CN111146015A - Nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, application and preparation method thereof - Google Patents
Nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, application and preparation method thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode, application and a preparation method thereof. The powder method has simple process, the prepared N-GQD/CNS/CC composite electrode has high capacitance performance, and the N-GQD/CNS/CC electrode prepared by the method has attractive application prospect in the technical field of new energy nano devices.
Description
Technical Field
The invention relates to a carbon composite material electrode, application and a preparation method thereof, in particular to a nitrogen-doped two-dimensional porous carbon composite material electrode, application and a preparation method thereof, which are applied to the technical field of carbon composite material electrodes and devices.
Background
The metal organic framework Materials (MOFs) have the characteristics of excellent porosity, extremely large specific surface area, high thermal stability, adjustable pore diameter and the like, and are widely applied to the fields of catalysis, hydrogen storage, gas adsorption, drug delivery and energy storage. However, the poor conductivity of MOFs limits its practical application. In recent years, researchers use MOFs as templates to obtain derived MOFs pure carbon materials through thermal cracking reaction, the materials keep the basic skeleton of the original MOFs, have high specific surface area and pore channel structures, and meanwhile, the conductivity of the materials is greatly improved, so that the materials are used as carbon-based skeletons with high double electric layer capacitive energy to be applied to energy storage devices.
Graphene Quantum Dots (GQDs) are quasi-zero-dimensional nano materials, have many unique properties, and have application prospects in the fields of photoelectric devices, biomedical treatment, sensors and the like. The graphene quantum dots have the characteristics of small-size assembly advantage, high specific surface area, high conductivity, high chemical stability, rich functional groups, excellent solvent dispersibility, light weight and the like.
However, the capacitance capacity, rate capability, cycle life and safety of the existing electrode are not ideal enough, and the pollution problem is not overcome well, so that the application performance of the carbon material in the field of the super capacitor is not effectively exerted, and the carbon composite electrode has good application prospect in the super capacitor.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, application and a preparation method thereof. The porous carbon nanosheet array is prepared by taking two-dimensional Co-MOF growing on carbon cloth as a template through high-temperature thermal cracking. The method comprises the steps of preparing high-concentration nitrogen-doped graphene quantum dots (N-GQDs) by an alkali catalysis aqueous phase molecular fusion method, loading the N-GQDs onto a Co-MOF-derived porous carbon nanosheet array through electrodeposition, and constructing a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth (N-GQD/CNS/CC) composite electrode which is of a self-supporting structure, mainly comprises carbon elements and is a green, nontoxic and environment-friendly electrode material. The high-power-density super capacitor has the advantages of high power density, high energy density, long cycle life and the like, and shows outstanding capacitance performance in the aspect of application of the super capacitor.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode is prepared by taking two-dimensional Co-MOF growing on carbon cloth as a template and preparing the porous carbon nanosheet array through a high-temperature thermal cracking method; preparing nitrogen-doped graphene quantum dots (N-GQDs) by adopting an alkali catalysis aqueous phase molecular fusion method, loading the N-GQDs onto a Co-MOF derived porous carbon nanosheet array by an electrodeposition method, and constructing a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode to form a self-supporting composite structure of N-GQD/CNS/CC.
The invention discloses application of a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode, wherein two pieces of N-GQD/CNS/CC electrode materials are respectively taken and treated with H with the concentration not lower than 1M2SO4The solution is an electrolyte and is assembled into a symmetrical N-GQD/CNS/CC supercapacitor.
The invention discloses a preparation method of a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode, which comprises the following steps:
a. acidifying the carbon cloth substrate:
acidizing the carbon cloth to enable the surface of the carbon cloth to be combined with oxygen-containing functional groups to form metal ion attachment sites for later use;
b. preparation of porous carbon nanosheet array/carbon cloth (CNS/CC):
directly putting the carbon cloth with the oxygen-containing functional group subjected to acidification treatment in the step a into a mixed solution of cobalt nitrate hexahydrate and 2-methylimidazole, and growing a Co-MOF nanosheet array in situ to obtain a Co-MOF/CC composite material;
then preparing a Co-MOF derived porous carbon composite material by a high-temperature thermal cracking method to form a porous carbon nanosheet array/carbon cloth (CNS/CC) composite material structure for later use;
c. preparing a nitrogen-doped graphene quantum dot (N-GQDs) solution:
preparing a nitrogen-doped graphene quantum dot solution by taking an aromatic compound with a benzene ring as a precursor and adopting an alkali-catalyzed aqueous phase molecular fusion method for later use;
d.N-preparation of GQD/CNS/CC composite electrode:
taking the nitrogen-doped graphene quantum dot solution obtained in the step c as an electrolyte, taking the Co-MOF-derived porous carbon nanosheet array/carbon cloth (CNS/CC) composite material obtained in the step b as a working electrode material, and taking a platinum electrode as a counter electrode; and preparing the nitrogen-doped graphene quantum dot/Co-MOF-derived porous carbon nanosheet array/carbon cloth N-GQD/CNS/CC composite material electrode by adopting an electrodeposition method.
As a preferred technical scheme of the invention, in the step a, when the carbon cloth substrate is acidified, concentrated nitric acid with the concentration not lower than 8M is used as an acidification treating agent, firstly, impurities on the surface of the carbon cloth are cleaned, then, the clean carbon cloth is put into a mixed solution of the concentrated nitric acid and deionized water for acid treatment, then, the carbon cloth is taken out, and the carbon cloth is washed to be neutral by the deionized water and then is dried; the surface of the carbon cloth after acid treatment contains oxygen-containing functional groups which are subsequent Co2+Attachment sites are provided.
As a preferred technical solution of the present invention, in the step b, when preparing the porous carbon nanosheet array/carbon cloth (CNS/CC), the specific steps are as follows:
first, 0.121g of Co (NO) was weighed3)2·6H2Dissolving O in at least 30mL of deionized water, and marking as a solution A;
then weighing 1.642g of 2-methylimidazole and dissolving in at least 30mL of deionized water, and marking as a solution B;
then, quickly pouring the solution B into the solution A to obtain a mixed solution; putting the carbon cloth subjected to acidification treatment in the step a into the mixed solution, standing for at least 4h at room temperature, taking out the carbon cloth, washing the surface of the carbon cloth with deionized water, washing off Co-MOF which does not grow on the surface of the carbon cloth, and finally putting the carbon cloth into a vacuum oven for drying to obtain a Co-MOF/CC composite material;
then putting the prepared Co-MOF/CC composite material into a high-temperature tube furnace, and putting the material in Ar/H2Carrying out high-temperature thermal cracking reaction treatment under mixed gas, and comprising the following steps:
firstly, heating to be not less than 350 ℃ at a heating rate of not less than 1 ℃/min, and keeping the temperature for at least 1 h;
then raising the temperature to be not less than 800 ℃ at a temperature rise rate of not less than 2 ℃/min, and preserving the temperature for at least 1 h;
then cooling to room temperature, and taking out the carbon cloth; the taken-out carbon cloth is then soaked in FeCl with the concentration not less than 1M3Removing metal Co in the solution for at least 6 h;
and finally, washing the carbon cloth with deionized water, and putting the carbon cloth into an oven for drying, thereby obtaining the porous carbon nanosheet array/carbon cloth (CNS/CC) composite material.
As a preferable technical solution of the present invention, in the step c, when the nitrogen-doped graphene quantum dot (N-GQDs) solution is prepared, the aromatic compound having a benzene ring is a light-yellow monoclinic pyrene having an aromatic odor.
As a preferred technical solution of the present invention, in the step c, when the nitrogen-doped graphene quantum dot (N-GQDs) solution is prepared, the specific steps are as follows:
slowly adding 1g of pyrene into 60-90ml of concentrated nitric acid with the concentration not lower than 8M under the stirring condition, carrying out reflux reaction for 25-35h at the temperature of 60-80 ℃, cooling to room temperature, and taking out to obtain a reactant solution;
adding the obtained reactant solution into an ice water solution, performing vacuum filtration, and washing with distilled water until the pH value of the filtrate is 7;
then ultrasonically dispersing the washed chrysanthemum yellow solid in not less than 160mL of distilled water for at least 2h to obtain a dispersion liquid;
then, at least 40mL of dispersion liquid is taken and put into a reaction kettle, 4mL of hydrazine hydrate is added into the reaction kettle, and the reaction is carried out for 10-24h at the temperature of 170-;
then, after cooling to room temperature, filtering, and collecting the original solution after filtering to obtain a nitrogen-doped graphene quantum dot (N-GQDs) solution.
As a preferred technical solution of the present invention, in the step d, when the N-GQD/CNS/CC composite electrode is prepared, the nitrogen-doped graphene quantum dot (N-GQDs) solution obtained in the step c is used as an electrolyte, the Co-MOF-derived porous carbon nanosheet array/carbon cloth (CNS/CC) composite material obtained in the step b is used as a working electrode material, and a platinum wire is used as a counter electrode; and depositing for at least 3h under the voltage of not less than 2V by adopting an electrodeposition method, so that N-GQDs are loaded on the Co-MOF derived porous carbon nanosheet array, and the N-GQD/CNS/CC composite material electrode which is full-carbon and has a self-supporting structure is obtained.
In the preferred technical scheme of the invention, in the step a, a mixed solution is prepared by adopting concentrated nitric acid and deionized water in a volume ratio of 1:5, and the mixed solution is used as an acidification treatment solution.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method adopts an electrodeposition method to load N-GQDs with high capacitance activity on a Co-MOF derived porous carbon nanosheet array, so as to construct an N-GQD/CNS/CC composite electrode with full carbon and a self-supporting structure; the electrode has a capacitance capacity of up to 423F g-1(Current sealingDegree 1 A.g-1) At a high current density of 20A g-1The capacity retention rate reaches 64.3%, and good rate performance is shown; after 10000 cycles, the capacity of the composite electrode is 95.65 percent of the first capacity, the composite electrode has excellent cycle performance, and the excellent performance of the composite electrode indicates that the composite electrode has good application prospect in a super capacitor;
2. the method is simple and easy to implement and low in cost, and the material of the N-GQD/CNS/CC composite material electrode is a green, non-toxic and environment-friendly electrode material, has the advantages of high power density, high energy density and long cycle life, and shows outstanding capacitance performance in the aspect of application of the super capacitor.
Drawings
FIG. 1 is an SEM image of Co-MOF/CC, CNS/CC and N-GQD/CNS/CC prepared by the preferred embodiment of the present invention.
FIG. 2 is a TEM image of nitrogen-doped graphene quantum dots (N-GQDs) prepared by the preferred embodiment of the present invention.
FIG. 3 is a TEM image of N-GQD/CNS/CC prepared by the preferred embodiment of the present invention.
FIG. 4 is an XRD pattern of Co-MOF/CC, CNS/CC and N-GQD/CNS/CC prepared by a preferred embodiment of the present invention.
Fig. 5 is a graph of the capacitive performance of an N-GQD/CNS/CC composite electrode prepared in accordance with a preferred embodiment of the present invention. Wherein FIG. 5(a) is a graph of CV at different sweep rates; FIG. 5(b) is a charge-discharge curve at different current densities; FIG. 5(c) is a graph of rate performance at different current densities; fig. 5(d) is an impedance diagram of the electrode material.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
in the embodiment, the porous carbon nanosheet array is prepared by a high-temperature thermal cracking method by taking two-dimensional Co-MOF growing on carbon cloth as a template; preparing nitrogen-doped graphene quantum dots (N-GQDs) by adopting an alkali catalysis aqueous phase molecular fusion method, loading the N-GQDs onto a Co-MOF derived porous carbon nanosheet array by an electrodeposition method, and constructing a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode to form a self-supporting composite structure of N-GQD/CNS/CC.
The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode comprises the following steps:
a. acidifying the carbon cloth substrate:
carbon cloth directly purchased from the market needs to be cleaned before loading the material; firstly, cut the carbon cloth to 1cm2Ultrasonically treating the cut carbon cloth in acetone, ethanol and deionized water for 30min to clean impurities on the surface of the carbon cloth; then, concentrated nitric acid with the concentration of 8M is used as an acidification treating agent, and the cleaned clean carbon cloth is put into a reaction kettle containing 60mL of mixed solution of concentrated nitric acid and deionized water with the volume ratio of 1: 5; carrying out acidification reaction for 12h at 120 ℃, taking out the carbon cloth after the acid treatment is finished, washing the carbon cloth to be neutral by using deionized water, and putting the carbon cloth into an oven for drying for later use; the surface of the carbon cloth after acid treatment is loaded with a large number of oxygen-containing groups, so that the hydrophilicity is improved, and attachment sites are provided for subsequent metal Co ions;
b. preparation of porous carbon nanosheet array/carbon cloth (CNS/CC):
b-1. preparation of Co-MOF/CC composite material:
first, 0.121g of Co (NO) was weighed3)2·6H2Dissolving O in 30mL of deionized water, and marking as a solution A;
then weighing 1.642g of 2-methylimidazole and dissolving in 30mL of deionized water, and marking as a solution B;
then, quickly pouring the solution B into the solution A to obtain a mixed solution; putting the carbon cloth subjected to acidification treatment in the step a into the mixed solution, standing for 4 hours at room temperature, taking out the carbon cloth, washing with deionized water, washing off Co-MOF (metal organic framework) which does not grow on the surface of the carbon cloth, finally putting the carbon cloth into a vacuum oven, and drying for 12 hours at 80 ℃, so that a Co-MOF nanosheet array grows in situ, and the Co-MOF/CC composite material is obtained;
b-2. preparation of porous carbon nanosheet array/carbon cloth (CNS/CC) composite material:
putting the Co-MOF/CC composite material prepared in the step b-1 into a high-temperature tubular furnace, and performing Ar/H treatment on the obtained product2Carrying out high-temperature thermal cracking reaction treatment under mixed gas, and comprising the following steps:
firstly, heating to 350 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 1 h;
then raising the temperature to 800 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 1 h;
after the high-temperature thermal cracking reaction of the high-temperature tubular furnace is finished, cooling to room temperature, and taking out the carbon cloth; the removed carbon cloth was then soaked in FeCl at a concentration of 1M3Removing metal Co in the solution for 6 hours;
finally, washing the carbon cloth with deionized water, putting the carbon cloth into an oven for drying, and drying at 80 ℃ for 12h to prepare the Co-MOF derived porous carbon composite material, so as to obtain a porous carbon nanosheet array/carbon cloth (CNS/CC) composite material for later use;
c. preparing a nitrogen-doped graphene quantum dot (N-GQDs) solution:
the preparation method comprises the following steps of preparing a nitrogen-doped graphene quantum dot (N-GQDs) solution by taking a light yellow monoclinic crystal pyrene with aromatic odor as a raw material aromatic compound with a benzene ring and adopting an alkali-catalyzed aqueous phase molecular fusion method, wherein the specific steps are as follows:
slowly adding 1g of raw material pyrene into 60-90ml of 8M concentrated nitric acid under the stirring condition, carrying out reflux reaction for 25-35h at the temperature of 60-80 ℃, cooling to room temperature, and taking out to obtain a reactant solution;
adding the obtained reactant solution into an ice water solution, performing vacuum filtration, and washing with distilled water until the pH value of the filtrate is 7;
then ultrasonically dispersing the washed chrysanthemum yellow solid in 160mL of distilled water for 2h to obtain a dispersion liquid;
then, taking 40mL of dispersion liquid to put into a polytetrafluoroethylene reaction kettle, adding 4mL of hydrazine hydrate into the polytetrafluoroethylene reaction kettle, and reacting for 10-24h at the temperature of 170-;
then, after cooling to room temperature, filtering, and collecting the filtered original solution to obtain a nitrogen-doped graphene quantum dot (N-GQDs) solution for later use;
d.N-preparation of GQD/CNS/CC composite electrode:
taking the nitrogen-doped graphene quantum dot (N-GQDs) solution obtained in the step c as an electrolyte, taking the Co-MOF derived porous carbon nanosheet array/carbon cloth (CNS/CC) composite material obtained in the step b as a working electrode material, and taking a platinum wire as a counter electrode; and (3) depositing for 3h at 2V voltage by adopting an electrodeposition method, so that N-GQDs are loaded on the Co-MOF-derived porous carbon nanosheet array, and the N-GQD/CNS/CC composite material electrode which is full-carbon and has a self-supporting structure is obtained. The pH of the nitrogen-doped quantum dot solution prepared in this example is 7, and the graphene quantum dot has a negative charge, so that the N-GQD/CNS/CC composite electrode with a self-supporting structure and all carbon can be obtained by performing electrophoretic deposition on the CNS/CC electrode as an anode.
In this example, two pieces of N-GQD/CNS/CC electrode material were separately prepared and treated with H at a concentration of 1M2SO4The solution is an electrolyte and is assembled into a symmetrical N-GQD/CNS/CC supercapacitor.
Experimental test analysis:
the capacitance of the N-GQD/CNS/CC composite electrode is measured under a Chi660e electrochemical workstation three-electrode system of Shanghai Chenghua. An Ag/AgCl electrode is used as a reference electrode, an N-GQD/CNS/CC electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and 1mol/L H is used2SO4The solution serves as an electrolyte. The intermediate product, the N-GQD/CNS/CC composite electrode, and the symmetric N-GQD/CNS/CC supercapacitor prepared by the method of this embodiment were used as samples, and were characterized by instrumental detection, and the results were as follows:
FIG. 1 is SEM images of Co-MOF/CC, CNS/CC and N-GQD/CNS/CC prepared by the method of this example, and it can be seen that the two-dimensional structure of Co-MOF in FIG. 1(a) and FIG. 1(b) is uniformly grown on the surface of carbon cloth, the average thickness of the lamella is 110nm, and the thickness of the lamella is in Ar/H2Gas annealing of FeCl3The solution etched CNS/CC, see FIGS. 1(c) and 1(d), retains its original basic formAnd still well grown in an array shape on the carbon cloth, which benefits from the prior acidification treatment of the carbon cloth to make the CNS more tightly attached to the carbon cloth. Since the Co-MOF ligand is calcined, the gap between sheets becomes large, as shown in fig. 1(d), which helps the sheet electrode material to make sufficient contact with the electrolyte and facilitates the diffusion flow of the electrolyte. In the N-GQD/CNS/CC graphs shown in fig. 1(e) and fig. 1(f), it can be clearly seen that the surfaces of the CNSs are uniformly covered with the nitrogen-doped graphene quantum dots. The gaps between the CNSs sheets are beneficial to full contact between the electrodes and the N-GQDs, so that the nitrogen-doped graphene quantum dots can be well deposited on the surfaces of the CNSs.
Fig. 2 is a TEM image of the nitrogen-doped graphene quantum dot prepared by the method in this embodiment, and it can be seen that the average size of the quantum dot prepared by the method in this embodiment is 4.2nm, and the quantum dot has a very small size particle diameter, and the excellent edge effect and quantum effect thereof enable the nitrogen-doped graphene quantum dot to have a wide application.
Fig. 3 is a TEM image of N-GQD/CNS/CC prepared by the method of this embodiment, and when N-GQDs are deposited on the surfaces of CNSs, it can be clearly seen that the distribution of nitrogen-doped graphene quantum dots is relatively uniform, no large-scale agglomeration and accumulation phenomenon occurs, and the combination effect of the two is better, which provides more active sites for CNS/CC, which is also the main reason for obtaining excellent electrochemical performance.
In addition, XRD patterns of the Co-MOF/CC, CNSs/CC and N-GQD/CNS/CC materials prepared by the method of the embodiment are shown in FIG. 4. From the XRD pattern curves of N-GQD/CNS/CC, distinct broad peaks at 25 ° and 43 ° are clearly visible, which corresponds to the (002) interface with graphene (100) interface with low levels of graphite for graphitic carbon, while no diffraction peaks for CoO and Co are found, indicating that Co has been completely etched away. Compared with Co-MOF/CC prepared in the earlier stage of the method, the morphology of the CNS/CC and N-GQD/CNS/CC composite materials is not changed greatly, a two-dimensional sheet structure is basically maintained, but the internal structure of the carbonized material is changed, which corresponds to the previous SEM result.
FIG. 5 is a graph of capacitance performance of the N-GQD/CNS/CC composite electrode prepared by the method of this example. Therein is shown5(a) is a graph of CV at different sweep rates; FIG. 5(b) is a charge-discharge curve at different current densities; FIG. 5(c) is a graph of rate performance at different current densities; fig. 5(d) is an impedance diagram of the electrode material. In order to fully study the electrochemical properties of the N-GQD/CNS electrode material, the N-GQD/CNS electrode material prepared by the method of this example was tested by a three-electrode system. As shown in FIG. 5(a), the CV curves of N-GQD/CNS at different scan rates, i.e., 10-100mV s-1. As can be seen from the CV curves at different scanning rates, the overall shape of the CV curve is not greatly changed when the scanning rate is gradually increased, and the result shows that the N-GQD/CNS composite material has rapid current response and low ion diffusion resistance in the material. Fig. 5(b) is a GCD curve graph of N-GQD/CNS at different current densities, and it can be clearly seen from the GCD curve that the charging and discharging curves at different current densities are substantially consistent, are all close to symmetrical shapes, and have no obvious voltage drop, which indicates that the ion diffusion resistance inside the material is reduced, and can adapt to large-current charging and discharging, and is consistent with the CV result. The trend of the change of the specific capacity rate performance of fig. 5(c) is obtained by calculation according to the charge-discharge curve. At 1 A.g-1The specific capacity of N-GQD/CNS is 423 F.g under the current density-1. Compared with the range of 1 A.g-1Specific capacity at Current Density, 2A. g-1、5A·g-1、10A·g-1And 20A. g-1The capacity of (a) accounts for 90%, 79.2%, 71.87% and 64.3% respectively, and shows good rate performance. Fig. 5(d) shows Electrochemical Impedance Spectroscopy (EIS) tests to analyze charge transfer kinetics and ion diffusion processes. For the N-GQD/CNS material, it exhibits a very small half circle at high frequencies, indicating a lower interfacial transfer resistance, and at low frequencies, a nearly perpendicular slope, indicating excellent electric double layer capacitive behavior. Under the high-frequency condition, the inherent impedance is 0.8 omega, the equivalent series resistance is only 1.5 omega, the excellent ion diffusion rate and the excellent conductivity are shown, and the N-GQD/CNS/CC prepared by the method is an excellent electrode material of the super capacitor.
