CN115000382B - Nickel-rich lithium ion positive electrode material with surface nitrogen modified, preparation method thereof and lithium ion battery - Google Patents

Nickel-rich lithium ion positive electrode material with surface nitrogen modified, preparation method thereof and lithium ion battery Download PDF

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CN115000382B
CN115000382B CN202210745444.2A CN202210745444A CN115000382B CN 115000382 B CN115000382 B CN 115000382B CN 202210745444 A CN202210745444 A CN 202210745444A CN 115000382 B CN115000382 B CN 115000382B
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nickel
lithium ion
rich
positive electrode
electrode material
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CN115000382A (en
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王克伟
张伟
杨李娜
哈钧川
赵岩
熊家祥
王海峰
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Shandong Aia Kesimao New Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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

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Abstract

The present disclosure relates to a method for preparing a surface nitrogen modified nickel-rich lithium ion positive electrode material, comprising the steps of: (1) Mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion anode material; (2) And nitriding the nickel-rich lithium ion positive electrode material in the presence of ammonia gas at 480-540 ℃ for 0.5-3 h. According to the preparation method, a small amount of nitrogen elements can be doped on the surface of the material through low-temperature nitriding treatment under an ammonia gas condition, so that the content of unstable active oxygen on the surface layer of the material can be reduced, the oxygen losing phenomenon of the battery is reduced, and the explosion caused by thermal runaway of the battery is avoided; and secondly, the ammonia gas can reduce oxygen atoms in nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies not only can form an important lithium ion diffusion channel to improve the capacity of the battery, but also can adsorb active oxygen to reduce the oxygen loss phenomenon, thereby improving the cycle performance and the safety performance of the battery.

Description

Nickel-rich lithium ion positive electrode material with surface nitrogen modified, preparation method thereof and lithium ion battery
Technical Field
The disclosure relates to the field of preparation of lithium ion battery cathode materials, in particular to a nickel-rich lithium ion cathode material with surface nitrogen modification, a preparation method thereof and a lithium ion battery.
Background
With the widespread use of intermittent renewable energy sources such as wind energy, solar energy, geothermal energy, tidal energy, and the like, the demand for large-sized energy storage power stations is increasing. The rechargeable Lithium Ion Batteries (LIBs) have the advantages of high energy density, high conversion efficiency, quick reaction, long cycle life and the like, and have wide prospects in large-scale energy storage. The electrochemical performance of the positive electrode material is critical for lithium ion battery applications because the positive electrode material has a relatively low capacity and poor cycle performance compared to the graphite negative electrode material (372 mAh g -1), limiting the application of the material to some extent. Most of the existing cathode materials are still insufficient to meet the increasing energy demand due to the relatively poor energy density. The development of nickel-rich lithium ion batteries with high capacity and long life is considered as a viable strategy to solve the problems of "mileage anxiety" and "short life" of electric vehicles. In practical application, lithium ion battery can produce a large amount of oxygen in continuous charge and discharge use, and oxygen can react with electrolyte, causes battery bulk capacity and cycle performance to drop, further leads to battery thermal runaway, causes the potential safety hazard.
Disclosure of Invention
The invention aims to provide a nickel-rich lithium ion positive electrode material with surface nitrogen modified, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, a first aspect of the present disclosure provides a method for preparing a surface nitrogen-modified nickel-rich lithium ion positive electrode material, the method comprising the steps of:
(1) Mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion anode material;
(2) And nitriding the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitriding temperature is 480-540 ℃, and the heat preservation time is 0.5-3 h.
Optionally, in the step (2), the nitriding treatment is performed under pure ammonia gas, and the heat preservation time of the nitriding treatment is 0.5-1.5 h.
Optionally, in step (1), the molar ratio of the nickel-rich precursor to the lithium source is (1.005-1.06): 1, preferably (1.01 to 1.04): 1, more preferably (1.01 to 1.025): 1.
Optionally, in the step (1), the sintering is a sectional type sintering, the sectional type sintering comprises a first sintering and a second sintering, the temperature of the first sintering is 400-600 ℃, preferably 500-550 ℃, and the heat preservation time is 5-8 h; the temperature of the second sintering is 750-850 ℃, and the heat preservation time is 10-15 h; the sintering is performed under pure oxygen atmosphere.
