Chlorine oxide solid electrolyte as well as preparation method and application thereof

Abstract

The embodiment of the invention relates to an oxychloride solid electrolyte as well as a preparation method and application thereof, and the preparation method comprises the following steps: determining the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride according to the stoichiometric ratio of Li < 2.5-x > ZrC < 5.5-x > O < 0.5 > (0 < = x < = 0.75), performing batching, performing uniform mixing, and performing pretreatment to obtain a first mixture, a second mixture and a third mixture; the first mixture, the second mixture and the third mixture are subjected to first-time ball milling treatment in a ball milling tank, and intermediate products Li4ZrCl4O2, Li ZrCl5 and Li2ZrCl6 are obtained; uniformly mixing the intermediate products Li4ZrC l4O2, Li ZrC l5 and Li2ZrC l6 according to a preset proportion, and carrying out second ball milling treatment in the ball milling tank to obtain an oxychloride solid electrolyte precursor; and sintering the oxychloride solid electrolyte precursor to obtain the oxychloride solid electrolyte.

Description

Technical Field

[0001] This invention relates to the field of materials technology, and in particular to a chlorine oxide solid electrolyte, its preparation method, and its application. Background Technology

[0002] Lithium-ion batteries are widely used in industrial manufacturing and daily life due to their high energy density and high output power. However, traditional liquid lithium-ion batteries pose safety hazards such as flammability and explosiveness, causing significant risks to human health and safety. All-solid-state lithium-ion batteries can significantly improve battery safety performance and solve the flammability and explosiveness problems of liquid batteries.

[0003] Solid-state electrolytes are a crucial component of all-solid-state lithium-ion batteries. Among various solid-state electrolytes, halide electrolytes have attracted widespread attention due to their excellent physicochemical properties, such as high ionic conductivity, wide electrochemical window, and low interfacial impedance. However, some halides, such as bromides and iodides, require demanding preparation conditions, and their ionic conductivity is not as high as that of chlorides. Although the ionic conductivity of Li₂ZrCl₆ in chloride solid-state electrolytes is 0.2 × 10⁻⁶ at room temperature... -3 ~0.4×10 - 3 mS·cm -1 However, to promote its application in all-solid-state lithium batteries, its conductivity needs to be further improved. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by providing a chlorine oxide solid electrolyte, its preparation method, and its application. The preparation method is simple, has good reaction stability, and the prepared chlorine oxide solid electrolyte has high ionic conductivity.

[0005] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing a chlorine oxide solid electrolyte, the method comprising:

[0006] According to Li 2.5-x ZrC l 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio, determine the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride, mix them and then pre-treat them to obtain the first mixture, the second mixture and the third mixture;

[0007] The first mixture, the second mixture, and the third mixture were respectively subjected to a first ball milling process in a ball mill jar to obtain intermediate products Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6.

[0008] After the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 are mixed in a preset ratio, they are subjected to a second ball milling process in the ball mill jar to obtain the chloride oxide solid electrolyte precursor.

[0009] The chlorine oxide solid electrolyte precursor is sintered to obtain the chlorine oxide solid electrolyte.

[0010] Preferably, the preset ratio is 0.25:0.75-b:b, where 0≤b≤0.75.

[0011] Preferably, the method based on Li 2.5-x ZrC l 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio: Determine the stoichiometric ratio of zirconium tetrachloride, lithium oxide, and anhydrous lithium chloride for batching, specifically including:

[0012] According to Li 2.5-x ZrC l 5.5-x O 0.5 Determine the stoichiometric ratio of the intermediate product by using the stoichiometric ratio of (0≤x≤0.75).

[0013] Based on the stoichiometric ratio of the intermediate products, the stoichiometric ratio of zirconium tetrachloride, lithium oxide, and anhydrous lithium chloride is determined for batching.

[0014] Preferably, the pretreatment includes grinding and drying;

[0015] The grinding process specifically involves placing the raw material in a mortar and grinding it for 1 to 3 hours under an inert atmosphere.

[0016] The drying process specifically involves drying in a vacuum drying oven at 100℃-150℃ for 2-4 hours.

[0017] Preferably, the size of the zirconium balls in the first ball milling treatment is 3mm-10mm; the ball-to-material mass ratio is M:1, where 4≤M≤20.

[0018] Preferably, the first ball milling process is performed at a rotation speed of 200 r / min to 2400 r / min for a duration of 5 to 70 hours.

[0019] Preferably, the sintering temperature is 200℃-400℃ and the time is 2 hours-12 hours.

[0020] Preferably, the atmosphere of the ball mill jar is any one of a vacuum atmosphere, a nitrogen atmosphere, or an argon atmosphere.

[0021] In a second aspect, the present invention provides a chlorine oxide solid electrolyte, which is prepared by any of the preparation methods described in the first aspect above.

[0022] Thirdly, the present invention provides a lithium-ion battery, wherein the lithium-ion battery includes the chlorine oxide solid electrolyte described in the second aspect above.

[0023] This invention provides a method for preparing a chloride-based solid electrolyte. The method involves determining the stoichiometric ratio of raw materials based on the stoichiometric ratio of the target product. Different raw materials are mixed separately, followed by a first ball milling process to obtain oxygen-doped and oxygen-free intermediate products. These intermediate products are then mixed in a predetermined ratio and subjected to a second ball milling process, which alters the crystal structure and generates more amorphous chloride-based solid electrolyte precursors. Finally, the chloride-based solid electrolyte precursors are sintered at low temperature to obtain a chloride-based solid electrolyte with high ionic conductivity. This preparation method is simple, exhibits good reaction stability, and has low material costs. Attached Figure Description

[0024] Figure 1 A flowchart illustrating a method for preparing a chlorine oxide solid electrolyte according to an embodiment of the present invention;

[0025] Figure 2 XRD patterns of chlorine oxide solid electrolytes prepared in Example 1 and Comparative Example 1 of this invention. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0027] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0028] This invention provides a method for preparing a chlorine oxide solid electrolyte, the process of which is as follows: Figure 1 As shown, it includes the following steps:

[0029] Step 110, according to Li 2.5-x ZrC l 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio, determine the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride, mix them and then pre-treat them to obtain the first mixture, the second mixture and the third mixture;

[0030] Specifically, the purity of zirconium tetrachloride, lithium oxide, and anhydrous lithium chloride is not less than 99.9 wt%. The first mixture includes zirconium tetrachloride and lithium oxide. The second and third mixtures both include zirconium tetrachloride and anhydrous lithium chloride. Pretreatment may specifically include two steps: grinding and drying. Grinding mainly involves further mixing the raw materials, which can be achieved using an agate mortar. The raw materials are placed in the mortar, which is then placed in a glove box. An inert gas is then introduced into the glove box to create an inert atmosphere. The inert atmosphere can be nitrogen and / or argon. The grinding time can be 1-3 hours, preferably 2 hours. Drying can be carried out in a vacuum drying oven to remove moisture from the raw materials and prevent hydrolysis and deterioration. The drying temperature can be 100℃-150℃, preferably 120℃, and the time can be 2-4 hours, preferably 3 hours.

[0031] More specifically, firstly, according to Li 2.5-x ZrC l 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio, used to determine the stoichiometric ratio of intermediate products. Specifically, the intermediate products include Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6. The stoichiometric ratio of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 is 0.25:(0.75-b):b, where 0≤b≤0.75. This stoichiometric ratio can serve as a preset range for selecting the mixing ratio of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 in subsequent processes.

[0032] Secondly, the stoichiometric ratios of each raw material are determined based on the stoichiometric ratios of the intermediate products, and the ingredients are then formulated. The stoichiometric ratio of each raw material can be understood as the stoichiometric ratio of each raw material in the mixture used to synthesize each intermediate product. For example, in the synthesis of Li₄ZrCl₄O₂, the stoichiometric ratio of zirconium tetrachloride to lithium oxide in the first mixture; in the synthesis of LiZrCl₅, the stoichiometric ratio of zirconium tetrachloride to anhydrous lithium chloride in the second mixture; and in the synthesis of Li₂ZrCl₆, the stoichiometric ratio of zirconium tetrachloride to anhydrous lithium chloride in the third mixture.

[0033] As an optional step, the lithium source can be in excess of 1%-10%, preferably 5%. Specifically, the excess lithium source can be selected from lithium oxide, anhydrous lithium chloride, anhydrous lithium hydroxide, lithium hydride, and lithium sheets. For example, to obtain a first mixture, an excess of anhydrous lithium hydroxide and / or lithium oxide can be added. To obtain a second or third mixture, an excess of lithium hydride and / or lithium sheets and / or anhydrous lithium chloride can be added.

[0034] Step 120: The first mixture, the second mixture, and the third mixture are subjected to a first ball milling process in a ball mill jar to obtain intermediate products Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6.

[0035] Specifically, the atmosphere in the ball mill jar is any one of vacuum, nitrogen, or argon. The size of the zirconium balls used in the first ball milling treatment can be 3mm-10mm, preferably 5mm. The ball-to-material mass ratio is M:1, where 4≤M≤20, preferably 2≤M≤4. The rotational speed of the first ball milling treatment is 200r / min-2400r / min, preferably 400r / min-1600r / min, and the time is 5 hours-70 hours, preferably 10 hours-40 hours. The purpose of the first ball milling is mainly to obtain chlorides and oxygen-doped chlorides.

