CN113620352B - High-voltage monocrystal ternary positive electrode material and preparation method thereof - Google Patents

High-voltage monocrystal ternary positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN113620352B
CN113620352B CN202110762982.8A CN202110762982A CN113620352B CN 113620352 B CN113620352 B CN 113620352B CN 202110762982 A CN202110762982 A CN 202110762982A CN 113620352 B CN113620352 B CN 113620352B
Authority
CN
China
Prior art keywords
positive electrode
temperature
electrode material
ternary
voltage
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
CN202110762982.8A
Other languages
Chinese (zh)
Other versions
CN113620352A (en
Inventor
周志度
李宇东
吴建华
范江
万国江
文雅
贺亚峰
韩学武
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.)
Jiangmen Kanhoo Industry Co ltd
Original Assignee
Jiangmen Kanhoo Industry 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 Jiangmen Kanhoo Industry Co ltd filed Critical Jiangmen Kanhoo Industry Co ltd
Priority to CN202110762982.8A priority Critical patent/CN113620352B/en
Publication of CN113620352A publication Critical patent/CN113620352A/en
Application granted granted Critical
Publication of CN113620352B publication Critical patent/CN113620352B/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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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
    • 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)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a high-voltage monocrystal ternary positive electrode material, and belongs to the technical field of battery materials. The preparation method of the high-voltage monocrystal ternary positive electrode material comprises the following steps: uniformly mixing lithium salt, ternary precursor and metal compound to obtain a mixture; the mixture is sintered for the first time and then crushed to obtain crushed materials; adding the crushed materials into ethanol solution containing the pre-packaged materials, stirring and mixing, evaporating ethanol, and drying to obtain powder; and (3) carrying out secondary sintering on the powder, and sieving to obtain the high-voltage monocrystal ternary anode material. The invention is doped with a doping agent with the surface capable of forming a lithium ion conductor, improves the electrochemical performance of the material, and effectively prevents the dissolution of lattice lithium in the wet cladding process; aluminum hydroxide is used as a pre-coating, so that the reaction in the secondary combustion process is uniform; the firing mode of the four heat preservation platforms is adopted, so that the dispersity of monocrystalline particles is improved, and the roundness of the monocrystalline particles is improved.

Description

High-voltage monocrystal ternary positive electrode material and preparation method thereof
Technical Field
The invention relates to a high-voltage monocrystal ternary positive electrode material and a preparation method thereof, and belongs to the technical field of battery materials.
Background
Lithium cobaltate containing 60% of cobalt by mass is subject to huge cost tests due to shortage of cobalt resources and explosion of cobalt prices, and battery cell manufacturers search for low-cost positive electrode material solutions with low cobalt and no cobalt. The field of direct replacement of lithium cobaltate with a multi-element material is partly possible, for example, a notebook cylindrical lithium battery has been replaced with a multi-element material substantially entirely. In some smart phones and tablet computers, soft package battery projects, lithium power plant manufacturers begin to gradually adopt a mode of mixing lithium cobaltate with a multi-component material in high-voltage products, so that the purpose of reducing cost is achieved. It is conceivable that the technology of replacing lithium cobaltate with a multi-element material is becoming mature, and the application of the multi-element material with high voltage will be wider. The working voltage of the existing high-voltage ternary NCM positive electrode material is basically 4.4V or below, and the stability and electrochemical performance of the material under high voltage are ensured mainly by preparing the single-crystal ternary material and combining a doping cladding process. The currently reported doping mode is mainly to select doped A ions with the radius similar to that of lithium ions and B ions with the radius similar to that of transition metal ions to carry out dry mixing doping on the precursor, and the coating mode is mainly dry coating or wet coating of metal oxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-voltage single crystal ternary positive electrode material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the high-voltage monocrystal ternary positive electrode material is characterized by comprising the following steps of:
(1) Uniformly mixing lithium salt, ternary precursor containing nickel, cobalt and manganese, an element A compound, an element B compound and an element C compound to obtain a mixture; (2) The mixture is sintered for the first time and then crushed to obtain crushed materials; (3) Adding the crushed material into an ethanol solution containing a pre-package, stirring and mixing, evaporating ethanol, and drying to obtain powder wrapped by the pre-package; (4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper to obtain the high-voltage monocrystal ternary anode material, wherein the element A is one of Y, mg, the element B is one of Al, ti and W, and the element C is one of Zr and Nb.
Research shows that the ternary positive electrode material is mainly prepared by dry mixing and doping precursor by selecting doped A ions with similar radius to lithium ions and doped B ions with similar radius to transition metal ions, while the method is characterized in that one of Y, mg with similar radius to lithium ions and one of Al, ti and W with similar radius to transition metal ions are doped before one-step firing, and meanwhile, a lithium ion semiconductor (such as Li 2 Zr0 3 、Li 3 NbO 4 ) Zr or Nb of (c). Zr adopts a doping coating mode, compared with a single coating mode, the structure can be stabilized, the surface can be improved, the phase transition from a layer to spinel can be effectively inhibited, the interval between lithium layers can be increased, and the diffusion of lithium ions can be promoted.
The stability of the material under high voltage is realized by a ternary doping coating mode, and the dissolution of lattice lithium in the subsequent wet coating process is prevented.
As a preferred embodiment of the method for preparing a high-voltage single crystal ternary cathode material of the present invention, in the step (2), the primary sintering is: firstly, raising the temperature to 450-550 ℃ at the speed of 3-5 ℃/min for 2 hours, then raising the temperature to 650-850 ℃ at the speed of 2-3 ℃/min for 3-6 hours, raising the temperature to 950-970 ℃ at the speed of 1-2 ℃/min for 10-14 hours, finally lowering the temperature to 700-900 ℃ at the speed of 2-3 ℃/min for 2-6 hours, and lowering the temperature to room temperature at the speed of 2-3 ℃/min after the heat preservation; the sintering atmosphere for the primary sintering is an oxygen-containing atmosphere, preferably air. The firing mode of four heat preservation platforms is adopted in the primary sintering process, compared with the firing mode of one platform or two platforms in the prior art, the dispersity of monocrystalline particles is improved, and the roundness of the monocrystalline particles is improved.
As a preferred embodiment of the method for preparing a high-voltage single crystal ternary cathode material, in the step (3), the pre-coating is aluminum hydroxide; the mass ratio of the pre-package is 0.05% -0.3%. Research shows that certain damage can be caused to the bulk material in the conventional wet coating process, the surface of the coated bulk is not protected, the dissolution of lattice lithium is easy to cause in the wet coating process, such as wet coating by adopting aluminum oxide, and the conventional wet coating does not recycle the solvent, so that the material manufacturing cost is increased. The wet coating of the invention adopts aluminum hydroxide as a pre-coating, and the activity of the hydroxide is higher than that of the oxide, so that the uniformity of the coating can be improved in the wet coating, and the reaction uniformity in the secondary sintering process can be facilitated. In addition, ethanol is used as a solvent for wet coating, and the solvent is recycled through distillation recovery.
As a preferred embodiment of the method for preparing a high-voltage single crystal ternary cathode material of the present invention, in the step (4), the secondary sintering is: firstly, the sintering temperature is raised to 500-700 ℃ within 6 hours, then the temperature is kept for 6-10 hours, and finally the mixture is cooled to room temperature; the sintering atmosphere is an oxygen-containing atmosphere, preferably air.
As a preferred embodiment of the method for preparing a high-voltage single crystal ternary cathode material, in the step (1), the lithium salt is at least one of lithium carbonate, lithium nitrate and lithium sulfate; the ternary precursor is Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 。
In the step (1), the molar ratio of lithium metal ions in the lithium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 1.03-1.06.
As a preferred embodiment of the preparation method of the high-voltage single crystal ternary cathode material, in the step (1), the doping amount of the metal element A in the A element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05 to 0.3 percent of the mass of the ternary positive electrode material; the doping amount of the metal element B in the B element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05 to 0.3 percent of the mass of the ternary positive electrode material; the doping amount of the metal element C in the C element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.1 to 0.3 percent of the mass of the ternary positive electrode material, and the total doping amount of the three metal elements is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Ternary positive electrode0.2% -0.5% of the mass of the material.
In a preferred embodiment of the method for producing a high-voltage single crystal ternary positive electrode material according to the present invention, in the step (2), the pulverized material has a particle size d50=4.0 to 6.0 μm.
In the step (4), the mesh number of the sieving treatment is 300-400 mesh as a preferred embodiment of the preparation method of the high-voltage single crystal ternary cathode material.
The invention also provides a high-voltage single crystal ternary positive electrode material, which is prepared by the preparation method of the high-voltage single crystal ternary positive electrode material.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a high-voltage monocrystal ternary cathode material and a preparation method thereof.
Drawings
FIG. 1 is an electron micrograph of a burned intermediate (not pulverized) of comparative example 3.
FIG. 2 is an electron micrograph of a burned intermediate product (not pulverized) of example 2.
Fig. 3 is a finished electron microscope image of example 2.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
An embodiment of the preparation method of the high-voltage monocrystal ternary anode material comprises the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.03:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element Al is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.3% of Al of ternary positive electrode material 2 O 3 And the doping amount of the metal element Nb is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Nb 0.15% of the mass of the ternary positive electrode material 2 O 5 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered for the first time in a roller kiln, wherein the sintering curve is that firstly, the temperature is raised to 450 ℃ at the speed of 5 ℃/min for 2 hours, then the temperature is raised to 650 ℃ at the speed of 2 ℃/min for 5 hours, then the temperature is raised to 950 ℃ at the speed of 1 ℃/min for 14 hours, finally, the temperature is lowered to 700 ℃ at the speed of 3 ℃/min for 6 hours, the temperature is lowered to the room temperature at the speed of 2 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=6.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.05% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 2h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 500 ℃ for 6 hours, preserving heat for 6 hours, cooling to room temperature, and screening with 400 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Example 2
An embodiment of the preparation method of the high-voltage monocrystal ternary anode material comprises the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element Al is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05% of Al of the ternary positive electrode material 2 O 3 And the doping amount of the metal element Nb is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Nb 0.1% of the mass of the ternary positive electrode material 2 O 5 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Example 3
An embodiment of the preparation method of the high-voltage monocrystal ternary anode material comprises the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.05:1 is placed in a coulter mixture, and then the doping amount of metal element Mg is LiNi 0.5 Co 0.2 Mn 0.3 O 2 MgO accounting for 0.3 percent of the mass of the ternary positive electrode material, wherein the doping amount of the metal element Ti is LiNi 0.5 Co 0.2 Mn 0.3 O 2 TiO 0.05% of the mass of the ternary positive electrode material 2 And the doping amount of the metal element Zr is LiNi 0.5 Co 0.2 Mn 0.3 O 2 ZrO 0.15% of the mass of the ternary cathode material 2 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for one time, wherein the sintering curve is that firstly, the temperature is raised to 550 ℃ at the speed of 4 ℃/min for 2 hours, then the temperature is raised to 850 ℃ at the speed of 2.5 ℃/min for 6 hours, then the temperature is raised to 970 ℃ at the speed of 1.5 ℃/min for 10 hours, finally the temperature is lowered to 900 ℃ at the speed of 2.5 ℃/min for 6 hours, the temperature is lowered to the room temperature at the speed of 2.5 ℃/min, and then the crushed material with the grain diameter of D50=5.0 mu m is obtained by crushing by using a jet mill;
(3) Adding the crushed material into an ethanol solution containing 0.3% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 2.5h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 700 ℃ for 10 hours, cooling to room temperature, and screening with a screen mesh of 350 meshes in a dehumidification room with humidity of less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Example 4
An embodiment of the preparation method of the high-voltage monocrystal ternary anode material comprises the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.1% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element Ti is LiNi 0.5 Co 0.2 Mn 0.3 O 2 TiO 0.1% of the ternary positive electrode material mass 2 And the doping amount of the metal element Zr is LiNi 0.5 Co 0.2 Mn 0.3 O 2 ZrO 0.3% of the mass of the ternary cathode material 2 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 2h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Example 5
An embodiment of the preparation method of the high-voltage monocrystal ternary anode material comprises the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.15% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element W is LiNi 0.5 Co 0.2 Mn 0.3 O 2 WO 0.1% of ternary positive electrode material mass 3 And the doping amount of the metal element Nb is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Nb 0.1% of the mass of the ternary positive electrode material 2 O 5 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Comparative example 1
The comparative example differs from example 2 only in that the raw materials do not contain a metal oxide corresponding to the metal element B and a metal oxide corresponding to the metal element C, and specifically includes the steps of:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Comparative example 2
The comparative example differs from example 2 only in that the raw material does not contain a metal oxide corresponding to the metal element C, and specifically includes the steps of:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 The doping amount of Al is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05% of Al of the ternary positive electrode material 2 O 3 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Comparative example 3
The comparative example differs from example 2 only in the one-burn curve, and specifically includes the following steps:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element Al is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05% of Al of the ternary positive electrode material 2 O 3 And the doping amount of the metal element Nb is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Nb 0.1% of the mass of the ternary positive electrode material 2 O 5 Uniformly mixing to obtain a mixture;
(2) Sintering the mixture in a roller kiln for one time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to room temperature at the speed of 3 ℃/min, and then, the mixture is crushed to the particle size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of aluminum hydroxide by mass percent, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Comparative example 4
The comparative example differs from example 2 only in that the two-bake coated aluminum hydroxide is changed to aluminum oxide, specifically comprising the steps of:
(1) Lithium carbonate and ternary precursor Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 According to the mole ratio of 1.06:1 is placed in a coulter mixture, and then the doping amount of the metal element Y is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Y0.05% of the mass of the ternary positive electrode material 2 O 3 The doping amount of the metal element Al is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05% of Al of the ternary positive electrode material 2 O 3 And the doping amount of the metal element Nb is LiNi 0.5 Co 0.2 Mn 0.3 O 2 Nb 0.1% of the mass of the ternary positive electrode material 2 O 5 Uniformly mixing to obtain a mixture;
(2) The mixture is sintered in a roller kiln for the first time, wherein the sintering curve is that firstly, the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then the temperature is raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally, the temperature is lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, the temperature is lowered to the room temperature at the speed of 3 ℃/min after the temperature is maintained, and then the mixture is crushed to the grain size D50=4.0 mu m by using a jet mill, so as to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing 0.15% of alumina by mass, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapper in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapper;
(4) And (3) carrying out secondary sintering on the powder wrapped by the pre-wrapper in a roller kiln, heating to 600 ℃ for 8 hours, cooling to room temperature, and screening with 300 meshes in a dehumidification room with humidity less than 30% to obtain the high-voltage single crystal ternary positive electrode material which is uniformly wrapped.
Effect example
1. The one-burned, uncrushed product of comparative example 3, the one-burned, uncrushed product of example 2, and the finished product of example 2 were characterized by a scanning electron microscope, and the results are shown in fig. 1, 2, and 3, respectively.
2. The electrochemical properties of the materials were tested according to the following method: the positive electrode materials prepared in examples 1 to 5 and comparative examples 1 to 4, acetylene black as a conductive agent and PVDF as a binder were mixed in a mass ratio of 9.2:0.5:0.3 in 12ml of N-methylpyrrolidone, stirred sufficiently to form a slurry, then coated on the surface of an aluminum foil by a coater, dried and cut into a proper size, a lithium sheet was used as a negative electrode, a lithium hexafluorophosphate solution was used as an electrolyte, a 2032 button cell case was used to assemble a button cell in an argon-protected glove box, and electrochemical performance tests were performed at a temperature of 25 ℃ and a voltage range of 3.0-4.5V at 45 ℃ respectively, and the results are shown in table 1.
TABLE 1
As shown in Table 1, the high-voltage ternary positive electrode material of the invention has a 1C discharge specific capacity of 175mAh/g or more in a high voltage range of 3.0-4.5V, a constant temperature of 25 ℃ for 100 weeks, a cycle capacity retention rate of 93% or more, and a high temperature of 45 ℃ for 100 weeks, a cycle capacity retention rate of 93% or more.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The preparation method of the high-voltage monocrystal ternary positive electrode material is characterized by comprising the following steps of:
(1) Uniformly mixing lithium salt, ternary precursor containing nickel, cobalt and manganese, an element A compound, an element B compound and an element C compound to obtain a mixture;
(2) The mixture is sintered for the first time and then crushed to obtain crushed materials;
(3) Adding the crushed material into an ethanol solution containing a pre-package, stirring and mixing, evaporating ethanol, and drying to obtain powder wrapped by the pre-package;
(4) Carrying out secondary sintering on the powder wrapped by the pre-wrapper to obtain the high-voltage monocrystal ternary anode material;
wherein, the element A is one of Y, mg, the element B is one of Al, ti and W, and the element C is one of Zr and Nb;
in the step (2), the primary sintering is as follows: firstly, raising the temperature to 450-550 ℃ at the speed of 3-5 ℃/min for 2 hours, then raising the temperature to 650-850 ℃ at the speed of 2-3 ℃/min for 3-6 hours, raising the temperature to 950-970 ℃ at the speed of 1-2 ℃/min for 10-14 hours, finally lowering the temperature to 700-900 ℃ at the speed of 2-3 ℃/min for 2-6 hours, and cooling to room temperature at the speed of 2-3 ℃/min after the heat preservation;
in the step (3), the pre-coating is aluminum hydroxide;
in the step (2), the sintering atmosphere of the primary sintering is an oxygen-containing atmosphere;
in the step (4), the secondary sintering is as follows: firstly, the sintering temperature is raised to 500-700 ℃ within 6 hours, then the temperature is kept for 6-10 hours, and finally the temperature is cooled to room temperature; the sintering atmosphere is an oxygen-containing atmosphere;
in the step (1), the ternary precursor is Ni 0.5 Co 0.2 Mn 0.3 (0H) 2 。
2. The method for producing a high-voltage single crystal ternary cathode material according to claim 1, wherein in the step (2), the sintering atmosphere for the primary sintering is air.
3. The method for producing a high-voltage single crystal ternary cathode material according to claim 1, wherein in the step (3), the coating amount of the pre-coating is LiNi 0.5 Co 0.2 Mn 0.3 O 2 And the mass of the ternary positive electrode material is 0.05-0.3%.
4. The method for producing a high-voltage single crystal ternary cathode material according to claim 1, wherein in the step (4), the sintering atmosphere for the secondary sintering is air.
5. The method for producing a high-voltage single crystal ternary cathode material according to claim 1, wherein in the step (1), the lithium salt is at least one of lithium carbonate, lithium nitrate and lithium sulfate.
6. The method for preparing a high-voltage single crystal ternary cathode material according to claim 1, wherein in the step (1), the molar ratio of lithium metal ions in the lithium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 1.03-1.06.
7. The method for producing a high-voltage single crystal ternary cathode material according to claim 1, wherein in step (1), the doping amount of the metal element A in the A-element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05 to 0.3 percent of the mass of the ternary positive electrode material; the doping amount of the metal element B in the B element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.05 to 0.3 percent of the mass of the ternary positive electrode material; the doping amount of the metal element C in the C element compound is LiNi 0.5 Co 0.2 Mn 0.3 O 2 0.1 to 0.3 percent of the mass of the ternary positive electrode material, and the total doping amount of the three metal elements is LiNi 0.5 Co 0.2 Mn 0.3 O 2 And 0.2 to 0.5 percent of the mass of the ternary positive electrode material.
8. The method for producing a high-voltage single crystal ternary positive electrode material according to claim 1, wherein in the step (2), the particle size of the pulverized material is d50=4.0 to 6.0 μm.
9. The method for producing a high-voltage single crystal ternary positive electrode material according to claim 1, wherein in the step (4), sieving treatment is performed after secondary sintering; the number of the screen meshes of the screening treatment is 300-400 meshes.
10. A high voltage single crystal ternary cathode material prepared by the method of any one of claims 1 to 9.
CN202110762982.8A 2021-07-06 2021-07-06 High-voltage monocrystal ternary positive electrode material and preparation method thereof Active CN113620352B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110762982.8A CN113620352B (en) 2021-07-06 2021-07-06 High-voltage monocrystal ternary positive electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110762982.8A CN113620352B (en) 2021-07-06 2021-07-06 High-voltage monocrystal ternary positive electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113620352A CN113620352A (en) 2021-11-09
CN113620352B true CN113620352B (en) 2023-07-21

Family

ID=78379126

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110762982.8A Active CN113620352B (en) 2021-07-06 2021-07-06 High-voltage monocrystal ternary positive electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113620352B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116169261A (en) * 2022-12-22 2023-05-26 北京当升材料科技股份有限公司 Single crystal type multielement positive electrode material, preparation method thereof and lithium ion battery
CN116835674A (en) * 2023-08-28 2023-10-03 新乡天力锂能股份有限公司 Preparation method of ternary positive electrode material with high compaction and high energy density

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140127581A1 (en) * 2012-11-07 2014-05-08 Huawei Technologies Co., Ltd. Lithium-Rich Anode Material, Lithium Battery Anode, and Lithium Battery
CN105958038A (en) * 2016-07-11 2016-09-21 湖南美特新材料科技有限公司 Quickly-rechargeable long-life high-voltage lithium cobaltate positive electrode material and preparation method
CN109326781B (en) * 2018-09-29 2021-09-14 湖南长远锂科股份有限公司 Preparation method of high-voltage lithium cobalt oxide positive electrode material
CN109516509B (en) * 2018-11-16 2021-08-10 中伟新材料股份有限公司 High-compaction single crystal ternary positive electrode material and preparation method and application thereof
CN111987294A (en) * 2019-05-23 2020-11-24 天津国安盟固利新材料科技股份有限公司 Positive electrode active material, method for producing same, and positive electrode and lithium ion secondary battery comprising same
CN112054173B (en) * 2019-06-12 2022-01-28 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
CN112080800A (en) * 2020-05-26 2020-12-15 宜宾锂宝新材料有限公司 Modification method of single crystal ternary cathode material

Also Published As

Publication number Publication date
CN113620352A (en) 2021-11-09

Similar Documents

Publication Publication Date Title
CN109273710B (en) Preparation method of doped coated single crystal ternary cathode material
US10790506B2 (en) Spherical or spherical-like cathode material for lithium-ion battery and lithium-ion battery
CN110718688B (en) Single crystal ternary positive electrode material and preparation method thereof
EP4024523A1 (en) Gradient doped cobalt-free positive electrode material and preparation method therefor, lithium-ion battery positive electrode, and lithium battery
KR20180070435A (en) Spherical or Spherical-like Cathode Material for a Lithium Battery, a battery and preparation method and application thereof
CN110233253A (en) A kind of binary doped monocrystalline tertiary cathode material and preparation method thereof
CN112582594B (en) Cobalt-free single crystal cathode material and preparation method and application thereof
CN110391417B (en) Preparation method of mono-like crystal lithium-rich manganese-based positive electrode material
WO2023071409A1 (en) Single-crystal ternary positive electrode material, preparation method therefor, and application thereof
CN113620352B (en) High-voltage monocrystal ternary positive electrode material and preparation method thereof
CN109279659B (en) Preparation method of single crystal ternary cathode material
CN111916727A (en) Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof
JP2006156032A (en) Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method
CN112993241B (en) Preparation method of single-crystal lithium manganate material
CN113809320A (en) Quaternary polycrystalline positive electrode material, and preparation method and application thereof
CN114520318A (en) High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method thereof
CN112614988B (en) Positive electrode material and preparation method and application thereof
CN117071072A (en) High-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material and preparation method and application thereof
CN114975984A (en) Preparation method of porous core-shell structure nickel-rich cathode material
CN114005977A (en) High-energy-density superconducting lithium ion battery cathode material and preparation method thereof
CN113224287A (en) Strontium-doped ternary lithium ion battery positive electrode material and preparation method and application thereof
CN113353993A (en) Preparation method and application of composite high-nickel ternary material
CN113937256A (en) Method for coating lithium nickel manganese oxide cathode material by spraying
CN111933929B (en) F-doped anode material and preparation method thereof
CN116247197B (en) Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery

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