CN111498915A - Cathode material, preparation method thereof and lithium ion battery - Google Patents

Cathode material, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN111498915A
CN111498915A CN202010337768.3A CN202010337768A CN111498915A CN 111498915 A CN111498915 A CN 111498915A CN 202010337768 A CN202010337768 A CN 202010337768A CN 111498915 A CN111498915 A CN 111498915A
Authority
CN
China
Prior art keywords
cobalt
nickel
source
manganese
hollow
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.)
Granted
Application number
CN202010337768.3A
Other languages
Chinese (zh)
Other versions
CN111498915B (en
Inventor
刘兰英
喻权
朱振华
杜俊波
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.)
Zhuzhou Distillation Science And Technology Ltd
Original Assignee
Zhuzhou Distillation Science And Technology 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 Zhuzhou Distillation Science And Technology Ltd filed Critical Zhuzhou Distillation Science And Technology Ltd
Priority to CN202010337768.3A priority Critical patent/CN111498915B/en
Publication of CN111498915A publication Critical patent/CN111498915A/en
Application granted granted Critical
Publication of CN111498915B publication Critical patent/CN111498915B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • 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
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a positive electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the cathode material comprises the following steps: mixing raw materials including a metal compound, a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precipitate with a core-shell structure; pre-burning the precipitate to obtain a metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor; performing coordination reaction on the precursor and a ligand solution to obtain a hollow agglomeration type nickel-cobalt-manganese oxide precursor with (010) plane orientation growth; then mixing with a lithium source and sintering to obtain the cathode material. The cathode material is prepared by using a preparation method of the cathode material. The lithium ion battery is prepared by using the cathode material. The cathode material provided by the application has excellent rate performance and cycle performance.

Description

Cathode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery is used as a novel high-energy battery successfully developed in the 20 th century, and is rapidly applied to various fields due to the advantages of high energy density, environmental friendliness, long storage life and the like, the positive electrode material of the lithium ion battery is used as a core part, the performance of the positive electrode material has obvious influence on the performance of the lithium ion battery, and the agglomerated lithium nickel cobalt manganese oxide positive electrode material (L i [ Ni ] has a layered structurexCoyMn(1-x-y)]O2Wherein x is more than 0.3) is the most promising anode material applied to power batteries due to the characteristics of high energy density, high stacking density, good process performance, low price and the like, but the spherical particles have larger stress change inside the crystal grains in the charging and discharging process, and generate lattice anisotropic expansion and contraction, so that cracks are generated at the grain boundary gap, the generation of the cracks increases the side reaction of the anode material and electrolyte, the impedance is increased, the lithium ion diffusion is more difficult, and the electrochemical performance of the ternary anode material is continuously reducedxCoyMn(1-x-y)]O2And x is more than 0.3), the cycle stability and the rate capability of the material are improved, and the synthesis process still needs to be further optimized.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide a positive electrode material, a preparation method thereof and a lithium ion battery, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a positive electrode material, comprising:
mixing raw materials including a metal compound, a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precipitate with a core-shell structure;
pre-burning the precipitate to obtain a metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor;
carrying out coordination reaction on the metal ion modified hollow agglomeration type nickel-cobalt-manganese oxide precursor and a ligand solution to obtain a (010) plane oriented growth hollow agglomeration type nickel-cobalt-manganese oxide precursor;
mixing the hollow agglomerated nickel-cobalt-manganese oxide precursor with the (010) plane oriented growth and a lithium source, and sintering to obtain the cathode material;
the metal compound is insoluble in water and is easily decomposed by heating; the ligand in the ligand solution comprises one or more of 2, 6-bis (3-5) dicarboxyphenylpyridine, 2, 5-dicarboxy-1, 4 terephthalic acid and thiophene-2, 5-dicarboxylic acid.
In a lithium ion battery, L i+The insertion and the separation are carried out along the (010) direction, the increase of the (010) surface can increase the contact surface of an active substance and an electrolyte, improve the diffusion coefficient of lithium ions, provide L i ion transmission power and effectively improve ion transmission, in addition, the hollow interior not only can provide extra active sites and short diffusion paths for lithium ion storage, but also can buffer volume change, relieve mutual extrusion of the lithium ions in material particles in the charging and discharging processes, improve the structural stability of the material in the charging and discharging processes, further greatly improve the rate capability and the cycle performance of the cathode material, and solve the electrochemical performance degradation caused by spherical cracks in the charging and discharging processes.
Preferably, the metal compound is D obtained by granulating and molding a corresponding compound with a primary particle size of less than or equal to 100nm50Is 2-8 μm of agglomerated particles;
preferably, the metal compound is mixed with water to obtain a metal template suspension for use;
preferably, the solid content of the metal template suspension is 30-70%.
The particle size of the metal compound is adjusted to adjust the size of the hollow cavity, so that the anode material with excellent performance is obtained.
Optionally, D of the agglomerate particle50Can be any value between 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm and 2-8 μm; fixing the metal template suspensionThe content may be any value between 30%, 40%, 50%, 60%, 70% and 30-70%.
Preferably, the nickel source comprises one or more of nickel sulfate, nickel acetate, nickel nitrate, nickel chloride;
preferably, the cobalt source comprises one or more of cobalt sulfate, cobalt acetate, cobalt nitrate, cobalt chloride;
preferably, the manganese source comprises one or more of manganese sulfate, manganese acetate, manganese nitrate, manganese chloride;
preferably, the nickel source, the cobalt source and the manganese source are mixed in advance to prepare a metal salt solution for use;
preferably, the molar concentration of the metal ions in the metal salt solution is 0.1-5 mol/L.
Alternatively, the molar concentration of the metal ions in the metal salt solution may be any value between 0.1 mol/L, 0.5 mol/L, 1 mol/L0, 1.5 mol/L1, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L, 5 mol/L, and 0.1-5 mol/L.
Preferably, the precipitant comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate;
preferably, the complexing agent comprises ammonia or ammonium bicarbonate;
preferably, the precipitant and the complexing agent are mixed in advance and then used;
preferably, the molar concentration of the mixed solution of the precipitator and the complexing agent is 0.1-5 mol/L.
Alternatively, the molar concentration of the mixed solution of the precipitant and the complexing agent may be any one of values between 0.1 mol/L, 0.5 mol/L, 1 mol/L0, 1.5 mol/L1, 2 mol/L, 2.5 mol/L, 3 mol/L, 3.5 mol/L, 4 mol/L, 4.5 mol/L, 5 mol/L, and 0.1 to 5 mol/L.
Preferably, the temperature of the coprecipitation reaction is 25-60 ℃, the pH value of the reaction system is 10-12, and the reaction time is 2-56 h;
preferably, the precipitation reaction is carried out under stirring;
preferably, the stirring speed is 500-.
Optionally, the temperature of the coprecipitation reaction may be any value between 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and 25-60 ℃, the pH of the reaction system may be any value between 10, 11, 12 and 10-12, and the reaction time may be any value between 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 56h and 2-56 h; the stirring speed can be any value between 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min and 500-.
Preferably, the temperature of the pre-sintering treatment is 400-650 ℃, and the treatment time is 5-30 h;
preferably, the pre-firing treatment further comprises:
washing the precipitate with water for 2-5 times;
preferably, the diameter of the hollow cavity of the metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor is 2-8 μm.
Optionally, the temperature of the pre-sintering treatment may be any value between 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and 400-650 ℃, and the treatment time may be any value between 5h, 10h, 15h, 20h, 25h, 30h and 5-30 h; the number of washing of the precipitate with water may be any value between 2, 3, 4, 5 and 2-5; the diameter of the hollow cavity of the metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor can be any value among 2 micrometers, 3 micrometers, 4 micrometers, 5 micrometers, 6 micrometers, 7 micrometers, 8 micrometers and 2-8 micrometers.
Preferably, the dosage of the ligand is 0.1-5% of the mass of the metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor;
preferably, the coordination reaction is carried out under stirring;
preferably, the stirring speed is 500-;
preferably, the coordination reaction further comprises, after the completion of the coordination reaction:
drying the reaction product to obtain the hollow agglomerated nickel-cobalt-manganese oxide precursor with the (010) plane oriented growth;
preferably, the drying temperature is 60-250 ℃, and the drying time is 10-48 h.
Alternatively, the amount of the ligand may be any one of 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and 0.1% -5% of the mass of the metal ion-modified hollow agglomerated nickel-cobalt-manganese oxide precursor; the stirring speed can be any value between 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min and 500-; the drying temperature can be any value between 60 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 60-250 ℃, and the drying time can be any value between 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h and 10-48 h.
Preferably, the molar ratio of the sum of the nickel source, cobalt source and manganese source to the lithium source is 1: (1.0-1.2);
preferably, the sintering temperature is 670-;
preferably, the outer diameter of the cathode material is 12-14 μm, and the diameter of the hollow cavity of the cathode material is 3.5-9.4 μm.
Alternatively, the molar ratio of the sum of the nickel source, cobalt source, and manganese source to the lithium source may be 1:1. 1:1.1, 1:1.2 and 1: (1.0-1.2); the sintering temperature can be any value between 670 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 670 and 950 ℃, the heating rate can be any value between 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min and 2-5 ℃/min, and the heat preservation time can be any value between 6h, 10h, 15h, 20h, 25h, 30h and 6-30 h; the outer diameter of the positive electrode material may be any value between 12 μm, 13 μm, 14 μm and 12-14 μm, and the diameter of the hollow cavity of the positive electrode material may be any value between 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.4 μm and 3.5-9.4 μm.
The cathode material is prepared by the preparation method of the cathode material.
The positive electrode of the lithium ion battery is prepared by using the positive electrode material.
A lithium ion battery is prepared by using the cathode material.
An electric device comprises the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the anode material, a metal compound is used as a carrier and a template, a ternary precursor grows on the surface of the metal compound through a coprecipitation reaction, the metal compound is decomposed after pre-sintering treatment, and metal ions enter into a precursor lattice to form a hollow spherical oxide precursor with metal ion modification; then, performing coordination reaction with a ligand to obtain a hollow agglomeration type nickel-cobalt-manganese oxide precursor with a (010) plane oriented growth; the hollow agglomerated lithium nickel cobalt manganese oxide cathode material with (010) plane oriented growth is obtained by mixing and sintering with a lithium source, and the cathode material has a larger (010) plane lithium ion diffusion path, improves the lithium ion diffusion coefficient, and has a structure for relieving the mutual extrusion of internal particles caused by anisotropic stress generated in the charging and discharging process, so that the material has good rate capability and cycle performance;
2. the preparation method of the cathode material is simple in process, easy to control, high in repeatability and suitable for large-scale production.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 shows L iNi prepared in example 1 and comparative example 10.5Co0.2Mn0.3O2Of positive electrode materialsXRD profile;
FIG. 2 shows L iNi prepared in example 1 and comparative example 10.5Co0.2Mn0.3O2The first circle C-V (specific capacity-voltage) curve of the anode material under the conditions of 3-4.3V and 0.1C;
FIG. 3 is a drawing showing a hollow agglomerate type L iNi grown in (010) plane orientation prepared in example 20.8Co0.1Mn0.1O2TEM photograph of the positive electrode material;
FIG. 4 is a drawing showing a hollow agglomerate type L iNi grown in (010) plane orientation prepared in example 30.6Co0.2Mn0.2O2SEM photograph of the positive electrode material;
FIG. 5 is a drawing showing a hollow agglomerate type L iNi grown in (010) plane orientation prepared in example 40.8Co0.1Mn0.1O2The first circle C-V (specific capacity-voltage) curve of the anode material under the conditions of 3-4.3V and 0.1C;
FIG. 6 is L iNi prepared in example 2 and comparative example 20.8Co0.1Mn0.1O2The capacity of the anode material is kept on a curve under 1C circulation at 3-4.3V;
FIG. 7 is L iNi prepared in example 2 and comparative example 30.8Co0.1Mn0.1O2The rate capability of the anode material is 3-4.3V.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Weighing particles with a primary particle size of 80nm, granulating, and molding50Mixing 8 mu m aluminum hydroxide, titanium oxide and deionized water to prepare a template suspension with a solid content of 30%, stirring at a rotating speed of 500rpm/min, weighing manganese acetate, nickel acetate and cobalt acetate according to a molar ratio of Mn to Ni to Co of 5:2:3, dissolving the manganese acetate, the nickel acetate and the cobalt acetate in deionized water to prepare a 3 mol/L mixed metal salt solution, preparing a mixed solution of a precipitator and a complexing agent, dropwise adding the mixed solution of the mixed metal salt solution, the precipitator and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 12, controlling the solution temperature to be 60 ℃, after the coprecipitation reaction is finished, adjusting the rotating speed to 1000rpm/min, continuously stirring for 50h, standing for 6h, carrying out suction filtration and washing for 2 times repeatedly, then carrying out heat preservation for 30h at 650 ℃ to obtain a hollow agglomerated aluminum and titanium ion modified hollow agglomerated type NCM oxide precursor, then taking 2-5-dicarboxyl ligand to 1-523 h according to obtain an agglomerated lithium carbonate agglomerated type NCM oxide precursor with a mass fraction of 5%, uniformly stirring rate of 5-523, adding the agglomerated NCM and a temperature of the agglomerated lithium carbonate to obtain an agglomerated NCM precursor of the agglomerated NCM precursor with a temperature of 30.010.010.5 ℃ under a temperature of 500 ℃ and a temperature of 30.010.5 ℃ under a temperature of 500 ℃ under a temperature of a 500.5.5.5.5.5 ℃ and a temperature of an agglomerated NC5.010.5.5.5.5.5.5.5 ℃ under stirring, and a temperature of an agglomerated NCK, and a temperature of an agglomerated NC5.0.5Co0.2Mn0.3O2And (3) a positive electrode material.
Example Al3+And Ti4+Ion-modified (010) plane-oriented grown hollow agglomerate L iNi0.5Co0.2Mn0.3O2D of (A)5014 μm, hollow cavity about 9.4 μm, 0.1C first discharge capacity 165.4mAh/g, first effect 88.3%, 7CThe discharging specific capacity is 118.5mAh/g, and the capacity retention rate of 50 cycles is 97.3%.
