A method of preparing tungsten-doped Li9B 19 S 33 ​

Abstract

The application relates to a preparation method of tungsten-doped Li9B 19 S 33 , comprising the following steps: providing pre-prepared raw materials containing only Li, B, W and S elements, and regulating the molar ratio of Li, B, W and S in the pre-prepared raw materials to be 9-3x: 19-x: x: 33; grinding the pre-prepared raw materials and then performing ball milling to obtain a powder; pressing the powder into a sheet to obtain a pre-prepared sheet; and performing heat treatment on the pre-prepared sheet, cooling after heat preservation at a predetermined temperature for a predetermined time to obtain the tungsten-doped Li9B 19 S 33 , wherein the stoichiometric formula of the tungsten-doped Li9B 19 S 33 is Li 9‑3x B 19‑x W x S 33 , and x is a value in the range of 0.01-0.1. According to the application, the molar ratio of Li, B, W and S in the pre-prepared raw materials is regulated to be 9-3x: 19-x: x: 33, and then the pre-prepared raw materials are ground and ball milled, and solid-phase synthesis is performed at high temperature, so that the tungsten-doped Li9B 19 S 33 is obtained, the conductivity of which can reach 0.53 mS / cm, and the conductivity is significantly improved compared with that of Li9B 19 S 33 crystal.

Description

Technical Field

[0001] This application relates to the field of lithium batteries, and in particular to solid electrolytes. Background Technology

[0002] Currently, most commercially available lithium-ion batteries use liquid electrolytes, which face a bottleneck in energy density, with an upper limit of 350 Wh / kg, and also pose safety hazards such as high-temperature thermal runaway. Compared to flammable organic liquid electrolytes, solid-state electrolytes have advantages such as high thermal stability, non-flammability, no leakage, and non-volatility, which are beneficial to improving battery safety and stability. At the same time, the use of solid-state electrolytes makes the application of lithium metal anodes possible, thereby increasing battery energy density. Therefore, research on solid-state electrolytes has become a hot topic now and in the future. Solid-state electrolyte systems mainly include three types: polymers, oxides, and sulfides. Among them, sulfide solid-state electrolytes have the highest ionic conductivity and good mechanical ductility, making them one of the most promising technologies for developing all-solid-state lithium batteries. In 2018, the New Energy and Industrial Technology Development Organization (NEDO) of Japan predicted that sulfide all-solid-state batteries would account for 50% of the power battery market by 2025 and more than 90% by 2030.

[0003] Li-BS (lithium thioborate) fast ion conductors are among the earliest sulfide solid-state electrolyte material systems to receive attention and research. As early as the 1980s and 1990s, pioneering work was conducted on Li₂S-B₂S₃ and Li₂S-B₂S₃-LiI glass systems, exploring the potential applications of Li-BS glasses in solid-state batteries. Subsequently, research on Li-BS glass systems expanded to quaternary systems such as Li₂S-B₂S₃-LiI-SiO₂. Regarding crystals, one of the earliest studied thioborate crystals is Li₆+2x[B 10 S 18 ]S x (x≈2). This crystal is composed of superadamantanoid clusters B. 10 S 20 The structural units form a thioborate network. Cations and anions are distributed in the pores between the hypertetrahedral clusters of this network structure. The relatively large pore space results in weaker binding between cations and surrounding anions, which facilitates cation migration within the structure. In recent years, theoretical calculations on Li-BS crystal materials have shown that several Li-BS crystal materials possess extremely high ionic conductivity and high electrochemical stability, further increasing the attention given to this material system and making it a promising next-generation solid-state sulfide electrolyte system. However, the conductivity of Li-BS crystal materials containing only Li, B, and S elements is still not ideal and needs further improvement. Summary of the Invention

[0004] This application provides a tungsten-doped Li9B embodiment. 19 S 33 The preparation method is proposed to solve the technical problem of insufficient electrical conductivity of Li-BS crystal materials.

[0005] This application provides a tungsten-doped Li9B embodiment. 19 S 33 The preparation method of the tungsten-doped Li9B 19 S 33 The preparation method includes the following steps:

[0006] Provide a pre-formulated raw material containing only Li, B, W, and S elements, and adjust the molar ratio of Li, B, W, and S in the pre-formulated raw material to 9-3x:19-x:x:33;

[0007] The pre-prepared raw materials are ground and then ball-milled to obtain powder.

[0008] The powder is pressed into sheets to obtain preformed sheets;

[0009] The preform is heat-treated, held at a predetermined temperature for a predetermined time, and then cooled to obtain the tungsten-doped Li9B. 19 S 33 ,

[0010] Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 ,

[0011] x is a value in the range of 0.01 to 0.1.

