CN115000382A - Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery - Google Patents

Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN115000382A
CN115000382A CN202210745444.2A CN202210745444A CN115000382A CN 115000382 A CN115000382 A CN 115000382A CN 202210745444 A CN202210745444 A CN 202210745444A CN 115000382 A CN115000382 A CN 115000382A
Authority
CN
China
Prior art keywords
lithium ion
nickel
rich
equal
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210745444.2A
Other languages
Chinese (zh)
Inventor
王克伟
张伟
杨李娜
哈钧川
赵岩
熊家祥
王海峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Aia Kesimao New Materials Co ltd
Original Assignee
Shandong Aia Kesimao New Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Aia Kesimao New Materials Co ltd filed Critical Shandong Aia Kesimao New Materials Co ltd
Priority to CN202210745444.2A priority Critical patent/CN115000382A/en
Publication of CN115000382A publication Critical patent/CN115000382A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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

Abstract

The disclosure relates to a preparation method of a surface nitrogen modified nickel-rich lithium ion cathode material, which comprises the following steps: (1) mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion positive electrode material; (2) and carrying out nitridation treatment on the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitridation treatment temperature is 480-540 ℃, and the heat preservation time is 0.5-3 h. According to the preparation method, a small amount of nitrogen can be doped on the surface of the material through low-temperature nitriding treatment under the condition of ammonia gas, the content of unstable active oxygen on the surface layer of the material can be reduced by the nitrogen, 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 the nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies can form an important lithium ion diffusion channel to improve the capacity of the battery, and can also adsorb active oxygen to reduce the phenomenon of oxygen loss, thereby improving the cycle performance and the safety performance of the battery.