Hollow agglomerate type L iNi grown in (010) plane orientation prepared in example 10.5Co0.2Mn0.3O2The XRD photographs of the cathode material and the first C-V (specific capacity-voltage) curves at 0.1C are shown in fig. 1 and fig. 2, respectively.
Example 2
Weighing particles with the particle size of 10nm for granulation molding, weighing magnesium hydroxide and zirconium oxide with the D50 of 2 mu m for mixing with deionized water to prepare a template suspension with the solid content of 50%, stirring at the rotating speed of 500rpm/min, weighing manganese sulfate, nickel sulfate and cobalt sulfate according to the molar ratio Mn: Ni: Co ═ 8:1:1, dissolving in deionized water to prepare a mixed metal salt solution with the solid content of 1 mol/L, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is a sodium hydroxide solution with the particle size of 1 mol/L, the complexing agent is an ammonium bicarbonate solution with the particle size of 0.1 mol/L, dropwise adding the mixed metal salt solution, the precipitator and the mixed solution of the precipitating agent and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 10, the solution temperature to be 25 ℃, standing for 2h of agglomeration after the coprecipitation reaction is finished, washing and suction filtration after the reaction is finished, carrying out 5 times, then carrying out low-temperature hollow pre-sintering on the precipitate for 10h by keeping the temperature at 550 ℃, forming hollow agglomeration of a hollow agglomeration type hollow agglomeration of a hollow agglomerated type hollow magnesium and zirconium ion modified hollow type oxide precursor of the hollow type oxide with the magnesium oxide, then taking the precursor with the NCM811 with the weight fraction of the NCM811 of the NC010-811 of the NCK, the temperature of the 500 ℃ of the NCM811, the temperature of the NCH, adding0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Mg of the present example2+And Zr4+Ion-modified (010) plane-oriented growth hollow agglomerate type L iNi0.8Co0.1Mn0.1O2The D50 is 13 mu m, the hollow cavity is about 3.5 mu m, the 0.1C first discharge capacity is 213.5mAh/g, the first effect is 90.5%, the discharge specific capacity under 7C is 163.1mAh/g, and the capacity retention rate of 50 cycles of circulation is 97.5%.
A TEM photograph of the prepared cathode material is shown in fig. 3.
Example 3
Weighing granules with a primary particle size of 50nm, granulating, and molding50Mixing yttrium hydroxide with the thickness of 5 mu m, aluminum oxide and deionized water to prepare a template suspension with the solid content of 70%, stirring at the rotating speed of 800rpm/min, weighing manganese nitrate, nickel nitrate and cobalt nitrate according to the molar ratio of Mn to Ni to Co of 6:2:2, dissolving the manganese nitrate, the nickel nitrate and the cobalt nitrate in deionized water to prepare a 5 mol/L mixed metal salt solution, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is a 5 mol/L mixed solution of sodium carbonate and sodium bicarbonate, the complexing agent is a 0.2 mol/L aqueous ammonia solution, dropwise adding the mixed metal salt solution, the precipitator and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 11, controlling the solution temperature to be 50 ℃, after the coprecipitation reaction is finished, adjusting the rotating speed to 800rpm/min, continuing stirring for 35h, standing for 4h, performing suction filtration after the reaction is finished, repeatedly washing for 3 times, removing impurity ions, performing hollow heat preservation for 20h at the precipitate at the temperature of 500 ℃, forming an yttrium and aluminum ion modified hollow pre-sintered precursor of an agglomerated NCM type NCM622, adding an NCM precursor of an NCM 2-010 mol ratio of an oriented lithium oxide, uniformly-1H, heating and drying to obtain an agglomerated NCM 2h, and uniformly-1H mixed metal oxide, and adding an NCM precursor, and heating surface, and uniformly-1-010-1H mixture of an NCM precursor, and heating, and uniformly-1-010-1-0100.6Co0.2Mn0.2O2And (3) a positive electrode material.
The (010) plane oriented hollow agglomerate type L iNi prepared by the method0.6Co0.2Mn0.2O2The SEM photograph of the positive electrode material is shown in fig. 4.
Example Y3+And Al3+Ion-modified (010) plane oriented growth hollow agglomeration type ternary cathode material L iNi0.6Co0.2Mn0.2O2D of (A)50The discharge capacity at 0.1C is 185.2mAh/g, the first effect is 89.3%, the discharge specific capacity at 7C is 133.2mAh/g, and the capacity retention rate of 50 cycles is 97.5%.
