CN112978714A - Nitrogen-doped carbon nanotube aerogel material and preparation method thereof - Google Patents
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Abstract
The invention discloses a nitrogen-doped carbon nanotube aerogel material, a preparation method thereof and application of the nitrogen-doped carbon nanotube aerogel material in a super capacitor electrode material. The nitrogen-doped carbon nanotube aerogel material is obtained by taking a supramolecular polymer prepared in an organic solution as a nitrogen source and a carbohydrate compound as a carbon source through hydrothermal reaction and heating carbonization; the nitrogen-doped carbon nanotube aerogel material is of a nanotube-shaped structure, and the wall thickness of the nitrogen-doped carbon nanotube aerogel material is uniform. The preparation method comprises the following steps: mixing a melamine solution and a melamine solution to obtain a supramolecular polymer; dispersing the supramolecular polymer and the carbohydrate into a solvent, and performing hydrothermal reaction on the mixed solution in a reaction kettle to prepare the supramolecular polymer-based carbon aerogel; carbonizing the mixture to obtain the nitrogen-doped carbon nanotube aerogel material. The invention has unique one-dimensional structure, excellent conductivity and ultrahigh specific surface area, and the symmetrical capacitor assembled by the electrode material has higher specific capacitance, energy density and power density.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-doped carbon nanotube aerogel material, which is used for a capacitor energy storage electrode in alkaline electrolyte.
Background
Carbon materials are a new electrode material, and have excellent conductivity, high specific capacitance, high electrochemical properties, and the like. Common carbon materials include graphene, graphdiyne, carbon quantum dots, carbon nanofibers, carbon nanospheres, carbon nanotubes, and the like.
The carbon nano tube has a special one-dimensional structure, excellent conductivity and unique surface chemical properties, and is widely applied to various fields such as catalysis, sensing, gas separation and storage, drug transmission, energy storage and the like, thereby attracting wide attention of people. The conventional methods for preparing carbon nanotubes are mainly chemical vapor deposition and template methods, the chemical vapor deposition is widely used for mass production, and the commercial carbon nanotubes are mainly prepared by chemical vapor deposition. However, the carbon nanotube material prepared by the method has disordered appearance, small size, poor hydrophilicity and relatively low specific surface area, and is not beneficial to the application of the carbon nanotube material in a super capacitor. The carbon nanotube material prepared by the template method has relatively large size and uniform appearance, but a template with special appearance needs to be prepared, a complex post-treatment process and a harsh solvent and the like are needed to remove the template, the appearance and the structure of the carbon nanotube material can be damaged in the post-treatment process, so that the performance of the carbon nanotube material is influenced, the carbon nanotube material is difficult to produce in a large scale, and the use of the carbon nanotube material is greatly limited. Moreover, most carbon nanotube materials have a low specific surface area and poor electrochemical activity, which limits their wide application. Therefore, it is highly desirable to design and prepare a material for a supercapacitor, which has a simple method, a high specific surface area, good electrode conductivity, and high cycling stability.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the carbon nanotube material used in the super capacitor has the technical problems of disordered appearance, small size, poor hydrophilicity and relatively low specific surface area.
In order to solve the problems, the invention provides a nitrogen-doped carbon nanotube aerogel material which is characterized by being prepared by taking a supramolecular polymer prepared in an organic solution as a nitrogen source and a carbohydrate compound as a carbon source through hydrothermal reaction and heating carbonization; the nitrogen-doped carbon nanotube aerogel material is of a nanotube-shaped structure, and the wall thickness of the nitrogen-doped carbon nanotube aerogel material is uniform.
Preferably, the nitrogen-doped carbon nanotube aerogel material has an inner diameter of 20-500nm, an outer diameter of 200-1500nm and a length of 0.1-20 μm.
Preferably, the specific surface area of the nitrogen-doped carbon nanotube aerogel material is 500-2000m2(ii) g, bulk density of 1-30kg/m3Wherein the amount of nitrogen doped is 1-20%.
The invention also provides a preparation method of the nitrogen-doped carbon nanotube aerogel material, which is characterized by comprising the following steps of:
step 1): mixing a melamine solution and a melamine solution, stirring, centrifuging, washing, and drying in vacuum to obtain a supramolecular polymer;
step 2): dispersing the supramolecular polymer and the carbohydrate into a solvent to obtain a mixed solution;
step 3): performing hydrothermal reaction on the obtained mixed solution in a reaction kettle to obtain the supramolecular polymer-based carbon aerogel;
step 4): and carbonizing the obtained gas supermolecule polymer-based carbon aerogel in an inert gas atmosphere to obtain the nitrogen-doped carbon nanotube aerogel material.
Preferably, the solvent of the melamine solution and the melamine solution in the step 1) is any one or more of water, methanol, ethanol, isopropanol, N-butanol, diethyl ether, benzene, toluene, xylene, dichloromethane, chloroform, cyclohexane, cyclopentane, acetone, dimethyl sulfoxide, petroleum ether, N-dimethylformamide and N, N-dimethylacetamide; the carbohydrate in the step 2) is any one or more of glucose, maltose, fructose, sucrose, lactose, galactose, starch, glycogen and myoglycogen; the solvent in the step 2) is any one or more of water, methanol, ethanol, isopropanol, N-butanol, diethyl ether, benzene, toluene, xylene, dichloromethane, chloroform, cyclohexane, cyclopentane, acetone, dimethyl sulfoxide, petroleum ether, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the concentration of the melamine solution in the step 1) is 1-200g/L, and the concentration of the melamine solution is 1-200 g/L; the concentration of the supramolecular polymer in the mixed solution obtained in the step 2) is 5-500g/L, and the concentration of the carbohydrate is 5-500 g/L; the mass ratio of the supramolecular polymer to the carbohydrate in the step 2) is 1 (0.1-20).
Preferably, the temperature of the hydrothermal reaction in the step 3) is 80-250 ℃.
Preferably, the temperature of the carbonization in the step 4) is 400-1200 ℃; the inert gas is any one or more of argon, helium, nitrogen and neon.
The invention also provides a supercapacitor electrode material which is characterized in that the raw materials comprise the nitrogen-doped carbon nanotube aerogel material as described in any one of claims 1 to 3, a conductive agent and a binder.
Preferably, the mass ratio of the nitrogen-doped carbon nanotube aerogel material to the conductive agent to the binder is (7-9): (0.1-2): (0.5-2).
Preferably, the conductive agent is any one or more of conductive carbon black, conductive graphite, graphene and carbon nanofibers; the binder is any one or more of polyvinyl alcohol (PVA), Polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC) and polyvinylidene fluoride (PVDF).
Compared with the prior art, the invention has the beneficial effects that:
(1) the nitrogen-doped carbon nanotube aerogel material is prepared by the method, the template is formed in situ in the hydrothermal reaction process by utilizing the supermolecule polymer prepared from melamine and cyanuric acid, and meanwhile, the carbohydrate compound is polymerized to form the carbon layer which is uniformly coated on the surface of the polymer, and the polymer template is cracked at high temperature, so that only the outer carbon layer is left, and the nitrogen-doped carbon nanotube aerogel is formed.
(2) The carbon shell layer formed by the carbohydrate has good conductivity and protective effect, and the prepared nitrogen-doped carbon nano tube has uniform wall thickness, larger inner diameter and uniform size, thereby greatly improving the electron transmission performance of the carbon nano tube, increasing the electrochemical activity and specific capacitance characteristic of the carbon nano tube and increasing the stability of the material.
(3) According to the nitrogen-doped carbon nanotube material prepared by the invention, a large amount of nitrogen-containing gas is generated when the nitrogen-rich polymer on the inner layer is cracked, and the nitrogen-containing gas can react with a carbon layer at high temperature and is doped into a carbon skeleton in situ; on the other hand, when the nitrogen-containing gas overflows from the carbon layer, a large number of pores are left in the carbon layer, so that the specific surface area of the material is greatly improved. The carbon nano tube prepared by the unique one-dimensional hollow structure, nitrogen atom doping and high specific surface area has good conductivity and rich active sites, shortens the path of the ions shuttling at the surface of the material and the interface of the solution, and is beneficial to the storage and the transfer of charges. When the capacitor is used as a capacitor, the internal resistance of the electrode can be greatly reduced, and the energy storage capacity is improved.