Description

Surface nitrogen modified nickel-rich lithium ion positive electrode material, 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 surface nitrogen modified nickel-rich lithium ion cathode material, a preparation method thereof and a lithium ion battery.
Background
With the widespread use of intermittent renewable energy sources such as wind, solar, geothermal, tidal energy, etc., the demand for large energy storage power stations is increasing. Rechargeable Lithium Ion Batteries (LIBs) have the advantages of high energy density, high conversion efficiency, fast 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 of the graphite negative electrode material (372mAh g) -1 ) Compared with the prior art, the positive electrode material has relatively low capacity and poor cycle performance, and the application of the material is limited to a certain extent. Due to the relatively poor energy density, most of the existing cathode materials are still insufficient to meet the increasing energy demand. 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" in electric vehicles. In practical application, a large amount of oxygen is generated in the continuous charging and discharging use process of the lithium ion battery, and the oxygen reacts with the electrolyte, so that the overall capacity and the cycle performance of the battery are reduced, the thermal runaway of the battery is further caused, and potential safety hazards are caused.
Disclosure of Invention
The purpose of the disclosure is to provide a surface nitrogen modified nickel-rich lithium ion positive electrode material, 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 cathode material, the method comprising the following steps:
(1) mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion positive electrode material;
(2) and nitriding the nickel-rich lithium ion anode material in the presence of ammonia gas at 480-540 ℃ for 0.5-3 h.
Optionally, in the step (2), the nitriding treatment is performed under the condition of pure ammonia gas, and the heat preservation time of the nitriding treatment is 0.5-1.5 hours.
Optionally, in the step (1), the molar ratio of the nickel-rich precursor to the lithium source is (1.005-1.06): 1, preferably (1.01-1.04): 1, more preferably (1.01 to 1.025): 1.
optionally, in the step (1), the sintering is sectional sintering, the sectional sintering comprises first sintering and second sintering, the temperature of the first sintering is 400-600 ℃, preferably 500-550 ℃, and the holding 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 carried out under a 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 nickel-rich precursor has a chemical formula shown in formula (i): ni x Co y Mn z (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 is 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 cathode material is shown as formula (II): LiNi x Co y Mn z O 2 (II), 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 is 1.
The second aspect of the present disclosure provides a surface nitrogen-modified nickel-rich lithium ion positive electrode 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 positive electrode material is 0.1 to 0.5 wt%, and preferably 0.1 to 0.3 wt%, based on the total weight of the surface nitrogen-modified nickel-rich lithium ion positive electrode material.
In a third aspect of the present disclosure, a lithium ion battery is provided, which includes the surface nitrogen-modified nickel-rich lithium ion positive electrode material according to the second aspect of the present disclosure.
According to the technical scheme, the preparation method provided by the disclosure can dope a small amount of nitrogen element on the surface of the material through low-temperature nitriding treatment under the condition of ammonia gas, wherein the nitrogen element can reduce the content of unstable active oxygen on the surface layer of the material, reduce the oxygen loss phenomenon of the battery and avoid explosion caused by thermal runaway of the battery; and secondly, the ammonia gas can reduce oxygen atoms in the nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies can form an important lithium ion diffusion channel to improve the capacity of the battery, and can also adsorb active oxygen to reduce the phenomenon of oxygen loss, thereby improving the cycle performance and the safety performance of the battery.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a first charge-discharge specific capacity at 0.2C of the surface nitrogen-modified nickel-rich lithium ion cathode material 1 prepared in example 1 of the present disclosure;
fig. 2 is a cycle performance graph at 1.0C for the surface nitrogen-modified nickel-rich lithium ion cathode material 1 prepared in example 1 of the present disclosure;
fig. 3 is an X-ray energy spectrum of the surface nitrogen-modified nickel-rich lithium ion positive electrode material 1 prepared in example 1 of the present disclosure;
fig. 4 is XRD patterns before and after nitridation treatment of the surface nitrogen-modified nickel-rich lithium ion positive electrode material prepared in example 1 of the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the present disclosure provides a method for preparing a surface nitrogen modified nickel-rich lithium ion cathode material, including the following steps:
(1) mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion positive electrode material;
(2) and carrying out nitridation treatment on the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitridation treatment 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 nitridation treatment under the condition of ammonia gas to form nitrogen doping (namely, the nitrogen element occupies the position of part of oxygen element), the content of unstable active oxygen on the surface layer of the material can be reduced through the nitrogen doping, 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 the nitriding treatment to generate a plurality of oxygen vacancies, and the oxygen vacancies can form an important lithium ion diffusion channel to improve the capacity of the battery, and can also adsorb active oxygen to reduce the phenomenon of oxygen loss, 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 a pure ammonia gas condition, and the heat preservation time of the nitriding treatment is 0.5 to 1.5 hours. In the embodiment, the preferable nitriding heat preservation time is selected, so that nitrogen elements can be doped on the surface of the anode material, and 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 (1.01-1.04): 1, more preferably (1.01 to 1.025): 1. in the above embodiment, the raw materials are selected in a preferred ratio for reaction, which is beneficial to improving the stability of the nickel-rich lithium ion positive electrode material.
In one embodiment of the disclosure, in the step (1), the sintering is a sectional sintering, the sectional sintering comprises a first sintering and a second sintering, the temperature of the first sintering is 400-600 ℃, preferably 500-550 ℃, and the holding 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 carried out under a pure oxygen atmosphere. In the above embodiment, by selecting the preferred sectional sintering, lithium can be continuously diffused into the nickel-rich precursor, so as to form the nickel-rich lithium ion positive electrode material with stable thermodynamics, thereby improving the cycle performance and rate capability of the nickel-rich lithium ion positive electrode material.
In one embodiment of the present disclosure, the method further includes, before the nitriding treatment, pulverizing and sieving the nickel-rich lithium ion positive electrode material, wherein a particle size of the sieved material is D50 ═ 5 to 6 μm. In the above embodiment, the preferred crushing and sieving operation is adopted to facilitate the dispersion of the sintered agglomerate material and to remove large particles, thereby increasing the contact area and reaction sites of the nitriding treatment.
In one embodiment of the present disclosure, the nickel-rich precursor has a chemical formula as shown in formula (i): ni x Co y Mn z (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 is 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 preferred 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 chemical formula of the nickel-rich lithium ion positive electrode material is as shown in formula (II): LiNi x Co y Mn z O 2 (II), 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 + z1. In the above embodiment, the nickel-rich lithium ion positive electrode material with a preferred structure is selected for nitridation treatment, which is beneficial to doping nitrogen element on the surface of the material and generating a large number of oxygen vacancies, and the oxygen vacancies can form an important lithium ion diffusion channel, thereby improving the capacity and cycle performance of the battery.
The second aspect of the present disclosure provides a surface nitrogen-modified nickel-rich lithium ion positive electrode material prepared by the preparation method according to the first aspect of the present disclosure, and the content of nitrogen element doped on the surface of the surface nitrogen-modified nickel-rich lithium ion positive electrode 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 positive electrode material.
The third aspect of the present disclosure provides a lithium ion battery, which comprises the surface nitrogen modified nickel-rich lithium ion cathode material according to the second aspect of the present disclosure.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
In the following examples and comparative examples, the starting materials used were all commercial products unless otherwise specified.
In the following examples and comparative examples, the specific test methods were as follows:
the particle size test method is a laser particle sizer, and the instrument model is Mastersizer 3000;
the method for testing the content of the nitrogen element is an element analyzer, and the model of the apparatus is VarioueLCube;
the test instrument for the electrochemical cycle performance is a blue test system.
Example 1
(1) Nickel-rich precursor (chemical formula is Ni) 0.65 Co 0.15 Mn 0.2 (OH) 2 ) With LiOH. H 2 O is added at a ratio of 1.015: 1, heating to 500 ℃ in a box furnace after uniformly mixing, keeping the temperature for 6h, then heating to 750 ℃ and keeping the temperature for 12h, then naturally cooling to room temperature, and carrying out the whole process under pure oxygen atmosphere;
(2) the obtained nickel-rich lithium ion cathode material (chemical formula is LiNi) 0.65 Co 0.15 Mn 0.2 O 2 ) Crushing and sieving until the particle size D50 is 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, then, naturally cooling to room temperature to obtain the surface nitrogen modified nickel-rich lithium ion positive electrode material 1, and testing the first charge-discharge specific capacity, the cycle performance, the X-ray energy spectrum and the XRD of the material, wherein the result is shown in figures 1-4:
as can be seen from fig. 1-2, the nickel-rich lithium ion cathode material 1 modified by surface nitrogen has a high discharge specific capacity at 0.2C and a good cycling stability at 1.0C;
as can be seen from fig. 3, the surface of the material contains a large amount of oxygen and a small amount of nitrogen, which indicates that a part of nitrogen is introduced after the nitridation treatment;
as can be seen from fig. 4, before and after the nitridation treatment, the diffraction peak of the positive electrode material 1 does not change, and an impurity peak does not appear, indicating that the matrix structure does not change, and the material is only doped in the nitridation treatment process.
Example 2
The method of example 1 is used, with the only difference that: and the heat preservation time of the nitridation treatment is 1.5h, and the nickel-rich lithium ion cathode material 2 modified by surface nitrogen is obtained.
Example 3
The method of example 1 is used, with the only difference that: and (3) keeping the heat preservation time of the nitriding treatment to be 0.5h to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 3.
Example 4
The method of example 1 is used, with the only difference that: and the heat preservation time of the nitriding treatment is 0.3h, and the nickel-rich lithium ion anode material 4 with the nitrogen-modified surface is obtained.
Example 5
The method of example 1 is used, with the only difference that: and (3) keeping the heat preservation time of the nitriding treatment to be 0.8h to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 5.
Example 6
The method of example 1 is used, with the only difference that: and the heat preservation time of the nitridation treatment is 1.3h, and the nickel-rich lithium ion cathode material 6 with the nitrogen modified surface is obtained.
Example 7
The method of example 1 is used, with the only difference that: mixing the nickel-rich precursor with LiOH & H 2 O is calculated at a ratio of 1.025: 1 to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 7.
Example 8
The method of example 1 is used, with the only difference that: mixing the nickel-rich precursor with LiOH & H 2 O is calculated at a ratio of 1.025: 1, nitriding at 540 ℃, and keeping the temperature for 0.5h to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 8.
Example 9
The method of example 1 is used, with the only difference that: mixing the nickel-rich precursor with LiOH & H 2 O is 1.025: 1, the temperature of the nitridation treatment is 540 ℃, and the heat preservation time is 1h, so as to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 9.
Example 10
The method of example 1 is used, with the only difference that: will have the chemical formula of Ni 0.65 Co 0.15 Mn 0.2 (OH) 2 By replacing the nickel-rich precursor with Ni of the same weight 0.9 Co 0.05 Mn 0.05 (OH) 2 Obtaining the nickel-rich lithium ion cathode material with the chemical formula of LiNi 0.9 Co 0.05 Mn 0.05 O 2 And nitriding the lithium ion battery under pure ammonia gas at 480 ℃ for 0.5h to obtain the surface nitrogen modified nickel-rich lithium ion cathode material 10.
Example 11
The method of example 1 is used, with the only difference that: the molar ratio of the nickel-rich precursor to the lithium source is 1.1: 1.
comparative example 1
The method of example 1 is used, with the only difference that: comparative material 1 was obtained without performing nitriding treatment.
Comparative example 2
The method of example 1 is used, with the only difference that: the heat-retaining time of the nitriding treatment was 5 hours, and comparative material 2 was obtained.
Comparative example 3
The method of example 1 is used, with the only difference that: the temperature of the nitriding treatment was 570 ℃ to obtain comparative material 3.
Comparative example 4
The method of example 10 is used, with the only difference that: no nitriding treatment was performed, and comparative material 4 was obtained.
Test example
Electrochemical performance was tested as follows: the materials prepared by the examples and the comparative examples, the conductive agent acetylene black and the binder PVDF 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 90 ℃ by blowing air, tabletting the aluminum foil by using a tablet machine after complete drying, then punching the tabletted pole piece into a circular electrode piece with the diameter of 14mm, and drying for 2 hours at 120 ℃ in a vacuum drying oven; in a glove box protected by argon, a Celgard 2400 membrane is taken as a diaphragm, a metal lithium sheet is taken as a cathode, and 1mol L of lithium is added -1 The LiPF6/EC + DEC + DMC (volume ratio is 1: 1: 1) is used as an electrolyte to assemble the button cell. And (3) carrying out charge and discharge tests on the assembled battery above a blue test, wherein the temperature is 25 +/-1 ℃, and the test voltage range is 3.0-4.3V.
Figure BDA0003716697350000091
Figure BDA0003716697350000101
In embodiments 1 to 11, the surface nitrogen-modified nickel-rich lithium ion positive electrode material prepared by the preparation method disclosed by the present disclosure has a higher discharge specific capacity at 1.0C, and has a better capacity retention rate after being cycled for 100 times at 1.0C; in comparative examples 1-4, the capacity retention rate of the obtained positive electrode material is low and the cycle stability is poor without adopting the preparation method disclosed by the disclosure. Therefore, the preparation methods provided by the examples 1 to 11 of the present disclosure are more excellent than those of the comparative examples 1 to 4.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. A preparation method of a surface nitrogen modified nickel-rich lithium ion cathode material is characterized by comprising the following steps:
(1) mixing and sintering the nickel-rich precursor and a lithium source to obtain a nickel-rich lithium ion positive electrode material;
(2) and carrying out nitridation treatment on the nickel-rich lithium ion positive electrode material in the presence of ammonia gas, wherein the nitridation treatment temperature is 480-540 ℃, and the heat preservation time is 0.5-3 h.
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 according to claim 1, wherein in the step (1), the molar ratio of the nickel-rich precursor to the lithium source is (1.005-1.06): 1, preferably (1.01-1.04): 1, more preferably (1.01 to 1.025): 1.
4. the preparation method according to claim 1, wherein in the step (1), the sintering is step-type sintering, the step-type sintering comprises first sintering and second sintering, the temperature of the first sintering is 400-600 ℃, preferably 500-550 ℃, and the holding 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 carried out under a pure oxygen atmosphere.
5. The preparation method of claim 1, further comprising 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.
6. The method of claim 1, wherein the nickel-rich precursor has a chemical formula of formula (i): ni x Co y Mn z (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 is equal to 1.
7. 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.
8. The preparation method according to claim 1, wherein the chemical formula of the nickel-rich lithium ion positive electrode material is represented by formula (II): LiNi x Co y Mn z O 2 (II), 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 is equal to 1.
9. The surface nitrogen-modified nickel-rich lithium ion positive electrode material prepared by the preparation method of any one of claims 1 to 8, wherein the content of nitrogen element doped on the surface of the surface nitrogen-modified nickel-rich lithium ion positive electrode 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 positive electrode material.
10. A lithium ion battery comprising the surface nitrogen-modified nickel-rich lithium ion positive electrode material of claim 9.
CN202210745444.2A 2022-06-27 2022-06-27 Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery Pending CN115000382A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210745444.2A CN115000382A (en) 2022-06-27 2022-06-27 Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210745444.2A CN115000382A (en) 2022-06-27 2022-06-27 Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery

Publications (1)

Publication Number Publication Date
CN115000382A true CN115000382A (en) 2022-09-02

Family

ID=83036955

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210745444.2A Pending CN115000382A (en) 2022-06-27 2022-06-27 Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN115000382A (en)

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
CHEN XIAN等: "Nitrogen-doped carbon coated LiNi0.6Co0.2Mn0.2O2 cathode with enhanced electrochemical performance for Li-Ion batteries", 《ELECTROCHIMICA ACTA》, pages 526 - 533 *
陈仙: "基于氮掺杂碳改性的高性能锂离子电池正负极材料", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, pages 020 - 919 *

Similar Documents

Publication Publication Date Title
KR101886592B1 (en) Powder for negative electrode of lithium ion secondary cell, and method for producing such powder
CN111092220A (en) M-element bulk phase doped modified manganese-based positive electrode material of tunnel-type sodium-ion battery and preparation method thereof
CN109904408B (en) MoS2Preparation method and application of composite material with nanosheet embedded in carbon substrate
CN112133909B (en) Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof
CN103050694B (en) A kind of positive electrode active materials and preparation method thereof, battery
CN104241642B (en) Lithium molybdate negative material of lithium ion battery and preparation method thereof
CN111211308A (en) Loofah sponge biomass carbon-loaded red phosphorus lithium ion battery negative electrode material and preparation method thereof
CN115050957B (en) Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN114628677A (en) Copper-doped potassium manganate electrode material, preparation method thereof and application thereof in potassium ion battery
CN111943149A (en) General preparation method of transition metal nitride
CN109546099B (en) Graphite composite negative electrode material, preparation method thereof and lithium ion battery
CN107611378A (en) Nitrogen-containing composite material for zinc-based battery and preparation method thereof
CN111484247B (en) Glass positive electrode material and preparation method and application thereof
CN115275166A (en) Long-life graphite composite material and preparation method thereof
CN111883746B (en) Modified lithium-rich manganese-based oxide positive electrode material and preparation method and application thereof
CN111129493B (en) Transition metal sulfide positive electrode material of sodium ion battery and preparation method and application thereof
CN115000382A (en) Surface nitrogen modified nickel-rich lithium ion positive electrode material, preparation method thereof and lithium ion battery
CN113540460A (en) Composite material and preparation method and application thereof
CN112952081A (en) Lithium ion battery layered perovskite structure negative electrode material and preparation method thereof
CN107785566A (en) A kind of long-life nickel cobalt lithium aluminate cathode material and preparation method thereof
CN111071998A (en) Preparation method of GaN porous micron square/carbon composite material
CN115092962B (en) Molybdenum dioxide/carbon composite electrode material and preparation method and application thereof
CN108232188A (en) A kind of high power capacity lithium-rich positive electrode and preparation method thereof
CN110556525B (en) Lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery
CN108682798B (en) Preparation method of cubic carbon-coated vanadium-based positive electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination