Halide or oxyhalide solid-state electrolyte and its sonication-assisted preparation method and application

Abstract

The application relates to the technical field of all-solid-state battery materials, and discloses a halide or oxyhalide solid electrolyte and an acoustic resonance assisted preparation method and application thereof. The method is carried out under inert gas protection, raw materials are subjected to acoustic resonance mechanical chemical mixing in a sealed reaction tank, and a mixed precursor is obtained. The method utilizes high acceleration generated by acoustic wave resonance, is favorable for reducing the risk of impurity introduction, improving the uniformity of raw material mixing and the reaction efficiency, and reducing the risk of side reaction occurrence, and is suitable for the preparation of halide and oxyhalide solid electrolytes. The obtained solid electrolyte has high phase purity and can be used as a solid electrolyte layer material in an all-solid-state battery.

Description

Technical Field

[0001] This invention relates to the field of all-solid-state battery materials technology, and in particular to a halide or halide oxide solid electrolyte and its acoustic resonance-assisted preparation method and application. Background Technology

[0002] With the continuous development of new energy vehicles, large-scale energy storage, and portable electronic devices, the requirements for energy density, safety, and cycle stability of secondary batteries are constantly increasing. Traditional liquid lithium-ion batteries typically use organic liquid electrolytes, which have problems such as flammability, leakage, and potential thermal runaway under extreme conditions. Replacing liquid electrolytes with non-flammable solid electrolytes has become an important technical route to improve the intrinsic safety of batteries and realize high-energy-density energy storage devices.

[0003] Among existing solid-state electrolyte systems, halide solid-state electrolytes and halide oxide solid-state electrolytes have attracted widespread attention due to their typically high room-temperature ion conductivity and good electrochemical compatibility with high-voltage cathode materials. Especially in the field of all-solid-state batteries, these electrolyte systems are considered to have promising application prospects.

[0004] Currently, the main methods for preparing halide solid electrolytes and halide oxide solid electrolytes include mechanical ball milling, high-temperature solid-phase methods, and liquid-phase methods. Although mechanical ball milling can achieve raw material mixing and mechanical activation, it usually requires a long processing time, and the milling media and milling jar are prone to wear during long-term operation, thereby introducing impurities into the product and affecting the phase purity and electrochemical performance of the obtained solid electrolyte.

[0005] For halide oxide solid electrolytes, high-temperature solid-state methods often lead to the volatilization, side reactions, or decomposition of some halogen-containing components, resulting in the formation of insulating impurities, increasing interfacial impedance, and hindering the acquisition of high-purity target products. These problems are particularly pronounced when the raw material system is highly temperature-sensitive.

[0006] Liquid-phase methods typically require the introduction of specific solvents, which are beneficial for raw material dispersion. However, subsequent processes such as solvent removal, residue control, and heat treatment not only increase the complexity of the preparation process but may also create pores inside or between particles, affecting the densification degree and ion conduction performance of the material.

[0007] Therefore, there is an urgent need for a preparation method suitable for halide solid electrolytes and halide oxide solid electrolytes to overcome the defects in existing preparation methods, such as easy introduction of impurities, insufficient uniformity of raw material mixing, low reaction efficiency, and easy occurrence of side reactions during subsequent heat treatment, so as to obtain solid electrolyte materials with high phase purity that are suitable for application in all-solid-state batteries. Summary of the Invention

[0008] The first objective of this invention is to provide an acoustic resonance-assisted preparation method for halide solid electrolytes or halide oxide solid electrolytes, which can reduce the risk of impurity introduction, while improving the uniformity of raw material mixing and reaction efficiency, thereby obtaining solid electrolyte materials with high phase purity that are suitable for use in all-solid-state batteries.

