CN113620352A - High-voltage single-crystal ternary cathode material and preparation method thereof - Google Patents

High-voltage single-crystal ternary cathode material and preparation method thereof Download PDF

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CN113620352A
CN113620352A CN202110762982.8A CN202110762982A CN113620352A CN 113620352 A CN113620352 A CN 113620352A CN 202110762982 A CN202110762982 A CN 202110762982A CN 113620352 A CN113620352 A CN 113620352A
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cathode material
voltage single
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ternary cathode
sintering
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CN113620352B (en
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周志度
李宇东
吴建华
范江
万国江
文雅
贺亚峰
韩学武
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Jiangmen Kanhoo Industry Co ltd
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    • 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
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    • 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
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    • 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
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a high-voltage single crystal ternary cathode material, and belongs to the technical field of battery materials. The preparation method of the high-voltage single crystal ternary cathode material comprises the following steps: uniformly mixing the lithium salt, the ternary precursor and the metal compound to obtain a mixture; the mixture is subjected to primary sintering and then crushed to obtain crushed materials; adding the crushed materials into an ethanol solution containing the pre-coated materials, stirring and mixing, evaporating ethanol, and drying to obtain powder materials; and carrying out secondary sintering on the powder and then sieving to obtain the high-voltage single crystal ternary cathode material. The invention is doped with a doping agent which can form a lithium ion conductor on the surface, improves the electrochemical performance of the material, and effectively prevents the dissolution of lattice lithium in the wet coating process; aluminum hydroxide is used as a pre-coating material, so that the reaction in the secondary sintering process is uniform; the firing mode of four heat preservation platforms is adopted, the dispersity of the single crystal particles is improved, and the roundness of the single crystal particles is improved.

Description

High-voltage single-crystal ternary cathode material and preparation method thereof
Technical Field
The invention relates to a high-voltage single crystal ternary cathode material and a preparation method thereof, belonging to the technical field of battery materials.
Background
Due to shortage of cobalt resources and sudden rise of cobalt price, lithium cobaltate with cobalt content accounting for 60% by mass bears huge cost test, and battery manufacturers find solutions of low-cobalt and cobalt-free low-cost cathode materials in many times. The lithium cobaltate can be partially directly replaced by the multi-component material, for example, the cylindrical lithium battery of a notebook computer is basically and completely replaced by the multi-component material. In some smart phone and tablet computer soft package battery projects, lithium battery manufacturers begin to gradually adopt a mode of blending lithium cobaltate with a multi-element material in high-voltage products, so that the purpose of reducing cost is achieved. It is expected that the technology of replacing lithium cobaltate by the multi-component material is mature day by day, and the application of the high-voltage multi-component material is wider. The working voltage of the current high-voltage ternary NCM anode material is basically 4.4V or below, and the stability and the electrochemical performance of the material under high voltage are ensured mainly by preparing a single crystal ternary material and combining a doping coating process. The doping mode reported at present is mainly to select doping 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 a precursor, and the coating mode is mainly dry coating or wet coating of metal oxides.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-voltage single crystal ternary cathode material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-voltage single-crystal ternary cathode material is characterized by comprising the following steps:
(1) uniformly mixing a lithium salt, a 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 subjected to primary sintering and then crushed to obtain crushed materials; (3) adding the crushed materials into an ethanol solution containing the pre-coated materials, stirring and mixing, evaporating ethanol, and drying to obtain powder materials coated by the pre-coated materials; (4) and sintering the powder wrapped by the pre-wrapping object for the second time to obtain the high-voltage single crystal ternary cathode material, wherein the element A is Y, Mg, the element B is Al, Ti or W, and the element C is Zr or Nb.
Research shows that the doping mode of the ternary cathode material 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 perform dry mixing doping on a precursor, while the invention is doped with one of Y, Mg ions with the radius similar to that of the lithium ions and one of Al, Ti and W with the radius similar to that of the transition metal ions before firing, and simultaneously doped with a lithium semiconductor (such as Li) which can occupy a lithium layer or a transition metal layer and respectively form lithium ion semiconductors on the surface (such as Li2Zr03、Li3NbO4) Zr or Nb. Zr adopts a doping coating mode, compared with the pure coating mode, the Zr-based lithium ion battery can stabilize the structure, improve the surface, effectively inhibit the phase transition from the layered structure to the spinel structure, increase the spacing between lithium layers and promote the diffusion of lithium ions.
The stability of the material under high voltage and the dissolution of lattice lithium in the subsequent wet coating process are realized by a ternary doping coating mode.
As a preferred embodiment of the method for preparing the high-voltage single-crystal ternary cathode material of the present invention, in the step (2), the primary sintering is: firstly, heating to 450-550 ℃ at the speed of 3-5 ℃/min, preserving heat for 2 hours, then heating to 650-850 ℃ at the speed of 2-3 ℃/min, preserving heat for 3-6 hours, then heating to 950-970 ℃ at the speed of 1-2 ℃/min, preserving heat for 10-14 hours, finally cooling to 700-900 ℃ at the speed of 2-3 ℃/min, preserving heat for 2-6 hours, and then cooling to room temperature at the speed of 2-3 ℃/min; the sintering atmosphere of the primary sintering is oxygen-containing atmosphere, and air is preferred. Compared with the prior art that the firing mode of one platform or two platforms is adopted, the firing mode of four heat-preservation platforms is adopted in the primary sintering process, so that the dispersity of the single crystal particles is improved, and the roundness of the single crystal particles is improved.
As a preferred embodiment of the preparation method of the high-voltage single-crystal ternary cathode material, in the step (3), the pre-inclusion is aluminum hydroxide; the mass ratio of the pre-coated material is 0.05-0.3%. Research shows that certain damage can be caused to a body material in the conventional wet coating process, the surface of the coated body is not protected, the dissolution of lattice lithium can be easily caused in the wet coating process, for example, aluminum oxide is adopted for wet coating, and the conventional wet coating does not recycle a solvent, so that the manufacturing cost of the material is increased. The wet coating of the invention selects the aluminum hydroxide as the pre-coating material, and because the activity of the hydroxide is higher than that of the oxide, the coating uniformity can be improved in the wet coating, and the reaction uniformity in the secondary sintering process is facilitated. In addition, the wet coating uses ethanol as a solvent, and the solvent is recycled by distillation.
As a preferred embodiment of the method for preparing the high-voltage single-crystal ternary cathode material of the present invention, in the step (4), the secondary sintering is: firstly, heating the sintering temperature to 500-700 ℃ within 6 hours, then preserving the heat for 6-10 hours, and finally cooling to room temperature; the sintering atmosphere is an oxygen-containing atmosphere, preferably air.
As a preferable embodiment of the method for preparing the high-voltage single-crystal ternary positive electrode material, in the step (1), the lithium salt is at least one of lithium carbonate, lithium nitrate and lithium sulfate; the ternary precursor is Ni0.5Co0.2Mn0.3(0H)2。
In a preferred embodiment of the method for preparing the high-voltage single-crystal ternary cathode material, 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 to 1.06.
As a preferred embodiment of the method for preparing the high-voltage single-crystal ternary cathode material, in the step (1), the doping amount of the metal element a in the element a compound is LiNi0.5Co0.2Mn0.3O20.05-0.3% of the mass of the ternary cathode material; the doping amount of the metal element B in the B element compound is LiNi0.5Co0.2Mn0.3O20.05-0.3% of the mass of the ternary cathode material; the doping amount of the metal element C in the C element compound is LiNi0.5Co0.2Mn0.3O20.1-0.3% of the ternary anode material by mass, and the total doping amount of the three metal elements is LiNi0.5Co0.2Mn0.3O20.2-0.5% of the mass of the ternary cathode material.
In a preferred embodiment of the method for preparing the high-voltage single-crystal ternary positive electrode material according to the present invention, in the step (2), the particle size of the pulverized material is 4.0 to 6.0 μm in size D50.
As a preferred embodiment of the preparation method of the high-voltage single-crystal ternary cathode material, in the step (4), the mesh number of the screen subjected to sieving treatment is 300-400 meshes.
The invention also provides a high-voltage single crystal ternary cathode material which is prepared by the preparation method of the high-voltage single crystal ternary cathode material.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a high-voltage single crystal ternary cathode material and a preparation method thereof.
Drawings
FIG. 1 is an electron micrograph of a calcined intermediate (not pulverized) of comparative example 3.
FIG. 2 is an electron micrograph of a calcined intermediate (not pulverized) of example 2.
FIG. 3 is an electron micrograph of a finished product of example 2.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
One embodiment of the preparation method of the high-voltage single crystal ternary cathode material comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.03: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.05% of the mass of the ternary positive electrode material2O3The doping amount of the metal element Al is LiNi0.5Co0.2Mn0.3O20.3 percent of Al based on the mass of the ternary cathode material2O3And the doping amount of the metal element Nb is LiNi0.5Co0.2Mn0.3O2Nb of 0.15 percent of the mass of the ternary cathode material2O5Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 450 ℃ at a speed of 5 ℃/min for 2 hours, then raised to 650 ℃ at a speed of 2 ℃/min for 5 hours, then raised to 950 ℃ at a speed of 1 ℃/min for 14 hours, finally lowered to 700 ℃ at a speed of 3 ℃/min for 6 hours, cooled to room temperature at a speed of 2 ℃/min after heat preservation, and then crushed to a particle size D50 of 6.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.05% of aluminum hydroxide by mass, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 2h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 500 ℃ for 6 hours, preserving the heat for 6 hours, cooling to room temperature, and sieving with a sieve with 400 meshes in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single-crystal ternary cathode material.
Example 2
One embodiment of the preparation method of the high-voltage single crystal ternary cathode material comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.05% of the mass of the ternary positive electrode material2O3The doping amount of the metal element Al is LiNi0.5Co0.2Mn0.3O20.05 percent of Al based on the mass of the ternary cathode material2O3And the doping amount of the metal element Nb is LiNi0.5Co0.2Mn0.3O2Nb of 0.1 percent of the mass of the ternary cathode material2O5Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Example 3
One embodiment of the preparation method of the high-voltage single crystal ternary cathode material comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2The molar ratio of the raw materials is 1.05: 1, placing the mixture in a colter mixer, and adding LiNi with the doping amount of metal element Mg0.5Co0.2Mn0.3O2MgO accounting for 0.3 percent of the mass of the ternary cathode material, and the doping amount of the metal element Ti is LiNi0.5Co0.2Mn0.3O2TiO 0.05% of the ternary anode material2And the doping amount of the metal element Zr is LiNi0.5Co0.2Mn0.3O2ZrO 0.15% by mass of the ternary positive electrode material2Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is increased to 550 ℃ at a speed of 4 ℃/min for 2 hours, then is increased to 850 ℃ at a speed of 2.5 ℃/min for 6 hours, then is increased to 970 ℃ at a speed of 1.5 ℃/min for 10 hours, finally is decreased to 900 ℃ at a speed of 2.5 ℃/min for 6 hours, is decreased to room temperature at a speed of 2.5 ℃/min after heat preservation, and is crushed by a jet mill until the particle size D50 is 5.0 mu m to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.3 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 2.5h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 700 ℃ for 6 hours, preserving the heat for 10 hours, cooling to room temperature, and sieving with a sieve with 350 meshes in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single-crystal ternary cathode material.
Example 4
One embodiment of the preparation method of the high-voltage single crystal ternary cathode material comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.1% by mass of the ternary positive electrode material2O3The doping amount of the metal element Ti is LiNi0.5Co0.2Mn0.3O2TiO 0.1% of the ternary anode material2And the doping amount of the metal element Zr is LiNi0.5Co0.2Mn0.3O2ZrO of 0.3% by mass of the ternary positive electrode material2Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 2h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Example 5
One embodiment of the preparation method of the high-voltage single crystal ternary cathode material comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2In mole ratioThe ratio of 1.06: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.15% of the ternary positive electrode material mass2O3The doping amount of the metal element W is LiNi0.5Co0.2Mn0.3O2WO 0.1% of the mass of the ternary cathode material3And the doping amount of the metal element Nb is LiNi0.5Co0.2Mn0.3O2Nb of 0.1 percent of the mass of the ternary cathode material2O5Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Comparative example 1
The comparative example is different 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 comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then Y is added with LiNi with the doping amount of Y0.5Co0.2Mn0.3O2Ternary positive electrode materialY is 0.05% of the mass of the material2O3Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Comparative example 2
The comparative example is different from the example 2 only in that the raw materials do not contain the metal oxide corresponding to the metal element C, and specifically comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then Y is added with LiNi with the doping amount of Y0.5Co0.2Mn0.3O2Y of 0.05% of the mass of the ternary positive electrode material2O3The doping amount of Al is LiNi0.5Co0.2Mn0.3O20.05 percent of Al based on the mass of the ternary cathode material2O3Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Comparative example 3
The comparative example is different from the example 2 only in the difference of the one-burning curve, and specifically comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.05% of the mass of the ternary positive electrode material2O3The doping amount of the metal element Al is LiNi0.5Co0.2Mn0.3O20.05 percent of Al based on the mass of the ternary cathode material2O3And the doping amount of the metal element Nb is LiNi0.5Co0.2Mn0.3O2Nb of 0.1 percent of the mass of the ternary cathode material2O5Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein the sintering curve is that the temperature is increased to 500 ℃ at the speed of 3 ℃/min for 2 hours, then the temperature is increased to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally the temperature is reduced to room temperature at the speed of 3 ℃/min, and then the mixture is crushed by a jet mill until the particle size is D50-4.0 mu m to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of aluminum hydroxide, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Comparative example 4
The comparative example differs from example 2 only in that the double-fired coated aluminum hydroxide is changed into alumina, and specifically comprises the following steps:
(1) lithium carbonate and ternary precursor Ni0.5Co0.2Mn0.3(0H)2According to a molar ratio of 1.06: 1 is placed in a colter mixer, and then the doping amount of the metal element Y is added to LiNi0.5Co0.2Mn0.3O2Y of 0.05% of the mass of the ternary positive electrode material2O3The doping amount of the metal element Al is LiNi0.5Co0.2Mn0.3O20.05 percent of Al based on the mass of the ternary cathode material2O3And the doping amount of the metal element Nb is LiNi0.5Co0.2Mn0.3O2Nb of 0.1 percent of the mass of the ternary cathode material2O5Uniformly mixing to obtain a mixture;
(2) carrying out primary sintering on the mixture in a roller kiln, wherein a sintering curve is that the temperature is raised to 500 ℃ at the speed of 3 ℃/min for 2 hours, then raised to 700 ℃ at the speed of 2 ℃/min for 3 hours, then raised to 960 ℃ at the speed of 2 ℃/min for 10 hours, finally lowered to 800 ℃ at the speed of 2 ℃/min for 2 hours, cooled to room temperature at the speed of 3 ℃/min after heat preservation, and then crushed to the particle size D50 of 4.0 mu m by using a jet mill to obtain crushed materials;
(3) adding the crushed material into an ethanol solution containing 0.15 mass percent of alumina, stirring and mixing, evaporating ethanol after 10min, and drying the obtained powder wrapped by the pre-wrapped object in a vacuum drying oven at 120 ℃ for 3h to obtain the powder wrapped by the pre-wrapped object;
(4) and (3) sintering the powder wrapped by the pre-wrapping object in a roller kiln for the second time, heating to 600 ℃ for 6 hours, preserving the heat for 8 hours, cooling to room temperature, and sieving with a sieve with the mesh number of 300 in a dehumidification room with the humidity of less than 30% to obtain the uniformly-wrapped high-voltage single crystal ternary cathode material.
Examples of effects
1. The one-shot uncrushed product of comparative example 3, the one-shot uncrushed product of example 2 and the finished product of example 2 were respectively characterized by a scanning electron microscope, and the results are shown in fig. 1, fig. 2 and fig. 3.
2. The electrochemical properties of the materials were tested according to the following methods: the positive electrode materials prepared in examples 1 to 5 and comparative examples 1 to 4 were mixed with 12ml of N-methylpyrrolidone as a conductive agent, acetylene black, and PVDF as a binder in a mass ratio of 9.2:0.5:0.3, sufficiently stirred to form a slurry, then coated on the surface of an aluminum foil by a coating machine, dried and cut into a suitable size, a lithium sheet was used as a negative electrode, a lithium hexafluorophosphate solution was used as an electrolyte, a 2032 type button cell case was assembled into a button cell in an argon-protected glove box, and then electrochemical performance tests were performed at a temperature of 25 ℃ and a voltage of 45 ℃ in a range of 3.0 to 4.5V, respectively, with the results shown in table 1.
TABLE 1
Figure BDA0003149651460000101
Figure BDA0003149651460000111
As can be seen from Table 1, the high-voltage ternary cathode material has a 1C specific discharge capacity of more than 175mAh/g in a high-voltage range of 3.0-4.5V, a circulating capacity retention rate of more than 93% at a constant temperature of 25 ℃ for 100 weeks, and a circulating capacity retention rate of more than 93% at a high temperature of 45 ℃ for 100 weeks.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.

