CN115215384B - High-nickel ternary precursor and preparation method thereof - Google Patents

High-nickel ternary precursor and preparation method thereof Download PDF

Info

Publication number
CN115215384B
CN115215384B CN202110421947.XA CN202110421947A CN115215384B CN 115215384 B CN115215384 B CN 115215384B CN 202110421947 A CN202110421947 A CN 202110421947A CN 115215384 B CN115215384 B CN 115215384B
Authority
CN
China
Prior art keywords
reaction kettle
ammonia
equal
nickel
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110421947.XA
Other languages
Chinese (zh)
Other versions
CN115215384A (en
Inventor
杨亚强
李肖萌
蔡增富
高炯信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huayou New Energy Technology Quzhou Co ltd
Zhejiang Huayou Cobalt Co Ltd
Original Assignee
Huayou New Energy Technology Quzhou Co ltd
Zhejiang Huayou Cobalt Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huayou New Energy Technology Quzhou Co ltd, Zhejiang Huayou Cobalt Co Ltd filed Critical Huayou New Energy Technology Quzhou Co ltd
Priority to CN202110421947.XA priority Critical patent/CN115215384B/en
Publication of CN115215384A publication Critical patent/CN115215384A/en
Application granted granted Critical
Publication of CN115215384B publication Critical patent/CN115215384B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a high nickel ternary precursor and a preparation method thereof, wherein the primary particles are ultrathin slat sheets and are arranged in parallel to form slat groups, and the slat groups are crowded into secondary particle balls in a pistil shape; the lithium-ion battery anode material has higher specific surface area, can be more fully contacted with lithium source during the preparation of the anode material by mixing and sintering, has more uniform mixing and higher reaction activity, can be sintered at a lower calcination temperature, has lower Li/Ni mixing and discharging degree, and can obviously improve the capacity and the cycle performance of the obtained anode active material.