(4) The capacitor assembled by the nitrogen-doped carbon nanotube aerogel material serving as an electrode has high storage capacity and high stability.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of nitrogen-doped carbon nanotube aerogel material of example 1 in different proportions;
FIG. 2 is a Transmission Electron Microscope (TEM) image of nitrogen-doped carbon nanotube aerogel material in example 1 with different proportions and elements;
FIG. 3 is a Scanning Electron Microscope (SEM) image of carbon nanoball of comparative example 1 in different proportions;
FIG. 4 is a cyclic voltammogram of the nitrogen doped carbon nanotube aerogel electrode in 6mol/L KOH in example 4;
FIG. 5 is a constant current charge/discharge diagram of the nitrogen-doped carbon nanotube aerogel electrode in 6mol/L KOH according to example 4;
FIG. 6 is a graph showing the discharge capacity variation of the nitrogen-doped carbon nanotube aerogel electrode in example 5 within 10000 charge-discharge cycles in 6mol/L KOH;
FIG. 7 is a constant current charging/discharging diagram of a symmetrical capacitor assembled by the nitrogen-doped carbon nanotube aerogel electrode in example 6 in 6mol/L KOH;
FIG. 8 is a graph of energy density and power density in 6mol/L KOH for a symmetric capacitor assembled from the nitrogen-doped carbon nanotube aerogel electrodes of example 6.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
The embodiment provides a preparation method of a nitrogen-doped carbon nanotube aerogel material, which comprises the following steps:
respectively dissolving 25g of melamine and 50g of cyanuric acid in 1L of dimethyl sulfoxide, then mixing the two solutions at room temperature, centrifuging at 6000r/min, washing with ethanol for several times, drying at 60 ℃ to obtain a supramolecular polymer, then reacting the synthesized supramolecular polymer with a saccharide compound at a mass ratio of 1:4 under a hydrothermal condition at 180 ℃ for 10 hours, washing with water for several times, and drying to obtain the supramolecular polymer-based carbon aerogel. And then placing the obtained aerogel in a tube furnace for high-temperature carbonization, wherein the high-temperature carbonization process comprises the steps of heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 3 hours at the temperature, and cooling to obtain the nitrogen-doped carbon nanotube aerogel material.
The surface morphology of the material was observed using a scanning electron microscope, and the electron micrograph is shown in FIG. 1. The surface and internal appearance of the material are observed by adopting a transmission electron microscope, a transmission electron microscope picture is shown in figure 2, the nanofiber keeps a large length-diameter ratio and a unique one-dimensional nanotube structure, the surface is smooth, the wall thickness is uniform, and the inner diameter of the prepared carbon nanotube is 160nm, and the outer diameter of the prepared carbon nanotube is 30 nm. The element distribution diagram shows that the three elements of carbon, nitrogen and oxygen are uniformly distributed on the carbon nano tube.
Example 2
The embodiment provides a preparation method of a nitrogen-doped carbon nanotube aerogel material, which comprises the following steps:
respectively dissolving 25g of melamine and 50g of cyanuric acid in 1L of dimethyl sulfoxide, then mixing the two solutions at room temperature, centrifuging at 6000r/min, washing with ethanol for several times, drying at 60 ℃ to obtain a supramolecular polymer, then reacting the synthesized supramolecular polymer with a carbohydrate compound at a mass ratio of 1:4 under a hydrothermal condition at 160 ℃ for 10 hours, washing with water for several times, and drying to obtain the supramolecular polymer-based carbon aerogel. And then placing the obtained supramolecular polymer-based carbon aerogel in a tubular furnace for high-temperature carbonization, wherein the high-temperature carbonization process comprises the steps of heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 3 hours at the temperature, and cooling to obtain the nitrogen-doped carbon nanotube aerogel material.
Example 3
The embodiment provides a preparation method of a nitrogen-doped carbon nanotube aerogel material, which comprises the following steps:
respectively dissolving 25g of melamine and 50g of cyanuric acid in 1L of dimethyl sulfoxide, then mixing the two solutions at room temperature, centrifuging at 6000r/min, washing with ethanol for several times, drying at 60 ℃ to obtain a supramolecular polymer, then reacting the synthesized supramolecular polymer with a saccharide compound at a mass ratio of 1:1 under a hydrothermal condition at 180 ℃ for 10 hours, washing with water for several times, and drying to obtain the supramolecular polymer-based carbon aerogel. And then placing the obtained supramolecular polymer-based carbon aerogel in a tubular furnace for high-temperature carbonization, wherein the high-temperature carbonization process comprises the steps of heating to 900 ℃ at the heating rate of 5 ℃/min, preserving heat for 3 hours at the temperature, and cooling to obtain the nitrogen-doped carbon nanotube aerogel material.
