CN115472440A - Graphene-based N, S doped electrode material and preparation method thereof - Google Patents

Graphene-based N, S doped electrode material and preparation method thereof Download PDF

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CN115472440A
CN115472440A CN202210994493.XA CN202210994493A CN115472440A CN 115472440 A CN115472440 A CN 115472440A CN 202210994493 A CN202210994493 A CN 202210994493A CN 115472440 A CN115472440 A CN 115472440A
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拜永孝
刘天福
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Lanzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
    • Y02E60/13—Energy storage using capacitors

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Abstract

The application discloses a graphene-based N, S doped electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor; adding graphene oxide into the dispersion liquid to obtain a mixed solution; carrying out solvent heat treatment on the mixed solution; and washing and drying the product after the solvent heat treatment, and then carrying out heat shock treatment to obtain the electrode material. According to the preparation method, the nano carbon material is inserted between the graphene oxide layers to construct the mutual embedded structure, so that the conductivity of the graphene oxide layers is improved, and the nano carbon material is inserted to prevent the stacking of the graphene oxide layers; according to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transfer is promoted, and the conductivity and the energy storage effect of the material are improved.

Description

Graphene-based N, S doped electrode material and preparation method thereof
Technical Field
The application belongs to the technical field of capacitor material preparation, and particularly relates to a graphene-based N, S doped electrode material and a preparation method thereof.
Background
The wide use of fossil energy such as coal and petroleum can cause negative effects such as environmental pollution to climate change, so that a clean pollution-free green energy system to replace the traditional fossil energy and an efficient and convenient energy use mode become a hot problem to be researched at present. In the existing energy system, the green energy system such as solar energy, wind energy, tidal energy and the like suffers from the problems of climate conditions, intermittency, low energy density and the like, and the generated electric energy is difficult to be directly connected to a grid for use. Therefore, the development of new energy storage and supply devices with high power density, high energy density, and high conversion efficiency has become an important research topic.
In order to solve these problems, some new energy storage technologies, such as electrochemical, compressed air, heat pump water and electricity, have been proposed in recent years. Among the technologies, electrochemical energy storage has the characteristics of greenness, high efficiency, sustainability and the like, and is the first choice for solving the problems of effective conversion and storage of renewable energy sources and providing stable energy output. Currently, common electrochemical energy storage technologies include secondary batteries including air batteries, lithium ion batteries, lithium sulfur batteries, and the like, and novel electrochemical energy storage technologies such as supercapacitors, and the like. At present, electrochemical energy storage systems represented by lithium ion batteries and super capacitors are widely applied in the fields of standby power supplies, base station communication, portable mobile equipment and the like. However, due to the limitation of the mechanism of action, neither lithium ion batteries nor supercapacitors can meet the high energy density, high power density and good cycling stability required in many applications.
Electrode materials play a crucial role in the electrochemical performance of lithium ion capacitors. The common cathode materials include carbon materials, metal oxides, lithium titanate and the like, and the common anode materials include carbon materials, metal oxides, conductive polymers and the like. Although the theoretical capacity of the carbon material is low, the carbon material has the characteristics of no toxicity, high conductivity, low cost, abundant raw materials, strong reproducibility, high specific surface area, stable physicochemical property and the like, so that the carbon material is suitable for being used as an electrode, especially a graphene material. However, the graphene material as an electrode mainly has the problem that graphene tends to stack from layer to reduce surface energy, resulting in significantly lower conductivity and specific surface area than single-layer or few-layer graphene, so that the electrochemical performance of the capacitor of the graphene material is reduced.
Disclosure of Invention
The application aims to overcome the defects of the prior art, and provides a graphene-based N, S doped electrode material and a preparation method thereof, so as to solve the technical problems of low capacity and poor cycle stability of the conventional graphene-based electrode material.
