CN115340135A - Modified ternary cathode material and preparation method and application thereof - Google Patents

Modified ternary cathode material and preparation method and application thereof Download PDF

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Publication number
CN115340135A
CN115340135A CN202211156423.3A CN202211156423A CN115340135A CN 115340135 A CN115340135 A CN 115340135A CN 202211156423 A CN202211156423 A CN 202211156423A CN 115340135 A CN115340135 A CN 115340135A
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additive
modified ternary
cathode material
mixing
calcination
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宋英杰
吕菲
景乐乐
周志平
伏萍萍
秦孙德禄
张超
其他发明人请求不公开姓名
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Tianjin B&M Science and Technology Co Ltd
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Tianjin B&M Science and Technology Co Ltd
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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

Abstract

The invention provides a modified ternary cathode material and a preparation method thereof, wherein the chemical formula of the modified ternary cathode material is LiNi x Co y Mn z M 1‑x‑y‑z O 2 ·aAO，0.5≤x＜1，0.04≤y＜0.3，Z is more than or equal to 0.05 and less than or equal to 0.4, a is more than 0 and less than or equal to 0.05. The preparation method provided by the invention comprises the steps of firstly uniformly mixing the nickel-cobalt-manganese compound, the lithium salt and the M additive serving as raw materials under high-speed stirring, calcining for 4-24 hours in an oxidizing atmosphere, crushing the sintered materials, adding the additive A and the additive M, uniformly stirring and mixing at high speed, and calcining for 4-24 hours in an oxidizing atmosphere to obtain the modified ternary positive electrode material LiNi x Co y Mn z M 1‑x‑y‑z O 2 aAO. The modified ternary cathode material provided by the invention has the advantages of stable crystal structure, excellent cycle performance, simple preparation method, easiness in operation and capability of realizing large-scale production.

Description

Modified ternary cathode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion secondary battery anode materials, and particularly relates to a modified ternary anode material and a preparation method and application thereof.
Background
In the field of new energy automobiles, new energy automobiles using lithium ion batteries as power sources develop most rapidly. The positive electrode, the negative electrode, the diaphragm and the electrolyte are four core materials of the lithium ion battery, and compared with a negative electrode material, the energy density and the power density of the positive electrode material are relatively low, which is one of important influencing factors for restricting the development of the lithium ion battery. The positive electrode material is closely related to the performance of the power battery, and the optimization of the performance of the positive electrode material is directly related to the improvement of the performance of the power battery, so that the research of the positive electrode material becomes the most core technology of the current lithium ion power battery.
In the existing anode material system, the ternary material has the advantages of high specific energy density and the like, and is a mainstream material of a new energy automobile. With the increase of the demand of new energy industry for the energy density of lithium ion batteries, the proportion of nickel element content is continuously increased, and how to maintain the cycle stability and the crystal structure stability while increasing the nickel element content becomes a hard point of key research.
Disclosure of Invention
In view of the above, the invention aims to provide a modified ternary cathode material, and a preparation method and an application thereof.
The invention provides a modified ternary cathode material, which has a chemical formula as follows:
LiNi x Co y Mn z M 1-x-y-z O 2 aAO of the formula I,
in the formula I, x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.04 and less than 0.3, z is more than or equal to 0.05 and less than 0.4, and a is more than 0 and less than or equal to 0.1;
m is one or more selected from Ti, mg, sr, la, zr, al and Y;
a is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
Preferably, x is 0.5 to 0.8, y is 0.04 to 0.1, z is 0.1 to 0.3, and a is 0.01 to 0.05.
Preferably, M is selected from one or more of Zr, al and Mg.
The A is selected from one or more of Co, li, ti, al, sr and La.
The invention provides a preparation method of a modified ternary cathode material, which comprises the following steps:
carrying out first mixing on lithium salt, a nickel-cobalt-manganese compound and a first additive, and then carrying out first calcination to obtain a semi-finished product;
carrying out second mixing on the semi-finished product, a second additive and a third additive, and then carrying out second calcination to obtain a modified ternary cathode material;
the first additive is a compound containing M;
the second additive is a compound containing A;
the third additive is a compound containing M;
the M is selected from one or more of Ti, mg, sr, la, zr, al and Y;
the A is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
Preferably, the molar ratio of the lithium salt, the nickel-cobalt-manganese compound and the first additive is (1-1.1): 1: (0-0.1);
the molar ratio of the semi-finished product, the second additive and the third additive is preferably 1: (0 to 0.1): (0-0.1).
Preferably, the first mixing and the second mixing are performed independently in a high-speed mixer; the time of the first mixing and the second mixing is 0.1-1 h independently.
Preferably, the first calcination is carried out in an oxidizing gas; the temperature of the first calcination is 800-1000 ℃; the first calcining time is 3-24 h;
the second calcination is carried out in an oxidizing gas; the temperature of the second calcination is 700-1000 ℃; the second calcination time is 3-24 h;
the oxidizing gas is selected from oxygen and/or air.
Preferably, the lithium salt is selected from one or more of lithium nitrate, lithium hydroxide, lithium carbonate, lithium citrate and lithium acetate;
the nickel-cobalt-manganese compound is nickel-cobalt-manganese hydroxide;
the M-containing compound and the A-containing compound are independently selected from one or more of oxide, hydroxide, carbonate and acid salt.
The invention provides an electrode sheet, comprising: the modified ternary cathode material in the technical scheme is provided; or the modified ternary cathode material prepared by the method in the technical scheme.
The present invention provides a battery comprising: the electrode slice of the technical scheme.
In the invention, the stability of the crystal grain structure can be improved by metal doping, so that the electrode process has good dynamic property, thereby improving the cycle performance of the electrode; after the oxide is coated, the electrochemical activity of the interface in the application process of the material can be reduced, and the stability of the interface is improved. The method provided by the invention can improve the stability of the crystal structure of the ternary material, the prepared ternary material has excellent cycle performance, the preparation method is simple, the operation is easy, and the large-scale production can be realized.
Drawings
FIG. 1 is a cycle diagram of a modified ternary cathode material prepared in example 1 of the present invention;
fig. 2 is a charge-discharge curve of the modified ternary cathode material prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a modified ternary cathode material, which has a chemical formula as follows:
LiNi x Co y Mn z M 1-x-y-z O 2 aaO of the formula I,
in the formula I, x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.04 and less than 0.3, z is more than or equal to 0.05 and less than 0.4, and a is more than 0 and less than or equal to 0.1;
m is one or more selected from Ti, mg, sr, la, zr, al and Y;
a is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
In the invention, in order to further improve the cycle performance and the discharge capacity characteristic of the modified ternary cathode material provided by the invention, the x is preferably 0.5 to 0.8, and more preferably 0.6 to 0.7; y is preferably 0.04 to 0.1, more preferably 0.06 to 0.08, most preferably 0.07; z is preferably 0.1 to 0.3, more preferably 0.2; a is preferably 0.01 to 0.05, more preferably 0.02 to 0.04, and most preferably 0.03.
In the invention, in order to further improve the discharge capacity characteristics of the modified ternary cathode material provided by the invention, the M is preferably selected from one or more of Zr, al and Mg; the A is preferably selected from one or more of Co, li, ti, al, sr and La.
The invention provides a preparation method of a modified ternary cathode material, which comprises the following steps:
carrying out first mixing on lithium salt, a nickel-cobalt-manganese compound and a first additive, and then carrying out first calcination to obtain a semi-finished product;
carrying out second mixing on the semi-finished product, a second additive and a third additive, and then carrying out second calcination to obtain a modified ternary cathode material;
the first additive is a compound containing M;
the second additive is a compound containing A;
the third additive is a compound containing M;
the M is selected from one or more of Ti, mg, sr, la, zr, al and Y;
the A is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
In the invention, in order to facilitate industrialized popularization, a better material selection advantage is obtained; the lithium salt is preferably selected from one or more of lithium nitrate, lithium hydroxide, lithium carbonate, lithium citrate and lithium acetate.
In the invention, in order to obtain a better sintering effect and further improve the cycle performance of the modified ternary cathode material, the nickel-cobalt-manganese compound is preferably nickel-cobalt-manganese hydroxide; the nickel-cobalt-manganese hydroxide has the following formula:
Ni x1 Co y1 Mn 1-x1-y1 (OH) 2 the compound of the formula II is shown in the specification,
in the formula II, x1 is more than or equal to 0.5 and less than 1, and y1 is more than or equal to 0.04 and less than 0.3.
In the present invention, x1 is preferably 0.5 to 0.8, more preferably 0.6 to 0.7; y1 is preferably 0.04 to 0.1, more preferably 0.06 to 0.08.
In the invention, in order to obtain better sintering effect and further improve the cycle performance of the modified ternary cathode material, the M-containing compound or A-containing compound is preferably selected from one or more of M-or A-containing oxide, hydroxide, carbonate and acid salt.
In the present invention, in order to further improve the discharge capacity characteristics and cycle performance of the modified ternary positive electrode material, the molar ratio of the lithium salt, the nickel-cobalt-manganese compound, and the first additive is preferably (1 to 1.1): 1: (0 to 0.1), more preferably 1.05:1:0.05.
in the present invention, in order to obtain a better mixing effect, the first mixing is preferably performed in a high-speed mixer; the time for the first mixing is preferably 0.1 to 1 hour, more preferably 0.2 to 0.8 hour, more preferably 0.3 to 0.6 hour, most preferably 0.4 to 0.5 hour.
In the present invention, in order to obtain a better sintering effect of the first calcination, which is preferably performed in an oxidizing gas, the oxidizing gas is preferably selected from oxygen and/or air; the temperature of the first calcination is preferably 800 to 1000 ℃, more preferably 850 to 950 ℃, and most preferably 900 ℃; the time of the first calcination is preferably 3 to 24 hours, more preferably 5 to 20 hours, and most preferably 10 to 15 hours; in order to further improve the discharge capacity and the cycle performance of the modified ternary cathode material, the temperature rise speed of the first calcination is preferably 1-30 ℃/min, more preferably 5-25 ℃/min, most preferably 10-20 ℃/min, and most preferably 15 ℃/min; it is preferable to raise the temperature from room temperature to the temperature of the first calcination.
In the present invention, it is preferable that the semi-finished product is crushed and then secondarily mixed with the second additive and the third additive.
In the present invention, in order to further improve the discharge capacity and cycle performance of the modified ternary cathode material, the molar ratio of the semi-finished product, the second additive and the third additive is preferably 1: (0-0.1): (0 to 0.1), more preferably 1: (0.02-0.08): (0.02 to 0.08), more preferably 1: (0.03-0.06): (0.03 to 0.06), most preferably 1: (0.04-0.05): (0.04-0.05).
In the present invention, in order to obtain a better mixing effect, the second mixing is preferably performed in a high-speed mixer; the time for the second mixing is preferably 0.1 to 1 hour, more preferably 0.2 to 0.8 hour, more preferably 0.3 to 0.6 hour, most preferably 0.4 to 0.5 hour.
In the present invention, in order to obtain a better sintering effect of the second calcination, which is preferably performed in an oxidizing gas preferably selected from oxygen and/or air, and further improve the discharge capacity of the modified ternary positive electrode material; the temperature of the second calcination is preferably 700 to 1000 ℃, more preferably 800 to 900 ℃, and most preferably 850 ℃; the time of the second calcination is preferably 3 to 24 hours, more preferably 5 to 20 hours, and most preferably 10 to 15 hours; in order to further improve the discharge capacity and the cycle performance of the modified ternary cathode material, the temperature rise speed of the second calcination is preferably 1-30 ℃/min, more preferably 5-25 ℃/min, most preferably 10-20 ℃/min, and most preferably 15 ℃/min; it is preferable to raise the temperature from room temperature to the temperature of the second calcination.
The invention provides an electrode slice, comprising: the modified ternary cathode material in the technical scheme is provided; or the modified ternary cathode material prepared by the method in the technical scheme.
The present invention provides a battery comprising: the electrode slice of the technical scheme.
The method provided by the invention can improve the stability of the crystal structure of the ternary material, the prepared ternary material has excellent cycle performance, the preparation method is simple, the operation is easy, and the large-scale production can be realized.
The precursor used in the following examples of the invention has the following compositional formula: ni 0.7 Co 0.05 Mn 0.25 (OH) 2 Is a commercially available Grignard precursor 700503.
Example 1
98.5g of LiOH. H 2 Accurately weighing and proportioning O, 200g of precursor, 1g of zirconium dioxide and 0.5g of alumina, mixing at a high speed in a high-speed mixer for 20min, and calcining at 910 ℃ in oxygen gas for 20h to obtain a semi-finished product;
crushing the obtained semi-finished product, and weighing 100g of the semi-finished product and 3g of LiOH & H 2 Mixing O, 2g of cobalt hydroxide, 0.2g of titanium dioxide and 0.3g of alumina at high speed in a high-speed mixer for 30min, and calcining at 800 ℃ in oxygen gas for 8h to obtain the catalystTo LiNi 0.7 Co 0.05 Mn 0.22 Zr 0.01 O 2 ·0.01CoTi 0.5 Al 0.5 O。
Example 2
98.5g of LiOH. H 2 Accurately weighing and mixing O, 200g of precursor, 1g of zirconium dioxide and 0.5g of aluminum oxide, mixing at high speed for 20min in a high-speed mixer, and calcining for 20h in oxygen gas at 910 ℃ to obtain a semi-finished product;
crushing the semi-finished product, weighing 100g of the semi-finished product and 3g of LiOH. H 2 Mixing O, 2g of cobaltosic oxide, 0.15g of metatitanic acid, 0.3g of alumina and 0.1g of lanthanum oxide at high speed in a high-speed mixer for 30min, and calcining at 790 ℃ in oxygen gas for 8h to obtain LiNi 0.7 Co 0.05 Mn 0.22 Zr 0.01 O 2 ·0.01Co 1.01 Ti 0.5 La 0.2 Al 0.5 O。
Example 3
100g of LiOH H 2 Accurately weighing and mixing O, 200g of precursor, 1g of zirconium dioxide and 0.5g of aluminum oxide, mixing at high speed for 20min in a high-speed mixer, and calcining for 20h in oxygen gas at 910 ℃ to obtain a semi-finished product;
crushing the semi-finished product, weighing 100g of the semi-finished product and 3g of LiOH H 2 Mixing O, 2g of cobalt oxide, 0.2g of titanium hydroxide and 0.3g of alumina at high speed in a high-speed mixer for 30min, and calcining at 800 ℃ in oxygen gas for 8h to obtain LiNi 0.7 Co 0.05 Mn 0.22 Zr 0.01 O 2 ·0.01CoTi 0.3 Al 0.5 O。
Comparative example 1
98.5g of LiOH. H 2 And accurately weighing and mixing O, 200g of precursor, 1g of zirconium dioxide and 0.5g of aluminum oxide, mixing at high speed for 20min in a high-speed mixer, and calcining for 20h at 910 ℃ in oxygen gas to obtain the anode material.
Performance detection
The performance of the positive electrode materials prepared in the embodiment of the invention and the comparative example 1 is detected, and the button cell is prepared:
active material in positive electrode (positive electrode material prepared in example): conductive agent (carbon black): the mass ratio of the binder (PVDF) is 90; lithium is taken as a negative electrode; the electricity buckling manufacture and detection mainly comprises the following procedures of material preparation, coating, baking, tabletting, punching, assembly and testing:
(1) And (3) batching, namely adding the anode material, the carbon black, the PVDF and a solvent NMP into a beaker according to a set proportion, stirring the mixture into uniform slurry by using a stirrer, and controlling the adding amount of the NMP to enable the fluidity of the slurry to be similar to that of glue.
(2) And (3) coating, namely uniformly coating the slurry on the aluminum foil by using a coater.
(3) And (3) baking, namely baking the coated pole piece in a vacuum oven at 120 ℃ for 2 hours.
(4) And (4) tabletting, namely cutting the edges of the baked pole pieces orderly, putting the cut pole pieces into a tabletting machine, and compacting the pole pieces under the pressure of 30 MPa.
(5) Punching, namely cutting 5-10 small wafers from the pressed pole piece in a cutting piece, simultaneously cutting 5-10 comparison samples of the foil which is not coated with the slurry, and weighing and then selecting 5 qualified small wafers.
(6) Assembling, namely performing assembly in a glove box filled with dry nitrogen, wherein the content of water vapor and oxygen is less than 0.1ppm, putting a qualified small round piece into the positive side of a buckling electricity shell with a gasket in advance, wherein the coating surface faces back to the positive electrode, then dripping 2 drops of electrolyte (lithium hexafluorophosphate) on the positive electrode piece, then putting a diaphragm and dripping 1-2 drops of electrolyte, then putting a pure lithium piece, the gasket and an elastic piece, finally putting the buckling electricity negative side shell, and sealing by using a sealing machine after the combination.
(7) And testing, namely calculating the content of the active substances according to the weight of the weighed small disks, and calculating the charge and discharge current required by charging according to the estimated gram volume of the active substances to perform charge and discharge testing.
Testing the 50-week cycle retention rate of the button cell at 45 ℃, 1.0-C charging, 1.5-C discharging and 3.0-4.5V test interval; testing the discharge capacity of the button cell at room temperature at 0.1C current and 2.8-4.45V; as shown in fig. 1 and 2, the 50-cycle retention rate of the battery obtained from the positive electrode material prepared in example 1 was 92.33% as can be seen from fig. 1 and 2; the first discharge capacity reaches 207.1mAh/g.
The 50-cycle retention rate of the battery obtained from the positive electrode material prepared in example 2 was 89.37%; the first discharge capacity reaches 205.6mAh/g.
The 50-cycle retention rate of the battery obtained from the positive electrode material prepared in example 3 was 91.64%; the first discharge capacity reaches 206.2mAh/g.
The 50-cycle retention rate of the battery obtained from the positive electrode material prepared in comparative example 1 was 88.66%; the first discharge capacity reaches 200.1mAh/g.
The preparation method of the modified ternary cathode material provided by the invention is simple, can realize large-scale production, and has a certain promotion effect on the development and application of lithium ion battery materials.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A modified ternary cathode material has a chemical formula:
LiNi x Co y Mn z M 1-x-y-z O 2 aaO of the formula I,
in the formula I, x is more than or equal to 0.5 and less than 1, y is more than or equal to 0.04 and less than 0.3, z is more than or equal to 0.05 and less than 0.4, and a is more than 0 and less than or equal to 0.1;
m is selected from one or more of Ti, mg, sr, la, zr, al and Y;
a is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
2. The modified ternary positive electrode material according to claim 1, wherein x is 0.5 to 0.8, y is 0.04 to 0.1, z is 0.1 to 0.3, and a is 0.01 to 0.05.
3. The modified ternary cathode material according to claim 1, wherein said M is selected from one or more of Zr, al, mg;
the A is selected from one or more of Co, li, ti, al, sr and La.
4. A method of preparing the modified ternary cathode material of claim 1, comprising:
carrying out first mixing on lithium salt, a nickel-cobalt-manganese compound and a first additive, and then carrying out first calcination to obtain a semi-finished product;
carrying out second mixing on the semi-finished product, a second additive and a third additive, and then carrying out second calcination to obtain a modified ternary cathode material;
the first additive is a compound containing M;
the second additive is a compound containing A;
the third additive is a compound containing M;
the M is selected from one or more of Ti, mg, sr, la, zr, al and Y;
the A is selected from one or more of Co, li, ti, mg, sr, la, zr, al and Y.
5. The method of claim 4, wherein the molar ratio of the lithium salt, the nickel cobalt manganese compound, and the first additive is (1-1.1): 1: (0 to 0.1);
the molar ratio of the semi-finished product to the second additive to the third additive is 1: (0-0.1): (0-0.1).
6. The method of claim 4, wherein the first mixing and the second mixing are performed independently in a high-speed mixer; the time of the first mixing and the second mixing is 0.1-1 h independently.
7. The method according to claim 4, characterized in that the first calcination is carried out in an oxidizing gas; the temperature of the first calcination is 800-1000 ℃; the first calcining time is 3-24 h;
the second calcination is carried out in an oxidizing gas; the temperature of the second calcination is 700-1000 ℃; the second calcination time is 3-24 h;
the oxidizing gas is selected from oxygen and/or air.
8. The method of claim 4, wherein the lithium salt is selected from one or more of lithium nitrate, lithium hydroxide, lithium carbonate, lithium citrate, lithium acetate;
the nickel-cobalt-manganese compound is nickel-cobalt-manganese hydroxide;
the M-containing compound and the A-containing compound are independently selected from one or more of oxide, hydroxide, carbonate and acid salt.
9. An electrode sheet, comprising: the modified ternary positive electrode material of claim 1; or the modified ternary cathode material prepared by the method of claim 4.
10. A battery, comprising: the electrode sheet of claim 9.
CN202211156423.3A 2022-09-22 2022-09-22 Modified ternary cathode material and preparation method and application thereof Pending CN115340135A (en)

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