CN111900380A - Method for preparing nickel cobalt lithium manganate single crystal ternary material - Google Patents

Method for preparing nickel cobalt lithium manganate single crystal ternary material Download PDF

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CN111900380A
CN111900380A CN202010796638.6A CN202010796638A CN111900380A CN 111900380 A CN111900380 A CN 111900380A CN 202010796638 A CN202010796638 A CN 202010796638A CN 111900380 A CN111900380 A CN 111900380A
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precursor
single crystal
particle size
nickel cobalt
jaw
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郝长旺
梅京
孙杰
熊奇
程欢
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Hubei RT Advanced 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
    • H01M4/52—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
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M2004/028—Positive electrodes
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Abstract

The invention relates to the technical field of lithium ion battery anode ternary materials, and discloses a method for preparing a nickel cobalt lithium manganate single crystal ternary material. The method comprises the following steps: (1) lithium carbonate and precursor (Ni)0.55Co0.15Mn0.3)(OH)2Uniformly mixing with a zirconium compound to obtain a mixture; (2) placing the mixture in a sagger, scribing, cutting into pieces, and calcining to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block; (3) the material blocks are subjected to coarse crushing, airflow crushing and sieving in sequence to obtain black powder; (4) mixing black powder with additivesMixing by a high-speed dry method, and sintering to obtain the black powder material coated by the additive. Li (Ni) prepared by the method0.55Co0.15Mn0.3)O2The nickel cobalt lithium manganate single crystal ternary material has the advantages of prominent single crystal appearance, high crystallinity, stable material performance and excellent cycle performance.

Description

Method for preparing nickel cobalt lithium manganate single crystal ternary material
Technical Field
The invention relates to the technical field of lithium ion battery anode ternary materials, in particular to a method for preparing a nickel cobalt lithium manganate single crystal ternary material.
Background
Research data of a high-industrial lithium battery research institute (GGII) shows that the market scale of the Chinese lithium battery ternary cathode material in 2019 reaches 285 hundred million yuan, and the increase is 8.4% on a par; the shipment volume is 19.2 ten thousand tons, the year by year increases 40.4%, wherein the shipment volume of 5 series materials accounts for 68%. The nickel-cobalt-manganese ternary material is still one of the most mainstream products in the commercial anode materials at the present stage, in particular to the fields of digital codes and electric vehicles. Because the safety and stability of the NCM811 and NCA materials still have certain problems at present, the market acceptance is still to be recovered, and the mainstream enterprises still select 5 series products for loading. In order to reduce the cost and obtain larger product performance, part of enterprises increase the development of medium-nickel and low-cobalt materials, in particular the development of 55 polycrystal and 55 monocrystal materials.
With conventional Li (Ni)0.5Co0.2Mn0.3)O2Comparison of materials, Li (Ni)0.55Co0.15Mn0.3)O2Single crystal materials have certain drawbacks: 1. ni2+The Li/Ni mixed discharge of the material is easily aggravated due to the increase of the content, the layered structure of the material is not kept due to the low cobalt content, and the multiplying power and the cycle performance of the material are damaged; 2. high content of Ni, Ni3+The material is easy to drift to the surface of a crystal, and water and CO2 are adsorbed, so that residual alkali and pH on the surface of the material are increased, and the material is not beneficial to the use of a battery in the later processing of the material; 3. the precursors with different shapes and different particle sizes are used for preparing the single crystal material, different temperatures are needed, the single crystal material is easy to sinter into a single crystal shape due to the fact that the primary particles are piled and dispersed, the precursor with dense primary particles is not easy to sinter, and the agglomerate shape is easy to form; 4. sintering of single crystal materials requires higher temperatures, strongly oxidizing Ni at high temperatures3+Is easy to be reduced into Ni2+This causes Li/Ni misclassification.
Disclosure of Invention
The invention aims to solve the problems of high Li/Ni mixed-arrangement degree, poor electrochemical performance and difficult sintering of single crystal appearance of a nickel cobalt lithium manganate single crystal material in the prior art, and provides a method for preparing a nickel cobalt lithium manganate single crystal ternary material, wherein Li (Ni) prepared by the method0.55Co0.15Mn0.3)O2The nickel cobalt lithium manganate single crystal ternary material has the advantages of prominent single crystal appearance, high crystallinity, stable material performance and excellent cycle performance.
In order to achieve the purpose, the invention provides a method for preparing a nickel cobalt lithium manganate single crystal ternary material, which is characterized by comprising the following steps:
(1) lithium carbonate and precursor (Ni)0.55Co0.15Mn0.3)(OH)2Uniformly mixing with a zirconium compound to obtain a mixture, wherein the lithium carbonate and the precursor are mixed according to Li (Ni)0.55Co0.15Mn0.3) 1, x is more than or equal to 0.04 and less than or equal to 0.1, and the Zr content in the mixture is controlled to be 0.05-0.4 wt% of the precursor;
(2) placing the mixture obtained in the step (1) in a sagger, scribing, cutting into pieces and calcining to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) carrying out coarse crushing, airflow crushing and sieving on the material blocks obtained in the step (2) in sequence to obtain black powder;
(4) and (4) mixing the black powder obtained in the step (3) with an additive by a high-speed dry method, and sintering to obtain the additive-coated black powder material.
Preferably, in step (1), the lithium carbonate has an average particle size D50 of 4-8 μm.
Preferably, in step (1), the precursor (Ni)0.55Co0.15Mn0.3)(OH)2The shape of (A) is ellipsoidal or spheroidal.
Preferably, in step (1), the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Average of (2)The particle size D50 is 3-4.5 μm, the minimum particle size Dmin is more than 1 μm, and the maximum particle size Dmax is less than 12 μm.
Preferably, in step (1), the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Has a specific surface area of 8-15m2/g。
Preferably, in step (1), the zirconium compound is nano-zirconia.
Preferably, in step (1), the particle size of the zirconium compound is 20 to 200 nm.
Preferably, in the step (1), the content of Zr in the mixed material is controlled to be 0.05-0.3 wt% of the precursor.
Preferably, in step (1), 0.05. ltoreq. x.ltoreq.0.08.
Preferably, in step (1), the lithium carbonate, the precursor, and the zirconium compound are mixed in a high-speed mixer.
Preferably, in step (1), the mixing time is 15-40 min.
Preferably, in the step (1), the rotation speed of the high-speed mixer is 500-1000 rpm.
Preferably, in step (2), the calcination conditions include: the calcination temperature is 930-.
Preferably, in step (3), the rough breaking is performed in a jaw crusher and a twin roll crusher.
Preferably, in the step (3), the jaw breaking fixed jaw gap in the jaw crusher is 3-8 mm.
Preferably, in step (3), the gap between the pair of roll nips of the pair of roll crushers is 1-2.5 mm.
Preferably, in the step (3), the jet milling conditions include: the air inlet pressure is 0.2-0.6MPa, the grading frequency is 80-160Hz, and the induced air frequency is 30-80 Hz.
Preferably, the sieving is a vibratory sieving, the sieving conditions including: the mesh number of the screen is 300-400 meshes, and the tension of the screen is 15-25N/cm.
Preferably, in the step (4), the additive is at least one selected from the group consisting of alumina, titania, yttria, zinc oxide, magnesia, monoammonium phosphate and boric acid.
Preferably, in step (4), the particle size of the additive is 20 to 200 nm.
Preferably, in the step (4), the sintering conditions include: the sintering temperature is 200-.
The method for preparing the nickel cobalt lithium manganate single crystal ternary material easily generates Li (Ni) with low Li/Ni mixed arrangement degree and prominent single crystal appearance0.55Co0.15Mn0.3)O2Particles; the preparation process is simple, the reproducibility is good, the appearance is easy to control, and the method is easy for large-scale industrial production and application; simultaneous production of Li (Ni)0.55Co0.15Mn0.3)O2The nickel cobalt lithium manganate single crystal ternary material has high crystallinity, stable material performance and excellent cycle performance.
Drawings
FIG. 1 is an SEM photograph of a precursor raw material used in example 1;
FIG. 2 is an SEM photograph of the precursor raw materials used in example 2;
FIG. 3 is an SEM photograph of the precursor raw materials used in example 3;
FIG. 4 is an SEM image of the material made in example 1;
FIG. 5 is an SEM image of the material made in example 2;
FIG. 6 is an SEM photograph of the material produced in comparative example 1;
figure 7 is an XRD pattern of the material prepared in example 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing a nickel cobalt lithium manganate single crystal ternary material, which comprises the following steps:
(1) lithium carbonate and precursor (Ni)0.55Co0.15Mn0.2)(OH)2Uniformly mixing with a zirconium compound to obtain a mixture, wherein the lithium carbonate and the precursor are mixed according to Li (Ni)0.55Co0.15Mn0.3) 1, x is more than or equal to 0.04 and less than or equal to 0.1, and the Zr content in the mixture is controlled to be 0.05-0.4 wt% of the precursor;
(2) placing the mixture obtained in the step (1) in a sagger, scribing, cutting into pieces and calcining to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) carrying out coarse crushing, airflow crushing and sieving on the material blocks obtained in the step (2) in sequence to obtain black powder;
(4) and (4) mixing the black powder obtained in the step (3) with an additive by a high-speed dry method, and sintering to obtain the additive-coated black powder material.
The lithium nickel cobalt manganese oxide single crystal ternary material raw material lithium carbonate and precursor (Ni) are prepared by reasonable matching0.55Co0.15Mn0.3)(OH)2And the raw materials are mixed according to a specific proportion, and then a proper preparation step is adopted, so that the nickel cobalt lithium manganate single crystal ternary material has the advantages of prominent single crystal appearance, high crystallinity, stable material performance and excellent cycle performance.
In the method of the present invention, there is no particular requirement for the selection of the lithium carbonate, which may be a routine choice in the art. In a particular embodiment, the lithium carbonate may be battery grade lithium carbonate. The battery-grade lithium carbonate refers to lithium carbonate with performance parameters meeting the national standard GB/T11075-2013.
In a specific embodiment, in step (1), the lithium carbonate may have an average particle size D50 of 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, or any value in the range of any two of these values. In a preferred embodiment, the lithium carbonate may have an average particle size D50 of 5 to 7 μm.
Herein, the particle size refers to a diameter of a particle measured by a particle sizer, unless otherwise specified. The average particle size D50 means that the volume average particle size of the sample is greater than 50% of the particles and less than 50% of the particles.
In the method of the present invention, the precursor (Ni) is subjected to0.55Co0.15Mn0.2)(OH)2The morphology of (a) is not particularly required and can be a routine choice in the art. In a specific embodiment, in step (1), the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Can be ellipsoidal or spheroidal.
In a specific embodiment, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2The average particle size D50 of (a) may be any of 3 μm, 3.2 μm, 3.6 μm, 3.8 μm, 4 μm, 4.2 μm, 4.4 μm, 4.5 μm and a range of any two of these values, the minimum particle size Dmin > 1 μm and the maximum particle size Dmax < 12 μm.
In a preferred embodiment, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2The average particle size D50 is 3.5-4 μm, the minimum particle size Dmin is more than 1.2 μm, and the maximum particle size Dmax is less than 10 μm.
In the method of the present invention, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Has a specific surface area of 8-15m2(ii)/g; specifically, for example, it may be 8m2/g、9m2/g、10m2/g、11m2/g、12m2/g、13m2/g、14m2G or 15m2(ii)/g; preferably, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Has a specific surface area of 9-13m2/g。
In the process of the present invention, the zirconium compound may be a conventional choice in the art. In a specific embodiment, in step (1), the zirconium compound is nano zirconia.
In a specific embodiment, the particle size of the zirconium compound may be any value in the range of 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, or any two of these values; preferably, the particle size of the zirconium compound is 50 to 100 nm; more preferably, the particle size of the zirconium compound is 60 to 80 nm.
In the method of the present invention, lithium carbonate and a precursor (Ni)0.55Co0.15Mn0.3)(OH)2When the lithium nickel cobalt manganese oxide is mixed with a zirconium compound, the content of the zirconium compound needs to be reasonably controlled in order to obtain the nickel cobalt lithium manganese oxide single crystal ternary material with high crystallinity, stable material performance and excellent cycle performance.
In particular embodiments, the Zr content of the mix may be controlled to be 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt% of the precursor, and any value within a range defined by any two of these points.
In a preferred embodiment, the Zr content in the mixture is controlled to be 0.05-0.3 wt% of the precursor. In a more preferred embodiment, the Zr content in the mix is controlled to be 0.15-0.35 wt% of the precursor.
In the method of the invention, in order to obtain the nickel cobalt lithium manganate single crystal ternary material with high crystallinity, stable material performance and excellent cycle performance, the proportion of lithium carbonate and precursor needs to be reasonably controlled, namely the proportion of lithium carbonate and precursor is as follows Li: (Ni)0.55Co0.15Mn0.3) (1+ x) and 1 in a molar ratio.
In particular embodiments, in step (1), x may be 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1. In a preferred embodiment, in step (1), 0.05. ltoreq. x.ltoreq.0.08. In a more preferred embodiment, 0.07. ltoreq. x.ltoreq.0.08.
In the method of the present invention, there is no particular requirement for an apparatus for mixing lithium carbonate, the precursor, and the zirconium compound, and various apparatuses conventionally used in the art may be used. In a specific embodiment, in step (1), the lithium carbonate, the precursor, and the zirconium compound are mixed in a high-speed mixer.
In the step (1), the mixing time is 15-40 min; specifically, for example, the average value may be any value in a range of 15min, 17min, 20min, 23min, 25min, 28min, 30min, 32min, 35min, 37min, 40min, or any two of these values. Preferably, in step (1), the mixing time is 20 to 30 min.
In the step (1), the rotating speed of the high-speed mixer is 500-1000 rpm; specifically, for example, the rotation speed may be 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, 850rpm, 900rpm, 950rpm, 1000rpm, or any value in a range formed by any two of these points. Preferably, in the step (1), the rotation speed of the high-speed mixer is 600-900 rpm.
In a specific embodiment, the calcination process in step (2) comprises: placing the mixture obtained in the step (1) in a mullite-cordierite sagger, scribing and cutting according to a 6 multiplied by 6 grid, and calcining by using sintering equipment.
In the method of the present invention, the sagger is not limited to a mullite-cordierite sagger, and may be a sagger made of other materials which contain alumina components and are not easily oxidized.
In the method of the present invention, the equipment for carrying out calcination is not particularly limited, and may be various equipment conventionally used in the art. In a specific embodiment, the calcination is performed in a box furnace.
In a specific embodiment, in the step (2), the calcination temperature may be any value in the range of 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃ and any two of these values.
In specific embodiments, in step (2), the temperature increase rate may be 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, or 5 ℃/min.
In a specific embodiment, in step (2), the incubation time may be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, or 16 h.
In a preferred embodiment, the calcination temperature is 945-950 ℃, the temperature rise rate is 2-3 ℃/min, and the heat preservation time is 10-14 h.
In the method of the present invention, there is no particular requirement for selecting the calcination atmosphere as long as it can provide an atmosphere having an oxygen volume concentration of more than 20%.
Preferably, after the calcination is finished, the material is discharged when the ventilation is naturally cooled to be below 100 ℃.
In the method according to the invention, in step (3), the rough breaking is performed in a jaw crusher and a counter roll crusher. In a specific embodiment, the lumps are crushed first in the jaw crusher and then transferred to the twin roll crusher for rough crushing.
In the step (3), the gap between the jaw crushing fixed jaw and the jaw crushing jaw in the jaw crusher is 3-8 mm; specifically, for example, it may be 3mm, 4mm, 5mm, 6mm, 7mm, or 8 mm; preferably, the jaw breaking fixed jaw gap in the jaw crusher is 3-5 mm.
In the step (3), the gap between the double-roll gaps of the double-roll crusher is 1-2.5 mm; specifically, for example, it may be 1mm, 1.5mm, 2mm, or 2.5 mm; preferably, the gap between the double-roll gaps of the double-roll crusher is 2 mm.
In the method of the present invention, in the step (3), the inlet pressure of the jet milling is 0.2 to 0.6 MPa; specifically, for example, it may be 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6 MPa; preferably, in the step (3), the inlet pressure of the jet milling is 0.4 to 0.6 MPa.
In the method of the present invention, in the step (3), the classification frequency of the jet milling is 80 to 160 Hz; specifically, for example, 80Hz, 90Hz, 100Hz, 110Hz, 120Hz, 130Hz, 140Hz, 150Hz, or 160 Hz; preferably, in the step (3), the classification frequency of the jet milling is 100-130 Hz.
In the method, in the step (3), the induced air frequency of the jet milling is 30-80 Hz; specifically, for example, 30Hz, 40Hz, 50Hz, 60Hz, 70Hz, or 80 Hz; preferably, in the step (3), the induced air frequency of the jet milling is 30-50 Hz.
Herein, the pressure is an absolute pressure unless otherwise specified.
In the method of the present invention, in the step (3), the selection of the sieving apparatus is not particularly required, and may be various sieving apparatuses conventionally used in the art. In a particular embodiment, the sieving is performed in an ultrasonic vibration sieve.
In a specific embodiment, in step (3), the number of the sieved meshes may be 300 meshes, 320 meshes, 340 meshes, 360 meshes, 380 meshes, 400 meshes, or any value in a range formed by any two of these values.
In particular embodiments, in step (3), the screened screen tension may be 15N/cm, 17N/cm, 19N/cm, 21N/cm, 23N/cm, or 25N/cm.
In a preferred embodiment, in step (3), the screened mesh number is 400 mesh and the screened mesh tension is 22-25N/cm.
In the method, in order to obtain the nickel cobalt lithium manganate single crystal ternary material with high crystallinity, stable material performance and excellent cycle performance, in the step (4), the additive is selected from at least one of alumina, titanium oxide, yttrium oxide, zinc oxide, magnesium oxide, ammonium dihydrogen phosphate and boric acid.
In a preferred embodiment, in step (4), the additive is alumina, titania or ammonium dihydrogen phosphate.
In the method of the present invention, in the step (4), the particle size of the additive may be any of 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, and a range of any two of these points.
In a preferred embodiment, in step (4), the particle size of the additive is 50 to 100 nm. In a more preferred embodiment, in step (4), the particle size of the additive is 60 to 80 nm.
The particle size of the additive as described herein refers to the length dimension of the particles as counted by electron microscopy.
In the method, in order to obtain the nickel cobalt lithium manganate single crystal ternary material with excellent performance, the sintering condition in the step (4) needs to be reasonably controlled.
In the step (4), the sintering temperature is 200-800 ℃; specifically, for example, the temperature may be 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or any value in the range of any two of these values.
In the step (4), the temperature rise rate of the sintering is 1-5 ℃/min; specifically, it can be, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min.
In the step (4), the sintering heat preservation time is 4-8 h; specifically, for example, 4h, 5h, 6h, 7h, or 8h may be used.
In a preferred embodiment, the sintering temperature is 400-600 ℃, the temperature rise rate of the sintering is 2-3 ℃/min, and the heat preservation time of the sintering is 7-8 h.
The method for preparing the nickel cobalt lithium manganate single crystal ternary material easily generates Li (Ni) with low Li/Ni mixed arrangement degree and prominent single crystal appearance0.55Co0.15Mn0.3)O2Particles; the preparation process is simple, the reproducibility is good, the appearance is easy to control, and the method is easy for large-scale industrial production and application; simultaneous production of Li (Ni)0.55Co0.15Mn0.3)O2The nickel cobalt lithium manganate single crystal ternary material has high crystallinity, stable material performance and excellent cycle performance.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
(1) 874g of battery grade Li2CO3(average particle size D50 5.659 μm) 2000g of an ellipsoidal precursor (Ni)0.55Co0.15Mn0.3)(OH)2(the SEM photograph is shown in FIG. 1, and the average particle size D50 is 3.91 μm, and the specific surface area is 12.72m2Per g) and 6.76g of zirconium oxide (size 50-90nm) are mixed homogeneously using a high-speed mixer, under which conditions Li and (Ni)0.55Co0.15Mn0.3) The molar ratio of (A) to (B) is 1.08:1, the rotating speed of a high-speed mixer is controlled to be 800rpm, and the mixing time is 20 min;
(2) filling the mixture obtained in the step (1) into a mullite-cordierite sagger, marking and cutting according to a 6 multiplied by 6 grid, and calcining for 12 hours at 950 ℃ by using a box furnace to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) performing coarse crushing on the material blocks obtained in the step (2) in a jaw crusher and a roll crusher, performing jet milling, and finally performing ultrasonic vibration screening (the mesh number of a screen is 400 meshes) to obtain black powder;
(4) mixing 1000g of the powder obtained in the step (3) with 2.51g of titanium dioxide (with particle size of 50-90nm) by high-speed dry method, sintering at 500 ℃ for 8h by using a box furnace, and sieving by using ultrasonic vibration (with the mesh number of 400) to obtain coated Li (Ni)0.55Co0.15Mn0.3)O2A nickel cobalt lithium manganate single crystal ternary material S1;
wherein, the jaw of jaw breaker breaks and decides jaw clearance and is 4mm, the double-roll crack interval of double-roll crusher is 1mm, the jet milling condition is: the air inlet pressure is 0.5MPa, the grading frequency is 110Hz, and the induced air frequency is 50 Hz.