Example 4
Weighing granules with a primary particle size of 55nm, granulating, and molding50Mixing yttrium oxide with the thickness of 6 mu m, magnesium oxide and deionized water to prepare a template suspension with the solid content of 70%, stirring at the rotating speed of 800rpm/min, weighing manganese chloride, nickel chloride and cobalt chloride according to the molar ratio of Mn to Ni to Co of 8:1:1, dissolving the manganese chloride, nickel chloride and cobalt chloride in deionized water to prepare a 2 mol/L mixed metal salt solution, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is a 2 mol/L mixed solution of sodium carbonate and sodium bicarbonate, the complexing agent is a 0.2 mol/L aqueous ammonia solution, dropwise adding the mixed metal salt solution, the precipitator and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 10, controlling the solution temperature to be 35 ℃, after the coprecipitation reaction is finished, adjusting the rotating speed to 800rpm/min, continuing stirring for 24 hours, standing for 6 hours, performing suction filtration after the reaction is finished, repeatedly washing for 4 times, removing impurity ions, performing heat preservation for 25 hours at the temperature of 400 ℃, forming a hollow agglomeration of an yttrium and magnesium ion modified hollow agglomerated precursor of a hollow yttrium and magnesium oxide, forming a hollow agglomerated precursor of an agglomerated type NCM 811-5% of an NCM precursor, adding an oriented lithium hydroxide, heating and an agglomerated precursor with a hollow lithium hydroxide, uniformly stirred precursor of an oriented surface, and an NCM precursor of 3-5 hours, and an NCM precursor of a temperature of an NCM for forming process of a temperature of 3-811, and a hollow surface, and an NCM of an NCPoly type L iNi0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Example Y3+And Mg2+Ion-modified (010) plane oriented growth hollow spherical ternary cathode material L iNi0.8Co0.1Mn0.1O2D of (A)50The discharge capacity at 0.1C is 212.9mAh/g, the first effect is 88.3%, the discharge specific capacity at 7C is 166.2mAh/g, and the capacity retention rate of 50 cycles is 98.5%.
Hollow agglomerate type L iNi grown in (010) plane orientation prepared in example 40.8Co0.1Mn0.1O2The first-turn C-V (specific capacity-voltage) curve of the positive electrode material under the conditions of 3-4.3V and 0.1C is shown in figure 5.
Comparative example 1
Weighing particles with a primary particle size of 80nm, granulating, and molding50Mixing 8 mu m aluminum hydroxide, titanium oxide and deionized water to prepare a template suspension with a solid content of 30%, stirring at a rotating speed of 500rpm/min, weighing manganese acetate, nickel acetate and cobalt acetate according to a molar ratio of Mn to Ni to Co of 5:2:3, dissolving the manganese acetate, nickel acetate and cobalt acetate in deionized water to prepare a 3 mol/L mixed metal salt solution, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is a 3 mol/L potassium hydroxide solution, the complexing agent is a 0.1 mol/L ammonia water solution, dropwise adding the mixed metal salt solution, the mixed metal salt solution of the precipitator and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 12 and the solution temperature to be 60 ℃, after the coprecipitation reaction is finished, regulating the rotating speed to 1000rpm/min, continuously stirring for 50 hours, standing for 6 hours, carrying out suction filtration and washing, repeating for 2 times, then carrying out heat preservation for 30 hours at 650 ℃, forming a hollow agglomerated aluminum and titanium ion modified hollow agglomerated precursor, placing the agglomerated aluminum and titanium ion precursor into a high-temperature-preserving furnace, uniformly, heating and cooling the agglomerated aluminum oxide precursor for 30 hours, and lithium ion-modified titanium oxide precursor, and then carrying out heat preservation at a high temperature of L iNi ℃ according to obtain an agglomerated aluminum-modified lithium carbonate agglomeration rate of 1, 5, and a temperature of L iNi, and a0.5Co0.2Mn0.3O2Positive electrode material。
Comparative example Al3+And Ti4+Ion-modified hollow agglomerate type L iNi0.5Co0.2Mn0.3O2D of (A)5013.8 μm, a hollow cavity of about 9.38 μm, a 0.1C first discharge capacity of 160.3mAh/g, a first efficiency of 86.8%, a 7C discharge specific capacity of 112.4mAh/g, and a capacity retention rate of 97.1% after circulating 50 circles.
L iNi from comparative example 10.5Co0.2Mn0.3O2XRD curves of the anode material and first-circle C-V (specific capacity-voltage) curves under 3-4.3V and 0.1C are shown in figures 1 and 2.