[0036] Step 130: After mixing the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 in a preset ratio, they are subjected to a second ball milling process in a ball mill jar to obtain the chloride oxide solid electrolyte precursor.

[0037] Specifically, the preset ratio can be selected from the stoichiometric ratio of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 in step 110. The size of the zirconium balls for the first ball milling treatment can be 3mm-10mm, preferably 5mm. The ball-to-material mass ratio is M:1, where 4≤M≤20, preferably M=4. The rotation speed of the first ball milling treatment is 200r / min-2400r / min, preferably 1200r / min, and the time is 5 hours-70 hours, preferably 20 hours.

[0038] During the secondary ball milling process, by rationally proportioning Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6, the ratio of lithium cations to anions is controlled, increasing the lithium content and creating more anion vacancies. Simultaneously, the P-3m1 space group structure of LiZrCl5 and Li2ZrCl6 and the C2 / m structure of Li4ZrCl4O2 undergo structural changes due to mechanical stress, resulting in the generation of more amorphous phases. The generation of amorphous phases has the following advantages: the disordered atomic arrangement of amorphous phases provides more transport channels and shorter transport paths for ions, thereby reducing the migration resistance of ions in the material. Amorphous materials typically have a higher point defect concentration, which can act as ion transport carriers, increasing ion mobility. The interface between the amorphous phase and the electrode material is usually more uniform, which helps reduce interfacial resistance, thereby improving the overall ion transport efficiency.

[0039] Step 140: Sinter the chlorine oxide solid electrolyte precursor to obtain the chlorine oxide solid electrolyte.

[0040] Specifically, the sintering crucible can be any one of corundum crucible, quartz crucible, or platinum crucible. Sintering can be carried out in a tube furnace under a nitrogen atmosphere and / or an argon atmosphere. The sintering temperature can be 200℃-400℃, preferably 300℃, and the sintering time can be 2 hours-12 hours, preferably 8 hours-10 hours.

[0041] Sintering makes the product denser, further improving ionic conductivity and also helps to improve the overall performance and mechanical strength of the material.

[0042] This invention provides a method for preparing a chloride-based solid electrolyte. The method involves determining the stoichiometric ratio of raw materials based on the stoichiometric ratio of the target product. Different raw materials are mixed separately, followed by a first ball milling process to obtain oxygen-doped and oxygen-free intermediate products. These intermediate products are then mixed in a predetermined ratio and subjected to a second ball milling process, which alters the crystal structure and generates more amorphous chloride-based solid electrolyte precursors. Finally, the chloride-based solid electrolyte precursors are sintered at low temperature to obtain a chloride-based solid electrolyte with high ionic conductivity. This preparation method is simple, exhibits good reaction stability, and has low material costs.

[0043] The chlorine oxide solid electrolyte provided by this invention can be used as an electrode material in energy storage devices such as supercapacitors, lithium-ion batteries, sodium-ion batteries, dye-sensitized batteries, and solid-state batteries.

[0044] To better understand the technical solution provided by the present invention, the following uses several specific examples to illustrate the specific process of preparing chlorine oxide solid electrolytes using the method provided in the above embodiments of the present invention, as well as the electrochemical characteristics of the prepared chlorine oxide solid electrolytes.

[0045] Example 1

[0046] The first step, according to Li 1.75 ZrC l 4.75 O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0.75:0.

[0047] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2 as 2:1, and to determine the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of LiZrCl5 as 1:1.

[0048] Thirdly, according to the above stoichiometric ratio, 6g of Li₂O and 23.3g of ZrCl₄ were taken, and 5wt% excess anhydrous lithium hydroxide was added and mixed well. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the first mixture. Next, 23.3g of ZrCl₄ and 4.3g of LiCl₄ were taken, and 5wt% excess lithium hydride was added and mixed well. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the second mixture.

[0049] Fourth, according to a ball-to-material ratio of 2:1, 10mm zirconium balls and the first mixture were placed in a vacuum ball mill jar, and the jar was placed in a planetary ball mill. The milling speed was set to 400 r / min, and the mixture was milled for 5 hours to obtain the intermediate product Li₄ZrCl₄O₂. According to a ball-to-material ratio of 2:1, 10mm zirconium balls and the second mixture were placed in a vacuum ball mill jar, and the jar was placed in a planetary ball mill. The milling speed was set to 400 r / min, and the mixture was milled for 5 hours to obtain the intermediate product LiZrCl₅.

[0050] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 10 mm and the mixed intermediate products were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the ball milling speed was set to 400 r / min. The mixture was ball milled again for 5 hours to obtain the chloride oxide solid electrolyte precursor.