[0009] The above-mentioned technical objective of the present invention is achieved through the following technical solution: An acoustic resonance-assisted preparation method for a halide solid electrolyte or a halide oxide solid electrolyte includes the following steps: S1. Under an inert gas protective environment, weigh the raw materials according to the stoichiometric ratio of the target solid electrolyte; wherein, when the target solid electrolyte is a halide solid electrolyte, the raw materials include lithium halides and metal halides; when the target solid electrolyte is a halide oxide solid electrolyte, the raw materials include metal halides and a lithium source, wherein the lithium source is one of lithium carbonate, lithium oxide or lithium hydroxide. S2. Place the raw material obtained in step S1 into a sealed acoustic resonance reaction vessel, and make the acoustic resonance reaction vessel reciprocate at a resonance frequency of 30Hz to 100Hz, with a vibration acceleration of 10g to 100g, and a processing time of 10 minutes to 2 hours to obtain a mixed precursor.

[0010] Further settings: In step S2, the resonant frequency is 50Hz to 80Hz, the vibration acceleration is 30g to 80g, and the processing time is 20 minutes to 1 hour.

[0011] By adopting the above technical solution, by limiting the resonance frequency of the acoustic resonance mechanochemical mixing step to 50Hz~80Hz, the vibration acceleration to 30g~80g, and the processing time to 20 minutes~1 hour, the acoustic resonance pretreatment is kept stable within the process range that is conducive to uniform mixing and mechanical activation of raw materials, thereby obtaining a more uniformly mixed precursor in a shorter processing time.

[0012] Further setup: In step S2, during the acoustic resonance treatment, the temperature of the reaction system is controlled between 0°C and 80°C through a circulating cooling system.

[0013] By adopting the above technical solution, and by setting up a circulating cooling system during the acoustic resonance mixing process and controlling the temperature of the reaction system between 0°C and 80°C, the temperature rise caused by mechanochemical action during the acoustic resonance treatment can be controlled, avoiding local overheating of the reaction system. This helps maintain the stability of the raw material components, reduces the risk of volatilization or side reactions of halogen-containing components during the pretreatment stage, and helps maintain the continuity and uniformity of the acoustic resonance mixing process.

[0014] Further configuration: The halide solid electrolyte is Li x MZ6, where M is at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga, Z is at least one of F, Cl, Br, and I, and x is the proportion of each element component, where 0 < x ≤ 3 and is an integer.

[0015] Further configuration: The halide oxide solid electrolyte is Li x MO y X z M is at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga; X is a halogen element selected from at least one of F, Cl, Br, and I; x, y, and z are the proportions of each element component, and the subscripts satisfy 1≤x≤8, 1≤y≤6, and 1≤z≤6, and the overall system satisfies charge balance.

[0016] In summary, the present invention has the following beneficial effects: The preparation method of this application involves preparing raw materials under an inert gas protective environment and using acoustic resonance mechanochemical mixing to complete the mixing and activation of raw materials without the participation of grinding media. This helps to reduce the risk of impurity introduction caused by wear of grinding media and tank in existing mechanical ball milling processes. At the same time, the acoustic resonance effect improves the uniformity of raw material mixing and the degree of precursor activation, thereby obtaining a relatively pure halide or halide oxide solid electrolyte.

[0017] Another object of the present invention is to provide a halide solid electrolyte or a halide oxide solid electrolyte, wherein the halide solid electrolyte or halide oxide solid electrolyte is prepared by the aforementioned acoustic resonance-assisted preparation method.

[0018] Another object of the present invention is to provide an all-solid-state battery, comprising a positive electrode layer, a negative electrode layer, and a solid electrolyte layer located between the positive electrode layer and the negative electrode layer, wherein the solid electrolyte layer comprises the aforementioned halide solid electrolyte or halide oxide solid electrolyte; the aforementioned halide or halide oxide solid electrolyte can be used as a solid electrolyte layer material in an all-solid-state battery to demonstrate its application in an all-solid-state battery. Attached Figure Description