Comparative example 2
Weighing manganese sulfate, nickel sulfate and cobalt sulfate according to a molar ratio of Mn to Ni to Co of 8 to 1, dissolving the manganese sulfate, nickel sulfate and cobalt sulfate in deionized water to prepare 1 mol/L mixed metal salt solution, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is 1 mol/L sodium hydroxide solution, the complexing agent is 0.1 mol/L ammonium bicarbonate solution, dropwise adding the mixed solution of the mixed metal salt solution, the precipitator and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 10, controlling the temperature of the solution to be 25 ℃, standing the solution to form 2h after the coprecipitation reaction is finished, performing suction filtration and washing after the reaction is finished, repeating for 5 times, performing low-temperature presintering treatment on the precipitate by using a heat preservation method at 550 ℃ for 10h to form a hollow agglomerated NCM811 oxide precursor, then taking a ligand 2, 6-bis (3-5) dicarboxylphenylpyridine according to the mass fraction of 0.1%, mixing the ligand 2, 6-bis (3-5) dicarboxylphenylpyridine with the deionized water, adding the hollow NCM811 oxide, stirring the precursor for 2h at 500rpm/min, stirring for 2h, performing heat preservation for 48h to obtain an agglomerated NCM 811-oriented growth precursor, and uniformly heating the agglomerated lithium hydroxide surface growth rate of the obtained NCM811, and uniformly to obtain an NCM 811-oriented lithium hydroxide surface, and then placing the agglomerated lithium hydroxide surface, and uniformly heating the agglomerated lithium hydroxide surface, and uniformly0.8Co0.1Mn0.1O2And (3) a positive electrode material.
The (010) plane-oriented hollow agglomerate type L iNi of this comparative example0.8Co0.1Mn0.1O2The D50 of (1) is 12.5 mu m, the first discharge capacity at 0.1C is 211.6mAh/g, the first effect is 90.2%, the discharge specific capacity at 7C is 163.1mAh/g, and the capacity retention rate of 50 cycles of circulation is 94.5%.
L iNi from this comparative example0.8Co0.1Mn0.1O2The capacity retention curve of the positive electrode material under the circulation of 3-4.3V and 1C is shown in FIG. 6.
Comparative example 3
Weighing particles with the particle size of 10nm for granulation molding, weighing magnesium hydroxide and zirconium oxide with the D50 of 1 mu m for mixing with deionized water to prepare a template suspension with the solid content of 50%, stirring at the rotating speed of 500rpm/min, weighing manganese sulfate, nickel sulfate and cobalt sulfate according to the molar ratio Mn: Ni: Co ═ 8:1:1, dissolving in deionized water to prepare a mixed metal salt solution with the solid content of 1 mol/L, preparing a mixed solution of a precipitator and a complexing agent, wherein the precipitator is a sodium hydroxide solution with the particle size of 1 mol/L, the complexing agent is an ammonium bicarbonate solution with the particle size of 0.1 mol/L, dropwise adding the mixed metal salt solution, the precipitator and the mixed solution of the precipitating agent and the complexing agent into a metal compound solution by adopting a coprecipitation method, controlling the pH value of a reaction system to be 10, the solution temperature to be 25 ℃, standing for 2h of agglomeration after the coprecipitation reaction is finished, washing, performing suction filtration for 5 times, then performing low-temperature hollow pre-sintering treatment on the precipitate for 10h by keeping the temperature for 10h at 550 ℃, forming hollow agglomeration of a hollow agglomerated magnesium and zirconium ion modified hollow agglomerated hollow magnesium oxide precursor with a NCM811 with the NCM811 of the NCM811, the mixed metal oxide precursor with the temperature of the NCM811, the NC010-811, adding the NCH, the NC010, the NCH, adding the NCH of the NCH, and the NCH of0.8Co0.1Mn0.1O2And (3) a positive electrode material.
Mg of this comparative example2+And Zr4+Ion modified (010)Hollow agglomerate type L iNi with planar orientation growth0.8Co0.1Mn0.1O2The D50 of (1) is 12.7 mu m, the hollow cavity is about 2.4 mu m, the first discharge capacity at 0.1C is 212.3mAh/g, the first effect is 90.1%, the discharge specific capacity at 7C is 160.1mAh/g, and the capacity retention rate of 50 cycles of circulation is 95.9%.
L iNi from this comparative example0.8Co0.1Mn0.1O2The capacity retention curve of the positive electrode material under 1C cycle at 3-4.3V is shown in FIG. 7.
The application provides a cathode material belongs to the hollow agglomeration type nickel cobalt lithium manganate cathode material of metal ion modified (010) face orientation growth, can solve the inside extrusion problem of granule, improves lithium ion diffusion coefficient to obtain good rate capability and cyclicity ability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. A method for preparing a positive electrode material, comprising:
mixing raw materials including a metal compound, a nickel source, a cobalt source, a manganese source, a precipitator and a complexing agent, and carrying out coprecipitation reaction to obtain a precipitate with a core-shell structure;
pre-burning the precipitate to obtain a metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor;
carrying out coordination reaction on the metal ion modified hollow agglomeration type nickel-cobalt-manganese oxide precursor and a ligand solution to obtain a (010) plane oriented growth hollow agglomeration type nickel-cobalt-manganese oxide precursor;
mixing the hollow agglomerated nickel-cobalt-manganese oxide precursor with the (010) plane oriented growth and a lithium source, and sintering to obtain the cathode material;
the metal compound is insoluble in water and is easily decomposed by heating; the ligand in the ligand solution comprises one or more of 2, 6-bis (3-5) dicarboxyphenylpyridine, 2, 5-dicarboxy-1, 4 terephthalic acid and thiophene-2, 5-dicarboxylic acid.