Optionally, the method further comprises the step of crushing and sieving the nickel-rich lithium ion positive electrode material before the nitriding treatment, wherein the particle size of the sieved material is d50=5-6 μm.
Optionally, the chemical formula of the nickel-rich precursor is shown as formula (I): ni xCoyMnz(OH)2 (I), wherein x is more than or equal to 0.5 and less than or equal to 0.95, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x+y+z=1.
Optionally, the lithium source is selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide, and lithium nitrate.
Optionally, the chemical formula of the nickel-rich lithium ion positive electrode material is shown as a formula (II): liNi xCoyMnzO2 (II), wherein 0.5.ltoreq.x.ltoreq.0.95, 0.ltoreq.y.ltoreq.0.5, 0.ltoreq.z.ltoreq.0.5, x+y+z=1.
The second aspect of the present disclosure provides a surface nitrogen-modified nickel-rich lithium ion cathode material prepared by the preparation method of the first aspect of the present disclosure, wherein the content of nitrogen element doped on the surface of the surface nitrogen-modified nickel-rich lithium ion cathode material is 0.1 to 0.5 wt%, preferably 0.1 to 0.3 wt%, based on the total weight of the surface nitrogen-modified nickel-rich lithium ion cathode material.
A third aspect of the present disclosure provides a lithium ion battery comprising the surface nitrogen modified nickel-rich lithium ion positive electrode material of the second aspect of the present disclosure.
Through the technical scheme, the preparation method provided by the disclosure can be used for doping a small amount of nitrogen elements on the surface of the material through low-temperature nitriding treatment under the ammonia gas condition, the nitrogen elements can reduce the content of unstable active oxygen on the surface layer of the material, the oxygen loss phenomenon of the battery is reduced, and the explosion caused by thermal runaway of the battery is avoided; and secondly, the ammonia gas can reduce oxygen atoms in nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies not only can form an important lithium ion diffusion channel to improve the capacity of the battery, but also can adsorb active oxygen to reduce the oxygen loss phenomenon, thereby improving the cycle performance and the safety performance of the battery.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a first charge-discharge specific capacity at 0.2C of a surface nitrogen-modified nickel-rich lithium ion positive electrode material 1 prepared in example 1 of the present disclosure;
FIG. 2 is a graph of the cycling performance at 1.0C of the surface nitrogen modified nickel-rich lithium ion positive electrode material 1 prepared in example 1 of the present disclosure;
FIG. 3 is an X-ray energy spectrum of a surface nitrogen-modified nickel-rich lithium ion cathode material 1 prepared in example 1 of the present disclosure;
Fig. 4 is an XRD pattern of the surface nitrogen-modified nickel-rich lithium ion positive electrode material prepared in example 1 of the present disclosure before and after nitriding treatment.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The first aspect of the present disclosure provides a method for preparing a surface nitrogen-modified nickel-rich lithium ion positive electrode material, the method comprising the steps of:
(1) Mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion anode material;
(2) And nitriding the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitriding temperature is 480-540 ℃, and the heat preservation time is 0.5-3 h.
According to the preparation method provided by the disclosure, a small amount of nitrogen element can be doped on the surface of the material through low-temperature nitriding treatment under an ammonia gas condition to form nitrogen doping (namely, the nitrogen element occupies part of the oxygen element), the nitrogen doping can reduce the content of unstable active oxygen on the surface layer of the material, the oxygen losing phenomenon of the battery is reduced, and the thermal runaway of the battery is avoided so as to cause explosion; and secondly, the ammonia gas can reduce oxygen atoms in nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies not only can form an important lithium ion diffusion channel to improve the capacity of the battery, but also can adsorb active oxygen to reduce the oxygen loss phenomenon, thereby improving the cycle performance and the safety performance of the battery.
In one embodiment of the present disclosure, in the step (2), the nitriding treatment is performed under pure ammonia gas, and the heat preservation time of the nitriding treatment is 0.5 to 1.5 hours. In the embodiment, the nitrogen element is doped on the surface of the positive electrode material by selecting the optimal nitriding heat preservation time, so that the cycle performance and the safety performance of the material are improved.
In one embodiment of the present disclosure, in step (1), the molar ratio of the nickel-rich precursor to the lithium source is (1.005-1.06): 1, preferably (1.01 to 1.04): 1, more preferably (1.01 to 1.025): 1. in the above embodiment, the reaction is performed by selecting the raw materials in the preferable ratio, which is advantageous to improve the stability of the nickel-rich lithium ion positive electrode material.
In one embodiment of the present disclosure, in step (1), the sintering is a sectional sintering, the sectional sintering includes a first sintering and a second sintering, the temperature of the first sintering is 400-600 ℃, preferably 500-550 ℃, and the heat preservation time is 5-8 hours; the temperature of the second sintering is 750-850 ℃, and the heat preservation time is 10-15 h; the sintering is performed under pure oxygen atmosphere. In the embodiment, the lithium source can be continuously diffused into the nickel-rich precursor by selecting the preferred sectional sintering, so that the nickel-rich lithium ion positive electrode material with relatively stable thermodynamics is formed, and the cycle performance and the multiplying power performance of the nickel-rich lithium ion positive electrode material are improved.
In one embodiment of the present disclosure, the method further comprises, before the nitriding treatment, crushing and sieving the nickel-rich lithium ion positive electrode material, wherein the sieved material has a particle size d50=5 to 6 μm. In the above embodiment, the preferred crushing and sieving operation is adopted, so that the sintered agglomerate material is dispersed, and large particles are removed through sieving, and the contact area and the reaction site of nitriding treatment are increased.
In one embodiment of the present disclosure, the nickel-rich precursor has a chemical formula as shown in formula (i): ni xCoyMnz(OH)2 (I), wherein x is more than or equal to 0.5 and less than or equal to 0.95, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and x+y+z=1.
In one embodiment of the present disclosure, the lithium source is selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide, and lithium nitrate. In the above embodiment, by selecting a preferable lithium source, a nickel-rich lithium ion positive electrode material having a stable structure can be formed, and the reversible discharge specific capacity of the battery can be improved.
In one embodiment of the present disclosure, the nickel-rich lithium ion positive electrode material has a chemical formula as shown in formula (II): liNi xCoyMnzO2 (II), wherein 0.5.ltoreq.x.ltoreq.0.95, 0.ltoreq.y.ltoreq.0.5, 0.ltoreq.z.ltoreq.0.5, x+y+z=1. In the embodiment, the nickel-rich lithium ion positive electrode material with a preferred structure is selected for nitriding treatment, so that nitrogen element is doped on the surface of the material, a large number of oxygen vacancies are generated, the oxygen vacancies form important lithium ion diffusion channels, and the capacity and the cycle performance of the battery are improved.
The second aspect of the present disclosure provides a surface nitrogen-modified nickel-rich lithium ion cathode material prepared by the preparation method of the first aspect of the present disclosure, wherein the content of nitrogen element doped on the surface of the surface nitrogen-modified nickel-rich lithium ion cathode material is 0.1 to 0.5 wt%, preferably 0.1 to 0.3 wt%, based on the total weight of the surface nitrogen-modified nickel-rich lithium ion cathode material.
A third aspect of the present disclosure provides a lithium ion battery comprising the surface nitrogen modified nickel-rich lithium ion positive electrode material of the second aspect of the present disclosure.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
In the following examples and comparative examples, the raw materials used were all commercially available products unless otherwise specified.
In the following examples and comparative examples, specific test methods are as follows:
the particle size testing method is a laser particle size analyzer, and the instrument model is Mastersizer 3000;
The method for testing the nitrogen content is an element analyzer, and the model of the instrument is VariouELcube;
The electrochemical cycle performance test instrument is a blue-ray test system.
Example 1
(1) The nickel-rich precursor (chemical formula: ni 0.65Co0.15Mn0.2(OH)2) was reacted with LiOH H 2 O at 1.015:1, heating to 500 ℃ in a box-type furnace for 6h after uniform mixing, then heating to 750 ℃ for 12h, naturally cooling to room temperature, and carrying out the whole process in pure oxygen atmosphere;
(2) Crushing and sieving the obtained nickel-rich lithium ion positive electrode material (with a chemical formula of LiNi 0.65Co0.15Mn0.2O2) until the particle size D50=5 mu m, putting the sieved material into a tube furnace for nitriding treatment, wherein the nitriding treatment temperature is 500 ℃, the heat preservation time is 1h, the process is carried out under the condition of pure ammonia, and then naturally cooling to room temperature to obtain the nickel-rich lithium ion positive electrode material 1 with the surface nitrogen modified, and the initial charge-discharge specific capacity, the cycle performance, the X-ray energy spectrum and the XRD of the nickel-rich lithium ion positive electrode material are tested, wherein the results are shown in figures 1-4:
From the figures 1-2, the nickel-enriched lithium ion positive electrode material 1 with the surface modified by nitrogen has higher discharge specific capacity at 0.2C and better cycle stability at 1.0C;
as can be seen from fig. 3, the surface of the material contains a large amount of oxygen elements and a small amount of nitrogen elements, which means that a part of nitrogen elements are introduced after nitriding treatment;
As can be seen from fig. 4, the diffraction peak of the positive electrode material 1 is not changed, and no impurity peak appears before and after nitriding, which indicates that the matrix structure is not changed, and the nitriding process is only to dope the material.
Example 2
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 1.5h, and the nickel-enriched lithium ion anode material 2 with the surface nitrogen modified is obtained.
Example 3
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 0.5h, and the nickel-rich lithium ion anode material 3 with the surface nitrogen modified is obtained.
Example 4
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 0.3h, and the nickel-enriched lithium ion anode material 4 with the surface nitrogen modified is obtained.
Example 5
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 0.8h, and the nickel-rich lithium ion anode material 5 with the surface nitrogen modified is obtained.
Example 6
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 1.3h, and the nickel-enriched lithium ion anode material 6 with the surface nitrogen modified is obtained.
Example 7
The procedure of example 1 was used, with the only difference that: mixing a nickel-rich precursor with LiOH.H 2 O at a ratio of 1.025: and (3) mixing the materials according to the molar ratio of 1 to obtain the nickel-enriched lithium ion positive electrode material 7 with the surface modified by nitrogen.
Example 8
The procedure of example 1 was used, with the only difference that: mixing a nickel-rich precursor with LiOH.H 2 O at a ratio of 1.025: and mixing the materials according to the molar ratio of 1, wherein the nitriding treatment temperature is 540 ℃, and the heat preservation time is 0.5h, so as to obtain the nickel-enriched lithium ion positive electrode material 8 with the surface modified by nitrogen.
Example 9
The procedure of example 1 was used, with the only difference that: mixing a nickel-rich precursor with LiOH.H 2 O at a ratio of 1.025: and mixing the materials according to the molar ratio of 1, wherein the nitriding treatment temperature is 540 ℃, and the heat preservation time is 1h, so as to obtain the nickel-enriched lithium ion positive electrode material 9 with the surface modified by nitrogen.
Example 10
The procedure of example 1 was used, with the only difference that: and replacing the nickel-rich precursor with the chemical formula of Ni 0.65Co0.15Mn0.2(OH)2 with Ni 0.9Co0.05Mn0.05(OH)2 with the same weight to obtain the nickel-rich lithium ion positive electrode material, nitriding the nickel-rich lithium ion positive electrode material with the chemical formula of LiNi 0.9Co0.05Mn0.05O2 under pure ammonia gas, wherein the nitriding temperature is 480 ℃, and the heat preservation time is 0.5h to obtain the nickel-rich lithium ion positive electrode material 10 with the surface nitrogen modified.
Example 11
The procedure of example 1 was used, with the only difference that: the molar ratio of the nickel-rich precursor to the lithium source was 1.1:1.
Comparative example 1
The procedure of example 1 was used, with the only difference that: no nitriding treatment was performed, and comparative material 1 was obtained.
Comparative example 2
The procedure of example 1 was used, with the only difference that: the heat preservation time of the nitriding treatment is 5 hours, and the comparative material 2 is obtained.
Comparative example 3
The procedure of example 1 was used, with the only difference that: the nitriding temperature was 570℃to obtain comparative material 3.
Comparative example 4
The procedure of example 10 was used, with the only difference that: no nitriding treatment was performed, and comparative material 4 was obtained.
Test case
The electrochemical performance test was as follows: the materials prepared by the examples and the comparative examples, the conductive agent acetylene black and the binder PVDF are mixed according to the mass ratio of 90:5:5, adding NMP (N-methyl-pyrrolidone) and fully and uniformly mixing to obtain slurry with certain viscosity; uniformly coating the obtained slurry on an aluminum foil, drying for 2 hours at the temperature of 90 ℃ by air blast, tabletting the aluminum foil by a tabletting machine after the drying is completed, punching the tabletting pole piece into a circular electrode piece with the diameter of 14mm, and drying for 2 hours at the temperature of 120 ℃ in a vacuum drying oven; in a glove box protected by argon, a Celgard 2400 film is used as a diaphragm, a metal lithium sheet is used as a negative electrode, and 1mol L -1 of LiPF6/EC+DEC+DMC (volume ratio is 1:1:1) is used as electrolyte to assemble the button cell. And (3) carrying out charge and discharge test on the assembled battery above a blue electric test, wherein the temperature is 25+/-1 ℃, and the test voltage range is 3.0-4.3V.
Examples 1-11 nickel-rich lithium ion positive electrode materials with surface nitrogen modification prepared by the preparation method disclosed by the disclosure have higher specific discharge capacity at 1.0C and better capacity retention rate after being cycled for 100 times at 1.0C; and comparative examples 1 to 4 do not adopt the preparation method of the present disclosure, the capacity retention rate of the obtained positive electrode material is low, and the cycle stability is poor. The preparation methods provided in examples 1 to 11 of the present disclosure are therefore more excellent than comparative examples 1 to 4.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the embodiments described above, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. The preparation method of the nickel-rich lithium ion positive electrode material with the surface modified by nitrogen is characterized by comprising the following steps of:
(1) Mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion anode material; the chemical formula of the nickel-rich precursor is shown as the formula (I): ni xCoyMnz(OH)2 (I), wherein 0.5.ltoreq.x <0.9, 0.05.ltoreq.y.ltoreq.0.5, 0.05.ltoreq.z.ltoreq.0.5, x+y+z=1;
the molar ratio of the nickel-rich precursor to the lithium source is (1.005-1.06): 1, a step of; the sintering is sectional sintering, the sectional sintering comprises a first sintering and a second sintering, the temperature of the first sintering is 400-600 ℃, and the heat preservation time is 5-8 hours; the temperature of the second sintering is 750-850 ℃, and the heat preservation time is 10-15 h;
(2) Nitriding the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitriding temperature is 480-540 ℃, and the heat preservation time is 0.5-3 h;
The method further comprises the steps of crushing and sieving the nickel-rich lithium ion positive electrode material before nitriding treatment, wherein the particle size of the sieved material is D50=5-6 mu m.
2. The preparation method according to claim 1, wherein in the step (2), the nitriding treatment is performed under pure ammonia gas, and the heat preservation time of the nitriding treatment is 0.5-1.5 h.
3. The method of claim 1, wherein in step (1), the molar ratio of the nickel-rich precursor to the lithium source is (1.01-1.04): 1.
4. The method of claim 3, wherein the molar ratio of the nickel-rich precursor to the lithium source is (1.01-1.025): 1.
5. The method according to claim 1, wherein in the step (1), the temperature of the first sintering is 500-550 ℃, and the sintering is performed under pure oxygen atmosphere.
6. The method according to claim 1, wherein the lithium source is one or more selected from the group consisting of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide, and lithium nitrate.
7. The method of claim 1, wherein the nickel-rich lithium ion positive electrode material has a chemical formula as shown in formula (II): liNi xCoyMnzO2 (II), wherein 0.5-0.9, 0.05-0.5, x+y+z=1.
8. The surface nitrogen-modified nickel-rich lithium ion cathode material prepared by the preparation method according to any one of claims 1-7, wherein the surface nitrogen-modified nickel-rich lithium ion cathode material has a nitrogen element content of 0.1-0.5 wt% based on the total weight of the surface nitrogen-modified nickel-rich lithium ion cathode material.
9. The surface nitrogen-modified nickel-rich lithium ion positive electrode material according to claim 8, wherein the surface nitrogen-modified nickel-rich lithium ion positive electrode material has a surface doped nitrogen element content of 0.1-0.3 wt%.
10. A lithium ion battery comprising the surface nitrogen-modified nickel-rich lithium ion positive electrode material of any one of claims 8-9.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0845437A2 (en) * 1996-09-12 1998-06-03 Dowa Mining Co., Ltd. Positive electrode active material for nonaqueous secondary cells and a process for producing said active material
JP2008300188A (en) * 2007-05-31 2008-12-11 Fuji Heavy Ind Ltd Manufacturing method of electrode material, electrode material, and non-aqueous system lithium-ion secondary battery
CN106711421A (en) * 2017-01-08 2017-05-24 合肥国轩高科动力能源有限公司 Lithium ion anode material coated with metal nitride on surface and preparation method thereof
KR20170105873A (en) * 2016-03-10 2017-09-20 삼성에스디아이 주식회사 Positive active material composition for lithium secondary battery, and positive electrode and lithium secondary battery including the same
CN109473656A (en) * 2018-11-27 2019-03-15 深圳大学 A kind of nitridation lithium titanate/nitrided silicon dioxide titanium combination electrode material and preparation method thereof
CN110104677A (en) * 2019-04-01 2019-08-09 桂林电子科技大学 Composite titanic acid lithium material and the preparation method and application thereof
CN111847400A (en) * 2020-05-14 2020-10-30 清华大学 Method for preparing non-noble metal hydrogen fuel cell cathode material
CN111908519A (en) * 2020-07-24 2020-11-10 四川长虹电器股份有限公司 High-capacity nickel-rich precursor, positive electrode material and preparation method thereof
WO2021042981A1 (en) * 2019-09-02 2021-03-11 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method therefor, positive electrode plate, lithium ion secondary battery, and battery module, battery pack and device comprising lithium ion secondary battery
CN113636606A (en) * 2021-07-13 2021-11-12 北京科技大学 Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0845437A2 (en) * 1996-09-12 1998-06-03 Dowa Mining Co., Ltd. Positive electrode active material for nonaqueous secondary cells and a process for producing said active material
JP2008300188A (en) * 2007-05-31 2008-12-11 Fuji Heavy Ind Ltd Manufacturing method of electrode material, electrode material, and non-aqueous system lithium-ion secondary battery
KR20170105873A (en) * 2016-03-10 2017-09-20 삼성에스디아이 주식회사 Positive active material composition for lithium secondary battery, and positive electrode and lithium secondary battery including the same
CN106711421A (en) * 2017-01-08 2017-05-24 合肥国轩高科动力能源有限公司 Lithium ion anode material coated with metal nitride on surface and preparation method thereof
CN109473656A (en) * 2018-11-27 2019-03-15 深圳大学 A kind of nitridation lithium titanate/nitrided silicon dioxide titanium combination electrode material and preparation method thereof
CN110104677A (en) * 2019-04-01 2019-08-09 桂林电子科技大学 Composite titanic acid lithium material and the preparation method and application thereof
WO2021042981A1 (en) * 2019-09-02 2021-03-11 宁德时代新能源科技股份有限公司 Positive electrode active material, preparation method therefor, positive electrode plate, lithium ion secondary battery, and battery module, battery pack and device comprising lithium ion secondary battery
CN111847400A (en) * 2020-05-14 2020-10-30 清华大学 Method for preparing non-noble metal hydrogen fuel cell cathode material
CN111908519A (en) * 2020-07-24 2020-11-10 四川长虹电器股份有限公司 High-capacity nickel-rich precursor, positive electrode material and preparation method thereof
CN113636606A (en) * 2021-07-13 2021-11-12 北京科技大学 Preparation method and application of nickel-rich cobalt-free single crystal cathode material of lithium ion battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Nitrogen-doped carbon coated LiNi0.6Co0.2Mn0.2O2 cathode with enhanced electrochemical performance for Li-Ion batteries;Chen Xian等;《ELECTROCHIMICA ACTA》;第526-533页 *
基于氮掺杂碳改性的高性能锂离子电池正负极材料;陈仙;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;第B020-919页 *

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