CN114229915B - Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof - Google Patents

Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof Download PDF

Info

Publication number
CN114229915B
CN114229915B CN202111375488.2A CN202111375488A CN114229915B CN 114229915 B CN114229915 B CN 114229915B CN 202111375488 A CN202111375488 A CN 202111375488A CN 114229915 B CN114229915 B CN 114229915B
Authority
CN
China
Prior art keywords
nickel
cobalt
core
polycrystalline
low
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
CN202111375488.2A
Other languages
Chinese (zh)
Other versions
CN114229915A (en
Inventor
龚黎明
蒋文
夏晟
任浩华
钟欢
黄杰
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.)
Jiangsu Xiangying New Energy Technology Co ltd
Original Assignee
Jiangsu Xiangying New Energy Technology 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 Jiangsu Xiangying New Energy Technology Co ltd filed Critical Jiangsu Xiangying New Energy Technology Co ltd
Priority to CN202111375488.2A priority Critical patent/CN114229915B/en
Publication of CN114229915A publication Critical patent/CN114229915A/en
Application granted granted Critical
Publication of CN114229915B publication Critical patent/CN114229915B/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
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, a preparation method and application thereof.

Description

Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and relates to a positive electrode material, in particular to a core-shell type middle-nickel low-cobalt polycrystalline ternary positive electrode material, and a preparation method and application thereof.
Background
The nickel cobalt lithium manganate (NCM) ternary positive electrode material has been widely studied since the first report in 1999, and the ternary positive electrode material combines the advantages of three materials of lithium cobaltate, lithium nickelate and lithium manganate through the synergistic effect of Ni-Co-Mn: the lithium cobaltate has the characteristics of high capacity, high safety performance and low cost of lithium manganate, and good multiplying power performance of lithium cobaltate, and is widely applied to the fields of new energy automobiles, electric tools and electric two-wheel vehicles. At present, different product systems are respectively developed for different market demands of ternary anode materials. Aiming at the high energy density (more than or equal to 260 Wh/Kg) requirement in the field of electric automobiles, a high-nickel polycrystal ternary system is developed; aiming at the high safety and long cycle in the field of electric automobiles and considering the requirement of energy density (240-260 Wh/Kg), a high-voltage medium-nickel monocrystal ternary system is developed; aiming at the requirements of the electric tool on the requirements of multiplying power (more than or equal to 10C discharge) and high-temperature performance, a nickel polycrystal ternary system in small particles is developed; aiming at the requirements that the ternary and lithium manganate of an electric two-wheeled vehicle are mixed, the ternary is utilized to improve the capacity, the circulation and the high-temperature performance and the cost performance is improved as much as possible, a nickel low-cobalt polycrystalline ternary positive electrode material is being developed.
1. The ternary positive electrode material with high nickel content (total content of nickel, cobalt and manganese is 1) has higher gram capacity, meanwhile, the content of nickel accounts for higher content (more than or equal to 0.9) and can reduce the cobalt content to be within 0.1, but the high nickel ternary material needs oxygen atmosphere, a water washing process and high processing cost in the sintering process, in addition, a lithium source needs to adopt lithium hydroxide, lithium carbonate with relatively low cost cannot be adopted, and the production cost is increased. Therefore, the comprehensive calculation is carried out, the cost performance of the high-nickel ternary positive electrode material is low, and the yield in the battery manufacturing process is low, so that the high-nickel ternary positive electrode material is difficult to meet the requirements of the electric two-wheeled vehicle;
2. the precursor adopted by the middle nickel monocrystal ternary anode material is a small particle precursor, the production capacity is low, the yield is relatively low, and therefore the precursor cost is high; the temperature is high in the sintering process, the production capacity is low, and the cost of the medium nickel monocrystal is also increased; in addition, the middle nickel monocrystal has to adopt a high-voltage design to exert the advantages of the middle nickel monocrystal, and the voltage cannot be increased by a system mixed with lithium manganate, so that the middle nickel monocrystal also cannot meet the requirements of the system;
3. the middle nickel polycrystal ternary anode material adopts lithium carbonate with lower price as a raw material, adopts a conventional precursor with higher productivity as a precursor, adopts air as a sintering atmosphere, has high cost performance, and is easy to match with the performance of lithium manganate during mixing, so that the material is suitable for the requirements of electric two-wheeled vehicles. In order to further reduce the cost performance of such products, it is desirable to reduce the cobalt content while maintaining the nickel content. However, the ternary material cannot reduce the use amount of cobalt at will, otherwise, more serious Li is easy to occur during sintering + /Ni 2+ Mix and discharge to hinder Li + In addition, the covalence of the O-M-O layer in the low cobalt material is weakened, so that M-O is weakened, and the M-O bond is weakened, so that Li-O bond is enhanced, the phase change of lithium ions in the charge and discharge process is more serious, and rock salt is more easily formed on the surfacePhase, leading to reduced initial efficiency, gram capacity and cycle performance of the material;
therefore, if the use amount of cobalt can be reduced in the middle nickel polycrystalline ternary system so that the preparation process can adopt low-cost air atmosphere and lithium carbonate source, the prepared ternary positive electrode material still has good first charge and discharge efficiency, capacity retention rate, cycle performance, safety performance and the like on the premise, and the method has important practical significance for reducing the cost of lithium ion battery materials and promoting the development of new energy industry.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a core-shell type polycrystalline ternary cathode material which can adopt cheaper raw materials, low cobalt content and moderate nickel content, and the core-shell type polycrystalline ternary cathode material prepared by the method has excellent primary charge and discharge efficiency, capacity retention rate, cycle performance and safety performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material comprises the following steps:
(1) Mixing a nickel cobalt manganese hydroxide precursor with lithium carbonate, sintering in an air atmosphere, and granulating to prepare polycrystalline nickel cobalt lithium manganate; wherein the sintering temperature of the sintering is 800-1000 ℃ and the sintering time is 4-20h; the chemical formula of the nickel cobalt manganese hydroxide precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.60,0.04, y is more than or equal to 0.10,1-x-y is more than 0;
(2) Adding nickel cobalt lithium manganate and sodium borohydride into water to prepare slurry, sanding to prepare nano nickel cobalt lithium manganate slurry, uniformly mixing, spray drying and crushing to obtain nano-sized doped nickel cobalt lithium manganate; wherein the doped lithium nickel cobalt manganese oxide is a compound shown in the following formula: li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 ，0.9≤b≤1.05，0≤i≤0.5，0.2≤j≤1.0，0≤k≤0.5，1-i-j-k＞0；
(3) Adding the nano-sized doped nickel cobalt lithium manganate prepared in the step (2) and the polycrystalline nickel cobalt lithium manganate prepared in the step (1) into a fusion machine to obtain an intermediate product, and sintering the obtained intermediate product in an air atmosphere to prepare the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material.
According to some preferred aspects of the invention, in step (1), the time from room temperature to the sintering temperature is controlled to be 4-10 hours during the sintering process.
According to some preferred aspects of the invention, in step (1), the molar ratio of lithium in the lithium carbonate to the sum of nickel, cobalt, manganese elements in the nickel cobalt manganese hydroxide precursor is 1.00-1.15:1.
According to some preferred aspects of the invention, in step (1), the polycrystalline lithium nickel cobalt manganate is spherical.
According to some preferred aspects of the invention, in the step (2), the adding amount of the sodium borohydride is controlled so that the feeding mole ratio of boron to the sum of nickel, cobalt and manganese elements in the nickel cobalt lithium manganate is 0.01-0.0.05:1.
According to some preferred aspects of the invention, in the step (3), the feeding mass ratio of the doped lithium nickel cobalt manganese oxide to the polycrystalline lithium nickel cobalt manganese oxide is 1:10-200.
According to some preferred aspects of the invention, in step (3), the core layer has an average particle size of 6-13 microns.
According to some preferred aspects of the invention, in step (3), the fusion speed in the fusion machine is 2000-3000rpm, and the fusion time is 2-20 minutes.
According to some preferred aspects of the invention, in step (3), the sintering temperature of the intermediate product obtained is 600-800 ℃ and the sintering time is 3-6h.
The invention provides another technical scheme that: the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material prepared by the preparation method is characterized in that in the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, a core layer is made of a compound shown in the following general formula (I): li (Li) a (Ni x Co y Mn 1-x-y )O 2 In the formula, a is more than or equal to 1.0 and less than or equal to1.15,0.5 x is less than or equal to 0.60,0.04 y is less than or equal to 0.10,1-x-y > 0, and the material of the nuclear layer is a polymorphism; the shell layer is made of a compound shown in the following general formula (II): li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 (II) wherein b is not less than 0.9 and not more than 1.05,0, i is not less than 0.5, j is not less than 0.2 and not more than 1.0, k is not less than 0 and not more than 0.5, and 1-i-j-k is more than 0.
The invention provides another technical scheme that: the application of the mixed material formed by mixing the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and lithium manganate in the battery of the electric two-wheeled vehicle.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
in the method, when preparing a nuclear layer material, low-cost air atmosphere and lithium carbonate source are used for preparing low-cobalt-content polycrystalline nickel cobalt lithium manganate, and simultaneously, a shell layer material doped with boron in a sodium borohydride doping mode is combined, so that intermediate products of a nuclear shell structure are prepared by mixing the low-cobalt-content polycrystalline nickel cobalt lithium manganate and the shell layer material, and then sintering is carried out, and the prepared ternary positive electrode material not only has excellent primary charge and discharge efficiency and capacity retention rate, but also has excellent cycle performance and safety performance; in particular, in the method, the nickel cobalt manganese hydroxide precursor with higher productivity and moderate nickel content and lithium carbonate can be used as raw materials, and meanwhile, the sintering can be carried out in the air atmosphere, so that the method has excellent cost performance.