2. The method according to claim 1, wherein the metal compound comprises one or more of magnesium hydroxide, magnesium oxide, aluminum hydroxide, aluminum oxide, zirconium oxide, yttrium hydroxide, yttrium oxide, and titanium oxide;
preferably, the metal compound is D obtained by granulating and molding a corresponding compound with a primary particle size of less than or equal to 100nm50Is 2-8 μm of agglomerated particles;
preferably, the metal compound is mixed with water to obtain a metal template suspension for use;
preferably, the solid content of the metal template suspension is 30-70%.
3. The method of claim 1, wherein the nickel source comprises one or more of nickel sulfate, nickel acetate, nickel nitrate, nickel chloride;
preferably, the cobalt source comprises one or more of cobalt sulfate, cobalt acetate, cobalt nitrate, cobalt chloride;
preferably, the manganese source comprises one or more of manganese sulfate, manganese acetate, manganese nitrate, manganese chloride;
preferably, the nickel source, the cobalt source and the manganese source are mixed in advance to prepare a metal salt solution for use;
preferably, the molar concentration of the metal ions in the metal salt solution is 0.1-5 mol/L.
4. The method of claim 1, wherein the precipitant comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate;
preferably, the complexing agent comprises ammonia or ammonium bicarbonate;
preferably, the precipitant and the complexing agent are mixed in advance and then used;
preferably, the molar concentration of the mixed solution of the precipitator and the complexing agent is 0.1-5 mol/L.
5. The preparation method according to claim 1, wherein the temperature of the coprecipitation reaction is 25-60 ℃, the pH value of the reaction system is 10-12, and the reaction time is 2-56 h;
preferably, the precipitation reaction is carried out under stirring;
preferably, the stirring speed is 500-.
6. The preparation method according to claim 1, wherein the pre-sintering treatment temperature is 400-650 ℃, and the treatment time is 5-30 h;
preferably, the pre-firing treatment further comprises:
washing the precipitate with water for 2-5 times;
preferably, the diameter of the hollow cavity of the metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor is 2-8 μm.
7. The preparation method according to claim 1, wherein the amount of the ligand is 0.1-5% of the mass of the metal ion modified hollow agglomerated nickel-cobalt-manganese oxide precursor;
preferably, the coordination reaction is carried out under stirring;
preferably, the stirring speed is 500-;
preferably, the coordination reaction further comprises, after the completion of the coordination reaction:
drying the reaction product to obtain the hollow agglomerated nickel-cobalt-manganese oxide precursor with the (010) plane oriented growth;
preferably, the drying temperature is 60-250 ℃, and the drying time is 10-48 h.
8. The method according to any one of claims 1 to 7, wherein the molar ratio of the sum of the nickel source, cobalt source and manganese source to the lithium source is 1: (1.0-1.2);
preferably, the sintering temperature is 670-;
preferably, the outer diameter of the cathode material is 12-14 μm, and the diameter of the hollow cavity of the cathode material is 3.5-9.4 μm.
9. A positive electrode material produced by the method for producing a positive electrode material according to any one of claims 1 to 8.
10. A lithium ion battery produced using the positive electrode material according to claim 9.
CN202010337768.3A 2020-04-26 2020-04-26 Cathode material, preparation method thereof and lithium ion battery Active CN111498915B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010337768.3A CN111498915B (en) 2020-04-26 2020-04-26 Cathode material, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010337768.3A CN111498915B (en) 2020-04-26 2020-04-26 Cathode material, preparation method thereof and lithium ion battery

Publications (2)

Publication Number Publication Date
CN111498915A true CN111498915A (en) 2020-08-07
CN111498915B CN111498915B (en) 2022-08-05

Family

ID=71873102

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010337768.3A Active CN111498915B (en) 2020-04-26 2020-04-26 Cathode material, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN111498915B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617289A (en) * 2015-01-15 2015-05-13 湘潭大学 Preparation method of hollow spherical lithium-enriched cathode material for lithium-ion battery
JP2015191847A (en) * 2014-03-28 2015-11-02 住友金属鉱山株式会社 Precursor of positive electrode active material for nonaqueous electrolyte secondary batteries and manufacturing method thereof, and method for manufacturing positive electrode active material for nonaqueous electrolyte secondary batteries
CN105914364A (en) * 2016-05-13 2016-08-31 安泰科技股份有限公司 Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof
CN106340638A (en) * 2016-10-10 2017-01-18 哈尔滨工业大学 High multiplying power lithium-enriched manganese-based anode material with double-layer hollow structure and preparation method thereof
CN106450278A (en) * 2016-11-03 2017-02-22 上海纳米技术及应用国家工程研究中心有限公司 Ternary positive electrode material with hollow microsphere structure, preparation method and application
CN107069023A (en) * 2017-03-30 2017-08-18 合肥工业大学 A kind of preparation method of hollow-core construction lithium ion battery electrode material
CN107445214A (en) * 2017-09-05 2017-12-08 中南大学 A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN107968202A (en) * 2017-11-21 2018-04-27 宁波纳微新能源科技有限公司 A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof
CN110676451A (en) * 2019-12-04 2020-01-10 湖南省正源储能材料与器件研究所 Hollow spherical anode material with crystal grain size arranged in growth direction and preparation method thereof
CN110980817A (en) * 2019-10-10 2020-04-10 格林美（无锡）能源材料有限公司 High-power and long-cycle lithium battery positive electrode material and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015191847A (en) * 2014-03-28 2015-11-02 住友金属鉱山株式会社 Precursor of positive electrode active material for nonaqueous electrolyte secondary batteries and manufacturing method thereof, and method for manufacturing positive electrode active material for nonaqueous electrolyte secondary batteries
CN104617289A (en) * 2015-01-15 2015-05-13 湘潭大学 Preparation method of hollow spherical lithium-enriched cathode material for lithium-ion battery
CN105914364A (en) * 2016-05-13 2016-08-31 安泰科技股份有限公司 Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof
CN106340638A (en) * 2016-10-10 2017-01-18 哈尔滨工业大学 High multiplying power lithium-enriched manganese-based anode material with double-layer hollow structure and preparation method thereof
CN106450278A (en) * 2016-11-03 2017-02-22 上海纳米技术及应用国家工程研究中心有限公司 Ternary positive electrode material with hollow microsphere structure, preparation method and application
CN107069023A (en) * 2017-03-30 2017-08-18 合肥工业大学 A kind of preparation method of hollow-core construction lithium ion battery electrode material
CN107445214A (en) * 2017-09-05 2017-12-08 中南大学 A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN107968202A (en) * 2017-11-21 2018-04-27 宁波纳微新能源科技有限公司 A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof
CN110980817A (en) * 2019-10-10 2020-04-10 格林美（无锡）能源材料有限公司 High-power and long-cycle lithium battery positive electrode material and preparation method thereof
CN110676451A (en) * 2019-12-04 2020-01-10 湖南省正源储能材料与器件研究所 Hollow spherical anode material with crystal grain size arranged in growth direction and preparation method thereof

Also Published As

Publication number Publication date
CN111498915B (en) 2022-08-05

Similar Documents

Publication Publication Date Title
CN110518219B (en) Core-shell structured high nickel gradient nickel-cobalt-manganese-aluminum quaternary positive electrode material and preparation method thereof
JP7241875B2 (en) Cathode material for high-power lithium-ion battery and method for producing the same
CN110518220B (en) Nickel-cobalt-manganese-aluminum quaternary positive electrode material with high nickel gradient and preparation method thereof
CN109336193B (en) Multi-element in-situ co-doped ternary material precursor and preparation method and application thereof
CN110085858B (en) Niobium-phosphorus co-doped high-nickel ternary cathode material and preparation method and application thereof
EP3557668A1 (en) Ternary material and preparation method therefor, battery slurry, positive electrode, and lithium battery
CN109713297B (en) High-nickel anode material with directionally arranged primary particles and preparation method thereof
EP3965188A1 (en) Composite positive electrode material for lithium ion battery, lithium ion battery, and vehicle
CN110540254A (en) Boron-magnesium co-doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN109721109A (en) A kind of lithium battery nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof and the positive electrode being prepared
CN110867573A (en) Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
CN110867576A (en) Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
CN113540436A (en) Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof
CN113851633B (en) Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof
CN111180688B (en) Micron-scale hollow porous sodium-ion battery positive electrode material and preparation method thereof
CN109879333B (en) Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method
CN112250091A (en) High-nickel ternary precursor, positive electrode material and preparation method
CN112952085B (en) Gradient high-nickel single crystal ternary material, preparation method thereof and battery using material
CN108807918B (en) Surface-coated composite lithium-rich manganese-based cathode material and preparation method thereof
CN112928250A (en) Nickel-cobalt-manganese ternary material and precursor thereof, and preparation method and application thereof
CN109962234B (en) Concentration gradient single crystal anode material and preparation method thereof
CN112928253A (en) Nickel-manganese-titanium composite material and preparation method and application thereof
CN115594230B (en) Yolk-shell structure ternary positive electrode material precursor and preparation method thereof
CN113445127A (en) Composite metal oxide doped anode material, preparation method thereof and lithium ion battery
CN114084914A (en) Ternary precursor and preparation method and application thereof

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