[0051] Step 6: Place the chlorine oxide solid electrolyte precursor in an alumina crucible, and place the alumina crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 2 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0052] Subsequently, the conductivity and XRD tests of the prepared oxide chloride solid electrolyte were performed, as detailed below:

[0053] Conductivity test: Open the solid electrolyte test mold, remove the column from the PEEK sleeve (sleeve diameter is 10mm), place Li-In as the negative electrode, put 0.6g of the prepared oxychloride solid electrolyte into the sleeve, and then place LiNi. 0.8 Mn 0.1 Co 0.1The O2 positive electrode was then placed, and the upper column was returned to its original position and pressed firmly. The test mold was placed in the pressure mold and placed under a press. The press pressure was 5-15t, and the pressure was kept constant. The pressure mold bolts were tightened, and the press pressure was released. The positive and negative electrodes on the solid electrolyte mold were aligned with the positive and negative electrodes on the test equipment. The conductivity was tested using an electrochemical workstation and a blue electric test system. The test results are shown in Table 1.

[0054] XRD Test: Place the sample stage in the glove box, place the sample in the center of the sample stage, and ensure the sample surface is flat. Cover the sample with a section of Mylar film, and secure the sample stage with clips to create a sealed environment. Place the sample stage in the X-ray diffractometer stage, set the scanning angle to 10°-80°, and the scanning speed to 8° / min. Results are as follows: Figure 2 As shown in the diagram, the LZCO peak represents the sample peak, and the Mylar membrane peak represents the Mylar membrane peak.

[0055] Example 2

[0056] The first step, according to Li2ZrCl5O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0.5:0.25.

[0057] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2 as 2:1, the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of LiZrCl5 as 1:1, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6 as 2:1.

[0058] Thirdly, according to the above stoichiometric ratio, 6g of Li₂O and 23.3g of ZrCl₄ were taken, and 5wt% excess anhydrous lithium hydroxide was added and mixed. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the first mixture. Next, 23.3g of ZrCl₄ and 4.3g of LiCl₄ were taken, and 5wt% excess lithium hydride was added and mixed. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the second mixture. Finally, 23.3g of ZrCl₄ and 8.5g of LiCl₄ were taken, and 5wt% excess lithium hydride was added and mixed. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the third mixture.

[0059] In the fourth step, zirconium balls of 10 mm size and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 400 r / min for 5 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls of 10 mm size and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 400 r / min for 5 hours to obtain the intermediate product LiZrCl5. Finally, zirconium balls of 10 mm size and the third mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 400 r / min for 5 hours to obtain the intermediate product Li2ZrCl6.

[0060] Fifth, the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 were mixed in a ratio of 0.25:0.5:0.25. Then, 10 mm zirconium balls and the mixed intermediate products were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the ball milling speed was set to 400 r / min. The mixture was ball milled again for 5 hours to obtain the chloride oxide solid electrolyte precursor.

[0061] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 2 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0062] The conductivity test process is the same as in Example 1.

[0063] Example 3

[0064] The first step, according to Li 2.25 ZrC l 5.25 O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0.25:0.5.

[0065] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2 as 2:1, the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of LiZrCl5 as 1:1, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6 as 2:1.

[0066] Steps three and four are the same as in Example 1.

[0067] Fifth, the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 were mixed in a ratio of 0.25:0.25:0.5. Then, 10 mm zirconium balls and the mixed intermediate products were placed in a vacuum ball mill jar at a ball-to-material ratio of 2:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the ball milling speed was set to 400 r / min. The mixture was ball milled again for 5 hours to obtain the chloride oxide solid electrolyte precursor.

[0068] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 2 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0069] The conductivity test process is the same as in Example 1.

[0070] Example 4

[0071] The first step, according to Li 2.5 ZrC l 5.5 O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0:0.5.

[0072] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6.

[0073] Thirdly, according to the above stoichiometric ratio, 6g of Li₂O and 23.3g of ZrCl₄ were taken, and 5wt% excess lithium oxide was added and mixed. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the first mixture. Next, 23.3g of ZrCl₄ and 8.5g of LiCl₄ were taken, and 5wt% excess lithium oxide was added and mixed. The mixture was then ground in an agate mortar for 2 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 120°C for 3 hours to obtain the third mixture.

[0074] Fourth, according to a ball-to-material ratio of 2:1, 10mm zirconium balls and the first mixture were placed in a vacuum ball mill jar, and the jar was placed in a planetary ball mill. The milling speed was set to 400 r / min, and the mixture was milled for 5 hours to obtain the intermediate product Li4ZrCl4O2. According to a ball-to-material ratio of 2:1, 10mm zirconium balls and the third mixture were placed in a vacuum ball mill jar, and the jar was placed in a planetary ball mill. The milling speed was set to 400 r / min, and the mixture was milled for 5 hours to obtain the intermediate product Li2ZrCl6.