In order to achieve the above purpose, in a first aspect of the present application, there is provided a method for preparing a graphene-based N, S doped electrode material, comprising the following steps:
preparing dispersion liquid containing the carbon nanomaterial and the heteroatom precursor;
adding graphene oxide into the dispersion liquid to obtain a mixed solution;
carrying out solvent heat treatment on the mixed solution;
and washing and drying the product after the solvent heat treatment, and then carrying out heat shock treatment to obtain the electrode material.
Further, the temperature of the solvent heat treatment is 150-200 ℃, and the time is 10-20 h.
Further, the temperature of the thermal shock treatment is 150-300 ℃, and the heating rate is 5-15 ℃/min.
Furthermore, the mass ratio of the nano carbon material to the heteroatom precursor in the dispersion liquid is 1 (0.8-10), and the concentration of the dispersion liquid is 0.5-2 mg/ml.
Further, the nano carbon material is at least one of carbon nanofiber, nano mesoporous carbon, carbon nanotube, fullerene, graphene quantum dot or carbon quantum dot.
Further, the heteroatom precursor is at least one of thiophene, thiourea, ammonium sulfate, ammonium sulfide and ammonium sulfite.
Further, the mass ratio of the graphene oxide to the dispersion liquid is (0.8-2): 1.
Further, the solvent of the mixed solution is any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
Further, the drying is freeze drying, and the temperature is-60 to-35 ℃.
In a second aspect of the present application, there is provided a graphene-based N, S doped electrode material, which is prepared by the preparation method described in any one of the above.
Compared with the prior art, the method has the following technical effects:
according to the preparation method of the graphene-based N, S doped electrode material, the heteroatom precursor is combined with the nano carbon material through molecular self-assembly by utilizing electrostatic interaction, N, S is introduced through solvothermal reaction for co-doping, further more active sites are introduced, and the conductivity and the electrochemical performance of the carbon material are improved.
According to the preparation method, the nano carbon material is inserted between the graphene oxide layers to construct the mutual embedded structure, so that the conductivity of the graphene oxide layers is improved, and the nano carbon material is inserted to prevent the stacking of the graphene oxide layers; the nano carbon material and the graphene oxide are self-assembled into a three-dimensional porous nano network structure, so that the specific surface area is greatly increased, the high specific surface area is provided for charge transfer, the ion transmission distance is shortened, and the electrochemical performance of the material is improved.
According to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transfer is promoted, and the conductivity and the energy storage effect of the material are improved.
The preparation method is simple, convenient to operate, beneficial to large-scale production and capable of providing possibility for commercialization.
The electrode material can be used for the anode or the cathode of a lithium ion capacitor, and when the electrode material is applied to the anode or the cathode of the lithium ion capacitor, the electrode material has excellent high-capacity characteristic, excellent cycling stability and ultrahigh rate performance.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a CV curve of a positive electrode of a lithium ion capacitor provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, an embodiment of the present application provides a preparation method of a graphene-based N, S doped electrode material, including the following steps:
(1) Preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor;
(2) Adding graphene oxide into the dispersion liquid to obtain a mixed solution;
(3) Carrying out solvent heat treatment on the mixed solution;
(4) And washing and drying the product after the solvent heat treatment, and then carrying out heat shock treatment to obtain the electrode material.
In the step (1), in the dispersion liquid of the embodiment of the present application, the mass ratio of the nanocarbon material to the heteroatom precursor is 1: (0.8-10), and the concentration of the dispersion liquid is 0.5-2 mg/ml. The nano carbon material may be at least one of carbon nanofiber, nano mesoporous carbon, carbon nanotube, fullerene, graphene quantum dot or carbon quantum dot, and the specific embodiment of the present application is described by taking the carbon nanotube as an example; the heteroatom precursor may be at least one selected from thiophene, thiourea, ammonium sulfate, ammonium sulfide, and ammonium sulfite, and the specific examples of the present application are given by taking thiourea and ammonium sulfate as examples. In the prepared dispersion liquid, under the electrostatic action, a heteroatom precursor is combined with the nano carbon material through molecular self-assembly, and the heteroatom precursor is used as a supply source of N, S.
In the step (2), the mass ratio of the added graphene oxide to the dispersion liquid is (0.8-2): 1. After the graphene oxide is added, the dispersion of the graphene oxide in the mixed solution can be promoted by adopting ultrasonic dispersion, the power of the ultrasonic dispersion is 200-500W, and the time of the ultrasonic dispersion is 5-30 min.
In the step (3), N, S co-doping is introduced through solvothermal reaction, so that more active sites are introduced, and the conductivity and the electrochemical performance of the prepared carbon material are improved. The temperature of the solvent heat treatment in the embodiment of the application is 150-200 ℃, and the time is 10-20 h. The solvent can be any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
In the step (4), the drying can adopt freeze drying, and the temperature is-60 to-35 ℃. The temperature of the thermal shock treatment in the embodiment of the application is 150-300 ℃, and the heating rate is 5-15 ℃/min. In the process of rapid temperature rise, heat is transferred to the graphene oxide lamella, so that the graphene oxide lamella is promoted to expand, and stacking among the graphene oxide lamellae is further reduced.
According to the preparation method, the nano carbon material is inserted between the graphene oxide layers to construct the mutual embedding structure, so that the conductivity of the graphene oxide layers is improved, and the insertion of the nano carbon material prevents the stacking of the graphene oxide layers; the nano carbon material and the graphene oxide are self-assembled into a three-dimensional porous nano network structure, so that the specific surface area is greatly improved, the high specific surface area is provided for charge transfer, the ion transmission distance is shortened, and the electrochemical performance of the material is improved. According to the preparation method, stacking among graphene oxide sheets is further reduced through thermal shock, the specific surface area of the material is increased, ion or charge transfer is promoted, and the conductivity and the energy storage effect of the prepared material are improved.
The preparation method of the embodiment of the application is simple, is convenient to operate, is beneficial to large-scale production, and provides possibility for commercialization.
In a second aspect of the embodiments of the present application, a graphene-based N, S doped electrode material obtained by the above preparation method is provided, the electrode material of the embodiments of the present application can be used for a positive electrode or a negative electrode of a lithium ion capacitor, and when the electrode material of the embodiments of the present application is applied to the positive electrode or the negative electrode of the lithium ion capacitor, the electrode material of the embodiments of the present application exhibits excellent high-capacity characteristics, cycle stability and ultrahigh rate performance.
The graphene-based N, S doped electrode material and the preparation method thereof according to the embodiments of the present application are illustrated in the following by a plurality of specific examples.
Example 1
The embodiment 1 of the application provides a graphene-based N, S doped electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) Adding 50ml of deionized water into 6mg of carbon nano tubes and 25mg of thiourea, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, carrying out ultrasonic treatment for 8min at the power of 200W;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing drying oven to carry out solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8.
Fig. 1 is a CV curve of a positive electrode of a lithium ion capacitor of example 1 of the present application, and it can be seen from fig. 1 that a good quasi-rectangular shape can be maintained even at a high scan speed. The test result shows that the anode of the lithium ion capacitor has surface adsorption capacitance behavior and good reversibility.
Example 2
The embodiment 2 of the application provides a graphene-based N, S doped electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) Adding 50ml of deionized water into 3mg of carbon nano tubes and 25mg of thiourea, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and carrying out ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing drying oven to carry out solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8.
Example 3
The embodiment 3 of the application provides a graphene-based N, S doped electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) Adding 50ml of deionized water into 10mg of carbon nano tubes and 25mg of thiourea, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and carrying out ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing drying oven to carry out solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is (8).
Example 4
The embodiment 4 of the application provides a graphene-based N, S doped electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) Adding 50ml of deionized water into 30mg of carbon nano tubes and 25mg of thiourea, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and carrying out ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing dry box to perform solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8.
Example 5
Embodiment 5 of the present application provides a graphene-based N, S doped electrode material and a preparation method thereof, including the following steps:
(1) Adding 50ml of deionized water into 15mg of carbon nano tubes and 25mg of thiourea, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and carrying out ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing drying oven to carry out solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8.
Example 6
The embodiment 6 of the application provides a graphene-based N, S doped electrode material and a preparation method thereof, and the preparation method comprises the following steps:
(1) Adding 50ml of deionized water into 10mg of carbon nano tubes and 25mg of ammonium sulfate, and stirring for 3 hours;
(2) Adding 50mg of graphene oxide into the dispersion liquid, wherein the power is 200W, and carrying out ultrasonic treatment for 8min;
(3) Transferring the mixed solution into a hydrothermal kettle, and placing the hydrothermal kettle in an electrothermal blowing drying oven to carry out solvent heat treatment at 180 ℃ for 12 hours;
(4) And heating to 260 ℃ (the heating rate is 15 ℃/min) after suction filtration washing and freeze drying, and preserving heat for 2h to obtain the graphene-based N, S doped electrode material.
(5) Graphene-based N, S doped electrode material is used as an electrode active material, conductive carbon black is used as a conductive agent, polyvinylidene fluoride is used as a binder, N-methyl pyrrolidone is used as a dispersing agent to prepare slurry, and copper foil and carbon-coated aluminum foil are used as current collectors. The mass ratio of the electrode active material to the conductive agent to the binder is 8.
Comparative example 1
The difference from the embodiment 3 is that the carbon nanotubes are not added in the step (1), and other process steps are the same.
Comparative example 2
The difference from the example 3 is that the step (4) does not undergo thermal shock treatment, and other process steps are the same.
The graphene-based N, S doped electrode materials prepared in examples 1-6 and comparative examples 1-2 of the present application were subjected to performance testing. The test conditions were: the current density is 0.1A/g, and the voltage window of the cathode is as follows: 0.01-3V, and the voltage window of the anode is as follows: 2 to 4.5V, the results are shown in the following table:
Figure BDA0003805018560000101
as seen from the table above, the graphene-based N, S doped electrode materials prepared in examples 1-6 of the present application all show higher positive and negative electrode capacities, high power performance and cycling stability. Compared with the comparative examples 1 and 2, the preparation method of the embodiment of the application adopts the nano carbon material for composite modification and is cooperated with thermal shock treatment, so that the capacity, the rate capability and the cycling stability of the prepared electrode material can be obviously improved.
The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of a graphene-based N, S doped electrode material is characterized by comprising the following steps:
preparing a dispersion liquid containing a nano carbon material and a heteroatom precursor;
adding graphene oxide into the dispersion liquid to obtain a mixed solution;
carrying out solvent heat treatment on the mixed solution;
and washing and drying the product subjected to the heat treatment of the solvent, and then carrying out heat shock treatment to obtain the electrode material.
2. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the temperature of the solvothermal treatment is 150-200 ℃ and the time is 10-20 hours.
3. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the temperature of the thermal shock treatment is 150-300 ℃, and the heating rate is 5-15 ℃/min.
4. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the mass ratio of the nanocarbon material to the heteroatom precursor in the dispersion is 1 (0.8-10), and the concentration of the dispersion is 0.5-2 mg/ml.
5. The method for preparing the graphene-based N, S doped electrode material of claim 4, wherein the nano-carbon material is at least one of carbon nanofiber, nano mesoporous carbon, carbon nanotube, fullerene, graphene quantum dot or carbon quantum dot.
6. The method for preparing the graphene-based N, S doped electrode material of claim 4, wherein the heteroatom precursor is at least one of thiophene, thiourea, ammonium sulfate, ammonium sulfide and ammonium sulfite.
7. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the mass ratio of the graphene oxide to the dispersion liquid is (0.8-2): 1.
8. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the solvent of the mixed solution is any one of water, absolute ethyl alcohol, ethylene glycol and dimethylformamide.
9. The method for preparing the graphene-based N, S doped electrode material of claim 1, wherein the drying is freeze drying at a temperature of-60 ℃ to-35 ℃.
10. A graphene-based N, S doped electrode material, characterized in that it is prepared by the preparation method of any one of claims 1 to 9.
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