Example 2
(1) 844g of battery grade Li2CO3(average particle size D50: 6.37 μm) 2000g of an ellipsoidal precursor (Ni)0.55Co0.15Mn0.3)(OH)2(the SEM photograph is shown in FIG. 2, and the average particle size D50 is 3.93 μm, and the specific surface area is 11.86m2Per g) and 5.41g of zirconium oxide (size 50-90nm) are mixed homogeneously using a high-speed mixer, under which conditions Li and (Ni)0.55Co0.15Mn0.3) At a molar ratio of 1.06:1, the speed of the high-speed mixer is controlled to 700rpm, and the mixing time is 25min；
(2) Loading the mixture obtained in the step (1) into a mullite-cordierite sagger, scribing according to a 6 multiplied by 6 grid, cutting into blocks, and calcining for 10 hours at 955 ℃ by using a box furnace to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) roughly crushing the material blocks obtained in the step (2) in a jaw crusher and a roll crusher, then carrying out air flow crushing, and finally sieving by using ultrasonic vibration (the mesh number of a screen is 400 meshes) to obtain black powder;
(4) mixing 1000g of the powder obtained in the step (3) with 2.83g of aluminum oxide (with the particle size of 50-90nm) by a high-speed dry method, sintering for 6 hours at 600 ℃ by using a box furnace, and sieving by using ultrasonic vibration (the mesh number of a sieve is 400 meshes) to obtain coated Li (Ni)0.55Co0.15Mn0.3)O2A nickel cobalt lithium manganate single crystal ternary material S2;
the jaw crushing fixed jaw gap of the jaw crusher is 5mm, the gap between double-roller cracks of the double-roller crusher is 1.5mm, the air flow crushing condition is that the air inlet pressure is 0.45MPa, the classification frequency is 120Hz, and the induced air frequency is 45 Hz.
Example 3
(1) 867g of battery grade Li2CO3(average particle size D50: 6.37 μm) 2000g of an ellipsoidal precursor (Ni)0.55Co0.15Mn0.3)(OH)2(the SEM photograph is shown in FIG. 3, and the average particle size D50 is 4 μm, and the specific surface area is 10.02m2Per g) and 4.06g of zirconium oxide (size 50-90nm) were mixed homogeneously using a high-speed mixer under which conditions Li and (Ni) were mixed0.55Co0.15Mn0.3) The molar ratio of (A) to (B) is 1.07:1, the rotating speed of a high-speed mixer is controlled to be 700rpm, and the mixing time is 25 min;
(2) filling the mixture obtained in the step (1) into a mullite-cordierite sagger, marking and cutting according to a 6 multiplied by 6 grid, and calcining for 14 hours at 945 ℃ by using a box furnace to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) performing coarse crushing on the material blocks obtained in the step (2) in a jaw crusher and a roll crusher, performing jet milling, and finally performing ultrasonic vibration screening (the mesh number of a screen is 350) to obtain black powder;
(4) mixing 1000g of the powder obtained in the step (3) with 8.52g of diammonium hydrogen phosphate by a high-speed dry method, sintering for 8 hours at 300 ℃ by using a box furnace, and sieving by using ultrasonic vibration (the mesh number of a screen is 400) to obtain coated Li (Ni)0.55Co0.15Mn0.3)O2A nickel cobalt lithium manganate single crystal ternary material S3;
the jaw crushing fixed jaw gap of the jaw crusher is 3mm, the gap between double rollers of the double-roller crusher is 2mm, the air inlet pressure is 0.55MPa, the classification frequency is 100Hz, and the induced air frequency is 45 Hz.
Example 4
The procedure is as in example 1, except that in step (1), Li and (Ni)0.55Co0.15Mn0.3) Was 1.06:1, yielding material S4.
Example 5
The procedure of example 1 was followed, except that in step (2), the calcination temperature was 970 ℃ to obtain material S5.
Example 6
Carried out according to the method of example 1, except that, in step (4), the sintering temperature was 200 ℃ to obtain material S6.
Comparative example 1
The procedure is as in example 1, except that neither the zirconium compound nor the additives are added, giving material D1.
Comparative example 2
The procedure of example 1 was followed, except that in step (4), no additive was added, to obtain material D2.
Comparative example 3
The procedure is as in example 1, except that in step (1), no zirconium compound is added, giving material D3.
Comparative example 4
The procedure is as in example 1, except that in step (1), Li and (Ni)0.55Co0.15Mn0.3) At a molar ratio of 1.02:1, to give material D4.
Comparative example 5
The procedure is as in example 1, except that in step (2), the calcination temperature is 850 ℃ to obtain material D5.
Comparative example 6
Carried out according to the method of example 1, except that, in step (4), the sintering temperature was 1000 ℃ to obtain material D6.
Test example 1
The precursor raw materials used in examples 1 to 3 were tested using a Scanning Electron Microscope (SEM), and the results are shown in fig. 1, 2, and 3.
The materials prepared in examples 1-2 and comparative example 1 were tested using a Scanning Electron Microscope (SEM), and the results are shown in fig. 4, 5 and 6.
As can be seen from FIGS. 4-6, the materials prepared in examples 1 and 2, example 1, had fewer agglomerated particles, larger single crystal particles with rounded surfaces, and more uniform surface coating additives; the material D1 prepared in comparative example 1 is mainly composed of particles with an agglomerate structure, and the shape of the particles is greatly different.
Test example 2
The material obtained in example 1 was tested using an X-ray diffractometer (XRD), and the results are shown in fig. 7. As can be seen from FIG. 7, the diffraction peak position of the material S1 prepared in example 1 is consistent with that of PDF #09-0063 card (. alpha. -NaFeO)2Structural LiNiO2Card) without significant impurity peaks. The splitting of the two-component splitting peaks (006)/(102), (108)/(110) clearly shows that the material maintains its layered structure, and that the synthesized material S1 is Li (Ni) with higher crystallinity and higher purity0.55Co0.15Mn0.3)O2A material.
Test example 3
The materials prepared in examples 1-5 and comparative examples 1-6 were assembled into button half cells as follows: fruit of Chinese wolfberryPreparing nickel cobalt lithium manganate slurry by the materials prepared in the embodiments 1-5 and the comparative examples 1-6, a conductive agent Super P and an adhesive PVDF according to a mass ratio of 90:5:5, adjusting the solid content of the slurry to 38% by adopting N-methyl pyrrolidone (NMP), coating the adjusted slurry on an aluminum foil by using an automatic coating machine, drying at 120 ℃ in a vacuum drying box, rolling by using a roller press, punching by using a slicing machine, assembling a button 2025 battery in a glove box, and obtaining LiPF with 1.2mol/L electrolyte6Wherein the solvent is EC: EMC 3:7 (volume ratio), the diaphragm is Celgard polypropylene membrane, and a metal lithium sheet is adopted as a counter electrode. And (3) carrying out charge-discharge test on the button half cell on a Xinwei tester in a voltage range of 3-4.35V. The first charge specific capacity, the first discharge specific capacity and the coulombic efficiency of 0.1C were tested, and the results are shown in table 1; the specific discharge capacity and capacity retention rate after 1C cycle of 50 cycles were tested, and the results are shown in table 2.