Comparative example 1
Reacting a carbohydrate compound solution without supramolecular polymer at 180 ℃ for 10h under a hydrothermal condition, centrifugally washing, drying, and then putting the obtained product into a tubular furnace for high-temperature carbonization, wherein the high-temperature carbonization process comprises the steps of increasing the temperature to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat at the temperature for 3h, and cooling to obtain the carbon nanosphere material. The surface morphology of the material was observed using a scanning electron microscope, and the electron micrograph is shown in FIG. 3.
Example 4
The electrode prepared from the nitrogen-doped carbon nanotube material described in example 1 was used as a working electrode, an Ag/AgCl (saturated potassium chloride) electrode was used as a reference electrode, and a platinum sheet was used as a counter electrode to form a three-electrode system, and cyclic voltammetry was performed in 6mol/L KOH aqueous solution at a voltage interval of-1 to 0V. FIG. 4 is a corresponding cyclic voltammogram at different sweep rates. At low scan rates, cyclic voltammograms exhibited a classical rectangular-like shape, indicating that the material exhibited typical double layer capacitance characteristics. And as the sweep rate increases, the cyclic voltammogram shape remains substantially unchanged. Even with an increase in scan rate to 200mV/s, the cyclic voltammogram maintained a good rectangular-like shape, indicating a rapid ion diffusion and charge transport process.
The electrode prepared from the nitrogen-doped carbon nanotube material described in example 1 was used as a working electrode, an Ag/AgCl (saturated potassium chloride) electrode was used as a reference electrode, and a platinum sheet was used as a counter electrode to form a three-electrode system, and a constant current charge-discharge test was performed in 6mol/L KOH aqueous solution, with a voltage interval of-1 to 0V. Fig. 5 is a diagram of the corresponding constant current charge and discharge at different current densities. At low current density, the constant current charge-discharge curve shows a typical triangular-like shape, which indicates that the material shows the characteristic of classical electric double layer capacitance. And the shape of the charge-discharge curve is basically kept unchanged along with the increase of the current density. The specific capacitance of the material is calculated as 563F/g under the condition that the current density is 1A/g, even when the current density is up to 20A/g, the specific capacitance is still up to 305F/g, and the surface material has excellent capacity retention rate.
Example 5
The electrode prepared from the nitrogen-doped carbon nanotube material described in example 1 was used as a working electrode, an Ag/AgCl (saturated potassium chloride) electrode was used as a reference electrode, and a platinum sheet was used as a counter electrode to form a three-electrode system. 10000 times of constant current charge and discharge tests are carried out in 6mol/L KOH aqueous solution, the voltage interval is-1 to 0V, and the charge and discharge current density is 5A/g. In fig. 6, it can be seen that the capacity retention rate was as high as 97% over 10000 cycles, which indicates that the material has excellent stability under alkaline conditions.
Example 6
The embodiment provides an energy storage application of an electrode prepared from the nitrogen-doped carbon nanotube material in a super capacitor, and the method comprises the following specific steps:
the electrode prepared from the nitrogen-doped carbon nanotube material prepared in the example 1 is assembled into a symmetrical capacitor by taking a cellulose membrane as a diaphragm, a constant-current charge-discharge experiment is carried out by taking 6mol/L KOH solution as an electrolyte solution and charging-discharging current density of 1-20A/g within a voltage interval of 0-1V, and the actual energy storage performance of the capacitor is tested. As shown in FIG. 7, the discharge capacity of 160F/g at a current density of 1A/g and 140F/g even at a current density of 20A/g was achieved, which is far superior to that of a metal oxide symmetrical supercapacitor.
The electrode prepared from the nitrogen-doped carbon nanotube material prepared in the example 1 is assembled into a symmetrical capacitor by taking a cellulose membrane as a diaphragm, a constant-current charge-discharge experiment is carried out by taking 6mol/L KOH solution as an electrolyte solution and charging-discharging current density of 1-20A/g within a voltage interval of 0-1V, and the actual energy storage performance of the capacitor is tested. As shown in FIG. 8, the energy density was as high as 21.0 Wh/kg by calculation at a low power density of 1217.4W/kg. When the high power density is 13440W/kg, the energy density can still keep 5.6 Wh/kg. The material has higher energy density and power density in the super capacitor, and the nitrogen-doped carbon nanotube material prepared by the method is expected to play an important role in the super capacitor.
