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CN116354416A - Nickel-rich ternary monocrystal positive electrode material and preparation method and application thereof - Google Patents

Nickel-rich ternary monocrystal positive electrode material and preparation method and application thereof Download PDF

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CN116354416A
CN116354416A CN202310377309.1A CN202310377309A CN116354416A CN 116354416 A CN116354416 A CN 116354416A CN 202310377309 A CN202310377309 A CN 202310377309A CN 116354416 A CN116354416 A CN 116354416A
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lithium
nickel
lithium source
sintering
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赵明钰
张伟
王克伟
赵岩
熊家祥
王殿刚
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Shandong Aia Kesimao New Materials Co ltd
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    • 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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

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Abstract

The present disclosure relates to a method for preparing a nickel-rich ternary single crystal positive electrode material, comprising: contacting and drying a mixed solution of sodium chloride, potassium chloride and a first lithium source with a nickel-rich precursor; mixing the nickel-rich precursor with a second lithium source and performing first sintering to obtain a sintered material; and washing and drying the sintering material, supplementing lithium, performing secondary sintering, and crushing and sieving after the sintering is completed to obtain the nickel-rich ternary monocrystal anode material. The nickel-rich ternary monocrystal positive electrode material prepared by the method is uniform in surface morphology and smooth in surface, and the lamellar structure of the material surface is more ordered, so that the charge-discharge specific capacity and the cycle performance of the battery are effectively improved.

Description

Nickel-rich ternary monocrystal positive electrode material and preparation method and application thereof
Technical Field
The present disclosure relates to the field of lithium ion battery positive electrode material preparation, and in particular, to a nickel-rich ternary single crystal positive electrode material, and a preparation method and use thereof.
Background
With the development of new energy automobiles, higher requirements are put forward on the energy density, service life, rate capability, thermal stability and other properties of lithium ion batteries. High nickel ternary cathode material (LiNi) x Co y Mn z O 2 X is more than or equal to 0.8 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.2, and x+y+z=1) becomes one of the lithium ion battery anode materials with the most application prospect and market competitiveness in the current power battery system due to the advantages of high energy density, low cost and the like. The increase of the nickel content correspondingly improves the specific capacity of the high-nickel ternary material, but also brings the problems of increased production process difficulty, poor cycle stability and thermal stability and the like, and severely limits the commercial application of the high-nickel ternary material.
Disclosure of Invention
The purpose of the disclosure is to provide a nickel-rich ternary monocrystal positive electrode material, a preparation method and application thereof, and the nickel-rich ternary monocrystal positive electrode material prepared by the method is uniform in surface morphology and smooth in surface, and the lamellar structure of the surface of the material is more ordered, so that the charge-discharge specific capacity, the first coulomb efficiency and the cyclic capacity retention rate of a battery are effectively improved.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a nickel-rich ternary single crystal positive electrode material, the method comprising:
(1) Contacting and drying a mixed solution of sodium chloride, potassium chloride and a first lithium source with a nickel-rich precursor;
(2) Mixing the nickel-rich precursor with a second lithium source and performing first sintering to obtain a sintered material;
(3) Washing and drying the sintering material, supplementing lithium and performing secondary sintering;
the method for supplementing lithium is a wet method, the wet method is performed by using an aqueous solution containing a third lithium source, the wet method is performed by adopting a ball milling method, and the ball milling time is 2-6 hours;
the third lithium source is used in an amount of 1000 to 6000ppm with respect to the mass of the sintering material.
Optionally, the third lithium source is used in an amount of 4000 to 6000ppm.
Optionally, in step (1), the mass ratio of the nickel-rich precursor to the mixed solution is (2-8): 1, preferably (2 to 6): 1, a step of;
wherein the mass ratio of the sodium chloride to the potassium chloride to the first lithium source to the water in the mixed solution is (0.5-1.5): (0.5-1.5): 1: (0.5-1.5), preferably (0.9-1.2): 1: (0.9-1.2).
Optionally, the molar ratio of the nickel-rich precursor to the total lithium source is (1.01-1.1): 1, preferably (1.01 to 1.08): 1, a step of;
wherein the total lithium source comprises the first lithium source and the second lithium source;
the second lithium source is used in an amount of 85 to 95 parts by mole, preferably 90 to 95 parts by mole, relative to 100 parts by mole of the total lithium source;
the first lithium source is used in an amount of 5 to 15 parts by mole, preferably 5 to 10 parts by mole, relative to 100 parts by mole of the total lithium source.