[0075] Fifth, the intermediate products Li4ZrCl4O2 and Li2ZrCl6 were mixed in a ratio of 0.25:0.5. Then, zirconium balls with a size of 10 mm and the mixed intermediate products were placed in a vacuum ball milling jar at a ball-to-material ratio of 2:1. The vacuum ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 400 r / min. The mixture was ball milled again for 5 hours to obtain the chloride oxide solid electrolyte precursor.

[0076] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 2 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0077] The conductivity test process is the same as in Example 1.

[0078] Example 5

[0079] Steps one through three are the same as in Example 1.

[0080] In the fourth step, zirconium balls with a size of 5 mm and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 800 r / min for 10 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls with a size of 5 mm and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 800 r / min for 10 hours to obtain the intermediate product LiZrCl5.

[0081] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 5 mm and the mixed intermediate products were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the ball milling speed was set to 800 r / min. The mixture was ball milled again for 10 hours to obtain the chloride oxide solid electrolyte precursor.

[0082] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 10 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0083] The conductivity test process is the same as in Example 1.

[0084] Example 6

[0085] Steps one through three are the same as in Example 1.

[0086] In the fourth step, zirconium balls with a size of 5 mm and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 1200 r / min for 20 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls with a size of 5 mm and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 1200 r / min for 20 hours to obtain the intermediate product LiZrCl5.

[0087] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 5 mm and the mixed intermediate products were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the ball milling speed was set to 1200 r / min. The mixture was ball milled again for 20 hours to obtain the chloride oxide solid electrolyte precursor.

[0088] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 10 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0089] The conductivity test process is the same as in Example 1.

[0090] Example 7

[0091] Steps one through three are the same as in Example 1.

[0092] In the fourth step, zirconium balls with a size of 5 mm and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 1600 r / min for 30 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls with a size of 5 mm and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 1600 r / min for 30 hours to obtain the intermediate product LiZrCl5.

[0093] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 5 mm and the mixed intermediate products were placed in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The vacuum ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 1600 r / min. The mixture was ball milled again for 30 hours to obtain the chloride oxide solid electrolyte precursor.

[0094] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 10 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0095] The conductivity test process is the same as in Example 1.

[0096] Example 8

[0097] Steps one through three are the same as in Example 1.

[0098] In the fourth step, zirconium balls with a size of 5 mm and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2000 r / min for 40 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls with a size of 5 mm and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2000 r / min for 40 hours to obtain the intermediate product LiZrCl5.

[0099] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 5 mm and the mixed intermediate products were placed in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The vacuum ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 2000 r / min. The mixture was ball milled again for 40 hours to obtain the chloride oxide solid electrolyte precursor.

[0100] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 10 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0101] The conductivity test process is the same as in Example 1.

[0102] Example 9

[0103] The first step, according to Li 2.05 ZrC l 5.05 O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0.45:0.3.

[0104] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2 as 2:1, the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of LiZrCl5 as 1:1, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6 as 2:1.

[0105] Thirdly, according to the above stoichiometric ratio, 6g of Li₂O and 23.3g of ZrCl₄ were taken, and 1wt% excess lithium oxide was added and mixed. The mixture was then ground in an agate mortar for 1 hour under an argon atmosphere, and dried in a vacuum drying oven at 100°C for 4 hours to obtain the first mixture. Next, 23.3g of ZrCl₄ and 4.3g of LiCl were taken, and 3wt% excess lithium hydride was added and mixed. The mixture was then ground in an agate mortar for 1 hour under an argon atmosphere, and dried in a vacuum drying oven at 100°C for 4 hours to obtain the second mixture. Finally, 23.3g of ZrCl₄ and 8.5g of LiCl were taken, and 5wt% excess anhydrous lithium chloride was added and mixed. The mixture was then ground in an agate mortar for 1 hour under an argon atmosphere, and dried in a vacuum drying oven at 100°C for 4 hours to obtain the third mixture.

[0106] In the fourth step, zirconium balls with a size of 3 mm and the first mixture were placed in a nitrogen atmosphere ball mill jar at a ball-to-material ratio of 20:1. The nitrogen atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 200 r / min for 70 hours to obtain the intermediate product Li4ZrCl4O2. Following the same ball-to-material ratio, zirconium balls with a size of 3 mm and the second mixture were placed in a nitrogen atmosphere ball mill jar at a ball-to-material ratio of 20:1. The nitrogen atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 200 r / min for 70 hours to obtain the intermediate product LiZrCl5. Finally, zirconium balls with a size of 3 mm and the third mixture were placed in a nitrogen atmosphere ball mill jar at a ball-to-material ratio of 20:1. The nitrogen atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 200 r / min for 70 hours to obtain the intermediate product Li2ZrCl6.