[0012] In some embodiments of this application, the heat treatment of the preform, including holding it at a predetermined temperature for a predetermined time, includes the following steps:

[0013] The preform is heated to 650-750°C, and then cooled to the predetermined temperature and maintained for a predetermined time, wherein the predetermined temperature is 450-550°C.

[0014] In some embodiments of this application, the step of ball milling the pre-prepared raw material after grinding includes the following steps:

[0015] Add a first number of large zirconia grinding balls and a second number of small zirconia grinding balls to the planetary ball mill;

[0016] The ground pre-formulated raw material is added to the planetary ball mill for ball milling.

[0017] The large zirconia spheres have a mass of 2-5g, and the small zirconia spheres have a mass of 0.5-1.5g.

[0018] In some embodiments of this application, the first quantity is 8-12;

[0019] The second quantity is 8-12;

[0020] The pre-ground raw material is added to the planetary ball mill, wherein 1-3g of the pre-ground raw material is taken.

[0021] In some embodiments of this application, the planetary ball mill rotates at a speed of 250-350 r / min and the milling time is not less than 15 h.

[0022] In some embodiments of this application, the powder is pressed into sheets by cold pressing.

[0023] In some embodiments of this application, the pressure of the cold pressing is 1-1.3 kPa.

[0024] In some embodiments of this application, the heating rate of the preform during the heating process is 1.5-2.5℃ / min.

[0025] In some embodiments of this application, the cooling rate of the preform during the cooling process is 4.5-5.5℃ / min.

[0026] In some embodiments of this application, the predetermined time is not less than 11 hours.

[0027] The technical solutions provided in this application have the following advantages compared with the prior art:

[0028] The tungsten-doped Li9B provided in this application embodiment 19 S 33 The preparation method involves adjusting the molar ratio of Li, B, W, and S in the pre-prepared raw material to 9-3x:19-x:x:33, followed by grinding and ball milling of the pre-prepared raw material and then performing solid-state synthesis at high temperature to obtain tungsten-doped Li9B. 19 S 33 Its conductivity can reach 0.53 mS / cm, which is higher than that of Li9B. 19 S 33 The crystal structure was significantly improved. Attached Figure Description

[0029] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0030] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0031] Figure 1 The tungsten-doped Li9B obtained in Examples 1-3 of this application 19 S 33 XRD pattern. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0033] Unless otherwise specified, the terminology used herein should be understood as having the meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. In case of any conflict, this specification shall prevail.

[0034] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0035] The electrical conductivity of Li-BS crystal materials containing only elements such as Li, B, and S is not ideal.

[0036] The technical solution provided in this application is to solve the above-mentioned technical problems, and the general idea is as follows:

[0037] This application provides a tungsten-doped Li9B embodiment. 19 S 33 The preparation method of the tungsten-doped Li9B 19 S 33 The preparation method includes the following steps:

[0038] S1: Provide a pre-formulated raw material containing only Li, B, W, and S elements, and adjust the molar ratio of Li, B, W, and S in the pre-formulated raw material to 9-3x:19-x:x:33;

[0039] S2: The pre-made raw materials are ground and then ball-milled to obtain powder;

[0040] S3: Press the powder into sheets to obtain preformed sheets;

[0041] S4: The preform is heat-treated, held at a predetermined temperature for a predetermined time, and then cooled to obtain the tungsten-doped Li9B. 19 S 33 ,

[0042] Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 ,

[0043] x is a value in the range of 0.01 to 0.1.

[0044] Those skilled in the art will understand that, since lithium ions, boron ions, and tungsten ions have valences of +1, +3, and +6, respectively, the molar ratio of Li, B, W, and S in the pre-formulated raw material can be adjusted to 9-3x:19-x:x:33.

[0045] Those skilled in the art will understand that in step S1, a variety of reagents containing at least one of Li, B, and S can be mixed to form the pre-prepared raw material, and the molar ratio of Li, B, and S in the pre-prepared raw material can be controlled by adjusting the mixing ratio of the reagents.

[0046] Those skilled in the art will understand that in step S2, ball milling can thoroughly grind the pre-prepared raw material, resulting in a more uniform distribution of Li, B, W, and S elements. The grinding before ball milling is to first reduce the particle size of the pre-prepared raw material to ensure the ball milling effect.

[0047] Those skilled in the art will understand that in step S3, pressing the powder into sheets is to reduce the particle distance in the preform, making them easier to mix during heat treatment; simultaneously, the subsequently obtained tungsten-doped Li9B 19 S 33 It is also a sheet material, and sheets have easily measurable area and thickness, which is beneficial for subsequent calculations after electrochemical testing.

