A method for high-throughput screening of high-performance sulfide solid electrolyte formulations

Abstract

The present invention relates to a method for high-throughput screening of high-performance sulfide solid electrolyte formulations. It includes: S1. According to the stoichiometric ratio of Li 6‑x PS 5‑ x Cl 1+x , weigh the sulfide solid electrolyte precursors and perform vortex ball milling at different rotation speeds respectively, then perform tabletting, encapsulation and sintering to obtain the sulfide solid electrolyte, and determine the optimal rotation speed of the vortex ball milling corresponding to its highest lithium ion conductivity; where x = 0; S2. At the optimal rotation speed, weigh 8-48 kinds of sulfide solid electrolyte precursors according to the stoichiometric ratio of Li 6‑x PS 5‑x Cl 1+x , perform vortex ball milling simultaneously, and perform tabletting, encapsulation and sintering to obtain the sulfide solid electrolyte, and determine the optimal formulation corresponding to its highest lithium ion conductivity; where x = 0.30-0.65. The method of the present invention can greatly improve the screening efficiency and contribute to the industrialization progress of sulfide all-solid-state lithium batteries.

Description

Technical Field

[0001] The present invention belongs to the field of high-throughput screening, and relates to a method for high-throughput screening of high-performance sulfide solid electrolyte formulations. Background Art

[0002] All-solid-state lithium batteries based on sulfide solid electrolytes have the advantages of high safety and high energy density, and high-performance sulfide solid electrolyte materials are the key among them. How to efficiently screen high-performance sulfide solid electrolyte materials has become one of the current focuses.

[0003] There are mainly two traditional mixing methods for sulfide solid electrolyte raw materials: one is the liquid-phase method, where the solid electrolyte raw materials are placed in a high-purity organic solvent in a certain proportion for uniform mixing. After mixing, the solvent is removed and high-temperature heat treatment is carried out to obtain the solid electrolyte material. This method can only synthesize one electrolyte formulation at a time, and dealing with the solvent is very troublesome, making it inconvenient to conduct multiple experiments. The other is the solid-phase method, where the solid electrolyte raw materials are mixed in a ball-milling tank in a certain proportion. By adding ball-milling beads with a certain ball-to-material ratio, uniformly mixed sulfide solid electrolyte raw materials are obtained through high-energy ball milling and other methods. Using planetary ball milling, four electrolyte formulations can be synthesized at one time, but this ball-milling method is still difficult to synthesize several different-formulation electrolytes on a large scale at one time. Currently, the smallest planetary ball-milling tank on the market is 50 mL, and the amount of raw materials that need to be added at one time is about 2 g, with a relatively high cost per time. Moreover, the power is about 0.55 kW, and the instrument mass is 55 kg.

[0004] Mixing sulfide solid electrolyte precursors using the traditional high-energy ball milling method takes too long, requires a large amount of precursor raw materials at one time to study the formulation, consumes a large amount of energy in high-energy ball milling, and the equipment is expensive, making it impossible to achieve low-cost high-throughput screening of solid electrolyte formulations. Summary of the Invention

[0005] The purpose of the present invention is to overcome the disadvantages and deficiencies of the prior art and provide a method for high-throughput screening of high-performance sulfide solid electrolyte formulations. The present invention uses a vortex ball mill to quickly prepare and screen high-performance sulfide solid electrolyte materials. Since organic solvents are likely to react with sulfides, a dry mixing method without adding organic solvents is adopted. This method can prepare a small amount (0.02 - 0.1 g) and a large batch (8 - 48 kinds) of sulfide electrolytes at one time in a short time (150 s), greatly improving the efficiency of screening high-performance sulfide solid electrolyte formulations and contributing to the industrialization progress of sulfide all-solid-state lithium batteries.

