows: A x MN y Cl x+3+z*y 0.25≤x≤5, 0≤y≤6, 2≤z≤5; It contains ceramic phase elements A, M, and Cl; where A is selected from Li and Na, and M is selected from La, Ce, Eu, Sm, Gd, and Y, or a combination thereof; It also contains ceramic phase elements A, N, and Cl; wherein A is selected from Li and Na, and N is selected from Al, Ga, Mg, Ca, Sr, Zn, Zr, Ta, Nb, and Hf or a combination thereof; the solid electrolyte material is a glass-ceramic phase.

[0009] The solid electrolyte material has a crystal structure of space group P63 / m.

[0010] The method for preparing the solid electrolyte material of the present invention is characterized by comprising the following steps: The solid electrolyte material of this invention is prepared from raw materials including precursor A, precursor M, and precursor N; the precursor A includes lithium chloride and sodium chloride; the precursor M includes chlorides corresponding to M such as lanthanum chloride, cerium chloride, samarium chloride, europium chloride, gadolinium chloride, and yttrium chloride; the precursor N includes chlorides corresponding to N such as aluminum chloride, gallium chloride, magnesium chloride, calcium chloride, strontium chloride, tantalum chloride, zinc chloride, niobium chloride, hafnium chloride, and zirconium chloride.

[0011] The solid electrolyte is obtained by ball milling a mixture of precursors A, M, and N under inert gas or vacuum conditions; wherein the molar ratio of precursors A, M, and N is balanced according to the stoichiometric ratio of the solid electrolyte.

[0012] Furthermore, the ball-milled product can be calcined under inert gas or vacuum conditions, or no post-treatment may be required. The calcination includes: raising the temperature from room temperature to 100-300°C, holding the temperature at 100-300°C, and then lowering the holding temperature back to room temperature.

[0013] The present invention further discloses a lithium battery having a positive electrode, a negative electrode and an electrolyte (liquid) layer between the positive electrode and the negative electrode, characterized in that the positive electrode, the negative electrode and the electrolyte layer contain at least the solid electrolyte material described above.

[0014] This invention also discloses the application of a type of solid electrolyte material in improving the lithium-ion conductivity of electrolytes. Experimental results show that a secondary battery containing the above-mentioned solid electrolyte according to this invention can achieve stable charging and discharging at room temperature.

[0015] The present invention is described in more detail below: First embodiment: A solid electrolyte material, wherein the electrolyte material can be represented by the following formula: A x+a MN b Cl 3+x+a+c (1) The solid electrolyte material is a glass-ceramic phase; the crystal structure of the solid electrolyte material is space group P63 / m.

[0016] The solid electrolyte material is prepared from raw materials including precursors A, M, and N; Preferably, the precursor of A includes lithium chloride and sodium chloride; Preferably, the precursor of M includes lanthanum chloride and samarium chloride; Preferably, the precursor of N includes tantalum chloride and zirconium chloride; The present invention further discloses a lithium battery having a positive electrode, a negative electrode and an electrolyte (liquid) layer between the positive electrode and the negative electrode, characterized in that at least one of the positive electrode, the negative electrode and the electrolyte layer contains the solid electrolyte material.

[0017] The preparation method of the solid electrolyte material as described above includes the following steps: A mixture of precursors A, M, and N is placed in a ball mill jar; the molar ratio of precursors A, M, and N is 0.1-2:1:0-4. Using a planetary ball mill or similar apparatus, the raw material powders collide with each other in the ball mill jar, undergoing a mechanochemical reaction to generate the target product. The raw material powders in the ball mill jar can be under vacuum or protected by an inert gas (such as nitrogen, argon, helium, etc.).

[0018] Preferably, the ball mill rotation speed is 200–600 rpm; Preferably, the ball milling time is 1 to 40 hours; Furthermore, in order to improve the thermal stability of solid electrolyte materials, the ball-milled product can be calcined under inert gas conditions.

[0019] Preferably, the calcination includes: raising the temperature from room temperature to 100-300°C, holding the temperature at 100-300°C, and then lowering the holding temperature to room temperature.

[0020] Furthermore, in order to improve the compatibility between the solid electrolyte material and the negative electrode active material, in the composition formula (1), M is preferably the metal La. 3+ Or Sm 3+ . Furthermore, in order to improve the compatibility between the solid electrolyte material and the negative electrode active material, in the composition formula (1), M can be made of metal Sr 2+ Ba 2+ Ca 2+ Partial replacement.

[0021] The electrolyte material obtained in the first embodiment should be a mixture of crystalline and amorphous phases.

[0022] The shape of the electrolyte material obtained in the first embodiment is not limited, such as granular, layered, needle-like, etc.

[0023] The size of the electrolyte material obtained in the first embodiment is not limited. Preferably, the particle size is between 0.1 µm and 10 µm.

[0024] Second implementation method: A lithium battery includes a positive electrode, a negative electrode, and an electrolyte (liquid) layer between the positive and negative electrodes. At least one of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material described in the first embodiment.

[0025] The electrolyte layer is located between the positive and negative electrodes.

[0026] The positive electrode consists of positive electrode active material particles and electrolyte particles.

[0027] The negative electrode consists of negative electrode active material particles and electrolyte particles.

[0028] Positive electrode active materials refer to materials that can absorb and release metal ions, such as lithium-containing transition metal oxides, transition metal fluorides, and polyanionic materials.

[0029] Negative electrode active materials refer to materials that can absorb and release metal ions, such as metallic materials, carbon materials, and nitrogen materials. Metallic materials can be elemental metals or alloys.

[0030] To ensure electrochemical cycle stability, chemical stability, and ionic conductivity, at least one of the positive electrode, negative electrode, and electrolyte layer of the aforementioned lithium battery may contain one or more additional electrolyte (liquid) materials. These additional electrolyte materials are not specified and may include oxide solid electrolytes, sulfide solid electrolytes, halide solid electrolytes, polymer electrolytes, and electrolyte solutions, etc.

[0031] Oxide solid electrolytes refer to oxygen-containing solid electrolytes, such as NASICON type, LISICON type, garnet type, perovskite type, Li3PO4 or its N-substituted forms.

[0032] Sulfide solid electrolytes refer to sulfur-containing solid electrolytes, such as Li₂S-P₂S₅, Li₂S-GeS₂, lithium-sulfur silver-germanium ore (Li₆PS₅Cl), and Li₂S-P₂S₅. 10 GeP2S 12 wait Halogenated solid electrolytes refer to solid electrolytes containing halogens, and may also contain other anions, such as Li3InCl6, Li3YCl6, Li3YBr6, or Li-Sc-Cl.

[0033] To ensure the electrochemical stability of the battery during cycling, the positive or negative electrode active materials can be modified. For example, molecular layer deposition (MLD) and atomic layer deposition (ALD) techniques can be used to prepare inorganic or organic thin films, modifying the surface and interface of the positive or negative electrode active materials. ALD technology can be used to prepare various oxide thin films, such as Al₂O₃, LiTaO₃, and LiNbO₃. MLD technology can be used to prepare various inorganic thin films, such as alucone.

[0034] The positive effects of the solid electrolyte material and its application disclosed in this invention are as follows: (1) The solid electrolyte material has high lithium-ion conductivity.

[0035] (2) The solid electrolyte material has electrochemical stability.

[0036] (3) The solid electrolyte material and the electrode material are compatible.

[0037] (4) The solid electrolyte material can be used in lithium secondary batteries that can be well charged and discharged at room temperature. Attached Figure Description

[0038] Figure 1 The Li obtained in Embodiment 1 of this invention 0.25 SmCl 3.25 Li 0.5 SmCl 3.5 X-ray diffraction phase analysis diagram of LiSmCl4 solid electrolyte; Figure 2 The Li obtained in Embodiment 1 of this invention 0.5 SmCl 3.5 Scanning electron microscope image of a solid electrolyte; Figure 3 The Li obtained in Embodiment 1 of this invention 0.5SmCl 3.5 Electrochemical performance test results of symmetric lithium-ion batteries with solid electrolytes; Figure 4 LiSmZr in Embodiment 2 of the present invention 0.5 X-ray diffraction phase analysis diagram of Cl6 solid electrolyte; Figure 5 It is NaSmTa in Embodiment 5 of the present invention 0.5 Cl 6.5 X-ray diffraction phase analysis diagram of solid electrolyte; Figure 6 This is a schematic diagram of the crystal structure of the crystalline phase (ceramic phase) in the solid electrolyte with the highest ion conductance obtained in Embodiment 5 of the present invention; Figure 7 This is a graph showing the electrochemical performance of an all-solid-state lithium-ion battery obtained in Application Example 1 of this invention. Figure 8 This is a graph showing the electrochemical performance of an all-solid-state lithium-ion battery obtained in Application Example 2 of this invention. Detailed Implementation

[0039] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the invention. Where specific techniques or conditions are not specified in the examples, they should be performed according to the techniques or conditions described in the literature in this field, or according to the product instructions. Raw materials, reagents, or instruments whose manufacturers are not specified are all conventional products that can be purchased from legitimate channels.

[0040] Example 1 A series of solid electrolyte materials with the chemical formula Li x SmCl x+3 (0.25≤x≤2) Commercially available LiCl and SmCl3 were uniformly mixed in an argon-protected glove box at different feed ratios. The molar ratio of LiCl to SmCl3 was 0.25:1, 0.5:1, 0.75:1, 1:1, 1.5:1, or 2:1, corresponding to the composition representation A in claim 1, respectively. x MN y Cl x+3+z*y For the cases where x = 0.25, 0.5, 0.75, 1, 1.5, 2, and y = 0, 1.5g of the mixed powder was placed in a 50mL ball mill jar, and 40g of grinding beads were added accordingly. The ball mill jar was sealed and run at a high speed of 450rpm for 20 hours. Subsequently, the ball mill jar was transferred to a glove box, and the powder inside was scraped out, which is the obtained electrolyte.

[0041] Weigh 100mg Li x SmCl 3+xElectrolyte powder was placed in an insulating outer cylinder and pressurized to 300 MPa. AC impedance spectroscopy was then performed. The ionic conductivity of the electrolyte material was calculated based on the impedance values ​​and the Arrhenius equation. The test results are shown in Table 1. The obtained Li... 0.25 SmCl 3.25 Li 0.5 SmCl 3.5 X-ray diffraction (XRD) phase analysis was performed on LiSmCl4, and the results are as follows: Figure 1 As shown, the analytical results indicate that the crystalline phase composition of the obtained electrolyte belongs to the P63 / m space group. Furthermore, the product with the highest ionic conductance was subjected to scanning electron microscopy (SEM). Figure 2 ) and symmetric lithium battery electrochemical performance testing ( Figure 3 Table 1: Example 2 A solid electrolyte material with the chemical formula LiSmZr 0.5 Cl6 Except for changing the raw materials to LiCl, SmCl3, and ZrCl4, with the molar ratio of LiCl, SmCl3, and ZrCl4 being 1:1:0.5, and adjusting the ball mill speed to 500 rpm, the other procedures are the same as in Example 1, corresponding to composition representation A in claim 1. x MN y Cl x+3+z*y The case is x=1, y=0.5, z=4, where A is Li, M is Sm, and N is Zr.

[0042] Example 3 A solid electrolyte material with the chemical formula Li 0.5 LaTa 0.5 Cl6 Except for the raw materials being changed to LiCl, LaCl3, and TaCl5, with the molar ratio of LiCl, LaCl3, and TaCl5 being 0.5:1:0.5, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=0.5, y=0.5, z=5, where A is Li, M is La, and N is Ta.

[0043] Example 4 A solid electrolyte material with the chemical formula Na 0.86 LaTa 0.43 Cl6 Except for the raw materials being changed to NaCl, LaCl3, and TaCl5, with the molar ratio of NaCl, LaCl3, and TaCl5 being 0.86:1:0.43, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=0.86, y=0.43, z=5, where A is Na, M is La, and N is Ta.

[0044] Example 5 A solid electrolyte material with the chemical formula NaSmTa 0.5 Cl 6.5 Except for changing the raw materials to NaCl, SmCl3, and TaCl5, with the molar ratio of NaCl, SmCl3, and TaCl5 being 1:1:0.5, and adjusting the ball mill speed to 600 rpm, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case is x=1, y=0.5, z=5, where A is Na, M is Sm, and N is Ta.

[0045] Example 6 A solid electrolyte material with the chemical formula NaSmZr 0.5 Cl6 Except for the raw materials being changed to NaCl, SmCl3, and ZrCl4, with the molar ratio of NaCl, SmCl3, and ZrCl4 being 1:1:0.5, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case is x=1, y=0.5, z=4, where A is Na, M is Sm, and N is Zr.

[0046] Example 7 A solid electrolyte material with the chemical formula Na 1.5 CeTa 0.5 Cl7 Except for the raw materials being changed to NaCl, CeCl3, and TaCl5, with the molar ratio of NaCl, CeCl3, and TaCl5 being 1.5:1:0.5, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=1.5, y=0.5, z=5, where A is Na, M is Ce, and N is Ta.

[0047] Example 8 A solid electrolyte material with the chemical formula Na 1.2 NdTa 0.6 Cl 7.2 Except for the raw materials being changed to NaCl, NdCl3, and TaCl5, with the molar ratio of NaCl, NdCl3, and TaCl4 being 1.2:1:0.6, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=1.2, y=0.6, z=7.2, where A is Na, M is Nd, and N is Ta.

[0048] Example 9 A solid electrolyte material with the chemical formula NaLaZr 0.5 Cl6 Except for the raw materials being changed to NaCl, LaCl3, and ZrCl4, with the molar ratio of NaCl, LaCl3, and ZrCl4 being 1:1:0.5, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=1, y=0.5, z=4, where A is Na, M is La, and N is Zr.

[0049] Example 10 A solid electrolyte material with the chemical formula Na₄YTa₄Cl 27 Except for the raw materials being changed to NaCl, YCl3, and TaCl5, with the molar ratio of NaCl, YCl3, and TaCl5 being 4:1:4, the procedure steps are the same as in Example 1, corresponding to the composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=4, y=4, z=5, where A is Na, M is Y, and N is Ta.

[0050] Example 11 A solid electrolyte material with the chemical formula Li₂LaAl₂Cl 11 Except for the raw materials being changed to LiCl, LaCl3, and AlCl3, with the molar ratio of LiCl, LaCl3, and AlCl3 being 2:1:2, the procedure steps are the same as in Example 1, corresponding to composition representation A in claim 1. x MN y Cl x+3+z*yThe case where x=2, y=2, z=3, where A is Li, M is La, and N is Al.

[0051] Example 12 A solid electrolyte material with the chemical formula LiLaMg 0.5 Cl5 Except for the raw materials being changed to LiCl, LaCl3, and MgCl2, with the molar ratio of LiCl, SmCl3, and MgCl2 being 1:1:0.5, the ball-milled sample was calcined under vacuum for 2 hours at a temperature of 150 degrees Celsius. All other procedures were the same as in Example 1, corresponding to composition representation A in claim 1. x MN y Cl x+3+z*y The case where x=1, y=0.5, z=2, where A is Li, M is La, and N is Mg.

[0052] Comparative Example 1 A solid electrolyte material with the chemical formula Li3InBr6 Except for the raw materials being changed to LiBr and InBr3, with the molar ratio of LiBr to InBr3 being 3:1, the procedure steps are the same as in Example 1.

[0053] The ion conductance testing methods for the solid electrolyte materials in Examples 2-9 and the comparative examples are the same as those in Example 1 above, except that the solid electrolyte materials are different. The results are shown in Table 2. Table 2 Application Example 1 The LiSmZr obtained in Example 2 0.5 Cl6 electrolyte powder and lithium nickel cobalt manganese oxide powder were mixed in a 30:70 ratio to serve as the counter electrode, and LiSmZr 0.5 Cl6 electrolyte powder was used as the electrolyte layer near the positive electrode, and Li-In alloy was used as the negative electrode. A solid-state battery was assembled using a mold battery in a glove box under argon atmosphere. Electrochemical charge-discharge tests were conducted on the solid-state battery at room temperature. The charge-discharge cutoff voltage was 1.90 – 3.60 V (vs. Li / Li-In), and the charge-discharge current density was 0.2C (1C = 200 mA g). -1 LiNi 0.83 Co 0.11 Mn 0.06 O2). Figure 7The figures show the charge-discharge curves of the all-solid-state lithium-ion battery at room temperature. This demonstrates that the solid electrolyte described in this invention can be applied to lithium-based all-solid-state batteries, providing a feasible option for broadening the range of applicable materials for all-solid-state batteries.

[0054] Application Example 2 The NaSmTa obtained in Example 5 0.5 Cl 6.5 Electrolyte powder and lithium nickel iron manganese oxide powder are mixed in a 40:60 ratio to form the counter electrode, NaSmTa 0.5 Cl 6.5 Electrolyte powder was used as the electrolyte layer near the positive electrode, Na3PS4 electrolyte powder as the electrolyte layer near the negative electrode, and Na-Sn alloy as the negative electrode. A solid-state battery was assembled using a mold battery in a glove box under argon atmosphere. Electrochemical charge-discharge tests were performed on the solid-state battery at room temperature, with a charge-discharge cutoff voltage of 2.3–4V (vs. Na3PS4). + / Na), the charge / discharge current density is 0.2C (1C = 120 mA g). -1 ). Figure 8 The figures show the charge-discharge curves of the all-solid-state lithium-ion battery at room temperature. This demonstrates that the solid electrolyte described in this invention can be applied to sodium-based all-solid-state batteries, providing a feasible option for broadening the range of applicable materials for all-solid-state batteries.

[0055] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A glass-ceramic phase solid electrolyte material, the composition of which is expressed as follows: A x MN y Cl x+3+z*y 0.25≤x≤5, 0≤y≤6, 2≤z≤5; It contains ceramic phase elements A, M, and Cl; wherein A is selected from Li and Na, M is selected from La, Ce, Eu, Sm, Gd, Y, or a combination thereof; N is selected from Al, Ga, Zr, Ta, Nb, Hf, or a combination thereof; the solid electrolyte material is a glass-ceramic phase, and the ceramic phase has... P 63 / m Space group.

2. The method for preparing a glass-ceramic phase solid electrolyte material according to claim 1, characterized in that, Includes the following steps: The solid electrolyte material is prepared from raw materials including precursors A, M, and N; the precursor of A includes lithium chloride and sodium chloride; the precursor of M includes the chloride corresponding to M, namely lanthanum chloride, cerium chloride, samarium chloride, europium chloride, gadolinium chloride, and yttrium chloride; The precursors of N include the chlorides corresponding to N, namely aluminum chloride, gallium chloride, tantalum chloride, niobium chloride, hafnium chloride, and zirconium chloride; The mixture of precursors A, M, and N was ball-milled under inert gas or vacuum conditions. The ball milling speed is 200-600 rpm; the ball-milled product is calcined under inert gas or vacuum conditions; The calcination includes: raising the temperature from room temperature to 100-300°C, holding the temperature at 100-300°C, and then lowering the holding temperature back to room temperature.

3. A lithium battery comprising a positive electrode, a negative electrode, and an electrolyte layer between the positive and negative electrodes, characterized in that... At least one of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material of claim 1.

4. The application of the glass-ceramic phase solid electrolyte material as described in claim 1 in improving the lithium-ion conductivity of electrolytes.

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