Drawings
FIG. 1 shows a core-shell type medium-nickel low-cobalt polycrystalline LiNi prepared in example 1 0.6 Co 0.1 Mn 0.3 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Scanning electron microscope images of (2);
FIG. 2 shows the polycrystalline LiNi obtained in comparative example 1 0.6 Co 0.1 Mn 0.3 O 2 Scanning electron microscope images of (2);
FIG. 3 is a graph showing charge-discharge cycle at 3.0 to 4.3V/1C (60 ℃ C.) for example 1 and comparative example 1;
FIG. 4 is a graph showing charge-discharge cycle at 3.0 to 4.3V/1C (60 ℃ C.) for example 1 and comparative example 2;
FIG. 5 is a graph showing charge-discharge cycles at 3.0 to 4.3V/1C (60 ℃ C.) for example 1 and comparative example 3.
Detailed Description
At present, in the prior art, when preparing a nickel cobalt lithium manganate (NCM) ternary cathode material, the requirements on raw materials and process conditions are high based on the performance requirements, so that the production cost is high, the application in the fields of new energy automobiles, electric tools, electric two-wheelers and the like is limited to a certain extent, and especially the market prospect is seriously influenced by the requirement control on low cost aiming at very popular electric two-wheelers. Particularly, the method mainly shows the selection of the dosage of cobalt, the dosage of nickel, the nickel cobalt manganese hydroxide precursor and the lithium source, is more favorable for preparing a high-performance product when the content of cobalt and nickel is relatively high, but the cobalt is expensive, the preparation of the high-nickel content product is combined with more expensive lithium hydroxide and is sintered in the oxygen atmosphere with higher cost, and meanwhile, the nickel cobalt manganese hydroxide precursor is also prepared by a method with higher productivity and lower cost, so that the method brings cost challenges to the large-scale application of the ternary anode material.
Based on research, the most important factor affecting the initial effect and initial capacity exertion of the ternary positive electrode material of the lithium battery is Li on the surface of the material + Conduction capability; when the Ni content is less than or equal to 0.65 (based on transition metal), the main reason for the inactivation of the ternary positive electrode material in the circulation process is surface phase transformation, and the original layered structure is converted into spinel and rock salt phases, and the two structures have lower lithium ion conductivity, so that the polarization is increased and the capacity is attenuated; based on the above, the invention provides a preparation method of an improved core-shell ternary cathode material, which mainly uses low cobalt content polycrystalline nickel cobalt lithium manganate as a core layer material and then combines a sodium borohydride doping type boron nickel cobalt lithium manganate shell material to solve the problems, so that the prepared core-shell ternary cathode material can adopt nickel cobalt manganese hydroxide precursor with higher productivity as a raw material and lower cost lithium carbonate as a raw material under the conditions of low cobalt content and medium nickel contentOn the premise that a lithium source and a more easily obtained air atmosphere are used as sintering atmosphere, the lithium source and the more easily obtained air atmosphere can still keep excellent first charge and discharge efficiency and capacity retention rate, have excellent cycle performance and safety performance, have extremely high cost performance and are favorable for expanding scale application.
Specifically, the invention provides a preparation method of a core-shell middle-nickel low-cobalt polycrystalline ternary cathode material, which comprises the following steps:
(1) Mixing a nickel cobalt manganese hydroxide precursor with lithium carbonate, sintering in an air atmosphere, and granulating to prepare polycrystalline nickel cobalt lithium manganate; wherein the sintering temperature of the sintering is 800-1000 ℃ and the sintering time is 4-20h; the chemical formula of the nickel cobalt manganese hydroxide precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.60,0.04, y is more than or equal to 0.10,1-x-y is more than 0;
(2) Adding nickel cobalt lithium manganate and sodium borohydride into water to prepare slurry, sanding to prepare nano nickel cobalt lithium manganate slurry, uniformly mixing, spray drying and crushing to obtain nano-sized doped nickel cobalt lithium manganate; wherein the doped lithium nickel cobalt manganese oxide is a compound shown in the following formula: li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 ，0.9≤b≤1.05，0≤i≤0.5，0.2≤j≤1.0，0≤k≤0.5，1-i-j-k＞0；
(3) Adding the nano-sized doped nickel cobalt lithium manganate prepared in the step (2) and the polycrystalline nickel cobalt lithium manganate prepared in the step (1) into a fusion machine to obtain an intermediate product, and sintering the obtained intermediate product in an air atmosphere to prepare the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material.
In a preferred aspect of the present invention, in the step (1), the time for raising the temperature from room temperature to the sintering temperature during the sintering is controlled to be 4 to 10 hours.
