Air-stable sodium-ion battery halide solid-state electrolyte and applications thereof

Abstract

This invention discloses an air-stabilized sodium-ion battery halide solid electrolyte and its application, belonging to the field of electrolyte materials technology. The molecular formula of the halide solid electrolyte is: Na X TaAl X O 2X Cl5, X=0.75-1.25, a halide electrolyte matrix obtained by grinding tantalum chloride and sodium aluminate in a molar ratio of 1:0.75-1.25 was prepared by adding volatile composite additives and zirconium oxide grinding balls. After ball milling, the matrix was subjected to cold isostatic pressing and pressure holding to obtain a sheet. After medium-temperature hot pressing, an air-stable sodium-ion battery halide solid electrolyte was obtained. This process achieved material densification and structural stability, and prepared a halide solid electrolyte with high air stability, high ionic conductivity and a wide electrochemical window.

Description

Technical Field

[0001] This invention belongs to the field of electrolyte materials technology, specifically an air-stabilized sodium-ion battery halide solid electrolyte and its application. Background Technology

[0002] The development of the new energy industry is driving up the demand for low-cost, high-safety energy storage batteries. Sodium-ion batteries, due to their abundant sodium resources and low cost, have become an important alternative technology to lithium-ion batteries. Traditional liquid sodium-ion batteries have safety hazards such as leakage and flammability. Solid-state sodium-ion batteries, with solid electrolytes at their core, can solve these problems at their source and have become a key area of ​​development.

[0003] Sodium-ion battery halide solid electrolytes, based on metal halides and doped with relevant elements, possess advantages such as high ionic conductivity, wide electrochemical window, and good compatibility with high-voltage cathodes, making them suitable for various cathode systems and showing significant application potential. However, traditional halide electrolytes exhibit extremely poor air stability, readily hydrolyzing upon contact with water and oxygen, leading to structural collapse, conductivity degradation, and electrode corrosion, increasing preparation and storage costs and hindering industrial applications. To address this bottleneck, air-stable halide solid electrolytes have become a research hotspot. Their design and preparation mainly employ approaches such as fluorine doping, metal cation regulation, structural modification, and coating, combined with processes like high-temperature solid-state sintering and mechanical ball milling, to balance stability and conductivity, significantly improve environmental tolerance, retain the core advantages of halides, and improve battery cycle performance.

[0004] Chinese invention patent application CN121439893A discloses a novel sodium-ion battery halide solid electrolyte with the molecular formula Na. x TaCl5F x (x=1-3) A halide electrolyte matrix was obtained by high-energy ball milling of tantalum chloride and sodium fluoride in a molar ratio of 1:1-3, followed by cold isostatic pressing and low-temperature (300℃) heat treatment. Nano-silica and zinc bromide were then ball-milled in a molar ratio of 1:2-4 to prepare a sintering aid. 100 parts of the matrix were mixed with 3-8 parts of the sintering aid and pressed into tablets. The tablets were then sintered at high temperature (500℃) and ball-milled again to finally obtain a solid electrolyte with a predominantly amorphous phase, high ionic conductivity, and a wide electrochemical window.

[0005] The above scheme uses sodium fluoride and tantalum chloride as reaction raw materials and adds non-volatile nano-silica / zinc bromide sintering aids. During preparation and subsequent use, the halide electrolyte matrix is ​​highly sensitive to moisture and is prone to hydrolysis and deterioration. In addition, the sintering aids remain at the grain boundaries to form an inert and inactive phase and lack chemical bonding sites with the matrix, resulting in poor air stability, significantly increased interfacial impedance and material contamination, which reduces ionic conductivity, narrows the electrochemical window and deteriorates the battery cycle stability. Summary of the Invention

[0006] The purpose of this invention is to provide an air-stable sodium-ion battery halide solid electrolyte and its application. By using tantalum chloride and sodium aluminate as reaction raw materials, and introducing a volatile composite additive of ammonium carbonate and ammonium chloride and a medium-temperature hot pressing process, the invention can improve the problems in the comparative patent caused by the use of sodium fluoride and non-volatile sintering additives, such as poor air stability, phase decomposition and unfavorable crystal transformation caused by high-temperature sintering, increased interfacial impedance and material contamination caused by inactive additive residues.