Description

High-nickel ternary precursor and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a high-nickel ternary precursor and a preparation method thereof.
Background
Currently, the nickel-cobalt-manganese ternary positive electrode material has the advantages of high unit gram capacity, high voltage platform, good cycle performance and the like, and has good market prospect and development potential in the field of power batteries. The performance of ternary cathode materials (lithium nickel cobalt manganese oxide) depends largely on the performance of ternary precursors (e.g., nickel cobalt manganese hydroxide), wet co-precipitation being a common method for preparing nickel cobalt manganese hydroxide. And synthesizing nickel cobalt manganese hydroxide by adding a lithium source and sintering at high temperature. The size, morphology, structure and the like of the nickel cobalt manganese hydroxide have direct influence on the technical index of nickel cobalt lithium manganate, and are critical to the production of ternary materials.
At present, the energy density of a battery is improved, the driving mileage of a vehicle is improved, and the current mainstream view is in a high nickel direction. In the preparation process of the high-nickel ternary anode, due to higher nickel content, the Li/Ni mixed arrangement is aggravated by higher calcination temperature, so that the crystal structure is damaged, and the cycle performance is seriously attenuated.
Particularly, the stress accumulation of the ternary material in the circulation process is a main cause for the circulation decline of the ternary material, and the connection structure between primary particles of the material in the circulation process can cause the rise of local current density to generate great stress. In the repeated charge and discharge process, great stress is generated in the particles in the Li embedding and extracting process, dislocation defects in the particles are continuously accumulated, the strength of NCM particles is continuously reduced, and when the strength of the NCM particles cannot bear the stress in the particles, the NCM particles are broken, and cracks are generated in the NCM particles. On one hand, the cracks can cause short circuit of electrons, on the other hand, with the generation of the cracks, electrolyte can invade the inside of NCM particles, and the fresh surface of the cracks can generate more negative reaction with the electrolyte, so that the cycle performance and safety of the whole battery are affected.
The generation of uneven stress and Li distribution in the particles is mainly caused by the morphology of secondary particles, so that some porous structure and open structure materials show better cycle performance, the structure can effectively absorb volume change, and reduce the phenomenon of uneven stress and Li distribution in the charging process, thereby achieving the effect of improving the cycle performance, but the structure can cause the reduction of the overall packing density, and the reduction of the overall specific capacity.
The doping technology is an important method for solving the problem of poor structural stability of the ternary material, for example, the structural stability of the ternary material can be remarkably improved by doping Al element, but the Al element has no electrochemical activity, and excessive doping of the Al element can cause the reduction of the reversible capacity of the ternary material.
No effective solution to the problem of stress build-up during cycling of ternary materials has been found in the prior art.
Disclosure of Invention
The invention provides a high-nickel ternary precursor, which is used as a precursor of an active material of a nickel cobalt lithium manganate battery anode material, wherein primary particles of the precursor are ultrathin slat pieces and are arranged in parallel to form slat groups, and the slat groups are clustered into secondary particle balls in a pistil shape; the ultra-thin lath primary particles enable the precursor to have higher specific surface area, can be more fully contacted, mixed more uniformly and have higher reaction activity when being sintered with a lithium source to prepare the positive electrode material, can be sintered at a lower calcination temperature, has lower Li/Ni mixing degree, and can remarkably improve the capacity and the cycle performance of the obtained positive electrode active material; meanwhile, the ultrathin battens are arranged in parallel and tightly to form a batten group, and the batten group is tightly clustered into pistil-shaped secondary particle spheres, so that the secondary particle spheres have high specific surface area and still maintain high compaction density, and the productivity of the high-nickel anode material is not influenced. Therefore, the method can be used for improving the problems of poor volume specific capacity and poor cycle performance of the synthesized nickel cobalt manganese-based oxide positive electrode material.
The second purpose of the invention is to provide a preparation method of the high-nickel ternary precursor, which comprises the steps of introducing nitrogen gas, then introducing nitrogen gas and air or a mixed gas of nitrogen and oxygen, controlling oxidation, reducing active sites on the surface of particles, and enabling the active sites to be in a low position, thereby effectively controlling agglomeration and improving sphericity and consistency of the particles; meanwhile, ammonia value is gradually increased in the synthesis process, primary particles are obviously thickened, and oxidation splitting is increased, so that an ultrathin slat is obtained, and slat groups which are closely arranged in parallel can be clustered into pistil-shaped secondary particle spheres, so that the characteristics of high specific surface and high compaction density are maintained.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a high nickel ternary precursor is represented by a general formula Ni xCoyMnz(OH)1+aOb, wherein x is more than or equal to 0.50 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.30,0 and less than or equal to z is more than or equal to 0.30, x+y+z=1, a is more than or equal to 0 and less than or equal to 2, and b is more than or equal to 0 and less than or equal to 1; the precursor is a secondary spherical or spheroidic particle formed by aggregation of primary crystal grains, the primary crystal grains of the precursor are in a lath shape and are arranged in parallel to form a lath group, and the lath group clusters are crowded to form a pistil-shaped secondary particle.
The valence state of Ni and Co in the precursor is a mixed state of +2 valence and +3 valence, the valence state of Mn in the precursor is a mixed state of +2 valence, +3 valence and +4 valence, and the values of a and b are determined by the valence state distribution of Ni, co and Mn.
The number of the plate sheets in the plate sheet group of the high-nickel ternary precursor is more than or equal to 2, and the number of the plate sheets in the plate sheet group of more than 50% is more than or equal to 5.
The length of the lath slice of the high-nickel ternary precursor is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm.
The granularity D50 of the secondary particles of the high-nickel ternary precursor is 2.0-6.0 mu m, the tap density is more than 1.3g/cm 3, the specific surface area is more than 15m 2/g, the bulk density is 0.6-1.1 g/cm 3, and the S content is less than 1200ppm.
The preparation method of the high-nickel ternary precursor is realized through the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni xCoyMnz(OH)1+aOb, namely x: y: z, selecting nickel, cobalt and manganese soluble salts as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2-2.7 mol/L, preparing a sodium hydroxide solution with the concentration of 1.0-13.0 mol/L, and preparing ammonia water with the concentration of 1.0-12.0 mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, and controlling the reaction temperature, the pH and the ammonia concentration to form seed crystals in the reaction kettle;
step 5, continuously adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water according to the step 4, reducing the reaction pH value when the seed crystal amount in the reaction kettle reaches the target requirement, and continuously controlling the reaction temperature and the ammonia concentration;
Step 6, continuously adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water according to the step 5, starting to introduce nitrogen and air or mixed gas of nitrogen and oxygen, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable;
step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle is detected to be close to the required requirement, and only introducing air or oxygen;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
And step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
The preparation method of the high-nickel ternary precursor comprises the following steps that in the step 3, the pH value of starting-up base solution is 11.2-12.5, and the ammonia concentration is 1.0 g/L-6.0 g/L.
In the step 4, the stirring speed is 50-600 rpm, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH value is controlled to be 11.2-12.5, and the ammonia concentration is controlled to be 1.0 g/L-6.0 g/L.
In the step 5, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH is controlled to be 10.5-11.3, and the ammonia concentration is controlled to be 1.0 g/L-6.0 g/L.
In the step 6, in the mixed gas of nitrogen and air or nitrogen and oxygen, the volume concentration of oxygen changes along with the change of the solid content in the reaction kettle, and the ratio of the volume concentration of oxygen to the solid content is 0.01% -30%: 1g/L.
In the step 6, the stable ammonia value is kept to be 6.5-14.0 g/L.
In the step 7, the method for preparing the high-nickel ternary precursor is close to the required particle size which is 1/3-5/6 of the required particle size.
In the step 7, the preparation method of the high-nickel ternary precursor can increase/decrease the air or oxygen flow according to the requirements of the slat and slat group parameters.
The invention has the following beneficial effects: the primary particles of the precursor are ultrathin slat pieces and are arranged in parallel to form slat groups, and the slat groups are clustered into secondary particle balls in a pistil shape; on one hand, the structure ensures that the sintered anode material is free from the phenomenon that particles are cracked due to stress change, so that the cycle performance of the material is improved, the material has higher tap density, the overall packing density can be further improved, and the overall specific capacity is improved; on the other hand, when the positive electrode material is sintered, the positive electrode material has more contact area with a lithium source, is favorable for full reaction, has higher specific surface area in a pistil shape, ensures that the sintered positive electrode material also has higher specific surface area, obviously improves the contact area with electrolyte, increases lithium ion transmission channels, is favorable for infiltration of the electrolyte, shortens the diffusion path of lithium ions, and further effectively improves the electrochemical performances of the lithium ion battery, such as multiplying power performance, cycle performance and the like.
The preparation method of the high-nickel ternary precursor comprises the steps of controlling oxidation by introducing nitrogen and air or a mixed gas of nitrogen and oxygen after low ammonia value and no nitrogen is introduced in the initial stage of synthesis, reducing active sites on the surfaces of particles, enabling the active sites to be in low positions, effectively controlling agglomeration, and improving sphericity and consistency of the particles; meanwhile, ammonia value is gradually increased in the synthesis process, primary particles are obviously thickened, and oxidation splitting is increased, so that an ultrathin slat is obtained, and slat groups which are closely arranged in parallel can be clustered into pistil-shaped secondary particle spheres, so that the characteristics of high specific surface and high compaction density are maintained. The method is simple to operate and suitable for industrial production. The product of the invention can be widely applied to the sintering production of the lithium battery anode material, in particular to the sintering production of the lithium battery anode material; the method can be widely applied to the production process of the lithium battery anode material precursor, and is particularly suitable for the production process of the high-nickel ternary precursor.
Drawings
FIG. 1 is a 5000-fold FESEM image of a high-nickel ternary precursor prepared according to example 1 of the present invention;
FIG. 2 is a 30000-fold FESEM image of a high nickel ternary precursor prepared according to example 2 of the present invention;
FIG. 3 is a 10000-fold FESEM image of a high-nickel ternary precursor prepared according to example 3 of the present invention;
Fig. 4 is a 20000-fold FESEM view of the high nickel ternary precursor prepared in example 4 of the present invention.
Detailed Description
The following examples will enable those skilled in the art to more fully understand the present invention and are not intended to limit the same in any way.
Example 1
A high nickel ternary precursor represented by the general formula Ni 0.5Co0.2Mn0.3(OH)2.1O0.1; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 4.0 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.5Co0.2Mn0.3(OH) 2.1O0.1, namely 5:2:3, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.7mol/L, preparing a sodium hydroxide solution with the concentration of 13.0mol/L, and preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 12.5 and the ammonia concentration of 2.5g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 600rpm, controlling the reaction temperature to be 70.0 ℃, controlling the pH value to be 12.5 and controlling the ammonia concentration to be 2.5g/L, and forming seed crystals in the reaction kettle;
Step 5, continuously feeding according to the step 4, reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, controlling the reaction temperature to be 70.0 ℃, controlling the pH to be 11.3 and controlling the ammonia concentration to be 2.5 g/L;
step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 10 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 9.5g/L;
Step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 5/6 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
And step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
Example 2
A high nickel ternary precursor represented by the general formula Ni 0.6Co0.2Mn0.2(OH) 2.2O0.1; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 3.5 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.6Co0.2Mn0.2(OH) 2.2O0.1, namely x: y: z, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.5mol/L, preparing a sodium hydroxide solution with the concentration of 10.0mol/L, and preparing ammonia water with the concentration of 10.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 12.0 and the ammonia concentration of 2.0g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 500rpm, controlling the reaction temperature to be 65.0 ℃, controlling the pH value to be 12.0 and controlling the ammonia concentration to be 2.0g/L, and forming seed crystals in the reaction kettle;
Step 5, continuously feeding according to the step 4, and reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, wherein the reaction temperature is controlled to be 65.0 ℃, the pH is controlled to be 10.9, and the ammonia concentration is controlled to be 2.0g/L;
step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 25 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 8.0g/L;
Step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 2/3 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
Example 3
A high nickel ternary precursor represented by the general formula Ni 0.8Co0.1Mn0.1(OH) 2.05O0.05; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 3.0 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.8Co0.1Mn0.1(OH) 2.05O0.05, namely 8:1:1, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 8.0mol/L, preparing a sodium hydroxide solution with the concentration of 8.0mol/L, and preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 11.8 and the ammonia concentration of 5.0g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 300rpm, controlling the reaction temperature to be 57.0 ℃, controlling the pH value to be 11.8 and controlling the ammonia concentration to be 5.0g/L, and forming seed crystals in the reaction kettle;
step 5, continuously feeding according to the step 4, reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, controlling the reaction temperature to 57.0 ℃, controlling the pH to 10.8 and controlling the ammonia concentration to 5.0g/L;
Step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 10 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 10.0g/L;
Step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 5/6 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
Example 4
A high nickel ternary precursor represented by the general formula Ni 0.7Co0.1Mn0.2(OH) 2.1O0.05; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 6.0 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.7Co0.1Mn0.2(OH) 2.1O0.05, namely 7:1:2, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.5mol/L, preparing a sodium hydroxide solution with the concentration of 6.0mol/L, and preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 11.2 and the ammonia concentration of 6.0g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 100rpm, controlling the reaction temperature to be 50.0 ℃, controlling the pH value to be 11.2 and controlling the ammonia concentration to be 6.0g/L, and forming seed crystals in the reaction kettle;
step 5, continuously feeding according to the step 4, and reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, wherein the reaction temperature is controlled to be 50.0 ℃, the pH is controlled to be 10.5, and the ammonia concentration is controlled to be 6.0g/L;
step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 30 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 14.0g/L;
Step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 5/6 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
Example 5
A high nickel ternary precursor represented by the general formula Ni 0.5Co0.2Mn0.3(OH) 2.4O0.05; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 2.0 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.5Co0.2Mn0.3(OH) 2.4O0.05, namely 5:2:3, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 2.0mol/L, preparing a sodium hydroxide solution with the concentration of 7.0mol/L, and preparing ammonia water with the concentration of 7.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 11.5 and the ammonia concentration of 1.0g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 600rpm, controlling the reaction temperature to be 59.0 ℃, controlling the pH value to be 11.5 and controlling the ammonia concentration to be 1.0g/L, and forming seed crystals in the reaction kettle;
Step 5, continuously feeding according to the step 4, reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, controlling the reaction temperature to be 59.0 ℃, controlling the pH to be 10.6 and controlling the ammonia concentration to be 1.0g/L;
step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 5 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 12.0g/L;
Step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 3/4 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
Example 6
A high nickel ternary precursor represented by the general formula Ni 0.8Co0.1Mn0.1(OH) 2.01O0.02; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a slat shape and are arranged in parallel to form a slat group, the slat group is crowded to form a pistil-shaped secondary particle, the number of the slats in the slat group is more than or equal to 2, and the number of the slats in the slat group is more than or equal to 5; the length of the lath slice is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm. The secondary particles have a particle size D50 of 5.5 μm, a tap density of > 1.3g/cm 3, a specific surface area of > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content of < 1200ppm. The method is realized by the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni 0.8Co0.1Mn0.1(OH) 2.01O0.02, namely 8:1:1, selecting soluble salts of nickel, cobalt and manganese as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.8mol/L, preparing a sodium hydroxide solution with the concentration of 12.0mol/L, and preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution with the pH value of 12.5 and the ammonia concentration of 3.0g/L, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, controlling the stirring speed to be 300rpm, controlling the reaction temperature to be 55.0 ℃, controlling the pH value to be 12.5 and controlling the ammonia concentration to be 3.0g/L, and forming seed crystals in the reaction kettle;
step 5, continuously feeding according to the step 4, reducing the reaction pH when the seed crystal amount in the reaction kettle reaches the target requirement, controlling the reaction temperature to 55.0 ℃, controlling the pH to 11.0 and controlling the ammonia concentration to 3.0g/L;
Step 6, feeding is continued according to the step 5, and the mixture of nitrogen and air or nitrogen and oxygen is started to be introduced, wherein the ratio of the volume concentration of the oxygen to the solid content is controlled to be 15 percent: 1g/L, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable at 12.0g/L;
step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 4/5 of the required particle size, introducing only air or oxygen, and increasing/reducing the air or oxygen flow according to the requirements of the slat and slat group parameters;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
and step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.

