CN112952096A - Nitrogen-doped carbon-coated lithium ion battery positive electrode material and preparation method thereof - Google Patents

Nitrogen-doped carbon-coated lithium ion battery positive electrode material and preparation method thereof Download PDF

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CN112952096A
CN112952096A CN202110190525.6A CN202110190525A CN112952096A CN 112952096 A CN112952096 A CN 112952096A CN 202110190525 A CN202110190525 A CN 202110190525A CN 112952096 A CN112952096 A CN 112952096A
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nitrogen
lithium ion
ion battery
positive electrode
electrode material
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CN112952096B (en
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黄仁忠
吴浩
高琦
郑江峰
张晨
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute Co Ltd
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Guangdong Jiana Energy Technology Co Ltd
Qingyuan Jiazhi New Materials Research Institute 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
    • H01M4/62—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
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    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 application relates to the field of lithium batteries, in particular to a nitrogen-doped carbon-coated lithium ion battery positive electrode material and a preparation method thereof. The material includes an inner core and an outer shell. The shell comprises carbon atoms and nitrogen atoms; the content of nitrogen atoms in the shell is 2.17-6.54% by mass percent. The nitrogen-doped carbon-coated lithium ion battery anode material has the advantages that the nitrogen atom content in the shell is within the range of 2.17% -6.54%, the nitrogen doping amount in the shell is high, and the carbon coating layer is thin, so that the electrochemical properties of the nitrogen-doped carbon-coated lithium ion battery anode material, such as charge-discharge cycle performance, multiplying power performance and the like, can be improved. Further, the nitrogen-doped carbon-coated lithium ion battery anode material can realize the controllability of the doping amount of nitrogen atoms in the shell, and is favorable for improving the uniformity of the shell.

Description

Nitrogen-doped carbon-coated lithium ion battery positive electrode material and preparation method thereof
Technical Field
The application relates to the field of lithium batteries, in particular to a nitrogen-doped carbon-coated lithium ion battery positive electrode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of large energy density, long cycle life, high working voltage, no memory effect, small self-discharge, wide working temperature and the like. Therefore, the lithium ion battery is widely used as an important energy source, and the lithium ion battery has wide application prospect and potential economic benefit in the fields of electronic communication, transportation and the like. The important component of the lithium ion battery is the key to limit the capacity and other performances of the lithium ion battery.
The ternary positive electrode material has gradually become the first choice of the positive electrode material of the power battery due to the characteristics of higher energy density, environmental friendliness and the like. However, the conductivity, cycle performance and rate capability of the material are still to be optimized.
The conventional surface modification method for the ternary cathode material at present comprises doping and cladding. For example, CN103474628A discloses a carbon-coated ternary cathode material prepared by mixing and sintering a ternary material and an organic carbon source. For example, CN104900869A discloses a preparation method of a carbon-coated nickel-cobalt-aluminum ternary cathode material.
However, the above composite ternary cathode material has unsatisfactory charge-discharge cycle performance and rate capability, and needs to be improved.
Disclosure of Invention
An object of the embodiments of the present application is to provide a nitrogen-doped carbon-coated lithium ion battery positive electrode material and a preparation method thereof, which can improve the nitrogen doping amount while coating a thin carbon layer on the surface of the positive electrode material.
In a first aspect, the present application provides a nitrogen-doped carbon-coated lithium ion battery positive electrode material, comprising:
the core is made of a positive electrode material; and
the shell is coated outside the kernel; the shell comprises carbon atoms and nitrogen atoms; the content of nitrogen atoms in the shell is 2.17-6.54% by mass percent.
The nitrogen-doped carbon-coated lithium ion battery anode material has the advantages that the nitrogen atom content in the shell is within the range of 2.17% -6.54%, the nitrogen doping amount in the shell is high, and the carbon coating layer is thin, so that the electrochemical properties of the nitrogen-doped carbon-coated lithium ion battery anode material, such as charge-discharge cycle performance, multiplying power performance and the like, can be improved. Furthermore, the nitrogen-doped carbon-coated lithium ion battery anode material can realize the controllability of the doping amount of nitrogen atoms in the shell, and is favorable for better adjusting the uniformity of the shell.
In other embodiments of the present application, the content of nitrogen atoms relative to carbon atoms in the outer shell is 4.05% to 7.56%.
In other embodiments of the present application, the core is a nickel-cobalt-manganese ternary positive electrode material;
alternatively, the chemical formula of the core is Li (Ni)1-x-yCoxMny)O2Wherein 0 is<x<1，0<y<1。
In a second aspect, the present application provides a method for preparing a nitrogen-doped carbon-coated lithium ion battery positive electrode material, including:
aniline and o-phenylenediamine are used as mixed monomers;
in-situ oxidation copolymerization is carried out on the mixed monomer and the ternary cathode material, so that the copolymer of aniline and o-phenylenediamine is coated on the surface of the ternary cathode material;
and then carbonizing.
According to the preparation method, aniline and o-phenylenediamine are used as mixed monomers, the carbon-nitrogen ratio content in the coating layer can be adjusted, and therefore the uniformity of the carbon layer can be adjusted better. The nitrogen-doped carbon coating layer with good uniformity can effectively improve the electronic conductivity of the material, so that the carbon layer can effectively inhibit side reactions between the electrode material and electrolyte. The preparation method has the advantages that the reaction conditions are easy to control, no special requirements are required on equipment, and the operation is simple and convenient; compared with the traditional chemical deposition method, the synthetic route is simple and the cost is low; compared with the traditional ball milling method and the solvent thermal method, the synthesized composite material has high structural strength and good cycle stability.
In other embodiments of the present application, the ratio of the amounts of the aniline and o-phenylenediamine is 10:1 to 1: 1.
alternatively, the ratio of the amount of aniline to o-phenylenediamine species is 4:1 to 0.1 to 1.
In the proportion range, the obtained mixed monomer can be well copolymerized, and the uniformity of a polymer shell formed on the surface of the ternary cathode material can be ensured to be good, so that the uniformity of a carbon-coated shell obtained subsequently is ensured to be good, the carbon coating layer is thin, the nitrogen doping amount is large, and the electrochemical performance of the ternary cathode material is improved.
In other embodiments of the present application, the total concentration of the aniline and o-phenylenediamine is 0.04mol/L to 0.2 mol/L.
In other embodiments of the present application, the step of in-situ oxidative copolymerization comprises:
mixing the ternary positive electrode material, the mixed monomer and the oxidant, and adjusting the pH value to 1-5 for reaction.
Optionally, the ternary cathode material comprises, by mass: mixing monomers in a ratio of 1: 1-1: within 5.
In other embodiments of the present application, the temperature of the in-situ oxidative copolymerization reaction is 20 ℃ to 30 ℃.
In other embodiments herein, the above-mentioned oxidizing agent is selected from at least one of ammonium persulfate or ammonium dichromate;
alternatively, the mass concentration of the oxidizing agent is 0.02mol/L to 0.1 mol/L.
In other embodiments of the present application, the temperature of the carbonization treatment is 700 ℃ to 800 ℃;
optionally, the carbonization time is 2h-5 h;
optionally, the carbonization atmosphere is an inert atmosphere.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is an SEM image of a nitrogen-doped carbon-coated lithium ion battery positive electrode material provided in example 1 of the present application;
fig. 2 is a comparison graph of cycle performance of the nitrogen-doped carbon-coated lithium ion battery positive electrode material provided in embodiments 1 to 2 of the present application and the positive electrode material provided in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments.
The embodiment of the application provides a preparation method of a nitrogen-doped carbon-coated lithium ion battery positive electrode material, which comprises the following steps:
and step S1, aniline and o-phenylenediamine are used as mixed monomers.
The mixed monomer is obtained by mixing aniline and o-phenylenediamine according to a specific proportion.
Specifically, the ratio of the amounts of aniline and o-phenylenediamine species is 50: 1-0.1: 1;
further optionally, the ratio of the amount of species of aniline to o-phenylenediamine is 50: 1 to 0.1 to 1.
Further optionally, the ratio of the amount of aniline to o-phenylenediamine species is 10:1 to 1: 1.
within the above range, the copolymerization of aniline and o-phenylenediamine can be favorably carried out.
Further optionally, the ratio of the amount of aniline to o-phenylenediamine species is 10:1 to 1: 1.
further optionally, the ratio of the amount of aniline to o-phenylenediamine species is 4:1 to 1: 1. illustratively, the ratio of the amount of aniline to o-phenylenediamine material is 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1: 1.
In the proportion range, the carbon-nitrogen ratio content in the coating layer can be adjusted, the mixed monomer can be well copolymerized, and the uniformity of a polymer shell formed on the surface of the ternary cathode material can be guaranteed to be good, so that the uniformity of a carbon coating shell obtained subsequently is guaranteed to be good, the carbon coating layer is thin, the nitrogen doping amount is large, and the electrochemical performance of the ternary cathode material is improved.
Further, the total concentration of the mixed monomers described above is set within a specific range.
Specifically, the total concentration of aniline and o-phenylenediamine is 0.04mol/L to 0.2 mol/L.
The total concentration of the aniline and the o-phenylenediamine is set to be 0.04 mol/L-0.2 mol/L, the carbon-nitrogen ratio content in the coating layer can be adjusted, the aniline and the o-phenylenediamine are copolymerized to form a uniform copolymer coating layer, and the uniform carbon coating layer can be obtained through subsequent treatment of the uniform copolymer coating layer.
Further optionally, the total concentration of aniline and o-phenylenediamine is in the range of 0.05mol/L to 0.19 mol/L.
Further optionally, the total concentration of aniline and o-phenylenediamine is 0.06mol/L to 0.18 mol/L.
Further optionally, the total concentration of aniline and o-phenylenediamine is from 0.07mol/L to 0.17 mol/L.
Illustratively, the total concentration of aniline and o-phenylenediamine is 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, or 0.16 mol/L.
And S2, carrying out in-situ oxidation copolymerization on the mixed monomer and the ternary cathode material obtained in the step S1, so that the copolymer of the aniline and the o-phenylenediamine is coated on the surface of the ternary cathode material.
Further, the step of in-situ oxidative copolymerization comprises:
mixing the ternary positive electrode material, the mixed monomer and the oxidant, and adjusting the pH value to 1-5 for reaction.
Through adjusting dispersion pH to 1 ~ 5, can guarantee that aniline and o-phenylenediamine copolymerization form even copolymer coating, through the subsequent processing to this even copolymer coating, can obtain even carbon coating.
Further optionally, mixing the ternary cathode material, the mixed monomer and the oxidant, and adjusting the pH value to 2-4 for reaction.
Further optionally, mixing the ternary cathode material, the mixed monomer and the oxidant, and adjusting the pH value to 3-4 for reaction.
Further, the ternary cathode material comprises the following components in percentage by mass: mixing monomers in a ratio of 1: 1-1: within 5.
Further optionally, the ternary cathode material comprises, by mass: mixing monomers in a ratio of 1: 1.5-1: 4.5.
Further optionally, the ternary cathode material comprises, by mass: mixing monomers in a ratio of 1: 2-1: 4 in the range of.
Further optionally, the ternary cathode material comprises, by mass: mixing monomers in a ratio of 1: 2-1: 3 range.
Further, in some embodiments of the present application, the acid is selected from sulfuric acid or hydrochloric acid. Further, the acid is added dropwise.
Further, before the ternary cathode material, the mixed monomer and the oxidant are mixed, the ternary cathode material is subjected to ultrasonic dispersion to obtain a dispersion liquid.
Alternatively, the above dispersant is selected from alcohols, illustratively ethanol; or an ether, illustratively diethyl ether.
Further, the ultrasonic dispersion time is 10 to 30 minutes.
Further optionally, the time of the ultrasonic dispersion is 15 minutes to 25 minutes. Illustratively, the time of ultrasonic dispersion is 16 minutes, 18 minutes, 20 minutes, or 23 minutes.
Further, while slowly dropping the acid, stirring is also performed, and optionally, stirring is continued for 10 to 20 minutes. Further optionally, stirring is continued for 12 minutes to 18 minutes. Illustratively, stirring is continued for 14 minutes, 15 minutes, or 16 minutes.
Furthermore, the temperature of the in-situ oxidation copolymerization reaction is 0-40 ℃.
Further selecting the temperature of the in-situ oxidation copolymerization reaction to be 5-38 ℃.
Further selecting the temperature of the in-situ oxidation copolymerization to be 20-30 ℃.
Illustratively, the temperature of the in situ oxidative copolymerization is 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C or 29 deg.C.
Further, the ternary cathode material, the mixed monomer and the oxidant are mixed and then stirred and dispersed. Optionally, ultrasonic dispersion is employed.
Further optionally, the ultrasonic dispersion time is 20 minutes to 30 minutes.
Further, the oxidizing agent is selected from at least one of ammonium persulfate and ammonium dichromate.
Further optionally, the species of the oxidizing agent is present in a concentration of 0.02mol/L to 0.1 mol/L. Further optionally, the species of the oxidizing agent is present in a concentration of 0.03mol/L to 0.09 mol/L. Further optionally, the species of the oxidizing agent is present in a concentration of 0.04mol/L to 0.08 mol/L. Illustratively, the species of the oxidizing agent is present in a concentration of 0.05mol/L, 0.06mol/L, or 0.07 mol/L.
Further, the oxidizing agent is added dropwise.
Further, after the reaction, washing and drying are performed.
Step S3, and then carbonization is performed.
Further, the ternary cathode material wrapped by the polymer obtained by the reaction in the step S2 is carbonized.
Further optionally, the temperature of the carbonization treatment is 700 ℃ to 800 ℃.
Further optionally, the temperature of the carbonization treatment is 710 ℃ to 790 ℃. Further optionally, the temperature of the carbonization treatment is 720 ℃ to 780 ℃. Illustratively, the temperature of the carbonization treatment is 730 ℃, 740 ℃, 750 ℃, 760 ℃ or 770 ℃.
Further, the carbonization time is 2h-5 h. Further alternatively, the carbonization time is 2.1h to 4.9 h. Further alternatively, the carbonization time is 2.2h to 4.8 h. Further alternatively, the carbonization time is 2.4h to 4.6 h. Illustratively, the carbonization time is 2.3h, 2.5h, 2.7h, 2.8h, 3.0h, 3.5h, 4.0h, or 4.5 h.
Further, the carbonization atmosphere is an inert atmosphere.
Alternatively, the inert atmosphere may be argon or the like.
Further, during carbonization treatment, the temperature rise rate is selected to be 1-3 ℃/min; further optionally, the heating rate is selected to be 1.5 ℃/min-2.5 ℃/min; further optionally, the heating rate is selected to be 1.6 ℃/min-2.4 ℃/min. Illustratively, the rate of temperature rise is 1.7 deg.C/min, 1.8 deg.C/min, 1.9 deg.C/min, 2.0 deg.C/min, 2.1 deg.C/min, 2.2 deg.C/min, 2.3 deg.C/min, or 2.4 deg.C/min.
Exemplarily, the polymer-coated ternary cathode material obtained by the reaction in the step S2 is placed in a tube furnace and treated at a high temperature of 700 ℃ to 800 ℃ for 2h to 5h under the protection of an inert atmosphere.
Some embodiments of the present application provide a nitrogen-doped carbon-coated lithium ion battery positive electrode material, which can be prepared by using the preparation method of the nitrogen-doped carbon-coated lithium ion battery positive electrode material provided in any one of the foregoing embodiments.
Further, the nitrogen-doped carbon-coated lithium ion battery positive electrode material comprises: a core and a shell.
Further, the inner core is a positive electrode material.
Further, the outer shell is coated outside the inner core; the shell includes carbon atoms and nitrogen atoms.
Further, the content of nitrogen atoms in the shell is 2.17-6.54% by mass percent.
Further optionally, the content of nitrogen atoms in the shell is 2.18-6.53% by mass. Further optionally, the content of nitrogen atoms in the shell is 2.19-6.52% by mass percent. Illustratively, the nitrogen atom content in the shell is 2.20%, 2.50%, 2.80%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 5.8%, 6.0%, 6.2%, or 6.5% by mass.
Further, the content of nitrogen atoms relative to carbon atoms in the shell is 4.05-7.56%. Further optionally, the content of nitrogen atoms relative to carbon atoms in the shell is 4.1% to 7.4%. Further optionally, the content of nitrogen atoms relative to carbon atoms in the shell is 4.5% to 7.0%. Illustratively, the shell has a nitrogen atom content of 4.8%, 5.0%, 5.5%, 6.0%, 6.5%, or 7.0% relative to a carbon atom content.
Further, the inner core is made of a nickel-cobalt-manganese ternary positive electrode material.
Alternatively, the chemical formula of the core is Li (Ni)1-x-yCoxMny)O2Wherein 0 is<x<1，0<y<1。
Illustratively, the nickel-cobalt-manganese ternary positive electrode material is selected from NCM523 type and the like.
The features and properties of the present application are described in further detail below with reference to examples:
example 1
The preparation method of the nitrogen-doped carbon-coated lithium ion battery positive electrode material is carried out according to the following steps:
300mg of the ternary cathode material NCM523 is weighed and dispersed into 100ml of ethanol, and ultrasonic dispersion is carried out for 20 minutes. 8.335mL of hydrochloric acid solution (12mol/L) was slowly added dropwise with stirring for 15 minutes. Then adding aniline and o-phenylenediamine monomer into the dispersion liquid according to the concentration ratio of 8:2 (the total substance amount is 0.01mol), ultrasonically dispersing for 20 minutes, and continuously stirring in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate is dissolved in 10mL of deionized water to obtain the ammonium persulfate aqueous solution) is slowly dropped into the reaction kettle to react for 4 hours, and the reaction kettle is washed and dried. And annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain the nitrogen-doped carbon-coated ternary cathode material.
Example 2
The preparation method of the nitrogen-doped carbon-coated lithium ion battery positive electrode material is carried out according to the following steps:
300mg of the ternary cathode material NCM523 is weighed and dispersed into 100ml of ethanol, and ultrasonic dispersion is carried out for 20 minutes. 8.335mL of hydrochloric acid solution (12mol/L) was slowly added dropwise with stirring for 15 minutes. Then adding aniline and o-phenylenediamine monomer into the dispersion liquid according to the concentration ratio of 7:3 (the total substance amount is 0.01mol), ultrasonically dispersing for 20 minutes, and continuously stirring in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate is dissolved in 10mL of deionized water to obtain the ammonium persulfate aqueous solution) is slowly dropped into the reaction kettle to react for 4 hours, and the reaction kettle is washed and dried. And annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain the nitrogen-doped carbon-coated ternary cathode material.
Example 3
The preparation method of the nitrogen-doped carbon-coated lithium ion battery positive electrode material is carried out according to the following steps:
300mg of the ternary cathode material NCM523 is weighed and dispersed into 100ml of ethanol, and ultrasonic dispersion is carried out for 20 minutes. 8.335mL of hydrochloric acid solution (12mol/L) was slowly added dropwise with stirring for 15 minutes. Then adding aniline and o-phenylenediamine monomer into the dispersion liquid according to the concentration ratio of 6:4 (the total substance amount is 0.01mol), carrying out ultrasonic treatment for 30 minutes, and continuously stirring the mixture in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate is dissolved in 10mL of deionized water to obtain the ammonium persulfate aqueous solution) is slowly dropped into the reaction kettle to react for 4 hours, and the reaction kettle is washed and dried. And annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain the nitrogen-doped carbon-coated ternary cathode material.
Example 4
300mg of the ternary cathode material NCM523 is weighed and dispersed into 100ml of ethanol, and ultrasonic dispersion is carried out for 20 minutes. 8.335mL of hydrochloric acid solution (12mol/L) was slowly added dropwise with stirring for 15 minutes. Then adding aniline and o-phenylenediamine monomer into the dispersion liquid according to the concentration ratio of 5:5 (the total substance amount is 0.01mol), carrying out ultrasonic treatment for 30 minutes, and continuously stirring the mixture in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate is dissolved in 10mL of deionized water to obtain the ammonium persulfate aqueous solution) is slowly dropped into the reaction kettle to react for 4 hours, and the reaction kettle is washed and dried. And annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain the nitrogen-doped carbon-coated ternary cathode material.
Comparative example 1
The preparation method of the lithium ion battery anode material is provided and comprises the following steps:
300mg of the ternary cathode material NCM523 is weighed and dispersed into 100ml of ethanol, and ultrasonic dispersion is carried out for 20 minutes. 8.335mL of hydrochloric acid solution (12mol/L) was slowly added dropwise with stirring for 15 minutes. Then adding aniline and o-phenylenediamine monomer into the dispersion liquid according to the concentration ratio of 10:0 (the total substance amount is 0.01mol), carrying out ultrasonic treatment for 30 minutes, and continuously stirring the mixture in a water bath kettle at 25 ℃. Finally, 10mL of ammonium persulfate aqueous solution (2.85 g of ammonium persulfate is dissolved in 10mL of deionized water to obtain the ammonium persulfate aqueous solution) is slowly dropped into the reaction kettle to react for 4 hours, and the reaction kettle is washed and dried. And annealing the obtained sample at 800 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon atmosphere gas to obtain the nitrogen-doped carbon-coated ternary cathode material.
Experimental example 1
The percentage content of nitrogen atoms and the percentage content of nitrogen atoms relative to carbon atoms in the lithium ion battery cathode material prepared in examples 1 to 4 and the lithium ion battery cathode material provided in comparative example 1 were measured.
The energy spectrum is adopted for detection, and the result is shown in table 1.
TABLE 1
Molar ratio of aniline/o-phenylenediamine addition Atomic percent of nitrogen Nitrogen relative to carbon content
Example 1 8：2 2.17％ 4.05％
Example 2 7：3 3.05％ 5.24％
Example 3 6：4 4.78％ 6.77％
Example 4 5：5 6.54％ 7.56％
Comparative example 1 10：0 2.09％ 3.32％
As can be seen from the results in table 1, the nitrogen-doped carbon-coated lithium ion battery positive electrode material provided in the embodiment of the present application has a nitrogen atom content of 2.17% to 6.54% in the carbon coating layer. The content of nitrogen atoms relative to carbon atoms is 4.05-7.56%. Therefore, the nitrogen-doped carbon-coated lithium ion battery cathode material provided by the embodiment of the application has a higher nitrogen doping amount, and the carbon coating layer is thinner, so that the electrochemical performance of the nitrogen-doped carbon-coated lithium ion battery cathode material is favorably improved.
Experimental example 2
The morphology of the positive electrode material of the nitrogen-doped carbon-coated lithium ion battery prepared in example 2 was detected by a scanning electron microscope, and the result is shown in fig. 1 of the specification.
The nitrogen-doped carbon-coated lithium ion battery anode material shell carbon layer provided by the embodiment of the application has the advantages that no blocky agglomeration occurs, the carbon layer coating effect is good, the carbon layer uniformity is good, and the carbon layer is thin.
Experimental example 3
The nitrogen-doped carbon-coated lithium ion battery positive electrode material prepared in examples 1-4 and the lithium ion battery positive electrode material provided in proportion 1 are respectively mixed with a binder and conductive carbon black into uniform slurry according to the mass ratio of 8:1:1, and then the slurry is coated on a copper foil, dried and sliced. And assembling the pole piece, a lithium piece, a diaphragm and electrolyte into a button cell in a glove box protected by argon atmosphere, and carrying out constant-current charge-discharge test. The results are shown in figure 2 of the specification.
As can be seen from fig. 2, the positive electrode materials of the lithium ion batteries coated with nitrogen-doped carbon provided in embodiments 1 to 4 of the present application have higher specific discharge capacity, and especially under a high cycle number (50 times), the positive electrode materials of the lithium ion batteries coated with nitrogen-doped carbon provided in embodiments 1 to 4 of the present application have significantly higher specific discharge capacity than that of comparative example 1. In addition, the discharge specific capacity of the nitrogen-doped carbon-coated lithium ion battery positive electrode material provided in embodiments 1 to 4 of the present application decreases slowly with the increase of the cycle number, while the discharge specific capacity of the lithium ion battery positive electrode material provided in comparative example 1 decreases almost linearly with the increase of the cycle number, and the decrease is very significant.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A nitrogen-doped carbon-coated lithium ion battery positive electrode material is characterized by comprising:
the inner core is made of a positive electrode material; and
a shell, the shell being wrapped outside the core; the shell comprises carbon atoms and nitrogen atoms; the content of nitrogen atoms in the shell is 2.17-6.54% by mass percent.
2. The nitrogen-doped carbon-coated lithium ion battery positive electrode material according to claim 1,
the content of nitrogen atoms relative to carbon atoms in the shell is 4.05-7.56%.
3. The nitrogen-doped carbon-coated lithium ion battery positive electrode material according to claim 1,
the inner core is made of a nickel-cobalt-manganese ternary positive electrode material;
optionally, the chemical formula of the core is Li (Ni)1-x-yCoxMny)O2Wherein 0 is<x<1，0<y<1。
4. A preparation method of a nitrogen-doped carbon-coated lithium ion battery anode material is characterized in that,
aniline and o-phenylenediamine are used as mixed monomers;
in-situ oxidation copolymerization is carried out on the mixed monomer and the ternary cathode material, so that the copolymer of aniline and o-phenylenediamine is coated on the surface of the ternary cathode material;
and then carbonizing.
5. The method of claim 4, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the mass ratio of the aniline to the o-phenylenediamine is 10: 1-1: 1;
optionally, the ratio of the aniline to the o-phenylenediamine is 4:1 to 1: 1.
6. the method of claim 4, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the total concentration of the aniline and the o-phenylenediamine is 0.04 mol/L-0.2 mol/L.
7. The method of claim 4, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the step of in-situ oxidative copolymerization comprises:
mixing a ternary positive electrode material, a mixed monomer and an oxidant, and adjusting the pH value to 1-5 for reaction;
optionally, the ternary cathode material comprises, by mass: the mixed monomer is prepared from the following components in percentage by weight: 1-1: within 5.
8. The method of claim 7, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the temperature of the in-situ oxidation copolymerization is 20-30 ℃.
9. The method of claim 7, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the oxidant is selected from at least one of ammonium persulfate or ammonium dichromate;
optionally, the mass concentration of the oxidant is between 0.02mol/L and 0.1 mol/L.
10. The method of claim 4, wherein the nitrogen-doped carbon-coated lithium ion battery positive electrode material is prepared by a method comprising the steps of,
the temperature of the carbonization treatment is 700-800 ℃;
optionally, the carbonization time is 2h-5 h;
optionally, the carbonization atmosphere is an inert atmosphere.
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