[0007] The objective of this invention can be achieved through the following technical solutions: An air-stabilized sodium-ion battery halide solid electrolyte, the molecular formula of which is: Na X TaAl X O 2X Cl5, X = 0.75-1.25.

[0008] Furthermore, the specific preparation method of the halide solid electrolyte for air-stabilized sodium-ion batteries is as follows: A volatile composite additive and zirconium oxide milling ball are added to the halide electrolyte matrix. After ball milling, the matrix is ​​subjected to cold isostatic pressing and pressure holding to obtain a sheet. The sheet is then subjected to medium-temperature hot pressing to obtain an air-stabilized sodium-ion battery halide solid electrolyte.

[0009] Furthermore, the halide electrolyte matrix is ​​obtained by mixing and grinding tantalum chloride and sodium aluminate in a molar ratio of 1:0.75-1.25.

[0010] Furthermore, the volatile composite additive is obtained by grinding and mixing ammonium carbonate and ammonium chloride at a mass ratio of 1:1-1.2.

[0011] Furthermore, the amount of volatile composite additives added is 8-10 wt% of the total mass of the halide electrolyte matrix.

[0012] Furthermore, the specific conditions for the zirconia grinding balls are as follows: zirconia grinding balls with a diameter of 4-6 mm are ball-milled with the corresponding raw materials at a mass ratio of 50-70:1.

[0013] Furthermore, the specific conditions for ball milling are 6-8 hours at 200-300 rpm.

[0014] Furthermore, the specific conditions for cold isostatic pressing are: holding pressure at 150-250 MPa for 3-7 minutes.

[0015] Furthermore, the specific conditions for the medium-temperature hot pressing process are as follows: under an argon atmosphere and a uniaxial pressure of 10-15 MPa, the temperature is increased to 350-400℃ at a rate of 5℃ / min and held for 10-15 min.

[0016] This invention also provides the application of an air-stabilized sodium-ion battery halide solid electrolyte in an all-solid-state sodium-ion battery.

[0017] The beneficial effects of this invention are: 1. This invention significantly improves the air stability of the electrolyte by using tantalum chloride and sodium aluminate as reaction raw materials, combined with a volatile composite additive composed of ammonium carbonate and ammonium chloride, and a medium-temperature hot-pressing process, thus avoiding the problem of easy hydrolysis and deterioration of traditional halides. Compared with the high-temperature pressureless sintering of the comparative patent, medium-temperature hot pressing effectively prevents phase decomposition and unfavorable crystal transformation, which is beneficial to retaining the beneficial defects and ion transition sites in the amorphous / nanocrystalline composite structure. The volatile additive can be completely decomposed and sublimated during the hot pressing process without residue, solving the problem of increased interfacial impedance and material contamination caused by the residual grain boundaries of non-volatile sintering additives in the comparative patent. At the same time, the synergistic effect of hot pressing pressure and medium temperature can achieve high density, reduce porosity, optimize ion conduction pathways, and improve ionic conductivity while maintaining a wide electrochemical window. In addition, the overall preparation process is simplified, the ball milling and heat treatment times are shortened, energy consumption and cycle time are significantly reduced, and it has good scalability.

[0018] 2. In this invention, tantalum chloride and sodium aluminate are used as reaction raw materials. The aluminum-oxygen bond structure in sodium aluminate is stable, and through a mechanically induced halogen-oxygen exchange reaction, oxygen-containing halides or oxyhalide composite phases are generated. These phases are naturally inert to water vapor, avoiding the problem of traditional halides easily hydrolyzing and producing harmful gases, thus reducing the environmental control requirements during preparation and use. Simultaneously, the introduction of oxygen intensifies the degree of lattice disorder, which is conducive to the formation of amorphous / nanocrystalline composite structures. This provides abundant sodium ion transition sites while retaining structural support. Furthermore, oxygen-containing species have strong antioxidant capabilities, which helps to broaden the electrochemical window.

[0019] 3. The volatile composite additive in this invention is composed of ammonium carbonate and ammonium chloride. During ball milling, the gas generated by the trace decomposition of ammonium carbonate can inhibit particle cold welding and agglomeration, while ammonium chloride promotes dispersion and mixing through surface adsorption and interfacial activation. The two work synergistically to accelerate the solid-phase reaction, helping to shorten the ball milling time and reduce mechanical energy input. In the subsequent hot pressing process, the composite additive can completely decompose or sublimate under medium temperature conditions, leaving no solid residue, thus ensuring the purity of the electrolyte grain boundaries and avoiding increased interfacial impedance and material contamination caused by inactive second phases. At the same time, the volatilization of the additive will not destroy the formed amorphous / nanocrystalline composite structure and favorable lattice defects, which is beneficial for maintaining high ionic conductivity and a wide electrochemical window. Attached Figure Description

[0020] Figure 1This is a scanning electron microscope (SEM) image of the air-stabilized sodium-ion battery halide solid electrolyte prepared in Example 1. Figure 2 Impedance spectrum of the air-stabilized sodium-ion battery halide solid electrolyte prepared in Example 1; Figure 3 Linear sweep voltammetry curve of the air-stabilized sodium-ion battery halide solid electrolyte prepared in Example 1.

[0021] Figure 4 Impedance spectra of the air-stabilized sodium-ion battery halide solid electrolytes prepared in Examples 1, 2, and 3; Figure 5 A summary graph showing the ionic conductivity of the halide solid electrolytes for air-stabilized sodium-ion batteries prepared in Examples 1, 2, and 3; Figure 6 The air stability impedance spectra of the halide solid electrolytes for air-stabilized sodium-ion batteries prepared in Examples 1, 2, and 3 are shown. Figure 7 This is a summary graph of the air-stability ionic conductivity of the halide solid electrolytes for air-stabilized sodium-ion batteries prepared in Examples 1, 2, and 3. Detailed Implementation

[0022] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] Example 1: An air-stabilized sodium-ion battery halide solid electrolyte, prepared by the following steps: S1: In an argon glove box, ammonium carbonate and ammonium chloride are added to a mortar in a mass ratio of 1:1.1 and ground manually for 6.5 minutes to obtain a volatile composite additive.

[0024] S2: Tantalum chloride and sodium aluminate are added to the ball milling jar of a planetary ball mill at a molar ratio of 1:1 to obtain a halide electrolyte matrix. Volatile composite additives and zirconia grinding balls with a total mass of 9 wt% of the halide electrolyte matrix are added. The mixture is ball-milled at 250 rpm for 7 hours, passed through a 200-mesh sieve, and the powder product is taken out to obtain a mixed powder of electrolyte matrix.

[0025] Through mechanically induced solid-phase reaction, tantalum chloride and sodium aluminate particles are repeatedly crushed and cold-welded to form an amorphous / nanocrystalline composite structure. The mechanical energy introduces a large number of lattice defects, reducing the activation energy of the reaction and allowing the halogen-oxygen exchange reaction to take place at room temperature. In synergy with volatile composite additives, trace amounts of ammonium carbonate decompose to produce gas, inhibiting particle agglomeration, while ammonium chloride adsorbs onto the surface, promoting dispersion and mixing, accelerating the solid-phase reaction, and effectively shortening the ball milling time.

[0026] S3: The electrolyte matrix mixed powder is subjected to cold isostatic pressing at 200MPa in an argon glove box for 5 minutes to form a sheet with a diameter of 10mm and a thickness of 1.0mm.

[0027] S4: Place the sheet in a hot press mold, heat it to 375°C at a rate of 5°C / min in an argon atmosphere and uniaxial pressure of 12.5 MPa, hold it at that temperature for 12.5 min, and then cool it with the furnace to obtain an air-stabilized sodium-ion battery halide solid electrolyte.

[0028] Hot pressing completely removes volatile additives, resulting in a pure product. Pressure and medium temperature work together to densify the product, reduce porosity, and simultaneously regulate the microstructure, retaining beneficial defects and optimizing ion conduction pathways, thereby improving density and stability without sacrificing electrochemical performance.

[0029] In step S2, during the ball milling process, the mass ratio of zirconia grinding balls to the corresponding raw material is 60:1; the diameter of the zirconia grinding balls is 5mm.

[0030] Figure 1 The image shows a scanning electron microscope (SEM) image of the air-stabilized sodium-ion battery halide solid electrolyte prepared in this embodiment. The image reveals that the halide solid electrolyte exhibits irregularly shaped particles, indicating that it is an amorphous powder electrolyte.

