CN113955745A - Nitrogen-doped graphene and preparation method and application thereof - Google Patents

Nitrogen-doped graphene and preparation method and application thereof Download PDF

Info

Publication number
CN113955745A
CN113955745A CN202111222746.3A CN202111222746A CN113955745A CN 113955745 A CN113955745 A CN 113955745A CN 202111222746 A CN202111222746 A CN 202111222746A CN 113955745 A CN113955745 A CN 113955745A
Authority
CN
China
Prior art keywords
nitrogen
doped graphene
grinding
graphite
preparation
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
CN202111222746.3A
Other languages
Chinese (zh)
Inventor
卢文
向富维
文浪
成方
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.)
Kunming Yunda New Energy Co ltd
Original Assignee
Kunming Yunda New Energy 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 Kunming Yunda New Energy Co ltd filed Critical Kunming Yunda New Energy Co ltd
Priority to CN202111222746.3A priority Critical patent/CN113955745A/en
Publication of CN113955745A publication Critical patent/CN113955745A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01M4/38—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
    • H01M4/58—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or 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
    • H01M2004/027—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 nitrogen-doped graphene and a preparation method and application thereof, and belongs to the technical field of new materials. The method comprises the steps of firstly, placing raw materials in a grinding device, adding grinding media, and grinding at the rotating speed of 50RPM-10000RPM under the nitrogen-containing atmosphere of 0.1-200Mpa to obtain the product; the raw material is graphite material and/or graphene; the mass ratio of the raw materials to the grinding medium is 1: 0.1-1000. Aiming at the defects of complex process, severe conditions, large raw material pollution, low and difficult control of nitrogen doping amount, difficult control of specific surface area, difficult large-scale production and the like in the preparation of the conventional nitrogen-doped graphene material, the invention provides a scheme with simple preparation process, simple conditions, no pollution, good safety, low equipment requirement and low energy consumption, and the obtained nitrogen-doped graphene has high and controllable nitrogen doping amount, high purity, adjustable specific surface area and easy realization of large-scale industrial production.

Description

Nitrogen-doped graphene and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to nitrogen-doped graphene and a preparation method and application thereof.
Background
Graphene, as a two-dimensional carbon material, has an extremely large specific surface area, excellent electrochemical and optical properties, and high mechanical properties (young's modulus of about 1.0TPa and breaking strength of 130 GPa). Since 2004, graphene was stripped from graphite, and has been continuously explored by researchers and industries for its application in various fields. The current application fields relate to catalysts, batteries, supercapacitors, sensors, transistors, flexible displays, seawater desalination, hydrogen storage materials, aerospace, photosensitive elements, biological sterilization and the like. And heteroatom doping is carried out on the graphene, so that atom arrangement, electronic arrangement and defects of the graphene can be regulated and controlled, and the performance is improved, so that the performance exertion of the graphene in various application fields is enhanced. The graphene is doped with nitrogen, so that the conductivity type of the graphene can be effectively changed, the free carrier density of the graphene is improved, and the electrochemical activity and stability of the graphene are improved. Therefore, the nitrogen-doped graphene has great application value and commercial value.
The existing preparation method of nitrogen-doped graphene mainly comprises chemical vapor deposition, an ammonia pyrolysis method, a nitrogen-containing precursor pyrolysis method, an arc discharge method, a plasma treatment method and N2H4A reduction method, a hydrothermal method and the like, but due to factors such as complex preparation process, high equipment requirement, high energy consumption, environmental pollution, poor product batch consistency, difficulty in expanded production and the like, the existing preparation method is difficult to meet the requirement on the nitrogen-doped graphene. Due to the difficulty in large-scale production, nitrogen-doped graphene in the market is generally expensive. Taking nitrogen-doped graphene of Nanjing Xiancheng nanomaterial science and technology Limited, the price of the graphene with the nitrogen content of 3.0wt% is 2000RMB g-1The price of graphene with the nitrogen content of 8wt% of Hezhou limited, a novel carbon material of high star is 3000RMB g-1It fully accounts for the large market demand of nitrogen-doped graphene and the high cost of existing production techniques. Chinese patent CN108706578A discloses a nitrogen-doped graphene and a preparation method thereof, wherein the nitrogen-doped graphene is obtained by ball-milling graphene and one or more of urea, melamine, pyridine, pyrrole or acrylamide mixed with nitrogen-containing compounds, and then calcining at high temperature. The method needs to prepare graphene in advance and needs high-temperature calcination treatment, so that the process is complex and the energy consumption is high. Chinese patent CN104505512A discloses a method for preparing microcrystalline graphene by ball milling, which comprises subjecting microcrystalline graphite to shock heating and shock cooling treatment, and then ball milling under nitrogen atmosphere to obtain nitrogen-doped microcrystalline graphene. The method needs to firstly carry out heat treatment on the microcrystalline graphite at 800-.
The existing preparation process of the nitrogen-doped graphene has the problems of complex process, high energy consumption, high pollution, poor process controllability, poor repeatability, high cost, high equipment requirement, great potential safety hazard, difficulty in expanded production and the like, and the application and commercialization of the nitrogen-doped graphene in various fields are seriously hindered. Therefore, the design and development of a nitrogen-doped graphene preparation method which has the advantages of simple equipment requirement, simple preparation process, small environmental pollution, low energy consumption, high controllability, good safety, good product consistency and controllable nitrogen content is irresistible to large-scale production and application.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides nitrogen-doped graphene and a preparation method and application thereof. According to the method, the graphite material and/or graphene is/are used as a carbon source, gas containing nitrogen is used as a nitrogen source, the graphite material is converted into graphene in the process through a grinding (including ball milling, sand milling and rod milling) method, and meanwhile, nitrogen is used as the nitrogen source for nitrogen doping, so that the nitrogen-doped graphene is finally obtained. Compared with other preparation schemes of nitrogen-doped graphene, the preparation method has the advantages of simple preparation process, simple conditions, no pollution, good safety, low equipment requirement and low energy consumption. Compared with the nitrogen-doped graphene obtained by other methods, the nitrogen-doped graphene prepared by the method has the advantages of high and controllable nitrogen doping amount, high purity, adjustable specific surface area and easiness in realization of large-scale industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a method for preparing nitrogen-doped graphene, comprising the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at a rotating speed of 50RPM-10000RPM under a nitrogen-containing atmosphere of 0.1-200Mpa to obtain nitrogen-doped graphene;
the raw material is graphite material and/or graphene;
the mass ratio of the raw materials to the grinding medium is 1: 0.1-1000.
The graphene is one or a mixture of two of single-layer graphene and/or multi-layer graphene.
Further, preferably, the grinding device is a ball mill, a sand mill or a rod mill, and the corresponding grinding media are grinding balls, a sand disc and grinding rods; the grinding time is 1min-3000 h.
The present invention is not limited to a specific type of ball mill, sand mill or rod mill, and for example, the ball mill may be a planetary ball mill or a horizontal ball mill.
Further, preferably, the inner wall of the grinding device, which is in contact with the raw material, is made of agate, stainless steel, zirconium oxide or tungsten carbide; the grinding medium is made of agate, stainless steel, zirconium oxide or tungsten carbide.
Further, preferably, the specific setting method of the nitrogen-containing atmosphere environment of 0.1-200Mpa comprises the following steps: vacuumizing the grinding device, filling nitrogen-containing gas, vacuumizing, filling nitrogen-containing gas, repeating the steps for many times, and filling nitrogen-containing gas of 0.1-200 Mpa;
wherein, in the nitrogen-containing atmosphere, the volume concentration of the nitrogen is 1-99.999%.
Further, it is preferable that the graphite-based material includes natural graphite and artificial graphite; the particle size range of the graphite material and the graphene is 0.1-100 mu m, and the purity is more than or equal to 80 wt%.
For example, the graphite-based material may be, but is not limited to, spherical graphite, expanded graphite, microcrystalline graphite, and graphite mesocarbon microbeads. The graphite-based material may be one of the above, such as spheroidal graphite, or may be a combination of a plurality of materials, such as expanded graphite, microcrystalline graphite, and natural graphite.
The invention preferably discloses a preparation method of nitrogen-doped graphene, which comprises the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at the rotating speed of 300-2000 RPM under the nitrogen-containing atmosphere of 0.4-50Mpa to obtain the nitrogen-doped graphene;
the raw material is graphite material and/or graphene;
the mass ratio of the raw materials to the grinding medium is 1: 3-100;
the grinding time is 20min-60 h;
in the nitrogen-containing atmosphere, the volume concentration of nitrogen is 50-99.999%.
Note: the grinding method is any one of ball milling, sand milling and rod milling.
The second aspect of the present invention provides the nitrogen-doped graphene prepared by the above method for preparing nitrogen-doped graphene. The nitrogen-doped graphene has a nano-sized structure and nitrogen-doped defects.
The third aspect of the invention provides an application of the nitrogen-doped graphene prepared by the preparation method of the nitrogen-doped graphene in preparation of lithium ion batteries, super capacitors and catalysts.
The invention provides a lithium ion battery, and the negative electrode of the lithium ion battery comprises the nitrogen-doped graphene. Generally speaking, the lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and the nitrogen-doped graphene prepared by the method can be used as a negative electrode material of the lithium ion battery and also can be used as a conductive additive.
In a fifth aspect of the present invention, a supercapacitor is provided, and a positive electrode and/or a negative electrode of the supercapacitor include the above nitrogen-doped graphene. Generally speaking, the supercapacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and the nitrogen-doped graphene prepared by the method can be used as a positive electrode material and/or a negative electrode material of the supercapacitor.
A sixth aspect of the present invention provides the above catalyst, wherein the catalyst contains the nitrogen-doped graphene; the catalyst is oxygen reduction catalyst, hydrogen oxidation catalyst, water decomposition catalyst, photocatalyst and biological sterilization catalyst.
It will be appreciated by those skilled in the art that a sufficient amount of nitrogen and pressure need to be maintained in the milling apparatus to allow the starting materials to complete the reaction. The amount of nitrogen doping in the raw material can also be controlled by one skilled in the art by controlling the amount of nitrogen, pressure and reaction time, and the present invention is not particularly limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a scheme with simple preparation process, simple conditions, no pollution, good safety, low equipment requirement and low energy consumption, aiming at the defects of complex process, severe conditions, large raw material pollution, large potential safety hazard, high equipment requirement, large energy consumption, low nitrogen doping amount and difficulty in control of the obtained nitrogen-doped graphene, difficulty in controlling specific surface area, difficulty in large-scale production and the like in the preparation of the conventional nitrogen-doped graphene material.
Compared with the prior art, the method has the following advantages:
1. the graphite material and the nitrogen-containing gas adopted by the invention have the advantages of wide source, low price, no pollution, easy storage and the like.
2. The method adopts a simple one-step method to prepare the nitrogen-doped graphene, has simple equipment requirement and low cost, and is easy to realize large-scale production.
3. According to the invention, the nitrogen doping amount, the specific surface area and the particle size of the obtained nitrogen-doped graphene can be controlled by controlling the gas pressure, the ratio of the raw material to the grinding medium, the equipment rotating speed and the operating time, so that the preparation conditions can be adjusted according to different use requirements to obtain corresponding products.
4. The nitrogen-doped graphene obtained by the invention has larger specific surface area, more defects and higher nitrogen doping amount, so that the reversible specific capacity of lithium storage is effectively improved compared with the original graphite material, and the nitrogen-doped graphene can be used as a negative electrode material or a conductive additive of a high-energy-density lithium ion battery.
5. The nitrogen-doped graphene obtained by the invention has larger specific surface area, more defects and higher nitrogen doping amount, so that the nitrogen-doped graphene has higher electric double layer and pseudocapacitance energy storage characteristics and can be used as an electrode material of a high-energy-density super capacitor.
6. The nitrogen-doped graphene obtained by the invention has larger specific surface area, more defects and higher nitrogen doping amount, so that more catalytic active sites can be provided when the nitrogen-doped graphene is used as a catalyst, and the catalytic activity of the catalyst is improved.
Therefore, the method provided by the invention has the advantages of simple preparation process, simple conditions, no pollution, good safety, low equipment requirement and low energy consumption, and the obtained nitrogen-doped graphene has the advantages of high and controllable nitrogen doping amount, adjustable specific surface area and easiness in realizing large-scale industrial production, and can be applied to a series of wide fields.
Drawings
FIG. 1 shows XPS spectra of comparative example 1, example 2 and example 3.
Fig. 2 shows isothermal nitrogen adsorption-desorption curves of comparative example 1, example 2, and example 3.
Fig. 3 is SEM images of comparative example 1, example 2, and example 3.
Fig. 4 is a discharge-charge curve at 0.1C current for comparative example 1, example 2, and example 3.
Fig. 5 is the rate performance data for comparative example 2, comparative example 3, example 4, example 5, example 6, example 7.
FIG. 6 is a cyclic voltammogram at a scan rate of 1mV/s for comparative example 4 and example 8.
FIG. 7 is a cyclic voltammogram of comparative example 5, example 9 at a scan rate of 1 mV/s.
FIG. 8 is a cyclic voltammogram of example 10 at different scan speeds.
FIG. 9 is a cyclic voltammogram of example 11 at different scan speeds.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.
Comparative example 1
1. Mixing artificial graphite with purity of 99wt% and particle diameter of 20 μm, and oxygenThe zirconium oxide grinding ball comprises 1 part by mass of: mixing 37.5 parts by mass, putting into a ball milling tank, mixing in the ball milling tank, sealing the ball milling tank, vacuumizing the ball milling tank, filling nitrogen-containing gas, repeating the process for several times, filling 99.99% argon of 0.4Mpa, fixing the ball milling tank on the ball mill, performing ball milling at the rotating speed of 1000RPM, and performing ball milling for 12 hours to obtain nitrogen-free doped graphene, which is marked as Gr-Ar-0.4-1000-12. The prepared nitrogen-free doped graphene is subjected to XPS, BET and SEM characterization, and the constant current charge and discharge performance when the nitrogen-free doped graphene is used as a lithium ion battery negative electrode material is tested, and Gr-Ar-0.4-1000-12 is used as an active substance. In the preparation of the negative electrode sheet, the active material: SP: PVDF =87:3:10 (mass ratio), electrochemical test was assembled in a glove box (water/oxygen content less than 0.3 ppm) using a button half cell test (i.e. with lithium sheet as reference/counter electrode), using a conventional electrolyte (i.e. 1M LiPF)6EC/DMC/EMC (1: 1: 1)), the assembled CR2025 button cell was tested after 12h standing at room temperature, with a charge-discharge voltage range of 0.005-3V. The test current was 0.1C. Here, the 1C current was defined as 372mA g-1。
2. And (4) analyzing results: in the nitrogen-free doped graphene obtained by ball milling in argon in the figure 1, the XPS of the nitrogen-free doped graphene does not have characteristic peaks of N elements, and only characteristic peaks of C and O elements exist; the adsorption-desorption curve of the nitrogen-free doped graphene ball-milled in argon in FIG. 2 is a typical mixed type of type I and type V, and the specific surface area of the nitrogen-free doped graphene is 466.38m2g-1(ii) a The SEM image of the nitrogen-free doped graphene ball-milled in argon in FIG. 3, from which it can be seen that the size is about 10-80 nm; in fig. 4, the charging and discharging curve of the nitrogen-free doped graphene ball-milled in argon gas at 0.1C has a specific discharge capacity of 1015.21mAh g-1The charging specific capacity is 562.51mAh g-1The first coulombic efficiency was 55.41%.
Example 1
1. The method comprises the following steps of mixing artificial graphite with the purity of 99wt% and the particle size of 20 mu m with zirconia grinding balls according to the mass ratio of 1 part: mixing 37.5 parts by mass, putting into a ball-milling tank, mixing in the ball-milling tank, sealing the ball-milling tank, vacuumizing the ball-milling tank, filling nitrogen-containing gas, repeating the process for several times, filling 99.99% of 0.4Mpa nitrogen-containing gas, fixing the ball-milling tank on a ball mill, performing ball milling at the rotating speed of 1000RPM, and performing ball milling for 12 hours to obtain the nitrogen-doped graphene, wherein the mark is Gr-N-0.4-1000-12. The prepared nitrogen-doped graphene is subjected to XPS, BET and SEM characterization, and the constant current charge and discharge performance when the nitrogen-doped graphene is used as a lithium ion battery cathode material is tested. The test method comprises the following steps: physical property characterization and electrochemical test methods were the same as in comparative example 1.
2. And (4) analyzing results: in the nitrogen-doped graphene obtained by ball milling in a nitrogen-containing gas in fig. 1, an obvious characteristic peak of an N element appears in XPS, and the N element content is about 6.83wt% by analysis; the adsorption-desorption curve of the nitrogen-doped graphene ball-milled in the nitrogen-containing gas in the figure 2 is a typical mixed type of type I and type V, and the specific surface area of the nitrogen-doped graphene is 414.76m2 g-1(ii) a The SEM image of the nitrogen-doped graphene ball-milled in a nitrogen-containing gas in FIG. 3 shows that the size of the nitrogen-doped graphene is about 10-80 nm; in fig. 4, the charging and discharging curve at 0.1C of the nitrogen-doped graphene obtained by ball milling in the nitrogen-containing gas has a specific discharge capacity of 1064.03mAh g-1The charging specific capacity is 616.89mAh g-1The first coulombic efficiency was 57.98%. Compared with the graphene without nitrogen doping, the lithium storage capacity and the first coulombic efficiency of the obtained nitrogen-doped graphene are obviously improved.
Example 2
1. The method comprises the following steps of mixing artificial graphite with the purity of 99wt% and the particle size of 20 mu m with zirconia grinding balls according to the mass ratio of 1 part: mixing 37.5 parts by mass, putting into a ball milling tank, mixing in the ball milling tank, sealing the ball milling tank, vacuumizing the ball milling tank, filling nitrogen-containing gas, repeating the process for several times, filling 99.99% of 2Mpa nitrogen-containing gas, fixing the ball milling tank on the ball mill, performing ball milling at the rotating speed of 1000RPM, and performing ball milling for 12 hours to obtain the nitrogen-doped graphene, wherein the mark is Gr-N-2-1000-12. The prepared nitrogen-doped graphene is subjected to XPS, BET and SEM characterization, and the constant current charge and discharge performance when the nitrogen-doped graphene is used as a lithium ion battery cathode material is tested. The test method comprises the following steps: physical property characterization and electrochemical test methods were the same as in comparative example 1.
2. And (4) analyzing results: in the nitrogen-doped graphene obtained by ball milling in a nitrogen-containing gas in fig. 1, a distinct N element characteristic peak appears in XPS, and the N element content is about 9.66wt% by analysis; the adsorption-desorption curve of the nitrogen-doped graphene ball-milled in the nitrogen-containing gas in the figure 2 is a typical mixed type of type I and type V, and the specific surface area of the nitrogen-doped graphene is 325.35m2g-1(ii) a The SEM image of the nitrogen-doped graphene ball-milled in a nitrogen-containing gas in FIG. 3 shows that the size of the nitrogen-doped graphene is about 10-80 nm; in fig. 4, the charging and discharging curve at 0.1C of the nitrogen-doped graphene obtained by ball milling in the nitrogen-containing gas has a specific discharge capacity of 1111.26mAh g-1The charging specific capacity is 697.31mAh g-1The first coulombic efficiency was 62.75%. The method has the advantages that the pressure of nitrogen-containing gas in the system in the ball milling process is increased, the nitrogen doping amount of the nitrogen-doped graphene can be increased, and the lithium storage capacity and the first coulomb efficiency of the material are improved.
Example 3
1. The method comprises the following steps of mixing artificial graphite with the purity of 99wt% and the particle size of 20 mu m with zirconia grinding balls according to the mass ratio of 1 part: mixing 37.5 parts by mass, putting into a ball milling tank, mixing in the ball milling tank, sealing the ball milling tank, vacuumizing the ball milling tank, filling nitrogen-containing gas, repeating the process for several times, filling 99.99% of 2Mpa nitrogen-containing gas, fixing the ball milling tank on the ball mill, performing ball milling at the rotating speed of 1000RPM, and performing ball milling for 24 hours to obtain the nitrogen-doped graphene, wherein the mark is Gr-N-2-1000-24. The prepared nitrogen-doped graphene is subjected to XPS, BET and SEM characterization, and the constant current charge and discharge performance when the nitrogen-doped graphene is used as a lithium ion battery cathode material is tested. The test method comprises the following steps: physical property characterization and electrochemical test methods were the same as in comparative example 1.
2. And (4) analyzing results: in the nitrogen-doped graphene obtained by ball milling in a nitrogen-containing gas in fig. 1, a distinct characteristic peak of an N element appears in XPS, and the N element content is about 11.16wt% by analysis; the adsorption-desorption curve of the nitrogen-doped graphene ball-milled in the nitrogen-containing gas in the figure 2 is a typical mixed type of type I and type V, and the specific surface area of the nitrogen-doped graphene is 212.89m2g-1(ii) a The SEM image of the nitrogen-doped graphene ball-milled in a nitrogen-containing gas in FIG. 3 shows that the size of the nitrogen-doped graphene is about 10-80 nm; in fig. 4, the charging and discharging curve at 0.1C of the nitrogen-doped graphene obtained by ball milling in the nitrogen-containing gas has a specific discharge capacity of 1145.79mAh g-1The charging specific capacity is 742.79mAh g-1The first coulombic efficiency was 64.83%. The method has the advantages that the ball milling time in the ball milling process is prolonged, the nitrogen doping amount of the nitrogen-doped graphene can be increased, and the lithium storage capacity and the first coulombic efficiency of the material are further improved.
Comparative example 2
1. The artificial graphite material used in the present invention was used for rate capability test. In preparing the negative electrode sheet, the artificial graphite: SP: PVDF =87:3:10, electrochemical testing was assembled using a button half cell test (i.e., with the lithium sheet as the reference/counter electrode) in a glove box (water/oxygen content less than 0.3 ppm) using a conventional electrolyte (i.e., 1M LiPF)6EC/DMC/EMC (1: 1: 1)), the assembled CR2025 button cell was tested after 12h standing at room temperature, with a charge-discharge voltage range of 0.005-3V. The multiplying power test is carried out by constant current charging and discharging with 0.1, 0.2, 0.5, 1, 3, 5 and 0.1C current in sequence. Here, the 1C current was defined as 372mA g-1。
2. And (4) analyzing results: in FIG. 5, the reversible specific capacity of the artificial graphite after 5 cycles of 0.1C cycle is about 360.69mAh g-1Reversible specific capacity at 1C current of about 208.73mAh g-1The 1C capacity retention was 57.87%.
Comparative example 3
1. Rate capability tests were performed on commercial silicon carbon materials. When the negative pole piece is prepared, the silicon-carbon material SP: PVDF =87:3:10, and the electrochemical test is the same as that of comparative example 2.
2. And (4) analyzing results: in the figure 5, the reversible specific capacity of the first loop of the silicon-carbon negative electrode at 0.1C is 547.65mAh g-1And the reversible specific capacity after 5 cycles of circulation is about 516.52mAh g-1Reversible specific capacity at 1C current of about 248mAh g-1The 1C capacity retention was 48.50%.
Example 4
1. The nitrogen-doped graphene Gr-N-2-1000-12 prepared in the embodiment 2 of the invention is used as a conductive agent to prepare the graphite negative pole piece instead of SP. When the negative pole piece is prepared, Gr-N-2-1000-12: PVDF =87:3:10 is used as artificial graphite, and the electrochemical test is the same as that of comparative example 2.
2. And (4) analyzing results: in the preparation process of the artificial graphite negative pole piece in the figure 5, after the SP is replaced by Gr-N-2-1000-12, the reversible specific capacity after 5 cycles of 0.1C circulation is about 395.68mAh g-1Reversible specific capacity at 1C current of about 313.18mAh g-1The 1C capacity retention was 79.15%. Compared with SP, the multiplying power performance of the graphite cathode can be improved by using the nitrogen-doped graphene as a conductive agent, and the reversible capacity can be improved to a certain extent.
Example 5
1. The nitrogen-doped graphene Gr-N-2-1000-12 prepared in the embodiment 2 of the invention is used for replacing 3wt% of artificial graphite as an active substance to prepare the graphite-nitrogen-doped graphene composite negative pole piece. When the negative pole piece is prepared, Gr-N-2-1000-12: SP: PVDF =84:3:3:10 is used as artificial graphite, and the electrochemical test is the same as that of comparative example 2.
2. And (4) analyzing results: in FIG. 5, Gr-N-2-1000-12 replaces 3wt% of artificial graphite, and the reversible specific capacity after 5 cycles of 0.1C circulation is about 377.11mAh g-1Reversible specific capacity at 1C current of about 288.95mAh g-1The 1C capacity retention was 76.62%. The method shows that after the nitrogen-doped graphene is used for replacing artificial graphite, the rate capability and the reversible specific capacity of the graphite cathode can be improved.
Example 6
1. The nitrogen-doped graphene Gr-N-2-1000-24 prepared in the embodiment 3 of the invention is used for replacing 34.8wt% of artificial graphite as an active substance to prepare the graphite-nitrogen-doped graphene composite negative pole piece. When the negative pole piece is prepared, Gr-N-2-1000-24: SP: PVDF =52.2:34.8:3:10 is used as artificial graphite, and the electrochemical test is the same as that of comparative example 2.
2. And (4) analyzing results: in figure 5, after 34.8wt% of artificial graphite is replaced by Gr-N-2-1000-24, the reversible specific capacity of the first circle at 0.1C is 540.00mAh g-1And the reversible specific capacity after 5 cycles of circulation is about 479.20mAhg-1Reversible specific capacity at 1C current of about 269.63mAh g-1The 1C capacity retention ratio was 56.27% of the total weight of the composition. The composite negative electrode with the reversible capacity equivalent to that of a commercial silicon-carbon material can be obtained by adjusting the proportion of the nitrogen-doped graphene to the artificial graphite, and the composite negative electrode provided by the invention has more excellent rate capability compared with the commercial silicon-carbon negative electrode.
Example 7
1. The nitrogen-doped graphene Gr-N-2-1000-24 prepared in the embodiment 3 of the invention is used for replacing 17.4wt% of silicon carbon material as an active substance to prepare the silicon carbon material-nitrogen-doped graphene composite negative pole piece. When the negative pole piece is prepared, the silicon-carbon material Gr-N-2-1000-24 SP PVDF =69.6:17.4:3:10, and the electrochemical test is the same as that of comparative example 2.
2. And (4) analyzing results: after 17.4wt% silicon carbon material is replaced by Gr-N-2-1000-24 in FIG. 5, the reversible specific capacity after 5 cycles of 0.1C cycle is about 587.09mAh g-1Reversible specific capacity at 1C current of about 344.09mAh g-1The 1C capacity retention rate was 58.61%. The silicon-carbon-nitrogen doped graphene composite electrode prepared by replacing a silicon-carbon material with nitrogen doped graphene has higher lithium storage capacity and more excellent rate capability compared with a commercial silicon-carbon cathode.
Comparative example 4
1. The artificial graphite used in the invention is used as an active material, the artificial graphite SP: CMC: SBR =90:5:1.7:3.3 is stirred by a magnetic stirrer, slurry stirred for 12 hours is dripped on a glassy carbon electrode, and the glassy carbon electrode is dried at 60 ℃ and then tested. Taking a glassy carbon electrode coated with artificial graphite as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode and N as an electrolyte2A saturated 0.1M KOH solution was scanned at a scan rate of 1mV/s over a range of-1V to 0.2V.
2. And (4) analyzing results: after cyclic voltammetric scanning of the artificial graphite in fig. 6, it can be seen that the reduction curve and the oxidation curve of the artificial graphite are substantially coincident and almost form a straight line, indicating that there is no contribution of electric double layer capacitance.
Example 8
1. The nitrogen-doped graphene Gr-N-2-1000-24 prepared in the embodiment 3 of the invention is used as an active material, and Gr-N-2-1000-24: SP: CMC: SBR =905:1.7:3.3, stirring by a magnetic stirrer, dripping the slurry stirred for 12 hours on a glassy carbon electrode, drying at 60 ℃, and then testing. Taking a glassy carbon electrode coated with Gr-N-2-1000-24 as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode and N as an electrolyte2A saturated 0.1M KOH solution was scanned at a scan rate of 1mV/s over a range of-1V to 0.2V.
2. And (4) analyzing results: after cyclic voltammetric scanning of Gr-N-2-1000-24 in FIG. 6, it can be seen that Gr-N-2-1000-24 has a nearly square cyclic voltammetric curve and has a larger current than that of artificial graphite, indicating that it has a more significant contribution to the double layer capacitance.
Comparative example 5
1. The artificial graphite used in the invention is used as an active material, the artificial graphite SP: CMC: SBR =90:5:1.7:3.3 is stirred by a magnetic stirrer, slurry stirred for 12 hours is dripped on a glassy carbon electrode, and the glassy carbon electrode is dried at 60 ℃ and then tested. The glassy carbon electrode coated with artificial graphite is used as a working electrode, a platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, and an electrolyte is O2A saturated 0.1M KOH solution was scanned at a scan rate of 1mV/s over a range of-1V to 0.2V.
2. And (4) analyzing results: after cyclic voltammetric scanning of the artificial graphite in fig. 7, it can be seen that the reduction curve and the oxidation curve of the artificial graphite substantially coincide and almost form a straight line, indicating that it has no redox catalytic activity.
Example 9
1. The nitrogen-doped graphene Gr-N-2-1000-24 prepared in the embodiment 3 of the invention is used as an active material, Gr-N-2-1000-24: SP: CMC: SBR =90:5:1.7:3.3, stirred by a magnetic stirrer, and the slurry stirred for 12 hours is dripped on a glassy carbon electrode and dried at 60 ℃ for testing. Taking a glassy carbon electrode coated with Gr-N-2-1000-24 as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode and O as an electrolyte2A saturated 0.1M KOH solution was scanned at a scan rate of 1mV/s over a range of-1V to 0.2V.
2. And (4) analyzing results: after cyclic voltammetry scanning is carried out on Gr-N-2-1000-24 in FIG. 7, it can be seen that Gr-N-2-1000-24 has an obvious reduction peak near-0.21V and an obvious oxidation peak near-0.071V, which indicates that the catalyst has reversible oxygen reduction and oxidation catalytic activities. Moreover, obvious polarization phenomena appear at about-1V and 0.2V, which belong to reduction and oxidative decomposition of water respectively, and show that the prepared nitrogen-doped graphene has excellent water decomposition catalytic activity.
Example 10
1. Taking the nitrogen-doped graphene Gr-N-2-1000-12 prepared in the embodiment 2 of the invention as an active substance, preparing a pole piece according to the proportion of Gr-N-2-1000-12: CB: CMC: SBR =90:5:1.7:3.3, drying at 60 ℃, assembling into a symmetrical capacitor, wherein the electrolyte is 1M TEA-ACN, and performing cyclic voltammetry test at the scanning speed of 5, 10, 20 and 50 mV/s.
2. And (4) analyzing results: the cyclic voltammograms of Gr-N-2-1000-12 in fig. 8 show that at different scan speeds the shape remains typically square, indicating good capacitive behaviour. And as the scanning speed is increased, the closed area of the cyclic voltammogram is gradually increased, which shows better rate capability.
Example 11
1. According to the invention, the nitrogen-doped graphene Gr-N-2-1000-12 and Activated Carbon (AC) prepared in example 2 are simultaneously used as active substances, a composite pole piece is prepared according to the proportion of AC Gr-N-2-1000-12: CB: CMC: SBR =67.5:22.5:5:1.7:3.3, the composite pole piece is dried at 60 ℃, and then assembled into a symmetrical capacitor, the electrolyte is 1M TEA-ACN, and cyclic voltammetry is carried out at the scanning speed of 5, 10, 20 and 50 mV/s.
2. And (4) analyzing results: the cyclic voltammogram of the composite electrode in fig. 9 shows that at different scan speeds the shape remains typically square, indicating good capacitive behavior. And as the scanning speed is increased, the closed area of the cyclic voltammogram is gradually increased, which shows better rate capability.
Example 12
1. The method comprises the following steps of mixing natural graphite with the purity of 80wt% and the particle size of 0.1 mu m with agate grinding balls according to the mass ratio of 1 part: mixing 0.1 part by mass of the components, putting the mixture into a ball milling tank, mixing the mixture in the ball milling tank, sealing the ball milling tank, vacuumizing the ball milling tank, filling nitrogen-containing gas, repeating the process for several times, filling the nitrogen-containing gas with the volume concentration of 99.999% of 200Mpa nitrogen, fixing the ball milling tank on a horizontal ball mill, performing ball milling at the rotating speed of 200RPM, and performing ball milling for 3000 hours to obtain the nitrogen-doped graphene.
2. And (4) analyzing results: through analysis, the nitrogen doping amount of the obtained nitrogen-doped graphene is 1.3wt%, and the specific surface area is 800m2g-1。
Example 13
1. Spherical graphite with the purity of 99wt% and the particle size of 60 mu m and a tungsten carbide sand plate are mixed according to the mass ratio of 1 part by mass: mixing 1000 parts by mass of the components, putting the components into a sand mill, mixing, sealing the sand mill, vacuumizing the sand mill, filling nitrogen-containing gas, repeating the process for several times, filling the nitrogen-containing gas with the volume concentration of 1% and 0.1Mpa, sanding at the rotating speed of 10000RPM, and obtaining the nitrogen-doped graphene after 1 min.
2. And (4) analyzing results: through analysis, the nitrogen doping amount of the obtained nitrogen-doped graphene is 0.3wt%, and the specific surface area is 600m2g-1。
Example 14
1. The expanded graphite with the purity of 90wt% and the particle size of 30 mu m and a stainless steel grinding rod are mixed according to the mass ratio of 1 part by mass: and (2) mixing 500 parts by mass, putting into a rod mill, mixing, sealing the rod mill, vacuumizing the rod mill, filling nitrogen-containing gas, repeating the process for several times, filling 100Mpa of nitrogen-containing gas with the volume concentration of 50%, rod milling at the rotating speed of 500RPM, and obtaining the nitrogen-doped graphene after 48 hours.
2. And (4) analyzing results: through analysis, the nitrogen doping amount of the obtained nitrogen-doped graphene is 2.6wt%, and the specific surface area is 387m2g-1。
Example 15
1. Microcrystalline graphite with the purity of 80wt% and the particle size of 5 mu m and zirconia grinding balls are mixed according to the mass ratio of 1 part by mass: mixing 800 parts by mass, putting into a planetary ball mill, mixing, sealing the ball mill tank, vacuumizing the ball mill tank, filling nitrogen-containing gas, repeating the process for several times, filling nitrogen-containing gas with the volume concentration of 80% of 50Mpa, performing ball milling at the rotating speed of 5000RPM, and obtaining the nitrogen-doped graphene after 1000 hours.
2. And (4) analyzing results: the obtained nitrogen-doped graphene has the nitrogen doping amount of 28wt% and the specific surface area of 186m through analysis2g-1。
Example 16
1. Graphite mesophase carbon microspheres with the purity of 90wt% and the particle size of 50 mu m and a tungsten carbide sand plate are mixed according to the mass ratio of 1 part by mass: mixing 800 parts by mass of the components, putting the components into a sand mill, mixing, sealing the sand mill, vacuumizing the sand mill, filling nitrogen-containing gas, repeating the process for several times, filling the nitrogen-containing gas with the volume concentration of 70% of 20Mpa, sanding at the rotating speed of 2000RPM, and obtaining the nitrogen-doped graphene after 500 hours.
2. And (4) analyzing results: through analysis, the nitrogen doping amount of the obtained nitrogen-doped graphene is 25wt%, and the specific surface area is 202m2g-1。
Example 17
1. Graphene with the purity of 99.9wt% and the particle size of 0.1 mu m and a stainless steel grinding rod are mixed according to the mass ratio of 1 part by mass: mixing 1 part by mass of the components, putting the components into a rod mill, mixing, sealing the rod mill, vacuumizing the rod mill, filling nitrogen-containing gas, repeating the process for several times, filling the nitrogen-containing gas with the volume concentration of 30% of 90Mpa, performing rod milling at the rotating speed of 800RPM, and obtaining the nitrogen-doped graphene after 2000 hours.
2. And (4) analyzing results: through analysis, the nitrogen doping amount of the obtained nitrogen-doped graphene is 26wt%, and the specific surface area is 180m2g-1。
Example 18
The preparation method comprises the following steps of mixing 90wt% of expanded graphite with the particle size of 100 mu m, 95wt% of graphene with the particle size of 100 mu m and a stainless steel grinding rod in a mass ratio of 1 part: 1 part by mass: and (2) mixing 0.2 part by mass, putting into a rod mill, mixing, sealing the rod mill, vacuumizing the rod mill, filling nitrogen-containing gas, repeating the process for several times, filling nitrogen-containing gas with the volume concentration of 1% and 0.1Mpa into the rod mill, performing rod milling at the rotating speed of 50RPM, and obtaining the nitrogen-doped graphene after 2000 hours.
The prepared nitrogen-doped graphene is used as an oxygen reduction catalyst, a hydrogen oxidation catalyst, a water decomposition catalyst, a photocatalyst or a biological sterilization catalyst.
Example 19
Mixing 95wt% of natural graphite with the particle size of 50 microns, 90wt% of spherical graphite with the particle size of 60 microns, 95wt% of graphene with the particle size of 40 microns and a tungsten carbide sand disc according to the mass ratio of 1 part by mass: 1 part by mass: 1 part by mass: and (2) mixing 500 parts by mass, putting into a sand mill, mixing, sealing the sand mill, vacuumizing the sand mill, filling nitrogen-containing gas, repeating the process for several times, filling the nitrogen-containing gas with the volume concentration of 70% of 200Mpa, sanding at the rotating speed of 1000RPM, and obtaining the nitrogen-doped graphene after 500 hours.
Example 20
A preparation method of nitrogen-doped graphene comprises the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at a rotating speed of 300RPM under a nitrogen-containing atmosphere of 0.4Mpa to obtain nitrogen-doped graphene;
the raw material is graphene, the particle size is 0.1 mu m, and the purity is 80 wt%;
the mass ratio of the raw materials to the grinding medium is 1: 3;
the grinding time is 20 minh;
in the nitrogen-containing atmosphere, the volume concentration of nitrogen is 50%.
The grinding mode is ball milling.
Example 21
A preparation method of nitrogen-doped graphene comprises the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at the rotating speed of 2000RPM under the nitrogen-containing atmosphere of 50Mpa to obtain nitrogen-doped graphene;
the raw material is microcrystalline graphite with the grain diameter of 0.1 mu m and the purity of 80 wt%;
the mass ratio of the raw materials to the grinding medium is 1: 100;
the grinding time is 60 hours;
in the nitrogen-containing atmosphere, the volume concentration of nitrogen is 99.999 percent.
The grinding mode is sanding.
Example 22
A preparation method of nitrogen-doped graphene comprises the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at the rotating speed of 1000RPM under the atmosphere of 20Mpa containing nitrogen to obtain the nitrogen-doped graphene;
the raw material is spherical graphite with the grain diameter of 0.1 mu m and the purity of 80 wt%;
the mass ratio of the raw materials to the grinding medium is 1: 50;
the grinding time is 10 hours;
in the nitrogen-containing atmosphere, the volume concentration of nitrogen is 82%.
The grinding mode is rod grinding.
The prepared nitrogen-doped graphene is used as a part of an oxygen reduction catalyst, a hydrogen oxidation catalyst, a water decomposition catalyst, a photocatalyst or a biological sterilization catalyst.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A preparation method of nitrogen-doped graphene is characterized by comprising the following steps: placing the raw materials in a grinding device, adding a grinding medium, and grinding at a rotating speed of 50RPM-10000RPM under a nitrogen-containing atmosphere of 0.1-200Mpa to obtain nitrogen-doped graphene;
the raw material is graphite material and/or graphene;
the mass ratio of the raw materials to the grinding medium is 1: 0.1-1000.
2. The method for preparing nitrogen-doped graphene according to claim 1, wherein the grinding device is a ball mill, a sand mill or a rod mill, and the corresponding grinding media are grinding balls, grinding discs and grinding rods; the grinding time is 1min-3000 h.
3. The method for preparing nitrogen-doped graphene according to claim 2, wherein the inner wall of the grinding device, which is in contact with the raw material, is made of agate, stainless steel, zirconia or tungsten carbide; the grinding medium is made of agate, stainless steel, zirconium oxide or tungsten carbide.
4. The method for preparing nitrogen-doped graphene according to claim 1, wherein the specific setting method of the nitrogen-containing atmosphere environment of 0.1-200Mpa comprises the following steps: vacuumizing the grinding device, filling nitrogen-containing gas, vacuumizing, filling nitrogen-containing gas, repeating the steps for many times, and filling nitrogen-containing gas of 0.1-200 Mpa;
wherein, in the nitrogen-containing atmosphere, the volume concentration of the nitrogen is 1-99.999%.
5. The method for preparing nitrogen-doped graphene according to claim 1, wherein the graphite-based material includes natural graphite and artificial graphite; the particle size range of the graphite material and the graphene is 0.1-100 mu m, and the purity is more than or equal to 80 wt%.
6. The nitrogen-doped graphene prepared by the preparation method of any one of claims 1 to 5.
7. The application of the nitrogen-doped graphene prepared by the preparation method of any one of claims 1 to 5 in preparation of lithium ion batteries, supercapacitors and catalysts.
8. A lithium ion battery, wherein a negative electrode of the lithium ion battery comprises the nitrogen-doped graphene according to claim 6.
9. A supercapacitor, wherein the positive electrode and/or the negative electrode of the supercapacitor comprise the nitrogen-doped graphene according to claim 6.
10. A catalyst, characterized in that the catalyst comprises the nitrogen-doped graphene according to claim 6; the catalyst is oxygen reduction catalyst, hydrogen oxidation catalyst, water decomposition catalyst, photocatalyst and biological sterilization catalyst.
CN202111222746.3A 2021-10-20 2021-10-20 Nitrogen-doped graphene and preparation method and application thereof Pending CN113955745A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111222746.3A CN113955745A (en) 2021-10-20 2021-10-20 Nitrogen-doped graphene and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111222746.3A CN113955745A (en) 2021-10-20 2021-10-20 Nitrogen-doped graphene and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN113955745A true CN113955745A (en) 2022-01-21

Family

ID=79465002

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111222746.3A Pending CN113955745A (en) 2021-10-20 2021-10-20 Nitrogen-doped graphene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113955745A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306781A (en) * 2011-09-05 2012-01-04 中国科学院金属研究所 Doped graphene electrode material, macro preparation method and application of doped graphene electrode material
CN105417532A (en) * 2015-12-22 2016-03-23 北京理工大学 One-step preparation method for high nitrogen doped graphene
CN105645401A (en) * 2016-03-17 2016-06-08 渤海大学 Preparation method of N-doped graphene nanosheet
CN110323443A (en) * 2019-05-27 2019-10-11 北京理工大学 A kind of spherical N doping redox graphene material and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102306781A (en) * 2011-09-05 2012-01-04 中国科学院金属研究所 Doped graphene electrode material, macro preparation method and application of doped graphene electrode material
CN105417532A (en) * 2015-12-22 2016-03-23 北京理工大学 One-step preparation method for high nitrogen doped graphene
CN105645401A (en) * 2016-03-17 2016-06-08 渤海大学 Preparation method of N-doped graphene nanosheet
CN110323443A (en) * 2019-05-27 2019-10-11 北京理工大学 A kind of spherical N doping redox graphene material and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王桂强等: "氮掺杂石墨烯纳米片的制备及其电化学性能", 物理学报, vol. 65, no. 17, pages 178102 *

Similar Documents

Publication Publication Date Title
CN106601490B (en) A kind of preparation method of biomass-based nitrogenous porous carbon and porous carbon and application thereof
Chen et al. Bamboo-derived porous carbons for Zn-ion hybrid supercapacitors
CN109796003B (en) Coal-based hard carbon surface oxygen functional group directional regulation and control method for sodium storage cathode
CN102376937A (en) Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof
CN107658474A (en) A kind of nitrogen sulphur codope porous carbon microsphere and preparation method, purposes and oxygen reduction electrode
CN107887613A (en) Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials
Ahmad et al. Advances in graphene-based electrode materials for high-performance supercapacitors: A review
CN110451489A (en) A kind of cobalt nitride is embedded in porous nitrogen-doped graphene material and preparation method and application
CN108630445B (en) method for preparing supercapacitor carbon material from alkali-activated nitrogen-containing heterocyclic metal complex and application thereof
CN111048324A (en) Manganese dioxide-porous carbon composite material and preparation method and application thereof
Xiang et al. Hydrothermally etching commercial carbon cloth to form a porous structure for flexible zinc-ion hybrid supercapacitors
Zhang et al. High performance flower-like Mn3O4/rGO composite for supercapacitor applications
Zhang et al. Preparation of high-value porous carbon by microwave treatment of chili straw pyrolysis residue
Shang et al. A Facile and Effective Method for Constructing Rambutan‐Like NiCo2O4 Hierarchical Architectures for Supercapacitor Applications
CN109449412A (en) A kind of preparation method and applications of lithium ionic cell cathode material lithium titanate/nitrogen-doped graphene
CN110212204B (en) Carbon nanosheet supported fuel cell anode material and preparation method and application thereof
CN105923632A (en) Preparation method of active carbon for super capacitor based on graphene composite modification
CN111689523B (en) Metallic chromium doped delta-MnO2Preparation method of nanosheet
Wu et al. Fe2O3/carbon derived from peanut shell hybrid as an advanced anode for high performance lithium ion batteries
CN107221458A (en) Nickel complex is carbon dope nickel oxide combination electrode material of precursor and preparation method thereof
Zhao et al. Preparation of zinc-doped bagasse-based activated carbon multilayer composite and its electrochemical performance as a supercapacitor
Koventhan et al. Development of a polyaniline/CMK-3/hydroquinone composite supercapacitor system
CN105529194B (en) A kind of MnO2@graphene capsule@MnO2The preparation method of composite
Hu et al. Facile fabrication of NiCo-LDH on activated rice husk carbon for high-performance all-solid-state asymmetric supercapacitors
CN109755039B (en) Preparation method and application of manganese oxide composite material based on red bayberry biomass carbon-based 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