CN110247032B - Nitrogen-doped graphene negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Nitrogen-doped graphene negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN110247032B
CN110247032B CN201910452744.XA CN201910452744A CN110247032B CN 110247032 B CN110247032 B CN 110247032B CN 201910452744 A CN201910452744 A CN 201910452744A CN 110247032 B CN110247032 B CN 110247032B
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graphene
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lithium
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CN110247032A (en
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曹宇
***
何佳琪
王野
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BAIC Motor 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a nitrogen-doped graphene negative electrode material, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: mixing a graphene raw material with an etching agent, and then carrying out etching treatment to obtain porous graphene; and mixing the obtained porous graphene with a nitrogen-containing solvent, and then carrying out doping treatment under the closed solvothermal condition to obtain the nitrogen-doped graphene negative electrode material. The nitrogen-doped graphene negative electrode material prepared by the method disclosed by the invention has high specific capacity when being applied to a lithium ion battery.

Description

Nitrogen-doped graphene negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The disclosure relates to the technical field of lithium batteries, in particular to a nitrogen-doped graphene negative electrode material, a preparation method thereof and a lithium ion battery.
Background
With the development of new energy vehicles, Hybrid Electric Vehicles (HEV), pure electric vehicles (BEV) and plug-in hybrid electric vehicles (PHEV) are receiving more and more attention. In the development process of the electric automobile, the specific capacity of the power battery becomes an important restriction factor for limiting the development of the electric automobile, so that the manufactured power battery with high specific capacity becomes an important factor for improving the endurance mileage of the electric automobile and accelerating the development of the electric automobile. In the lithium ion power battery produced at present, a graphite material is a main negative electrode material, and the theoretical specific capacity of the graphite material limits the improvement of the battery capacity.
The graphene is represented by sp2A monoatomic layer ultrathin two-dimensional crystal material composed of hybridized carbon atoms connected with each other exhibits extremely high specific capacity and excellent stability in use as a negative electrode material of a lithium ion battery. However, the intrinsic graphene lacks edge folds and active site structures for transmitting lithium ions, and nitrogen doping is performed on the graphene, so that the surface folds and defect structures of the graphene can be increased, the interlayer spacing of graphene stacking is increased, the barrier of lithium ion intercalation entering graphene layers is reduced, and the capacity and rate capability of the lithium ion battery are greatly improved (refer to Reddy A L M, Srivastava A, Gowda S R, et alynthesis of nitrogen-doped graphene films for lithium battery application[J]Acs Nano,2010,4(11): 6337-. However, in the nitrogen-doped graphene, the existence form of nitrogen exists in pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, and the controllable nitrogen-doped graphene is rarely reported. On the skeleton of graphene, pyridine nitrogen and pyrrole nitrogen can form a reversible nitrogen-containing lithium ion compound with lithium ions, so that the reversible capacity of the battery is greatly improved, and therefore, the improvement of the content of the pyridine nitrogen and the pyrrole nitrogen in the graphene is one of the directions for researching nitrogen-doped graphene.
Disclosure of Invention
The purpose of the disclosure is to provide a nitrogen-doped graphene negative electrode material, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, the present disclosure provides a preparation method of a nitrogen-doped graphene anode material, including:
mixing a graphene raw material with an etching agent, and then carrying out etching treatment to obtain porous graphene;
and mixing the obtained porous graphene with a nitrogen-containing solvent, and then carrying out doping treatment under the closed solvothermal condition to obtain the nitrogen-doped graphene negative electrode material.
Optionally, the graphene raw material is selected from graphene and/or reduced graphene oxide.
Optionally, the etchant is potassium hydroxide; the etching treatment conditions include: the temperature is 600-800 ℃, the time is 1-6 hours, and the weight ratio of the etching agent to the graphene raw material is 1: (0.1-10).
Optionally, the nitrogen-containing solvent is selected from one or more of hydrazine hydrate, ammonia, urea, acetonitrile and pyrrole.
Optionally, the doping treatment conditions include: the weight ratio of the porous graphene to the nitrogen-containing solvent is 1: (0.1-100) at 150-240 deg.c for 6-48 hr.
The disclosure also provides the nitrogen-doped graphene anode material prepared by the preparation method.
The disclosure also provides a nitrogen-doped graphene negative electrode material, which is determined by adopting X photoelectron spectroscopy, wherein the content of pyridine nitrogen is 40-50 wt%, the content of pyrrole nitrogen is 35-40 wt%, and the content of graphite nitrogen is 15-25 wt% based on the total weight of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen in the nitrogen-doped graphene negative electrode material.
The present disclosure also provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator and an electrolyte, where the negative electrode includes the nitrogen-doped graphene negative electrode material provided by the present disclosure.
The negative electrode further comprises acetylene black and polyvinylidene fluoride, and the weight ratio of the nitrogen-doped graphene negative electrode material to the acetylene black to the polyvinylidene fluoride is (75-85): (5-15): 10;
the anode material of the anode is selected from one or more of lithium iron phosphate, lithium manganate, lithium nickelate, lithium cobaltate and ternary lithium nickel cobalt manganese oxide;
the electrolyte comprises lithium hexafluorophosphate and/or lithium perchlorate.
Optionally, the electrolyte comprises lithium hexafluorophosphate, ethylene carbonate and dimethyl carbonate, the concentration of lithium hexafluorophosphate in the electrolyte is 0.5-2.5 mol/l, and the volume ratio of ethylene carbonate to dimethyl carbonate is 1: (0.5-2).
According to the method, the graphene is subjected to nitrogen doping in a mode of etching and doping treatment under a closed solvothermal condition, and the nitrogen-doped graphene is used as a negative electrode material, so that the specific capacity and the efficiency of the lithium ion battery can be improved, and the method has great significance for improving the cruising ability of an electric automobile.
The graphene etching doping process and the lithium ion power battery assembling process are simple and can be produced in large scale, and the obtained lithium ion power battery has high specific capacity. The lithium ion power battery with the nitrogen-doped graphene with the specific nitrogen type can be obtained through the form, and plays a demonstration role in the using and developing processes of the lithium ion power battery material, namely the application of the method in the modified graphene material forms the lithium ion power battery with the nitrogen-doped graphene mainly taking pyridine nitrogen and pyrrole nitrogen as the negative electrode material.
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 schematic diagram of a preparation principle of a nitrogen-doped graphene anode material mainly containing pyridine nitrogen and pyrrole nitrogen.
Fig. 2 is a transmission electron microscope photograph of a nitrogen-doped graphene negative electrode material mainly containing pyridine nitrogen and pyrrole nitrogen.
Fig. 3 is an X-ray photoelectron spectroscopy analysis spectrum (ordinate is unitless) of the nitrogen-doped graphene negative electrode material mainly containing pyridine nitrogen and pyrrole nitrogen.
Fig. 4 is a graph of performance testing of a half cell provided 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.
As shown in fig. 1, the present disclosure provides a preparation method of a nitrogen-doped graphene anode material, including:
mixing a graphene raw material with an etching agent, and then carrying out etching treatment to obtain porous graphene;
and mixing the obtained porous graphene with a nitrogen-containing solvent, and then carrying out doping treatment under the closed solvothermal condition to obtain the nitrogen-doped graphene negative electrode material.
Pyridine nitrogen and pyrrole nitrogen can form a reversible nitrogen-containing lithium ion compound with lithium ions, the reversible capacity of the battery can be greatly improved, and in the actual preparation process, nitrogen elements in the nitrogen-doped graphene randomly exist as pyrrole nitrogen, pyridine nitrogen and graphite nitrogen. Therefore, according to the method, firstly, porous activation treatment is carried out on graphene to obtain porous graphene, then nitrogen doping is carried out by using a nitrogen-containing solvent, so that the content of pyridine nitrogen and pyrrole nitrogen in the nitrogen-doped graphene negative electrode material can be increased, and the nitrogen-doped graphene negative electrode material mainly containing pyridine nitrogen and pyrrole nitrogen is obtained. The negative electrode material is used as a negative electrode material of a lithium ion power battery to assemble the battery, so that the nitrogen-doped graphene lithium ion power battery with pyridine nitrogen and pyrrole nitrogen as main forms is obtained, and the specific capacity of the battery is effectively improved.
Graphene starting materials are well known to those skilled in the art in light of the present disclosure, for example, the graphene starting materials are selected from graphene and/or reduced graphene oxide, and other graphene starting materials may also be employed by those skilled in the art, and are not described in further detail herein. The reduced graphene oxide can be obtained by reducing graphene oxide prepared by a modified Hummers method, which is well known to those skilled in the art and is not described in detail in this disclosure.
According to the disclosure, the etching treatment is used for generating a plurality of holes on the graphene raw material, so as to improve the efficiency of nitrogen doping in the solvent heat treatment process, the etchant may be potassium hydroxide, and the conditions of the etching treatment may include: the temperature is 600-800 ℃, the time is 1-6 hours, and the weight ratio of the etching agent to the graphene raw material is 1: (0.1-10). The etchant and the graphene raw material may be directly mixed, or the etchant may be loaded on the graphene raw material by a method such as dipping, for example, the mixing step of the two may include: and soaking the graphene raw material in an etchant aqueous solution with a certain concentration, and drying to obtain a mixture of graphene and the etchant for etching treatment.
According to the present disclosure, the doping treatment is used for doping nitrogen into porous graphene under a closed solvothermal condition, the nitrogen-containing solvent may be one or more selected from hydrazine hydrate, ammonia water, urea, acetonitrile and pyrrole, and the materials are cheap and easily available and low in cost. The conditions of the solvothermal treatment may include: the weight ratio of the porous graphene to the nitrogen-containing solvent is 1: (0.1-100) at 150-240 deg.c for 6-48 hr.
According to the present disclosure, the solvothermal process is well known to those skilled in the art, the doping treatment may be performed in a reaction kettle, and the material after the solvothermal treatment may be naturally cooled to room temperature, and then subjected to solid-liquid separation such as centrifugation, water washing, and drying to obtain the nitrogen-doped graphene anode material.
The disclosure also provides the nitrogen-doped graphene anode material prepared by the preparation method.
The disclosure also provides a nitrogen-doped graphene negative electrode material, which is determined by adopting X photoelectron spectroscopy, wherein the content of pyridine nitrogen is 40-50 wt%, the content of pyrrole nitrogen is 33-40 wt%, and the content of graphite nitrogen is 15-25 wt% based on the total weight of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen in the nitrogen-doped graphene negative electrode material. The nitrogen-doped graphene negative electrode material provided by the disclosure has high pyridine nitrogen content and pyrrole nitrogen content, and low graphite nitrogen content.
The present disclosure also provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator and an electrolyte, where the negative electrode includes the nitrogen-doped graphene negative electrode material provided by the present disclosure.
According to the present disclosure, in addition to the nitrogen-doped graphene negative electrode material provided in the present disclosure, other components and materials known to those skilled in the art may be used in the lithium ion battery, for example, the negative electrode may further include acetylene black and polyvinylidene fluoride, and the weight ratio of the nitrogen-doped graphene negative electrode material, the acetylene black and the polyvinylidene fluoride is (75-85): (5-15): 10; the anode material of the anode can be one or more selected from lithium iron phosphate, lithium manganate, lithium nickelate, lithium cobaltate and ternary lithium nickel cobalt manganese oxide. The electrolyte may include lithium hexafluorophosphate and/or lithium perchlorate, for example, the electrolyte may include lithium hexafluorophosphate, ethylene carbonate, and dimethyl carbonate, the concentration of lithium hexafluorophosphate in the electrolyte may be 0.5 to 2.5 mol/l, and the volume ratio of ethylene carbonate to dimethyl carbonate may be 1: (0.5-2).
The disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
In the disclosure, the reagents are all commercially available analytical reagents unless otherwise specified, and different reagents do not affect the use effect.
The graphene disclosed by the disclosure is obtained in the market, and the reduced graphene oxide is obtained by reducing the graphene oxide prepared by the modified Hummers method.
The Transmission Electron Microscope (TEM) is used for carrying out the morphological analysis on the prepared nitrogen-doped graphene negative electrode material and comprises the following steps: taking a trace sample to disperse in ethanol, ultrasonically dispersing the sample to a uniform suspension by using a cell crusher, sucking a small amount of dispersed liquid by using a liquid transfer gun to drop on a micro-grid, baking by using an infrared lamp, and carrying out TEM (transmission electron microscope) test after the ethanol is completely volatilized.
The method for analyzing the nitrogen-containing type and content of the nitrogen-doped graphene anode material by X Photoelectron Spectroscopy (XPS) comprises the following steps: firstly, the nitrogen-doped graphene negative electrode material is baked in a vacuum oven at 60 ℃ for 24 hours to remove water, and then an XPS test is carried out. And (3) testing conditions are as follows: excitation source MgK alpha (1253.6eV), power 450W and vacuum degree 10-8～10-9And (5) Torr. The instrument used was a PHI1600X photoelectron spectrometer from PERKIN ELMZR. Pyrrole nitrogen, pyridine nitrogen and graphite nitrogen correspond to characteristic peaks at 398, 400 and 402, and the relative contents of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen are calculated by the relative proportions of the peak areas of the characteristic peaks.
Example 1
Mixing the components in a weight ratio of 1: and 5, mixing the graphene with KOH in a tubular furnace, and then carrying out etching treatment for 2 hours at 600 ℃ to obtain the porous graphene with porous and defect structures on the surface.
Mixing the obtained porous graphene and urea according to a weight ratio of 1: 10, placing the mixture into a reaction kettle, reacting for 24 hours at 150 ℃ under sealed autogenous pressure, naturally cooling to room temperature after reaction, then centrifuging, washing and drying to obtain the nitrogen-doped graphene anode material, wherein a transmission electron microscope photo is shown in figure 2, and an X-ray photoelectron spectroscopy analysis spectrogram is shown in figure 3. Through detection, the content of pyridine nitrogen in the material is 48 wt%, the content of pyrrole nitrogen is 36 wt%, and the content of graphite nitrogen is 16 wt%.
Mixing a nitrogen-doped graphene negative electrode material, acetylene black and polyvinylidene fluoride according to a weight ratio of 80:10:10, then carrying out wet grinding in N-methylpyrrolidone (NMP) to obtain slurry, uniformly coating the slurry on a copper foil, placing the copper foil in a forced air oven to be dried for 2 hours at 55 ℃, and then placing the copper foil in a vacuum drying oven to be dried for 24 hours to obtain the negative electrode.
A solution of 1 mol/L lithium hexafluorophosphate in ethylene carbonate and dimethyl carbonate is used as an electrolyte, and the volume ratio of the ethylene carbonate to the dimethyl carbonate is 1: 1.
And assembling the positive electrode, the negative electrode, the diaphragm, the electrolyte and the battery shell in a glove box filled with argon. During assembly, the reference counter electrode is a metal lithium sheet, the diaphragm type is Celgrad3500, and then electrochemical performance test is carried out, wherein the test current density is 100mAh g-1The number of charging and discharging cycles is 1-100, and the performance test curve chart is shown in figure 4.
As can be seen from FIG. 4, the specific capacity of the battery after 100 cycles was 1100 mAh/g.
Example 2
The etching process is basically the same as the example 1, except that the etching process is carried out at the temperature of 800 ℃ for 1 hour, and the mixing weight ratio of the etching agent to the graphene raw material is 1: 10; the nitrogen-containing solvent used for doping treatment is hydrazine hydrate, and the weight ratio of the porous graphene to the hydrazine hydrate is 1: 50 at 240 ℃ for 12 hours. The content of pyridine nitrogen in the obtained nitrogen-doped graphene negative electrode material is 45 wt%, the content of pyrrole nitrogen is 34 wt%, and the content of graphite nitrogen is 21 wt%.
The nitrogen-doped graphene negative electrode material obtained in the embodiment is assembled into a battery to be subjected to electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 1000 mAh/g.
Example 3
The etching process was performed at 700 ℃ for 6 hours, and the weight ratio of the etchant to the graphene material was 1: 10; the nitrogen-containing solvent used for doping treatment is acetonitrile, and the weight ratio of the porous graphene to the urea is 1: 10 at a temperature of 200 ℃ for 24 hours. The content of pyridine nitrogen in the obtained nitrogen-doped graphene negative electrode material is 46 wt%, the content of pyrrole nitrogen is 38 wt%, and the content of graphite nitrogen is 16 wt%.
The nitrogen-doped graphene negative electrode material obtained in the embodiment is assembled into a battery to be subjected to electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 1100 mAh/g.
Example 4
The same as example 1 except that the graphene raw material used was reduced graphene oxide. The content of pyridine nitrogen in the obtained nitrogen-doped graphene negative electrode material is 40 wt%, the content of pyrrole nitrogen is 36 wt%, and the content of graphite nitrogen is 24 wt%.
The nitrogen-doped graphene negative electrode material obtained in the embodiment is assembled into a battery to be subjected to electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 900 mAh/g.
Comparative example 1
The preparation method of the nitrogen-doped graphene negative electrode material comprises the following steps: and (3) uniformly mixing urea and graphene, and reacting for 5 hours at 900 ℃ under the protection of argon. The content of pyridine nitrogen in the obtained nitrogen-doped graphene negative electrode material is 40 wt%, the content of pyrrole nitrogen is 28 wt%, and the content of graphite nitrogen is 32 wt%.
The nitrogen-doped graphene negative electrode material obtained in the comparative example is assembled into a battery to be subjected to electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 700 mAh/g.
Comparative example 2
The method is basically the same as example 1, except that the graphene is not etched, but is directly doped, and the nitrogen-doped graphene anode material obtained contains 32 wt% of pyridine nitrogen, 28 wt% of pyrrole nitrogen and 40 wt% of graphite nitrogen.
The nitrogen-doped graphene negative electrode material obtained in the comparative example is assembled into a battery for electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 650 mAh/g.
Comparative example 3
The method is basically the same as the embodiment 1, except that the preparation method of the nitrogen-doped graphene anode material comprises the following steps of doping treatment and etching treatment, and the specific method comprises the following steps:
mixing the obtained graphene and urea according to a weight ratio of 1: 10, placing the mixture into a reaction kettle, reacting for 24 hours at 150 ℃ under sealed autogenous pressure, naturally cooling to room temperature after reaction, centrifuging, washing with water and drying, and then mixing the obtained graphene according to a weight ratio of 1: and 5, mixing the mixture with KOH in a tubular furnace, and then carrying out etching treatment for 2 hours at the temperature of 600 ℃ to obtain the nitrogen-doped graphene negative electrode material. Through detection, the content of pyridine nitrogen in the material is 40 wt%, the content of pyrrole nitrogen is 15 wt%, and the content of graphite nitrogen is 45 wt%.
The nitrogen-doped graphene negative electrode material obtained in the comparative example is assembled into a battery to be subjected to electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 700 mAh/g.
Comparative example 4
Basically the same as example 1, except that the graphene is not subjected to etching treatment and nitrogen doping, and is directly used as a negative electrode material to prepare a battery.
The nitrogen-doped graphene negative electrode material obtained in the comparative example is assembled into a battery for electrochemical performance test, and after the battery is cycled for 100 times, the specific capacity of the battery is 400 mAh/g.
It can be seen from the examples and comparative examples that the prepared nitrogen-doped graphene mainly containing pyridine nitrogen and pyrrole nitrogen is used as the negative electrode material of the lithium ion battery, and the lithium ion power battery obtained by performing electrochemical performance test after assembling the negative electrode material into a half battery by the method disclosed by the invention has high specific capacity and efficiency.
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 (8)

1. A preparation method of a nitrogen-doped graphene negative electrode material comprises the following steps:
mixing a graphene raw material with an etching agent, and then carrying out etching treatment to obtain porous graphene; the etching treatment conditions include: the etching treatment temperature is 600-800 ℃, the time is 1-6 hours, and the mixing weight ratio of the etching agent to the graphene raw material is 1: (0.1-10); the etching agent is potassium hydroxide;
mixing the obtained porous graphene with a nitrogen-containing solvent, and then carrying out doping treatment under the closed solvothermal condition to obtain a nitrogen-doped graphene negative electrode material; the conditions of the doping treatment include: the weight ratio of the porous graphene to the nitrogen-containing solvent is 1: (0.1-100) at 150-240 deg.c for 6-48 hr.
2. The production method according to claim 1, wherein the graphene raw material is selected from graphene and/or reduced graphene oxide.
3. The method according to claim 1, wherein the nitrogen-containing solvent is one or more selected from hydrazine hydrate, aqueous ammonia, urea, acetonitrile, and pyrrole.
4. The nitrogen-doped graphene anode material prepared by the preparation method of any one of claims 1 to 3.
5. The nitrogen-doped graphene anode material prepared by the method of any one of claims 1 to 4, wherein the content of pyridine nitrogen is 40 to 50 wt%, the content of pyrrole nitrogen is 33 to 40 wt%, and the content of graphite nitrogen is 15 to 25 wt%, based on the total weight of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen in the nitrogen-doped graphene anode material, as determined by X-ray photoelectron spectroscopy.
6. A lithium ion battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode comprises the nitrogen-doped graphene negative electrode material as defined in claim 4 or 5.
7. The lithium ion battery of claim 6, wherein the negative electrode further comprises acetylene black and polyvinylidene fluoride, and the weight ratio of the nitrogen-doped graphene negative electrode material to the acetylene black to the polyvinylidene fluoride is (75-85): (5-15): 10;
the anode material of the anode is selected from one or more of lithium iron phosphate, lithium manganate, lithium nickelate, lithium cobaltate and ternary lithium nickel cobalt manganese oxide;
the electrolyte comprises lithium hexafluorophosphate and/or lithium perchlorate.
8. The lithium ion battery of claim 6, wherein the electrolyte comprises lithium hexafluorophosphate, ethylene carbonate and dimethyl carbonate, the concentration of lithium hexafluorophosphate in the electrolyte is 0.5-2.5 mol/l, and the volume ratio of ethylene carbonate to dimethyl carbonate is 1: (0.5-2).
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