A manganese-based battery positive electrode material precursor and its preparation method and application

Abstract

The present invention relates to the technical field of battery positive electrode materials, and discloses a manganese-based battery positive electrode material precursor, a preparation method and application thereof. The present invention discloses a manganese-based battery positive electrode material precursor, a preparation method and application thereof, and belongs to the technical field of battery preparation. The technology of the present invention mainly adopts a solid-phase method to prepare a manganese-based battery positive electrode material precursor. Through high-temperature melting technology, multiple elements are simultaneously doped and modified on the manganese-based positive electrode material, and then surface coating is implemented to improve the density of the synthesized positive electrode material and enhance its structural stability, optimize the morphology, crystal plane and grain boundary of the positive electrode material, inhibit the side reaction between the crystal interface of the positive electrode material and the electrolyte, extend its service life, and enhance its safety performance during use. The small amount of water vapor and carbon dioxide gas generated during the preparation process are discharged into the air and will not pollute the environment.

Description

Technical Field

[0001] The present invention relates to the technical field of battery positive electrode materials, and in particular to a manganese-based battery positive electrode material precursor, a preparation method thereof, and an application thereof. Background Art

[0002] With the widespread application of batteries in the growing electric vehicle market and energy storage systems, as well as their continuous expansion in smart devices, heavy trucks, ships, aircraft, construction machinery and other fields, the battery industry has entered a new stage of development. Battery positive electrode materials have also been continuously developing new technologies and new products to meet the market demand for high energy density, high safety, long life and low cost batteries.

[0003] Currently, lithium manganese oxide and lithium nickel cobalt manganese oxide are the main directions of manganese element application in lithium battery positive electrode materials. With the continuous advancement of lithium battery positive electrode material research and development technology, the industrialization process of new manganese-based positive electrode materials such as lithium-rich manganese-based, lithium iron manganese phosphate, high-voltage lithium nickel manganese oxide, single crystal lithium manganese oxide and other new products is gradually accelerating, and the application of manganese-based positive electrode material precursors has ushered in greater development space.

[0004] Manganese-based battery positive electrode material precursor is the raw material of manganese-based battery positive electrode material, and plays a key role in the crystal synthesis, structural stability, physical properties and electrochemical properties, and even cost reduction of manganese-based positive electrode materials.

[0005] Most of the precursors of manganese-based battery positive electrode materials are prepared into hydroxides or carbonates through co-precipitation technology by preparing mixed salt solutions, controlling metal cations with chelating agents, using caustic soda or carbonate as precipitants. During co-precipitation, due to the different reaction conditions and reaction rates of various cations, chemical component segregation will occur in the precipitation process of the new substance. Using this method, it is difficult to incorporate multiple modifying elements into the matrix at the same time, and the expected effect cannot be achieved. It is not conducive to the role of doping elements and coating materials in improving the electrochemical properties of the positive electrode material and stabilizing its structure. The doping and coating effects are not good, so modifying elements are usually added in the mixing process of the positive electrode material preparation, and the positive electrode material is modified and prepared by high-temperature sintering. However, before the modifying elements are fused with the main matrix elements, due to the various modifying elements and the main matrix elements respectively reacting with lithium or sodium or The reaction conditions and rates of potassium are different. Before and after the formation of crystals in the positive electrode material, lithium, sodium, or potassium and the modifying element synthesize a small amount of heterogeneous material with a different crystal structure from the positive electrode material. This prevents the modifying element from entering the structure of the synthesized positive electrode material, and the modification effect does not achieve the expected goal. During the charge and discharge process, the anisotropy generated by the phase change of the positive electrode material synthesized by this method causes uneven volume changes, leading to stress accumulation within the positive electrode particles and inducing the appearance of intercrystalline cracks, resulting in the pulverization of secondary particles. It cannot effectively inhibit the side reactions between the positive electrode material crystal interface and the electrolyte, which increases the safety risks of the battery and is not conducive to extending the battery life. In addition, a large amount of wastewater, waste gas, and solid waste is generated during the preparation process, making it difficult to achieve zero discharge of pollutants such as wastewater, waste gas, and waste residue, which will have an adverse impact on the ecological environment.

[0006] For example, the patent application with publication number CN117923561A discloses a method for preparing a single crystal or quasi-single crystal lithium-rich manganese-based positive electrode material precursor, comprising: flowing a metal salt solution, a composite precipitant, a complexing agent and an oxidant into a reaction vessel in parallel, conducting a co-precipitation reaction, and then crystallizing to obtain the lithium-rich manganese-based positive electrode material precursor; wherein the metal salt in the metal salt solution includes a manganese salt and an M salt, and the M salt includes a nickel salt and / or a cobalt salt; and the composite precipitant includes a solution containing an alkaline substance and a soluble carbonate.

[0007] The patent application with publication number CN117985771A discloses a manganese-based positive electrode material precursor, which contains particles with a chemical formula of MnxNiyCozCO3; wherein x+y+z=1, 0.5≤x≤0.75, 0.1≤y≤0.25, and z>0; the tap density of the manganese-based positive electrode material precursor is greater than 1.7 g / cm3; the relative crystallinity of the manganese-based positive electrode material precursor is greater than 80%; in the XRR spectrum of the manganese-based positive electrode material precursor, the value of I(014) / I(018) is 2.5-4.0, I(014) represents the peak intensity of the crystal plane (014), and I(018) represents the peak intensity of the crystal plane (018).

[0008] Patent application with publication number CN109879332A discloses a method for preparing a spherical lithium-rich manganese-based positive electrode material precursor coated with a lamellar object, characterized in that: the preparation method of the precursor comprises the following steps: (1) preparing a metal salt solution: mixing a manganese salt, a cobalt salt and a nickel salt with water and dissolving them to obtain the metal salt solution; (2) preparing a mixed solution of a precipitant and a complexing agent: dissolving the precipitant and the complexing agent in water to obtain a mixed solution of the precipitant and the complexing agent; (3) adding the metal salt solution of step (1) and the mixed solution of the precipitant and the complexing agent of step (2) into a reactor to carry out a liquid-liquid coprecipitation reaction to obtain a precipitate A; (4) washing the precipitate A obtained in step (3) with deionized water for 2 to 10 times to obtain a precipitate B; (5) vacuum drying the precipitate B obtained in step (4) to obtain a spherical lithium-rich manganese-based positive electrode material precursor coated with a lamellar object. Summary of the Invention

[0009] Based on the deficiencies in the prior art, the purpose of the present invention is to provide a manganese-based battery positive electrode material precursor and its preparation method and application.

[0010] The specific technical solutions of the present invention are as follows:

[0011] A manganese-based battery positive electrode material precursor, the chemical formula of the precursor is: 1-x[(Mn 1-a A a )3O4]•xR, where 0.001≤a<1.0, 0.001≤x<1.0;

[0012] Preferably, 0.01≤a≤0.325, 0.01≤x≤0.05;

[0013] A is a doping element of a positive divalent or positive trivalent metal;

[0014] R is at least one selected from oxides of monovalent to hexavalent metals, or R is an oxide generated by decomposition of at least one of hydroxides, carbonates, acetates, and oxalates of monovalent to hexavalent metals;

[0015] The precursor is a spinel structure (Mn 1-a A a )3O4 and R oxide are compounded into secondary granular materials.

[0016] Preferably, the doping element A is selected from at least one of Mg, Al, Zn, La, Ni, Co, Sb, Y, and Bi, and the R is selected from at least one oxide of TiO2, SiO2, ZrO2, CeO2, Nb2O5, MoO3, and WO3, or a compound that can decompose to form the oxide.

[0017] As a preferred solution, the manganese-based battery is one of a manganese-based lithium battery, a manganese-based sodium battery, and a manganese-based potassium battery.

[0018] The present invention also provides a method for preparing a manganese-based battery positive electrode material precursor, comprising the following steps:

[0019] S1, mixing a manganese source and a doping element A source with a dispersant and pure water, respectively, and grinding to obtain a nanoscale slurry;

[0020] S2, mixing the slurry of step S1 and drying it to obtain a mixture;

[0021] S3, in air atmosphere, the mixture is subjected to multi-stage high temperature solid phase melting to prepare spinel structure ( )3O4, under high temperature environment, the mixture melts into liquid (this is because the kinetic energy of the thermal motion of the molecules increases, resulting in the destruction of the crystal phase and the process of the material changing from solid phase to liquid phase). At this time, a thermal activation reaction occurs, and the atoms of multiple components migrate, fuse and penetrate each other to form a new solid solution, realizing the doping modification of manganese-based positive electrode materials with multiple elements at the same time;

[0022] S4, the R source is mixed with the dispersant and pure water to obtain a nano-scale slurry, and then mixed with the spinel structure ( )3O4 is dispersed and mixed for the second time, dried and then coated at a high temperature of 600-800 ° C for 5-20 hours to finally obtain a manganese-based battery positive electrode material precursor.

[0023] The coating material melts under high temperature and becomes liquid. )3O4 has wetting force and surface tension on its surface, and the glass phase generated after the liquid phase is cooled is enriched in the spinel structure ( )3O4's surface to achieve a coating effect.

[0024] As a preferred embodiment, the manganese source is one or more of manganese tetraoxide, manganese trioxide, manganese dioxide, manganese hydroxide, manganese carbonate, and manganese acetate; the doping element A source is one or more of oxides, hydroxides, carbonates, acetates, and oxalates containing Mg, Al, Zn, La, Ni, Co, Sb, Y, and Bi; the R source is selected from one or more of TiO2, SiO2, ZrO2, CeO2, Nb2O5, MoO3, and WO3; the dispersant is one of polyethylene glycol, polyvinyl alcohol, polyacrylamide, and polyvinyl pyrrolidone, and its amount is 1.0%-10.0% of the mass of the nanoscale slurry in S1.

[0025] As a preferred solution, the multi-stage high-temperature sintering and melting step in S3 includes: first decomposing and oxidizing at 400-800°C for 2-10 hours, then heating to 800-1200°C for reaction for 5-20 hours, and then cooling to 500-750°C for repair calcination for 2-10 hours.

[0026] As a preferred solution, the amount of the R source added is spinel structure (Mn 1-a A a )0.5%-5.0% of the total molar amount of 3O4 precursor.

[0027] The manganese-based battery cathode material precursor prepared by the present invention has the following characteristics: particle size PSD-R50 is 0.7-15.0 μm, specific surface area ≤5.0 m² / g, tap density ≥2.0 g / cm³, and has a core-shell structure, wherein the core layer is ( )3O4 spinel phase, the shell is a uniform coating layer of R oxide.

[0028] The present invention also provides an application of a manganese-based battery positive electrode material precursor, characterized in that the application field is the manganese-based battery field, the manganese-based battery includes a positive electrode, an electrolyte and a negative electrode, and the precursor used for the positive electrode material is a manganese-based battery positive electrode material precursor.

[0029] (3) Beneficial technical effects

[0030] The present invention primarily utilizes a solid-phase method to prepare a manganese-based battery cathode material precursor using a high-temperature melting technique. This involves mixing a ground nanoscale manganese source and a doping element A source, sintering the mixture at high temperature, and then applying a surface coating. During this process, the manganese source and the doping element A source fuse and penetrate each other, evenly distributing their atoms. This maximizes the doping effect of the doping element, achieving a stable structure. This also optimizes the size, morphology, crystal planes, and grain boundaries of the primary particles of the cathode material precursor, providing beneficial ductility and chemical corrosion resistance for the subsequent synthesized cathode material. This improves density, inhibits side reactions between the cathode material crystal interface and the electrolyte, extends its service life, and enhances its safety during use. The small amount of water vapor and carbon dioxide generated during the preparation process is discharged into the atmosphere, eliminating any environmental pollution.

[0031] The preparation method of the present invention is simple and easy to industrialize and produce. It can form a variety of products and can be used as raw materials for the synthesis and preparation of positive electrode materials such as lithium manganese oxide, spinel nickel lithium manganese oxide, lithium iron manganese phosphate, lithium-rich manganese-based, sodium ion battery manganese-based layered oxide, and potassium ion battery manganese-based layered oxide.

[0032] In the step of preparing the precursor of the positive electrode material of manganese-based battery, the manganese source and the doping element A source are first ground and mixed, and then sintered and melted at high temperature in multiple stages (during the multi-stage high-temperature sintering process, the raw materials can fully decompose and oxidize, melt, crystal nucleate, grow, and repair crystal defects to obtain a precursor with high crystallinity), and a spinel structure ( )3O4; then disperse and mix it with the nano-scale slurry containing R source for a secondary dispersion, and perform coating treatment to finally obtain a manganese-based battery positive electrode material precursor. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a particle morphology diagram of the manganese-based battery positive electrode material precursor prepared in Example 6.

[0034] Figure 2 This is the particle size distribution diagram of the manganese-based battery positive electrode material precursor prepared in Example 6.

[0035] Figure 3 The manganese-based battery positive electrode material precursor prepared in Example 3 is used as a raw material to prepare the electrical performance cycle capacity retention rate of lithium battery positive electrode materials.

[0036] Figure 4 This is a comparative sample of the manganese-based battery positive electrode material precursor prepared in Example 3, which is used as a raw material to prepare the electrical performance cycle capacity retention rate of the positive electrode material.

[0037] Figure 5The manganese-based battery positive electrode material precursor prepared in Example 6 is used as a raw material to prepare the electrical performance cycle capacity retention rate of lithium battery positive electrode materials.

[0038] Figure 6 This is a comparative sample of the manganese-based battery positive electrode material precursor prepared in Example 6, which is used as a raw material to prepare the electrical performance cycle capacity retention rate of the positive electrode material.

[0039] Figure 7 This is a comparative sample of the manganese-based battery positive electrode material precursor prepared in Example 6, which is used as a raw material to prepare the electrical performance cycle capacity retention rate of the positive electrode material. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0041] The specific implementation of the present invention is described in detail below with reference to specific embodiments.

[0042] Example 1

[0043] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0044] S1. Ingredient measurement and weighing process:

[0045] (1) Measurement and weighing of manganese hydroxide Mn(OH)2 and magnesium oxide MgO: weigh them separately at a molar ratio of 0.99:0.01 and mark them as QM and QA respectively;

[0046] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0047] Measure and weigh the first portion of dispersant: its mass is 3% of the mass of QA and is marked as FS1 after weighing;

[0048] Measure and weigh the second portion of dispersant: its mass is 3% of the mass of QM and is marked as FS2 after weighing;

[0049] (3) Pure water measurement and weighing:

[0050] Measure and weigh the first portion of pure water: its mass is 150% of the QA mass and is marked as W1 after weighing;

[0051] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0052] S2. Dispersion, mixing, grinding and drying process:

[0053] (1) W1, FS1, and QA are added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0nm~200.0nm;

[0054] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 800.0nm to 3000.0nm;

[0055] S3. High temperature calcination crystallization process:

[0056] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere and decomposed and oxidized at 550℃ for 3h. The temperature was raised to 950℃ for 2h and decomposed, oxidized, solid-phase melted, crystal nucleated, grown, and synthesized for 10h. The temperature was lowered to 550℃ and the crystal was repaired and calcined for 2h. The temperature was then lowered to room temperature. After crushing, screening, and demagnetization, the semi-finished product WAL2 with spinel structure was obtained. Its chemical formula is (Mn 0.99 Mg 0.01 )3O4, its particle size PSD-R50 reaches 2.0~5.0μm.

[0057] S4. Secondary batching and weighing process:

[0058] (1) Titanium dioxide TiO2 measurement and weighing: the molar ratio of TiO2 to MAL2 is 0.01:0.99, and the weighed TiO2 and MAL2 are marked as QR and QMAL2 respectively;

[0059] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0060] Measure and weigh the third portion of dispersant: its mass is 4% of the mass of QR and is marked as FS3 after weighing;

[0061] Measure and weigh the fourth portion of dispersant: its mass is 4% of the mass of QMAL2 and is marked as FS4 after weighing;

[0062] (3) Pure water measurement and weighing:

[0063] Measure and weigh the third portion of pure water: its mass is 120% of the mass of QR and is marked as W3 after weighing;

[0064] Measure and weigh the fourth portion of pure water: its mass is 100% of the mass of QMAL2, and mark it as W4 after weighing;

[0065] S5. Secondary dispersion, mixing and drying process:

[0066] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0067] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0068] S6. High temperature calcination coating process:

[0069] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 680°C for 10 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.99 (Mn 0.99 Mg 0.01 )3O4•0.01TiO2, with a particle size of 2.0~6.0μm and a BET surface area of ​​0.25~0.32m 2 / g, and the tap density is 2.9~3.1g / cm 3 .

[0070] Example 2

[0071] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0072] S1. Ingredient measurement and weighing process:

[0073] (1) Measurement and weighing of manganese carbonate MnCO3, aluminum hydroxide Al(OH)3, and zinc oxide ZnO: weigh them separately in a molar ratio of 0.97:0.02:0.01 and mark them as QM, QA1, and QA2 respectively.

[0074] (2) Measurement and weighing of water-based dispersant polyvinyl alcohol (PVA):

[0075] Measure and weigh the first portion of dispersant: its mass is 3.5% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0076] Measure and weigh the second portion of dispersant: its mass is 3% of the mass of QM and is marked as FS2 after weighing;

[0077] (3) Pure water measurement and weighing:

[0078] Measure and weigh the first portion of pure water: its mass is 140% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0079] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0080] S2. Dispersion, mixing, grinding and drying process:

[0081] (1) W1, FS1, QA1 and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nano-scale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0nm~200.0nm;

[0082] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 4000.0nm;

[0083] S3. High temperature calcination crystallization process:

[0084] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere and decomposed and oxidized at 400℃ for 5 hours. The temperature was then raised to 900℃ for 2 hours and continued to decompose, oxidize, solid-phase melt, crystal nucleate, grow, and synthesize for 15 hours. The temperature was then lowered to 580℃ and the crystal was repaired and calcined for 3 hours. The temperature was then lowered to room temperature. After crushing, screening, and demagnetization, the semi-finished product WAL2 with spinel structure was obtained. Its chemical formula is (Mn 0.97 Al 0.02 Zn 0.01 )3O4, its particle size PSD-R50 reaches 2.0~6.0μm.

[0085] S4. Secondary batching and weighing process:

[0086] (1) Measurement and weighing of zirconium oxide ZrO2: the molar ratio of ZrO2 to MAL2 is 0.01:0.99, and the weighed parts are marked as QR and QMAL2 respectively;

[0087] (2) Measurement and weighing of water-based dispersant polyvinyl alcohol (PVA):

[0088] Measure and weigh the third portion of dispersant: its mass is 4% of the mass of QR and is marked as FS3 after weighing;

[0089] Measure and weigh the fourth portion of dispersant: its mass is 3.5% of the mass of QMAL2 and is marked as FS4 after weighing;

[0090] (3) Pure water measurement and weighing:

[0091] Measure and weigh the third portion of pure water: its mass is 110% of the mass of QR and is marked as W3 after weighing;

[0092] Measure and weigh the fourth portion of pure water: its mass is 100% of the mass of QMAL2, and mark it as W4 after weighing;

[0093] S5. Secondary dispersion, mixing and drying process:

[0094] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0095] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0096] S6. High temperature calcination coating process:

[0097] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 700°C for 8 hours in an air atmosphere. After cooling to room temperature, the product MAL5, a composite spinel structure manganese-based battery positive electrode material precursor, was obtained through crushing, screening, and demagnetization. Its chemical formula is 0.99 (Mn 0.97 Al 0.02 Zn 0.01 )3O4•0.01ZrO2, with a particle size of 2.5~7.0μm and a BET surface area of ​​0.22~0.30m 2 / g, and the tap density is 3.0~3.3g / cm 3 .

[0098] Example 3

[0099] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0100] S1. Ingredient measurement and weighing process:

[0101] (1) Measurement and weighing of manganese trioxide Mn2O3, aluminum oxide Al2O3, and lanthanum oxide La2O3: weigh them separately in a molar ratio of 0.96:0.03:0.01 and mark them as QM, QA1, and QA2 respectively;

[0102] (2) Measurement and weighing of water-based dispersant polyacrylamide (PAM):

[0103] Measure and weigh the first portion of dispersant: its mass is 5.0% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0104] Measure and weigh the second portion of dispersant: its mass is 4.5% of the mass of QM and is marked as FS2 after weighing;

[0105] (3) Pure water measurement and weighing:

[0106] Measure and weigh the first portion of pure water: its mass is 120% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0107] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0108] S2. Dispersion, mixing, grinding and drying process:

[0109] (1) W1, FS1, QA1 and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nano-scale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0nm~200.0nm;

[0110] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 4000.0nm;

[0111] S3. High temperature calcination crystallization process:

[0112] MAL1 was placed in a high-temperature synthesis sintering furnace and decomposed at 950°C, solid-phase melted, crystal nucleated, grown, and synthesized under air atmosphere for 12 hours. The temperature was then lowered to 600°C, and the crystals were repaired and calcined for 2 hours. The crystals were then cooled to room temperature. After crushing, screening, and demagnetization, the semi-finished product WAL2 with a spinel structure was obtained. Its chemical formula is (Mn 0.96 Al 0.03 La 0.01 )3O4, and its particle size PSD-R50 reaches 3.0~7.0μm.

[0113] S4. Secondary batching and weighing process:

[0114] (1) Measure and weigh silicon dioxide SiO2: the molar ratio of SiO2 to MAL2 is 0.01:0.99. After weighing, mark them as QR and QMAL2 respectively.

[0115] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0116] The third portion of dispersant is measured and weighed: its mass is 4.2% of the mass of QR, and it is marked as FS3 after weighing;

[0117] Measure and weigh the fourth portion of dispersant: its mass is 5.1% of the mass of QMAL2 and is marked as FS4 after weighing;

[0118] (3) Pure water measurement and weighing:

[0119] Measure and weigh the third portion of pure water: its mass is 110% of the mass of QR and is marked as W3 after weighing;

[0120] Measure and weigh the fourth portion of pure water: its mass is 100% of the mass of QMAL2 and is marked as W4 after weighing;

[0121] S5. Secondary dispersion, mixing and drying process:

[0122] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0123] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0124] S6. High temperature calcination coating process:

[0125] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 670°C for 9 hours under air atmosphere. After cooling to room temperature, the product MAL5, a composite spinel structure manganese-based battery positive electrode material precursor, was obtained through crushing, screening, and demagnetization. Its chemical formula is 0.99 (Mn 0.96 Al 0.03 La 0.01 )3O4•0.01SiO2, with a particle size of 2.0~6.0μm and a specific surface area of ​​0.25~0.35m 2 / g, and the tap density is 3.05~3.3g / cm 3 .

[0126] Example 4

[0127] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0128] S1. Ingredient measurement and weighing process:

[0129] (1) Manganese acetate (CH3COO) 2Mn, nickelous oxide NiO, and antimony trioxide Sb2O3 are weighed and weighed in a molar ratio of 0.97:0.02:0.005. The weighed parts are marked as QM, QA1, and QA2 respectively.

[0130] (2) Measurement and weighing of aqueous dispersant polyvinylpyrrolidone (PVP):

[0131] Measure and weigh the first portion of dispersant: its mass is 1% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0132] Measure and weigh the second portion of dispersant: its mass is 1% of the mass of QM and is marked as FS2 after weighing;

[0133] (3) Pure water measurement and weighing:

[0134] Measure and weigh the first portion of pure water: its mass is 140% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0135] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0136] S2. Dispersion, mixing, grinding and drying process:

[0137] (1) W1, FS1, QA1 and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nano-scale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0nm~200.0nm;

[0138] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 700.0nm to 3000.0nm;

[0139] S3. High temperature calcination crystallization process:

[0140] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere, decomposed and oxidized at 450℃ for 3h, heated to 960℃ for 2h, decomposed, oxidized, solid-phase melted, crystal nucleated, crystal grew, and synthesized for 11h, cooled to 610℃, and repaired by calcination for 3h, cooled to room temperature, and crushed, sieved, and demagnetized to obtain the spinel structure semi-finished product WAL2, whose chemical formula is (Mn 0.97 Ni 0.02 Sb 0.01 )3O4, its particle size PSD-R50 reaches 2.5~5.0μm.

[0141] S4. Secondary batching and weighing process:

[0142] (1) Measurement and weighing of cerium dioxide CeO2: the molar ratio of CeO2 to MAL2 is 0.02:0.98. After weighing, they are marked as QR and QMAL2 respectively;

[0143] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0144] Measure and weigh the third portion of dispersant: its mass is 1% of the mass of QR and is marked as FS3 after weighing;

[0145] Measure and weigh the fourth portion of dispersant: its mass is 1% of the mass of QMAL2 and is marked as FS4 after weighing;

[0146] (3) Pure water measurement and weighing:

[0147] Measure and weigh the third portion of pure water: its mass is 110% of the mass of QR and is marked as W3 after weighing;

[0148] Measure and weigh the fourth portion of pure water: its mass is 100% of the mass of QMAL2 and is marked as W4 after weighing;

[0149] S5. Secondary dispersion, mixing and drying process:

[0150] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0151] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0152] S6. High temperature calcination coating process:

[0153] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 710°C for 11 hours under air atmosphere. After cooling to room temperature, the product MAL5, a composite spinel structure manganese-based battery positive electrode material precursor, was obtained through crushing, screening, and demagnetization. Its chemical formula is 0.98 (Mn 0.97 Ni 0.02 Sb 0.01 )3O4•0.02CeO2, with a particle size of 2.5~6.0μm and a BET surface area of ​​0.25~0.40m 2 / g, and the tap density is 3.1~3.3g / cm 3 .

[0154] Example 5

[0155] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0156] S1. Ingredient measurement and weighing process:

[0157] (1) Manganese oxalate MnC2O4, cobalt carbonate CoCO3, and aluminum hydroxide Al(OH)3, measurement and weighing: weigh the three in a molar ratio of 0.95:0.02:0.03, and mark them as QM, QA1, and QA2 respectively;

[0158] (2) Measurement and weighing of aqueous dispersant polyvinylpyrrolidone (PVP):

[0159] Measure and weigh the first portion of dispersant: its mass is 4.5% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0160] The second portion of dispersant is measured and weighed: its mass is 4.8% of the mass of QM and is marked as FS2 after weighing;

[0161] (3) Pure water measurement and weighing:

[0162] Measure and weigh the first portion of pure water: its mass is 140% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0163] Measure and weigh the second portion of pure water: its mass is 90% of the mass of QM and is marked as W2 after weighing;

[0164] S2. Dispersion, mixing, grinding and drying process:

[0165] (1) W1, FS1, QA1, and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0 nm to 200.0 nm.

[0166] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 3000.0nm;

[0167] S3. High temperature calcination crystallization process:

[0168] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere, decomposed and oxidized at 450℃ for 3h, heated to 960℃ for 2h, decomposed, oxidized, solid-phase melted, crystal nucleated, crystal grew, and synthesized for 11h, cooled to 610℃, and repaired by calcination for 3h, cooled to room temperature, and crushed, sieved, and demagnetized to obtain the spinel structure semi-finished product WAL2, whose chemical formula is (Mn 0.95 Co 0.02 Al 0.03 )3O4, its particle size PSD-R50 reaches 2.0~5.0μm.

[0169] S4. Secondary batching and weighing process:

[0170] (1) Molybdenum oxide MoO3 was measured and weighed: the molar ratio of MoO3 to MAL2 was 0.015:0.985. After weighing, they were marked as QR and QMAL2 respectively.

[0171] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0172] The third portion of dispersant is measured and weighed: its mass is 4.1% of the mass of QR and is marked as FS3 after weighing;

[0173] Measure and weigh the fourth portion of dispersant: its mass is 5.1% of the mass of QMAL2 and is marked as FS4 after weighing;

[0174] (3) Pure water measurement and weighing:

[0175] Measure and weigh the third portion of pure water: its mass is 120% of the mass of QR and is marked as W3 after weighing;

[0176] Measure and weigh the fourth portion of pure water: its mass is 100% of the mass of QMAL2 and is marked as W4 after weighing;

[0177] S5. Secondary dispersion, mixing and drying process:

[0178] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0179] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0180] S6. High temperature calcination coating process:

[0181] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 710°C for 11 hours under air atmosphere. After cooling to room temperature, the product MAL4, a composite spinel structure manganese-based battery positive electrode material precursor, was obtained through crushing, screening, and demagnetization. Its chemical formula is 0.985 (Mn 0.95 Co 0.02 Al 0.03 )3O4•0.015MoO3, with a particle size of 2.5~6.0μm and a BET surface area of ​​0.21~0.35m 2 / g, and the tap density is 3.1~3.4g / cm 3 .

[0182] Example 6

[0183] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0184] S1. Ingredient measurement and weighing process:

[0185] (1) Measurement and weighing of manganese tetraoxide (Mn3O4) and nickel carbonate (NiCO3): weigh them separately at a molar ratio of Mn to Ni of 0.75:0.25 and mark them as QM and QA respectively.

[0186] (2) Measurement and weighing of water-based dispersant polyacrylamide (PAM):

[0187] Measure and weigh the first portion of dispersant: its mass is 4.3% of the mass of QA and is marked as FS1 after weighing;

[0188] Measure and weigh the second portion of dispersant: its mass is 4.5% of the mass of QM and is marked as FS2 after weighing;

[0189] (3) Pure water measurement and weighing:

[0190] Measure and weigh the first portion of pure water: its mass is 100% of the QA mass and is marked as W1 after weighing;

[0191] Measure and weigh the second portion of pure water: its mass is 95% of the mass of QM and is marked as W2 after weighing;

[0192] S2. Dispersion, mixing, grinding and drying process:

[0193] (1) W1, FS1, and QA are added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0nm~200.0nm;

[0194] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 700.0nm to 4000.0nm;

[0195] S3. High temperature calcination crystallization process:

[0196] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere and decomposed and oxidized at 420℃ for 3.5h. The temperature was raised to 945℃ for 2h for decomposition, oxidation, solid phase melting, crystal nucleation, crystal growth, and crystal synthesis for 12h. The temperature was then lowered to 620℃ and the crystal was repaired and calcined for 3h. The crystal was then cooled to room temperature. After crushing, screening, and demagnetization, the semi-finished product WAL2 with spinel structure was obtained. Its chemical formula is (Mn 0.75 Ni 0.25 )3O4, and its particle size PSD-R50 reaches 2.5~6.0μm.

[0197] S4. Secondary batching and weighing process:

[0198] (1) Titanium dioxide TiO2 measurement and weighing: the molar ratio of TiO2 to MAL2 is 0.02:0.98, and the weighed TiO2 and MAL2 are marked as QR and QMAL2 respectively;

[0199] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0200] Measure and weigh the third portion of dispersant: its mass is 4.5% of the mass of QR and is marked as FS3 after weighing;

[0201] Measure and weigh the fourth portion of dispersant: its mass is 5.2% of the mass of QMAL2 and is marked as FS4 after weighing;

[0202] (3) Pure water measurement and weighing:

[0203] Measure and weigh the third portion of pure water: its mass is 130% of the mass of QR and is marked as W3 after weighing;

[0204] Measure and weigh the fourth portion of pure water: its mass is 90% of the mass of QMAL2 and is marked as W4 after weighing;

[0205] S5. Secondary dispersion, mixing and drying process:

[0206] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0207] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0208] S6. High temperature calcination coating process:

[0209] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 620°C for 8 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.98 (Mn 0.75 Ni0 .25 )3O4•0.02TiO2, with a particle size of 3.0~7.0μm and a BET surface area of ​​0.22~0.36m 2 / g, and the tap density is 3.2~3.35g / cm 3 .

[0210] Example 7

[0211] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0212] S1. Ingredient measurement and weighing process:

[0213] (1) Manganese dioxide (MnO2), cobalt carbonate (CoCO3), and nickelous oxide (NiO) were weighed in a molar ratio of 0.675:0.1625:0.1625, and marked as QM, QA1, and QA2 respectively.

[0214] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0215] Measure and weigh the first portion of dispersant: its mass is 3.0% of the sum of the masses of QA1 and QA2, and mark it as FS1 after weighing;

[0216] The second portion of dispersant is measured and weighed: its mass is 2.5% of the mass of QM and is marked as FS2 after weighing;

[0217] (3) Pure water measurement and weighing:

[0218] Measure and weigh the first portion of pure water: its mass is 110% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0219] Measure and weigh the second portion of pure water: its mass is 90% of the mass of QM and is marked as W2 after weighing;

[0220] S2. Dispersion, mixing, grinding and drying process:

[0221] (1) W1, FS1, QA1, and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0 nm to 200.0 nm.

[0222] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 4000.0nm;

[0223] S3. High temperature calcination crystallization process:

[0224] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere, decomposed and oxidized at 480℃ for 3h, heated to 980℃ for 2h, decomposed, oxidized, solid-phase melted, crystal nucleated, crystal grew, and synthesized for 20h, cooled to 680℃, and repaired by calcination for 3h, then cooled to room temperature, and crushed, sieved, and demagnetized to obtain the spinel structure semi-finished product WAL2, whose chemical formula is (Mn 0.675 Co 0.1625 Ni 0.1625 )3O4, its particle size PSD-R50 reaches 2.0~6.0μm.

[0225] S4. Secondary batching and weighing process:

[0226] (1) Measurement and weighing of niobium pentoxide Nb2O5: the molar ratio of Nb2O5 to MAL2 is 0.01:0.99. After weighing, mark them as QR and QMAL2 respectively;

[0227] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0228] Measure and weigh the third portion of dispersant: its mass is 3% of the mass of QR and is marked as FS3 after weighing;

[0229] Measure and weigh the fourth portion of dispersant: its mass is 3% of the mass of QMAL2 and is marked as FS4 after weighing;

[0230] (3) Pure water measurement and weighing:

[0231] Measure and weigh the third portion of pure water: its mass is 130% of the mass of QR and is marked as W3 after weighing;

[0232] Measure and weigh the fourth portion of pure water: its mass is 110% of the mass of QMAL2 and is marked as W4 after weighing;

[0233] S5. Secondary dispersion, mixing and drying process:

[0234] (1) W3, FS3, and QR are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm~200.0nm;

[0235] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0236] S6. High temperature calcination coating process:

[0237] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 650°C for 10 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.99(Mn 0.675 Co 0.1625 Ni 0.1625 )3O4•0.01Nb2O5, with a particle size of 2.5~7.0μm and a BET surface area of ​​0.20~0.36m 2 / g, and the tap density is 3.3~3.5g / cm 3 .

[0238] Example 8

[0239] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0240] S1. Ingredient measurement and weighing process:

[0241] (1) Manganese hydroxide Mn(OH)2, cobalt carbonate CoCO3, nickel hydroxide Ni(OH)2, and aluminum hydroxide Al(OH)3 are weighed and weighed in a molar ratio of 0.675:0.16:0.16:0.005. After weighing, they are marked as QM, QA1, QA2, and QA3 respectively.

[0242] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0243] Measure and weigh the first portion of dispersant: its mass is 3.5% of the total mass of QA1, QA2, and QA3, and mark it as FS1 after weighing;

[0244] The second portion of dispersant is measured and weighed: its mass is 3.5% of the mass of QM and is marked as FS2 after weighing;

[0245] (3) Pure water measurement and weighing:

[0246] Measure and weigh the first portion of pure water: its mass is 110% of the sum of the masses of QA1, QA2, and QA3, and mark it as W1 after weighing;

[0247] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0248] S2. Dispersion, mixing, grinding and drying process:

[0249] (1) W1, FS1, QA1, QA2, and QA3 were added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0 nm to 200.0 nm.

[0250] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 700.0nm to 4000.0nm;

[0251] S3. High temperature calcination crystallization process:

[0252] MAL1 was placed in a high-temperature synthesis sintering furnace under air atmosphere, decomposed and oxidized at 490℃ for 3h, heated to 970℃ for 2h, decomposed, oxidized, solid-phase melted, crystal nucleated, crystal grew, and synthesized for 18h, cooled to 660℃, and repaired by calcination for 3h, cooled to room temperature, and crushed, sieved, and demagnetized to obtain the spinel structure semi-finished product WAL2, whose chemical formula is (Mn 0.675 Co 0.16 Ni 0.16 Al 0.005 )3O4, its particle size PSD-R50 reaches 2.0~6.0μm.

[0253] S4. Secondary batching and weighing process:

[0254] (1) Niobium pentoxide Nb2O5 and cerium dioxide CeO2 were weighed and measured: the molar ratio of the two to MAL2 was 0.005:0.01:0.985. After weighing, they were marked as QR1, QR2, and QMAL2 respectively;

[0255] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0256] Measure and weigh the third portion of dispersant: its mass is 3.5% of the total mass of QR1 and QR2, and mark it as FS3 after weighing;

[0257] Measure and weigh the fourth portion of dispersant: its mass is 3.5% of the mass of QMAL2 and is marked as FS4 after weighing;

[0258] (3) Pure water measurement and weighing:

[0259] Measure and weigh the third portion of pure water: its mass is 100% of the sum of the masses of QR1 and QR2, and mark it as W3 after weighing;

[0260] Measure and weigh the fourth portion of pure water: its mass is 110% of the mass of QMAL2 and is marked as W4 after weighing;

[0261] S5. Secondary dispersion, mixing and drying process:

[0262] (1) W3, FS3, QR1, and QR2 are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm to 200.0nm;

[0263] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0264] S6. High temperature calcination coating process:

[0265] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 760°C for 10 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.985(Mn 0.675 Co 0.16 Ni 0.16 Al 0.005 )3O4•0.005Nb2O5•0.01CeO2, with a particle size of 3.0~7.0μm and a BET surface area of ​​0.21~0.37m 2 / g, and the tap density is 3.2~3.4g / cm 3 .

[0266] Example 9

[0267] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0268] S1. Ingredient measurement and weighing process:

[0269] (1) Measurement and weighing of manganese tetraoxide (Mn3O4) and yttrium trioxide (Y2O3): Weigh them separately at a molar ratio of Mn to Y of 0.98:0.02 and mark them as QM and QA respectively.

[0270] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0271] Measure and weigh the first portion of dispersant: its mass is 4.0% of the mass of QA and is marked as FS1 after weighing;

[0272] Measure and weigh the second portion of dispersant: its mass is 3.0% of the mass of QM and is marked as FS2 after weighing;

[0273] (3) Pure water measurement and weighing:

[0274] Measure and weigh the first portion of pure water: its mass is 110% of the QA mass and is marked as W1 after weighing;

[0275] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0276] S2. Dispersion, mixing, grinding and drying process:

[0277] (1) W1, FS1, and QA are added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0nm~200.0nm;

[0278] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 4000.0nm;

[0279] S3. High temperature calcination crystallization process:

[0280] MAL1 was placed in a high-temperature synthesis sintering furnace and oxidized at 500°C for 3 hours in an air atmosphere. The temperature was then raised to 990°C for 2 hours for oxidation, solid phase melting, crystal nucleation, crystal growth, and crystal synthesis for 18 hours. The temperature was then lowered to 650°C, and the crystal was repaired and calcined for 3 hours. The crystal was then cooled to room temperature and crushed, sieved, and demagnetized to obtain a spinel structure semi-finished product WAL2. Its chemical formula is (Mn 0.98 Y 0.02 )3O4, its particle size PSD-R50 reaches 2.0~6.0μm.

[0281] S4. Secondary batching and weighing process:

[0282] (1) Niobium pentoxide Nb2O5 and titanium dioxide TiO2 were weighed and measured in a molar ratio of 0.005:0.01:0.985 to MAL2. After weighing, they were marked as QR1, QR2, and QMAL2 respectively.

[0283] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0284] Measure and weigh the third portion of dispersant: its mass is 3.5% of the total mass of QR1 and QR2, and mark it as FS3 after weighing;

[0285] Measure and weigh the fourth portion of dispersant: its mass is 3.5% of the mass of QMAL2 and is marked as FS4 after weighing;

[0286] (3) Pure water measurement and weighing:

[0287] Measure and weigh the third portion of pure water: its mass is 100% of the sum of the masses of QR1 and QR2, and mark it as W3 after weighing;

[0288] Measure and weigh the fourth portion of pure water: its mass is 110% of the mass of QMAL2 and is marked as W4 after weighing;

[0289] S5. Secondary dispersion, mixing and drying process:

[0290] (1) W3, FS3, QR1, and QR2 are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm to 200.0nm;

[0291] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0292] S6. High temperature calcination coating process:

[0293] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 620°C for 10 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.985(Mn 0.98 Y 0.02 )3O4•0.005Nb2O5•0.01TiO2, with a PSD-R50 particle size of 2.5~7.0μm and a BET surface area of ​​0.25~0.35m 2 / g, and the tap density is 3.1~3.5g / cm 3 .

[0294] Example 10

[0295] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0296] S1. Ingredient measurement and weighing process:

[0297] (1) Manganese acetate (CH3COO)2Mn, bismuth oxide Bi2O3, and aluminum hydroxide Al(OH)3 were weighed and weighed separately in a molar ratio of 0.95:0.01:0.04. The weighed parts were marked as QM, QA1, and QA2 respectively.

[0298] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0299] Measure and weigh the first portion of dispersant: its mass is 4.5% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0300] The second portion of dispersant is measured and weighed: its mass is 3.5% of the mass of QM and is marked as FS2 after weighing;

[0301] (3) Pure water measurement and weighing:

[0302] Measure and weigh the first portion of pure water: its mass is 120% of the sum of the masses of QA1 and QA2, and mark it as W1 after weighing;

[0303] Measure and weigh the second portion of pure water: its mass is 100% of the mass of QM and is marked as W2 after weighing;

[0304] S2. Dispersion, mixing, grinding and drying process:

[0305] (1) W1, FS1, QA1, and QA2 were added to the grinding equipment in sequence, dispersed and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reached 100.0 nm to 200.0 nm.

[0306] (2) W2, FS2, and QM are sequentially added to the grinding equipment and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL, which is then dried in a drying equipment to obtain a mixed material MAL1, the particle size PSD-R50 of which is 600.0nm to 4000.0nm;

[0307] S3. High temperature calcination crystallization process:

[0308] MAL1 was placed in a high-temperature synthesis sintering furnace and oxidized at 460°C for 3 hours in an air atmosphere. The temperature was then raised to 910°C for 2 hours for oxidation, solid phase melting, crystal nucleation, crystal growth, and crystal synthesis for 12 hours. The temperature was then lowered to 620°C, and the crystal was repaired and calcined for 3 hours. The crystal was then cooled to room temperature and crushed, sieved, and demagnetized to obtain a spinel structure semi-finished product WAL2. Its chemical formula is (Mn 0.95 Bi 0.01 Al 0.04 )3O4, its particle size PSD-R50 reaches 2.0~6.0μm.

[0309] S4. Secondary batching and weighing process:

[0310] (1) Measure and weigh tungsten trioxide WO3 and aluminum oxide Al2O3: the molar ratio of the two to MAL2 is 0.01:0.02:0.97. After weighing, mark them as QR1, QR2 and QMAL2 respectively;

[0311] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0312] Measure and weigh the third portion of dispersant: its mass is 3.5% of the total mass of QR1 and QR2, and mark it as FS3 after weighing;

[0313] Measure and weigh the fourth portion of dispersant: its mass is 3.5% of the mass of QMAL2 and is marked as FS4 after weighing;

[0314] (3) Pure water measurement and weighing:

[0315] Measure and weigh the third portion of pure water: its mass is 100% of the sum of the masses of QR1 and QR2, and mark it as W3 after weighing;

[0316] Measure and weigh the fourth portion of pure water: its mass is 110% of the mass of QMAL2 and is marked as W4 after weighing;

[0317] S5. Secondary dispersion, mixing and drying process:

[0318] (1) W3, FS3, QR1, and QR2 are added to the grinding equipment in sequence, dispersed, uniformly mixed, and ground together to form a uniform nanoscale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0nm to 200.0nm;

[0319] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and evenly mix them with RL1 to obtain a uniformly mixed slurry, which is then dried in a drying equipment to obtain the mixed material MAL3;

[0320] S6. High temperature calcination coating process:

[0321] MAL3 was placed in a high-temperature synthesis sintering furnace and coated at 720°C for 10 hours in an air atmosphere. After cooling to room temperature, the product was crushed, sieved, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.97(Mn 0.95 Bi 0.01 Al 0.04 )3O4•0.01WO3•0.02Al2O3, with a particle size of 2.5~7.5μm and a BET surface area of ​​0.20~0.33m 2 / g, and the tap density is 3.1~3.4g / cm 3 .

[0322] Test Example 1

[0323] In order to illustrate the effect of the manganese-based battery positive electrode material precursor prepared by the technology of the present invention, the manganese-based battery positive electrode material precursor 0.99 (Mn 0.96 Al 0.03 La 0.01 )3O4•0.01SiO2, and lithium carbonate Li2CO3, are matched and uniformly mixed, sintered, crushed, sieved, and demagnetized to prepare the lithium battery positive electrode material 0.99Li (Mn 0.96 Al 0.03 La 0.01 )2O4•0.01SiO2, the electrical performance indicators of the simulated half-cell test are: in the power supply range of 3.0~4.3V, the 0.2C discharge capacity is 134.02mAh / g, and the 1C charge and discharge cycle is 60 weeks, with a capacity retention rate of 97.5% ( Figure 3 );

[0324] According to the combination of equivalent components, lithium carbonate Li2CO3 is matched with manganese trioxide Mn2O3, aluminum oxide Al2O3, and lanthanum oxide La2O3, and a semi-finished product is obtained through the steps of uniform mixing, sintering synthesis, crushing, screening, and demagnetization. The semi-finished product is then matched with SiO2, and a lithium battery positive electrode material 0.99Li (Mn 0.96 Al 0.03 La 0.01 )2O4•0.01SiO2, the electrical performance indicators of the simulated half-cell test are: in the power supply range of 3.0~4.3V, the 0.2C discharge capacity is 128.65mAh / g, and the 1C charge and discharge cycle is 60 weeks, with a capacity retention rate of 93.6% ( Figure 4 );

[0325] Compared with two different preparation methods, the lithium battery positive electrode material prepared by the technology of the present invention has a specific capacity increased by 5.37mAh / g and a cycle capacity retention rate increased by 3.9 percentage points compared with the same lithium battery positive electrode material prepared by other preparation methods.

[0326] Test Example 2

[0327] In order to illustrate the effect of the manganese-based battery positive electrode material precursor prepared by the technology of the present invention, the manganese-based battery positive electrode material precursor 0.98 (Mn 0.75 Ni 0.25 )3O4•0.02TiO2 and lithium carbonate Li2CO3 are matched and uniformly mixed, sintered, crushed, sieved, and demagnetized to prepare the lithium battery positive electrode material 0.98 (LiMn 1.5 Ni 0.5 O4)•0.02TiO2, the electrical performance indicators of the simulated half-cell test are: in the power supply range of 3.0~5.0V, the 0.2C discharge capacity is 142.31mAh / g, and the 1C charge and discharge cycle is 100 weeks, and the capacity retention rate is 99.89% ( Figure 5 ).

[0328] According to the combination of equivalent components, lithium carbonate Li2CO3 is matched with manganese tetraoxide Mn3O4 and nickel carbonate NiCO3, and a semi-finished product is obtained through the steps of uniform mixing, sintering synthesis, crushing, screening, and demagnetization. The semi-finished product is then matched with TiO2, and a lithium battery positive electrode material 0.98 (LiMn 1.5 Ni 0.5 O4)•0.02TiO2, the electrical performance indicators of the simulated half-cell test are: in the power supply range of 3.0~5.0V, the 0.2C discharge capacity is 135.12mAh / g, and the 1C charge and discharge cycle is 100 weeks, with a capacity retention rate of 96.2% ( Figure 6 ).

[0329] According to the combination of equal components, the metal salt solution obtained by dissolving manganese salt and nickel salt in water is mixed with a complexing agent and a precipitant to perform a coprecipitation reaction to prepare the precursor Mn 0.75 Ni 0.25 (OH)2, lithium carbonate Li2CO3 and the precursor Mn prepared by this co-precipitation method 0.75 Ni 0.25 (OH)2, and a semi-finished product is obtained through the steps of uniform mixing, sintering synthesis, crushing, screening, and demagnetization. The semi-finished product is then matched with TiO2, and a lithium battery positive electrode material 0.98 (LiMn 1.5 Ni 0.5O4)•0.02TiO2, the electrical performance indicators of the simulated half-cell test are: in the power supply range of 3.0~5.0V, the 0.2C discharge capacity is 138.89mAh / g, and the 1C charge and discharge cycle is 100 weeks, and the capacity retention rate is 98.1% ( Figure 7 );

[0330] Compared with three different preparation methods, the specific capacity of the lithium battery positive electrode material prepared by the technology of the present invention and the same positive lithium battery positive electrode material prepared by other preparation methods are respectively increased by 7.19mAh / g and 3.42mAh / g, and the cycle capacity retention rate is respectively increased by 3.69 percentage points and 1.79 percentage points.

Claims

1. A manganese-based battery positive electrode material precursor, characterized in that: The general chemical formula of the precursor is: 1-x[(Mn 1- a A a )3O4]•xR, where 0.001≤a<1.0, 0.001≤x<1.0; A is a doping element of a positive divalent or positive trivalent metal; R is at least one selected from monovalent to hexavalent metal oxides, or R is an oxide generated by decomposition of at least one substance selected from monovalent to hexavalent metal hydroxides, carbonates, acetates, and oxalates; The precursor is a spinel structure (Mn 1-a A a )3O4 and R oxide are combined to form secondary particle materials; The method for preparing the manganese-based battery positive electrode material precursor comprises the following steps: S1, mixing a manganese source and a doping element A source with a dispersant and pure water, respectively, and grinding to obtain a nanoscale slurry; S2, mixing the slurry of step S1 and drying it to obtain a mixture; S3, in air atmosphere, the mixture is subjected to multi-stage high temperature solid phase melting to prepare spinel structure ( )3O4; S4, the R source is mixed with the dispersant and pure water to obtain a nano-scale slurry, and then mixed with the spinel structure ( )3O4 is dispersed and mixed for the second time, dried and then coated at a high temperature of 600-800 ° C for 5-20 hours to finally obtain a manganese-based battery positive electrode material precursor.

2. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The doping element A is selected from at least one of Mg, Al, Zn, La, Ni, Co, Sb, Y, and Bi, and the R is selected from at least one oxide of TiO2, SiO2, ZrO2, CeO2, Nb2O5, MoO3, and WO3, or a compound that can decompose to form the oxide.

3. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The manganese-based battery is one of a manganese-based lithium battery, a manganese-based sodium battery, and a manganese-based potassium battery.

4. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The manganese source is one or more of manganese tetraoxide, manganese trioxide, manganese dioxide, manganese hydroxide, manganese carbonate, and manganese acetate; the doping element A source is one or more of oxides, hydroxides, carbonates, acetates, and oxalates containing Mg, Al, Zn, La, Ni, Co, Sb, Y, and Bi; the R source is one or more of TiO2, SiO2, ZrO2, CeO2, Nb2O5, MoO3, and WO3; the dispersant is one of polyethylene glycol, polyvinyl alcohol, polyacrylamide, and polyvinyl pyrrolidone, and its usage is 1.0%-10.0% of the mass of the nanoscale slurry in S1.

5. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The multi-stage high-temperature sintering and melting step in S3 includes: first decomposing and oxidizing at 400-800°C for 2-10 hours, then heating to 800-1200°C for reaction for 5-20 hours, and then cooling to 500-750°C for repair calcination for 2-10 hours.

6. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The amount of the R source added is spinel structure (Mn 1-a A a )0.5%-5.0% of the total molar amount of 3O4 precursor.

7. The manganese-based battery positive electrode material precursor according to claim 1, characterized in that: The prepared manganese-based battery cathode material precursor has the following characteristics: particle size PSD-R50 is 0.7-15.0μm, specific surface area ≤5.0m² / g, tap density ≥2.0g / cm³, and has a core-shell structure, in which the core layer is ( )3O4 spinel phase, the shell is a uniform coating layer of R oxide.

8. The use of the manganese-based battery positive electrode material precursor according to any one of claims 1 to 7, characterized in that: The application field is the field of manganese-based batteries. Manganese-based batteries include a positive electrode, an electrolyte and a negative electrode. The precursor used in the positive electrode material is a manganese-based battery positive electrode material precursor.

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