In a preferred aspect of the present invention, in the step (1), a molar ratio of lithium in the lithium carbonate to a sum of nickel, cobalt, and manganese elements in the nickel cobalt manganese hydroxide precursor is 1.00 to 1.15:1.
According to the invention, in the step (1), the polycrystalline lithium nickel cobalt manganese oxide is spherical.
According to the invention, in the step (1), the nickel content ratio of the core layer material is more than or equal to 0.5 and less than or equal to 0.60, and the higher gram specific capacity can be maintained under the condition of adopting air sintering.
In some embodiments of the present invention, in step (1), after the sintering, cooling is performed, and cooling is performed to below 80 ℃, and then jaw breaking, roller pair and crushing are performed, so as to obtain spherical middle-nickel low-cobalt polycrystalline lithium nickel cobalt manganate.
In a preferred aspect of the present invention, in the step (2), the addition amount of sodium borohydride is controlled so that the molar ratio of boron and/or phosphorus to the sum of nickel, cobalt and manganese elements in the lithium nickel cobalt manganese oxide is 0.01 to 0.05:1.
In some embodiments of the invention, in step (2), the particle size D of the lithium nickel cobalt manganese oxide added to water 50 1-50 micrometers; the sanding time is 4-8 h, the grinding body is zirconia balls with the particle size of 0.1-0.8 mm, the sanding rotating speed is 800-3000 rpm, and the particle size D of nickel cobalt lithium manganate in the nano nickel cobalt lithium manganate slurry is after sanding 50 20-200 nm.
In some embodiments of the invention, in step (2), the solid content of the slurry prepared is controlled to be 10-45%, and the water is deionized water.
In some embodiments of the present invention, in step (2), the spray drying is performed by a spray drying apparatus, the spray drying apparatus has an atomization frequency of 30 to 45Hz, an air inlet temperature of 250 to 350 ℃ and an air outlet temperature of 80 to 110 ℃; the crushing adopts air current crushing, the air current crushing adopts air current crushing equipment, the air current pressure of the air current crushing equipment is 0.3-0.8 MPa, and the classification frequency is 80-120 Hz, and the air extraction frequency is 30-50 Hz.
According to some preferred aspects of the invention, in the step (3), the feeding mass ratio of the doped lithium nickel cobalt manganese oxide to the polycrystalline lithium nickel cobalt manganese oxide is 1:10-200. In some embodiments of the invention, in step (3), the feed mass ratio of the doped lithium nickel cobalt manganese oxide to the polycrystalline lithium nickel cobalt manganese oxide is 1:10, 1:15, 1:20, 1:25, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190, 1:200, etc.
According to some preferred aspects of the invention, in step (3), the core layer has an average particle size of 6-13 microns. According to some specific aspects of the invention, the core layer has an average particle size of 9-12 microns.
According to some preferred aspects of the invention, in the step (3), the fusion rotating speed in the fusion machine is 2000-3000rpm, the fusion time is 2-20 minutes, and the shell layer material can be completely coated on the surface of the core layer material to form a uniform shell layer.
According to some preferred aspects of the invention, in step (3), the sintering temperature of the intermediate product obtained is 600-800 ℃ and the sintering time is 3-6h.
According to some specific aspects of the invention, in the step (3), after the sintering, cooling is performed, and the temperature is cooled to below 80 ℃, and then, twin-roll sieving is performed, so as to disperse the bonded particles, so as to obtain the nickel-low cobalt polycrystal ternary cathode material in the core-shell type.
According to the invention, in the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material prepared by the preparation method, the material of the core layer is a compound shown as the following general formula (I): li (Li) a (Ni x Co y Mn 1-x-y )O 2 Wherein a is more than or equal to 1.0 and less than or equal to 1.15,0.5, x is more than or equal to 0.60,0.04 and y is more than or equal to 0.10,1-x-y > 0, and the material of the nuclear layer is in a polymorphism; the shell layer is made of a compound shown in the following general formula (II): li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 (II) wherein b is not less than 0.9 and not more than 1.05,0, i is not less than 0.5, j is not less than 0.2 and not more than 1.0, k is not less than 0 and not more than 0.5, and 1-i-j-k is more than 0.
The performance of the obtained core-shell type middle-nickel low-cobalt polycrystalline ternary anode material is easy to match when the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material is mixed with lithium manganate, and the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material is suitable for the requirements of electric two-wheeled vehicles.
For a better understanding of the present invention, reference will be made to the following description of specific embodiments and accompanying drawings. It is to be understood that these examples are provided only for further illustration of the present invention and are not intended to limit the scope of the present invention. It will be appreciated that upon reading the present disclosure, those skilled in the art will appreciate numerous modifications and adaptations to the present invention without departing from the principles thereof. In the following, all starting materials were obtained commercially unless otherwise specified.
Example 1
The embodiment provides a preparation method of a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, which comprises the following steps:
(1) Preparation of spherical polycrystalline lithium nickel cobalt manganese oxide LiNi 0.6 Co 0.1 Mn 0.3 O 2
Ni, a nickel cobalt manganese hydroxide precursor with the granularity of 8-11 mu m is prepared 0.6 Co 0.1 Mn 0.3 (OH) 2 And battery grade lithium carbonate with average grain diameter of 4-10 mu m according to Li to Ni 0.6 Co 0.1 Mn 0.3 The molar ratio=1.05:1 was mixed uniformly with a high-speed mixer, then put into a sagger, placed in an air atmosphere furnace, and sintered at about 900 ℃ for 12 hours. Crushing the sintered block material with jaw crushing, roller pair and airflow crushing to obtain spherical polycrystalline nickel cobalt lithium manganate, S613 (polycrystalline LiNi with grain size of 9-12 microns 0.6 Co 0.1 Mn 0.3 O 2 )；
(2) Preparation of nano nickel cobalt lithium manganate LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Nanometer powder
Micron-sized LiNi with granularity of 5-12 mu m 0.33 Co 0.33 Mn 0.34 O 2 Adding deionized water into sodium borohydride, regulating to obtain slurry with solid content of 23+ -1%, stirring for 0.5 hr, grinding with a sand mill for 6 hr, wherein the grinding body is zirconia balls with particle diameter of 0.2mm, grinding at 2500rpm, and grinding to obtain nanometer LiNi with average particle diameter of 80-180 nm 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Transferring the slurry into a stirring tank, pumping the slurry into an atomizer of spray drying equipment by a peristaltic pump, and feeding the slurry into the atomizer of the spray drying equipment at an atomization frequency of 35HzSpray drying at air temperature of 220deg.C and air outlet temperature of 90deg.C to obtain LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding the micropowder into an air flow pulverizer, and air-flow pulverizing under air inlet pressure of 0.6MPa, classification frequency of 100Hz, and exhaust frequency of 45Hz to obtain LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 A nano powder;
(3) Preparation of core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate LiNi 0.6 Co 0.1 Mn 0.3 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2
The process product S613 and nano powder LiNi prepared in the step (1) are processed 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding into a mechanical fusion machine, wherein LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 The weight ratio of the intermediate product to S613 is 2:100, the intermediate product is prepared by fusing under the conditions that the rotating speed of a mechanical fusion machine is 2500rpm and the fusion time is 10 minutes, the intermediate product is placed in an air atmosphere furnace to be sintered for 6 hours at 700-800 ℃, cooled to below 80 ℃, and the intermediate product is subjected to roller pair and sieving to obtain the core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate positive electrode material (LiNi 0.6 Co 0.1 Mn 0.3 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 ) S613-333.
Example 2
The embodiment provides a preparation method of a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, which comprises the following steps:
(1) Preparation of spherical polycrystalline lithium nickel cobalt manganese oxide LiNi 0.55 Co 0.07 Mn 0.38 O 2
Ni, a nickel cobalt manganese hydroxide precursor with the granularity of 8-11 mu m is prepared 0.55 Co 0.07 Mn 0.38 (OH) 2 And battery grade lithium carbonate with average grain diameter of 4-10 mu m according to Li to Ni 0.55 Co 0.07 Mn 0.38 =1.05:1The molar ratio is mixed uniformly by a high-speed mixer, then the mixture is put into a sagger, and is placed into an air atmosphere furnace to be sintered for 12 hours at the temperature of about 900 ℃. Crushing the sintered block material with jaw crushing, roller pair and airflow crushing to obtain spherical polycrystalline nickel cobalt lithium manganate, i.e. process product S5507 (polycrystalline LiNi with particle size of 9-12 microns 0.55 Co 0.07 Mn 0.38 O 2 )；
(2) Preparation of nano nickel cobalt lithium manganate LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Nanometer powder
Micron-sized LiNi with granularity of 5-12 mu m 0.33 Co 0.33 Mn 0.34 O 2 Adding deionized water into sodium borohydride, regulating to obtain slurry with solid content of 23+ -1%, stirring for 0.5 hr, grinding with a sand mill for 6 hr, wherein the grinding body is zirconia balls with particle diameter of 0.2mm, grinding at 2500rpm, and grinding to obtain nanometer LiNi with average particle diameter of 80-180 nm 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Transferring the slurry into a stirring tank, pumping the slurry into an atomizer of spray drying equipment by a peristaltic pump, and spray drying under the conditions that the atomization frequency of the spray drying equipment is 35Hz, the air inlet temperature is 220 ℃ and the air outlet temperature is 90 ℃ to obtain the LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding the micropowder into an air flow pulverizer, and air-flow pulverizing under air inlet pressure of 0.6MPa, classification frequency of 100Hz, and exhaust frequency of 45Hz to obtain LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 A nano powder;
(3) Preparation of core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate LiNi 0.55 Co 0.07 Mn 0.38 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2
The process product S5507 and nano powder LiNi prepared in the step (1) are processed 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding into a mechanical fusion machine, wherein LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 The weight ratio of S5507 is 2:100,fusing under the condition that the rotating speed of a mechanical fusion machine is 2500rpm and the fusion time is 10 minutes, preparing an intermediate product, sintering the intermediate product in an air atmosphere furnace at 700-800 ℃ for 6 hours, cooling to below 80 ℃, and carrying out roller pair and sieving to obtain the core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate positive electrode material (LiNi 0.55 Co 0.07 Mn 0.38 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 ) S5507-333.
Example 3
The embodiment provides a preparation method of a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, which comprises the following steps:
(1) Preparation of spherical polycrystalline lithium nickel cobalt manganese oxide LiNi 0.55 Co 0.05 Mn 0.4 O 2
Ni, a nickel cobalt manganese hydroxide precursor with the granularity of 8-11 mu m is prepared 0.55 Co 0.05 Mn 0.4 (OH) 2 And battery grade lithium carbonate with average grain diameter of 4-10 mu m according to Li to Ni 0.55 Co 0.05 Mn 0.4 The molar ratio=1.05:1 was mixed uniformly with a high-speed mixer, then put into a sagger, placed in an air atmosphere furnace, and sintered at about 900 ℃ for 12 hours. Crushing the sintered block material with jaw crushing, roller pair and airflow crushing to obtain spherical polycrystalline nickel cobalt lithium manganate, i.e. process product S5505 (polycrystalline LiNi with particle size of 9-12 microns 0.55 Co 0.05 Mn 0.4 O 2 )；
(2) Preparation of nano nickel cobalt lithium manganate LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Nanometer powder
Micron-sized LiNi with granularity of 5-12 mu m 0.33 Co 0.33 Mn 0.34 O 2 Adding deionized water into sodium borohydride, regulating to obtain slurry with solid content of 23+ -1%, stirring for 0.5 hr, grinding with a sand mill for 6 hr, wherein the grinding body is zirconia balls with particle diameter of 0.2mm, grinding at 2500rpm, and grinding to obtain nanometer LiNi with average particle diameter of 80-180 nm 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Slurry, slurryTransferring into stirring tank, pumping into atomizer of spray drying equipment by peristaltic pump, spray drying under the conditions of spray drying equipment atomization frequency of 35Hz, air inlet temperature of 220 deg.C and air outlet temperature of 90 deg.C to obtain LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding the micropowder into an air flow pulverizer, and air-flow pulverizing under air inlet pressure of 0.6MPa, classification frequency of 100Hz, and exhaust frequency of 45Hz to obtain LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 A nano powder;
(3) Preparation of core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate LiNi 0.55 Co 0.05 Mn 0.4 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2
The process product S5505 and nano powder LiNi prepared in the step (1) are processed 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 Adding into a mechanical fusion machine, wherein LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 The weight ratio of the intermediate product to S5505 is 2:100, the intermediate product is prepared by fusing under the conditions that the rotating speed of a mechanical fusion machine is 2500rpm and the fusion time is 10 minutes, the intermediate product is placed in an air atmosphere furnace to be sintered for 6 hours at 700-800 ℃, cooled to below 80 ℃, and the intermediate product is subjected to roller pair and sieving to obtain the core-shell type middle-nickel low-cobalt polycrystalline nickel cobalt lithium manganate positive electrode material (LiNi 0.55 Co 0.05 Mn 0.4 O 2 @LiNi 0.327 Co 0.326 Mn 0.327 B 0.02 O 2 ) S5505-333.
Comparative example 1
Substantially the same as in example 1, the only difference is that: in the step (2), sodium borohydride is not added, and the obtained product is abbreviated as S613.
Comparative example 2
Substantially the same as in example 1, the only difference is that: in the step (2), sodium borohydride is replaced by boric acid, and the obtained product is called S613-BH for short.
Comparative example 3
Substantially the same as in example 1, the only difference is that: in the step (2), sodium borohydride is replaced by boron oxide, and the obtained product is called S613-BO for short.
Performance testing
The positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to the following examination and experiments, and the specific results are shown in tables 1 and 2.
TABLE 1 physical Property data sheets for the final products of examples 1-3 and comparative examples 1-3
TABLE 2 gram Capacity, first Effect, high temperature cycle (60 ℃) cycle Performance data sheets for the end products of examples 1-3 and comparative examples 1-3
The result shows that the performance of the nickel low-cobalt polycrystalline ternary cathode material in the core-shell structure is obviously due to the common cladding type middle-nickel low-cobalt material, the loss of the material performance under the condition of low cobalt can be made up, the material performance is brought into the level close to that of the corresponding high-cobalt material with high nickel content, and the purpose of greatly improving the cost performance is achieved.