Claims (8)

1. A high-nickel ternary precursor is characterized in that the precursor is represented by a general formula Ni xCoyMnz(OH)1+aOb, wherein x is more than or equal to 0.50 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 0.30,0 and less than or equal to z is more than or equal to 0.30, x+y+z=1, a is more than or equal to 0 and less than or equal to 2, and b is more than or equal to 0 and less than or equal to 1; the precursor is a secondary spherical or spheroidic particle formed by gathering primary crystal grains, the primary crystal grains of the precursor are in a lath shape and are arranged in parallel to form a lath group, and the lath group clusters are crowded to form a pistil-shaped secondary particle;
the number of the plates in the plate group is more than or equal to 2, and more than 50% of the plates in the plate group are more than or equal to 5;
The length of the lath sheet is 50-600 nm, and the average length is 200-300 nm; the thickness of the lath is 8-40 nm, and the average thickness is 10-30 nm.
2. The high nickel ternary precursor according to claim 1, wherein the secondary particles have a particle size D50 of 2.0-6.0 μm, a tap density > 1.3g/cm 3, a specific surface area > 15m 2/g, a bulk density of 0.6-1.1 g/cm 3 and an S content < 1200ppm.
3. The method for preparing the high-nickel ternary precursor according to claim 1 or 2, which is characterized by comprising the following steps:
Step 1, according to the required molar ratio of nickel, cobalt and manganese in the high-nickel ternary precursor Ni xCoyMnz(OH)1+aOb, namely x: y: z, selecting nickel, cobalt and manganese soluble salts as raw materials, adding pure water to prepare a mixed metal salt solution with the concentration of 1.2-2.7 mol/L, preparing a sodium hydroxide solution with the concentration of 1.0-13.0 mol/L, and preparing ammonia water with the concentration of 1.0-12.0 mol/L as a complexing agent;
step 2, opening a jacket of the reaction kettle to feed water and return water, and introducing nitrogen into the reaction kettle;
Step 3, adding pure water into the reaction kettle until the pure water overflows the bottom stirring paddle, adding the sodium hydroxide solution and the ammonia water prepared in the step 1 to form a reaction starting base solution, and stopping introducing nitrogen after the reaction kettle is filled with nitrogen;
Step 4, adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water prepared in the step 1 into a reaction kettle in parallel under continuous stirring to react, and controlling the reaction temperature, the pH and the ammonia concentration to form seed crystals in the reaction kettle;
step 5, continuously adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water according to the step 4, reducing the reaction pH value when the seed crystal amount in the reaction kettle reaches the target requirement, and continuously controlling the reaction temperature and the ammonia concentration;
Step 6, continuously adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water according to the step 5, starting to introduce nitrogen and air or mixed gas of nitrogen and oxygen, gradually increasing the ammonia value in the reaction system, and then keeping the ammonia value stable;
step 7, stopping nitrogen gas to be introduced when the particle size of the materials in the reaction kettle reaches 1/3-5/6 of the required particle size, and only introducing air or oxygen;
Step 8, stopping feeding the reaction kettle when the particle size of the materials in the reaction kettle reaches the required requirement, and continuing stirring and ageing for 1-2 hours;
Step 9, carrying out solid-liquid separation on the aged material in the step 8, washing a separated filter cake with potassium hydroxide or sodium hydroxide solution, and washing with pure water to obtain a washed filter cake;
And step 10, drying the filter cake washed in the step 9 by using drying equipment, and sequentially sieving and demagnetizing to obtain the high-nickel ternary precursor.
4. The method for preparing a ternary precursor with high nickel content according to claim 3, wherein the pH value of the starting-up base solution in the step 3 is 11.2-12.5, and the ammonia concentration is 1.0 g/L-6.0 g/L.
5. The method for preparing a ternary precursor according to claim 3, wherein in step 4, the stirring speed is 50-600 rpm, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH value is controlled to be 11.2-12.5, and the ammonia concentration is controlled to be 1.0-6.0 g/L.
6. The method for preparing a ternary precursor according to claim 3, wherein in step 5, the reaction temperature is controlled to be 50.0-70.0 ℃, the pH is controlled to be 10.5-11.3, and the ammonia concentration is controlled to be 1.0-6.0 g/L.
7. The method for preparing a ternary precursor of high nickel according to claim 3, wherein in the step 6, the volume concentration of oxygen in the mixture of nitrogen and air or nitrogen and oxygen is changed along with the change of the solid content in the reaction kettle, and the ratio of the volume concentration of oxygen to the solid content is 0.01% -30%: 1g/L.
8. The method for preparing a ternary precursor according to claim 3, wherein in the step 6, the stable ammonia value is maintained at 6.5-14.0 g/L.
CN202110421947.XA 2021-04-20 2021-04-20 High-nickel ternary precursor and preparation method thereof Active CN115215384B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110421947.XA CN115215384B (en) 2021-04-20 2021-04-20 High-nickel ternary precursor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110421947.XA CN115215384B (en) 2021-04-20 2021-04-20 High-nickel ternary precursor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115215384A CN115215384A (en) 2022-10-21
CN115215384B true CN115215384B (en) 2024-05-10

