Sulfite oxygen halide solid electrolyte material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of solid electrochemistry and energy storage materials, and discloses a sulfite-based oxyhalide solid electrolyte material and a preparation method and application thereof. The sulfite-based oxyhalide solid electrolyte material is of an amorphous structure, and the chemical formula of the sulfite-based oxyhalide solid electrolyte material is (Na2SO3) xZrCl4, wherein x is more than or equal to 0.1 and less than or equal to 0.7. Compared with a traditional halide electrolyte, the sulfite-based oxygen halide solid electrolyte material has the advantages that the ionic conductivity is improved by one to two orders of magnitude, and an all-solid-state sodium ion battery assembled based on the material shows high efficiency, long cycle life, wide electrochemical stability window and excellent mechanical property; and the method has huge application potential in actual solid-state sodium ion battery devices.

Description

Technical Field

[0001] This invention relates to the field of solid-state electrochemistry and energy storage materials technology, specifically to a sulfite-based oxyhalide solid electrolyte material, its preparation method, and its application. Background Technology

[0002] Sodium-ion batteries, as a next-generation sustainable energy storage technology, have shown significant potential in large-scale energy storage. However, traditional sodium-ion batteries mostly use organic liquid electrolytes, which pose inherent safety risks such as flammability and leakage, limiting the improvement of battery energy density and the expansion of high-safety application scenarios. Therefore, solid-state electrolytes are considered a key material to replace liquid electrolytes. They not only completely eliminate the risks of combustion and leakage but are also compatible with high-capacity electrode materials such as metallic sodium anodes, potentially significantly improving battery energy density and cycle life. This represents a crucial technological direction for achieving high-safety, high-performance energy storage systems.

[0003] As a core component of all-solid-state batteries, the room-temperature ionic conductivity, electrochemical stability window, chemical / electrochemical stability of the counter electrode (especially sodium metal), interfacial compatibility with electrode materials, and machinability of the solid electrolyte directly affect the overall battery performance. Currently, mainstream solid electrolyte systems mainly include three categories: oxides, sulfides, and halides. Among them, oxide solid electrolytes possess excellent chemical and electrochemical stability, but their room-temperature ionic conductivity is generally low (typically below 10). -4 The conductivity is on the order of S / cm, making it difficult to meet high power requirements; more importantly, its extremely high hardness and rigidity result in a "point-to-point" contact with the electrode, leading to a huge solid-solid interface impedance, and the interface contact is extremely prone to deterioration during cycling. While sulfide solid electrolytes possess high ionic conductivity (up to 10⁻⁶), they are still less suitable for high-power applications. -2 While sodium-based halide electrolytes exhibit high conductivity (on the order of S / cm), they have poor compatibility with high-voltage cathode materials and are prone to oxidative decomposition. Furthermore, sulfides are extremely sensitive to water and oxygen in the air, readily generating highly toxic H₂S. Halide solid-state electrolytes, combining the advantages of some oxides (high stability) and sulfides (structural designability), typically exhibit a wider electrochemical window and better oxidative stability, with some systems also offering lower costs. However, the room-temperature ionic conductivity of most sodium-based halide electrolytes remains unsatisfactory (around 10⁻⁶ S / cm). -6 Its practical application is limited by the fact that it is on the order of S / cm.

[0004] It is evident that existing solid-state electrolyte systems based on a single anionic framework are limited by their inherent physicochemical properties, making it difficult to achieve synergistic optimization of key performance indicators such as ionic conductivity, electrochemical stability, interfacial compatibility, and environmental stability. This hinders the performance improvement and practical application of all-solid-state sodium-ion batteries. Therefore, there is an urgent need to develop a novel solid-state electrolyte material that maintains high ion transport capacity while improving its overall electrochemical performance and interfacial compatibility. This will drive the development of all-solid-state sodium-ion battery technology and meet the demands of large-scale energy storage and electric vehicles for high-performance, high-safety energy storage systems. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a sulfite-based oxyhalide solid electrolyte material, its preparation method, and its application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a sulfite-based oxyhalide solid electrolyte material, wherein the sulfite-based oxyhalide solid electrolyte material has an amorphous structure and the chemical formula (Na2SO3). x ZrCl4; wherein the value of x satisfies 0.1≤x≤0.7.

[0007] This invention utilizes a specific molar ratio of sodium sulfite and zirconium tetrachloride to introduce sulfite (SO3²⁻) anions into the crystal framework of a halide solid electrolyte for doping and structural reshaping, thereby constructing a sulfite-based oxyhalide solid electrolyte material with an amorphous structure at the molecular level. On one hand, sulfite has a large ionic radius and a unique trigonal pyramidal geometry, and its introduction can cause significant distortion and expansion in the original rigid halide lattice network, forming a more open ion transport space. On the other hand, this doping can disrupt the long-range order of the crystal structure, inducing the formation of an amorphous structure. In this amorphous network, the anionic framework has higher structural flexibility, enabling continuous and low-energy migration paths for sodium through local bond angle rotation and adjustment. Furthermore, the amorphous structure eliminates grain boundaries, allowing for uniform and efficient ion conduction both within the bulk phase and at the electrode interface, avoiding ion accumulation and charge concentration at grain boundaries. This results in excellent ion conduction stability and interface compatibility at the overall device level.

[0008] In a preferred embodiment of the sulfite-based oxyhalide solid electrolyte material of the present invention, the value of x satisfies 0.2≤x≤0.3.

[0009] Preferably, the value of x is 0.2.

[0010] Secondly, the present invention provides a method for preparing the sulfite-based oxyhalide solid electrolyte material, comprising the following steps: mixing an oxygen-containing sodium salt and a zirconium source under a protective atmosphere and then performing high-energy ball milling to obtain the sulfite-based oxyhalide solid electrolyte material.

[0011] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the oxygen-containing sodium salt is sodium sulfite; and / or, the zirconium source is zirconium tetrachloride.

[0012] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the molar ratio of the oxygen-containing sodium salt to the zirconium source is (0.1-0.7):1.

[0013] Preferably, the molar ratio of the oxygen-containing sodium salt to the zirconium source is (0.2-0.3):1.

[0014] More preferably, the molar ratio of the oxygen-containing sodium salt to the zirconium source is one or a range of two of the following: 0.2:1, 0.25:1, and 0.3:1.

[0015] More preferably, the molar ratio of the oxygen-containing sodium salt to the zirconium source is 0.2:1.

[0016] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the protective atmosphere is argon and / or nitrogen.

[0017] Preferably, the protective atmosphere is argon.

[0018] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the mixing is carried out by mechanical grinding; the mechanical grinding speed is 50 rpm-150 rpm, and the time is 3 h-30 h.

[0019] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the mass ratio of the ball milling media to the mixed material in the high-energy ball milling is (15-60):1, the ball milling speed is 60rpm-1000rpm, and the ball milling time is 48h-120h.

[0020] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the ball mill jar used in the high-energy ball mill is made of zirconium dioxide, stainless steel or cemented carbide.

[0021] In a preferred embodiment of the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention, the ball milling media are stainless steel balls or zirconium dioxide balls.

[0022] Preferably, the diameter of the ball milling media is 5mm-20mm.

[0023] Thirdly, the present invention provides a solid electrolyte sheet, which is obtained by pressing the aforementioned sulfite-based oxyhalide solid electrolyte material.

[0024] Compared with existing technologies, the beneficial effects of this invention are as follows: The sulfite-based oxyhalide solid electrolyte material of this invention exhibits high ionic conductivity, which is one to two orders of magnitude higher than that of undoped crystalline halide electrolytes, laying a material foundation for constructing high-performance all-solid-state sodium batteries. Secondly, the sulfite-based oxyhalide solid electrolyte material of this invention possesses excellent structural stability. On the one hand, its wide electrochemical window allows it to be stably compatible with high-capacity positive and negative electrode materials (such as layered oxides, sodium metal, etc.); on the other hand, its grain boundary-free characteristics and inherent flexibility ensure the formation of a low-impedance, high-stability solid-solid interface between it and the electrodes, which is beneficial to the long cycle life of the full battery. Simultaneously, the sulfite-based oxyhalide solid electrolyte material of this invention combines good mechanical flexibility with moderate hardness, allowing it to be fabricated into a dense and robust electrolyte membrane using conventional cold pressing processes, and also to fill interfacial voids through slight deformation in battery stacking, simplifying the assembly process of all-solid-state batteries. Furthermore, the preparation method of the sulfite-based oxyhalide solid electrolyte material of the present invention is an all-solid-state, one-step synthesis that does not require high-temperature sintering, harsh vacuum environment or complex post-processing. It can be completed by ball milling under an inert atmosphere. The process is simple, energy-efficient, has high raw material utilization and good repeatability, and has significant cost advantages and potential for large-scale production. Attached Figure Description

[0025] Figure 1 The image shows the XRD pattern of the solid electrolyte material in Example 1 of this invention. Figure 2 The image shows the XRD pattern of the solid electrolyte material in Comparative Example 1 of this invention. Figure 3 This is an electrochemical impedance spectroscopy (EIS) diagram of the solid electrolyte material in Example 1 of the present invention. Figure 4 This is an electrochemical impedance spectroscopy diagram of the solid electrolyte material in Comparative Example 1 of the present invention. Detailed Implementation

[0026] To better illustrate the objectives, technical solutions, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0027] The following description, in conjunction with specific embodiments, illustrates the practical effects of the present invention.

[0028] Unless otherwise specified, the experimental methods used in the examples are conventional methods; the materials, reagents, equipment, etc. used are all commercially available unless otherwise specified.

[0029] Example 1: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0030] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0031] like Figure 1 As shown, X-ray diffraction (XRD) analysis indicates that the sample has an amorphous structure.

[0032] Example 2: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.3:1 and place them in a mortar. Under nitrogen protection, mechanically grind and mix them at a speed of 80 rpm for 10 hours.

[0033] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (20 mm in diameter) to the sample in the jar is 40:1. Under nitrogen protection, perform high-energy ball milling at 60 rpm for 48 hours. After ball milling, open the jar in the glove box to obtain an amorphous solid electrolyte powder sample.

[0034] Example 3: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) in a molar ratio of 0.4:1 and place them in a mortar. Under nitrogen protection, mechanically grind and mix them at a speed of 120 rpm for 15 hours.

[0035] S2. Transfer the mixed sample to a stainless steel ball mill jar. The mass ratio of stainless steel balls (20 mm in diameter) to the sample in the ball mill jar is 15:1. Under nitrogen protection, perform high-energy ball milling at 600 rpm for 48 hours. After ball milling, open the ball mill jar in the glove box to obtain an amorphous solid electrolyte powder sample.

[0036] Example 4: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.5:1 and place them in a mortar. Under nitrogen protection, mechanically grind and mix them at a speed of 150 rpm for 20 h.

[0037] S2. Transfer the mixed sample to a stainless steel ball mill jar. The mass ratio of stainless steel balls (5 mm in diameter) to the sample in the ball mill jar is 60:1. Under nitrogen protection, perform high-energy ball milling at 1000 rpm for 72 hours. After ball milling, open the ball mill jar in the glove box to obtain an amorphous solid electrolyte powder sample.

[0038] Example 5: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.6:1 and place them in a mortar. Under nitrogen protection, mechanically grind and mix them at a speed of 50 rpm for 10 hours.

[0039] S2. Transfer the mixed sample to a stainless steel ball mill jar. The mass ratio of stainless steel balls (12 mm in diameter) to the sample in the ball mill jar is 30:1. Under nitrogen protection, perform high-energy ball milling at 500 rpm for 100 hours. After ball milling, open the ball mill jar in the glove box to obtain an amorphous solid electrolyte powder sample.

[0040] Example 6: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.7:1 and place them in a mortar. Under nitrogen protection, mechanically grind and mix them at a speed of 150 rpm for 30 h.

[0041] S2. Transfer the mixed sample to a stainless steel ball mill jar. The mass ratio of stainless steel balls (5 mm in diameter) to the sample in the ball mill jar is 50:1. Under nitrogen protection, perform high-energy ball milling at 800 rpm for 120 hours. After ball milling, open the ball mill jar in the glove box to obtain an amorphous solid electrolyte powder sample.

[0042] Example 7: This embodiment provides a sulfite-based oxyhalide solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.1:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0043] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0044] Comparative Example 1: This comparative example provides a solid electrolyte material with the chemical formula Na₂ZrCl₆; its preparation method includes the following steps: S1. Weigh sodium chloride (NaCl) and zirconium tetrachloride (ZrCl4) in a molar ratio of 2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0045] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0046] like Figure 2 As shown, X-ray diffraction (XRD) analysis indicates that the sample has a crystal structure with a certain degree of regularity.

[0047] Comparative Example 2: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrachloride (ZrCl4) in a molar ratio of 1.3:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0048] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0049] Comparative Example 3: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium carbonate (Na2CO3) and zirconium tetrachloride (ZrCl4) in a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0050] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0051] Comparative Example 4: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium oxalate (Na2C2O4) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0052] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0053] Comparative Example 5: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetrabromide (ZrBr4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0054] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0055] Comparative Example 6: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and zirconium tetraiodide (ZrI4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0056] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0057] Comparative Example 7: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh lithium sulfite (Li2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0058] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0059] Comparative Example 8: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh potassium sulfite (K2SO3) and zirconium tetrachloride (ZrCl4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0060] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0061] Comparative Example 9: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and hafnium tetrachloride (HfCl4) at a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0062] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0063] Comparative Example 10: This comparative example provides a solid electrolyte material, the preparation method of which includes the following steps: S1. Weigh sodium sulfite (Na2SO3) and aluminum trichloride (AlCl3) in a molar ratio of 0.2:1 and place them in a mortar. Under argon protection, mechanically grind and mix them at a speed of 100 rpm for 3 hours.

[0064] S2. Transfer the mixed sample to a zirconia ball mill jar. The mass ratio of zirconia balls (10 mm in diameter) to the sample in the jar is 20:1. Under argon protection, perform high-energy ball milling at 400 rpm for 72 hours. After ball milling, open the jar in the glove box to obtain the solid electrolyte powder sample.

[0065] Test Example: Electrochemical Impedance Testing Test method: The solid electrolyte materials of the above examples and comparative examples were placed in a mold and made into a thin sheet with a diameter of 10 mm under a pressure of 300 MPa. At room temperature, the two ends of the mold were connected to an electrochemical workstation (Autolab) for electrochemical impedance testing, and the ionic conductivity of the solid electrolyte was calculated according to the formula ρ = L / RS.

[0066] Table 1. Performance test results of the solid electrolyte materials in the embodiments and comparative examples of the present invention. From Table 1, Figure 3 , Figure 4The test results show that the amorphous sulfite-based oxyhalide solid electrolyte material of this invention achieves an improvement of one to two orders of magnitude in ionic conductivity compared with traditional crystalline halide electrolytes. Furthermore, the all-solid-state sodium-ion battery assembled based on the electrolyte material of this invention exhibits high efficiency, long cycle life, wide electrochemical stability window, and excellent mechanical properties. This fully verifies its huge application potential in practical solid-state sodium-ion battery devices and solves the key technical problems commonly found in traditional sodium-ion solid electrolytes, such as low ionic conductivity, poor compatibility with electrode interfaces, and narrow electrochemical window. It provides a competitive electrolyte solution for the development of next-generation high-safety, high-energy-density solid-state batteries.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A sulfite-based oxyhalide solid electrolyte material, characterized in that, The sulfite-based oxyhalide solid electrolyte material has an amorphous structure and the chemical formula (Na₂SO₃). x ZrCl4; wherein the value of x satisfies 0.1≤x≤0.

7.

2. The sulfite-based oxyhalide solid electrolyte material as described in claim 1, characterized in that, The value of x satisfies 0.2≤x≤0.

3.

3. The sulfite-based oxyhalide solid electrolyte material as described in claim 2, characterized in that, The value of x is 0.

2.

4. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 1, characterized in that, Includes the following steps: Under a protective atmosphere, the oxygen-containing sodium salt and zirconium source are mixed and then subjected to high-energy ball milling to obtain the sulfite-based oxyhalide solid electrolyte material.

5. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 4, characterized in that, The oxygen-containing sodium salt is sodium sulfite; and / or, the zirconium source is zirconium tetrachloride.

6. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 4, characterized in that, The molar ratio of the oxygen-containing sodium salt to the zirconium source is (0.1-0.7):

1.

7. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 4, characterized in that, The protective atmosphere is argon and / or nitrogen.

8. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 4, characterized in that, The mixing is carried out by mechanical grinding; the mechanical grinding speed is 50rpm-150rpm, and the time is 3h-30h.

9. The method for preparing the sulfite-based oxyhalide solid electrolyte material as described in claim 4, characterized in that, In the high-energy ball mill, the mass ratio of the ball milling media to the mixed material is (15-60):1, the ball milling speed is 60rpm-1000rpm, and the ball milling time is 48h-120h.

10. A solid electrolyte sheet, characterized in that, It is obtained by pressing the sulfite-based oxyhalide solid electrolyte material according to any one of claims 1-3.

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