[0031] Example 2: An air-stabilized sodium-ion battery halide solid electrolyte, prepared by the following steps: S1: In an argon glove box, ammonium carbonate and ammonium chloride are added to a mortar in a 1:1 mass ratio and ground manually for 5 minutes to obtain a volatile composite additive.

[0032] S2: Tantalum chloride and sodium aluminate are added to the ball milling jar of a planetary ball mill at a molar ratio of 1:0.75 to obtain a halide electrolyte matrix. Volatile composite additives and zirconia grinding balls with a total mass of 8 wt% of the halide electrolyte matrix are added. The mixture is ball-milled at 200 rpm for 6 hours, passed through a 200-mesh sieve, and the powder product is taken out to obtain a mixed powder of electrolyte matrix.

[0033] S3: The electrolyte matrix mixed powder is subjected to cold isostatic pressing at 150MPa in an argon glove box for 3 minutes to form a sheet with a diameter of 8mm and a thickness of 0.8mm.

[0034] S4: Place the sheet in a hot press mold, heat it to 350°C at a rate of 5°C / min in an argon atmosphere and uniaxial pressure of 10MPa, hold it at that temperature for 10min, and then cool it with the furnace to obtain an air-stabilized sodium-ion battery halide solid electrolyte.

[0035] In step S2, during the ball milling process, the mass ratio of zirconia grinding balls to the corresponding raw material is 50:1; the diameter of the zirconia grinding balls is 4 mm.

[0036] Example 3: An air-stabilized sodium-ion battery halide solid electrolyte, prepared by the following steps: S1: In an argon glove box, ammonium carbonate and ammonium chloride are added to a mortar in a mass ratio of 1:1.2 and ground manually for 8 minutes to obtain a volatile composite additive.

[0037] S2: Tantalum chloride and sodium aluminate are added to the ball milling jar of a planetary ball mill at a molar ratio of 1:1.25 to obtain a halide electrolyte matrix. Volatile composite additives and zirconium oxide grinding balls of 10 wt% of the total mass of the halide electrolyte matrix are added. The mixture is ball-milled at 300 rpm for 8 hours, passed through a 200-mesh sieve, and the powder product is taken out to obtain a mixed powder of electrolyte matrix.

[0038] S3: The electrolyte matrix mixed powder is subjected to cold isostatic pressing at 250MPa in an argon glove box for 7 minutes to form a sheet with a diameter of 12mm and a thickness of 1.2mm.

[0039] S4: Place the sheet in a hot press mold, heat it to 400°C at a rate of 5°C / min in an argon atmosphere and uniaxial pressure of 15MPa, hold it at that temperature for 15min, and then cool it with the furnace to obtain an air-stabilized sodium-ion battery halide solid electrolyte.

[0040] In step S2, during the ball milling process, the mass ratio of zirconia grinding balls to the corresponding raw material is 70:1; the diameter of the zirconia grinding balls is 6 mm.

[0041] In Examples 1-3, ammonium carbonate was selected from Suzhou Kangshuo Chemical Co., Ltd., CAS No. 506-87-6; ammonium chloride was selected from Shandong Kuoda Biotechnology Co., Ltd., CAS No. 12125-02-9; tantalum chloride was selected from Jiangsu Runfeng Synthetic Technology Co., Ltd., CAS No. 7721-01-9; sodium aluminate was selected from Fujian Feien New Material Technology Co., Ltd., CAS No. 1302-42-7; and the remaining raw materials were all commercially available products.

[0042] Application example: In an argon glove box, a sodium metal sheet is used as the negative electrode. The assembly is carried out in the following order: negative electrode shell / sodium sheet / air-stabilized sodium-ion battery halide solid electrolyte prepared in Example 1 / positive electrode sheet / pad / positive electrode shell. The battery is then cold-pressed and sealed with a stainless steel mold under a pressure of 50 MPa to obtain a CR2032 type all-solid-state sodium battery. The positive electrode sheet is made by mixing sodium vanadium phosphate, conductive carbon black, and polyvinylidene fluoride in a mass ratio of 85:10:5, adding 0.8-1.2 times the total solid mass of N-methylpyrrolidone, grinding into a slurry, coating it on aluminum foil, vacuum drying it, and then cutting it into electrode sheets with a diameter of 8mm.

[0043] Comparative Example 1: The difference from Example 1 is that step S1 is omitted, and the volatile composite additive in step S2 is replaced with ammonium chloride, while the other steps remain unchanged, to prepare an air-stable sodium-ion battery halide solid electrolyte.

[0044] Comparative Example 2: The difference from Example 1 is that step S1 is omitted, and no volatile composite additive is added in step S2. The remaining steps remain unchanged, and an air-stabilized sodium-ion battery halide solid electrolyte is prepared.

[0045] Comparative Example 3: The difference from Example 1 is that the molar ratio of tantalum chloride and sodium aluminate in step S2 is adjusted to 1:0.5, while the other steps remain unchanged, and an air-stable sodium-ion battery halide solid electrolyte is prepared.

[0046] Comparative Example 4: The difference from Example 1 is that the molar ratio of tantalum chloride and sodium aluminate in step S2 is adjusted to 1:1.5, while the other steps remain unchanged, and an air-stable sodium-ion battery halide solid electrolyte is prepared.

[0047] Comparative Example 5: The difference from Example 1 is that step S4 is skipped, and the finished product is obtained directly after step S3 cold isostatic pressing. The remaining steps remain unchanged, and an air-stabilized sodium-ion battery halide solid electrolyte is prepared.

[0048] The performance of the air-stabilized sodium-ion battery halide solid electrolytes prepared in Examples 1-3 and Comparative Examples 1-5 was tested: 1. Ionic Conductivity: Following the national standard GB / T 39864-2021 "Test Method for Ionic Conductivity of Solid Electrolytes", the AC impedance method was used, and the testing instrument was an electrochemical workstation (model CHI660E). Test conditions: The electrolyte sheet was assembled into a stainless steel blocked electrode symmetrical cell (SS|electrolyte|SS) in an argon glove box at 25℃ (H2O < 0.1 ppm, O2 < 0.1 ppm). The frequency range was 1 MHz - 0.1 Hz, and the AC disturbance voltage was 10 mV. The bulk resistance R (Ω) was measured, and the ionic conductivity was calculated using the formula σ = L / (R × S), where σ is the ionic conductivity (S / cm), L is the electrolyte sheet thickness (cm), R is the measured impedance (Ω), and S is the effective contact area of ​​the electrode (cm²). 2 Each group of samples was tested in parallel three times, and the average value was taken. The higher the value, the better the ion transport performance.

[0049] Figure 2 The air-stabilized sodium-ion battery halide solid electrolyte prepared in Example 1, from... Figure 2 It can be seen that the total impedance of the halide solid electrolyte is 55Ω, and the ionic conductivity of the halide solid electrolyte is calculated to be 1.390mS / cm.

[0050] 2. Electrochemical window: Following the linear scanning voltammetry method in GB / T 39864-2021, an electrochemical workstation was used. Test conditions: Sodium-tin alloy (Na...) 15 Sn4) was used as the counter electrode and reference electrode, and stainless steel was used as the working electrode. Na 15 Sn4|electrolyte|SS battery. In an argon glove box at a constant temperature of 25°C, with a scan rate of 1 mV / s and a voltage range of 0-5V (vs. Na... + A linear scan was performed on / Na). The current-voltage curve was recorded, and the current density was increased to 10 μA / cm². 2 The voltage value corresponding to the specified time is taken as the upper limit of the electrochemical window. The results are expressed as 0 - upper limit voltage (V), and the higher the value, the stronger the electrolyte's resistance to high-pressure oxidation.

[0051] Figure 3 The linear sweep voltammetry curve of the halide solid electrolyte for the air-stabilized sodium-ion battery prepared in Example 1 is shown below. Figure 3 It can be seen that the electrochemical window of the halide solid electrolyte is 4.05V.

[0052] 3. Air Stability: Following the environmental stability test guidelines in GB / T 39864-2021, a constant temperature and humidity chamber (model HWS-150B) was used. Test conditions: The electrolyte sheet was placed in the chamber at a temperature of 25±1℃ and a relative humidity of 50±5% for 50 consecutive hours. The electrolyte was removed at 5h, 10h, 20h, and 50h of exposure, and the room temperature ionic conductivity σ_t was measured at each time point using the aforementioned ionic conductivity test method. The smaller the difference between the ionic conductivity measured after exposure and before exposure, the slower the performance degradation of the electrolyte in humid air, and the better its air stability.

[0053] The results are shown in Table 1: Table 1 Performance test results of halide solid electrolytes for air-stabilized sodium-ion batteries As can be seen from Table 1, Examples 1-3 are significantly superior to the comparative examples in terms of ionic conductivity, air stability, and electrochemical window.

[0054] Comparative Example 1 replaced the volatile composite additive with a single ammonium chloride. Due to the lack of anti-agglomeration effect from the decomposition of ammonium carbonate, the dispersing effect of ammonium chloride alone was limited, resulting in decreased uniformity of raw material mixing during ball milling, incomplete reaction, and hindered formation of amorphous / nanocrystalline structures. Therefore, the ionic conductivity and air stability were significantly worse than those of the Example.

[0055] Comparative Example 2 was performed without any additives. In the absence of any dispersing and activating media, the particles agglomerated severely during ball milling, resulting in sluggish solid-phase reaction kinetics, insufficient mechanically induced defect density, low degree of halogen-oxygen exchange reaction, poor structural uniformity of the final product, increased difficulty in densification, and a significant decline in all properties.

[0056] Comparative Examples 3 and 4 deviated from the optimal molar ratio of tantalum chloride to sodium aluminate. A ratio that was too low (Comparative Example 3) or too high (Comparative Example 4) led to the formation of a non-stoichiometric, non-equilibrium phase, disrupting the ideal amorphous / nanocrystalline composite network structure and deteriorating ion transport channels. Furthermore, deviations from the optimal ratio reduced the electrolyte's resistance to deliquescence, resulting in a significant decrease in air stability.

[0057] Comparative Example 5 omitted the hot pressing process in step S4. Although it underwent cold isostatic pressing, the lack of mid-temperature densification and microstructure regulation during the hot pressing process resulted in numerous residual pores inside the sheet. Volatile additives could not be completely removed, and the beneficial defects introduced by mechanical force were not effectively preserved and optimized. This led to insufficient electrolyte density, obstructed ion conduction pathways, a reduced electrochemical window due to structural incompleteness, and air stability far inferior to the examples that underwent the complete hot pressing process.

[0058] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. An air-stabilized sodium-ion battery halide solid electrolyte, characterized in that, The molecular formula of this halide solid electrolyte is: Na X TaAl X O 2X Cl5, X = 0.75-1.

25.

2. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 1, characterized in that, The specific preparation method of the air-stabilized sodium-ion battery halide solid electrolyte is as follows: A volatile composite additive and zirconium oxide milling ball are added to the halide electrolyte matrix. After ball milling, the matrix is ​​subjected to cold isostatic pressing and pressure holding to obtain a sheet. The sheet is then subjected to medium-temperature hot pressing to obtain an air-stabilized sodium-ion battery halide solid electrolyte.

3. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The halide electrolyte matrix is ​​obtained by mixing and grinding tantalum chloride and sodium aluminate in a molar ratio of 1:0.75-1.

25.

4. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The volatile composite additive is obtained by grinding and mixing ammonium carbonate and ammonium chloride at a mass ratio of 1:1-1.

2.

5. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The amount of the volatile composite additive added is 8-10 wt% of the total mass of the halide electrolyte matrix.

6. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The specific conditions for the zirconia grinding balls are that zirconia grinding balls with a diameter of 4-6 mm are ball-milled with the corresponding raw materials at a mass ratio of 50-70:

1.

7. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The specific conditions for ball milling are as follows: ball milling at 200-300 rpm for 6-8 hours.

8. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The specific conditions for cold isostatic pressing are: holding pressure at 150-250 MPa for 3-7 minutes.

9. The air-stabilized sodium-ion battery halide solid electrolyte according to claim 2, characterized in that, The specific conditions for the medium-temperature hot pressing process are as follows: under an argon atmosphere and a uniaxial pressure of 10-15 MPa, the temperature is increased to 350-400℃ at a rate of 5℃ / min and held for 10-15 min.

10. The application of an air-stabilized sodium-ion battery halide solid electrolyte as described in any one of claims 1-9 in an all-solid-state sodium-ion battery.

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