Manganese-based battery positive electrode material precursor and preparation method and application thereof

Abstract

The invention relates to the technical field of battery positive electrode materials, discloses a manganese-based battery positive electrode material precursor as well as a preparation method and application thereof, and belongs to the technical field of battery preparation. According to the technology for preparing the manganese-based battery positive electrode material precursor, a solid-phase method is mainly adopted, a high-temperature melting technology is adopted, the manganese-based positive electrode material is subjected to doping modification through multiple elements at the same time, then surface coating is carried out, the density of the synthesized positive electrode material is improved, the structural stability of the synthesized positive electrode material is enhanced, and the morphology, the crystal face and the crystal boundary of the positive electrode material are optimized; the side reaction between the crystal interface of the positive electrode material and electrolyte is inhibited, the service life is prolonged, and the safety performance during use is enhanced. A small amount of water vapor and carbon dioxide gas generated in the preparation process are discharged at high altitude, so that the environment is not polluted.

Description

Technical Field

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

[0002] With the gradual expansion of the electric vehicle market and the wide application of energy storage systems, as well as the continuous expansion in the fields of smart devices, heavy trucks, ships, airplanes, construction machinery, etc., the battery industry has entered a new stage of development. New technologies and products of battery cathode materials have been continuously developed to meet the market demands of batteries with high energy density, high safety, long life, and low cost.

[0003] Currently, lithium manganate and lithium nickel cobalt manganate are the main directions of manganese element application in lithium-ion battery cathode materials. With the continuous progress of lithium-ion battery cathode material research and development technology, the industrialization process of new manganese-based cathode materials such as lithium-rich manganese-based, lithium iron phosphate manganese, high-voltage lithium nickel manganate, single-crystal lithium manganate, etc. has gradually accelerated, and the application of manganese-based battery cathode material precursors has a greater development space.

[0004] The manganese-based battery cathode material precursor is the raw material of the manganese-based battery cathode material, and plays a key role in aspects such as crystal synthesis, structural stability, physical properties, and electrochemical properties of the manganese-based battery cathode material, and even cost reduction.

[0005] Most of the precursors of the cathode materials for manganese-based batteries are prepared by formulating a mixed salt solution, controlling metal cations with a complexing agent, using sodium hydroxide or carbonate as a precipitating agent, and preparing hydroxides or carbonates through a co-precipitation technique. During co-precipitation, due to different reaction conditions and rates of various cations, chemical component segregation will occur during the precipitation process of the new substance formation. Using this method, it is difficult to incorporate multiple modified elements into the matrix simultaneously, and the expected effect cannot be achieved, which is not conducive to exerting the role of doping elements and coating substances in improving the electrochemical performance of the cathode material and stabilizing its structure. The doping and coating effects are not good. Therefore, modified elements are usually added during the mixing process of the cathode material preparation, and the cathode material is prepared by high-temperature sintering for modification. However, before the modified elements are fused with the main matrix elements, due to different reaction conditions and rates of various modified elements and main matrix elements with lithium, sodium, or potassium elements respectively, before and after the formation of crystals in the cathode material, lithium, sodium, or potassium elements and the modified elements synthesize a small amount of heterogeneous substances different from the crystal structure of the cathode material, resulting in the modified elements not being able to enter the structure of the synthesized cathode material, and the modification effect not reaching the expected goal. The cathode material synthesized by this method has uneven volume change due to the anisotropy generated by phase change during charge and discharge, resulting in the accumulation of internal stress in the cathode particles and inducing the appearance of intergranular cracks, causing the pulverization of secondary particles, being unable to effectively inhibit the side reaction between the crystal interface of the cathode material and the electrolyte, increasing the safety hazards of the battery, and being not conducive to extending the service life of the battery. In addition, a large amount of wastewater, waste gas, and solid waste are generated during the preparation process, and it is difficult to achieve zero emissions 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 the publication number CN117923561A discloses a method for preparing a single-crystal or quasi-single-crystal type lithium-rich manganese-based cathode material precursor, including: simultaneously introducing a metal salt solution, a composite precipitating agent, a complexing agent, and an oxidant into a reaction vessel for co-precipitation reaction, and then performing crystallization to obtain the lithium-rich manganese-based cathode 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; the composite precipitating agent includes a solution containing an alkaline substance and a soluble carbonate.

[0007] A patent application with the publication number CN117985771A discloses a manganese-based cathode material precursor, which comprises particles with the chemical formula MnₓNiᵧCoₓCO₃; wherein, x + y + z = 1, 0.5 ≤ x ≤ 0.75, 0.1 ≤ y ≤ 0.25, z > 0; the tap density of the manganese-based cathode material precursor is above 1.7 g / cm³; the relative crystallinity of the manganese-based cathode material precursor is above 80%; in the XRR pattern of the manganese-based cathode material precursor, the value of I(014) / I(018) is 2.5 - 4.0, where I(014) represents the peak intensity of the crystal plane (014) and I(018) represents the peak intensity of the crystal plane (018).

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

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

[0010] The specific technical solution of the present invention is as follows:

[0011] A manganese-based battery cathode material precursor, 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;

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

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

[0014] R is at least one selected from oxides of metals with valence from +1 to +6, or R is an oxide formed after decomposition of at least one substance selected from hydroxides, carbonates, acetates, and oxalates of metals with valence from +1 to +6;

[0015] The precursor is a composite of spinel-structured (Mn 1-a A a )3O4 and R oxide into secondary particle materials.

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

[0017] As a preferred embodiment, 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 precursor of a manganese-based battery cathode material, comprising the following steps:

[0019] S1. Mix and grind a manganese source, a doping element A source, a dispersant, and pure water respectively to obtain a nano-scale slurry;

[0020] S2. Dry the slurry obtained in step S1 to obtain a mixed material;

[0021] S3. Under an air atmosphere, subject the mixed material to multi-stage high-temperature solid-phase melting to prepare spinel-structured (Mn 1-a A a )3O4 with a particle size PSD-R50 of 0.7 - 10.0 μm. In a high-temperature environment, the mixed material melts into a liquid state (this is because the kinetic energy of the thermal motion of molecules increases, resulting in the destruction of the crystal phase and the process of the substance changing from a solid phase to a liquid phase). At this time, a thermal activation reaction occurs, and atoms of multiple components migrate, fuse, and penetrate each other to form a new solid solution, realizing the doping modification of the manganese-based cathode material by multiple elements simultaneously;

[0022] S4. Mix and grind an R source, a dispersant, and pure water to obtain a nano-scale slurry, and then perform secondary dispersion mixing with the spinel-structured (Mn 1-a A a )3O4 prepared in step S3. After drying, perform coating treatment at a high temperature of 600 - 800 °C for 5 - 20 h to finally obtain a precursor of a manganese-based battery cathode material.

[0023] The coating substance melts into a liquid state in a high-temperature environment and, on the spinel-structured (Mn 1-a A a) The wetting force and surface tension appear on the surface of 3O4, and the glass phase formed after the liquid phase cools is enriched on the surface of spinel-structured (Mn 1-a A a )3O4, achieving the effect of coating.

[0024] As a preferred solution, the manganese source is one or more of manganese tetroxide, manganese dioxide, 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 elements such as 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 polyvinylpyrrolidone, and its dosage is 1.0%-10.0% of the mass of the nanoscale slurry in S1.

[0025] As a preferred solution, the steps of multi-stage high-temperature sintering and melting in S3 include: first decomposing and oxidizing at 400-800°C for 2-10 h, then raising the temperature to 800-1200°C for reaction for 5-20 h, and then cooling to 500-750°C for reparative roasting for 2-10 h.

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

[0027] The manganese-based battery cathode material precursor prepared by the present invention has the following characteristics: the particle size PSD-R50 is 0.7-15.0 μm, the specific surface area ≤ 5.0 m 2 / g, the tapped density ≥ 2.0 g / cm 3 , and has a core-shell structure, where the core layer is the (Mn 1-a A a )3O4 spinel phase, and the shell layer is a uniform coating layer of R oxide.

[0028] The present invention also provides an application of a manganese-based battery cathode material precursor, which is 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 the manganese-based battery cathode material precursor.

[0029] (III) Beneficial technical effects

[0030] The precursor of the cathode material for the manganese-based battery prepared by the technology of the present invention mainly adopts the solid-phase method. Through the high-temperature melting technology, that is, taking the nanoscale manganese source and the doping element A source after grinding as the mixed materials, after high-temperature melting and sintering, surface coating is then carried out. During this process, the manganese source and the doping element A source are fused and penetrated with each other, and the atoms of the two are evenly distributed, exerting the site doping effect of the doping element and achieving the purpose of stabilizing the structure. At the same time, the size, morphology, crystal plane and crystal boundary of the primary particles of the precursor of the cathode material are optimized, which can provide beneficial ductility and chemical corrosion resistance for the cathode material synthesized in the next step, thereby increasing the density, suppressing the side reaction between the crystal interface of the cathode material and the electrolyte, prolonging the service life and enhancing the safety performance during use. A small amount of water vapor and carbon dioxide gas generated during the preparation process are discharged at high altitude and will not cause pollution to the environment.

[0031] The preparation method of the present invention is simple and easy to industrialize. Multiple products can be formed and used as raw materials for synthesizing cathode materials such as lithium manganate, spinel nickel manganese lithium, lithium iron manganese phosphate, lithium-rich manganese-based, sodium-ion battery manganese-based layered oxide, potassium-ion battery manganese-based layered oxide, etc.

[0032] In the step of preparing the precursor of the cathode material for the manganese-based battery, first grind and mix the manganese source and the doping element A source, and carry out multi-stage high-temperature sintering and melting (during the multi-stage high-temperature sintering process, the raw materials can be fully decomposed, oxidized, melted, crystal nucleated, crystal grown, and crystal defects repaired to obtain a precursor with high crystallinity), and prepare the spinel structure (Mn 1-a A a )3O4; then redisperse and mix it with the nanoscale slurry containing the R source, and carry out the coating treatment to finally obtain the precursor of the cathode material for the manganese-based battery. Description of the Drawings

[0033] Figure 1 It is a particle morphology diagram of the precursor of the cathode material for the manganese-based battery prepared in Example 6.

[0034] Figure 2 It is a particle size distribution diagram of the precursor of the cathode material for the manganese-based battery prepared in Example 6.

[0035] Figure 3 It is the cycle capacity retention rate of the electrical performance of the precursor of the cathode material for the manganese-based battery prepared in Example 3, which is used as a raw material for preparing the lithium-ion cathode material.

[0036] Figure 4 It is a comparison sample of the precursor of the cathode material for the manganese-based battery prepared in Example 3, and it is the cycle capacity retention rate of the electrical performance applied as a raw material for preparing the cathode material.

[0037] Figure 5The precursor of the manganese-based battery cathode material prepared in Example 6, which is used as a raw material for preparing the lithium battery cathode material, for the cycle capacity retention rate of the electrical performance.

[0038] Figure 6 The comparative sample of the precursor of the manganese-based battery cathode material prepared in Example 6, which is used as a raw material for preparing the cycle capacity retention rate of the electrical performance of the cathode material. Figure 7 The comparative sample of the precursor of the manganese-based battery cathode material prepared in Example 6, which is used as a raw material for preparing the cycle capacity retention rate of the electrical performance of the cathode material. Detailed implementation manners

[0039] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0040] The following describes the specific implementation of the present invention in detail with reference to specific embodiments.

[0041] Example 1

[0042] This example provides a precursor of a manganese-based battery cathode material and a preparation method thereof, including the following steps:

[0043] S1. Ingredients metering and weighing process:

[0044] (1) Manganese hydroxide Mn(OH)2 and magnesium oxide MgO are metered and weighed: They are respectively weighed according to a molar ratio of 0.99:0.01, and are respectively marked as QM and QA after weighing;

[0045] (2) The water-based dispersant polyethylene glycol PEG is metered and weighed:

[0046] The first portion of the dispersant is metered and weighed: Its mass is 3% of the mass of QA, and is marked as FS1 after weighing;

[0047] The second portion of the dispersant is metered and weighed: Its mass is 3% of the mass of QM, and is marked as FS2 after weighing;

[0048] (3) Pure water is metered and weighed:

[0049] The first portion of pure water is metered and weighed: Its mass is 150% of the mass of QA, and is marked as W1 after weighing;

[0050] The second portion of pure water is metered and weighed: Its mass is 100% of the mass of QM, and is marked as W2 after weighing;

[0051] S2. Dispersion, mixing, grinding and drying process:

[0052] (1) Add W1, FS1, and QA to the grinding equipment in sequence and perform dispersion and grinding together to obtain a nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0053] (2) Add W2, FS2, and QM to the grinding equipment and perform dispersion, uniform mixing, and grinding with AL1 together to obtain a mixed slurry MAL. Dry the mixed slurry MAL in a drying equipment to obtain a mixed material MAL1, whose particle size PSD-R50 is 800.0 nm to 3000.0 nm;

[0054] S3. High-temperature roasting and crystallization process:

[0055] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of an air atmosphere, decompose and oxidize at a temperature of 550 °C for 3 h, raise the temperature to 950 °C in 2 h and continue to decompose, oxidize, perform solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 10 h, then cool down to 550 °C, perform reparative roasting on the crystals for 2 h, and then cool down to room temperature. After the processes of crushing, sieving, and demagnetization, obtain a semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.99 Mg 0.01 )3O4, and its particle size PSD-R50 reaches 2.0 to 5.0 μm.

[0056] S4. Secondary batching metering and weighing process:

[0057] (1) Titanium dioxide TiO2 metering and weighing: Its molar ratio with MAL2 is 0.01:0.99. After weighing, they are respectively marked as QR and QMAL2;

[0058] (2) Aqueous dispersant polyethylene glycol PEG metering and weighing:

[0059] The third portion of the dispersant metering and weighing: Its mass is 4% of the mass of QR. After weighing, it is marked as FS3;

[0060] The fourth portion of the dispersant metering and weighing: Its mass is 4% of the mass of QMAL2. After weighing, it is marked as FS4;

[0061] (3) Pure water metering and weighing:

[0062] The third portion of pure water metering and weighing: Its mass is 120% of the mass of QR. After weighing, it is marked as W3;

[0063] The fourth portion of pure water metering and weighing: Its mass is 100% of the mass of QMAL2. After weighing, it is marked as W4;

[0064] S5. Secondary dispersion, mixing, and drying process:

[0065] (1) Add W3, FS3, and QR to the grinding equipment in sequence, and perform dispersion, uniform mixing, and grinding together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0066] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and perform dispersion and uniform mixing with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0067] S6. High-temperature roasting coating process:

[0068] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of an air atmosphere, coat it at a temperature of 680 °C for 10 hours, then cool it to room temperature. After the processes of crushing, sieving, and demagnetization, the finished product composite spinel-structured manganese-based battery cathode material precursor MAL4 is obtained. Its chemical formula is 0.99(Mn 0.99 Mg 0.01 )3O4·0.01TiO2. Its particle size reaches PSD-R50 of 2.0 to 6.0 μm, the specific surface area BET is 0.25 to 0.32 m 2 / g, and the tapped density is 2.9 to 3.1 g / cm 3 .

[0069] Example 2

[0070] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0071] S1. Batching, metering, and weighing process:

[0072] (1) Meter and weigh manganese carbonate MnCO3, aluminum hydroxide Al(OH)3, and zinc oxide ZnO: Weigh them separately according to a molar ratio of 0.97:0.02:0.01, and mark them as QM, QA1, and QA2 respectively after weighing;

[0073] (2) Meter and weigh the aqueous dispersant polyvinyl alcohol PVA:

[0074] Meter and weigh the first portion of the dispersant: Its mass is 3.5% of the total mass of QA1 and QA2, and mark it as FS1 after weighing;

[0075] Meter and weigh the second portion of the dispersant: Its mass is 3% of the mass of QM, and mark it as FS2 after weighing;

[0076] (3) Meter and weigh pure water:

[0077] Meter and weigh the first portion of pure water: Its mass is 140% of the total mass of QA1 and QA2, and mark it as W1 after weighing;

[0078] The second pure water metering and weighing: Its mass is 100% of the mass of QM, and after weighing, it is marked as W2;

[0079] S2. Dispersion, mixing, grinding and drying processes:

[0080] (1) Add W1, FS1, QA1 and QA2 to the grinding equipment in sequence, and perform dispersion and grinding together to obtain nano-sized slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0081] (2) Add W2, FS2, QM to the grinding equipment in sequence and perform dispersion, uniform mixing and grinding with AL1 together to obtain mixed slurry MAL. After drying in a drying equipment, obtain mixed material MAL1, whose particle size PSD-R50 is 600.0 nm to 4000.0 nm;

[0082] S3. High-temperature roasting and crystallization process:

[0083] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of air atmosphere, decompose and oxidize at a temperature of 400 °C for 5 h, raise the temperature to 900 °C in 2 h and continue to decompose, oxidize, solid-phase melting, crystal nucleation, crystal growth, crystal synthesis for 15 h, lower the temperature to 580 °C, perform reparative roasting on the crystal for 3 h, and then lower it to room temperature. After crushing, sieving and demagnetization processes, obtain semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.97 Al 0.02 Zn 0.01 )3O4, and its particle size PSD-R50 reaches 2.0 to 6.0 μm

[0084] S4. Secondary batching metering and weighing process:

[0085] (1) Zirconia ZrO2 metering and weighing: Its molar ratio to MAL2 is 0.01:0.99. After weighing, they are respectively marked as QR and QMAL2;

[0086] (2) Aqueous dispersant polyvinyl alcohol PVA metering and weighing:

[0087] The third dispersant metering and weighing: Its mass is 4% of the mass of QR, and after weighing, it is marked as FS3;

[0088] The fourth dispersant metering and weighing: Its mass is 3.5% of the mass of QMAL2, and after weighing, it is marked as FS4;

[0089] (3) Pure water metering and weighing:

[0090] The third pure water metering and weighing: Its mass is 110% of the mass of QR, and after weighing, it is marked as W3;

[0091] The 4th pure water metering and weighing: Its mass is 100% of the mass of QMAL2, and after weighing, it is marked as W4;

[0092] S5. Secondary dispersion, mixing and drying process:

[0093] (1) Add W3, FS3, and QR to the grinding equipment in sequence, and disperse, uniformly mix, and grind them together to form a uniform nano-sized slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0094] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and uniformly mix them with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0095] S6. High-temperature roasting coating process:

[0096] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of air atmosphere, coat it at 700 °C for 8 hours, then cool it to room temperature. After the processes of crushing, sieving, and demagnetization, the finished product composite spinel-structured manganese-based battery cathode material precursor MAL5 is obtained, and its chemical formula is 0.99(Mn 0.97 Al 0.02 Zn 0.01 )3O4·0.01ZrO2, its particle size reaches PSD-R50 of 2.5 to 7.0 μm, the specific surface area BET is 0.22 to 0.30 m 2 / g, and the tapped density is 3.0 to 3.3 g / cm 3 .

[0097] Example 3

[0098] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0099] S1. Batching metering and weighing process:

[0100] (1) Meter and weigh manganese sesquioxide Mn2O3, aluminum oxide Al2O3, and lanthanum oxide La2O3: Weigh them separately according to the molar ratio of 0.96:0.03:0.01, and after weighing, mark them as QM and QA1, QA2 respectively;

[0101] (2) Meter and weigh the aqueous dispersant polyacrylamide PAM:

[0102] The 1st dispersant metering and weighing: Its mass is 5.0% of the total mass of QA1 and QA2, and after weighing, it is marked as FS1;

[0103] The second dispersant metering and weighing: Its mass is 4.5% of the mass of QM, and after weighing, it is marked as FS2;

[0104] (3) Pure water metering and weighing:

[0105] The first pure water metering and weighing: Its mass is 120% of the total mass of QA1 and QA2, and after weighing, it is marked as W1;

[0106] The second pure water metering and weighing: Its mass is 100% of the mass of QM, and after weighing, it is marked as W2;

[0107] S2. Dispersion, mixing, grinding and drying process:

[0108] (1) Add W1, FS1, QA1 and QA2 to the grinding equipment in sequence, and disperse and grind them together to obtain nano-sized slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0109] (2) Add W2, FS2, QM to the grinding equipment in sequence and disperse, uniformly mix and grind them together with AL1 to obtain mixed slurry MAL. After drying in the drying equipment, the mixed material MAL1 is obtained, and its particle size PSD-R50 is 600.0 nm to 4000.0 nm;

[0110] S3. High-temperature roasting and crystallization process:

[0111] Place MAL1 in a high-temperature synthesis and sintering furnace, and decompose, solid-phase melt, crystal nucleate, crystal grow, and crystal synthesize for 12 hours at a temperature of 950 °C under an air atmosphere condition. Cool down to 600 °C, perform reparative roasting on the crystal for 2 hours, and then cool down to room temperature. After the processes of crushing, sieving, and demagnetization, the semi-finished product WAL2 with a spinel structure is obtained, and its chemical formula is (Mn 0.96 Al 0.03 La 0.01 )3O4, and its particle size PSD-R50 reaches 3.0 to 7.0 μm.

[0112] S4. Secondary batching metering and weighing process:

[0113] (1) Silicon dioxide SiO2 metering and weighing: Its molar ratio to MAL2 is 0.01:0.99, and after weighing, they are respectively marked as QR and QMAL2;

[0114] (2) Aqueous dispersant polyethylene glycol PEG metering and weighing:

[0115] The third dispersant metering and weighing: Its mass is 4.2% of the mass of QR, and after weighing, it is marked as FS3;

[0116] The 4th dispersant metering and weighing: Its mass is 5.1% of the mass of QMAL2, and after weighing, it is marked as FS4;

[0117] (3) Pure water metering and weighing:

[0118] The 3rd pure water metering and weighing: Its mass is 110% of the mass of QR, and after weighing, it is marked as W3;

[0119] The 4th pure water metering and weighing: Its mass is 100% of the mass of QMAL2, and after weighing, it is marked as W4;

[0120] S5. Secondary dispersion, mixing and drying process:

[0121] (1) Add W3, FS3, and QR to the grinding equipment in sequence, and disperse, uniformly mix, and grind them together to form a uniform nano-sized slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0122] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and disperse and uniformly mix them with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0123] S6. High-temperature roasting coating process:

[0124] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of air atmosphere, coat it at a temperature of 670 °C for 9 hours, cool it to room temperature, and through the processes of crushing, sieving, and demagnetization, obtain the finished product composite spinel-structured manganese-based battery cathode material precursor MAL5, whose chemical formula is 0.99(Mn 0.96 Al 0.03 La 0.01 )3O4·0.01SiO2, its particle size reaches PSD-R50 of 2.0 - 6.0 μm, the specific surface area BET is 0.25 - 0.35 m 2 / g, and the tapped density is 3.05 - 3.3 g / cm 3 .

[0125] Example 4

[0126] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0127] S1. Batching metering and weighing process:

[0128] (1) Meter and weigh manganese acetate (CH3COO)2Mn, nickel oxide NiO, and antimony trioxide Sb2O3: Weigh them respectively according to the molar ratio of 0.97:0.02:0.005, and after weighing, mark them as QM and QA1, QA2 respectively;

[0129] (2) Measurement and weighing of the aqueous dispersant polyvinylpyrrolidone PVP:

[0130] Measurement and weighing of the first portion of the dispersant: Its mass is 1% of the total mass of QA1 and QA2, and after weighing, it is labeled as FS1;

[0131] Measurement and weighing of the second portion of the dispersant: Its mass is 1% of the mass of QM, and after weighing, it is labeled as FS2;

[0132] (3) Measurement and weighing of pure water:

[0133] Measurement and weighing of the first portion of pure water: Its mass is 140% of the total mass of QA1 and QA2, and after weighing, it is labeled as W1;

[0134] Measurement and weighing of the second portion of pure water: Its mass is 100% of the mass of QM, and after weighing, it is labeled as W2;

[0135] S2. Dispersion, mixing, grinding, and drying processes:

[0136] (1) Add W1, FS1, QA1, and QA2 to the grinding equipment in sequence, and perform dispersion and grinding together to obtain a nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0137] (2) Add W2, FS2, and QM to the grinding equipment in sequence and perform dispersion, uniform mixing, and grinding with AL1 together to obtain a mixed slurry MAL. After drying in a drying equipment, a mixed material MAL1 is obtained, and its particle size PSD-R50 is 700.0 nm to 3000.0 nm;

[0138] S3. High-temperature calcination and crystallization process:

[0139] Place MAL1 in a high-temperature synthesis and sintering furnace. Under an air atmosphere condition, decompose and oxidize at a temperature of 450 °C for 3 h, raise the temperature to 960 °C in 2 h for decomposition, oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 11 h, lower the temperature to 610 °C, perform reparative calcination of the crystal for 3 h, and then lower the temperature to room temperature. After crushing, sieving, and demagnetization processes, a semi-finished product WAL2 with a spinel structure is obtained, and its chemical formula is (Mn 0.97 Ni 0.02 Sb 0.01 )3O4, and its particle size PSD-R50 reaches 2.5 to 5.0 μm.

[0140] S4. Secondary batching measurement and weighing process:

[0141] (1) CeO₂ metering and weighing: The molar ratio of CeO₂ to MAL₂ is 0.02:0.98. After weighing, they are respectively marked as QR and QMAL₂;

[0142] (2) Aqueous dispersant polyethylene glycol PEG metering and weighing:

[0143] The third portion of the dispersant is metered and weighed: Its mass is 1% of the mass of QR, and after weighing, it is marked as FS3;

[0144] The fourth portion of the dispersant is metered and weighed: Its mass is 1% of the mass of QMAL₂, and after weighing, it is marked as FS4;

[0145] (3) Pure water metering and weighing:

[0146] The third portion of pure water is metered and weighed: Its mass is 110% of the mass of QR, and after weighing, it is marked as W3;

[0147] The fourth portion of pure water is metered and weighed: Its mass is 100% of the mass of QMAL₂, and after weighing, it is marked as W4;

[0148] S5. Secondary dispersion, mixing and drying process:

[0149] (1) Add W3, FS3, and QR to the grinding equipment in sequence, and disperse, uniformly mix, and grind them together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0150] (2) Add W4, FS4, and QMAL₂ to the grinding equipment in sequence and disperse and uniformly mix them with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0151] S6. High-temperature calcination coating process:

[0152] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of air atmosphere, coat it at 710 °C for 11 hours, then cool it to room temperature. After crushing, sieving, and demagnetization processes, the finished product composite spinel structure manganese-based battery cathode material precursor MAL5 is obtained, and its chemical formula is 0.98(Mn 0.97 Ni 0.02 Sb 0.01 )3O4·0.02CeO2, its particle size reaches PSD-R50 of 2.5 - 6.0 μm, the specific surface area BET is 0.25 - 0.40 m 2 / g, and the tapped density is 3.1 - 3.3 g / cm 3 .

[0153] Example 5

[0154] This embodiment provides a precursor of a cathode material for a manganese-based battery and a preparation method thereof, including the following steps:

[0155] S1. Batching, metering, and weighing process:

[0156] (1) Manganese oxalate MnC2O4, cobalt carbonate CoCO3, and aluminum hydroxide Al(OH)3 are metered and weighed: The three are weighed respectively according to a molar ratio of 0.95:0.02:0.03, and are respectively marked as QM, QA1, and QA2 after weighing;

[0157] (2) The water-based dispersant polyvinylpyrrolidone PVP is metered and weighed:

[0158] The first portion of the dispersant is metered and weighed: Its mass is 4.5% of the total mass of QA1 and QA2, and is marked as FS1 after weighing;

[0159] The second portion of the dispersant is metered and weighed: Its mass is 4.8% of the mass of QM, and is marked as FS2 after weighing;

[0160] (3) Pure water is metered and weighed:

[0161] The first portion of pure water is metered and weighed: Its mass is 140% of the total mass of QA1 and QA2, and is marked as W1 after weighing;

[0162] The second portion of pure water is metered and weighed: Its mass is 90% of the mass of QM, and is marked as W2 after weighing;

[0163] S2. Dispersion, mixing, grinding, and drying process:

[0164] (1) W1, FS1, QA1, and QA2 are successively added to a grinding device and dispersed and ground together to obtain a nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0165] (2) W2, FS2, and QM are successively added to the grinding device and dispersed, uniformly mixed, and ground together with AL1 to obtain a mixed slurry MAL. The mixed slurry MAL is dried by a drying device to obtain a mixed material MAL1, and its particle size PSD-R50 is 600.0 nm to 3000.0 nm;

[0166] S3. High-temperature calcination and crystallization process:

[0167] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of air atmosphere, decompose and oxidize it at 450°C for 3 hours, then raise the temperature for 2 hours to 960°C for decomposition, oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 11 hours. Then cool down to 610°C and conduct a reparative roasting of the crystals for 3 hours. After cooling to room temperature, through the processes of crushing, sieving, and demagnetization, obtain the semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.95 Co 0.02 Al 0.03 )3O4, and its particle size PSD-R50 reaches 2.0 - 5.0 μm.

[0168] S4. Secondary batching metering and weighing process:

[0169] (1) Meter and weigh molybdenum trioxide MoO3: Its molar ratio to MAL2 is 0.015:0.985. After weighing, mark them as QR and QMAL2 respectively;

[0170] (2) Meter and weigh the aqueous dispersant polyethylene glycol PEG:

[0171] Meter and weigh the 3rd portion of the dispersant: Its mass is 4.1% of the mass of QR. After weighing, mark it as FS3;

[0172] Meter and weigh the 4th portion of the dispersant: Its mass is 5.1% of the mass of QMAL2. After weighing, mark it as FS4;

[0173] Meter and weigh pure water:

[0174] Meter and weigh the 3rd portion of pure water: Its mass is 120% of the mass of QR. After weighing, mark it as W3;

[0175] Meter and weigh the 4th portion of pure water: Its mass is 100% of the mass of QMAL2. After weighing, mark it as W4;

[0176] S5. Secondary dispersion, mixing, and drying process:

[0177] (1) Add W3, FS3, and QR into the grinding equipment in sequence, and conduct dispersion, uniform mixing, and grinding together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm - 200.0 nm;

[0178] (2) Add W4, FS4, and QMAL2 into the grinding equipment in sequence and conduct dispersion and uniform mixing with RL1 together to obtain a uniformly mixed slurry, and obtain the mixed material MAL3 after drying by the drying equipment; <l

[0179] S6. High-temperature roasting coating process:

[0180] 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 was crushed, screened, and demagnetized to obtain the finished composite spinel structure manganese-based battery positive electrode material precursor MAL4, whose chemical formula is 0.985(Mn 0.95 Co 0.02 Al 0.03 )3O4·0.015MoO3, the particle size reaches PSD-R50 of 2.5~6.0μm, and the specific surface area BET is 0.21~0.35m 2 / g, tap density is 3.1~3.4g / cm 3 .

[0181] Example 6

[0182] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0183] S1. Ingredient measurement and weighing process:

[0184] (1) Manganese tetraoxide (Mn3O4) and nickel carbonate (NiCO3) were weighed in a molar ratio of Mn to Ni of 0.75:0.25 and marked as QM and QA, respectively.

[0185] (2) Measurement and weighing of water-based dispersant polyacrylamide (PAM):

[0186] 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;

[0187] The second portion of dispersant is measured and weighed: its mass is 4.5% of the mass of QM and is marked as FS2 after weighing;

[0188] (3) Pure water measurement and weighing:

[0189] Measure and weigh the first portion of pure water: its mass is 100% of the QA mass and is marked as W1 after weighing;

[0190] 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;

[0191] S2. Dispersion, mixing, grinding and drying process:

[0192] (1) W1, FS1, and QA are sequentially added to a grinding device, dispersed, and ground together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm.

[0193] (2) Add W2, FS2, and QM to the grinding equipment in sequence and disperse, uniformly mix, and grind them together with AL1 to obtain a mixed slurry MAL. After drying with a drying equipment, a mixed material MAL1 is obtained, and its particle size PSD-R50 is 700.0 nm to 4000.0 nm;

[0194] S3. High-temperature roasting and crystallization process:

[0195] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of an air atmosphere, decompose and oxidize at a temperature of 420 °C for 3.5 h, raise the temperature for 2 hours to 945 °C for decomposition, oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 12 hours, then cool down to 620 °C, perform reparative roasting on the crystals for 3 hours, and then cool down to room temperature. Through the processes of crushing, sieving, and demagnetization, a semi-finished product WAL2 with a spinel structure is obtained, and its chemical formula is (Mn 0.75 Ni 0.25 )3O4, and its particle size PSD-R50 reaches 2.5 to 6.0 μm.

[0196] S4. Secondary batching, metering, and weighing process:

[0197] (1) Titanium dioxide TiO2 metering and weighing: Its molar ratio to MAL2 is 0.02:0.98. After weighing, they are respectively marked as QR and QMAL2;

[0198] (2) Aqueous dispersant polyethylene glycol PEG metering and weighing:

[0199] The third portion of the dispersant metering and weighing: Its mass is 4.5% of the mass of QR, and after weighing, it is marked as FS3;

[0200] The fourth portion of the dispersant metering and weighing: Its mass is 5.2% of the mass of QMAL2, and after weighing, it is marked as FS4;

[0201] (3) Pure water metering and weighing:

[0202] The third portion of pure water metering and weighing: Its mass is 130% of the mass of QR, and after weighing, it is marked as W3;

[0203] The fourth portion of pure water metering and weighing: Its mass is 90% of the mass of QMAL2, and after weighing, it is marked as W4;

[0204] S5. Secondary dispersion, mixing, and drying process:

[0205] (1) Add W3, FS3, and QR to the grinding equipment in sequence and disperse, uniformly mix, and grind them together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0206] (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;

[0207] S6. High temperature calcination coating process:

[0208] 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 3.0-7.0 μm in PSD-R50 and a specific surface area of 0.22-0.36 m 2 / g, tap density is 3.2~3.35g / cm 3 .

[0209] Example 7

[0210] This embodiment provides a manganese-based battery positive electrode material precursor and a preparation method thereof, comprising the following steps:

[0211] S1. Ingredient measurement and weighing process:

[0212] (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.

[0213] (2) Measurement and weighing of aqueous dispersant polyethylene glycol PEG:

[0214] 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;

[0215] 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;

[0216] (3) Pure water measurement and weighing:

[0217] 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;

[0218] 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;

[0219] S2. Dispersion, mixing, grinding and drying process:

[0220] (1) Add W1, FS1, QA1, and QA2 to the grinding equipment in sequence and perform dispersion and grinding together to obtain nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm.

[0221] (2) Add W2, FS2, and QM to the grinding equipment and perform dispersion, uniform mixing, and grinding together with AL1 to obtain mixed slurry MAL. After drying in the drying equipment, obtain mixed material MAL1, whose particle size PSD-R50 is 600.0 nm to 4000.0 nm.

[0222] S3. High-temperature roasting and crystallization process:

[0223] Place MAL1 in a high-temperature synthesis and sintering furnace. Under air atmosphere conditions, decompose and oxidize at 480 °C for 3 h, raise the temperature to 980 °C in 2 h for decomposition, oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 20 h, then cool down to 680 °C and perform reparative roasting on the crystals for 3 h, and then cool to room temperature. After crushing, sieving, and demagnetization processes, obtain semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.675 Co 0.1625 Ni 0.1625 )3O4, and its particle size PSD-R50 reaches 2.0 to 6.0 μm.

[0224] S4. Secondary batching, metering, and weighing process:

[0225] (1) Meter and weigh niobium pentoxide Nb2O5: Its molar ratio to MAL2 is 0.01:0.99. After weighing, mark them as QR and QMAL2 respectively.

[0226] (2) Meter and weigh water-based dispersant polyethylene glycol PEG:

[0227] Meter and weigh the 3rd portion of the dispersant: Its mass is 3% of the mass of QR, and after weighing, mark it as FS3.

[0228] Meter and weigh the 4th portion of the dispersant: Its mass is 3% of the mass of QMAL2, and after weighing, mark it as FS4.

[0229] (3) Meter and weigh pure water:

[0230] Meter and weigh the 3rd portion of pure water: Its mass is 130% of the mass of QR, and after weighing, mark it as W3.

[0231] Meter and weigh the 4th portion of pure water: Its mass is 110% of the mass of QMAL2, and after weighing, mark it as W4.

[0232] S5. Secondary dispersion, mixing, and drying process:

[0233] (1) Add W3, FS3, and QR to the grinding equipment in sequence, and perform dispersion, uniform mixing, and grinding together to form a uniform nano-sized slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0234] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and perform dispersion and uniform mixing with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixture MAL3;

[0235] S6. High-temperature roasting coating process:

[0236] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of an air atmosphere, perform coating at a temperature of 650 °C for 10 hours, then cool to room temperature. After the processes of crushing, sieving, and demagnetization, a finished product composite spinel-structured manganese-based battery cathode material precursor MAL4 is obtained, with the chemical formula 0.99(Mn 0.675 Co 0.1625 Ni 0.1625 )3O4·0.01Nb2O5, with a particle size reaching PSD-R50 of 2.5 to 7.0 μm, a specific surface area BET of 0.20 to 0.36 m 2 / g, and a tapped density of 3.3 to 3.5 g / cm 3 .

[0237] Example 8

[0238] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0239] S1. Batching, metering, and weighing process:

[0240] (1) Meter and weigh manganese hydroxide Mn(OH)2, cobalt carbonate CoCO3, nickel hydroxide Ni(OH)2, and aluminum hydroxide Al(OH)3: Weigh the four according to a molar ratio of 0.675:0.16:0.16:0.005 respectively, and mark them as QM and QA1, QA2, and QA3 after weighing;

[0241] (2) Meter and weigh the water-based dispersant polyethylene glycol PEG:

[0242] Weigh the first portion of the dispersant: Its mass is 3.5% of the total mass of QA1, QA2, and QA3, and mark it as FS1 after weighing;

[0243] Weigh the second portion of the dispersant: Its mass is 3.5% of the mass of QM, and mark it as FS2 after weighing;

[0244] (3) Meter and weigh pure water:

[0245] The first portion of pure water is measured and weighed: Its mass is 110% of the total mass of QA1, QA2, and QA3, and after weighing, it is marked as W1;

[0246] The second portion of pure water is measured and weighed: Its mass is 100% of the mass of QM, and after weighing, it is marked as W2;

[0247] S2. Dispersion, mixing, grinding, and drying processes:

[0248] (1) Add W1, FS1, QA1, QA2, and QA3 to the grinding equipment in sequence and perform dispersion and grinding together to obtain nano-scale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0249] (2) Add W2, FS2, and QM to the grinding equipment in sequence and perform dispersion, uniform mixing, and grinding with AL1 together to obtain mixed slurry MAL. After drying in the drying equipment, obtain mixed material MAL1, whose particle size PSD-R50 is 700.0 nm to 4000.0 nm;

[0250] S3. High-temperature roasting and crystallization process:

[0251] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of air atmosphere, decompose and oxidize at 490 °C for 3 h, raise the temperature to 970 °C in 2 h for decomposition, oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 18 h, lower the temperature to 660 °C, perform reparative roasting on the crystals for 3 h, and cool to room temperature. After the processes of crushing, sieving, and demagnetization, obtain semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.675 Co 0.16 Ni 0.16 Al 0.005 )3O4, and its particle size PSD-R50 reaches 2.0 to 6.0 μm.

[0252] S4. Secondary batching measurement and weighing process:

[0253] (1) Measure and weigh niobium pentoxide Nb2O5 and cerium dioxide CeO2: The molar ratio of the two to MAL2 is 0.005:0.01:0.985, and after weighing, they are marked as QR1, QR2, and QMAL2 respectively;

[0254] (2) Measure and weigh water-based dispersant polyethylene glycol PEG:

[0255] The third portion of the dispersant is measured and weighed: Its mass is 3.5% of the total mass of QR1 and QR2, and after weighing, it is marked as FS3;

[0256] The 4th dispersant metering and weighing: Its mass is 3.5% of the mass of QMAL2, and after weighing, it is marked as FS4;

[0257] (3) Pure water metering and weighing:

[0258] The 3rd pure water metering and weighing: Its mass is 100% of the total mass of QR1 and QR2, and after weighing, it is marked as W3;

[0259] The 4th pure water metering and weighing: Its mass is 110% of the mass of QMAL2, and after weighing, it is marked as W4;

[0260] S5. Secondary dispersion, mixing and drying process:

[0261] (1) Add W3, FS3, QR1, and QR2 into the grinding equipment in sequence, and perform dispersion, uniform mixing, and grinding together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0262] (2) Add W4, FS4, and QMAL2 into the grinding equipment in sequence and perform dispersion and uniform mixing with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0263] S6. High-temperature roasting and coating process:

[0264] Place MAL3 in a high-temperature synthesis and sintering furnace, and under the condition of air atmosphere, perform coating at a temperature of 760 °C for 10 hours, then cool to room temperature. After the processes of crushing, sieving, and demagnetization, the finished product composite spinel-structured manganese-based battery cathode material precursor MAL4 is obtained. Its chemical formula is 0.985(Mn 0.675 Co 0.16 Ni 0.16 Al 0.005 )3O4·0.005Nb2O5·0.01CeO2, its particle size reaches PSD-R50 of 3.0 to 7.0 μm, the specific surface area BET is 0.21 to 0.37 m 2 / g, and the tapped density is 3.2 to 3.4 g / cm 3 [[ID=3�]].

[0265] Example 9

[0266] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0267] S1. Batching metering and weighing process:

[0268] (1) Weighing of manganese tetraoxide (Mn3O4) and yttrium oxide (Y2O3): They are weighed respectively according to the molar ratio of Mn to Y of 0.98:0.02, and after weighing, they are respectively marked as QM and QA;

[0269] (2) Weighing of water-based dispersant polyethylene glycol (PEG):

[0270] Weighing of the first portion of the dispersant: Its mass is 4.0% of the mass of QA, and after weighing, it is marked as FS1;

[0271] Weighing of the second portion of the dispersant: Its mass is 3.0% of the mass of QM, and after weighing, it is marked as FS2;

[0272] (3) Weighing of pure water:

[0273] Weighing of the first portion of pure water: Its mass is 110% of the mass of QA, and after weighing, it is marked as W1;

[0274] Weighing of the second portion of pure water: Its mass is 100% of the mass of QM, and after weighing, it is marked as W2;

[0275] S2. Processes of dispersion, mixing, grinding and drying:

[0276] (1) Add W1, FS1, and QA to the grinding equipment in sequence, and disperse and grind them together to obtain a nano-level slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0277] (2) Add W2, FS2, and QM to the grinding equipment in sequence and disperse, uniformly mix, and grind them together with AL1 to obtain a mixed slurry MAL. After drying in a drying equipment, a mixed material MAL1 is obtained, and its particle size PSD-R50 is 600.0 nm to 4000.0 nm;

[0278] S3. High-temperature roasting and crystallization process:

[0279] Place MAL1 in a high-temperature synthesis and sintering furnace. Under the condition of air atmosphere, oxidize at a temperature of 500 °C for 3 h, raise the temperature to 990 °C in 2 h for oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 18 h, lower the temperature to 650 °C, perform reparative roasting of the crystal for 3 h, and then lower the temperature to room temperature. After the processes of crushing, sieving, and demagnetization, a semi-finished product WAL2 with a spinel structure is obtained, and its chemical formula is (Mn 0.98 Y 0.02 )3O4, and its particle size PSD-R50 reaches 2.0 to 6.0 μm.

[0280] S4. Process of secondary batching weighing:

[0281] (1) Weighing and metering niobium pentoxide (Nb2O5) and titanium dioxide (TiO2): Their molar ratio to MAL2 is 0.005:0.01:0.985. After weighing, they are respectively labeled as QR1, QR2, and QMAL2;

[0282] (2) Weighing and metering the aqueous dispersant polyethylene glycol (PEG):

[0283] Weighing and metering the third portion of the dispersant: Its mass is 3.5% of the total mass of QR1 and QR2. After weighing, it is labeled as FS3;

[0284] Weighing and metering the fourth portion of the dispersant: Its mass is 3.5% of the mass of QMAL2. After weighing, it is labeled as FS4;

[0285] (3) Weighing and metering pure water:

[0286] Weighing and metering the third portion of pure water: Its mass is 100% of the total mass of QR1 and QR2. After weighing, it is labeled as W3;

[0287] Weighing and metering the fourth portion of pure water: Its mass is 110% of the mass of QMAL2. After weighing, it is labeled as W4;

[0288] S5. Secondary dispersion, mixing, and drying process:

[0289] (1) Add W3, FS3, QR1, and QR2 to the grinding equipment in sequence, and perform dispersion, uniform mixing, and grinding together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm to 200.0 nm;

[0290] (2) Add W, FS4, and QMAL2 to the grinding equipment in sequence and perform dispersion and uniform mixing with RL1 to obtain a uniformly mixed slurry, which is dried by a drying equipment to obtain a mixed material MAL3;

[0291] S6. High-temperature calcination coating process:

[0292] Place MAL3 in a high-temperature synthesis and sintering furnace. Under an air atmosphere condition, coat it at a temperature of 620 °C for 10 hours, then cool it to room temperature. After the processes of crushing, sieving, and demagnetization, the finished product composite spinel-structured manganese-based battery cathode material precursor MAL4 is obtained. Its chemical formula is 0.985(Mn 0.98 Y 0.02 )3O4·0.005Nb2O5·0.01TiO2. Its particle size reaches PSD-R50 of 2.5 to 7.0 μm, the specific surface area BET is 0.25 to 0.35 m 2 / g, and the tapped density is 3.1 to 3.5 g / cm 3 .

[0293] Example 10

[0294] This example provides a manganese-based battery cathode material precursor and its preparation method, including the following steps:

[0295] S1. Batching, metering, and weighing process:

[0296] (1) Meter and weigh manganese acetate (CH3COO)2Mn, bismuth oxide Bi2O3, and aluminum hydroxide Al(OH)3: Mn, Bi, and Al are weighed respectively according to a molar ratio of 0.95:0.01:0.04, and after weighing, they are respectively marked as QM and QA1, QA2;

[0297] (2) Meter and weigh the aqueous dispersant polyethylene glycol PEG:

[0298] Weigh the first portion of the dispersant: Its mass is 4.5% of the total mass of QA1 and QA2, and after weighing, it is marked as FS1;

[0299] Weigh the second portion of the dispersant: Its mass is 3.5% of the mass of QM, and after weighing, it is marked as FS2;

[0300] (3) Meter and weigh pure water:

[0301] Weigh the first portion of pure water: Its mass is 120% of the total mass of QA1 and QA2, and after weighing, it is marked as W1;

[0302] Weigh the second portion of pure water: Its mass is 100% of the mass of QM, and after weighing, it is marked as W2;

[0303] S2. Dispersion, mixing, grinding, and drying process:

[0304] (1) Add W1, FS1, QA1, and QA2 to the grinding equipment in sequence, and disperse and grind them together to obtain a nanoscale slurry AL1. The particle size PSD-R50 of the ground slurry AL1 reaches 100.0 nm to 200.0 nm;

[0305] (2) Add W2, FS2, and QM to the grinding equipment in sequence and disperse, uniformly mix, and grind them together with AL1 to obtain a mixed slurry MAL. The mixed slurry MAL is dried by a drying equipment to obtain a mixed material MAL1, and its particle size PSD-R50 is 600.0 nm to 4000.0 nm;

[0306] S3. High-temperature roasting and crystallization process:

[0307] Place MAL1 in a high-temperature synthesis and sintering furnace. Under air atmosphere conditions, oxidize it at 460 °C for 3 hours, heat it up for 2 hours to 910 °C for oxidation, solid-phase melting, crystal nucleation, crystal growth, and crystal synthesis for 12 hours, then cool it down to 620 °C, conduct a reparative roasting of the crystals for 3 hours, and then cool it to room temperature. After going through the processes of crushing, sieving, and demagnetization, obtain the semi-finished product WAL2 with a spinel structure, whose chemical formula is (Mn 0.95 Bi 0.01 Al 0.04 )3O4, and its particle size PSD-R50 reaches 2.0 - 6.0 μm.

[0308] S4. Secondary batching metering and weighing process:

[0309] (1) Meter and weigh tungsten trioxide WO3 and aluminum oxide Al2O3: Their molar ratios to MAL2 are 0.01:0.02:0.97. After weighing, mark them as QR1, QR2, and QMAL2 respectively;

[0310] (2) Meter and weigh the aqueous dispersant polyethylene glycol PEG:

[0311] Meter and weigh the 3rd portion of the dispersant: Its mass is 3.5% of the total mass of QR1 and QR2. After weighing, mark it as FS3;

[0312] Meter and weigh the 4th portion of the dispersant: Its mass is 3.5% of the mass of QMAL2. After weighing, mark it as FS4;

[0313] (3) Meter and weigh pure water:

[0314] Meter and weigh the 3rd portion of pure water: Its mass is 100% of the total mass of QR1 and QR2. After weighing, mark it as W3;

[0315] Meter and weigh the 4th portion of pure water: Its mass is 110% of the mass of QMAL2. After weighing, mark it as W4;

[0316] S5. Secondary dispersion, mixing, and drying process:

[0317] (1) Add W3, FS3, QR1, and QR2 to the grinding equipment in sequence, and conduct dispersion, uniform mixing, and grinding together to form a uniform nano-scale slurry RL1. The particle size PSD-R50 of the ground slurry RL1 reaches 100.0 nm - 200.0 nm;

[0318] (2) Add W4, FS4, and QMAL2 to the grinding equipment in sequence and conduct dispersion and uniform mixing with RL1 to obtain a uniformly mixed slurry, and then dry it with a drying equipment to obtain the mixture MAL3;

[0319] S6. High-temperature roasting and coating process:

[0320] Place MAL3 in a high-temperature synthesis and sintering furnace. Under air atmosphere conditions, coat it at 720 °C for 10 hours, then cool it to room temperature. After the processes of crushing, sieving, and demagnetization, the finished product of the precursor of the cathode material for the manganese-based battery with a spinel structure, MAL4, is obtained. Its chemical formula is 0.97(Mn 0.95 Bi 0.01 Al 0.04 )3O4·0.01WO3·0.02Al2O3. Its particle size reaches PSD-R50 of 2.5 - 7.5 μm, the specific surface area BET is 0.20 - 0.33 m 2 / g, and the tap density is 3.1 - 3.4 g / cm 3 .

[0321] Test Example 1

[0322] To illustrate the implementation effect of the precursor of the cathode material for the manganese-based battery prepared by the technology of the present invention, use the precursor of the cathode material for the manganese-based battery prepared in Example 3, 0.99(Mn 0.96 Al 0.03 La 0.01 )3O4·0.01SiO2, match it with lithium carbonate Li2CO3. After steps such as uniform mixing, sintering synthesis, crushing, sieving, and demagnetization, prepare the cathode material for the lithium battery, 0.99Li(Mn 0.96 Al 0.03 La 0.01 )2O4·0.01SiO2. The simulated semi-cell test of the electrical performance indicators is as follows: in the power range of 3.0 - 4.3 V, the discharge specific capacity at 0.2C is 134.02 mAh / g, the 1C charge and discharge cycle is 60 weeks, and the capacity retention rate is 97.5%( Figure 3 );

[0323] According to the equivalent composition combination, match lithium carbonate Li2CO3 with manganese dioxide Mn2O3, aluminum oxide Al2O3, and lanthanum oxide La2O3. After steps such as uniform mixing, sintering synthesis, crushing, sieving, and demagnetization, obtain a semi-finished product. Then match the semi-finished product with SiO2. After steps such as uniform mixing, sintering coating, crushing, sieving, and demagnetization, prepare the cathode material for the lithium battery, 0.99Li(Mn 0.96 Al 0.03 La 0.01 )2O4·0.01SiO2. The simulated semi-cell test of the electrical performance indicators is as follows: in the power range of 3.0 - 4.3 V, the discharge specific capacity at 0.2C is 128.65 mAh / g, the 1C charge and discharge cycle is 60 weeks, and the capacity retention rate is 93.6%( Figure 4 );

[0324] Compared with two different preparation methods, the lithium-ion battery cathode material prepared by the technology of the present invention and the same lithium-ion battery cathode material prepared by other preparation methods have a specific capacity increased by 5.37 mAh / g and a cyclic capacity retention rate increased by 3.9 percentage points.

[0325] Test Example 2

[0326] To illustrate the implementation effect of the precursor of the cathode material for manganese-based batteries prepared by the technology of the present invention, 0.98 (Mn 0.75 Ni 0.25 )3O4·0.02TiO2 prepared in Example 6 was combined with lithium carbonate Li2CO3, and after steps such as uniform mixing, sintering synthesis, crushing, sieving, and demagnetization, the lithium-ion battery cathode material 0.98(LiMn 1.5 Ni 0.5 O4)·0.02TiO2 was prepared. The electrical performance indexes detected by simulating a half-cell were: in the power supply range of 3.0 - 5.0 V, the 0.2C discharge specific capacity was 142.31 mAh / g, the 1C charge-discharge cycle was 100 weeks, and the capacity retention rate was 99.89%( Figure 5 ).

[0327] According to the equivalent component combination, lithium carbonate Li2CO3 was combined with manganese tetroxide Mn3O4 and nickel carbonate NiCO3, and after steps such as uniform mixing, sintering synthesis, crushing, sieving, and demagnetization, a semi-finished product was obtained. The semi-finished product was then combined with TiO2, and after steps such as uniform mixing, sintering coating, crushing, sieving, and demagnetization, the lithium-ion battery cathode material 0.98(LiMn 1.5 Ni 0.5 O4)·0.02TiO2 was prepared. The electrical performance indexes detected by simulating a half-cell were: in the power supply range of 3.0 - 5.0 V, the 0.2C discharge specific capacity was 135.12 mAh / g, the 1C charge-discharge cycle was 100 weeks, and the capacity retention rate was 96.2%( Figure 6 ).

[0328] According to the equivalent component combination, the metal salt solution obtained by dissolving manganese salt and nickel salt in water was mixed with a complexing agent and a precipitating agent, and the precursor Mn 0.75 Ni 0.25 (OH)2 prepared by coprecipitation reaction was obtained. Lithium carbonate Li2CO3 was combined with the precursor Mn 0.75 Ni 0.25 (OH)2 prepared by this coprecipitation method, and after steps such as uniform mixing, sintering synthesis, crushing, sieving, and demagnetization, a semi-finished product was obtained. The semi-finished product was then combined with TiO2, and after steps such as uniform mixing, sintering coating, crushing, sieving, and demagnetization, the lithium-ion battery cathode material 0.98(LiMn 1.5 Ni 0.5O4)·0.02TiO2, the simulated half-cell test electrical performance indicators are: in the power range of 3.0 - 5.0V, the discharge specific capacity at 0.2C is 138.89 mAh / g, and the 1C charge-discharge cycle is 100 weeks, with a capacity retention rate of 98.1%( Figure 7 );

[0329] Compared with the three different preparation methods, the lithium-ion cathode material prepared by the technology of the present invention and the same lithium-ion cathode material prepared by other preparation methods have the discharge specific capacity increased by 7.19 mAh / g and 3.42 mAh / g respectively, and the cyclic capacity retention rate increased by 3.69 percentage points and 1.79 percentage points respectively.

Claims

1. A precursor of a cathode material for a manganese-based battery, characterized in that, The chemical general formula of the precursor is: 1-x[(Mn 1- a A a )3O4]·xR, where 0.001 ≤ a < 1.0 and 0.001 ≤ x < 1.0; The A is a doping element of divalent or trivalent metal; The R is at least one selected from metal oxides of monovalent to hexavalent, or an oxide formed by decomposing at least one substance selected from hydroxides, carbonates, acetates, and oxalates of monovalent to hexavalent metals; The precursor is a secondary particle material formed by the compounding of spinel-structured (Mn 1-a A a )3O4 and R oxide.

2. The manganese-based battery cathode material precursor according to claim 1, characterized in that, The doping element A is selected from at least one of the elements Mg, Al, Zn, La, Ni, Co, Sb, Y, and Bi, and the R is at least one oxide selected from TiO2, SiO2, ZrO2, CeO2, Nb2O5, MoO3, and WO3 or a compound capable of decomposing to form the oxide; 3. The manganese-based battery cathode material precursor according to claim 1, wherein The manganese-based battery is one of a lithium manganese-based battery, a sodium manganese-based battery, and a potassium manganese-based battery; 4. The preparation method of the manganese-based battery cathode material precursor according to any one of claims 1-3, characterized in that, It includes the following steps: S1. Mix and grind a manganese source, a doping element A source, a dispersant, and pure water respectively to obtain a nanoscale slurry; S2. Dry the slurry obtained in step S1 to obtain a mixture; S3. Under an air atmosphere, the mixed material is subjected to multi-stage high-temperature solid-phase melting to prepare spinel-structured (Mn 1-a A a )3O4 with a particle size PSD-R50 of 0.7 - 10.0 μm; S4. Mix the R source with a dispersant and pure water and grind them to obtain a nanoscale slurry, and then perform secondary dispersion mixing with the spinel-structured (Mn 1-a A a )3O4 prepared in step S3. After drying, perform a coating treatment at a high temperature of 600 - 800 °C for 5 - 20 h to finally obtain a manganese-based cathode material precursor.

5. The preparation method of the manganese-based battery cathode material precursor according to claim 4, 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 elements 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 polyvinylpyrrolidone, and its dosage is 1.0%-10.0% of the mass of the nanoscale slurry in S1; 6. The preparation method of the manganese-based battery cathode material precursor according to claim 4, 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|h, then raising the temperature to 800-1200°C for reaction for 5-20h, and then lowering the temperature to 500-750°C for restorative roasting for 2-10h; 7. The preparation method of the precursor of the cathode material of the manganese-based battery according to claim 4, wherein The addition amount of the R source is 0.5%-5.0% of the total molar amount of the spinel-structured (Mn 1-a A a )3O4 precursor.

8. The preparation method of the manganese-based battery cathode material precursor according to claim 4, wherein, The prepared manganese-based cathode material precursor has the following characteristics: the particle size PSD-R50 is 0.7 - 15.0 μm, the specific surface area ≤ 5.0 m 2 / g, the tapped density ≥ 2.0 g / cm 3 , and has a core-shell structure, where the core layer is (Mn 1-a A a )3O4 spinel phase, and the shell layer is a uniform coating layer of R oxide.

9. Use of a manganese-based battery cathode material precursor according to any one of claims 1-3 or a manganese-based battery cathode material precursor prepared by the preparation method according to any one of claims 4-8, 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. The precursor used for the positive electrode material is the precursor of the manganese-based battery positive electrode material.

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