[0107] Fifth, the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 were mixed in a ratio of 0.25:0.45:0.3. Then, zirconium balls with a size of 6 mm and the mixed intermediate products were placed in a nitrogen atmosphere ball milling jar at a ball-to-material ratio of 15:1. The nitrogen atmosphere ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 2400 r / min. The mixture was ball milled again for 5 hours to obtain the chloride oxide solid electrolyte precursor.

[0108] Step 6: Place the chlorine oxide solid electrolyte precursor in a quartz crucible, and place the quartz crucible in a tube furnace under an argon atmosphere. Sinter at 200°C for 12 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0109] Example 10

[0110] The first step, according to Li 2.35 ZrC l 5.35 O 0.5 The stoichiometric ratios of Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6 were determined to be 0.25:0.15:0.6.

[0111] The second step is to determine the ratio of Li2O to ZrCl4 based on the stoichiometric ratio of Li4ZrCl4O2 as 2:1, the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of LiZrCl5 as 1:1, and the ratio of LiCl to ZrCl4 based on the stoichiometric ratio of Li2ZrCl6 as 2:1.

[0112] Thirdly, according to the above stoichiometric ratio, 6g of Li₂O and 23.3g of ZrCl₄ were taken, and 7wt% excess anhydrous lithium hydroxide was added and mixed. The mixture was then ground in an agate mortar for 3 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 150°C for 2 hours to obtain the first mixture. Next, 23.3g of ZrCl₄ and 4.3g of LiCl were taken, and 4wt% excess lithium was added and mixed. The mixture was then ground in an agate mortar for 3 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 150°C for 2 hours to obtain the second mixture. Finally, 23.3g of ZrCl₄ and 8.5g of LiCl were taken, and 8wt% excess lithium hydride was added and mixed. The mixture was then ground in an agate mortar for 3 hours under a nitrogen atmosphere, and subsequently dried in a vacuum drying oven at 150°C for 2 hours to obtain the third mixture.

[0113] In the fourth step, zirconium balls with a size of 4 mm and the first mixture were placed in an argon atmosphere ball mill jar at a ball-to-material ratio of 10:1. The argon atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2400 r / min for 5 hours to obtain the intermediate product Li4ZrCl4O2. Following the same ball-to-material ratio, zirconium balls with a size of 4 mm and the second mixture were placed in an argon atmosphere ball mill jar at a ball-to-material ratio of 10:1. The argon atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2400 r / min for 50 hours to obtain the intermediate product LiZrCl5. Finally, zirconium balls with a size of 4 mm and the third mixture were placed in an argon atmosphere ball mill jar at a ball-to-material ratio of 10:1. The argon atmosphere ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2400 r / min for 5 hours to obtain the intermediate product Li2ZrCl6.

[0114] Fifth, the intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 were mixed in a ratio of 0.25:0.15:0.6. Then, zirconium balls with a size of 18 mm and the mixed intermediate products were placed in an argon atmosphere ball milling jar at a ball-to-material ratio of 8:1. The argon atmosphere ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 800 r / min. The mixture was ball milled again for 30 hours to obtain the chloride oxide solid electrolyte precursor.

[0115] Step 6: Place the chlorine oxide solid electrolyte precursor in a platinum crucible, and place the platinum crucible in a tube furnace under an argon atmosphere. Sinter at 400°C for 8 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0116] Example 11

[0117] Steps one through three are the same as in Example 1.

[0118] In the fourth step, zirconium balls with a size of 5 mm and the first mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2400 r / min for 50 hours to obtain the intermediate product Li4ZrCl4O2. Similarly, zirconium balls with a size of 5 mm and the second mixture were placed in a vacuum ball mill jar at a ball-to-material ratio of 4:1. The vacuum ball mill jar was then placed in a planetary ball mill, and the milling speed was set to 2400 r / min for 50 hours to obtain the intermediate product LiZrCl5.

[0119] Fifth, the intermediate products Li4ZrCl4O2 and LiZrCl5 were mixed in a ratio of 0.25:0.75. Then, zirconium balls with a size of 5 mm and the mixed intermediate products were placed in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The vacuum ball milling jar was then placed in a planetary ball mill, and the ball milling speed was set to 2400 r / min. The mixture was ball milled again for 50 hours to obtain the chloride oxide solid electrolyte precursor.

[0120] Step 6: Place the chlorine oxide solid electrolyte precursor in a corundum crucible, and place the corundum crucible in a tube furnace under an argon atmosphere. Sinter at 300°C for 10 hours, then grind and pass through a 200-mesh sieve to obtain the chlorine oxide solid electrolyte.

[0121] Comparative Example 1

[0122] The first step, according to Li 2.5 ZrC l 5.5 O 0.5 The stoichiometric ratio was determined to be 0.5:1:1.5 for Li₂O:ZrCl₄:LiCl.

[0123] The second step involves taking 1.5g of Li₂O, 23.3g of ZrCl₄ and 6.4g of LiCl according to the above stoichiometric ratio, adding 5wt% excess anhydrous lithium hydroxide and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0124] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chlorine oxide solid electrolyte precursor.

[0125] The fourth step involves placing the chlorine oxide solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chlorine oxide solid electrolyte is obtained.

[0126] The conductivity and XRD testing procedures are the same as in Example 1.

[0127] Comparative Example 2

[0128] The first step, according to Li 2.25 ZrC l 5.25 O 0.5 The stoichiometric ratio was determined to be 0.5:1:1.25 for Li₂O:ZrCl₄:LiCl.

[0129] The second step involves taking 1.5g of Li₂O, 23.3g of ZrCl₄ and 5.3g of LiCl according to the above stoichiometric ratio, adding 5wt% excess anhydrous lithium hydroxide and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0130] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chlorine oxide solid electrolyte precursor.

[0131] The fourth step involves placing the chlorine oxide solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chlorine oxide solid electrolyte is obtained.

[0132] The conductivity test process is the same as in Example 1.

[0133] Comparative Example 3

[0134] The first step, according to Li2ZrCl5O 0.5 Based on the stoichiometric ratio, the ratio of Li₂O:ZrCl₄:LiCl is determined to be 0.5:1:1.

[0135] The second step involves taking 1.5g of Li₂O, 23.3g of ZrCl₄ and 4.3g of LiCl according to the above stoichiometric ratio, adding 5wt% excess anhydrous lithium hydroxide and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0136] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chlorine oxide solid electrolyte precursor.

[0137] The fourth step involves placing the chlorine oxide solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chlorine oxide solid electrolyte is obtained.

[0138] The conductivity test process is the same as in Example 1.

[0139] Comparative Example 4

[0140] The first step, according to Li 1.75 ZrC l 4.75 O0.5 The stoichiometric ratio was determined to be 0.5:1:0.75 for Li₂O:ZrCl₄:LiCl.

[0141] The second step involves taking 1.5g of Li₂O, 23.3g of ZrCl₄ and 3.2g of LiCl according to the above stoichiometric ratio, adding 5wt% excess anhydrous lithium hydroxide and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0142] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chlorine oxide solid electrolyte precursor.

[0143] The fourth step involves placing the chlorine oxide solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chlorine oxide solid electrolyte is obtained.

[0144] The conductivity test process is the same as in Example 1.

[0145] Comparative Example 5

[0146] The first step is to determine the ZrCl4:LiCl ratio to be 1:1 based on the stoichiometric ratio of LiZrCl5.

[0147] The second step involves taking 23.3g of ZrCl4 and 4.3g of LiCl according to the above stoichiometric ratio, adding 5wt% excess lithium hydride and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0148] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chloride solid electrolyte precursor.

[0149] The fourth step involves placing the chloride solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chloride solid electrolyte is obtained.

[0150] The conductivity test process is the same as in Example 1.

[0151] Comparative Example 6

[0152] The first step is to determine the ZrCl4:LiCl ratio to be 1:2 based on the stoichiometric ratio of Li2ZrCl6.

[0153] The second step involves taking 23.3g of ZrCl4 and 8.5g of LiCl according to the above stoichiometric ratio, adding 5wt% excess anhydrous lithium chloride and mixing well. The mixture is then ground in an agate mortar for 2 hours under a nitrogen atmosphere and dried in a vacuum drying oven at 120°C for 3 hours to obtain the mixture.

[0154] The third step involves placing 5mm zirconium balls and the mixture in a vacuum ball milling jar at a ball-to-material ratio of 4:1. The jar is then placed in a planetary ball mill, and the milling speed is set to 1200 r / min. The mixture is milled for 20 hours to obtain the chloride solid electrolyte precursor.

[0155] The fourth step involves placing the chloride solid electrolyte precursor in an alumina crucible, then placing the alumina crucible in a tube furnace under an argon atmosphere and sintering it at 300°C for 10 hours. After grinding and passing it through a 200-mesh sieve, the chloride solid electrolyte is obtained.

[0156] The conductivity test process is the same as in Example 1.

[0157] Table 1 summarizes the ionic conductivity data of the solid electrolytes prepared in Examples 1-8 and Comparative Examples 1-6 of this invention.

[0158] Electrical conductivity (mS / cm) Example 1 0.21 Example 2 0.1 Example 3 0.087 Example 4 0.058 Example 5 0.5 Example 6 0.25 Example 7 0.19 Example 8 0.13 Comparative Example 1 <![CDATA[2.8×10 -2 ]]> Comparative Example 2 <![CDATA[6.7×10 -3 ]]> Comparative Example 3 <![CDATA[5.8×10 -3 ]]> Comparative Example 4 <![CDATA[4.3×10 -3 ]]> Comparative Example 5 <![CDATA[2.7×10 -4 ]]> Comparative Example 6 <![CDATA[3.3×10 -4 ]]>

[0159] Table 1

[0160] As shown in Table 1, compared with Comparative Examples 1-6, the chlorine oxide solid electrolytes prepared in Examples 1-8 of the present invention have very high conductivity. This is because the P-3m1 space point group structure of the products Li ZrCl5 and Li2ZrCl6 and the C2 / m structure of Li4ZrCl4O2, which were produced in the first ball milling, undergo structural changes due to mechanical stress during the second ball milling, resulting in more amorphous phases. The amorphous phases improve the lithium ion transport efficiency.

[0161] according to Figure 2 As can be seen, in the XRD pattern of the chlorine oxide solid electrolyte material obtained by sintering after two ball millings in Example 1, the crystal phase is complete and there are no impurity peaks. In contrast, in the XRD pattern of the chlorine oxide solid electrolyte material obtained by sintering after one ball milling in Comparative Example 1, some impurity peaks are still present in the phase.

[0162] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a chlorine oxide solid electrolyte, characterized in that, The preparation method includes: According to Li 2.5-x ZrCl 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio, determine the stoichiometric ratio of zirconium tetrachloride, lithium oxide and anhydrous lithium chloride, mix them and then pre-treat them to obtain the first mixture, the second mixture and the third mixture; The first mixture, the second mixture, and the third mixture were respectively subjected to a first ball milling process in a ball mill jar to obtain intermediate products Li4ZrCl4O2, LiZrCl5, and Li2ZrCl6. The intermediate products Li4ZrCl4O2, LiZrCl5 and Li2ZrCl6 are mixed in a preset ratio and then subjected to a second ball milling process in the ball mill jar to obtain the chlorine oxide solid electrolyte precursor. The chlorine oxide solid electrolyte precursor is sintered to obtain the chlorine oxide solid electrolyte.

2. The preparation method according to claim 1, characterized in that, The preset ratio is 0.25:0.75-b:b, where 0≤b≤0.

75.

3. The preparation method according to claim 1, characterized in that, According to Li 2.5-x ZrCl 5.5-x O 0.5 (0≤x≤0.75) Stoichiometric ratio: Determine the stoichiometric ratio of zirconium tetrachloride, lithium oxide, and anhydrous lithium chloride for batching, specifically including: According to Li 2.5-x ZrCl 5.5-x O 0.5 Determine the stoichiometric ratio of the intermediate product by using the stoichiometric ratio of (0≤x≤0.75). Based on the stoichiometric ratio of the intermediate products, the stoichiometric ratio of zirconium tetrachloride, lithium oxide, and anhydrous lithium chloride is determined for batching.

4. The preparation method according to claim 1, characterized in that, The pretreatment includes grinding and drying; The grinding process specifically involves placing the raw material in a mortar and grinding it for 1 to 3 hours under an inert atmosphere. The drying process specifically involves drying in a vacuum drying oven at 100℃-150℃ for 2-4 hours.

5. The preparation method according to claim 1, characterized in that, The zirconium balls used in the first ball milling process are 3mm-10mm in size; the ball-to-material mass ratio is M:1, where 4≤M≤20.

6. The preparation method according to claim 1, characterized in that, The first ball milling process involves a rotation speed of 200 r / min to 2400 r / min and a time of 5 to 70 hours.

7. The preparation method according to claim 1, characterized in that, The sintering temperature is 200℃-400℃, and the time is 2 hours-12 hours.

8. The preparation method according to claim 1, characterized in that, The atmosphere of the ball mill jar is any one of vacuum atmosphere, nitrogen atmosphere, or argon atmosphere.

9. A chlorine oxide solid electrolyte, characterized in that, The chlorine oxide solid electrolyte is prepared by any one of the preparation methods described in claims 1-8.

10. A lithium-ion battery, characterized in that, The lithium-ion battery includes the chlorine oxide solid electrolyte as described in claim 9.

Images