[0006] The purpose of the present invention can be achieved through the following solutions:

[0007] In a first aspect, the present invention provides a method for high-throughput screening of high-performance sulfide solid electrolyte formulations, the method comprising the following steps:

[0008] S1. According to the stoichiometric ratio of Li 6-x PS 5-x Cl 1+x , weigh the sulfide solid electrolyte precursors and perform vortex ball milling at different rotation speeds. Respectively, press and encapsulate and sinter the sulfide solid electrolyte precursors after vortex ball milling at different rotation speeds to obtain sulfide solid electrolytes, and determine the optimal rotation speed of the vortex ball milling corresponding to the highest lithium ion conductivity of the sulfide solid electrolyte; wherein, x =0;

[0009] S2. At the optimal rotation speed of step S1, weigh 8-48 sulfide solid electrolyte precursors according to the stoichiometric ratio of Li 6-x PS 5-x Cl 1+x , perform vortex ball milling simultaneously, press and encapsulate and sinter the sulfide solid electrolyte precursors after vortex ball milling to obtain sulfide solid electrolytes, and determine the optimal formulation corresponding to the highest lithium ion conductivity of the sulfide solid electrolyte; wherein, x = 0.30 - 0.65.

[0010] As an embodiment of the present invention, in step S1, the sulfide solid electrolyte precursors include lithium sulfide, phosphorus pentasulfide, and lithium halide. In some preferred embodiments, the lithium halide includes lithium chloride.

[0011] As an embodiment of the present invention, in step S1, the rotation speed of the vortex ball milling is 100 - 3000 rpm.

[0012] Preferably, in step S1, the rotation speed of the vortex ball milling is 800 - 2000 rpm.

[0013] As an embodiment of the present invention, in step S1 or S2, the vortex ball milling is performed using a vortex ball mill, and the capacity of the vortex ball mill does not exceed 15 mL; the mass of each sulfide solid electrolyte precursor is 0.02 - 0.1 g. Excessive capacity or dosage will result in poor mixing effect, and thus lower ionic conductivity.

[0014] Furthermore, the power of the vortex ball milling does not exceed 20 W.

[0015] In some preferred embodiments, the vortex ball mill is Shanghai Lichen Technology LC-Vortex MS; the volume of the vortex ball mill is 15 mL, and the power is 20 W.

[0016] As an embodiment of the present invention, in step S1 or S2, the vortex ball milling includes: first performing forward ball milling, then performing inverted ball milling, and repeating this process 5 - 7 times. Repeating the forward and inverted ball milling can make the mixing more sufficient, thereby improving the ionic conductivity of the electrolyte.

[0017] Further, the time for forward ball milling or inverted ball milling is 30s - 40s. The present invention can prepare a small amount (0.1g) and a large batch of sulfide electrolytes at one time in a short time (150s).

[0018] As an embodiment of the present invention, in step S1 or S2, the ball milling beads used in the vortex ball milling include zirconia ball milling beads; the ball - to - material ratio of the vortex ball milling is 20:1 - 40:1.

[0019] Further, the sintering temperature is 480 - 500°C and the time is 5 - 10h.

[0020] In some preferred embodiments, the stoichiometric ratio of Li 6-x PS 5-x Cl 1+x includes x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65. The screening method of the present invention prepares a small amount and a large batch (more than 8 kinds) of sulfide electrolytes at one time.

[0021] In some preferred embodiments, the optimal rotation speed is 1600 rpm; the optimal formula is Li 5.4 PS 4.4 Cl 1.6 , corresponding to a lithium - ion conductivity of 5.9 mS / cm.

[0022] The present invention weighs 8 groups of precursors of sulfide electrolytes (such as lithium sulfide, phosphorus pentasulfide, and lithium halide, etc.) according to Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65), with each group totaling about 0.1g, and respectively adding them into glass weighing bottles of a certain volume. The ball - to - material ratio is 20:1 - 40:1, and the material of the ball milling beads is zirconia. Place them in the jacks of a vortex ball mill (Shanghai Lichen Technology LC - Vortex MS), and mix them evenly at a rotation speed of 100 - 3000 RPM for 20s - 40s. Then invert the weighing bottles and mix them evenly for another 20s - 40s, and end after repeating 5 times. Take out the uniformly mixed solid electrolyte powder, press it into tablets, encapsulate it in a quartz tube and then sinter it to finally obtain the sulfide solid electrolyte. Determine the best formula among the 8 groups after testing.