Family

ID=83604130

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110421947.XA Active CN115215384B (en) 2021-04-20 2021-04-20 High-nickel ternary precursor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115215384B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115893517A (en) * 2022-10-24 2023-04-04 天津巴莫科技有限责任公司 Cluster structure precursor and preparation method and application thereof
CN116462243B (en) * 2023-06-19 2023-09-26 宜宾光原锂电材料有限公司 Battery, ternary positive electrode material thereof, precursor thereof and preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104979546A (en) * 2014-04-01 2015-10-14 宁德时代新能源科技有限公司 Preparation method of single-crystal-morphology lithium ion battery ternary positive material
CN107565125A (en) * 2017-08-25 2018-01-09 湖南杉杉能源科技股份有限公司 A kind of high voltage precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof and high voltage nickel-cobalt lithium manganate cathode material
CN111106345A (en) * 2020-01-04 2020-05-05 华友新能源科技（衢州）有限公司 Microcrystalline refined nickel-cobalt-manganese composite hydroxide and ternary cathode material prepared from same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3047693B2 (en) * 1993-07-22 2000-05-29 松下電器産業株式会社 Non-aqueous electrolyte secondary battery and method for producing positive electrode active material thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104979546A (en) * 2014-04-01 2015-10-14 宁德时代新能源科技有限公司 Preparation method of single-crystal-morphology lithium ion battery ternary positive material
CN107565125A (en) * 2017-08-25 2018-01-09 湖南杉杉能源科技股份有限公司 A kind of high voltage precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof and high voltage nickel-cobalt lithium manganate cathode material
CN111106345A (en) * 2020-01-04 2020-05-05 华友新能源科技（衢州）有限公司 Microcrystalline refined nickel-cobalt-manganese composite hydroxide and ternary cathode material prepared from same

Also Published As

Publication number Publication date
CN115215384A (en) 2022-10-21

Similar Documents

Publication Publication Date Title
CN112750999B (en) Cathode material, preparation method thereof and lithium ion battery
CN108767216B (en) Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof
CN112531158B (en) High-nickel ternary single crystal material and preparation method thereof
CN111785960B (en) Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof
US20230202866A1 (en) Single-crystal-type multi-element positive electrode material, and preparation method therefor and application thereof
WO2023071409A1 (en) Single-crystal ternary positive electrode material, preparation method therefor, and application thereof
KR20040044170A (en) Active material for positive electrode of lithium secondary battery
CN115215384B (en) High-nickel ternary precursor and preparation method thereof
CN111180724A (en) Preparation method of ternary single crystal cathode material
WO2024066892A1 (en) Manganese-rich oxide precursor, preparation method therefor, and use thereof
WO2023221625A1 (en) Large-particle-size single-crystal ternary positive electrode material, and preparation method therefor and use thereof
CN111170369B (en) Lithium manganate or lithium nickel manganese material and preparation method and application thereof
CN111540890A (en) Nickel cobalt lithium manganate ternary cathode material and preparation method thereof
CN115732674A (en) Sodium anode precursor material and preparation method and application thereof
CN114620777B (en) Ultrahigh nickel ternary precursor and preparation method thereof
CN115863604A (en) Positive electrode material, positive plate comprising positive electrode material and battery
CN112340785A (en) Doped high-nickel ternary material and preparation method thereof
CN116986649A (en) Low-residual-alkali sodium-electricity positive electrode material, preparation method thereof and sodium-ion battery
CN114597378A (en) Ultrahigh nickel polycrystalline positive electrode material and preparation method and application thereof
CN113764638A (en) Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery
CN115810757B (en) Positive electrode active material and lithium ion battery containing same
CN114715957B (en) Niobium-coated nickel-cobalt-manganese ternary precursor, and preparation method and application thereof
CN114975984B (en) Preparation method of porous core-shell structure nickel-rich cathode material
CN108807971B (en) Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof
KR20230159451A (en) Core-shell gradient ternary precursor, its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant