CN115050937A - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

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CN115050937A
CN115050937A CN202210665656.XA CN202210665656A CN115050937A CN 115050937 A CN115050937 A CN 115050937A CN 202210665656 A CN202210665656 A CN 202210665656A CN 115050937 A CN115050937 A CN 115050937A
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lithium ion
ion battery
crushing
positive electrode
lithium
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CN115050937B (en
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闫春运
郭海
陈一帆
王欣全
封锡胜
吴孟涛
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Zhejiang Bamo Technology Co ltd
Tianjin B&M Science and Technology Co Ltd
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Zhejiang Bamo Technology Co ltd
Tianjin B&M Science and Technology 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

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Abstract

The invention relates to the technical field of lithium ion battery anode materials, in particular to the field of IPC H01M4, and more particularly relates to a lithium ion battery anode material and a preparation method thereof. The organic combination of elements and the anode material in the process is realized by selecting raw materials of Me, M1 and M2 with different particle sizes for high-temperature roasting and crushing and carrying out integrated treatment on the raw materials through disc nest grinding or airflow crushing, the uniformity is high, the structure is stable, and the phase structure stability and the electrochemical performance of the material are further improved. This application can also be based on different characteristics of different component additives and arrange to obtain the product that satisfies different demands, not only improved simple solid phase mixed effect, still solved the surface interface problem of anode material in lithium ion battery, it is strong to prepare anode material expansibility, not only can be applied to cobalt lithium material, can also be applied to anode materials such as ternary material, nickelic material.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to the field of IPC H01M4, and more particularly relates to a lithium ion battery anode material and a preparation method thereof.
Background
Currently, lithium ion batteries have been widely used in the fields of consumer electronics, energy storage devices, power tools, and the like. The cathode material is one of core materials of the lithium ion battery, and a lot of researches are carried out aiming at different application fields, and at present, commercial cathode materials mainly comprise lithium cobaltate, lithium iron phosphate, lithium manganate, lithium nickel cobalt manganese and lithium nickel cobalt aluminate. More lithium ions can be extracted from the crystal structure at high voltage, but the cycle life and the safety performance of the battery are affected by the large extraction of lithium due to the damage of the crystal structure. Under higher requirements, the problems are more and more obvious, particularly the problem of an interface is more and more obvious, and the traditional cathode material is modified by a classical industrialized solid-phase mixing mode, so that the requirements of people on the fine improvement of the cathode material cannot be met. The surface coating of the positive electrode material is one of important means for effectively improving the surface interface problem. Currently, mainstream coating technologies of lithium battery anode materials are classified into a dry method and a wet method.
In the prior art, patent document No. CN 109994711B discloses a method for preparing a doped and coated lithium cobaltate positive electrode material, in which a compound containing a metal element is dissolved in an absolute ethanol solution, and a wet method is used to uniformly coat oxides of Al, Mg, and Si on the surface of lithium cobaltate, thereby improving the electrochemical performance of the lithium cobaltate material.
AuthorizationThe patent document with publication number CN104037407B discloses a lithium super-ion conductor coated lithium cobaltate composite material and a preparation method thereof, wherein a lithium super-ion conductor Li is coated by a dry method c Mg d Ti e M′ f (PO 4 ) 3 The coating is coated on the surface of lithium cobaltate, so that the surface resistance is reduced, the specific capacity of the lithium cobaltate is improved, and the cycling stability of the lithium cobaltate is lower.
Patent document with an authorization publication number of CN112993258B discloses a doping and coating method of a ternary cathode material, a ternary cathode material and a lithium ion battery, wherein a metal source, a nickel source, a manganese source and a cobalt source are doped with silicate, a coprecipitation method is firstly adopted to prepare a ternary cathode material precursor, a ternary cathode material core co-doped with silicon and metal elements is obtained after primary sintering, then the ternary cathode material core is cleaned by using a saturated solution of silicate, and simultaneously a metal salt is added for precipitation coating, and the ternary cathode material obtained after dehydration and sintering has a good coating effect and high material stability, but the steps are complicated.
At present, the industrial application is mainly dry coating, but the prior art still cannot solve the problems of poor coating firmness, element enrichment, discontinuous coating, uneven thickness and the like of the surface coating of the anode material. Improving these problems is critical to the stability and electrochemical performance of the positive electrode material as well as the battery.
Disclosure of Invention
In order to solve the above problems, in a first aspect of the present invention, a lithium ion battery cathode material is provided, where the chemical expression of the lithium ion battery cathode material is Li α Co (1-x-2y) Me x (M1M2) y M3 δ Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.6, alpha is more than or equal to 0.85 and less than or equal to 1.5, and delta is more than or equal to 1.70 and less than or equal to 2.40; more preferably, x is 0. ltoreq. x.ltoreq.0.3, y is 0. ltoreq.y.ltoreq.0.4, α is 0.95. ltoreq.1.4, and δ is 1.90. ltoreq.2.10.
Preferably, Me is one or more of Mg, Al, Y, Cu, Pb, Nb, Ti, Sc, Rb, Zr, Ca, B, Ac series rare earth metals, Pd, Ir, Ta, Bi, V, Cr, Mn, Fe, Ni, La series rare earth metals, Zn, Ru, P, Ce, W, Na and Sn; further preferably, it is one or more of Mg, Al, Y, Ti, Zr, V, Cr, Mn, Fe, Ni, La, Zn, Ru, Ce, W, Na and Sn.
Preferably, M3 is one or more of O, F, Cl and Br; further preferably O, F.
Preferably, M1 is a metal having an oxidation state of + 2; the M2 is a metal having an oxidation state of + 4.
The applicant has unexpectedly found that a protective layer is formed on the surface of a positive active material by physically mixing Mg, Al, Y, Cu, Pb, Nb, Ti, Sc, Rb, Zr, Ca, B, Ac-based rare earth metal, Pd, Ir, Ta, Bi, V, Cr, Mn, Fe, Ni, La-based rare earth metal, Zn, Ru, P, Ce, W, Na, Sn with a metal M1 having a +2 oxidation state and a metal M2 having a +4 oxidation state, so that the specific capacity of a battery can be ensured and the cycle stability of the battery can be improved. The reason is probably that the expansion of the cathode material in the circulating process is reduced due to the synergistic effect of the coating layer elements Me, M1 and M2, so that the dissolution of cobalt ions in the electrolyte is reduced, and meanwhile, the stress generated by lithium cobaltate crystal lattices in the lithium deintercalation process is reduced by the coating layer, so that the circulating stability of the material is improved. In addition, the reaction of electrolyte and the positive active material lithium cobaltate can be obstructed at lithium cobaltate surface coating material under the general condition, through multiple element compounding in this application, can make lithium cobaltate surface impedance increase minimum, when not reducing battery specific capacity, improve the cycling stability of battery, can also design the ratio of different elements according to the product of different demands, satisfy people's demand. However, in the solid phase mixing and coating process, elements are enriched, the requirement on the size of the raw material is high, the specific surface area of the raw material with the excessively high size is small, the coating is not firm enough, the specific surface is increased along with the reduction of the size of the additive, the viscosity of the material is increased, the water absorption is enhanced, the additive is easy to agglomerate and cake, and the mixing consistency among the additives is poor. The surface layer and subsurface layer coating structure defects caused by coating in the mode can increase the internal resistance of the material, reduce the electrochemical activity and cause serious lattice cracks and micro strain.
The second aspect of the invention provides a preparation method of a lithium ion battery anode material, which comprises the following steps: and mixing the precursor powder, the lithium salt, the compound of M1, the compound of M2 and the compound of Me, mixing with lithium cobaltate, roasting at high temperature and crushing to obtain the lithium cobaltate.
Preferably, the lithium salt is one or more of lithium hydroxide, lithium phosphate, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate and lithium fluoride; more preferably, lithium carbonate or lithium hydroxide.
Preferably, the precursor powder is one or more of cobaltosic oxide, cobalt hydroxide, cobalt oxide and cobalt carbonate.
Preferably, the compound of M1 is an oxide, oxalate, carbonate, hydroxide or metal organic of M1; further preferably, it is an oxide of M1.
Preferably, the compound of M2 is an oxide, oxalate, carbonate, hydroxide or metal organic of M2; further preferably, it is an oxide of M2.
Preferably, the Me compound is Me oxide, oxalate, carbonate, hydroxide or metallo-organic; further preferred is an oxide of Me.
Preferably, the preparation method of the lithium ion battery cathode material comprises the following steps:
s1, weighing a proper amount of precursor powder and lithium salt, adding a certain amount of M1 compound and M2 compound, and uniformly mixing to obtain powder I;
s2, roasting the powder in a bell-type furnace at high temperature, and crushing the powder in a crusher to obtain powder II;
s3, uniformly mixing Me compounds according to a certain element ratio to obtain the positive electrode additive;
and S4, uniformly mixing a proper amount of the positive electrode additive and a certain amount of the second powder, roasting at high temperature by using a hood-type furnace, and crushing the roasted material by using a crusher to obtain the lithium ion battery.
Preferably, the molar ratio of the Li element to the Co element in the first powder of step S1 is 1.0 to 1.1.
Preferably, the content of each element in Me in the cathode additive in a finished product is 100-3000 ppm; more preferably, it is 500-2000 ppm.
Preferably, in the step S3, the size of the Me compound is micro-nano.
Preferably, in step S3, the Me compound is premixed by a high-speed mixer according to a certain element ratio, and then crushed and homogenized to obtain the positive electrode additive.
Preferably, the crushing treatment mode is one or more of hydraulic crushing, mechanical crushing, airflow crushing, impact crushing, turbine crushing and disc nest grinding; further preferred is a disk nest mill or air stream breaker.
The applicant has unexpectedly found that the dry coating method is adopted to treat raw materials with different particle sizes, so that the dispersibility and uniformity of the additive can be improved, and the electrochemical performance of the positive electrode material and the battery can be improved. The reason for this is probably that the added elements are crushed after premixing, on one hand, the primary particle size of the added elements is further reduced, on the other hand, the materials are uniformly mixed in a micro-nano level after passing through the mixing bin and the crushing bin, and the integrated treatment of the added elements is completed. In addition, the dry coating does not need to use solution, has small influence on the environment and low cost, and is suitable for industrial large-scale application.
Preferably, the specific implementation manner of step S1 is: weighing a proper amount of large-particle precursor powder and lithium salt, adding a certain amount of M1 compound and M2 compound, and uniformly mixing to obtain large-particle uniformly mixed material; and weighing a proper amount of small-particle precursor powder and lithium salt, adding a certain amount of M1 compound and M2 compound, and uniformly mixing to obtain a small-particle uniformly-mixed material.
Preferably, the D50 of the large particles is in the range of 10-50 μm; more preferably, it is 10 to 20 μm.
Preferably, the D50 of the small particles is in the range of 1 μm to 10 μm.
The applicant unexpectedly finds that the anode additive prepared by mixing large particles with the D50 of 10-50 microns, small particles with the D50 of 1-10 microns and micro-nano particles can improve the element coating uniformity and the coating firmness, so that the problem of the surface interface between an electrolyte and an anode material is solved, and the stability of the anode material and a battery is further improved. The additive is premixed and crushed to be uniform, so that the additive is dispersed more uniformly, a multi-layer coating or synergistic coating effect can be formed according to the adding sequence, the bonding strength with the base material is improved, the phase change stress of the material in the electrochemical process is reduced, the impedance of the material is reduced, and the dynamic performance is improved.
Preferably, the specific implementation manner of step S2 is: roasting the large-particle uniformly-mixed material at high temperature by using a bell-type furnace; the roasting temperature is 950-; roasting the uniformly mixed small-particle materials at high temperature by using a bell-type furnace; the roasting temperature is 900-; the calcined samples were each pulverized with a pulverizer.
Preferably, the high-temperature roasting temperature in the step S4 is 750-1100 ℃, and the constant temperature time is 5-10 h.
In some preferred schemes, the raw materials with different particle sizes are subjected to high-temperature roasting at different temperatures and times. This is probably because the excessively high firing temperature causes abnormal growth of crystal grains, which makes the grain size excessively large, affecting electrochemical properties and stability, while the excessively low firing temperature causes a decrease in crystallinity and single crystallization of the material, affecting electrochemical properties of the positive electrode material and the battery.
Preferably, the firing atmosphere in the step S2 and the step S4 is not particularly limited.
Has the advantages that:
1. the invention prepares the lithium ion battery anode material by a dry coating method, and the chemical expression of the lithium ion battery anode material is Li α Co (1-x-2y) Me x (M1M2) y M3 δ Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.6, alpha is more than or equal to 0.85 and less than or equal to 1.5, and delta is more than or equal to 1.70 and less than or equal to 2.40.
2. The protective layer is formed on the surface of the positive active material by physically mixing Mg, Al, Y, Cu, Pb, Nb, Ti, Sc, Rb, Zr, Ca, B, Ac-based rare earth metals, Pd, Ir, Ta, Bi, V, Cr, Mn, Fe, Ni, La-based rare earth metals, Zn, Ru, P, Ce, W, Na, Sn, the metal M1 having a +2 oxidation state and the metal M2 having a +4 oxidation state, so that the specific capacity of the battery can be ensured, and the cycle stability of the battery can be improved.
3. By selecting a disc nest mill or an air flow pulverizer to treat the additives with different particle sizes, the dispersibility and uniformity of the additives can be improved, and the electrochemical properties of the positive electrode material and the battery can be improved.
4. The raw materials containing the elements Me, M1 and M2 with different particle sizes are selected for high-temperature roasting and crushing, and are subjected to integrated treatment through disc nest grinding or airflow crushing, so that the organic combination of the elements and the anode material in the process is realized, the uniformity is high, the structure is stable, and the phase structure stability and the electrochemical performance of the material are further improved.
5. The method can be matched according to different characteristics of different component additives to obtain products meeting different requirements, so that the coating effect of simple solid phase mixing is improved, the surface interface problem of the anode material in the lithium ion battery is solved, the expansibility for preparing the anode material is strong, and the method can be applied to cobalt-lithium materials and also can be applied to anode materials such as ternary materials.
Drawings
FIG. 1 shows the discharge capacity of example 1, example 2 and comparative example 1;
FIG. 2 shows the cycle stability of example 1, example 2 and comparative example 1;
FIG. 3 is the surface topography under a Scanning Electron Microscope (SEM) at 1000 magnifications for example 1;
FIG. 4 is the surface topography under a Scanning Electron Microscope (SEM) at 1000 magnifications for example 2;
FIG. 5 shows the surface topography of comparative example 1 under a Scanning Electron Microscope (SEM) at a magnification of 1000.
Detailed Description
Examples
Example 1
Example 1 a lithium ion battery positive electrode material was preparedThe chemical expression of the lithium ion battery anode material is Li α Co (1-x-2y) Me x (M1M2) y M3 δ . Wherein, alpha is 1.035, x is 0.001, y is 0, delta is 2.024.
Me is Mg, Al, Y, Ti and Zr.
The M3 is O.
The preparation method of the lithium ion battery anode material comprises the following steps:
s1, weighing 3kg of large-particle precursor powder, 1.43kg of lithium salt and 1000ppm of MgO, and uniformly mixing to obtain a large-particle uniformly-mixed material; then 3kg of precursor powder of the small particles, 1.43kg of lithium salt and 1000ppm of MgO are weighed and mixed uniformly to obtain a uniformly mixed material of the small particles;
s2, roasting the large-particle uniformly-mixed material at high temperature of 1050 ℃ for 12 hours in an air atmosphere by using a bell-type furnace; roasting the uniformly mixed small-particle materials at a high temperature of 1020 ℃ for 12 hours in an air atmosphere by using a bell-type furnace; crushing the roasted samples by using a crusher respectively;
s3, premixing the Me compound by using a high-speed mixer according to the element content ratio of 1:1:1:1:1, and crushing and homogenizing the mixture to obtain the anode additive;
s4, uniformly mixing a proper amount of the positive electrode additive obtained in the step S3 and 2.0kg of the sample obtained in the step S2 according to the content of each element Me in a finished product being 1000ppm as a design addition amount, carrying out high-temperature roasting in an air atmosphere by using a cover furnace, wherein the roasting temperature is 900 ℃, the constant temperature time is 8 hours, and crushing the roasted material by using a crusher to obtain the material.
The lithium salt is lithium carbonate.
The precursor powder is cobaltosic oxide.
In the step S3, Me compound is MgO or Al 2 O 3 、ZrO 2 、TiO 2 、Y 2 O 3 A mixture of (a).
In the step S3, the size of the Me compound is 50 nm.
The crushing treatment in step S3 is a disk nest mill.
The D50 of the large particles was 18 μm.
The D50 of the small particles was 5 μm.
Example 2
Embodiment 2 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that in embodiment 1, except that:
α＝1.032，x＝0.001，y＝0.001，δ＝2.023。
the M1 is Ni.
The M2 is Mn.
In the step S1, 3kg of precursor powder with large particles, 1.43kg of lithium salt, 1000ppm of MgO, 1000ppm of NiO and 1000ppm of Mn are weighed 3 O 4 Uniformly mixing to obtain large-particle uniformly mixed materials; then 3kg of precursor powder with small particles, 1.43kg of lithium salt, 1000ppm of MgO, 1000ppm of NiO and 1000ppm of Mn are weighed 3 O 4 Uniformly mixing to obtain a small-particle uniformly-mixed material;
in the step S2, the large-particle uniformly mixed material is roasted at a high temperature of 1065 ℃ in an air atmosphere by using a bell-type furnace for 12 hours; roasting the uniformly mixed small-particle materials at a high temperature of 1020 ℃ for 12 hours in an air atmosphere by using a bell-type furnace; the calcined samples were each pulverized with a pulverizer.
Example 3
Embodiment 3 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that in embodiment 1, except that:
α＝1.035，x＝0.001，y＝0，δ＝2.022。
me is La, Mn, Ni and Cr.
In the step S2, the large-particle uniformly mixed material is roasted at a high temperature of 1045 ℃ in an air atmosphere by a bell-type furnace for 12 hours; roasting the uniformly mixed small-particle material at high temperature of 1015 ℃ in an air atmosphere by using a bell-type furnace for 12 hours at constant temperature; the calcined samples were each pulverized with a pulverizer.
In the step S3, the compound of Me is La 2 O 3 、Mn 3 O 4 、NiO、Cr 2 O 3 A mixture of (a).
Example 4
Embodiment 4 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that in embodiment 1, except that:
in the step S2, the large-particle uniformly mixed material is roasted at high temperature in an air atmosphere by using a bell-type furnace, wherein the roasting temperature is 1050 ℃, and the constant temperature time is 12 hours; roasting the uniformly mixed small-particle materials at a high temperature of 1020 ℃ for 12 hours in an air atmosphere by using a bell-type furnace; the calcined samples were each pulverized with a pulverizer.
The crushing in step S3 is performed by mechanical crushing.
Example 5
Embodiment 5 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that in embodiment 1, except that:
α＝1.032，x＝0.001，y＝0.001，δ＝2.023。
the M1 is Ni.
The M2 is Mn.
In the step S1, 3kg of precursor powder with large particles, 1.43kg of lithium salt, 1000ppm of MgO, 1000ppm of NiO and 1000ppm of Mn are weighed 3 O 4 Uniformly mixing to obtain large-particle uniformly-mixed materials; then 3kg of precursor powder with small particles, 1.43kg of lithium salt, 1000ppm of MgO, 1000ppm of NiO and 1000ppm of Mn are weighed 3 O 4 And uniformly mixing to obtain a small-particle uniformly-mixed material.
The crushing processing in step S3 is performed by airflow crushing.
Example 6
Example 6 provides a lithium ion battery positive electrode material, and the specific implementation manner is the same as example 1, except that:
α＝1.032，x＝0.001，y＝0.001，δ＝2.025。
the M1 is Ni.
The M2 is Mn.
Me is W, V, Zn, Ce and Sn.
In the step S1, 3kg of large-particle precursor powder, 1.43kg of lithium salt, 1000ppm of MgO and 1000ppm of Al are weighed 2 O 3 、1000ppm Mn 3 O 4 Uniformly mixing to obtain large-particle uniformly mixed materials; then 3kg of precursor powder with small particles, 1.43kg of lithium salt, 1000ppm of MgO and 1000ppm of Al are weighed 2 O 3 、1000ppm Mn 3 O 4 And uniformly mixing to obtain a small-particle uniformly-mixed material.
In the step S3, the Me compound is WO 3 、V 2 O 3 、ZnO、CeO 2 、SnO 2 A mixture of (a).
Example 7
Example 7 provides a lithium ion battery positive electrode material, and the specific implementation manner is the same as example 1, except that:
α＝1.032，x＝0.001，y＝0.001，δ＝2.022。
me is Na, V, Mn, NiO and Ru.
In the step S3, the Me compound is Na 2 CO 3 、V 2 O 3 、Mn 3 O 4 、NiO、RuO 2 A mixture of (a).
Comparative example 1
A comparative example 1 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that of example 1, except that: in step S3, the crushing process is not performed.
Comparative example 2
A comparative example 2 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that of example 1, except that: the raw materials have no small particles.
Comparative example 3
A comparative example 3 provides a lithium ion battery cathode material, and the specific implementation manner is the same as that in example 1, except that: the raw material has no large particles.
Comparative example 4
Comparative example 6 provides a positive electrode material for a lithium ion battery, and the specific embodiment is the same as example 6, except that: the size of the compound of Me in step S3 was 2 μm.
Preparation of the Battery
Adding 90 wt% of the prepared positive electrode material, 5 wt% of a conductive agent and 5 wt% of a binder into N-methyl pyrrolidone, uniformly stirring to prepare positive electrode slurry, coating the positive electrode slurry on a current collector, drying for 6 hours at 80 ℃ to obtain a positive electrode sheet, and assembling the positive electrode sheet, a negative electrode, electrolyte and a diaphragm into the button cell.
The conductive agent is conductive carbon black, the adhesive is PVDF, the negative electrode consists of 90 wt% of graphite, 2 wt% of conductive carbon black and 8 wt% of negative electrode adhesive (CMC), and the electrolyte is 1M LiPF 6 The membrane of the propylene carbonate solution is Celgard 2400.
Performance test method
1. Capacity of
The button cells prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to discharge capacity test by one cycle of constant current charging to 4.55V at a current density of 0.1C, constant voltage charging to 50uA, and then 0.1C discharging to 3V, and the results are shown in table 1, and example 1, example 2, and comparative example 1 are shown in fig. 1.
2. Stability of circulation
The button cells prepared in examples 1 to 7 and comparative examples 1 to 4 were charged and discharged 50 times at a charge and discharge rate of 0.1C in a voltage range of 3.0V to 4.6V, and the capacity retention ratio of the cells was measured and reported in table 1, and the results of example 1, example 2 and comparative example 1 are shown in fig. 2.
3. DCR (direct current resistance)
The DC resistance was measured according to the capacity values measured in examples 1 to 7 and comparative examples 1 to 4, and the results are shown in Table 1.
4. Surface topography
The surface morphology of the positive electrode materials prepared in examples 1 to 2 and comparative example 1 was observed by a Scanning Electron Microscope (SEM), and the results are shown in fig. 3 to 5.
TABLE 1
Figure BDA0003691507810000151
Figure BDA0003691507810000161

Claims (10)

1. The lithium ion battery cathode material is characterized in that the chemical expression of the lithium ion battery cathode material is Li α Co (1-x-2y) Me x (M1M2) y M3 δ Wherein x is more than or equal to 0 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 0.6, alpha is more than or equal to 0.85 and less than or equal to 1.5, and delta is more than or equal to 1.70 and less than or equal to 2.40.
2. The lithium ion positive electrode material according to claim 1, wherein Me is one or more of Mg, Al, Y, Cu, Pb, Nb, Ti, Sc, Rb, Zr, Ca, B, Ac-based rare earth metals, Pd, Ir, Ta, Bi, V, Cr, Mn, Fe, Ni, La-based rare earth metals, Zn, Ru, P, Ce, W, Na, and Sn.
3. The lithium ion positive electrode material of claim 1 or 2, wherein M3 is one or more of O, F, Cl and Br.
4. The lithium ion positive electrode material of claim 3, wherein the M1 is a metal having a +2 oxidation state; the M2 is a metal having an oxidation state of + 4.
5. A preparation method of the lithium ion battery positive electrode material according to any one of claims 1 to 4, characterized by mixing the precursor powder, the lithium salt, the compound of M1, the compound of M2 and the compound of Me, mixing with lithium cobaltate, roasting at high temperature and crushing to obtain the lithium ion battery positive electrode material.
6. The preparation method of the positive electrode material of the lithium ion battery according to claim 5, characterized by comprising the following steps:
s1, weighing a proper amount of precursor powder and lithium salt, adding a certain amount of M1 compound and M2 compound, and uniformly mixing to obtain powder I;
s2, roasting the powder in a bell-type furnace at high temperature, and crushing the powder in a crusher to obtain powder II;
s3, mixing Me compounds to obtain a positive electrode additive;
and S4, uniformly mixing a proper amount of the positive electrode additive and a certain amount of the second powder, roasting at high temperature by using a hood-type furnace, and crushing the roasted material by using a crusher to obtain the lithium ion battery.
7. The method as claimed in claim 6, wherein the content of each element in Me in the positive electrode additive in the final product is 100-3000 ppm.
8. The method according to claim 7, wherein in step S3, the compound size of Me is in micro-nanometer level.
9. The method of claim 7, wherein in step S3, the Me compound is premixed by a high-speed mixer according to a certain element ratio, and then crushed and homogenized to obtain the positive electrode additive.
10. The method for preparing the lithium ion battery cathode material according to claim 9, wherein the crushing treatment is one or more of hydraulic crushing, mechanical crushing, airflow crushing, impact crushing, turbine crushing and disk nest grinding.
CN202210665656.XA 2022-06-13 Lithium ion battery anode material and preparation method thereof Active CN115050937B (en)

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