Under the condition of the same nickel, cobalt and manganese content, the performance of the middle-nickel low-cobalt polycrystalline ternary cathode material prepared by the method is obviously improved, at present, the development of battery performance in industry is approaching to the limit, and tiny improvement is difficult to realize, and the inventor surprisingly discovers that under the specific preparation process condition of the invention, the ternary cathode material prepared by adopting a shell material doped with boron in a sodium borohydride doping mode and combining the nickel cobalt lithium manganate in a low-cost air atmosphere and a polycrystalline nickel cobalt lithium carbonate with a lithium carbonate source low cobalt content has excellent first charge and discharge efficiency, capacity retention rate, excellent cycle performance and safety performance; in particular, in the method, the nickel cobalt manganese hydroxide precursor with higher productivity and moderate nickel content and lithium carbonate can be used as raw materials, and meanwhile, the sintering can be carried out in the air atmosphere, so that the method has excellent cost performance.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. The preparation method of the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material is characterized by comprising the following steps of:
(1) Mixing a nickel cobalt manganese hydroxide precursor with lithium carbonate, sintering in an air atmosphere, and granulating to prepare polycrystalline nickel cobalt lithium manganate; wherein the sintering temperature of the sintering is 800-1000 ℃ and the sintering time is 4-20h; the chemical formula of the nickel cobalt manganese hydroxide precursor is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.60,0.04, y is more than or equal to 0.10,1-x-y is more than 0;
(2) Adding nickel cobalt lithium manganate and sodium borohydride into water to prepare slurry, sanding to prepare nano nickel cobalt lithium manganate slurry, uniformly mixing, spray drying and crushing to obtain nano-sized doped nickel cobalt lithium manganate; wherein the doped lithium nickel cobalt manganese oxide is a compound shown in the following formula: li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 ，0.9≤b≤1.05，0≤i≤0.5，0.2≤j≤1.0，0≤k≤0.5，1-i-j-k＞0；
(3) Adding the nano-sized doped nickel cobalt lithium manganate prepared in the step (2) and the polycrystalline nickel cobalt lithium manganate prepared in the step (1) into a fusion machine to obtain an intermediate product, and sintering the obtained intermediate product in an air atmosphere to prepare the core-shell type middle-nickel low-cobalt polycrystalline ternary anode material.
2. The method for preparing a ternary cathode material with low nickel and cobalt in a core-shell type polycrystalline structure according to claim 1, wherein in the step (1), the time from room temperature to the sintering temperature is controlled to be 4-10h in the sintering process.
3. The method for preparing a ternary cathode material with low nickel and cobalt in a core-shell polycrystal according to claim 1, wherein in the step (1), the molar ratio of lithium in the lithium carbonate to the sum of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor is 1.00-1.15:1.
4. The method for preparing a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material according to claim 1, wherein in the step (1), the polycrystalline lithium nickel cobalt manganese oxide is spherical.
5. The method for preparing a ternary cathode material with low nickel and cobalt in a core-shell type polycrystalline structure according to claim 1, wherein in the step (2), the adding amount of sodium borohydride is controlled so that the feeding mole ratio of boron to the sum of nickel, cobalt and manganese elements in the lithium nickel cobalt manganese oxide is 0.01-0.05:1.
6. The preparation method of the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, which is characterized in that in the step (3), the feeding mass ratio of the doped nickel cobalt lithium manganate to the polycrystalline nickel cobalt lithium manganate is 1:10-200; and/or, in the step (3), the average particle diameter of the core layer is 6-13 micrometers.
7. The method for preparing the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material according to claim 1, wherein in the step (3), the fusion rotating speed in the fusion machine is 2000-3000rpm, and the fusion time is 2-20 minutes.
8. The method for preparing a ternary cathode material with low nickel and cobalt in a core-shell type polycrystal according to claim 1, wherein in the step (3), the sintering temperature of the obtained intermediate product is 600-800 ℃ and the sintering time is 3-6h.
9. A core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material prepared by the preparation method of any one of claims 1-8, wherein in the core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material, a core layer is a compound shown in the following general formula (i): li (Li) a (Ni x Co y Mn 1-x-y )O 2 Wherein a is more than or equal to 1.0 and less than or equal to 1.15,0.5, x is more than or equal to 0.60,0.04 and y is more than or equal to 0.10,1-x-y > 0, and the material of the nuclear layer is in a polymorphism; the shell layer is made of a compound shown in the following general formula (II): li (Li) b (Ni i Co j Mn k B 1-i-j-k )O 2 (II) wherein b is not less than 0.9 and not more than 1.05,0, i is not less than 0.5, j is not less than 0.2 and not more than 1.0, k is not less than 0 and not more than 0.5, and 1-i-j-k is more than 0.
10. The use of a mixed material formed by mixing a core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and lithium manganate in a battery of an electric two-wheeled vehicle.
CN202111375488.2A 2021-11-19 2021-11-19 Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof Active CN114229915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111375488.2A CN114229915B (en) 2021-11-19 2021-11-19 Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111375488.2A CN114229915B (en) 2021-11-19 2021-11-19 Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114229915A CN114229915A (en) 2022-03-25
CN114229915B true CN114229915B (en) 2023-09-01

Family

ID=80750186

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111375488.2A Active CN114229915B (en) 2021-11-19 2021-11-19 Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114229915B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115465901B (en) * 2022-11-01 2023-08-11 贺州学院 Method for completely coating surface of positive electrode material of lithium ion battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110165193A (en) * 2019-06-12 2019-08-23 江苏翔鹰新能源科技有限公司 Hud typed high Ni-monocrystal nickel-cobalt lithium manganate cathode material of one kind and its preparation method and application
CN110518219A (en) * 2019-09-04 2019-11-29 中南大学 The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method
CN112054173A (en) * 2019-06-12 2020-12-08 江苏翔鹰新能源科技有限公司 Preparation method of core-shell type high-voltage single-crystal nickel cobalt lithium manganate positive electrode material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101621125B (en) * 2009-02-13 2011-03-30 成都晶元新材料技术有限公司 Nickel-cobalt-manganese multi-doped lithium ion battery cathode material and preparation method thereof
CN106532029A (en) * 2016-12-28 2017-03-22 四川富骅新能源科技有限公司 High-voltage ternary positive electrode material for lithium-ion battery and preparation method of high-voltage ternary positive electrode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110165193A (en) * 2019-06-12 2019-08-23 江苏翔鹰新能源科技有限公司 Hud typed high Ni-monocrystal nickel-cobalt lithium manganate cathode material of one kind and its preparation method and application
CN112054172A (en) * 2019-06-12 2020-12-08 江苏翔鹰新能源科技有限公司 Preparation method of core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material
CN112054173A (en) * 2019-06-12 2020-12-08 江苏翔鹰新能源科技有限公司 Preparation method of core-shell type high-voltage single-crystal nickel cobalt lithium manganate positive electrode material
CN110518219A (en) * 2019-09-04 2019-11-29 中南大学 The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method

Also Published As

Publication number Publication date
CN114229915A (en) 2022-03-25

Similar Documents

Publication Publication Date Title
CN112054172B (en) Preparation method of core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material
CN110718688B (en) Single crystal ternary positive electrode material and preparation method thereof
CN114050257B (en) Manganese-iron-copper positive electrode precursor material and preparation method and application thereof
CN110165192B (en) Core-shell type high-voltage monocrystal nickel cobalt lithium manganate cathode material and preparation method and application thereof
CN109778301A (en) The preparation of one type monocrystalline lithium-rich oxide material and application
CN113023794B (en) Cobalt-free high-nickel positive electrode material, preparation method thereof, lithium ion battery positive electrode and lithium ion battery
CN108550843B (en) Preparation method of nickel-cobalt-manganese ternary material, lithium ion battery positive electrode material and lithium ion battery
CN106711435B (en) Preparation method of layered lithium-rich manganese-based/graphene nanoribbon positive electrode composite material
CN112151797B (en) Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof
CN105449178B (en) A kind of preparation method of nano lithium manganese phosphate of lithium/graphene/carbon composite material
CN114000195B (en) Preparation method of monodisperse high-nickel ternary monocrystal positive electrode material
CN109411724A (en) A kind of preparation method of core-shell structure tertiary cathode material
CN114229915B (en) Core-shell type middle-nickel low-cobalt polycrystalline ternary cathode material and preparation method and application thereof
CN110350162B (en) Multiplying power type nickel-cobalt-aluminum positive electrode material and preparation method and application thereof
CN116750741A (en) Preparation method and application of titanium-doped carbon-coated sodium ferric pyrophosphate material
CN114628657B (en) Cobalt-free lithium-rich monocrystal gradient material and preparation method thereof
CN116143191A (en) Preparation method of surface-modified monocrystalline lithium-rich manganese-based positive electrode material
CN114551862A (en) Cobalt-free binary single crystal material and preparation method thereof
CN110182780B (en) Densification spherical lithium iron phosphate and preparation method thereof
CN112635728A (en) Graphene composite lithium-rich manganese-based positive electrode material, reconstruction preparation method thereof and lithium ion battery
CN111244514A (en) Method for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis and scandium-zirconium powder prepared by method
WO2023164986A1 (en) Single crystal sodium ion battery positive electrode active material, preparation method therefor, and use thereof
CN115417394B (en) Lithium iron phosphate material and preparation process and application thereof
CN108574094A (en) Negative material and preparation method thereof for lithium ion battery
CN109786672B (en) Preparation method of micron-sized single crystal ternary cathode material

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