[0023] The present invention can prepare a small amount (0.1 g) and a large number of batches (more than 8 kinds) of sulfide electrolytes at one time in a short time (150 s), greatly improving the efficiency of screening high-performance sulfide solid electrolyte formulations and contributing to the industrialization progress of sulfide all-solid-state lithium batteries.

[0024] In a second aspect, the present invention provides a high-performance sulfide solid electrolyte formulation obtained by screening using the method.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The present invention creatively uses the vortex ball milling method to screen high-performance sulfide solid electrolyte formulations. It has a high rotation speed, high ball milling efficiency, and a short vortex ball milling time. At the same time, ball milling beads are creatively added, which can be mixed more quickly, greatly reducing the time. It only takes 150 s to quickly mix the sulfide solid electrolyte precursor powder evenly.

[0027] 2. By performing short-range high-speed vortex ball milling at a low volume, the solid powder and the ball milling beads are in a vortex state, and almost all the solid powder attached to the tube wall can be mixed evenly. On the one hand, it can greatly reduce the amount of sulfide solid electrolyte precursor required for exploring the formulation. Only 0.1 g of precursor raw material is needed at a time to prepare a high-performance sulfide electrolyte formulation, greatly reducing the cost. On the other hand, low-volume vortex ball milling can improve the mixing adequacy of the precursor raw material, thereby screening out sulfide solid electrolyte formulations with higher ionic conductivity.

[0028] 3. The vortex ball milling method adopted by the present invention can mix a large number of batches (8 - 48 kinds) of sulfide electrolytes, greatly improving the efficiency of screening high-performance sulfide solid electrolyte formulations and contributing to the industrialization progress of sulfide all-solid-state lithium batteries.

[0029] 4. By reversing the vortex ball milling method of ball milling and adding ball milling beads at the same time, the mixing adequacy of the precursor raw material is improved together, thereby increasing the conductivity of the sulfide solid electrolyte, and then screening out high-performance sulfide solid electrolyte formulations.

[0030] 5. The present invention uses a direct current brushless motor. Compared with a high-energy ball milling motor, it has a low power (20 W) and high efficiency, the instrument is small and inexpensive, further reducing the cost of high-throughput screening. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, objects, and advantages of the present invention will become more apparent:

[0032] Figure 1 XRD patterns of sulfide solid electrolytes prepared in Example 1 at various rotation speeds;

[0033] Figure 2 The impedance diagram of the sulfide solid electrolyte prepared in Example 1 at various rotational speeds;

[0034] Figure 3 The XRD pattern of the sulfide solid electrolyte prepared in Example 1 at various stoichiometric ratios;

[0035] Figure 4 The impedance diagram of the sulfide solid electrolyte prepared in Example 1 at various stoichiometric ratios;

[0036] Figure 5 The XRD pattern of the sulfide solid electrolyte prepared in Comparative Example 1;

[0037] Figure 6 The impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 1;

[0038] Figure 7 The XRD pattern of the sulfide solid electrolyte prepared in Comparative Example 1;

[0039] Figure 8 The impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 1;

[0040] Figure 9 The XRD pattern of the sulfide solid electrolyte prepared in Comparative Example 2;

[0041] Figure 10 The impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 2;

[0042] Figure 11 The impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 3;

[0043] Figure 12 The impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 4;

[0044] Figure 13 The schematic diagram of the mechanism of the present invention. Detailed implementation manners

[0045] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The following examples are implemented on the premise of the technical solution of the present invention, providing detailed implementation manners and specific operation processes, which will help those skilled in the art to further understand the present invention. It should be noted that the protection scope of the present invention is not limited to the following embodiments. Any several adjustments and improvements made under the premise of the concept of the present invention belong to the protection scope of the present invention.

[0046] Example 1

[0047] In this embodiment, the raw materials of the sulfide electrolyte are uniformly mixed by using vortex ball milling, and the argyrodite-type sulfide electrolyte material is prepared by high-temperature heat treatment. The principle is as Figure 13 shown, and the specific steps are as follows:

[0048] First, determine the optimal rotation speed of the vortex ball mill:

[0049] Weigh lithium sulfide, phosphorus pentasulfide, and lithium chloride according to the stoichiometric ratio of Li6PS5Cl, which is 5:1:2, with a total of about 0.1 g. Add them to a 15 mL glass weighing bottle (the vortex ball milling test tube module is 8 * diameter 13 mm). Wrap the contact between the bottle cap and the glass with tape. The ball-to-material ratio is 30:1, and the milling beads are made of zirconia. Mix uniformly at rotation speeds of 800 rpm, 1000 rpm, 1200 rpm, 1400 rpm, 1600 rpm, 1800 rpm, and 2000 rpm for 30 s respectively. After the machine stops rotating, invert the weighing bottle and mill for another 30 s. Repeat the above operation 5 times (the total time is 150 s). Open the uniformly mixed weighing bottle in the argon atmosphere glove box, separate the powder and the milling beads using a sieve, place the obtained powder in a tablet pressing mold for tablet pressing, then place the tablet in a quartz tube for encapsulation, sinter at 480 °C in a muffle furnace for 8 h, and then grind to obtain the sulfide solid electrolyte powder Li6PS5Cl.

[0050] In this embodiment and the following embodiments, the vortex ball milling method used for mixing materials has the effect of being able to prepare a small amount of various solid electrolyte powders at one time, greatly accelerating the development speed of high-performance solid electrolyte components and significantly reducing the raw material and equipment costs. By relying on the high-speed vortex ball milling method for mixing materials, the raw materials of the sulfide solid electrolyte show a vortex-like mixing method, which can be mixed evenly in a relatively short time, and then a high-performance sulfide solid electrolyte can be obtained after high-temperature heat treatment.

[0051] As Figure 1 shown, it is the XRD pattern of the sulfide solid electrolyte prepared in Example 1 at each rotation speed. Preferably, at a rotation speed of 1600 rpm, the precursor after being mixed evenly by vortex ball milling can obtain the pure argyrodite-type sulfide solid electrolyte material Li6PS5Cl after sintering at 500 °C for 8 h.

[0052] As Figure 2As shown, it is the impedance diagram of the sulfide solid electrolyte prepared in Example 1 at various rotation speeds. After conversion, the lithium-ion conductivities of the sulfide electrolytes prepared at rotation speeds of 800 rpm, 1000 rpm, 1200 rpm, 1400 rpm, 1600 rpm, 1800 rpm, and 2000 rpm are 0.3 mS / cm, 0.7 mS / cm, 1.3 mS / cm, 1.8 mS / cm, 2.8 mS / cm, 2.7 mS / cm, and 2.7 mS / cm respectively. Preferably, the sulfide electrolyte material with the highest lithium-ion conductivity is obtained at a rotation speed of 1600 rpm.

[0053] Secondly, determine the optimal formulation:

[0054] Mix lithium sulfide, phosphorus pentasulfide, and lithium chloride in a stoichiometric ratio of Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65), 0.1 g for each group, and add them to a 15 mL weighing bottle, with a ball-to-material ratio of 30:1 and the ball milling beads made of zirconia.

[0055] Mix uniformly at a rotation speed of 1600 rpm for 30 s. After the machine stops rotating, invert the weighing bottle and then ball mill for another 30 s, repeating the above operation 5 times. Open the uniformly mixed weighing bottle in an argon atmosphere glove box, separate the powder and the ball milling beads using a sieve, place the obtained powder in a tablet press mold for tableting, then place the tablet in a quartz tube for encapsulation, sinter at 480 °C in a muffle furnace for 8 h, and then grind to obtain the sulfide solid electrolyte powder Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65).

[0056] As Figure 3 shown, it is the XRD pattern of the sulfide solid electrolyte prepared in Example 1 at various stoichiometric ratios. Preferably, at a rotation speed of 1600 rpm, a high-purity sulfide solid electrolyte material Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65) can be obtained after sintering the precursor mixed by vortex ball milling at 480 °C for 8 h.

[0057] As Figure 4As shown, it is the impedance diagram of the sulfide solid electrolyte prepared in Example 1 under various stoichiometric ratios. After conversion, x When = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60 and 0.65, the lithium ion conductivities are 1.3 mS / cm, 1.5 mS / cm, 2.2 mS / cm, 2.9 mS / cm, 3.7 mS / cm, 4.7 mS / cm, 5.9 mS / cm and 3.8 mS / cm respectively. Preferably, in x = 0.60, the sulfide electrolyte material with the highest lithium ion conductivity (5.9 mS / cm) is obtained.

[0058] Comparative Example 1

[0059] First, determine the optimal rotation speed of the planetary ball mill:

[0060] Weigh lithium sulfide, phosphorus pentasulfide and lithium chloride according to the stoichiometric ratio of 5:1:2, totaling about 2 g, and place them in a 50 mL zirconia ball mill jar with a ball-to-material ratio of 30:1. Using the traditional planetary ball milling process, the rotation speeds are 500 rpm, 1000 rpm and 1500 rpm, and the ball milling time is 8 h. Take out the uniformly mixed solid electrolyte powder, press it into tablets, encapsulate it in a quartz tube and then sinter it at 500 °C for 8 h to finally obtain the sulfide solid electrolyte Li6PS5Cl.

[0061] As Figure 5 shown, it is the XRD pattern of the sulfide solid electrolyte prepared in Comparative Example 1. The traditional planetary ball milling process yields the pure argyrodite-type sulfide solid electrolyte material Li6PS5Cl. Pure-phase sulfide electrolytes can be prepared at different rotation speeds.

[0062] As Figure 6 shown, it is the impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 1. The lithium ion conductivities of the sulfide electrolytes prepared at rotation speeds of 500 rpm, 1000 rpm and 1500 rpm are 1.8 mS / cm, 2.4 mS / cm and 2.1 mS / cm respectively. The solid electrolyte with the highest lithium ion conductivity is obtained when the rotation speed of the ball mill is 1000 rpm.

[0063] Secondly, determine the optimal formula:

[0064] Weigh lithium sulfide, phosphorus pentasulfide and lithium chloride according to Li 6-x PS 5-x Cl 1+x ( x= 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65) stoichiometric ratios, 2 g each, were added to a 50 mL zirconia ball milling jar, with a ball-to-powder ratio of 30:1 and the milling beads made of zirconia. The planetary ball mill was in batches of 4 groups, with a rotation speed of 1000 rpm and a ball milling time of 8 h. The 8 groups of components were ball milled in two batches, with a total time of approximately 16 h. The zirconia ball milling jar containing the uniformly mixed precursor powder was opened in an argon atmosphere glove box. The powder and the milling beads were separated using a sieve. The obtained powder was placed in a tablet pressing mold for tablet pressing, and then the tablets were placed in a quartz tube for encapsulation. Sintering was carried out in a muffle furnace at 480 °C for 8 h, and then grinding was performed to obtain the sulfide solid electrolyte powder Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65).

[0065] As Figure 7 shown, the XRD patterns of the sulfide solid electrolytes prepared in Comparative Example 1 at various stoichiometric ratios are presented. Preferably, at a rotation speed of 1000 rpm, the precursor after being homogenized by high-energy planetary ball milling can obtain a high-purity sulfide solid electrolyte material Li 6-x PS 5-x Cl 1+x ( x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65).

[0066] As Figure 8 shown, the impedance diagrams of the sulfide solid electrolytes prepared in Comparative Example 1 at various stoichiometric ratios are presented. After conversion, x = 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and 0.65 have lithium ion conductivities of 1.1 mS / cm, 1.3 mS / cm, 1.7 mS / cm, 2.0 mS / cm, 2.4 mS / cm, 2.7 mS / cm, 4.2 mS / cm, and 2.9 mS / cm, respectively. Preferably, also at x = 0.60, the sulfide electrolyte material with the highest lithium ion conductivity is obtained.

[0067] It can be seen that the traditional planetary ball mill requires a long time (16 h), few batches (4 kinds), and a large amount of raw materials (2 g) to complete the screening, with low efficiency and high cost; and the conductivity of the best formula screened out is much lower than that of Example 1.

[0068] Comparative Example 2

[0069] In this comparative example, the raw materials of the sulfide electrolyte were uniformly mixed by vortex ball milling, and the argyrodite-type sulfide electrolyte material was prepared by high-temperature heat treatment. The specific steps are as follows:

[0070] Weigh lithium sulfide, phosphorus pentasulfide, and lithium chloride according to the stoichiometric ratio of Li6PS5Cl of 5:1:2, totaling about 0.1 g, and add them to a 15 mL glass weighing bottle. Wrap the contact between the bottle cap and the glass with tape. The ball-to-material ratio is 30:1, and the ball milling beads are made of zirconia. Mix uniformly at a speed of 1600 rpm for 30 s. After the machine stops rotating, repeat the above operation 5 times. Open the uniformly mixed weighing bottle in an argon atmosphere glove box, separate the powder and the ball milling beads using a sieve, place the obtained powder in a tablet pressing mold for tablet pressing, then place the tablet in a quartz tube for encapsulation, sinter at 480 °C in a muffle furnace for 8 h, and then grind to obtain the sulfide solid electrolyte powder Li6PS5Cl.

[0071] As Figure 9 shown, it is the XRD pattern of the sulfide solid electrolyte prepared in Comparative Example 2, and no pure-phase argyrodite-type sulfide electrolyte material was obtained.

[0072] As Figure 10 shown, it is the impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 2. After conversion, the lithium ion conductivity of the sulfide electrolyte prepared at a speed of 1600 rpm is only 0.2 mS / cm.

[0073] It can be seen that in the vortex ball milling method without reverse ball milling, the conductivity of the best selected formula is much lower than that of Example 1.

[0074] Comparative Example 3

[0075] In this comparative example, the raw materials of the sulfide electrolyte were uniformly mixed by vortex ball milling, and the argyrodite-type sulfide electrolyte material was prepared by high-temperature heat treatment. The specific steps are as follows:

[0076] Weigh lithium sulfide, phosphorus pentasulfide, and lithium chloride according to the stoichiometric ratio of Li6PS5Cl of 5:1:2, totaling about 0.1 g, and add them to a 15 mL glass weighing bottle. Wrap the contact between the bottle cap and the glass with tape. Mix uniformly at a speed of 1600 rpm for 30 s. After the machine stops rotating, invert the weighing bottle and then mix uniformly for 30 s. Repeat the above operation 5 times. Open the uniformly mixed weighing bottle in an argon atmosphere glove box, place the obtained powder in a tablet pressing mold for tablet pressing, then place the tablet in a quartz tube for encapsulation, sinter at 480 °C in a muffle furnace for 8 h, and then grind to obtain the sulfide solid electrolyte powder Li6PS5Cl.

[0077] As Figure 11Shown is the impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 3. After conversion, the lithium-ion conductivity of the sulfide electrolyte prepared at a rotation speed of 1600 rpm is 0.07 mS / cm.

[0078] It can be seen that without adding milling beads, the conductivity of the best formula screened is much lower than that of Example 1.

[0079] Comparative Example 4

[0080] In this example, the raw materials of the sulfide electrolyte were uniformly mixed by vortex ball milling, and a thioargentite-type sulfide electrolyte material was prepared by high-temperature heat treatment. The specific steps are as follows:

[0081] First, determine the optimal rotation speed of the vortex ball mill:

[0082] Weigh lithium sulfide, phosphorus pentasulfide, and lithium chloride according to the stoichiometric ratio of Li6PS5Cl of 5:1:2, totaling about 0.2 g, and add them to a 30 mL glass weighing bottle. Tape is used to wrap and seal the contact between the bottle cap and the glass. The ball-to-material ratio is 30:1, and the milling beads are made of zirconia. Mix uniformly at a rotation speed of 1600 rpm for 30 s. After the machine stops rotating, invert the weighing bottle and mill for another 30 s. Repeat the above operation 5 times. Open the uniformly mixed weighing bottle in an argon atmosphere glove box, separate the powder and the milling beads using a sieve, place the obtained powder in a tablet press mold for tablet forming, then place the tablet in a quartz tube for encapsulation, sinter at 480 °C in a muffle furnace for 8 h, and then grind to obtain the sulfide solid electrolyte powder Li6PS5Cl.

[0083] As Figure 12 shown, the impedance diagram of the sulfide solid electrolyte prepared in Comparative Example 4. After conversion, the lithium-ion conductivity of the sulfide electrolyte prepared at a rotation speed of 1600 rpm is 1.4 mS / cm.

[0084] It can be seen that compared with the traditional ball milling method, the higher the capacity and dosage, the better the mixing effect; the present invention unexpectedly finds that too high capacity and dosage in Comparative Example 4 will result in a poor mixing effect, thereby leading to a lower ionic conductivity, and the conductivity of the best formula screened is much lower than that of Example 1.

[0085] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A method for high-throughput screening of high-performance sulfide solid electrolyte formulations, characterized in that: The following steps are involved: S1. According to Li 6-x PS 5-x Cl 1+x The stoichiometric ratio of the sulfide solid electrolyte precursor is weighed and subjected to vortex ball milling at different speeds, and the sulfide solid electrolyte precursor subjected to vortex ball milling at different speeds is pressed into tablets, packaged and sintered to obtain a sulfide solid electrolyte, and the optimal speed of the vortex ball milling corresponding to the highest lithium ion conductivity of the sulfide solid electrolyte is determined; wherein, x =0; S2, at the optimal speed of step S1, according to Li 6-x PS 5-x Cl 1+x 8-48 kinds of sulfide solid electrolyte precursors are weighed in a stoichiometric ratio and vortex ball milled at the same time. The sulfide solid electrolyte precursors after vortex ball milling are tableted, packaged and sintered to obtain a sulfide solid electrolyte, and the optimal formula corresponding to the highest lithium ion conductivity of the sulfide solid electrolyte is determined; wherein x=0.30~0.

65.

2. The method according to claim 1, characterized in that In step S1, the sulfide solid electrolyte precursor includes lithium sulfide, phosphorus pentasulfide and lithium chloride.

3. The method according to claim 1, characterized in that: In step S1, the rotation speed of the vortex ball milling at different rotation speeds is 100-3000 rpm.

4. The method according to claim 1, characterized in that: In step S1, the rotation speed of the vortex ball milling at different rotation speeds is 800-2000 rpm.

5. The method according to claim 1, characterized in that In step S1 or S2, the vortex ball milling is performed using a vortex ball mill, and the capacity of the vortex ball mill does not exceed 15 mL; the mass of the sulfide solid electrolyte precursor is 0.02-0.1 g.

6. The method according to claim 1, characterized in that In step S1 or S2, the ball milling beads used in the vortex ball mill include zirconium oxide ball milling beads; the ball-to-material ratio of the vortex ball mill is 20:1-40:

1.

7. The method according to claim 1, characterized in that In step S1 or S2, the vortex ball milling includes: first forward ball milling, then inverted ball milling, repeating 5-7 times, and the time of forward ball milling or inverted ball milling is 30s-40s.

8. The method according to claim 1, characterized in that The sintering temperature is 480-500° C. and the sintering time is 5-10 hours.

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