TABLE 1
Figure BDA0002625882430000151
Figure BDA0002625882430000161
TABLE 2
Figure BDA0002625882430000162
As can be seen from the results in table 1, compared with comparative examples 1 to 6, the first discharge specific capacity and the coulombic efficiency of the lithium nickel cobalt manganese oxide single crystal ternary material assembled batteries prepared in examples 1 to 6 are obviously improved; as can be seen from the results in Table 2, 1 of the nickel cobalt lithium manganate single crystal ternary material-assembled batteries prepared in examples 1 to 6 are compared with those of comparative examples 1 to 6stDischarge capacity, 50thThe discharge capacity and the capacity retention efficiency are obviously improved, so that the nickel cobalt lithium manganate single crystal ternary material prepared by the method has excellent cycle performance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. The method for preparing the nickel cobalt lithium manganate single crystal ternary material is characterized by comprising the following steps of:
(1) lithium carbonate and precursor (Ni)0.55Co0.15Mn0.3)(OH)2Uniformly mixing with a zirconium compound to obtain a mixture, wherein the lithium carbonate and the precursor are mixed according to Li (Ni)0.55Co0.15Mn0.3) 1, x is more than or equal to 0.04 and less than or equal to 0.1, and the Zr content in the mixture is controlled to be 0.05-0.4 wt% of the precursor;
(2) placing the mixture obtained in the step (1) in a sagger, scribing, cutting into pieces and calcining to obtain single crystal Li (Ni)0.55Co0.15Mn0.3)O2A material block;
(3) carrying out coarse crushing, airflow crushing and sieving on the material blocks obtained in the step (2) in sequence to obtain black powder;
(4) and (4) mixing the black powder obtained in the step (3) with an additive by a high-speed dry method, and sintering to obtain the additive-coated black powder material.
2. The process according to claim 1, characterized in that in step (1), the lithium carbonate has an average particle size D50 of 4-8 μ ι η.
3. The method according to claim 2, wherein in step (1), the precursor (Ni)0.55Co0.15Mn0.3)(OH)2The shape of the spherical surface is ellipsoidal or spheroidal;
preferably, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Has an average particle size D50 of 3-4.5 μm and a minimum particle size Dmin > 1 μmm, the maximum granularity Dmax is less than 12 mu m;
preferably, the precursor (Ni)0.55Co0.15Mn0.3)(OH)2Has a specific surface area of 8-15m2/g。
4. The method according to claim 1 or 2, wherein in step (1), the zirconium compound is nano zirconia;
preferably, the particle size of the zirconium compound is 20 to 200 nm;
preferably, the Zr content in the mixed material is controlled to be 0.05-0.3 wt% of the precursor.
5. The method as claimed in claim 4, wherein in step (1), 0.05. ltoreq. x.ltoreq.0.08.
6. The method according to claim 1 or 2, characterized in that, in step (1), the lithium carbonate, the precursor, and the zirconium compound are mixed in a high-speed mixer;
preferably, the mixing time is 15-40 min;
preferably, the rotation speed of the high-speed mixer is 500-.
7. The method according to claim 1, wherein in step (2), the calcination conditions comprise: the calcination temperature is 930-.
8. A method according to claim 7, characterized in that in step (3) the rough breaking is performed in a jaw crusher and a counter roll crusher;
preferably, the gap between the jaw breaking fixed jaw and the jaw breaking fixed jaw in the jaw crusher is 3-8 mm;
preferably, the gap between the double-roll gaps of the double-roll crusher is 1-2.5 mm.
9. The method according to claim 8, wherein in step (3), the conditions of the jet milling include: the air inlet pressure is 0.2-0.6MPa, the grading frequency is 80-160Hz, and the induced air frequency is 30-80 Hz;
preferably, the sieving is a vibratory sieving, the sieving conditions including: the mesh number of the screen is 300-400 meshes, and the tension of the screen is 15-25N/cm.
10. The method according to claim 1, wherein in step (4), the additive is selected from at least one of alumina, titania, yttria, zinc oxide, magnesia, ammonium dihydrogen phosphate, and boric acid;
preferably, the particle size of the additive is 20-200 nm;
preferably, in the step (4), the sintering conditions include: the sintering temperature is 200-.
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