Argyrodite-type solid electrolyte, preparation method therefor, and use thereof

Abstract

An argyrodite-type solid electrolyte, a preparation method therefor, and use thereof. The molecular formula of the argyrodite-type solid electrolyte is Li5.5-xP1-xWxS4.5-3xO3xClyBr1.5-y. During preparation, raw materials are premixed according to a molar ratio and subjected to ball milling to obtain a solid electrolyte powder; then, the solid electrolyte powder is pressed into an electrolyte sheet, which is sintered to obtain the argyrodite-type solid electrolyte. The multifunctional electrolyte exhibits good stability in air while improving ionic conductivity.

Description

A sulfide-silver-germanium ore type solid electrolyte, its preparation method, and its application Technical Field

[0001] This invention belongs to the field of solid electrolytes, specifically relating to a sulfide-silver-germanium ore type solid electrolyte, its preparation method and application, and in particular, the controllable construction of a multifunctional solid electrolyte and its application in all-solid-state batteries. Background Technology

[0002] With the widespread use of electric vehicles and portable electronic devices, the demand for battery technologies with high energy density and superior safety is increasing. Solid-state electrolytes, as a key component, have attracted widespread attention due to their ability to replace traditional liquid electrolytes. Solid-state electrolytes offer advantages such as preventing electrolyte leakage, improving battery safety, and enhancing cycle life, providing crucial support for the development of next-generation battery technologies.

[0003] Traditional liquid electrolytes (such as organic solvents and salts) are volatile and flammable at high temperatures, and suffer from problems such as battery capacity decay and poor safety, which limit the further development of batteries in terms of high performance and high safety. Solid electrolytes, due to their characteristics of being less prone to leakage, high chemical stability, and wide operating temperature range, are considered an effective way to overcome these problems.

[0004] Australite-based solid-state electrolytes possess unique advantages, such as: 1) Excellent ionic conductivity: The australite structure provides a stable ion transport pathway, contributing to improved battery conductivity and charge / discharge efficiency. 2) Strong chemical stability: Under high temperature and high voltage conditions, australite-based electrolytes exhibit good chemical stability, reducing the risk of electrolyte decomposition and battery degradation. 3) Excellent interfacial compatibility: Australite-based electrolytes can effectively form good interfaces with electrode materials, reducing interfacial resistance and improving battery cycle stability and energy efficiency. Currently, australite-based solid-state electrolytes are attracting increasing attention from researchers.

[0005] Despite the advantages mentioned above, sulfide-germanium ore-based solid-state electrolytes still face several challenges in practical applications: 1) Optimization of ionic conductivity. The ionic conductivity of solid-state electrolytes is typically lower than that of liquid electrolytes, which can lead to a decrease in the energy density and power density of the battery. Improving the ionic conductivity of sulfide-germanium ore-based electrolytes is a key issue, involving research in multiple aspects such as material synthesis and structural optimization. 2) Air stability. Sulfide solid-state electrolytes readily react with water in the air to produce hydrogen sulfide gas. 3) Mechanical properties. Solid-state electrolyte materials typically need to possess certain mechanical strength and flexibility to withstand pressure changes and mechanical stresses during battery assembly. The performance of sulfide-germanium ore-based electrolytes in these aspects needs further improvement to meet the requirements of practical applications.

[0006] Currently, to address the above challenges, relevant reports have been made, and the published patents mainly include CN114883642A, CN114744287A, CN114914527A, CN114649562A, and CN114899480A. These primarily employ doping modification methods. However, achieving both high ionic conductivity and good air stability simultaneously remains a significant challenge. Summary of the Invention

[0007] The purpose of this invention is to address the problems existing in the prior art by providing a sulfide-silver-germanium ore-type solid electrolyte, its preparation method, and its application.

[0008] While there have been numerous reports on the modification of sulfide electrolytes with metal oxide doping, these methods still fall short of current requirements (either exhibiting low ionic conductivity, poor electrochemical performance, or poor air stability). A system that simultaneously achieves high ionic conductivity, high air stability, and stable electrochemical performance has not yet been developed. This multifunctionality is precisely the innovation of the electrolyte developed in this invention. This invention is based on Li... 5.5 PS 4.5 Cl 1.5 By doping the substrate with W, O, and Br, the ionic conductivity can be increased to 10 mS / cm. This invention's multifunctional electrolyte not only improves ionic conductivity but also exhibits good air stability.

[0009] The objective of this invention can be achieved through the following methods:

[0010] On the one hand, the present invention provides a sulforaphite-germanium ore type solid electrolyte with the general chemical formula Li. 5.5-x P 1-x W x S 4.5-3x O 3x Cl y Br 1.5-y ;

[0011] Where x takes the values ​​0.001 < x < 0.5 and 0.7 < y < 0.9.

[0012] The preferred molecular formula for sulfide-germanium ore type solid electrolytes is Li. 5.5-x P 1-x W x S 4.5-3x O 3x Cl 0.8 Br 0.7 This invention improves the ionic conductivity of the system by doping with Br, thereby increasing the system's disorder (i.e., entropy increase process) and accelerating lithium-ion migration, thus reducing the influence of the interface layer formed between the cathode and electrolyte.

[0013] In addition to improving air stability, the introduction of oxygen in this invention primarily helps form a stable interface layer, reducing the interfacial resistance between the solid electrolyte and the electrodes, thereby improving battery performance and cycle stability. Furthermore, the electrochemical reaction kinetics within the battery contribute to regulating the charge / discharge rate and cycle life.

[0014] The introduction of tungsten in this invention not only broadens ion channels and improves ion conductivity, but also helps optimize the crystal structure of the sulfide solid electrolyte, improves its ion conductivity, and enhances the battery's power density and durability. Tungsten doping does not damage the original crystal structure, as can be seen from the measured XRD pattern.

[0015] Furthermore, sulfide solid electrolytes may experience sulfide precipitation under high temperatures or prolonged use. Adding tungsten can effectively suppress this precipitation, maintaining electrolyte stability. Tungsten can also alter ion transport pathways and kinetics in sulfide solid electrolytes, optimizing battery charge / discharge performance and cycle stability.

[0016] On one hand, the present invention provides a method for preparing the aforementioned silver-germanium sulfide-type solid electrolyte, comprising the following steps:

[0017] S1. The raw materials are premixed according to the molar ratio and then ball-milled to obtain solid electrolyte powder;

[0018] S2. The solid electrolyte powder is pressed into tablets to obtain electrolyte tablets, which are then vacuum sintered to obtain a sulfosilver germanium ore type solid electrolyte.

[0019] As one embodiment of the present invention, in step S1, the raw materials include Li source Li2S, P source P2S5, Cl source LiCl, Br source LiBr, W and O source WO3.

[0020] As a preferred option, the molar ratio of Li2S to P2S5, WO3, LiCl, and LiBr is 1:(0.1-0.5):(0.01-0.1):0.4:0.35.

[0021] In one embodiment of the present invention, in step S1, the raw materials are premixed in an inert gas (argon) environment. The ball milling is performed in a sealed ball mill jar, using a planetary ball mill.

[0022] In one embodiment of the present invention, in step S1, the ball mill rotation speed is 200 rpm-600 rpm, and the ball milling time is 5 h-20 h. The ball-to-material ratio is 1:(1-30).

[0023] In one embodiment of the present invention, in step S2, the tableting pressure is 120MPa-600MPa.

[0024] In one embodiment of the present invention, in step S2, the sintering heating rate is 0.1℃ / min-5℃ / min, the sintering temperature is 200℃-600℃, and the sintering time is 4h-24h.

[0025] In one embodiment of the present invention, in step S2, vacuum sintering involves placing the electrolyte sheet in a quartz tube or glass tube, sealing it under vacuum, and then placing the sealed quartz tube or glass tube in a muffle furnace for sintering.

[0026] In one embodiment of the present invention, in step S2, the sintered electrolyte sheet is ground for 15-60 minutes.

[0027] In addition, the present invention provides an application of an air-stabilized silver-germanium ore-type solid electrolyte in all-solid-state batteries.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) To address the problem of low ionic conductivity in sulfide solid electrolytes, this invention employs doping modification with ions having large ionic radii. Introducing ions with large ionic radii can increase the cell size, widen the lithium-ion transport channels, and ultimately improve ionic conductivity, thereby enhancing its energy density in the solid electrolyte system.

[0030] (2) In response to the problem of poor air stability, the present invention uses O element to replace part of the sulfur element in the sulfide solid electrolyte. Since the PO bond strength is greater than the PS bond, a more stable chemical bond is generated, thereby improving its air stability and making it possible to carry out large-scale production in air.

[0031] (3) Regarding the issue of interface stability, the electrolyte of the present invention can suppress the formation of a spatial layer between the cathode and the electrolyte interface. The increased ionic conductivity of the electrolyte system of the present invention can reduce the possibility of Li ion deposition at the electrode interface, reduce interface impedance, and improve its electrochemical performance in solid electrolyte systems. Attached Figure Description

[0032] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings:

[0033] Figure 1 is a SEM image of the solid electrolyte prepared in Example 1;

[0034] Figure 2 is the XRD pattern of the solid electrolyte prepared in Example 1;

[0035] Figure 3 shows the air stability test results of the solid electrolytes obtained in the examples and comparative examples;

[0036] Figure 4 shows the test of the ionic conductivity of the solid electrolytes obtained in the examples and comparative examples;

[0037] Figure 5 shows a comparison of the first charge-discharge performance of the solid electrolytes obtained in the examples and comparative examples;

[0038] Figure 6 shows the cycle stability test (1C) of the solid electrolytes prepared in Example 1, Comparative Examples 2 and 3 in an all-solid-state battery.

[0039] Figure 7 shows the impedance comparison of solid-state batteries assembled with solid electrolytes prepared in Comparative Example 1, Comparative Example 3 and Example 1 after 10 cycles.

[0040] Figure 8 shows the electrolyte membrane prepared by dry method for solid electrolyte in Example 1. Detailed Implementation

[0041] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. The following examples are implemented under the premise of the technical solution of the present invention, providing detailed implementation methods and specific operating procedures, which will help those skilled in the art to further understand the present invention. It should be noted that the scope of protection of the present invention is not limited to the following embodiments; any adjustments and improvements made under the concept of the present invention are all within the scope of protection of the present invention.

[0042] The present invention employs the following steps to test charge-discharge performance:

[0043] First, the NCM811 composite cathode material was prepared: NCM811, the solid electrolyte prepared in step 2) above, and vapor-grown carbon fiber (VGCF) were weighed into a 25 mL zirconia ball mill jar at a mass ratio of 16:3:1. The total mass of the materials was 1 g, the ball-to-material ratio was controlled at 20:1, and the diameter of the zirconia grinding beads used was 5 mm. Then, the sealed ball mill jar was fixed on a high-energy planetary ball mill and ball-milled at 400 r / min for 4 h. Finally, the NCM811 composite cathode material was obtained. Then, using Li / In as the negative electrode and the prepared solid electrolyte as the electrolyte layer, an all-solid-state battery was assembled, and the charge-discharge performance was tested.

[0044] Example 1

[0045] In an argon-filled glove box, Li₂S (0.6138 g), P₂S₅ (0.7366 g), LiCl (0.227 g), LiBr (0.4072 g), and WO₃ (0.0156 g) were premixed in a molar ratio of 1.995:0.495:0.8:0.7:0.01. The mixture was then placed in a sealed ball mill jar and ball-to-material ratio of 30:1. The mixture was then ball-milled for 7 hours at a fixed planetary ball mill speed of 500 rpm to obtain a preliminary solid electrolyte powder. The obtained electrolyte powder was pressed into tablets at 400 MPa to obtain electrolyte tablets, which were then vacuum-sealed. The sealed quartz or glass tubes were placed in a muffle furnace and heated to 480℃ at a rate of 0.5℃ / min for 7 hours. After natural cooling to room temperature, the tablets were ground to obtain the final solid electrolyte (Li₂S₅). 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7 The SEM image of the solid electrolyte is shown in Figure 1, and the XRD pattern is shown in Figure 2.

[0046] Performance testing:

[0047] Ionic conductivity test: Weigh 100 mg of the prepared solid electrolyte (Li) 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7 An electrolyte sheet was pressed into a 10mm stainless steel die under a pressure of 360MPa. Then, 9mm lithium sheets (15μm thick) were added to both sides of the electrolyte sheet. Cu current collectors were then inserted into both sides to complete the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed under a pressure of 50MPa to obtain a sandwich-type all-solid-state battery. The ionic conductivity of the solid electrolyte was then measured to be σ = 13ms / cm.

[0048] Air stability test: The obtained solid electrolyte (Li) 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7 The solid electrolyte was placed in dry air, and the gas release over time before and after exposure to air was measured. After 15 minutes, the amount of gas released by the prepared solid electrolyte was 0.36 cm³. 3 / g.

[0049] Pressure battery performance test: Weigh 100mg of the prepared solid electrolyte (Li) 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7 An electrolyte sheet was pressed into a 10mm stainless steel die at 360MPa. Then, 10mg of the composite positive electrode material prepared using the above method was added to one side of the electrolyte sheet, and it was pressed again at 150MPa. The sheet was then demolded and placed into a specially designed battery test mold. A 9mm lithium-indium sheet (with thicknesses of 30 and 100 micrometers, respectively) was added to the other side of the electrolyte sheet. Finally, an Al current collector was placed on the positive electrode side, and a Cu current collector on the negative electrode side, completing the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed at 50MPa to obtain a sandwich-type all-solid-state battery. The assembled battery underwent a capacitor discharge test. At room temperature and a 0.1C rate, the first-cycle discharge specific capacity reached 221mAh / g.

[0050] Example 2

[0051] In an argon-filled glove box, Li₂S (0.6166 g), P₂S₅ (0.7444 g), LiCl (0.2277 g), LiBr (0.4082 g), and WO₃ (0.00312 g) were premixed in a molar ratio of 1.999:0.499:0.8:0.7:0.002. The mixture was then placed in a sealed ball mill jar and ball-milled at a ball-to-material ratio of 30:1. The mixture was then ball-milled at a fixed planetary ball mill speed of 500 rpm for 7 hours to obtain a preliminary solid electrolyte powder. The obtained electrolyte powder was pressed into tablets at a pressure of 400 MPa to obtain electrolyte tablets, which were then vacuum-sealed. The sealed quartz or glass tubes were placed in a muffle furnace and heated to 480℃ at a rate of 0.5℃ / min for 7 hours. After natural cooling to room temperature, the tablets were ground to obtain the final solid electrolyte (Li₂S₅). 5.498 P 0.998 W 0.002 S 4.494 O 0.006 Cl 0.8 Br 0.7 ).

[0052] Performance testing:

[0053] Ionic conductivity test: Weigh 100 mg of the prepared solid electrolyte (Li) 5.498 P 0.998 W 0.002 S 4.494 O 0.006 Cl0.8 Br 0.7 An electrolyte sheet was pressed into a 10mm stainless steel die under a pressure of 360MPa. Then, 9mm lithium sheets (15μm thick) were added to both sides of the electrolyte sheet. Cu current collectors were then inserted into both sides to complete the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed under a pressure of 50MPa to obtain a sandwich-type all-solid-state battery. The ionic conductivity of the solid electrolyte was then measured to be σ = 9ms / cm.

[0054] Air stability test: The obtained solid electrolyte (Li) 5.498 P 0.998 W 0.002 S 4.494 O 0.006 Cl 0.8 Br 0.7 The solid electrolyte was placed in dry air, and the gas release over time before and after exposure to air was measured. After 15 minutes, the amount of gas released by the prepared solid electrolyte was 0.56 cm³. 3 / g.

[0055] Pressure battery performance test: Weigh 100mg of the prepared solid electrolyte (Li) 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7 An electrolyte sheet was pressed into a 10mm stainless steel die at 360MPa. Then, 10mg of the composite positive electrode material prepared by the above method was added to one side of the electrolyte sheet, and it was pressed again at 150MPa. The sheet was then demolded and placed into a specially designed battery test mold. A 9mm lithium-indium sheet (with thicknesses of 30 and 100 micrometers, respectively) was added to the other side of the electrolyte sheet. Finally, an Al current collector was placed on the positive electrode side, and a Cu current collector was placed on the negative electrode side to complete the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed at 50MPa to obtain a sandwich-type all-solid-state battery. The assembled battery underwent a capacitor discharge test. At room temperature and a 0.1C rate, the first-cycle discharge specific capacity reached 200mAh / g.

[0056] Example 3

[0057] In an argon-filled glove box, Li₂S (0.5824 g), P₂S₅ (0.65 g), LiCl (0.1506 g), LiBr (0.2204 g), and WO₃ (0.396 g) were premixed in a molar ratio of 1.95:0.45:0.8:0.7:0.1. The mixture was then placed in a sealed ball mill jar and ball-to-material ratio of 30:1. The mixture was then ball-milled for 7 hours at a fixed planetary ball mill speed of 500 rpm to obtain a preliminary solid electrolyte powder. The obtained electrolyte powder was pressed into tablets at a pressure of 400 MPa to obtain electrolyte tablets, which were then vacuum-sealed. The sealed quartz or glass tubes were placed in a muffle furnace and heated to 480℃ at a rate of 0.5℃ / min for 7 hours. After natural cooling to room temperature, the tablets were ground to obtain the final solid electrolyte.

[0058] Performance testing:

[0059] Ionic conductivity test: Weigh 100 mg of the prepared solid electrolyte (Li) 5.4 P 0.9 W 0.1 S 4.2 O 0.3 Cl 0.8 Br 0.7 An electrolyte sheet was pressed into a 10mm stainless steel die under a pressure of 360MPa. Then, 9mm lithium sheets (15μm thick) were added to both sides of the electrolyte sheet. Cu current collectors were then inserted into both sides to complete the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed under a pressure of 50MPa to obtain a sandwich-type all-solid-state battery. The ionic conductivity of the solid electrolyte was then measured to be σ = 8ms / cm.

[0060] Air stability test: The obtained solid electrolyte (Li) 5.4 P 0.9 W 0.1 S 4.2 O 0.3 Cl 0.8 Br 0.7 The solid electrolyte was placed in dry air, and the gas release over time before and after exposure to air was measured. After 15 minutes, the amount of gas released by the prepared solid electrolyte was 0.80 cm³. 3 / g.

[0061] Pressure battery performance test: Weigh 100mg of the prepared solid electrolyte (Li) 5.49 P 0.99 W 0.01 S 4.47 O 0.03 Cl 0.8 Br 0.7An electrolyte sheet was pressed into a 10mm stainless steel die at 360MPa. Then, 10mg of the composite positive electrode material prepared by the above method was added to one side of the electrolyte sheet, and it was pressed again at 150MPa. The sheet was then demolded and placed into a specially designed battery test mold. A 9mm lithium-indium sheet (with thicknesses of 30 and 100 micrometers, respectively) was added to the other side of the electrolyte sheet. Finally, an Al current collector was added to the positive electrode side, and a Cu current collector to the negative electrode side, completing the encapsulation. The battery mold was removed, placed in a battery fixture, and pressed at 50MPa to obtain a sandwich-type all-solid-state battery. The assembled battery underwent a capacitor discharge test. At room temperature and a 0.1C rate, the first-cycle discharge specific capacity reached 180mAh / g.

[0062] Comparative Example 1

[0063] The difference between this comparative example and Example 1 is that the raw materials Li₂S, P₂S₅, LiCl, LiBr, and WO₃ are replaced with Li₂S, P₂S₅, and LiCl in a molar ratio of 2:0.5:1.5, used to prepare undoped Li₂. 5.5 PS 4.5 Cl 1.5 Electrolyte. Then the ionic conductivity of the solid electrolyte was measured to be σ = 6 mS / cm.

[0064] Comparative Example 2

[0065] The difference between this comparative example and Example 1 is that it is undoped with W, and the raw materials are Li₂S, P₂O₅, LiCl, and LiBr. The molar ratio is 4.47:0.006:0.8:0.7, used to prepare undoped Li₂. 10.44 P 0.012 S 4.47 O 0.03 Cl 0.8 Br 0.7 Electrolyte. The testing steps and methods are the same as in Example 1. Then, the ionic conductivity of the solid electrolyte σ = 5 mS / cm was measured.

[0066] Comparative Example 3

[0067] The difference between this comparative example and Example 1 is that it is undoped with oxygen, and the raw materials are Li₂S, P₂S₅, LiCl, LiBr, and WS₃. The molar ratio is 2.025:0.495:0.8:0.7:0.01, used to prepare undoped Li₂. 5.55 P 0.99 W 0.01 S 4.53 Cl 0.8 Br 0.7 Electrolyte. The testing steps and methods are the same as in Example 1. Then, the ionic conductivity of the solid electrolyte, σ = 3 mS / cm, was measured.

