CN113140410A - Nitrogen-doped carbon nanosheet/MXene composite nanomaterial, and preparation method and application thereof - Google Patents
Nitrogen-doped carbon nanosheet/MXene composite nanomaterial, and preparation method and application thereof Download PDFInfo
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- 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
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- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
- H01G11/84—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
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- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention relates to a nitrogen-doped carbon nanosheet/MXene composite nanomaterial, and a preparation method and application thereof. In the composite nano material, the carbon nano sheet and MXene form an interpenetrating lamellar structure, and nitrogen is doped in the carbon nano sheet and the MXene. The method aims at the problem that the electrochemical performance cannot be fully utilized due to the stacking and accumulation of MXene nanosheets in the prior art. The composite material can effectively overcome the defects of self stacking and accumulation of MXene, and greatly improves the cycle stability of the battery; besides, the redox reaction and pseudo-capacitance active sites with obvious MXene lamella spacing are increased, and the specific capacity of the super capacitor is improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy, and particularly relates to a nitrogen-doped carbon nanosheet/MXene composite nanomaterial, and a preparation method and application thereof.
Background
Based on the rapid development of portable electronic and microelectronic devices, various energy storage technologies have emerged. Among them, flexible electrochemical capacitors (also called supercapacitors) have great potential for commercialization due to high power density, fast charge and discharge and long cycle life. The supercapacitor stores electrochemical energy by absorbing ions in an electrolyte through the surface of an electrode material having a high specific surface area, and thus, it can store and transport a large amount of charges in a short time, compared to a battery. One of the major challenges in making supercapacitor electrode sheets is excellent mechanical flexibility, and the other challenge is to increase the energy density of the overall capacitor.
MXene is a novel two-dimensional material and gradually becomes a new choice of a supercapacitor capacitance material. Compared with other two-dimensional materials, MXene is rich in oxygen surface groups and has extremely high volume specific capacity, so that the energy density is effectively improved. However, MXene has the same disadvantages as other two-dimensional nanomaterials, so that stacking and accumulation of MXene nanosheets are caused, so that electrochemical performance cannot be fully utilized.
CN106328890B discloses a carbon pillared MXene composite material and application thereof, wherein the carbon pillared MXene composite material comprises a two-dimensional layered MXene carrier and carbon nanosheets loaded between MXene layers; the preparation method comprises the following steps: (1) taking MAX raw materials, and treating in HF solution to obtain MXene materials; (2) soaking the MXene material obtained in the step (1) in a solution with the cationic carbon precursor content of 0.005-20 g/mL, stirring for 0.5-72 h at 30-100 ℃, and then centrifuging, washing and drying to obtain a pre-pillared MXene material; (3) heating the pre-pillared MXene material to 300-800 ℃ at the speed of 2-10 ℃/min in a protective atmosphere, and carrying out heat preservation and calcination treatment for 0.5-4 h to obtain the carbon pillared MXene material. However, the MXene material obtained by the method is easy to stack by itself and has poor electrochemical performance.
Therefore, there is a need in the art to develop a novel MXene composite material, which can overcome the defects of MXene self-stacking and accumulation, and the prepared battery has better cycle stability
Disclosure of Invention
The method aims at the problem that the electrochemical performance cannot be fully utilized due to the stacking and accumulation of MXene nanosheets in the prior art. The invention aims to provide a nitrogen-doped carbon nanosheet/MXene composite nanomaterial, and a preparation method and application thereof. The nano-sheet/MXene composite nano-material can effectively overcome the defects of self stacking and accumulation of MXene, and greatly improve the cycle stability of the battery; the prepared super capacitor has higher specific capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objectives of the present invention is to provide a nitrogen-doped carbon nanosheet/MXene composite nanomaterial, in which the carbon nanosheet and MXene form an interpenetrating lamellar structure, and nitrogen is doped in the carbon nanosheet and the MXene.
The carbon nanosheet and MXene in the composite material form an interpenetrating lamellar structure, and due to the synergistic effect of the lamellar structure, the defects of self stacking and accumulation of the MXene are effectively overcome, so that the cycle stability of the battery is greatly improved; according to the invention, through nitrogen doping, the oxidation-reduction reaction and pseudo-capacitance active sites with obvious MXene lamella spacing are increased; the carbon nanosheet can improve the specific surface area of the composite electrode, can promote capacitance characteristics on the surface of the electrode, and improves the specific capacity of the supercapacitor.
Preferably, the number of the nitrogen-doped carbon nano sheet/MXene composite nano material layers is 10-30, such as 12 sheets, 15 sheets, 18 sheets, 20 sheets, 22 sheets, 25 sheets or 28 sheets.
Preferably, in the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, the content of nitrogen element is 5-30 At%, such as 10 At%, 12 At%, 15 At%, 18 At%, 20 At%, 25 At%, 28 At%, and the like.
The invention selects proper nitrogen doping proportion to increase the obvious oxidation-reduction reaction and pseudo-capacitance active sites of MXene lamella spacing.
Preferably, in the nitrogen-doped carbon nano sheet/MXene composite nano material, the content of the carbon nano sheet is 20-40 wt%, such as 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt% or 38 wt%.
Preferably, the content of MXene in the nitrogen-doped carbon nanosheet/MXene composite nanomaterial is 15-50 wt%, such as 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, and the like.
The second purpose of the present invention is to provide a method for preparing the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, wherein the nitrogen-doping reaction of the carbon nanosheet and MXene and the growth of the carbon nanosheet on the MXene surface are simultaneously performed.
The preparation method of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial has concise steps, and the carbon nanosheet and the MXene are synchronously nitrogen-doped and generated at the same time, so that the experimental steps can be greatly simplified, and the industrial practice is facilitated.
Preferably, the preparation method comprises: mixing MXene, transition metal salt, nitrogen source and carbon source in water, and sintering to obtain the nitrogen-doped carbon nanosheet/MXene composite nanomaterial.
Preferably, the nitrogen source comprises a dihydrodiamine and/or melamine.
Preferably, the carbon source comprises sucrose and/or glucose.
Preferably, the transition metal salt is a transition metal acetate salt, preferably nickel acetate tetrahydrate or cobalt acetate tetrahydrate.
The transition metal acetate of the present invention functions as a catalyst in the reaction.
Preferably, theMXene has a chemical formula of Mn+1XnTxOr Mn+1XnWherein M represents a transition metal; x represents carbon or nitrogen; t isxRepresents a surface functional group comprising any one or a combination of at least two of-O, -OH and-F; n is an integer of 1 to 3.
Preferably, the mass ratio of MXene to the carbon source is (3-4): (1-2), such as 3.1:1.1, 3.3:1.2, 3.5:1.5, 3.7:1.7, 3.9:1.8, 3.1:1.2, 3.3:1.9, 3.4:1.4, 3.6:1.6, 3.8:1.7 or 3.9: 1.3.
The mass ratio of MXene to a carbon source is (3-4): 1-2), and if the mass ratio is too large, the MXene content is too high, the carbon source is too low, and carbon nano sheets cannot uniformly grow on the MXene surface; if the mass ratio is too small, the MXene content is too low, the carbon source is too much, the carbon nanosheets cover the MXene, and the MXene performance cannot be fully exerted.
Preferably, the mass ratio of MXene to transition metal acetate is (3-4): (1-2), such as 3.1:1.1, 3.3:1.2, 3.5:1.5, 3.7:1.7, 3.9:1.8, 3.1:1.2, 3.3:1.9, 3.4:1.4, 3.6:1.6, 3.8:1.7 or 3.9: 1.3.
The mass ratio of MXene to transition metal acetate is (3-4): 1-2, and if the mass ratio is too large, the content of the transition metal acetate is too low, and the growth of carbon nano sheets cannot be sufficiently catalyzed; the mass ratio is too small, namely the content of the transition metal acetate is too large, so that the environmental pollution is large.
Preferably, the mass ratio of MXene to nitrogen source is (3-4): 15-25, such as 3.1:16, 3.3:18, 3.5:20, 3.7:22, 3.9:23, 3.1:24, 3.3:17, 3.4:19, 3.6:18, 3.8:22 or 3.9: 21.
The mass ratio of MXene to a nitrogen source is (3-4): 15-25), the mass ratio is too large, namely the nitrogen source is too little, the influence on the interlayer spacing of MXene is small, and the defect of MXene stacking cannot be improved; the mass ratio is too small, namely the content of the nitrogen source is too much, the MXene lamella is too dispersed to form more macropores, and the mesopores and the micropores are reduced, so that the ion transmission is not facilitated.
Preferably, the sintering process comprises: preheated and then heated to the sintering temperature.
Preferably, the preheating temperature is 500 to 600 ℃, such as 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ or the like.
Preferably, the preheating heat preservation time is 1-3 h, such as 1.1h, 1.3h, 1.5h, 1.8h, 2h, 2.1h, 2.3h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9 h.
Preferably, the sintering temperature is 600 to 800 ℃, such as 610 ℃, 630 ℃, 650 ℃, 670 ℃, 690 ℃, 700 ℃, 710 ℃, 720 ℃, 740 ℃, 750 ℃, 760 ℃, 780 ℃, 790 ℃ and the like.
Preferably, the holding time at the sintering temperature is 1 to 3 hours, such as 1.1 hour, 1.3 hour, 1.5 hour, 1.8 hour, 2 hour, 2.1 hour, 2.3 hour, 2.5 hour, 2.6 hour, 2.7 hour, 2.8 hour or 2.9 hour.
Preferably, the atmosphere of the sintering is a protective atmosphere, preferably an argon atmosphere.
Preferably, before sintering, a drying process is also included.
Preferably, after the sintering, a grinding process is also included.
The invention also aims to provide a preparation method of the electrode plate, which comprises the following steps:
(1) mixing the nitrogen-doped carbon nano sheet/MXene composite nano material, a conductive agent, a binder and a solvent to obtain nitrogen-doped carbon nano sheet/MXene composite nano material slurry;
(2) and coating the nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry on a current collector to obtain the electrode plate.
Preferably, the conductive agent in step (1) includes any one or a combination of at least two of conductive graphite, carbon nanotubes and graphene.
Preferably, the binder in the step (1) is polyvinylidene fluoride.
Preferably, the solvent in step (1) is N-methylpyrrolidone.
Preferably, the mass ratio of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial in the step (1) to the conductive agent to the binder is (80-98): (1-10), such as 80:10:10, 85:5:10, 90:5:5, 91:2:2, 92:3:2, 93:4:2, 94:2:3, 95:2:4, 96:2:2, 97:3:2, 91:4:2, 92:2:4, 93:2:2, 94:3:2, 95:2:3, 96:4:3, 97:3:4, 91:3:4, or 95:3: 4.
Preferably, the current collector in the step (2) is carbon paper.
Preferably, after the step (2), a drying process is also included.
The fourth object of the present invention is to provide an electrode sheet obtained by the production method according to the third object.
The fifth purpose of the invention is to provide a three-electrode test system of a super capacitor, which comprises the electrode plate of the fourth purpose.
Preferably, in the three-electrode test system of the supercapacitor, the working electrode is the electrode plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon nanosheet and MXene in the composite material form an interpenetrating lamellar structure, and due to the synergistic effect of the lamellar structure, the defects of self stacking and accumulation of the MXene are effectively overcome, so that the cycle stability of the battery is greatly improved;
(2) according to the invention, by adjusting a proper nitrogen doping proportion, the oxidation-reduction reaction and pseudo-capacitance active sites with obvious MXene lamella spacing are increased;
(3) the carbon nanosheet can improve the specific surface area of the composite electrode, can promote capacitance characteristics on the surface of the electrode, and improves the specific capacity of a super capacitor;
(4) the preparation method of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial has concise steps, and the carbon nanosheet and the MXene are synchronously nitrogen-doped and generated at the same time, so that the experimental steps can be greatly simplified, and the industrial practice is facilitated.
Drawings
FIG. 1 is a flow chart of the preparation of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial in example 1 of the present invention;
fig. 2 is a flow chart of composite electrode sheet preparation and three-electrode system assembly in example 1 of the present invention;
FIG. 3 is a CV diagram, an electrochemical test chart of the N-doped carbon nanosheet/MXene composite nanomaterial in example 1 of the present invention;
FIG. 4 is a GCD diagram, which is an electrochemical test diagram of the N-doped carbon nanosheet/MXene composite nanomaterial in example 1 of the present invention;
fig. 5 is an electrochemical test chart-EIS chart of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial in example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
S1, a preparation flow chart of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial is shown in FIG. 1, and the specific preparation method comprises the following steps:
(1) according to the weight fraction, 4 parts of Ti3C2Uniformly mixing the powder with 1 part of nickel acetate tetrahydrate, 20 parts of dihydrodiamine and 2 parts of sucrose, adding a little (10mL) of deionized water to completely dissolve the mixture, fully stirring, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain a powdery mixture containing MXene;
(2) preheating the mixture to 600 ℃ under the protection of argon gas flow, preserving heat for 2h, heating to 800 ℃, preserving heat for 2h, cooling to room temperature, taking out, and carefully grinding to obtain the nitrogen-doped carbon nanosheet/MXene composite nanomaterial;
s2, the composite electrode plate and a preparation flow chart of the three-electrode system assembly prepared by adopting the composite electrode plate are shown in figure 2, and the specific preparation method of the composite electrode plate comprises the following steps:
(3) uniformly mixing the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, a conductive agent and polyvinylidene fluoride according to the weight ratio of 8:1:1, adding N-methylpyrrolidone as a solvent, and fully and uniformly stirring to obtain nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry;
(4) uniformly coating the nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry on the surface of sheared carbon paper of a current collector of a super capacitor, and carrying out vacuum drying at 60 ℃ for 12h to completely remove N-methylpyrrolidone to obtain a composite electrode slice;
s3, the specific preparation method of the three-electrode system assembly comprises the following steps:
(5) the nitrogen-doped carbon nano sheet/MXene composite nano material is used for a working electrode, the high-purity graphite is used for a counter electrode, and the Ag/AgCl is used for a reference electrode in a three-electrode test system; the test system adopted 3mol/L H2SO4As an electrolyte;
(6) the electrochemical performance of a single electrode plate is tested by a three-electrode system;
(7) the electrochemical performance of the three-electrode system was tested using an electrochemical workstation: the specific capacitance is about 321F/g at 5mV/s sweep rate, after the sweep rate is expanded to 100 times (500mV/s), the specific capacitance is about 137F/g, the electrochemical cycle charge-discharge performance is stable, the internal resistance is small, the CV curve is shown in figure 3, the GCD curve is shown in figure 4, and the EIS curve is shown in figure 5.
Example 2
S1, a preparation method of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial comprises the following steps:
(1) according to the weight fraction, 3 parts of Ti3C2Uniformly mixing the powder with 1 part of nickel acetate tetrahydrate, 20 parts of dihydrodiamine and 1 part of cane sugar, adding a little (10mL) of deionized water to completely dissolve the mixture, fully stirring, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain a powdery mixture containing MXene;
preheating the mixture to 600 ℃ under the protection of argon gas flow, preserving heat for 3h, then heating to 700 ℃, preserving heat for 2h, cooling to room temperature, taking out, and carefully grinding to obtain the nitrogen-doped carbon nanosheet/MXene composite nanomaterial;
s2, the preparation method of the composite electrode plate comprises the following steps:
(3) uniformly mixing the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, a conductive agent and polyvinylidene fluoride according to the weight ratio of 8:1:1, adding N-methylpyrrolidone as a solvent, and fully and uniformly stirring to obtain nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry;
(4) uniformly coating the nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry on the surface of sheared carbon paper of a current collector of a super capacitor, and carrying out vacuum drying at 60 ℃ for 12h to completely remove N-methylpyrrolidone to obtain a composite electrode slice;
s3, the preparation method of the three-electrode system assembly comprises the following steps:
(5) the nitrogen-doped carbon nano sheet/MXene composite nano material is used for a working electrode, the high-purity graphite is used for a counter electrode, and the Ag/AgCl is used for a reference electrode in a three-electrode test system; the test system adopted 3mol/L H2SO4As an electrolyte;
(6) the electrochemical performance of a single electrode plate is tested by a three-electrode system;
(7) testing the electrochemical performance of the super capacitor by using a battery testing instrument: the specific capacitance is about 238F/g under the sweep speed of 2mV/s, and after the sweep speed is expanded to 100 times (500mV/s), the specific capacitance is about 106F/g, the electrochemical cycle charge-discharge performance is stable, and the internal resistance is small.
Example 3
The difference from the example 1 is that the weight fraction of the dihydrodiamine in the step (1) is 40 parts;
preparing a composite electrode plate and a super capacitor in the same manner as in example 1, and testing the electrochemical performance of the super capacitor by using a battery testing instrument: the specific capacitance is about 334F/g under 5mV/s sweep speed, and after the sweep speed is enlarged to 100 times (500mV/s), the specific capacitance is about 124F/g, the electrochemical cycle charge-discharge performance is stable, and the internal resistance is small.
Example 4
The difference from the example 1 is that the weight fraction of the dihydrodiamine in the step (1) is 10 parts;
preparing a composite electrode plate and a super capacitor in the same manner as in example 1, and testing the electrochemical performance of the super capacitor by using a battery testing instrument: the specific capacitance at a sweep rate of 5mV/s was about 282F/g, and after the sweep rate was increased to 100 times (500mV/s), the specific capacitance was about 118F/g.
Comparative example 1
The difference from example 1 is that step (1) does not add the dihydrodiamine;
preparing a composite electrode plate and a super capacitor in the same manner as in example 1, and testing the electrochemical performance of the super capacitor by using a battery testing instrument: the specific capacitance at a sweep rate of 5mV/s was about 243F/g, and after the sweep rate was increased to 100 times (500mV/s), the specific capacitance was about 102F/g.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The nitrogen-doped carbon nanosheet/MXene composite nanomaterial is characterized in that in the composite nanomaterial, the carbon nanosheet and the MXene form an interpenetrating lamellar structure, and nitrogen is doped in the carbon nanosheet and the MXene.
2. The nitrogen-doped carbon nanosheet/MXene composite nanomaterial of claim 1, wherein the number of layers of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial is 10-30;
preferably, in the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, the content of nitrogen element is 5-30 At%;
preferably, in the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, the content of the carbon nanosheet is 20-40 wt%;
preferably, in the nitrogen-doped carbon nanosheet/MXene composite nanomaterial, the content of MXene is 15-50 wt%.
3. A method for preparing the nitrogen-doped carbon nano sheet/MXene composite nano material as claimed in claim 1 or 2, wherein the nitrogen-doping reaction of the carbon nano sheet and MXene and the growth of the carbon nano sheet on the MXene surface are carried out simultaneously;
preferably, the preparation method comprises: mixing MXene, transition metal salt, nitrogen source and carbon source in water, and sintering to obtain the nitrogen-doped carbon nanosheet/MXene composite nanomaterial.
4. The method according to claim 3, wherein the nitrogen source comprises a dihydrodiamine and/or a melamine;
preferably, the carbon source comprises sucrose and/or glucose;
preferably, the transition metal salt is a transition metal acetate salt, preferably nickel acetate tetrahydrate or cobalt acetate tetrahydrate;
preferably, the MXene has the chemical formula of Mn+1XnTxOr Mn+1XnWherein M represents a transition metal; x represents carbon or nitrogen; t isxRepresents a surface functional group comprising any one or a combination of at least two of-O, -OH and-F; n is an integer of 1 to 3.
5. The method according to claim 3 or 4, wherein the mass ratio of MXene to the carbon source is (3-4): (1-2);
preferably, the mass ratio of MXene to the transition metal acetate is (3-4): (1-2);
preferably, the mass ratio of MXene to the nitrogen source is (3-4): 15-25).
6. The method of any one of claims 3 to 5, wherein the sintering process comprises: preheating and then heating to a sintering temperature;
preferably, the preheating temperature is 500-600 ℃;
preferably, the preheating heat preservation time is 1-3 h;
preferably, the sintering temperature is 600-800 ℃;
preferably, the heat preservation time at the sintering temperature is 1-3 h;
preferably, the atmosphere of the sintering is a protective atmosphere, preferably an argon atmosphere;
preferably, before the sintering, a drying process is also included;
preferably, after the sintering, a grinding process is also included.
7. The preparation method of the electrode plate is characterized by comprising the following steps:
(1) mixing the nitrogen-doped carbon nanosheet/MXene composite nanomaterial of claim 1 or 2, a conductive agent, a binder and a solvent to obtain a slurry of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial;
(2) and coating the nitrogen-doped carbon nanosheet/MXene composite nanomaterial slurry on a current collector to obtain the electrode plate.
8. The method according to claim 7, wherein the conductive agent of step (1) comprises any one of conductive graphite, carbon nanotubes and graphene or a combination of at least two thereof;
preferably, the binder in the step (1) is polyvinylidene fluoride;
preferably, the solvent of step (1) is N-methylpyrrolidone;
preferably, the mass ratio of the nitrogen-doped carbon nanosheet/MXene composite nanomaterial in the step (1) to the conductive agent to the binder is (80-98): (1-10): 1-10);
preferably, the current collector in the step (2) is carbon paper;
preferably, after the step (2), a drying process is also included.
9. An electrode sheet, characterized in that it is obtained by the production method according to claim 7 or 8.
10. A three-electrode test system of a supercapacitor, comprising the electrode sheet of claim 9;
preferably, in the three-electrode testing system of the supercapacitor, the working electrode is the electrode plate according to claim 9.
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