Optionally, the temperature of the first sintering is 450-600 ℃, preferably 500-550 ℃, and the heat preservation time is 4-8 h; the temperature of the second sintering is 810-860 ℃, the heat preservation time is 10-15 h, the sintering is performed in an oxygen atmosphere, and the oxygen content is 90-100%.
Optionally, the method further comprises the step of crushing and sieving after the second sintering is completed, wherein the particle size of the sieved material D50 is 1-1.8 mu m.
The temperature of the drying in the step (1) is 100-180 ℃ and the time is 2-6 h;
in the step (3), the washing mode is that ultrapure water with the temperature of 5 ℃ is used for washing according to the water-material ratio, and the water-material ratio is (0.8-1.2): 1, preferably 1:1, the water washing time is 8-10 min; the drying temperature is 100-150 ℃ and the drying time is 2-6 h.
Optionally, the chemical formula of the nickel-rich precursor is shown as formula (I): ni (Ni) x Co y Mn z (OH) 2 (I) Wherein x is more than or equal to 0.8 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.2, and x+y+z=1.
Optionally, the first lithium source, the second lithium source and the third lithium source are the same or different and are selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate.
A second aspect of the present disclosure provides a nickel-rich ternary single crystal positive electrode material prepared by the preparation method according to the first aspect of the present disclosure, where the chemical formula of the nickel-rich ternary single crystal positive electrode material is shown in formula (II): liNi x Co y Mn z O 2 (II) wherein 0.8.ltoreq.x.ltoreq.0.95, 0.05.ltoreq.y.ltoreq.0.2, 0.05.ltoreq.z.ltoreq.0.2, and x+y+z=1.
A third aspect of the present disclosure provides a lithium ion battery comprising the nickel-rich ternary single crystal positive electrode material of the second aspect of the present disclosure.
According to the technical scheme, in the preparation method, part of lithium sources enter the surface and the surface layer of the precursor in advance in the pretreatment process of the nickel-rich precursor, so that a driving force is provided for forming the nickel-rich ternary single crystal material, and meanwhile, the single crystal material is not easy to agglomerate in the sintering process, so that the better capacity retention rate is facilitated; on the other hand, the preparation method provided by the disclosure carries out lithium supplementation by a wet lithium supplementation mode before secondary sintering, so that a lithium source can be more uniformly attached to the surface of a material, defects existing on the surface of the material can be more sufficiently repaired, the surface of the material is smoother, the appearance is more uniform, and the charge-discharge specific capacity, the first coulomb efficiency and the circulating capacity retention rate of the battery are improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
fig. 1 is an SEM image of a nickel-rich ternary single crystal positive electrode material prepared in example 1 of the present disclosure.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The first aspect of the invention provides a preparation method of a nickel-rich ternary monocrystal anode material, which comprises the following steps:
(1) Contacting and drying a mixed solution of sodium chloride, potassium chloride and a first lithium source with a nickel-rich precursor;
(2) Mixing the nickel-rich precursor with a second lithium source and performing first sintering to obtain a sintered material;
(3) Washing and drying the sintering material, supplementing lithium and performing secondary sintering;
according to the preparation method, part of lithium sources enter the surface and the surface layer of the precursor in advance in the pretreatment process of the nickel-rich precursor, so that a driving force is provided for forming the high-nickel ternary single crystal material. And lithium is supplemented by a wet lithium supplementing mode before secondary sintering, so that a lithium source can be more uniformly attached to the surface of a material, defects existing on the surface of the material are more fully repaired, the surface of the material is smoother, the appearance is more uniform, and the charge-discharge specific capacity, the first coulomb efficiency and the circulating capacity retention rate of the battery are improved.
In a specific embodiment of the disclosure, the lithium supplementing mode is wet lithium supplementing, the wet lithium supplementing uses an aqueous solution containing a third lithium source, the wet lithium supplementing mode is performed by adopting a ball milling method, and the ball milling time is 2-6 hours, preferably 2-4 hours; the third lithium source is used in an amount of 1000 to 6000ppm, preferably 4000 to 6000ppm, more preferably 4000 to 5000ppm, with respect to the mass of the sintered material. In the above embodiment, lithium is supplemented by a wet method before secondary sintering, so that a lithium source can be more uniformly attached to the surface of a material, defects existing on the surface of the material can be more fully repaired, the battery efficiency and the energy density can be effectively improved, and the cycle performance can be improved.
In one specific embodiment of the disclosure, in the step (1), the mass ratio of the nickel-rich precursor to the mixed solution is (2-8): 1, preferably (2 to 6): 1, more preferably (2 to 5): 1, a step of;
in one specific embodiment of the present disclosure, the mass ratio of sodium chloride, potassium chloride, the first lithium source and water in the mixed solution is (0.5 to 1.5): (0.5-1.5): 1: (0.5 to 1.5), preferably (0.9 to 1.2): (0.9-1.2): 1: (0.9 to 1.2), more preferably 1:1:1:7.5. In the embodiment, the performance of the nickel-rich ternary single crystal positive electrode material is improved by selecting the raw materials with the preferable proportion for reaction.
In one embodiment of the present disclosure, the molar ratio of the nickel-rich precursor to the total lithium source is (1.01-1.1): 1, preferably (1.01 to 1.08): 1, more preferably (1.01 to 1.05): 1, a step of;
wherein the total lithium source comprises the first lithium source and the second lithium source;
the second lithium source is used in an amount of 85 to 95 parts by mole, preferably 90 to 95 parts by mole, more preferably 92 to 95 parts by mole, relative to 100 parts by mole of the total lithium source; the amount of the first lithium source is 5 to 15 parts by mole, preferably 5 to 10 parts by mole, more preferably 5 to 8 parts by mole, relative to 100 parts by mole of the total lithium source. In the above embodiment, the nickel-rich precursor is pretreated by using the lithium source twice, and the lithium source can be in contact with the surface of the nickel-rich precursor in advance and enter the surface layer structure of the precursor to provide driving force for forming the high-nickel ternary single crystal material.
In one embodiment of the present disclosure, the temperature of the first sintering is 450 to 600 ℃, preferably 500 to 550 ℃, and the heat preservation time is 4 to 8 hours, preferably 4 to 6 hours; the temperature of the second sintering is 810-860 ℃, preferably 810-850 ℃, and the heat preservation time is 10-15 h, preferably 10-13 h; the sintering is carried out under an oxygen atmosphere with an oxygen content of 90 to 100%, preferably 98 to 100%. In the embodiment, the lithium source can be continuously diffused into the nickel-rich precursor by selecting the preferred sectional sintering, so that the nickel-rich lithium ion positive electrode material with relatively stable thermodynamics is formed, and the cycle performance and the multiplying power performance of the nickel-rich lithium ion positive electrode material are improved.
In one embodiment of the present disclosure, the method further comprises, after the second sintering is completed, pulverizing and sieving, wherein the sieved material D50 has a particle size of 1-1.8 μm, preferably 1-1.5 μm. In the above embodiments, the dispersion of the sintered agglomerate material is facilitated by the selection of a preferred pulverizing and sieving operation.
In one embodiment of the present disclosure, the drying temperature in step (1) is 100 to 180 ℃, preferably 100 to 150 ℃, for 2 to 6 hours, preferably 3 to 5 hours;
in a specific embodiment of the present disclosure, in the step (3), the washing is performed by using ultrapure water at 5 ℃ according to a water-to-material ratio of (0.8-1.2): 1, preferably 1:1, the water washing time is 8-10 min, preferably 8min; the drying temperature is 100-150 ℃, preferably 100-130 ℃, and the drying time is 2-6 h, preferably 3-5 h.
In one embodiment of the present disclosure, the nickel-rich precursor has a chemical formula as shown in formula (i): ni (Ni) x Co y Mn z (OH) 2 (I) Wherein x is more than or equal to 0.8 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.2, and x+y+z=1.
In a specific embodiment of the present disclosure, the first lithium source, the second lithium source and the third lithium source are the same or different and are selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate, preferably lithium hydroxide monohydrate, lithium hydroxide anhydrous.
A second aspect of the present disclosure provides a nickel-rich ternary single crystal positive electrode material prepared by the preparation method according to the first aspect of the present disclosure, where the chemical formula of the nickel-rich ternary single crystal positive electrode material is shown in formula (II):LiNi x Co y Mn z O 2 (II) wherein 0.8.ltoreq.x.ltoreq.0.95, 0.05.ltoreq.y.ltoreq.0.2, 0.05.ltoreq.z.ltoreq.0.2, and x+y+z=1.
The nickel-rich ternary monocrystal positive electrode material prepared by the method is uniform in surface morphology and smooth in surface, and the lamellar structure of the material surface is more ordered, so that the charge-discharge specific capacity, the first coulomb efficiency and the cyclic capacity retention rate of the battery are effectively improved.
A third aspect of the present disclosure provides a lithium ion battery comprising the nickel-rich ternary single crystal positive electrode material of the second aspect of the present disclosure.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
In the following examples and comparative examples, the raw materials used were all commercially available products unless otherwise specified.
Example 1
Preparing a mixed solution of sodium chloride, potassium chloride and lithium hydroxide monohydrate with 160g of ultrapure water according to a mass ratio of 1:1:1, and uniformly spraying the mixed solution on 600g of nickel-rich precursor (with a chemical formula of Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 ) And (3) fully and uniformly mixing, and vacuumizing and drying the precursor in a vacuum oven for 4 hours, wherein the drying temperature is 150 ℃.
b, mixing the rest lithium hydroxide monohydrate with the dried precursor in the step a uniformly according to the lithium ratio of 1.015. Wherein the mole fraction of lithium hydroxide monohydrate in step a is 5 mole fractions. Sintering in a box furnace to raise the temperature to 550 ℃, keeping the temperature for 6 hours, raising the temperature to 550 ℃ per minute at 5 ℃, keeping the temperature for 6 hours, and naturally cooling to room temperature to obtain the sintered material.
c, mechanically crushing the sintered material in the step b, washing with water by using a suction filtration device, wherein the temperature of ultrapure water is 5 ℃, and the water-material ratio is 1:1, washing time is 8 minutes, and washing is carried out twice.
d, vacuumizing and drying the material in the step c in a vacuum oven for 4 hours, wherein the drying temperature is 150 ℃. And c, calculating according to the mass of the sintered material in the step b, and carrying out secondary lithium supplementation on the material, wherein the consumption of lithium hydroxide monohydrate is 4500ppm, the lithium supplementation mode is a ball milling mode, and the ball milling time is 4 hours. And (3) carrying out secondary sintering on the ball-milled material in a box furnace, heating to 500 ℃, keeping the temperature for 3 hours, and then heating to 760 ℃ per minute at 5 ℃ for 6 hours.
And e, taking out the secondary sintering material, carrying out jet milling and crushing, wherein the jet pressure is 5MPa, and the crushing granularity reaches 1.3 mu m, so as to obtain the nickel-rich ternary monocrystal anode material.
Example 2
The procedure of example 1 was followed except that the molar fraction of lithium hydroxide monohydrate in step a was 20 parts by mole based on the total lithium source.
Example 3
The procedure of example 1 was used, except that in step d, lithium hydroxide monohydrate was used in an amount of 3500ppm.
Example 4
The method of example 1 is adopted, the difference is that in the step b, sintering is carried out in a box furnace, the temperature is raised to 400 ℃, the heat preservation time is 2-3 h, the temperature is raised to 805 ℃ per minute at 5 ℃, and the heat preservation time is 8-10 h; in the step d, the ball-milled material is sintered for the second time in a box furnace, the temperature is raised to 350 ℃, the heat preservation time is 2-3 h, and then the temperature is raised to 600 ℃ per minute at 5 ℃ and the heat preservation time is 2-3 h.
Example 5
The procedure of example 1 was employed, except that in step a, the chemical formula was Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Is replaced by Ni with the same weight of the nickel-rich precursor 0.92 Co 0.03 Mn 0.05 (OH) 2 。
Comparative example 1
600g of a nickel-rich precursor (chemical formula: ni 0.9 Co 0.05 Mn 0.05 (OH) 2 ) Mixing with lithium hydroxide monohydrate, sintering in a box furnace to raise the temperature to 550 ℃ after uniform mixing, keeping the temperature for 4 hours, raising the temperature to 850 ℃ every minute at 5 ℃ and keeping the temperature for 10 hours, and naturally cooling to room temperature to obtain a sintered material.
b, mechanically crushing the sintered material in the step a, washing with water by using a suction filtration device, wherein the temperature of ultrapure water is 5 ℃, and the water-material ratio is 1:1, washing time is 8 minutes, and washing is carried out twice.
c, vacuumizing and drying the material in the step b in a vacuum oven for 4 hours, wherein the drying temperature is 150 ℃. And d, calculating according to the mass of the sintered material in the step a, and carrying out secondary lithium supplementation on the material, wherein the dosage of lithium hydroxide monohydrate is 4500ppm, the lithium supplementation mode is a ball milling mode, and the ball milling time is 4 hours. And (3) carrying out secondary sintering on the ball-milled material in a box furnace, heating to 500 ℃, keeping the temperature for 3 hours, and then heating to 550 ℃ per minute at 5 ℃ and keeping the temperature for 6 hours.
d, taking out the secondary sintering material, carrying out jet milling and crushing, wherein the jet pressure is 5MPa, and the crushing granularity reaches 1.3 mu m, so as to obtain the nickel-rich ternary monocrystal anode material.
Comparative example 2
The procedure of example 1 was used, except that in step d, no secondary lithium supplementation was performed.
Comparative example 3
The procedure of example 1 was used, except that in step d, the amount of lithium hydroxide monohydrate used was 6500ppm.
Test case
The materials of examples 1 to 5 and comparative examples 1 to 3 were subjected to electrochemical performance tests as follows:
the materials prepared in the examples and the comparative examples, acetylene black serving as a conductive agent and PVDF serving as a binder are mixed according to the mass ratio of 90:5:5, adding NMP (N-methyl-pyrrolidone) and fully and uniformly mixing to obtain slurry with certain viscosity; uniformly coating the obtained slurry on an aluminum foil, drying for 2 hours at the temperature of 90 ℃ by air blast, tabletting the aluminum foil by a tabletting machine after the drying is completed, punching the tabletting pole piece into a circular electrode piece with the diameter of 14mm, and drying for 2 hours at the temperature of 120 ℃ in a vacuum drying oven; in a glove box protected by argon, a Celgard 2400 membrane is used as a diaphragm, a metal lithium sheet is used as a negative electrode, and 1mol/L LiPF6/EC+DEC+DMC (volume ratio is 1:1:1) is used as electrolyte to assemble the button cell. And (3) carrying out charge and discharge test on the assembled battery above a blue electric test, wherein the temperature is 25+/-1 ℃, and the test voltage range is 3.0-4.3V.
The electrochemical cycle performance test instrument is a blue-ray test system.
TABLE 1
Figure BDA0004173841100000091
Figure BDA0004173841100000101
As can be seen from the test results in Table 1, compared with the comparative example, the nickel-rich ternary positive electrode material prepared by the preparation method provided by the invention has smoother material surface and more uniform morphology, can realize higher specific capacity of charging and discharging at 1.0C, has higher initial coulomb efficiency, and has better capacity retention rate after 100 times of circulation at 1.0C.
From the test results of examples 1 to 5, it is understood that when the preparation method, the amounts of the first lithium source, the second lithium source and the third lithium source, the lithium supplementing method, the sintering reaction conditions, and the types of the lithium sources are within the scope of the present disclosure, the effects and performances of the prepared product of the present invention can be further improved.
As shown by the test results of comparative examples 1-3, the lithium source and the nickel-rich precursor are directly mixed without pretreatment in comparative example 1, so that the lithium source and the nickel-rich precursor are not uniformly contacted, the single crystal material is easy to agglomerate in the sintering process, the specific capacity of charging and discharging at 1.0C is low, and the capacity retention rate of 1.0C for 100 times is obviously lower than that of examples 1-5; because comparative example 2 does not carry out secondary lithium supplementation before secondary sintering, defects exist on the surface of the material in sintering, the surface of the material is not smooth, and the morphology is uneven, so that the specific capacity of charging and discharging at 1.0 ℃ is low, the initial coulomb efficiency is low, and the capacity retention rate of 100 times of 1.0 ℃ circulation is obviously lower than that of examples 1-5; since the amount of the third lithium source in comparative example 3 is not within the range defined in the present disclosure, the residual alkali on the surface of the material is high after the secondary sintering, so that the specific charge-discharge capacity of the prepared material is reduced, the initial coulombic efficiency is reduced, and the capacity retention rate of 1.0C cycle for 100 times is significantly lower than that of examples 1 to 5.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (10)

1. A preparation method of a nickel-rich ternary monocrystal anode material, wherein the method comprises the following steps:
(1) Contacting and drying a mixed solution of sodium chloride, potassium chloride and a first lithium source with a nickel-rich precursor;
(2) Mixing the nickel-rich precursor with a second lithium source and performing first sintering to obtain a sintered material;
(3) Washing and drying the sintering material, supplementing lithium and performing secondary sintering;
the method for supplementing lithium is a wet method, the wet method is performed by using an aqueous solution containing a third lithium source, the wet method is performed by adopting a ball milling method, and the ball milling time is 2-6 hours;
the third lithium source is used in an amount of 1000 to 6000ppm with respect to the mass of the sintering material.
2. The preparation method according to claim 1, wherein the third lithium source is used in an amount of 4000 to 6000ppm.
3. The production method according to claim 1, wherein in the step (1), a mass ratio of the nickel-rich precursor to the mixed solution is (2 to 8) with respect to a mass of the nickel-rich precursor: 1, preferably (2 to 6): 1, a step of;
wherein the mass ratio of the sodium chloride to the potassium chloride to the first lithium source to the water in the mixed solution is (0.5-1.5): 1: (0.5-1.5), preferably (0.9-1.2): 1: (0.9-1.2).
4. The preparation method according to claim 1, wherein the molar ratio of the nickel-rich precursor to the total lithium source is (1.01 to 1.1): 1, preferably (1.01 to 1.08): 1, a step of;
wherein the total lithium source comprises the first lithium source and the second lithium source;
the second lithium source is used in an amount of 85 to 95 parts by mole, preferably 90 to 95 parts by mole, relative to 100 parts by mole of the total lithium source;
the first lithium source is used in an amount of 5 to 15 parts by mole, preferably 5 to 10 parts by mole, relative to 100 parts by mole of the total lithium source.
5. The preparation method according to claim 1, wherein the temperature of the first sintering is 450-600 ℃, preferably 500-550 ℃, and the holding time is 4-8 h; the temperature of the second sintering is 810-860 ℃ and the heat preservation time is 10-15 h; the sintering is carried out in an oxygen atmosphere, and the oxygen content is 90-100%.
6. The preparation method according to claim 1, wherein the method further comprises, after the completion of the second sintering, pulverizing and sieving, wherein the sieved material D50 has a particle size of 1-1.8 μm;
wherein the temperature of the drying in the step (1) is 100-180 ℃ and the time is 2-6 h;
in the step (3), the washing mode is that ultrapure water with the temperature of 5 ℃ is used for washing according to the water-material ratio, and the water-material ratio is (0.8-1.2): 1, preferably 1:1, the water washing time is 8-10 min; the drying temperature is 100-150 ℃ and the drying time is 2-6 h.
7. The preparation method of claim 1, wherein the chemical formula of the nickel-rich precursor is shown as formula (i): ni (Ni) x Co y Mn z (OH) 2 (I) Wherein x is more than or equal to 0.8 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.2, and x+y+z=1.
8. The production method according to claim 1, wherein the first lithium source, the second lithium source, and the third lithium source are the same or different and are one or more selected from the group consisting of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide, and lithium nitrate.
9. The nickel-rich ternary single crystal positive electrode material prepared by adopting the preparation method of any one of claims 1 to 8, wherein the chemical formula of the nickel-rich ternary single crystal positive electrode material is shown as a formula (II): liNi x Co y Mn z O 2 (II) wherein 0.8.ltoreq.x.ltoreq.0.95, 0.05.ltoreq.y.ltoreq.0.2, 0.05.ltoreq.z.ltoreq.0.2, and x+y+z=1.
10. A lithium ion battery comprising the nickel-rich ternary single crystal positive electrode material of claim 9.
CN202310377309.1A 2023-04-04 2023-04-04 Nickel-rich ternary monocrystal positive electrode material and preparation method and application thereof Pending CN116354416A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114804233A (en) * 2022-05-17 2022-07-29 无锡零一未来新材料技术研究院有限公司 High-nickel ternary cathode material for lithium battery and preparation method thereof
CN115676911A (en) * 2021-07-30 2023-02-03 比亚迪股份有限公司 Single crystal ternary positive electrode material, preparation method thereof and lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115676911A (en) * 2021-07-30 2023-02-03 比亚迪股份有限公司 Single crystal ternary positive electrode material, preparation method thereof and lithium ion battery
CN114804233A (en) * 2022-05-17 2022-07-29 无锡零一未来新材料技术研究院有限公司 High-nickel ternary cathode material for lithium battery and preparation method thereof

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