[0068] This invention primarily involves simultaneously introducing multiple elements (W, O, Br) into a sulfide-germanium ore-type solid electrolyte. Specifically, by substituting some P sites with the large-ionic-radius metal element W, the cell size can be expanded, thus further benefiting Li… + Transport within the structure. Br substitutes for some Cl positions to increase the disorder of Br and Cl in the electrolyte system, thereby lowering their activation energy and improving ionic conductivity. O substitution for S increases the binding energy of the MP4 tetrahedron, thus improving the air stability of the sulfide electrolyte. This results in a solid-state electrolyte with high ionic conductivity, air stability, and electrochemical stability, fundamentally addressing various challenges in the development of all-solid-state batteries and providing a solution for all-solid-state battery systems pursuing high energy density, high safety, and long cycle life.

[0069] The discharge specific capacity and coulombic efficiency of the various embodiments and comparative examples of the present invention in the first cycle are shown in Table 1 below:

[0070] Table 1

[0071] The air stability test results of the solid electrolytes obtained in the examples and comparative examples are shown in Figure 3;

[0072] The ionic conductivity of the solid electrolytes obtained in the examples and comparative examples is shown in Figure 4.

[0073] Figure 5 shows a comparison of the first-cycle charge-discharge performance of the solid electrolytes obtained in the examples and comparative examples.

[0074] The solid electrolytes prepared in Example 1 and Comparative Example 2 were used in all-solid-state batteries for cycle stability testing (1C), as shown in Figure 6.

[0075] Figure 7 shows the impedance comparison of solid-state batteries assembled with solid electrolytes prepared in Example 1 and Comparative Examples 1 and 3 after 10 cycles.

[0076] Figure 8 shows the electrolyte membrane prepared by the dry method for the solid electrolyte in Example 1. Figure 8 shows the film-forming property test (film formation is possible) of the modified solid electrolyte of the present invention. However, in the comparative test, film formation is not possible without doping or with W or O elements alone. Therefore, only when W and O are doped simultaneously can the film-forming performance of the solid electrolyte be improved.

[0077] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A sulforaphane-germanium ore type solid electrolyte, characterized in that, The general chemical formula is Li 5.5-x P 1-x W x S 4.5-3x O 3x Cl y Br 1.5-y ; Where x takes the values ​​0.001 < x < 0.01 and 0.7 < y < 0.

9.

2. A method for preparing a sulfide-germanium ore-type solid electrolyte as described in claim 1, characterized in that, Includes the following steps: S1. The raw materials are premixed according to the molar ratio and then ball-milled to obtain solid electrolyte powder; S2. Press the solid electrolyte powder into tablets to obtain electrolyte tablets, and then perform vacuum sintering to obtain a sulfosilver germanium ore type solid electrolyte.

3. The preparation method according to claim 2, characterized in that, In step S1, the raw materials include Li source Li2S, P source P2S5, Cl source LiCl, Br source LiBr, W and O source WO3.

4. The preparation method according to claim 2, characterized in that, In step S1, the raw materials are premixed in an inert gas environment; ball milling is performed by placing the raw materials in a sealed ball mill jar and fixing it in a planetary ball mill.

5. The preparation method according to claim 2, characterized in that, In step S1, the ball mill speed is 200rpm-600rpm, the ball milling time is 5h-20h, and the ball-to-material ratio is 1:(1-30).

6. The preparation method according to claim 2, characterized in that, In step S2, the tableting pressure is 120MPa-600MPa.

7. The preparation method according to claim 2, characterized in that, In step S2, the sintering temperature is 200℃-600℃, and the sintering time is 4h-24h; And / or, the sintering heating rate is 0.1℃ / min-5℃ / min.

8. The preparation method according to claim 2, characterized in that, In step S2, sintering involves placing the electrolyte sheet in a quartz tube or glass tube, sealing it under vacuum, and then placing the sealed quartz tube or glass tube in a muffle furnace for sintering.

9. The preparation method according to claim 2, characterized in that, In step S2, the sintered electrolyte sheet is ground for 15-60 minutes.

10. The application of the sulfide-germanium ore-type solid electrolyte as described in claim 1 in an all-solid-state battery.

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