Halogen-oxygen compound-containing positive electrode material and preparation method therefor, and positive electrode plate

Abstract

To provide a halogen-oxygen compound-containing positive electrode material having a relatively high ion conductivity and a relatively low expansion coefficient and having a high capacity and good cycle characteristics, and to provide a method for producing the same and use thereof.SOLUTION: The preparation method of the cathode material comprises the following steps: subjecting at least one crystalline phase cathode material and at least one halide to a ball milling treatment to realize the transformation of the halide into a halogen-oxygen compound by corrosion and solid solution reaction during the ball milling to obtain a halogen-oxygen compound-containing cathode material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to the technical field of battery materials, in particular to halogen-oxygen compound-containing positive electrode materials and their manufacturing methods and uses. [Background technology]

[0002] Alkali metal-ion batteries and supercapacitors are considered ideal energy storage devices for next-generation energy storage systems. These energy storage devices are essential for future green energy. Therefore, the development of high-performance, low-cost, and environmentally friendly electrode materials is urgently needed to meet the requirements of high energy density and long cycle life. Extensive research has been conducted on various crystalline electrodes, including carbon-based, alloy-based, and organic-based crystalline electrodes. Strategies to improve the electrochemical properties of these electrodes include: (1) unique structural design to balance morphology and surface area, (2) reduction in the size of the active material, (3) doping with heteroatoms / introduction of vacancies, (4) self-supporting substrates, and (5) construction of heterostructures. While these methods have significantly improved the electrochemical properties of various energy storage systems, current research often finds it difficult to simultaneously satisfy the two key performance metrics of the positive electrode material: capacity and cycle performance. For example, lithium iron phosphate has high safety and long cycle life, but its energy density is relatively low. Lithium cobalt oxide has a relatively high energy density but a relatively short cycle life, ternary materials have relatively good overall properties but a relatively high material cost, while lithium manganese oxide is a low-cost material but has a relatively low energy density.

[0003] Therefore, finding a cathode material for alkali metal-ion batteries that satisfies both high capacity and good cycle characteristics has become a major goal for researchers. Cathode material modification is the main method for improving the battery performance of cathode materials. Surface coating is a commonly used modification method, but currently, most coating materials are "insulators" of lithium and sodium, inhibiting the migration and diffusion of lithium and sodium ions. The lithium and sodium ion transport rate and stability of the material at high rates are low, resulting in poor rate performance. Therefore, how to design a cathode material for alkali metal-ion batteries that combines high specific capacity, long cycle life, and high safety has become one of the most urgent challenges facing the industry. Summary of the Invention [Problem to be solved by the invention]

[0004] The technical problems solved by the present invention are as follows: a novel positive electrode material and a manufacturing method thereof are provided; the present invention solves the above problems by providing a halogen-oxygen compound-containing positive electrode material, a manufacturing method thereof, and use thereof. The present invention employs a one-step ball milling method, which eliminates complex and laborious synthesis steps and effectively reduces production costs. Furthermore, the method is highly versatile. Finally, a novel positive electrode material has been developed that combines excellent cycle stability and high capacity, laying the foundation for large-scale production of next-generation halogen-oxygen compound-containing positive electrode materials. [Means for solving the problem]

[0005] The present invention is achieved by the following technical solutions:

[0006] The present invention provides a method for producing a cathode comprising: y and ball milling the halide MX to convert it into a halogen-oxygen compound through corrosion and solid-solution reaction during the ball milling process, thereby obtaining a halogen-oxygen compound-containing cathode material,y wherein M includes at least one metal element and metalloid element other than radioactive metal elements, X includes at least one halogen element selected from the group consisting of F, Cl, Br, and I, and y is an integer between 1 and 6; when there is one type of crystalline phase positive electrode material, the crystalline phase positive electrode material is a positive electrode material for a lithium ion battery or a positive electrode material for a sodium ion battery; when there are two or more types of crystalline phase positive electrode materials, the crystalline phase positive electrode material is a positive electrode material for a lithium ion battery, and the positive electrode materials for lithium ion batteries and the positive electrode materials for sodium ion batteries are all oxygen-containing materials.

[0007] In the method for producing a positive electrode material according to the present invention, the corrosion and solid-solution reaction refers to a chemical reaction that occurs between the halide and the crystalline phase positive electrode material during ball milling, resulting in the conversion of the halide to a halogen-oxygen compound, thereby obtaining a halogen-oxygen compound-containing positive electrode material. The halogen-oxygen compound-containing positive electrode material obtained by the above-described method has defects and vacancies and can be used as a lithium / sodium storage cathode material. The halogen-oxygen compound in the positive electrode material can reduce the mechanical strain caused by ion absorption and release, mitigating the volume change during cycling, reducing the volume change by more than 30%, thereby ensuring the cycle stability of the structure during lithium or sodium release. The halogen-oxygen compound can slow the decomposition process of the positive electrode material and also slow the release of oxygen in the positive electrode material through the oxidative decomposition of the halogen-oxygen compound. Furthermore, the halogen-oxygen compound can promote the phase transition of oxidized chlorides to oxides, capturing oxygen species, thereby suppressing the release of flammable oxygen gas and improving the thermal stability of the positive electrode material. The halogen-oxygen compound-containing cathode material of the present invention also has a relatively high ionic conductivity, >10 -7 High ionic conductivity of >10 S / cm -4 Both high S / cm and high electronic conductivity can be achieved, even >10 -5 High ionic conductivity of >10 S / cm -2It can achieve high electronic conductivity of 5 S / cm and has excellent electrochemical properties.

[0008] Optionally, the lithium ion battery positive electrode material comprises at least one of a layered material, a spinel material, and an olivine material.

[0009] Further, optionally, the layered material comprises Li x CoO2, Li x NiO2, Li x MnO2, Li x Ni 1-y Mn y O2, Li x Ni 1-y Co y O2, Li x Ni z Co y Mn 1-x-y O2, Li x Co 1-y Mn y O2, and at least one of Li2MnO3, wherein 0.5 <x<1.10であり、Li x Ni 1-y Mn y In O2, 0.1≦y≦0.5, and Li x Ni 1-y Co y In O2, 0.1≦y≦0.5, and Li x Ni z Co y Mn 1-x-y In O2, 0.1≦z≦0.8, 0.1≦y≦0.8, and 0.2≦z+y≦0.9; x Co 1-y Mn y In O2, 0.1≦y≦0.5.

[0010] where Li x CoO2 is preferably LiCoO2, and Li x NiO2 is preferably LiNiO2, and Li x The MnO2 is preferably LiMnO2, and Li x Ni 1-y Co yO2 is preferably LiNi 1-y Co y O2 and Li x Ni z Co y Mn 1-z-y O2 is preferably LiNi 0.8 Co 0.1 Mn 0.1 It is O2.

[0011] Further, optionally, the spinel material is selected from the group consisting of LiMn2O4, and LiNi 0.5 Mn 1.5 Contains at least one of O4.

[0012] Further, optionally, the olivine material is LiNPO4, where N is at least one selected from Fe, Co, Mn, and Ni, such as LiFePO4, LiCoPO4, lithium manganese iron phosphate (LiFe 0.6 Mn 0.4 PO4).

[0013] Optionally, the positive electrode material of the sodium-ion battery comprises at least one of a transition metal oxide material, a polyanion compound material, and a Prussian blue-based compound material.

[0014] Further, optionally, the transition metal oxide material is Na 0.5 Mn 0.75 Ni 0.25 O2, Na 7 / 9 Cu 2 / 9 Fe 1 / 9 Mn 2 / 3 O2, NaNi 0.5 Mn 0.5 O2, Na 2 / 3 Mn 0.8 Fe 0.1 Ti 0.1 O2, Na 2 / 3 Mn 0.8 Fe 0.2 O2, Na 0.5 Fe 0.5 Mn 0.5 O2 or Na 2 / 3 Mn 0.8 Ni0.1 Ti 0.05 Fe 0.05 Contains O2.

[0015] Further, optionally, the polyanionic compound material comprises at least one of a sodium vanadium phosphate and a sodium iron phosphate material.

[0016] Optionally, the crystalline phase positive electrode material is of one type. When one type of crystalline phase positive electrode material is used, the halogen-oxygen compound-containing cathode material obtained by ball milling with a halide has a shell-core structure including a core and a shell covering the core, the core being the crystalline phase positive electrode material, and the shell being an amorphous halogen-oxygen compound. From the core to the shell, the halogen content increases in a gradient manner, and the metal element content decreases in a gradient manner. The metal element is the metal element in the crystalline phase positive electrode material. Unlike conventional amorphous cathode materials, which have the disadvantage of being unable to deeply release lithium or sodium, the amorphous halogen-oxygen compound obtained by the present invention can reduce mechanical strain caused by ion absorption and release, is relatively less affected by shape rearrangement and volume change, and ensures structural stability during lithium or sodium release. For example, in the present invention, aluminum chloride, a halide, is used as a dissociating agent to ball-mill lithium cobalt oxide, which then undergoes corrosion and solid-solution reactions. This results in the formation of numerous defect sites and an amorphous Al-O-Cl structure on the surface of the lithium cobalt oxide. This provides numerous channels for rapid lithium ion transport, significantly improving the cycling capacity of the cathode material and increasing the ionic conductivity at room temperature by more than 500 times compared to the corresponding crystalline cathode material. The existence of this amorphous structure can also be confirmed by subsequent corresponding XRD and TEM data. Furthermore, in current practical applications, the synthesis processes for most amorphous materials are complex and expensive. Unlike conventional methods such as solid-state, solution-gel, and combustion methods, this invention employs a simple one-step ball-milling synthesis method to enable rapid and large-scale production, laying a solid foundation for commercial applications.

[0017] Furthermore, optionally, the type of halide is one, the type of crystalline phase positive electrode material is one, and the mass ratio of the metal halide to the crystalline phase positive electrode material is 1:1 to 1:19.

[0018] To reduce production costs, the proportion of crystalline phase positive electrode material in the total mass of crystalline phase positive electrode material and halide should be 50% or more. If the proportion of crystalline phase positive electrode material added is too low and the proportion of halide added is too high, the halide content in the final positive electrode material will be too high, and sufficient specific capacity will not be obtained.

[0019] Experimental test results show that to ensure the actual battery application effect after dissociation of the halide material, the proportion of halide in the total mass of the crystalline phase positive electrode material and halide must be 5% or more.Of course, the proportion of halide added must not be too low; if it is too low, the crystalline phase positive electrode material and halide cannot effectively form a halogen-oxygen compound, and the performance of the positive electrode material will not be significantly improved.

[0020] Furthermore, optionally, there are two kinds of halides, one kind of crystalline phase positive electrode material, and the mass ratio of the two kinds of halides to the crystalline phase positive electrode material is 1:1:18 to 1:1:2.

[0021] In consideration of suppressing actual production costs, the proportion of the crystalline phase positive electrode material in the total mass of the crystalline phase positive electrode material and halide is set to 50% or more.

[0022] According to the experimental test results, in order to ensure the practical application effect of the battery after dissociation of the halide materials, the proportion of each halide in the total mass of the crystalline phase positive electrode material and the two halides must be 5% or more.

[0023] Optionally, the crystalline phase positive electrode material may be of at least two types, e.g., two or three types. Using multiple types of crystalline phase positive electrode materials simultaneously allows different crystalline phase positive electrode materials to be solid-solubilized to form a solid-solution type positive electrode material. Forming a solid solution of different crystalline phase positive electrode materials can improve the cycle characteristics of the positive electrode material. For example, when lithium cobalt oxide and lithium iron phosphate are ball-milled to form a solid solution, the lithium iron phosphate layer serves as both the active material and a resistance barrier layer to prevent overcharge and thermal runaway. This solid-solution type positive electrode material not only has high resistance to overcharge currents but also significantly reduces the surface temperature during overcharge, significantly improving the cycle stability of lithium cobalt oxide. For example, lithium iron phosphate has advantages such as high specific capacity, high safety, and low cost, but its discharge platform voltage is not high. When it is ball-milled together with lithium manganese oxide to form a solid solution, the submicron-sized lithium iron phosphate particles can fill the gaps between the micron-scale lithium manganese oxide particles, effectively blocking direct contact between the electrolyte and the lithium manganese oxide, inhibiting manganese dissolution, improving electron transport between the particles, reducing the internal resistance of the battery, and increasing the average operating voltage of the battery.

[0024] If the halide content is too high, most of the capacity of the solid-solution cathode material comes from the halide, resulting in significantly insufficient battery capacity and poor electrochemical performance. If the halide content is too low, the difficulty of forming a solid solution between different crystalline phase cathode materials increases significantly, the synergistic effect between the different crystalline phase cathode materials is not fully realized, and cycle stability decreases. Therefore, it is necessary to control the ratio of halide to crystalline phase cathode material.

[0025] Furthermore, optionally, there is one type of halide and two types of crystalline phase positive electrode materials, and the mass ratio of the halide to the two types of crystalline phase positive electrode materials is 2:1:1 to 2:19:19.

[0026] Furthermore, optionally, there is one type of halide, three types of crystalline phase positive electrode materials, and the mass ratio of the halide to the three types of crystalline phase positive electrode materials is 3:1:1:1 to 1:33:33:33.

[0027] More preferably, the type of halide is one, the types of crystalline phase positive electrode materials are three, and the mass ratio of the halide to the three types of crystalline phase positive electrode materials is 1:3:3:3 to 3:4:4:4.

[0028] Further, optionally, there are two types of halides, there are two types of crystalline phase positive electrode materials, and the mass ratio of the two types of halides to the two types of crystalline phase positive electrode materials is 1:1:1:1 to 1:1:99:99.

[0029] More preferably, there are two types of halides, two types of crystalline phase positive electrode materials, and the mass ratio of the two types of halides to the two types of crystalline phase positive electrode materials is 1:1:9:9 to 1:1:4:4.

[0030] Further, optionally, there are two types of halides and three types of crystalline phase positive electrode materials, and the mass ratio of the two types of halides to the three types of crystalline phase positive electrode materials is 3:3:2:2:2 to 1:1:66:66:66.

[0031] More preferably, there are two types of halides and three types of crystalline phase positive electrode materials, and the mass ratio of the two types of halides to the three types of crystalline phase positive electrode materials is 1:1:6:6:6 to 3:3:8:8:8.

[0032] Optionally, said halide MX y wherein M includes metal elements other than radioactive metal elements (e.g., polonium, radon, francium, radium, actinium, thorium, protactinium, uranium, neptunium, plutonium), including, but not limited to, lithium, sodium, potassium, magnesium, calcium, aluminum, lanthanum, tantalum, hafnium, zirconium, etc.

[0033] Further, optionally, said halide MX y wherein M includes at least one of aluminum, lanthanum, tantalum, hafnium, and zirconium.

[0034] Optionally, the halide comprises at least one of aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide, lanthanum fluoride, lanthanum chloride, lanthanum bromide, lanthanum iodide, tantalum fluoride, tantalum chloride, tantalum bromide, tantalum iodide, hafnium fluoride, hafnium chloride, hafnium bromide, hafnium iodide, zirconium fluoride, zirconium chloride, zirconium bromide, and zirconium iodide.

[0035] Further optionally, the halide is a combination of two halides, wherein the two halides are aluminum chloride and any of the following halides: lanthanum chloride, tantalum chloride, hafnium chloride, zirconium chloride, lanthanum fluoride, lanthanum bromide, lanthanum iodide, tantalum fluoride, tantalum bromide, tantalum iodide, hafnium fluoride, hafnium bromide, hafnium iodide, zirconium fluoride, zirconium bromide, and zirconium iodide.

[0036] Furthermore, the halide may be a combination of aluminum chloride and lanthanum chloride, a combination of aluminum chloride and lanthanum fluoride, a combination of aluminum chloride and lanthanum bromide, a combination of aluminum chloride and lanthanum iodide, a combination of aluminum chloride and tantalum chloride, a combination of aluminum chloride and tantalum fluoride, a combination of aluminum chloride and tantalum bromide, a combination of aluminum chloride and tantalum iodide, a combination of aluminum chloride and hafnium chloride, a combination of aluminum chloride and hafnium fluoride, a combination of aluminum chloride and hafnium bromide, a combination of aluminum chloride and hafnium iodide, a combination of aluminum chloride and zirconium chloride, a combination of aluminum chloride and zirconium fluoride, a combination of aluminum chloride and zirconium bromide, or a combination of aluminum chloride and zirconium iodide.

[0037] Optionally, the crystalline phase positive electrode material is one type, the ball milling speed is 100 rpm to 700 rpm, and the ball milling time is 0.1 hours to 48 hours.

[0038] Optionally, there are at least two types of crystalline phase positive electrode materials, and the ball milling rotation speed is 100 rpm to 700 rpm, and the ball milling time is 0.1 hours to 22 hours, more preferably the ball milling rotation speed is 300 rpm to 600 rpm, and the ball milling time is 0.1 hours to 6 hours.

[0039] The present invention provides a halogen-oxygen compound-containing positive electrode material produced by the above-mentioned production method.

[0040] When a crystalline phase positive electrode material is used, the resulting halogen-oxygen compound-containing positive electrode material includes a core and a shell coated around the core, where the core is the crystalline phase positive electrode material and the shell is an amorphous halogen-oxygen compound. From the core to the shell, the halogen content increases gradually, and the metal element content decreases gradually. The term "metal element" used here refers to the metal element in the crystalline phase positive electrode material.

[0041] When two or more crystalline phase positive electrode materials are used, the halogen-oxygen compound-containing positive electrode material produced is a solid solution type positive electrode material.

[0042] The present invention provides a positive electrode sheet comprising the above-mentioned halogen-oxygen compound-containing positive electrode material or a positive electrode material produced by the above-mentioned production method.

[0043] The present invention provides a battery including the above-described positive electrode sheet. [Effects of the Invention]

[0044] The present invention has the following advantageous effects compared to the prior art.

[0045] The method for producing a halogen-oxygen compound-containing positive electrode material of the present invention mainly involves directly ball-milling a halide and a crystalline phase positive electrode material using a simple ball-milling method, which has simple operational steps and does not require complex synthesis conditions, thereby significantly improving production efficiency and reducing production costs.In the production method of the present invention, a chemical reaction occurs between the halide and the crystalline phase positive electrode material during ball-milling, and this reaction converts the halide to a halogen-oxygen compound, thereby producing a halogen-oxygen compound-containing positive electrode material.

[0046] The halogen-oxygen compound-containing positive electrode material prepared according to the present invention has defects and vacancies and can be used as a lithium / sodium storage positive electrode material. The halogen-oxygen compound in the positive electrode material can reduce the mechanical strain caused by ion absorption and release, mitigating volume changes during cycling and thereby improving the cycling stability of the structure during lithium or sodium release. The halogen-oxygen compound can delay the decomposition process of the positive electrode material and can also slow the release of oxygen in the positive electrode material through the oxidative decomposition of the halogen-oxygen compound. Furthermore, the halogen-oxygen compound can promote the phase transition of oxidized chlorides to oxides, capturing oxygen species, thereby suppressing the release of flammable oxygen gas and improving the thermal stability of the positive electrode material. Furthermore, the halogen-oxygen compound-containing positive electrode material of the present invention has multiple alkali metal ion storage sites and diffusion channels, resulting in relatively high ionic conductivity and excellent electrochemical properties. Therefore, the halogen-oxygen compound-containing positive electrode material prepared according to the present invention has both good capacity and cycle characteristics. [Brief explanation of the drawings]

[0047] [Figure 1] 1 is a TEM lattice image of a halogen-oxygen compound-containing positive electrode material according to Example 1. [Figure 2] 1 is a TEM morphology image of the halogen-oxygen compound-containing positive electrode material prepared in Example 1. [Figure 3] 1 is an SEM morphology image of the positive electrode material prepared in Comparative Example 1. [Figure 4] 1 is an SEM morphology image of the positive electrode material prepared in Comparative Example 2. [Figure 5] FIG. 2 is an XRD diagram of the halogen-oxygen compound-containing positive electrode material prepared in Example 1. [Figure 6] 1 shows the charge-discharge curves at a current density of 0.5 A g −1 of the halogen-oxygen compound-containing positive electrode material prepared in Example 1. [Figure 7]1 shows cycle curves at a current density of 0.5 A g-1 for the halogen-oxygen compound-containing positive electrode material prepared in Example 1. Here, the curve formed by squares represents the coulombic efficiency, and the curve formed by circles represents the capacity. [Figure 8] 1 shows the cycle curves at a current density of 0.5 A g-1 of the positive electrode material produced in Comparative Example 1. Here, the curve formed by squares represents the coulombic efficiency, and the curve formed by circles represents the capacity. [Figure 9] 1 shows the cycle curves at a current density of 0.5 A g-1 of the positive electrode material produced in Comparative Example 2. Here, the curve formed by squares represents the coulombic efficiency, and the curve formed by circles represents the capacity. [Figure 10] 1 is an SEM lattice image of the halogen-oxygen compound-containing positive electrode material prepared in Example 15. [Figure 11] 1 is an SEM morphology image of the positive electrode material prepared in Comparative Example 5. [Figure 12] 1 is an SEM morphology image of the positive electrode material prepared in Comparative Example 6. [Figure 13] 10 is an SEM morphology image of the positive electrode material prepared in Comparative Example 7. [Figure 14] 1 is an SEM morphology image of the positive electrode material prepared in Comparative Example 8. [Figure 15] 1 shows the cycle curves of the halogen-oxygen compound-containing positive electrode material prepared in Example 15 at a current density of 0.3 A g-1, where the curve formed by squares represents the coulombic efficiency and the curve formed by circles represents the capacity. [Figure 16] 1 shows the cycle curves at a current density of 0.3 A g-1 of the positive electrode material produced in Comparative Example 3. Here, the curve formed by squares represents the coulombic efficiency, and the curve formed by circles represents the capacity. [Figure 17] 1 shows the cycle curves at a current density of 0.3 A g-1 of the positive electrode material produced in Comparative Example 4. Here, the curve formed by squares represents the coulombic efficiency, and the curve formed by circles represents the capacity. DETAILED DESCRIPTION OF THE INVENTION

[0048] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be described in more detail below with reference to examples and drawings. However, the outline embodiments of the present invention and their description are for the purpose of interpreting the present invention, and are not intended to limit the present invention.

[0049] Example 1 This example provides a halogen-oxygen compound-containing positive electrode material, and the specific preparation method is shown below. Step 1: Add 0.4 g of aluminum chloride and 1.6 g of lithium cobalt oxide LiCoO solid powder to a 500 mL high-energy ball mill tank. Here, the mass ratio of aluminum chloride to lithium cobalt oxide is 1:4. Step 2: After every 10 minutes of ball milling, there was a 5-minute pause and then the ball milling continued. Then, the above steps were repeated to control the total ball milling time to 0.5 hours, and the ball milling speed was kept at 500 rpm. Here, except for the ball milling process, all loading and unloading operations are carried out in a vacuum glove box, and the oxygen and water contents are all controlled to less than 0.1 ppm.

[0050] Comparative Example 1 The only difference between this comparative example and Example 1 is the following: 10 g of aluminum chloride and 1 g of lithium cobalt oxide (LiCoO) solid powder were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride to lithium cobalt oxide was 10:1. Comparative Example 2 The only difference between this comparative example and Example 1 is that 0.1 g of aluminum chloride and 3.0 g of lithium cobalt oxide (LiCoO) solid powder were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride to lithium cobalt oxide was 1:30.

[0051] Example 2 This example differs from Example 1 only in the following points: Aluminum chloride was changed to tantalum chloride.

[0052] Example 3 This example differs from Example 1 only in the following points: Aluminum chloride was changed to zirconium chloride.

[0053] Example 4 This example differs from Example 1 only in the following points: Lithium cobalt oxide was changed to lithium manganese oxide Li2MnO3.

[0054] Example 5 This example differs from Example 1 only in the following points: aluminum chloride was changed to zirconium chloride, and lithium cobalt oxide was changed to lithium iron phosphate LiFePO4.

[0055] Example 6 This example differs from Example 1 only in the following points: Lithium cobalt oxide was changed to sodium vanadium phosphate.

[0056] Example 7 This example differs from Example 1 only in the following points: Lithium cobalt oxide was changed to sodium iron phosphate.

[0057] Example 8 This example provides a halogen-oxygen compound-containing positive electrode material, and the specific preparation method is shown below. Step 1: Add 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, and 1.6 g of lithium cobalt oxide LiCoO solid powder to a 500 mL high-energy ball mill tank. Here, the mass ratio of aluminum chloride, lanthanum chloride, and lithium cobalt oxide was 1:1:8. Step 2: After every 10 minutes of ball milling, there was a 5-minute pause and then the ball milling continued. Then, the above steps were repeated to control the total ball milling time to 0.5 hours, and the ball milling speed was kept at 500 rpm. Here, except for the ball milling process, all loading and unloading operations are carried out in a vacuum glove box, and the oxygen and water contents are all controlled to less than 0.1 ppm.

[0058] Example 9 The only difference between this example and Example 8 is that 0.1 g of aluminum chloride, 0.1 g of lanthanum chloride, and 1.8 g of lithium cobalt oxide (LiCoO) solid powder were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, and lithium cobalt oxide was 1:1:18.

[0059] Example 10 This example differs from Example 8 only in the following points: lanthanum chloride was changed to zirconium chloride.

[0060] Example 11 This example differs from Example 8 only in the following points: Lanthanum chloride was changed to hafnium chloride.

[0061] Example 12 This example provides a halogen-oxygen compound-containing positive electrode material, and the specific preparation method is shown below. Step 1: Add 0.2 g of aluminum chloride, 0.2 g of tantalum chloride, and NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O2) 1.6 g of solid powder was added. Here, aluminum chloride, tantalum chloride, and NCM811(LiNi 0.8 Co 0.1 Mn 0.1 O2) mass ratio is 1:1:8. Step 2: Ball milling was performed for 10 minutes, and the ball milling speed was maintained at 500 rpm. Here, except for the ball milling process, all loading and unloading operations are carried out in a vacuum glove box, and the oxygen and water contents are all controlled to less than 0.1 ppm.

[0062] Example 13 The only difference between this example and Example 8 is that 0.1 g of aluminum chloride, 0.1 g of lanthanum chloride, and 1.8 g of lithium iron phosphate LiFePO4 solid powder were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, and lithium iron phosphate LiFePO4 was 1:1:18.

[0063] Example 14 The only difference between this example and Example 8 is that 0.1 g of aluminum chloride, 0.1 g of lanthanum chloride, and 1.8 g of solid iron sodium phosphate powder were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, and iron sodium phosphate was 1:1:18.

[0064] Example 15 This example provides a halogen-oxygen compound-containing positive electrode material, and the specific preparation method is shown below. Step 1: Add 0.4 g of aluminum chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium manganese oxide (LiMnO) to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lithium cobalt oxide, and lithium manganese oxide was 1:2:2. Step 2: After every 10 minutes of ball milling, there was a 5-minute pause and then the ball milling continued. Then, the above steps were repeated to control the total ball milling time to 0.5 hours, and the ball milling speed was kept at 500 rpm. Here, except for the ball milling process, all loading and unloading operations are carried out in a vacuum glove box, and the oxygen and water contents are all controlled to less than 0.1 ppm.

[0065] Comparative Example 3 This comparative example differs from Example 15 only in the following respect: 1.2 g of aluminum chloride, 0.4 g of lithium cobalt oxide (LiCoO), and 0.4 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lithium cobalt oxide, and lithium manganese oxide was 3:1:1.

[0066] Comparative Example 4 This comparative example differs from Example 15 only in the following respect: 0.04 g of aluminum chloride, 0.98 g of lithium cobalt oxide (LiCoO), and 0.98 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lithium cobalt oxide, and lithium manganese oxide was 2:49:49.

[0067] Comparative Example 5 This comparative example differs from Example 15 only in the following points: The total time of ball milling was controlled to 1 minute.

[0068] Comparative Example 6 In this comparative example, the only difference from Example 15 is as follows: The total time of ball milling was controlled to 24 hours.

[0069] Comparative Example 7 This comparative example differs from Example 15 only in the following points: The ball milling speed was maintained at 50 rpm.

[0070] Comparative Example 8 This comparative example differs from Example 15 only in the following points: The ball milling speed was maintained at 800 rpm.

[0071] Example 16 This example differs from Example 15 only in the following respect: 0.4 g of aluminum chloride, 0.53 g of lithium cobalt oxide LiCoO2, 0.53 g of lithium manganese oxide LiMnO2, and 0.53 g of lithium iron phosphate LiFePO4 were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lithium cobalt oxide, lithium manganese oxide, and lithium iron phosphate was 3:4:4:4.

[0072] Example 17 This example differs from Example 15 only in the following respect: 0.4 g of tantalum chloride, 0.53 g of lithium cobalt oxide LiCoO2, 0.53 g of lithium manganese oxide LiMnO2, and 0.53 g of lithium iron phosphate LiFePO4 were added to a 500 mL high-energy ball mill tank. The mass ratio of tantalum chloride, lithium cobalt oxide, lithium manganese oxide, and lithium iron phosphate was 3:4:4:4.

[0073] Example 18 This example differs from Example 15 only in the following respects: 0.4 g of aluminum chloride, 0.53 g of lithium cobalt oxide (LiCoO), and 0.53 g of lithium manganese iron phosphate (LiFe) were added to a 500 mL high-energy ball mill tank. 0.6 Mn 0.4 0.53 g of aluminum chloride, lithium cobalt oxide, lithium manganese iron phosphate, and lithium iron phosphate were added to the aluminum chloride solution. The mass ratio of aluminum chloride, lithium cobalt oxide, lithium manganese iron phosphate, and lithium iron phosphate was 3:4:4:4.

[0074] Example 19 This example differs from Example 15 only in the following respects: 0.4 g of aluminum chloride, 0.53 g of lithium cobalt oxide (LiCoO), and 0.53 g of lithium manganese iron phosphate (LiFe) were added to a 500 mL high-energy ball mill tank. 0.6 Mn 0.4PO4 0.53g, lithium iron phosphate LiFePO4 0.53g were added. The mass ratio of aluminum chloride, lithium cobalt oxide, lithium iron manganese phosphate, and lithium iron phosphate was 3:4:4:4, and the total time of ball milling was controlled to 2 hours.

[0075] Example 20 This example differs from Example 15 only in the following respects: 0.4 g of aluminum chloride, 0.53 g of lithium cobalt oxide (LiCoO), and 0.53 g of lithium manganese iron phosphate (LiFe) were added to a 500 mL high-energy ball mill tank. 0.6 Mn 0.4 0.53 g of aluminum chloride, lithium cobalt oxide, lithium manganese iron phosphate, and lithium iron phosphate were added to the mixture, where the mass ratio of aluminum chloride, lithium cobalt oxide, lithium manganese iron phosphate, and lithium iron phosphate was 3:4:4:4, the total ball milling time was controlled to 2 hours, and the ball milling rotation speed was maintained at 600 rpm.

[0076] Example 21 This example differs from Example 15 only in the following respect: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, and lithium manganese oxide was 1:1:4:4.

[0077] Example 22 This example differs from Example 15 only in the following respects: 0.2 g of aluminum chloride, 0.2 g of zirconium chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, zirconium chloride, lithium cobalt oxide, and lithium manganese oxide was 1:1:4:4.

[0078] Example 23 This example differs from Example 15 only in the following: 0.2 g of aluminum chloride, 0.2 g of zirconium chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium iron phosphate (LiFePO) were added to a 500 mL high-energy ball mill tank, where the mass ratio of aluminum chloride, zirconium chloride, lithium cobalt oxide, and lithium iron phosphate was 1:1:4:4.

[0079] Example 24 This example differs from Example 15 only in the following: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, and lithium manganese oxide was 1:1:4:4, and the total ball milling time was controlled to 4 hours.

[0080] Example 25 This example differs from Example 15 only in the following respects: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.8 g of lithium cobalt oxide (LiCoO), and 0.8 g of lithium manganese oxide (LiMnO) were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, and lithium manganese oxide was 1:1:4:4, and the ball milling speed was maintained at 600 rpm.

[0081] Example 26 This example differs from Example 15 only in the following respect: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.53 g of lithium cobalt oxide (LiCoO), and 0.53 g of lithium manganate were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, and lithium manganate was 3:3:8:8.

[0082] Example 27 This example differs from Example 15 only in the following: 0.2 g of aluminum chloride, 0.2 g of zirconium chloride, 0.53 g of lithium cobalt oxide (LiCoO), and 0.53 g of lithium manganese oxide were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, zirconium chloride, lithium cobalt oxide, and lithium manganese oxide was 3:3:8:8.

[0083] Example 28 This example differs from Example 15 only in the following respect: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.53 g of lithium cobalt oxide (LiCoO), 0.53 g of lithium manganese oxide (LiMnO), and 0.53 g of lithium iron phosphate were added to a 500 mL high-energy ball mill tank. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, lithium manganese oxide, and lithium iron phosphate was 3:3:8:8:8.

[0084] Example 29 This example differs from Example 15 only in the following: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.53 g of lithium cobalt oxide LiCoO2, 0.53 g of lithium manganese oxide, and 0.53 g of lithium manganese iron phosphate LiFe were added to a 500 mL high-energy ball mill tank. 0.6 Mn 0.4 0.53 g of PO4 was added. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, lithium manganate, and lithium iron manganese phosphate was 3:3:8:8:8, and the total time of ball milling was controlled at 2 hours.

[0085] Example 30 This example differs from Example 15 only in the following respects: 0.2 g of aluminum chloride, 0.2 g of lanthanum chloride, 0.53 g of lithium cobalt oxide LiCoO2, 0.53 g of lithium manganese oxide LiMnO2, and 0.53 g of lithium manganese iron phosphate LiFe were added to a 500 mL high-energy ball mill tank. 0.6 Mn 0.40.53 g of PO4 was added. The mass ratio of aluminum chloride, lanthanum chloride, lithium cobalt oxide, lithium manganese oxide, and lithium iron manganese phosphate was 3:3:8:8:8, and the rotation speed of the ball mill was maintained at 600 rpm.

[0086] 1. Structural characterization 1. Electron microscopy analysis: FIG. 1 is a TEM lattice image of the halogen-oxygen compound-containing cathode material of Example 1. The TEM image in FIG. 1 reveals the presence of clear amorphous regions in the material obtained after ball milling lithium cobalt oxide and aluminum chloride. The clear lattice regions in the image represent the remaining lithium cobalt oxide. The material obtained by ball milling the crystalline phase cathode material and the halide was shown to have a core-shell structure, with the core being the crystalline phase cathode material and the shell being the amorphous halogen-oxygen compound.

[0087] 2 is a TEM morphology image of the halogen-oxygen compound-containing positive electrode material prepared in Example 1. It was found that the structures of lithium cobalt oxide and aluminum chloride themselves were still completely maintained without any obvious destruction after ball milling.

[0088] 3 is an SEM image of the positive electrode material prepared in Comparative Example 1. When the mass ratio of aluminum chloride is too high, most of the particles formed are halide, and no clear crystalline phase positive electrode material particles are observed, indicating that the halogen-oxygen compound-containing positive electrode material is not normally prepared.

[0089] 4 is an SEM image of the positive electrode material produced in Comparative Example 2. When the mass ratio of lithium cobalt oxide is too high, most of the particles are in the form of lithium cobalt oxide particles themselves, and a small amount of crystalline positive electrode material particles dissociate from the aluminum chloride, resulting in an undesirable product.

[0090] The morphology of the positive electrode material prepared in Example 15 was photographed using a scanning electron microscope, and the effects of different ball milling speeds and ball milling times on the morphology of the positive electrode material were compared. The results are shown in Figures 10 to 14.

[0091] As shown in FIG. 10 , in Example 15, by appropriately controlling the ball milling speed and time, a solid-solution type positive electrode material having regular spherical particles with no apparent amorphous regions and a relatively intact morphology was produced.

[0092] As shown in FIGS. 11 and 13 , in Comparative Examples 5 and 7, when the ball milling time was too short or the ball milling speed was too slow, the morphology of the sample became close to that of the initial positive electrode material particles, and no obvious solid-solution reaction with the halide occurred.

[0093] As shown in Figures 12 and 14, in Comparative Examples 6 and 8, it was found that when the ball milling time was too long or the ball milling speed was too fast, the morphology of the samples was significantly impaired and particles of different sizes and shapes were formed. 2. X-ray Diffraction Analysis

[0094] Figure 5 shows the XRD pattern of the halogen-oxygen compound-containing cathode material prepared in Example 1. It can be clearly seen from Figure 5 that the sharp peak of lithium cobalt oxide around 20° has disappeared and become a broad diffraction peak. This further proves that an amorphous phase structure is produced by using the crystalline phase cathode material and the material obtained by ball-milling the halide.

[0095] 2. Characteristics testing 1. Battery manufacturing

[0096] Batteries were assembled in an argon-filled glove box using the prepared halogen-oxygen compound-containing positive electrode material and LiIn negative electrode. First, approximately 120 mg of Li6PS5Cl powder was pressed at 100 MPa for 1 minute (10 mm diameter) to obtain a solid electrolyte. The positive electrode material, Li6PS5Cl, and carbon black were mixed in a weight ratio of 70:30:1 to prepare a composite positive electrode mixture. Approximately 10 mg of the composite positive electrode mixture was spread on one side of the solid electrolyte Li6PS5Cl and pressed at 300 MPa for 2 minutes. A thin indium foil (10 mm diameter) was attached to the other side of the solid electrolyte, and approximately 2 mg of lithium foil was thinly pressed and placed on the indium foil to obtain a composite positive electrode. The mass loading of the positive electrode material in the composite positive electrodes corresponding to Example 1, Comparative Example 1, and Comparative Example 2 was 8 mg cm. -2 The mass loading of the positive electrode material in the composite positive electrodes corresponding to Example 15, Comparative Example 3, and Comparative Example 4 was 6 mg cm. -2 is. 2. Test Method

[0097] The constant current charge / discharge voltage is + The voltages were set to 2.5 V to 4.3 V vs. / Li. The charge-discharge curves were tested at a current density of 0.1 c. The batteries corresponding to Example 1, Comparative Example 1, and Comparative Example 2 were charged at a current density of 0.5 A g -1 The batteries corresponding to Example 15, Comparative Example 3, and Comparative Example 4 were subjected to a cycle characteristic test at a current density of 0.3 A g -1 The cycle characteristics were tested at a current density of 1000 kJ / s. 3. Test Results

[0098] As shown in FIGS. 6 and 7, the capacity of the positive electrode material according to Example 1 was 110 mAh g after 50 cycles at 0.5 C. -1 The discharge capacity was maintained at 130 mAh g for the first cycle at a current density of 0.1 c. -1 The coulombic efficiency of the first cycle is 94.8%.

[0099] As shown in Figures 8 and 9, the positive electrode materials according to Comparative Example 1 and Comparative Example 2 exhibited completely different electrochemical properties after 50 cycles at 0.5 C. The positive electrode prepared according to Comparative Example 1 had a first cycle capacity of only 70 mAh g -1 and 25mAh g for the next 50 cycles. -1 The capacity gradually decreased to 100 mAh g. This is because the mass ratio of the halide was too high, and most of the obtained positive electrode material became halide, resulting in a decrease in battery capacity. The positive electrode produced in Comparative Example 2 had more stable cycle characteristics than Comparative Example 1, but the capacity was still significantly lower than that of Example 1. After 50 cycles, the capacity was only 75 mAh g. -1 This is because the mass ratio of the halide is too low, and the content of the halogen-oxygen compound in the resulting positive electrode material is too low, so the effect of improving battery performance is extremely limited.

[0100] As shown in Figure 15, in Example 15, the solid-solution cathode material synthesized by appropriately controlling the mass ratio of halide to crystalline phase cathode material exhibited excellent cycle performance and high reversible capacity, with a capacity of 218 mAh g after 50 cycles at 0.3 C. -1 maintains its quality.

[0101] As shown in FIG. 16, in Comparative Example 3, the mass ratio of the halide was too high, resulting in a decrease in battery capacity of 100.5 mAh g -1 It was.

[0102] As shown in FIG. 17, in Comparative Example 4, the mass ratio of the halide was too low, which resulted in a rapid deterioration in the performance of the all-solid-state battery, a serious capacity loss phenomenon, and poor cycle stability. After 50 cycles, the capacity was only 124.9 mAh g -1 It was.

[0103] The specific embodiments described above have further detailed the objectives, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and do not limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are also included in the protection scope of the present invention.

Claims

1. A method for producing a halogen-oxygen compound-containing cathode material, comprising: At least one crystalline phase positive electrode material and at least one halide MX ｙ ball milling the resulting mixture to obtain a halogen-oxygen compound-containing positive electrode material; The halide MX ｙ wherein M includes at least one of a metal element and a metalloid element other than a radioactive metal element, X includes at least one of F, Cl, Br, and I, and y is an integer between 1 and 6; A method for producing a halogen-oxygen compound-containing positive electrode material, wherein when there is one type of crystalline phase positive electrode material, the crystalline phase positive electrode material is a positive electrode material for a lithium ion battery or a positive electrode material for a sodium ion battery, and when there are two or more types of crystalline phase positive electrode materials, the crystalline phase positive electrode material is a positive electrode material for a lithium ion battery, and the positive electrode materials for lithium ion batteries and the positive electrode materials for sodium ion batteries are all oxygen-containing materials.

2. 2. The method for producing a halogen-oxygen compound-containing positive electrode material according to claim 1, wherein the positive electrode material of the lithium ion battery contains at least one of a layered material, a spinel material, and an olivine material.

3. The layered material is Li ｘ CoO ２ , Li ｘ NiO ２ , Li ｘ MnO ２ , Li ｘ Ni １－ｙ Mn ｙ O ２ , Li ｘ Ni １－ｙ Co ｙ O ２ , Li ｘ Ni ｚ Co ｙ Mn １－ｘ－ｙ O ２ , Li ｘ Co １－ｙ Mn ｙ O ２ , and Li ２ MnO ３ wherein 0.5<x<1.10, and Li ｘ Ni １－ｙ Mn ｙ O ２ In the formula, 0.1≦y≦0.5, and Li ｘ Ni １－ｙ Co ｙ O ２ In the formula, 0.1≦y≦0.5, and Li ｘ Ni ｚ Co ｙ Mn １－ｘ－ｙ O ２ In the formula, 0.1≦z≦0.8, 0.1≦y≦0.8, and 0.2≦z+y≦0.9; ｘ Co １－ｙ Mn ｙ O ２ In this case, 0.1≦y≦0.5; and / or the spinel material is LiMn ２ O ４ , and LiNi ０．５ Mn １．５ O ４ and and / or the olivine material is LiNPO ４ 3. The method for producing a halogen-oxygen compound-containing positive electrode material according to claim 2, wherein N is at least one element selected from the group consisting of Fe, Co, Mn, and Ni.

4. 2. The method for producing a halogen-oxygen compound-containing positive electrode material according to claim 1, wherein the positive electrode material of the sodium ion battery contains at least one of a transition metal oxide material, a polyanion compound material, and a Prussian blue-based compound material.

5. 5. The method for producing a halogen-oxygen compound-containing positive electrode material according to claim 4, wherein the polyanion compound material contains at least one of sodium vanadium phosphate and sodium iron phosphate.

6. 2. The method for producing a halogen-oxygen compound-containing positive electrode material according to claim 1, wherein the halide MXy includes at least one of aluminum fluoride, aluminum chloride, aluminum bromide, aluminum iodide, lanthanum fluoride, lanthanum chloride, lanthanum bromide, lanthanum iodide, tantalum fluoride, tantalum chloride, tantalum bromide, tantalum iodide, hafnium fluoride, hafnium chloride, hafnium bromide, hafnium iodide, zirconium fluoride, zirconium chloride, zirconium bromide, and zirconium iodide.

7. The halide MX ｙ the mass ratio of the halide MXy to the crystalline phase positive electrode material is 1:1 to 1:19; Alternatively, the number of types of the halide MXy is two, the number of types of the crystalline phase positive electrode material is one, and the mass ratio of the two types of the halide MXy to the crystalline phase positive electrode material is 1:1:18 to 1:1:2; Alternatively, the type of the halide MXy is one type, the types of the crystalline phase positive electrode materials are two types, and the mass ratio of the halide MXy to the two types of crystalline phase positive electrode materials is 2:1:1 to 2:19:19; Alternatively, the type of the halide MXy is one type, the types of the crystalline phase positive electrode materials are three types, and the mass ratio of the halide MXy to the three types of crystalline phase positive electrode materials is 3:1:1:1 to 1:33:33:33; Alternatively, the number of types of the halide MXy is two, the number of types of the crystalline phase positive electrode material is two, and the mass ratio of the two types of the halide MXy to the two types of the crystalline phase positive electrode material is 1:1:1:1 to 1:1:99:99; Alternatively, the method for producing a halogen-oxygen compound-containing positive electrode material according to claim 1, wherein the number of types of the halide MXy is two, the number of types of the crystalline phase positive electrode material is three, and the mass ratio of the two types of the halide MXy to the three types of the crystalline phase positive electrode material is 3:3:2:2:2 to 1:1:66:66:

66.

8. The crystalline phase positive electrode material is one type, the ball milling rotation speed is 100 rpm to 700 rpm, and the ball milling time is 0.1 hours to 48 hours; Alternatively, the method for producing a halogen-oxygen compound-containing positive electrode material according to claim 1, wherein the crystalline phase positive electrode material is at least two types, the ball milling rotation speed is 100 rpm to 700 rpm, and the ball milling time is 0.1 hours to 22 hours.

9. A halogen-oxygen compound-containing positive electrode material obtained by the method of claim 1.

10. A positive electrode sheet comprising the halogen-oxygen compound-containing positive electrode material according to claim 9.

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