[0019] Figure 1 This is a SEM image of the Li3InCl6 halide solid electrolyte prepared in Example 1. Figure 2The room temperature AC impedance spectroscopy (EIS) of the Li3InCl6 halide solid electrolyte prepared in Example 1. Figure 3 The XRD pattern of the Li3InCl6 halide solid electrolyte prepared in Example 1; Figure 4 Here is a SEM image of the solid electrolyte of Li2ZrCl6 halide prepared in Example 2. Figure 5 The room temperature AC impedance spectroscopy (EIS) of the Li2ZrCl6 halide solid electrolyte prepared in Example 2. Figure 6 The XRD pattern of the Li2ZrCl6 halide solid electrolyte prepared in Example 2 is shown below. Figure 7 The room temperature AC impedance spectroscopy (EIS) of the Li3YBr6 halide solid electrolyte prepared in Example 3. Figure 8 The XRD pattern of the Li3YBr6 halide solid electrolyte prepared in Example 3; Figure 9 The image shows the SEM microstructure of the Li2ZrOCl4 halide oxide solid electrolyte prepared in Example 4. Figure 10 The room temperature AC impedance spectrum (EIS) of the Li2ZrOCl4 halide oxide solid electrolyte prepared in Example 4. Figure 11 The XRD pattern of the Li2ZrOCl4 halide oxide solid electrolyte prepared in Example 4; Figure 12 The room temperature electrochemical impedance spectroscopy (EIS) of the LiTaOCl4 halide solid electrolyte in Example 6. Figure 13 The room temperature electrochemical impedance spectroscopy (EIS) of the LiNbOCl4 halide solid electrolyte in Example 6. Figure 14 The room temperature electrochemical impedance spectroscopy (EIS) of the Li2HfOCl4 halide solid electrolyte in Example 6. Figure 15 The room temperature electrochemical impedance spectroscopy (EIS) of the LiAlOCl2 halide solid electrolyte in Example 6. Figure 16 The XRD pattern of the LiTaOCl4 halide solid electrolyte in Example 6 is shown. Figure 17 The XRD pattern of the LiNbOCl4 halide oxide solid electrolyte in Example 6; Figure 18The XRD pattern of the Li2HfOCl4 halide solid electrolyte in Example 6; Figure 19 The image shows the XRD pattern of the LiAlOCl2 halide solid electrolyte in Example 6. Detailed Implementation

[0020] The present invention will be further described below with reference to specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention.

[0021] The acoustic resonance-assisted preparation method of the present invention is applicable to both the preparation of halide solid electrolytes and halide oxide solid electrolytes. The halide route uses lithium halides and metal halides as raw materials, while the halide oxide route uses lithium carbonate and metal halides as raw materials. Both routes are carried out in an inert gas protection environment, and the raw materials are obtained by sequentially undergoing acoustic resonance mechanochemical mixing and post-treatment.

[0022] Example 1: Acoustic resonance-assisted synthesis of halide solid electrolyte Li3InCl6; (1) Raw material preparation: In a glove box filled with high-purity argon, weigh 100 grams of dry LiCl and InCl3 raw material powder in a stoichiometric ratio of 3:1.

[0023] (2) Acoustic resonance synthesis treatment: Placed in an acoustic resonance reaction vessel, the resonance frequency was set to 60Hz, the vibration acceleration was 60g, the treatment time was 25 minutes, and the temperature of the reaction system was controlled at 30±5℃.

[0024] (3) Receiving materials: Li3InCl6 solid electrolyte powder is obtained by opening the glove box.

[0025] Performance characterization: such as Figure 1 As shown, the SEM microstructure images confirmed that the product has a fine and uniform particle size; Figure 2 As shown, its excellent electrochemical performance was determined by room-temperature electrochemical impedance spectroscopy (EIS); Figure 3 As shown, the XRD pattern confirmed that the product had a pure phase structure with no impurity diffraction peaks.

[0026] Example 2: Acoustic resonance-assisted synthesis of halide solid electrolyte Li₂ZrCl₆; (1) Raw material preparation: Weigh 100 grams of LiCl and ZrCl4 raw materials according to a stoichiometric ratio of 2:1.

[0027] (2) Acoustic resonance synthesis treatment: Placed in an acoustic resonance reaction vessel, the resonance frequency was set to 80Hz, the vibration acceleration to 70g, the treatment time to 35 minutes, and the temperature of the reaction system was controlled at 30±5℃.

[0028] (3) Receiving materials: Li2ZrCl6 solid electrolyte powder is obtained by opening the glove box.

