CN116344765A - Preparation method of graphite-like carbon nitride coated lithium ion battery high-nickel ternary cathode material, product and application thereof - Google Patents

Preparation method of graphite-like carbon nitride coated lithium ion battery high-nickel ternary cathode material, product and application thereof Download PDF

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CN116344765A
CN116344765A CN202310310312.1A CN202310310312A CN116344765A CN 116344765 A CN116344765 A CN 116344765A CN 202310310312 A CN202310310312 A CN 202310310312A CN 116344765 A CN116344765 A CN 116344765A
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nickel ternary
graphite
carbon nitride
cathode material
ternary cathode
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佘圣贤
周扬帆
洪子健
黄玉辉
吴勇军
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 discloses a preparation method of a graphite-like phase carbon nitride coated high-nickel ternary positive electrode material, which comprises the following steps: (1) melamine is dissolved in deionized water to obtain a solution; (2) Adding a high-nickel ternary positive electrode material into the solution obtained in the step (1), and uniformly stirring to obtain a mixed solution; (3) Evaporating the mixed solution in the step (2) to dryness, and drying to obtain a melamine-coated high-nickel ternary anode material; (4) And (3) heating the high-nickel ternary cathode material obtained in the step (3) to obtain the graphite-phase carbon nitride coated high-nickel ternary cathode material. The invention also discloses a graphite-like phase carbon nitride coated high-nickel ternary anode material prepared by adopting the preparation method and application of the graphite-like phase carbon nitride coated high-nickel ternary anode material in a lithium ion battery. The graphite-like carbon nitride coated high-nickel ternary positive electrode material provided by the invention can effectively protect the high-nickel ternary positive electrode material, and the multiplying power performance of the high-nickel ternary positive electrode material is not obviously affected; the method is used for overcoming the defect of poor cycle life of the traditional high-nickel ternary cathode material.

Description

Preparation method of graphite-like carbon nitride coated lithium ion battery high-nickel ternary cathode material, product and application thereof
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a preparation method of a graphite-like carbon nitride coated lithium ion battery high-nickel ternary anode material, a product and application thereof.
Background
Since the industrial revolution, the problems of environmental pollution, warming in climate and the like caused by the large-scale use of fossil fuels are increasingly prominent, and new renewable clean energy sources replace limited and polluting fossil energy sources and have become the necessary trend of human society development. Transportation is a large scene of fossil energy consumption in modern society, and the rapid development of electric automobiles is changing in the field. As a power battery, a lithium ion battery with high energy storage density and materials thereof are key technologies.
The high nickel ternary positive electrode material is one of the positive electrode materials currently mainstream in lithium ion power batteries, and has been attracting attention because of its advantages such as high energy density and low cost. However, the high-nickel ternary cathode material has a certain problem in the practical use process. The first is that the cycling stability is still difficult to meet thousands of charge and discharge uses, and the thermal runaway problem caused by lattice oxygen release causes the cathode material to have potential safety hazards compared with other cathode materials.
The surface of the high-nickel ternary positive electrode material is coated with a layer of protective material, so that the contact between the high-nickel ternary positive electrode material and electrolyte can be isolated in the use process of the battery, the mechanical property of the positive electrode material is improved, and capacity degradation of the positive electrode material caused by volume change in the circulation process is inhibited. The selection of suitable coating materials is critical, and in order to achieve industrialization, the materials and techniques of coating also need to have good scale potential. For example, chinese patent publication No. CN108206279a discloses a high-nickel ternary positive electrode material for a lithium ion battery, where a lithium salt coating layer is coated on the surface of the high-nickel ternary positive electrode material for a lithium ion battery, and a stable lithium salt coating layer is formed by modifying residual lithium on the surface of the high-nickel material, so that the residual lithium on the surface can be removed and coated on the surface of the material to form a protective layer, and generation of lithium carbonate can be inhibited, and the crystal structure of the material is not damaged.
Thus, finding readily available, scalable coating materials and techniques is a major challenge in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a graphite-like phase carbon nitride coated high-nickel ternary positive electrode material, the prepared graphite-like phase carbon nitride coated high-nickel ternary positive electrode material and application of the graphite-like phase carbon nitride coated high-nickel ternary positive electrode material in a lithium ion battery; the graphite-like phase carbon nitride coated high-nickel ternary positive electrode material provided by the invention has good cycle performance.
The invention provides the following technical scheme:
the preparation method of the graphite-like phase carbon nitride coated high-nickel ternary cathode material comprises the following steps of:
(1) Dissolving melamine in deionized water to obtain a solution;
(2) Adding a high-nickel ternary positive electrode material into the solution obtained in the step (1), and uniformly stirring to obtain a mixed solution;
(3) Evaporating the mixed solution in the step (2) to dryness, and drying to obtain a melamine-coated high-nickel ternary anode material;
(4) And (3) heating the melamine-coated high-nickel ternary cathode material obtained in the step (3) to obtain the graphite-phase carbon nitride-coated high-nickel ternary cathode material.
The preparation method provided by the invention adopts melamine with low cost and easy acquisition as a precursor, and the melamine is pre-coated on the high-nickel ternary positive electrode material by a solution dissolving and evaporation precipitation method, and the melamine is heated at a certain temperature to obtain an improved final product: and the graphite-like phase carbon nitride coats the high-nickel ternary anode material. The graphite-like phase carbon nitride coated high-nickel ternary cathode material obtained by the preparation method provided by the invention can effectively protect the high-nickel ternary cathode material, and the multiplying power performance of the high-nickel ternary cathode material is not obviously affected; the method is used for overcoming the defect of poor cycle life of the traditional high-nickel ternary cathode material.
Preferably, in step (1), the temperature of dissolution in deionized water is 60 to 80 ℃.
Preferably, the mass of the melamine added in the step (1) is 2.5-10% of the mass of the high-nickel ternary cathode material added in the step (2); the chemical general formula of the high-nickel ternary positive electrode material is LiNi x Co y Mn 1-x-y O 2 Wherein, 0.6<x<1，0<y<0.2. According to the invention, the thickness of the coating layer can be controlled by adjusting the proportion of the melamine and the high-nickel ternary cathode material, so that the electrochemical performance of the modified high-nickel ternary cathode material can be regulated and controlled.
It is further preferred that the mass of melamine added in step (1) is 5% of the mass of the high nickel ternary cathode material added in step (2). The electrochemical performance of the high-nickel ternary positive electrode material under the condition is better.
In the step (3), the temperature of evaporating the solution to dryness is 70-90 ℃, so that the solution environment of the high-nickel ternary anode material is not damaged.
In the step (4), the heating rate is 1-3 ℃/min, and the temperature is heated to 550-600 ℃ to enable the melamine coated on the surface to react to generate graphite-like carbon nitride.
Preferably, the heating in step (4) is protected with an oxygen atmosphere.
The invention also provides the graphite-like phase carbon nitride coated high-nickel ternary anode material prepared by the preparation method. The graphite-like phase carbon nitride coated high-nickel ternary anode material provided by the invention has the advantages of high specific capacity and long cycle life.
The invention also provides application of the graphite-like phase carbon nitride coated high-nickel ternary cathode material in a lithium ion battery.
Compared with the prior art, the invention has the obvious advantages and beneficial effects as follows:
(1) The precursor of the coating material graphite-like carbon nitride adopts melamine, which is a chemical raw material with low cost and easy acquisition. The solution precipitation method adopted by the method is simple and can be scaled, and the industrialized application is easy to realize.
(2) The graphite-like carbon nitride is an intrinsic semiconductor, has good electron conductivity, and simultaneously has a graphite-like structure providing a larger interlayer spacing, can be used as a rapid transmission channel of lithium ions, can be used as a coating layer to provide a protection effect, improve the cycle performance, and can not adversely affect the multiplying power performance of the high-nickel ternary positive electrode material.
(3) According to the invention, the thickness of the coating layer can be controlled by adjusting the proportion of the melamine and the high-nickel ternary cathode material, so that the electrochemical performance of the modified high-nickel ternary cathode material can be regulated and controlled.
Drawings
FIG. 1 shows a high nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Scanning electron microscope photographs before and after coating: (a) a starting material; (b) 5% by mass of melamine; n-energy spectrum of (c, d) b.
Fig. 2 is a graph of specific discharge capacity of a lithium battery in cyclic test, wherein the graphite-like phase carbon nitride coated high-nickel ternary positive electrode material is obtained by 5% of melamine by mass fraction and is used as a positive electrode for positive electrode assembly.
Fig. 3 is a first-turn charge-discharge electrogram of the lithium battery assembled by taking a graphite-like phase carbon nitride coated high-nickel ternary positive electrode material obtained by 5% of melamine by mass fraction as a positive electrode.
Fig. 4 is a graph of capacity test of a graphite-like phase carbon nitride coated high-nickel ternary positive electrode material obtained by 5% melamine by mass fraction as a positive electrode assembly for lithium batteries at different charge and discharge currents.
Detailed Description
The graphite-like phase carbon nitride coated high-nickel ternary positive electrode material is beneficial to optimizing the overall performance of the positive electrode, and other conditions in the preparation process are preferably obtained. The present invention will be described in further detail with reference to the following examples and the accompanying drawings. The examples and descriptions of the present invention are provided herein for the purpose of explaining the present invention, but are not intended to be limiting.
Example 1
The preparation method of the graphite-like phase carbon nitride coated high-nickel ternary cathode material provided by the embodiment specifically comprises the following steps:
(1) Melamine and high nickel ternary anode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The mass ratio is 2.5: weighing 100; melamine was dissolved in deionized water at 60 ℃ using 100ml of deionized water as solvent per 10g of melamine.
(2) Adding the high-nickel ternary cathode material into the solution, stirring, and evaporating the solution in a water bath at 85 ℃ to dryness, so that melamine is separated out on the surface of the high-nickel ternary cathode material. And transferring the pre-coated high-nickel ternary cathode material into a vacuum oven at 80 ℃ for drying for 12 hours.
(3) The obtained pre-coated high-nickel ternary cathode material is placed in a crucible, heated to 550 ℃ in an oxygen-protected tube furnace at a speed of 2 ℃/min, and then kept at 550 ℃ for 4 hours.
Wherein, the original LiNi in the embodiment 0.8 Co 0.1 Mn 0.1 O 2 The scanning electron microscope of (a) is shown in fig. 1.
Example 2
The preparation method of the graphite-like carbon nitride coated high-nickel ternary cathode material provided by the embodiment is except that in the step (1), melamine and high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The mass ratio is 5:100, the rest of the procedure is the same as in example 1.
The graphite-like carbon nitride coated high-nickel ternary cathode material (g-C) 3 N 4 Scanning electron microscope images of @ CM 811) are shown in fig. 1 (b), and energy spectra are shown in fig. 1 (c) and fig. 1 (d).
Example 3
The preparation method of the graphite-like carbon nitride coated high-nickel ternary cathode material provided by the embodiment is except that in the step (1), melamine and high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The mass ratio is 7.5:100, the rest of the procedure is the same as in example 1.
Example 4
The preparation method of the graphite-like carbon nitride coated high-nickel ternary cathode material provided by the embodiment is except that in the step (1), melamine and high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 The mass ratio is 10:100, the rest of the procedure is the same as in example 1.
Application example
The graphite-like carbon nitride coated high-nickel ternary cathode material prepared in example 2 is used as an electrode, and 1M LiPF 6 The long cycle capacity at 1C for lithium batteries assembled with the electrolyte solution in the EC-dmc=3:7 volume ratio is shown in fig. 2, the first charge-discharge curve is shown in fig. 3, and the capacity at different current densities is shown in fig. 4.

Claims (6)

1. The preparation method of the graphite-like phase carbon nitride coated high-nickel ternary cathode material is characterized by comprising the following steps of:
(1) Dissolving melamine in deionized water to obtain a solution;
(2) Adding a high-nickel ternary positive electrode material into the solution obtained in the step (1), and uniformly stirring to obtain a mixed solution;
(3) Evaporating the mixed solution in the step (2) to dryness, and drying to obtain a melamine-coated high-nickel ternary anode material;
(4) And (3) heating the melamine-coated high-nickel ternary cathode material obtained in the step (3) to obtain the graphite-phase carbon nitride-coated high-nickel ternary cathode material.
2. The method for preparing the graphite-like phase carbon nitride coated high-nickel ternary cathode material according to claim 1, wherein the mass of melamine added in the step (1) is 2.5% -10% of the mass of the high-nickel ternary cathode material added in the step (2), and the chemical formula of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein, 0.6<x<1，0<y<0.2。
3. The method for preparing a graphite-like phase carbon nitride coated high-nickel ternary cathode material with good cycle performance according to claim 1 or 2, wherein in the step (3), the temperature of evaporating the solution to dryness is 70-90 ℃.
4. The method for preparing a graphite-like phase carbon nitride coated high-nickel ternary cathode material according to claim 1, wherein in the step (4), the heating rate is 1-3 ℃/min, and the temperature is heated to 550-600 ℃.
5. A graphite-like phase carbon nitride coated high nickel ternary cathode material obtained according to the preparation method of any one of claims 1 to 4.
6. Use of the graphite-like phase carbon nitride coated high-nickel ternary cathode material according to claim 5 in a lithium ion battery.
CN202310310312.1A 2023-03-24 2023-03-24 Preparation method of graphite-like carbon nitride coated lithium ion battery high-nickel ternary cathode material, product and application thereof Pending CN116344765A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117712366A (en) * 2024-02-05 2024-03-15 济南中瑞泰新材料科技有限公司 Preparation method of coated electrode material, coated electrode material and lithium ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117712366A (en) * 2024-02-05 2024-03-15 济南中瑞泰新材料科技有限公司 Preparation method of coated electrode material, coated electrode material and lithium ion battery

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