Claims (10)

1. A preparation method of a high-voltage single-crystal ternary cathode material is characterized by comprising the following steps:
(1) uniformly mixing a lithium salt, a 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 subjected to primary sintering and then crushed to obtain crushed materials;
(3) adding the crushed materials into an ethanol solution containing the pre-coated materials, stirring and mixing, evaporating ethanol, and drying to obtain powder materials coated by the pre-coated materials;
(4) carrying out secondary sintering on the powder wrapped by the pre-wrapping object to obtain the high-voltage single crystal ternary cathode material;
wherein, the element A is Y, Mg, the element B is Al, Ti or W, and the element C is Zr or Nb.
2. The method for preparing a high-voltage single-crystal ternary cathode material according to claim 1, wherein in the step (2), the primary sintering is as follows: firstly, heating to 450-550 ℃ at the speed of 3-5 ℃/min, preserving heat for 2 hours, then heating to 650-850 ℃ at the speed of 2-3 ℃/min, preserving heat for 3-6 hours, then heating to 950-970 ℃ at the speed of 1-2 ℃/min, preserving heat for 10-14 hours, finally cooling to 700-900 ℃ at the speed of 2-3 ℃/min, preserving heat for 2-6 hours, and then cooling to room temperature at the speed of 2-3 ℃/min; the sintering atmosphere of the primary sintering is oxygen-containing atmosphere, and air is preferred.
3. The method for preparing a high-voltage single-crystal ternary positive electrode material according to claim 1, wherein in the step (3), the pre-inclusion is aluminum hydroxide; the coating amount of the pre-coating is LiNi0.5Co0.2Mn0.3O20.05-0.3% of the mass of the ternary cathode material.
4. The method for preparing a high-voltage single-crystal ternary positive electrode material according to claim 1, wherein in the step (4), the secondary sintering is as follows: firstly, heating the sintering temperature to 500-700 ℃ within 6 hours, then preserving the heat for 6-10 hours, and finally cooling to room temperature; the sintering atmosphere is an oxygen-containing atmosphere, preferably air.
5. The method for preparing a high voltage single crystal ternary positive electrode 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; the ternary precursor is Ni0.5Co0.2Mn0.3(0H)2。
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 preparing a high-voltage single-crystal ternary positive electrode material according to claim 1, wherein in the step (1), the doping amount of the metal element A in the A element compound is LiNi0.5Co0.2Mn0.3O20.05-0.3% of the mass of the ternary cathode material; the doping amount of the metal element B in the B element compound is LiNi0.5Co0.2Mn0.3O20.05-0.3% of the mass of the ternary cathode material; the doping amount of the metal element C in the C element compound is LiNi0.5Co0.2Mn0.3O20.1-0.3% of the ternary anode material by mass, and the total doping amount of the three metal elements is LiNi0.5Co0.2Mn0.3O20.2-0.5% of the mass of the ternary cathode material.
8. The method for preparing 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 4.0-6.0 μm when D50 is larger than a value.
9. The method for preparing a high-voltage single-crystal ternary positive electrode material according to claim 1, wherein in the step (4), a sieving treatment is performed after the secondary sintering; preferably, the mesh number of the sieving screen is 300-400 meshes.
10. A high-voltage single-crystal ternary cathode material prepared by the preparation method of any one of claims 1-9.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023169064A1 (en) * 2022-12-22 2023-09-14 北京当升材料科技股份有限公司 Single crystal multi-element positive electrode material, preparation method therefor, 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

Citations (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
CN109326781A (en) * 2018-09-29 2019-02-12 湖南长远锂科有限公司 A kind of preparation method of high voltage lithium cobalt oxide anode
CN109516509A (en) * 2018-11-16 2019-03-26 中伟新材料有限公司 A kind of high-pressure solid monocrystalline tertiary cathode material and preparation method thereof, application
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
CN112054173A (en) * 2019-06-12 2020-12-08 江苏翔鹰新能源科技有限公司 Preparation method of core-shell type high-voltage single-crystal nickel cobalt lithium manganate positive electrode material
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

Patent Citations (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
CN109326781A (en) * 2018-09-29 2019-02-12 湖南长远锂科有限公司 A kind of preparation method of high voltage lithium cobalt oxide anode
CN109516509A (en) * 2018-11-16 2019-03-26 中伟新材料有限公司 A kind of high-pressure solid monocrystalline tertiary cathode material and preparation method thereof, application
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
CN112054173A (en) * 2019-06-12 2020-12-08 江苏翔鹰新能源科技有限公司 Preparation method of core-shell type high-voltage single-crystal nickel cobalt lithium manganate positive electrode material
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
宋世湃等: "Al_2O_3包覆优化LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2正极材料性能研究", 《电子元件与材料》 *
王伟东等: "《锂离子电池三元材料-工艺技术及生产应用》", 31 May 2015, 化学工业出版社 *
王睿等: "不同元素掺杂对LiNi_(0.6)Mn_(0.2)Co_(0.2)O_2正极材料的影响", 《汽车科技》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023169064A1 (en) * 2022-12-22 2023-09-14 北京当升材料科技股份有限公司 Single crystal multi-element positive electrode material, preparation method therefor, and lithium ion battery
US11955635B1 (en) 2022-12-22 2024-04-09 Beijing Easpring Material Technology Co., Ltd. Single crystal multi-element positive electrode material, preparation method therefor, 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

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