In summary, the above-described embodiments of the present invention provide two-dimensional Co grown on carbon clothAnd taking the MOF as a template, and preparing the porous carbon nanosheet array through high-temperature thermal cracking. The method comprises the steps of preparing high-concentration nitrogen-doped graphene quantum dots (N-GQDs) by an alkali-catalyzed aqueous phase molecular fusion method, loading the N-GQDs onto a Co-MOF-derived porous carbon nanosheet array through electrodeposition, and constructing a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth (N-GQD/CNS/CC) composite electrode which is of a self-supporting structure, mainly comprises carbon elements and is a green, nontoxic and environment-friendly electrode material. The method has simple process, and the prepared N-GQD/CNS/CC composite electrode has high capacitance performance and current density of 1 A.g-1The gram capacity of the composite electrode can be as high as 432F g-1. The N-GQD/CNS/CC electrode prepared by the method shows attractive application prospects in the technical field of new energy nano devices.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, as long as the purpose of the present invention is met, and the technical principle and inventive concept of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode, the application thereof and the preparation method thereof shall all fall within the protection scope of the present invention.
Claims (9)
1. A nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material electrode is characterized in that: preparing a porous carbon nanosheet array by using two-dimensional Co-MOF growing on carbon cloth as a template through a high-temperature thermal cracking method; preparing nitrogen-doped graphene quantum dots (N-GQDs) by adopting an alkali catalysis aqueous phase molecular fusion method, loading the N-GQDs onto a Co-MOF derived porous carbon nanosheet array by an electrodeposition method, and constructing a nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode to form a self-supporting composite structure of N-GQD/CNS/CC.
2. The method of claim 1 wherein said nitrogen is dopedThe application of the electrode of the hybrid graphene quantum dot/porous carbon nanosheet array/carbon cloth composite material is characterized in that: respectively taking two pieces of N-GQD/CNS/CC electrode materials, and adding H with concentration not less than 1M2SO4The solution is an electrolyte and is assembled into a symmetrical N-GQD/CNS/CC supercapacitor.
3. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode as claimed in claim 1, is characterized by comprising the following steps:
a. acidifying the carbon cloth substrate:
acidizing the carbon cloth to enable the surface of the carbon cloth to be combined with oxygen-containing functional groups to form metal ion attachment sites for later use;
b. preparation of porous carbon nanosheet array/carbon cloth (CNS/CC):
directly putting the carbon cloth with the oxygen-containing functional group subjected to acidification treatment in the step a into a mixed solution of cobalt nitrate hexahydrate and 2-methylimidazole, and growing a Co-MOF nanosheet array in situ to obtain a Co-MOF/CC composite material;
then preparing a Co-MOF derived porous carbon composite material by a high-temperature thermal cracking method to form a porous carbon nanosheet array/carbon cloth (CNS/CC) composite material structure for later use;
c. preparing a nitrogen-doped graphene quantum dot (N-GQDs) solution:
preparing a nitrogen-doped graphene quantum dot solution by taking an aromatic compound with a benzene ring as a precursor and adopting an alkali-catalyzed aqueous phase molecular fusion method for later use;
d.N-preparation of GQD/CNS/CC composite electrode:
taking the nitrogen-doped graphene quantum dot solution obtained in the step c as an electrolyte, taking the Co-MOF-derived porous carbon nanosheet array/carbon cloth (CNS/CC) composite material obtained in the step b as a working electrode material, and taking a platinum electrode as a counter electrode; and preparing the nitrogen-doped graphene quantum dot/Co-MOF-derived porous carbon nanosheet array/carbon cloth N-GQD/CNS/CC composite material electrode by adopting an electrodeposition method.
4. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step a, when the carbon cloth substrate is acidified, concentrated nitric acid with the concentration not lower than 8M is used as an acidification treatment agent, firstly, impurities on the surface of the carbon cloth are cleaned, then, the clean carbon cloth is put into a mixed solution of the concentrated nitric acid and deionized water for acid treatment, then, the carbon cloth is taken out, and the carbon cloth is washed to be neutral by the deionized water and then dried; the surface of the carbon cloth after acid treatment contains oxygen-containing functional groups which are subsequent Co2+Attachment sites are provided.
5. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step b, when the preparation of the porous carbon nanosheet array/carbon cloth (CNS/CC) is performed, the specific steps are as follows:
first, 0.121g of Co (NO) was weighed3)2·6H2Dissolving O in at least 30mL of deionized water, and marking as a solution A;
then weighing 1.642g of 2-methylimidazole and dissolving in at least 30mL of deionized water, and marking as a solution B;
then, quickly pouring the solution B into the solution A to obtain a mixed solution; putting the carbon cloth subjected to acidification treatment in the step a into the mixed solution, standing for at least 4h at room temperature, taking out the carbon cloth, washing the surface of the carbon cloth with deionized water, washing off Co-MOF which does not grow on the surface of the carbon cloth, and finally putting the carbon cloth into a vacuum oven for drying to obtain a Co-MOF/CC composite material;
then putting the prepared Co-MOF/CC composite material into a high-temperature tube furnace, and putting the material in Ar/H2Carrying out high-temperature thermal cracking reaction treatment under mixed gas, and comprising the following steps:
firstly, heating to be not less than 350 ℃ at a heating rate of not less than 1 ℃/min, and keeping the temperature for at least 1 h;
then raising the temperature to be not less than 800 ℃ at a temperature rise rate of not less than 2 ℃/min, and preserving the temperature for at least 1 h;
then cooling to room temperature, and taking out the carbon cloth; the taken-out carbon cloth is then soaked in FeCl with the concentration not less than 1M3Removing metal Co in the solution for at least 6 h;
and finally, washing the carbon cloth with deionized water, and putting the carbon cloth into an oven for drying, thereby obtaining the porous carbon nanosheet array/carbon cloth (CNS/CC) composite material.
6. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step c, when the nitrogen-doped graphene quantum dot (N-GQDs) solution is prepared, the aromatic compound with the benzene ring is light yellow monoclinic pyrene with aromatic odor.
7. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step c, when the nitrogen-doped graphene quantum dot (N-GQDs) solution is prepared, the specific steps are as follows:
slowly adding 1g of pyrene into 60-90ml of concentrated nitric acid with the concentration not lower than 8M under the stirring condition, carrying out reflux reaction for 25-35h at the temperature of 60-80 ℃, cooling to room temperature, and taking out to obtain a reactant solution;
adding the obtained reactant solution into an ice water solution, performing vacuum filtration, and washing with distilled water until the pH value of the filtrate is 7;
then ultrasonically dispersing the washed chrysanthemum yellow solid in not less than 160mL of distilled water for at least 2h to obtain a dispersion liquid;
then, at least 40mL of dispersion liquid is taken and put into a reaction kettle, 4mL of hydrazine hydrate is added into the reaction kettle, and the reaction is carried out for 10-24h at the temperature of 170-;
then, after cooling to room temperature, filtering, and collecting the original solution after filtering to obtain a nitrogen-doped graphene quantum dot (N-GQDs) solution.
8. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step d, when the N-GQD/CNS/CC composite electrode is prepared, the nitrogen-doped graphene quantum dot (N-GQDs) solution obtained in the step c is used as an electrolyte, the Co-MOF-derived porous carbon nanosheet array/carbon cloth (CNS/CC) composite material obtained in the step b is used as a working electrode material, and a platinum wire is used as a counter electrode; and depositing for at least 3h under the voltage of not less than 2V by adopting an electrodeposition method, so that N-GQDs are loaded on the Co-MOF derived porous carbon nanosheet array, and the N-GQD/CNS/CC composite material electrode which is full-carbon and has a self-supporting structure is obtained.
9. The preparation method of the nitrogen-doped graphene quantum dot/porous carbon nanosheet array/carbon cloth composite electrode according to claim 3, wherein the preparation method comprises the following steps: in the step a, concentrated nitric acid and deionized water in a volume ratio of 1:5 are adopted to prepare a mixed solution as an acidification treatment solution.
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