[0029] Performance characterization: such as Figure 4 As shown, the particle size distribution was determined using SEM images; Figure 5 As shown, its room temperature ionic conductivity was determined using EIS; Figure 6 As shown, the pure material properties of the Li2ZrCl6 phase were determined using XRD.

[0030] Example 3: Acoustic resonance-assisted synthesis of halide solid electrolyte Li3YBr6; (1) Raw material preparation: In a glove box filled with high-purity argon, weigh 100 grams of dry LiBr and YBr3 raw material powder in a stoichiometric ratio of 3:1.

[0031] (2) Acoustic resonance synthesis treatment: Placed in an acoustic resonance reaction vessel, the resonance frequency was set to 60Hz, the vibration acceleration to 90g, the treatment time to 45 minutes, and the temperature of the reaction system was controlled at 30±5℃.

[0032] (3) Receiving materials: Li3YBr6 solid electrolyte powder is obtained by opening the glove box.

[0033] Performance characterization: such as Figure 7 As shown, its excellent electrochemical performance was determined by room-temperature electrochemical impedance spectroscopy (EIS); Figure 8 As shown, the XRD pattern confirmed that the product had a pure phase structure with no impurity diffraction peaks.

[0034] Example 4: Acoustic resonance-assisted synthesis of halide oxide solid electrolyte Li2ZrOCl4; (1) Raw material preparation: In the glove box, accurately weigh 100 grams of lithium carbonate (Li2CO3) powder and zirconium tetrachloride (ZrCl4) powder in a stoichiometric ratio of 1:1.

[0035] (2) Acoustic resonance synthesis treatment: The mixture was placed in an acoustic resonance reaction vessel, with the resonance frequency set at 70 Hz, the vibration acceleration at 80 g, and the treatment time at 30 minutes. The strong mechanochemical action promoted the reaction of Li2CO3 and ZrCl4 and released CO2 gas in situ. The temperature was controlled below 40 ℃ by circulating water cooling.

[0036] (3) Performance characterization: such as Figure 9 As shown, the SEM microstructure images confirmed that the product has a fine and uniform particle size; Figure 10 As shown, its excellent electrochemical performance was determined by room-temperature electrochemical impedance spectroscopy (EIS); Figure 11As shown, the XRD comparison results confirmed that the product synthesized by the acoustic resonance method is a high-purity phase with no obvious impurities.

[0037] Comparative Example 1: Preparation of halide solid electrolyte Li3InCl6 by conventional high-energy ball milling method; In a glove box filled with high-purity argon, 100g of dry lithium chloride (LiCl) and indium trichloride (InCl3) powders were weighed at a stoichiometric ratio of 3:1. The raw materials were placed in a ball mill jar and ball-milled at 400 rpm for 18 hours to achieve mixing and mechanical activation. After ball milling, the resulting mixture was heat-treated at 260℃ for 6 hours under argon protection. The product was then ground and sieved to obtain Li3InCl6 solid electrolyte powder. Characterization by XRD showed the presence of ZrO2 impurity phase in the product, indicating that impurities are easily introduced into the product during traditional ball milling due to wear of the milling media and jar. Simultaneously, the room temperature ionic conductivity decreased to 1.35 × 10⁻⁶. -3 S / cm. This comparative example shows that the traditional high-energy ball milling method not only has a long processing time, but also carries the risk of introducing impurities, which is not conducive to obtaining Li3InCl6 solid electrolytes with relatively pure phase and superior performance.

[0038] Comparative Example 2: Preparation of halide solid electrolyte Li2ZrCl6 by conventional high-energy ball milling method; Lithium chloride (LiCl) and zirconium tetrachloride (ZrCl4) raw materials were weighed according to a stoichiometric ratio of 2:1, totaling 100g. The weighed raw materials were placed in a ball mill jar and ball-milled at 600 rpm for 20 hours to mix the raw materials under mechanical impact. After ball milling, the resulting product underwent further processing to obtain Li2ZrCl6 solid electrolyte. Characterization, XRD results showed the presence of a ZrO2 impurity phase introduced by the wear of the ball milling media in the product, with a room temperature ionic conductivity of 0.41 × 10⁻⁶. -3 S / cm. This comparative example illustrates that for the Li2ZrCl6 system, the traditional high-energy ball milling method also suffers from problems such as long processing cycles, easy introduction of impurities, and decreased electrochemical performance, further demonstrating the limitations of existing ball milling processes in the preparation of halide solid electrolytes.

[0039] Comparative Example 3: Preparation of Li2ZrOCl4, a halide oxide solid electrolyte, by the conventional high-temperature solid-state method; In a glove box, lithium carbonate (Li₂CO₃) and zirconium tetrachloride (ZrCl₄) were weighed according to the same raw material composition and stoichiometry as in Example 4, and then simply ground and mixed. Since this method does not introduce an acoustic resonance mechanochemical activation step, to promote the formation of the target product, the mixed raw materials needed to be sintered at 400°C for 12 hours under inert gas protection. After heat treatment, the obtained product was characterized. The results showed that under high-temperature conditions, the halogen-containing components underwent significant volatilization, accompanied by side reactions such as oxygen evolution, resulting in the formation of a large amount of insulating byproducts in the product. XRD testing did not show a pure target phase, and the room temperature ionic conductivity dropped significantly to 0.2 × 10⁻⁶. -3 S / cm. This comparative example illustrates that traditional high-temperature solid-state methods in the Li2ZrOCl4 halide oxide system are prone to initiating high-temperature side reactions, making it difficult to obtain target products with relatively pure phases and good ion conductivity.

[0040] Example 5: Acoustic Resonance-Assisted Synthesis of Other Halogen Solid Electrolytes Li x MY6; The metal element M is selected as at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga; the halogen element Y is selected as at least one of F, Cl, Br, and I; and x is the proportion of each element component, where 0 < x ≤ 3 and is an integer. Taking the preparation of other halide solid electrolytes containing Ta, Nb, Al, and Ga as an example, lithium halides and corresponding metal halide raw materials are weighed in a glove box according to the stoichiometric ratio of the target product; lithium chloride (LiCl) and the corresponding metal chloride can be used as the raw material system. The above raw materials are placed in a sealed acoustic resonance reaction vessel, and mechanochemical mixing is performed by acoustic resonance. The preferred process conditions are: resonance frequency 70 Hz, vibration acceleration 90 g, and processing time 30 min; the corresponding halide solid electrolyte is obtained.

[0041] This embodiment demonstrates that the method of the present invention is applicable not only to representative halide systems such as Li3InCl6, Li2ZrCl6 and Li3YBr6, but also to the preparation of other halide solid electrolytes, thus exhibiting good system adaptability and universality.

[0042] Example 6: Acoustic Resonance-Assisted Synthesis of Other Halogen Oxide Solid Electrolytes Li x MO y X z ; The metal element M is selected from at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga, and the halogen element X is selected from at least one of F, Cl, Br, and I. x, y, and z represent the proportions of each element in the composition, satisfying 1≤x≤8, 1≤y≤6, and 1≤z≤6, while maintaining overall charge balance. Taking a halide oxide solid electrolyte containing Ta, Nb, Hf, and Al as an example, lithium carbonate (Li2CO3) and the corresponding metal halide raw materials are weighed in a glove box according to the stoichiometric ratio of the target product, wherein the ratio of lithium carbonate to the corresponding metal halide can be 0.6-1:1. The above raw materials were placed in a sealed acoustic resonance reaction vessel and subjected to acoustic resonance mechanochemical mixing. The preferred process conditions were: resonance frequency 80 Hz, vibration acceleration 70 g, and processing time 30 min. The corresponding halide oxide solid electrolytes were obtained, namely LiTaOCl4, LiNbOCl4, Li2HfOCl4, and LiAlOCl2.

[0043] The obtained product was characterized, such as Figures 12-15 As shown, EIS test results indicate that the obtained halide oxide solid electrolyte exhibits good ion conductivity; Figures 16-19 As shown, the XRD results indicate that the corresponding pure phase can be obtained, verifying the effectiveness of the method of the present invention in suppressing side reactions in halide oxide systems.