[0048] This application obtains tungsten-doped Li9B by adjusting the molar ratio of Li, B, W, and S in the pre-prepared raw material to 9-3x:19-x:x:33, followed by grinding and ball milling of the pre-prepared raw material and then performing solid-state synthesis at high temperature. 19 S 33 Its conductivity can reach 0.53 mS / cm, which is higher than that of Li9B. 19 S 33 The crystal structure was significantly improved.

[0049] In some embodiments of this application, the heat treatment of the preform, including holding it at a predetermined temperature for a predetermined time, includes the following steps:

[0050] S41: The preform is heated to 650-750°C, and then cooled to the predetermined temperature and maintained for a predetermined time, wherein the predetermined temperature is 450-550°C.

[0051] In step S41, this application first heats the preform to 650-750°C, then cools it to 450-550°C and holds it thereafter. Currently, the general method for preparing Li-BS crystal materials in this field is to heat the pressed sheet (corresponding to the preform described in this application) to approximately 700°C, hold it at that temperature for solid-state synthesis, and then cool it to obtain the Li-BS crystal material. The problem with this preparation method is that the material electrode is prone to cracking, and the material sheet is too brittle and easily broken. This application first heats the preform to approximately 700°C, i.e., 650-750°C, then cools it to approximately 500°C, i.e., 450-550°C and holds it therefore for solid-state synthesis. This technique prevents cracks from appearing on the surface of the material electrode and makes it less prone to breakage.

[0052] In some embodiments of this application, the pre-formulated raw materials include LiS, elemental B, elemental W, and elemental S.

[0053] Those skilled in the art will understand that Li2S, elemental B, elemental W, and elemental S are common raw materials, and their proportions are easy to adjust.

[0054] In some embodiments of this application, the step of ball milling the pre-prepared raw material after grinding includes the following steps:

[0055] S21: Add the first number of large zirconia grinding balls and the second number of small zirconia grinding balls to the planetary ball mill;

[0056] S22: Add the ground pre-prepared raw material to the planetary ball mill for ball milling.

[0057] The large zirconia spheres have a mass of 2-5g, and the small zirconia spheres have a mass of 0.5-1.5g.

[0058] In some embodiments of this application, the first quantity is 8-12;

[0059] The second quantity is 8-12;

[0060] The pre-ground raw material is added to the planetary ball mill, wherein 1-3g of the pre-ground raw material is taken.

[0061] In some embodiments of this application, the planetary ball mill rotates at a speed of 250-350 r / min and the milling time is not less than 15 h.

[0062] The beneficial effect of using a planetary ball mill at a speed of 250-350 r / min is that it can make the precursor powder particles finer and more uniform in size. A ball milling time of no less than 15 hours ensures that the pre-processed raw materials are fully ball-milled.

[0063] In some embodiments of this application, the powder is pressed into sheets by cold pressing.

[0064] The advantages of cold pressing are that the surface quality of the material electrode is high and the compaction density of the material sheet can be increased.

[0065] In some embodiments of this application, the pressure of the cold pressing is 1-1.3 kPa.

[0066] The advantages of controlling the pressure of cold pressing to 1-1.3 kPa are that it can save time and cost and achieve good compaction effect.

[0067] In some embodiments of this application, the heating rate of the preform during the heating process is 1.5-2.5℃ / min.

[0068] The beneficial effect of the preform heating rate of 1.5-2.5℃ / min is that the preform is heated more uniformly and the phase transformation is more stable when it melts at high temperature.

[0069] In some embodiments of this application, the cooling rate of the preform during the cooling process is 4.5-5.5℃ / min.

[0070] The beneficial effect of a preform cooling rate of 4.5-5.5℃ / min is that it helps maintain the shape of the material electrode and prevents cracks from appearing.

[0071] In some embodiments of this application, the predetermined time is not less than 11 hours.

[0072] The advantage of setting a time of not less than 11 hours is that it allows the solid-phase synthesis reaction to proceed fully.

[0073] The present application is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0074] Example 1

[0075] This embodiment provides a tungsten-doped Li9B 19 S 33 The preparation method includes the following steps:

[0076] Sa: Provide pre-formed raw materials, which include LiS, elemental B, elemental W, and elemental S, and adjust the molar ratio of Li, B, W, and S in the pre-formed raw materials to be 9-3x:19-x:x:33;

[0077] Sb: Manually grind the pre-prepared raw materials in a mortar and pestle for 5 hours until the color is uniform and there is no grainy texture;

[0078] Sc: Add 10 large zirconia balls (3.0g each) and 10 small zirconia balls (1.0g each) for a total of 40g of grinding balls into the ball mill jar; add 2.0g of the ground pre-made raw material into the ball mill jar, and ball mill it for 20 hours at a rotation speed of 400r / min using a planetary ball mill to obtain powder.

[0079] Sd: The powder is cold-pressed at 1.2 kPa to obtain a preform;

[0080] Se: The preform was placed into a graphite crucible, which was then placed into a quartz glass tube. The tube was sealed under vacuum, and the material was synthesized using a muffle furnace solid-state melting method. The program was set to heat to 700°C at a rate of 1°C / min, cool to 500°C at a rate of 5°C / min, hold for 12 hours, and finally cool naturally to room temperature to obtain tungsten-doped Li9B. 19 S 33 .

[0081] Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 With x = 0.01, the tungsten-doped Li9B was tested and found to be... 19 S 33 Its ionic conductivity is 0.34 mS / cm.

[0082] Example 2

[0083] The only difference between this embodiment and Embodiment 1 is that x is 0.05, and the tungsten-doped Li9B was tested and obtained. 19 S 33 Its ionic conductivity is 0.53 mS / cm. Details are as follows:

[0084] This embodiment provides a tungsten-doped Li9B 19 S 33 The preparation method includes the following steps:

[0085] Sa: Provide pre-formed raw materials, which include LiS, elemental B, elemental W, and elemental S, and adjust the molar ratio of Li, B, W, and S in the pre-formed raw materials to be 9-3x:19-x:x:33;

[0086] Sb: Manually grind the pre-prepared raw materials in a mortar and pestle for 5 hours until the color is uniform and there is no grainy texture;

[0087] Sc: Add 10 large zirconia balls (3.0g each) and 10 small zirconia balls (1.0g each) for a total of 40g of grinding balls into the ball mill jar; add 2.0g of the ground pre-made raw material into the ball mill jar, and ball mill it for 20 hours at a rotation speed of 400r / min using a planetary ball mill to obtain powder.

[0088] Sd: The powder is cold-pressed at 1.2 kPa to obtain a preform;

[0089] Se: The preform was placed into a graphite crucible, which was then placed into a quartz glass tube. The tube was sealed under vacuum, and the material was synthesized using a muffle furnace solid-state melting method. The program was set to heat to 700°C at a rate of 1°C / min, cool to 500°C at a rate of 5°C / min, hold for 12 hours, and finally cool naturally to room temperature to obtain tungsten-doped Li9B. 19 S 33 .

[0090] Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 With x = 0.05, the tungsten-doped Li9B was tested and found to be... 19 S 33 Its ionic conductivity is 0.53 mS / cm.

[0091] Example 3

[0092] The only difference between this embodiment and Embodiment 1 is that x is 0.1, and the tungsten-doped Li9B was tested and obtained. 19 S 33 Its ionic conductivity is 0.41 mS / cm. Details are as follows:

[0093] This embodiment provides a tungsten-doped Li9B 19 S 33 The preparation method includes the following steps:

[0094] Sa: Provide pre-formed raw materials, which include LiS, elemental B, elemental W, and elemental S, and adjust the molar ratio of Li, B, W, and S in the pre-formed raw materials to be 9-3x:19-x:x:33;

[0095] Sb: Manually grind the pre-prepared raw materials in a mortar and pestle for 5 hours until the color is uniform and there is no grainy texture;

[0096] Sc: Add 10 large zirconia balls (3.0g each) and 10 small zirconia balls (1.0g each) for a total of 40g of grinding balls into the ball mill jar; add 2.0g of the ground pre-made raw material into the ball mill jar, and ball mill it for 20 hours at a rotation speed of 400r / min using a planetary ball mill to obtain powder.

[0097] Sd: The powder is cold-pressed at 1.2 kPa to obtain a preform;

[0098] Se: The preform was placed into a graphite crucible, which was then placed into a quartz glass tube. The tube was sealed under vacuum, and the material was synthesized using a muffle furnace solid-state melting method. The program was set to heat to 700°C at a rate of 1°C / min, cool to 500°C at a rate of 5°C / min, hold for 12 hours, and finally cool naturally to room temperature to obtain tungsten-doped Li9B. 19 S 33 .

[0099] Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 With x = 0.01, the tungsten-doped Li9B was tested and found to be... 19 S 33 Its ionic conductivity is 0.41 mS / cm.