[0044] The method of this invention can also be used to prepare other halide oxide systems and obtain better phase purity and ion conductivity, further demonstrating that the method of this invention has a wide range of applications in the preparation of halide oxide solid electrolytes.

[0045] As can be seen from the above embodiments and comparative examples, the acoustic resonance-assisted preparation method of the present invention has good applicability to both halide solid electrolytes and halide oxide solid electrolytes. For representative halide systems such as Li3InCl6, Li2ZrCl6, and Li3YBr6, solid electrolyte products with well-defined target phases, relatively uniform particle size, and good ion conductivity can be obtained after acoustic resonance-assisted treatment. For halide oxide systems such as Li2ZrOCl4, acoustic resonance mechanical pretreatment can reduce the occurrence of side reactions under high-temperature conditions, thereby facilitating the acquisition of relatively pure target products.

[0046] Further analysis using comparative examples reveals that while traditional high-energy ball milling can achieve raw material mixing, the processing time is significantly longer. Furthermore, wear and tear on the milling media and jar easily introduces impurities into the product, leading to decreased product phase purity, increased particle size, and impaired ion conductivity. Traditional high-temperature solid-state methods, lacking effective mechanical activation in halide oxide systems, are prone to side reactions such as halogen-containing component volatilization and oxygen evolution, resulting in insulating byproducts and making it difficult to obtain a pure target phase. In contrast, the method of this invention eliminates the need for grinding media, has a shorter pretreatment time, improves raw material mixing uniformity and reaction efficiency, and reduces the risk of side reactions. Therefore, it exhibits superior overall advantages in terms of preparation efficiency, product phase purity, particle size control, and ion conductivity.

[0047] The embodiments described above do not constitute a limitation on the scope of protection of this technical solution. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the above embodiments should be included within the scope of protection of this technical solution.

Claims

1. A method for acoustic resonance-assisted preparation of halide solid electrolytes or halide oxide solid electrolytes, characterized in that, Includes the following steps: S1. Under an inert gas protective environment, weigh the raw materials according to the stoichiometric ratio of the target solid electrolyte; wherein, when the target solid electrolyte is a halide solid electrolyte, the raw materials include lithium halides and metal halides; when the target solid electrolyte is a halide oxide solid electrolyte, the raw materials include metal halides and a lithium source, wherein the lithium source is one of lithium carbonate, lithium oxide or lithium hydroxide. S2. Place the raw material obtained in step S1 into a sealed acoustic resonance reaction vessel, and make the acoustic resonance reaction vessel reciprocate at a resonance frequency of 30Hz to 100Hz, with a vibration acceleration of 10g to 100g, and a processing time of 10 minutes to 2 hours to obtain a mixed precursor.

2. The preparation method according to claim 1, characterized in that, In step S2, the resonant frequency is 50Hz to 80Hz, the vibration acceleration is 30g to 80g, and the processing time is 20 minutes to 1 hour.

3. The preparation method according to claim 1, characterized in that, In step S2, during the acoustic resonance treatment, the temperature of the reaction system is controlled between 0°C and 80°C through a circulating cooling system.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The halide solid electrolyte is Li x MZ6, where M is at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga, Z is at least one of F, Cl, Br, and I, and x is the proportion of each element component, where 0 < x ≤ 3 and is an integer.

5. The preparation method according to any one of claims 1 to 3, characterized in that, The halide oxide solid electrolyte is Li x MO y X z M is at least one of In, Y, Zr, Nb, Ta, Hf, Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, and Ga; X is a halogen element selected from at least one of F, Cl, Br, and I; x, y, and z are the proportions of each element component, and the subscripts satisfy 1≤x≤8, 1≤y≤6, and 1≤z≤6, and the overall system satisfies charge balance.

6. A halide solid electrolyte or a halide oxide solid electrolyte, characterized in that, The halide solid electrolyte or halide oxide solid electrolyte is prepared by the acoustic resonance-assisted preparation method according to any one of claims 1 to 5.

7. An all-solid-state battery, characterized in that, It includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer located between the positive electrode layer and the negative electrode layer, wherein the solid electrolyte layer includes the halide solid electrolyte or halide oxide solid electrolyte as described in claim 6.

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