[0100] Comparative Example

[0101] The only difference between this comparative example and Example 1 is that:

[0102] Step Sa is as follows: Li2S, elemental B, and elemental S are mixed in a molar ratio of 9:38:57 to obtain a pre-prepared raw material. The molar ratio of Li, B, and S in the pre-prepared raw material is 9:19:33.

[0103] The Li9B obtained in this comparative example 19 S 33The ionic conductivity of the crystal is 0.25 mS / cm.

[0104] Relevant experimental and effect data:

[0105] Examples 1-3 all incorporated W doping, while the comparative example did not, and all other implementation conditions were identical between Examples 1-3 and the comparative example. Ionic conductivity tests showed that the ionic conductivity of Examples 1-3 ranged from 0.34 to 0.53 mS / cm, significantly higher than the 0.25 mS / cm of the comparative example. This indicates that W doping effectively improves the conductivity of Li9B. 19 S 33 The ionic conductivity of a crystal.

[0106] The products obtained in Examples 1-3 and the comparative examples were characterized by X-ray diffraction (XRD) to analyze the phase composition of the sintered material electrodes in order to determine the target product synthesized. Figure 1 Tungsten-doped Li9B obtained in Examples 1-3 are shown. 19 S 33 XRD pattern of tungsten-doped Li9B. 19 S 33 The standard characteristic peaks of the XRD pattern of Li9B 19 S 33 The results are largely consistent, indicating that the small amount of tungsten doping did not damage Li9B. 19 S 33 The microcrystalline structure of Li9B was observed. Furthermore, with increasing tungsten doping concentration, the characteristic peak at 40° gradually increased, further demonstrating the successful doping of tungsten. These results confirm the successful doping of tungsten-doped Li9B. 19 S 33 Successful preparation of the electrode sheet.

[0107] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0108] In this application, unless otherwise stated, directional terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. Furthermore, in the description of this application, the terms "comprising," "including," etc., mean "including but not limited to." Moreover, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between related objects, indicating that three relationships can exist; for example, A and / or B can represent: A alone, A and B simultaneously, or B alone. For associations involving three or more related objects described using "and / or", it indicates that any one of the three related objects can exist alone, or at least two of them can exist simultaneously. For example, for A, and / or B, and / or C, it can mean that any one of A, B, and C exists alone, or any two of them exist simultaneously, or all three of them exist simultaneously. In this document, "at least one" means one or more, and "more than one" means two or more. "At least one", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or multiple.

[0109] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A tungsten-doped Li9B 19 S 33 The preparation method of the [method] is characterized by, The tungsten-doped Li9B 19 S 33 The preparation method includes the following steps: Provide a pre-formulated raw material containing only Li, B, W, and S elements, and adjust the molar ratio of Li, B, W, and S in the pre-formulated raw material to 9-3x:19-x:x:33; The pre-prepared raw materials are ground and then ball-milled to obtain powder. The powder is pressed into sheets to obtain preformed sheets; The preform was heated to 650-750°C, then cooled to 450-550°C and maintained for 12 hours before being cooled again to obtain the tungsten-doped Li9B. 19 S 33 , Among them, the tungsten-doped Li9B 19 S 33 The stoichiometric formula is Li 9-3x B 19-x W x S 33 , x is a value in the range of 0.01 to 0.1; During the heating process, the heating rate of the preform is 1.5-2.5℃ / min; During the cooling process, the cooling rate of the preform is 4.5-5.5℃ / min.

2. The tungsten-doped Li9B according to claim 1 19 S 33 The preparation method of the [method] is characterized by, The process of grinding the pre-prepared raw materials followed by ball milling includes the following steps: Add a first number of large zirconia grinding balls and a second number of small zirconia grinding balls to the planetary ball mill; The ground pre-formulated raw material is added to the planetary ball mill for ball milling. The large zirconia spheres have a mass of 2-5 g, and the small zirconia spheres have a mass of 0.5-1.5 g.

3. The tungsten-doped Li9B according to claim 2 19 S 33 The preparation method of the [method] is characterized by, The first quantity is 8-12; The second quantity is 8-12; The pre-ground raw material is added to the planetary ball mill, wherein 1-3g of the pre-ground raw material is taken.

4. The tungsten-doped Li9B according to claim 3 19 S 33 The preparation method of the [method] is characterized by, The planetary ball mill rotates at a speed of 250-350 r / min, and the milling time is not less than 15 h.

5. The tungsten-doped Li9B according to claim 1 19 S 33 The preparation method of the [method] is characterized by, The powder is pressed into sheets by cold pressing.

6. The tungsten-doped Li9B according to claim 5 19 S 33 The preparation method of the [method] is characterized by, The pressure of the cold press is 1-1.3 kPa.

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