Claims (10)
1. The nitrogen-doped carbon nanotube aerogel material is characterized by being prepared by taking a supramolecular polymer prepared in an organic solution as a nitrogen source and a carbohydrate compound as a carbon source through hydrothermal reaction and heating carbonization; the nitrogen-doped carbon nanotube aerogel material is of a nanotube-shaped structure, and the wall thickness of the nitrogen-doped carbon nanotube aerogel material is uniform.
2. The nitrogen-doped carbon nanotube aerogel material of claim 1, wherein the nitrogen-doped carbon nanotube aerogel material has an inner diameter of 20-500nm, an outer diameter of 200-1500nm, and a length of 0.1-20 μm.
3. The nitrogen-doped carbon nanotube aerogel material of claim 1, wherein the nitrogen-doped carbon nanotube aerogel material has a specific surface area of 500-2000m2(ii) g, bulk density of 1-30kg/m3Wherein the amount of nitrogen doped is 1-20%.
4. The method for preparing nitrogen-doped carbon nanotube aerogel material according to any of claims 1 to 3, comprising the following steps:
step 1): mixing a melamine solution and a melamine solution, stirring, centrifuging, washing, and drying in vacuum to obtain a supramolecular polymer;
step 2): dispersing the supramolecular polymer and the carbohydrate into a solvent to obtain a mixed solution;
step 3): performing hydrothermal reaction on the obtained mixed solution in a reaction kettle to obtain the supramolecular polymer-based carbon aerogel;
step 4): and carbonizing the obtained gas supermolecule polymer-based carbon aerogel in an inert gas atmosphere to obtain the nitrogen-doped carbon nanotube aerogel material.
5. The method according to claim 4, wherein the solvent of the melamine solution or the melamine solution in step 1) is any one or more of water, methanol, ethanol, isopropanol, N-butanol, diethyl ether, benzene, toluene, xylene, dichloromethane, chloroform, cyclohexane, cyclopentane, acetone, dimethyl sulfoxide, petroleum ether, N-dimethylformamide and N, N-dimethylacetamide; the carbohydrate in the step 2) is any one or more of glucose, maltose, fructose, sucrose, lactose, galactose, starch, glycogen and myoglycogen; the solvent in the step 2) is any one or more of water, methanol, ethanol, isopropanol, N-butanol, diethyl ether, benzene, toluene, xylene, dichloromethane, chloroform, cyclohexane, cyclopentane, acetone, dimethyl sulfoxide, petroleum ether, N-dimethylformamide and N, N-dimethylacetamide.
6. The method according to claim 4, wherein the concentration of the melamine solution in step 1) is 1 to 200g/L, and the concentration of the melamine solution is 1 to 200 g/L; the concentration of the supramolecular polymer in the mixed solution obtained in the step 2) is 5-500g/L, and the concentration of the carbohydrate is 5-500 g/L; the mass ratio of the supramolecular polymer to the carbohydrate in the step 2) is 1 (0.1-20).
7. The method according to claim 4, wherein the temperature of the hydrothermal reaction in the step 3) is 80 to 250 ℃; the carbonization temperature in the step 4) is 400-1200 ℃, and the inert gas is any one or more of argon, helium, nitrogen and neon.
8. An electrode material of a super capacitor, which is characterized in that raw materials comprise the nitrogen-doped carbon nanotube aerogel material as described in any one of claims 1 to 3, a conductive agent and a binder.
9. The supercapacitor electrode material according to claim 8, wherein the mass ratio of the nitrogen-doped carbon nanotube aerogel material to the conductive agent to the binder is (7-9): (0.1-2): (0.5-2).
10. The electrode material of the supercapacitor according to claim 8, wherein the conductive agent is any one or more of conductive carbon black, conductive graphite, graphene and carbon nanofibers; the binder is any one or more of polyvinyl alcohol, polytetrafluoroethylene, carboxymethyl cellulose and polyvinylidene fluoride.
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| CN113526492A (en) * | 2021-07-29 | 2021-10-22 | 深圳齐锂纳米科技有限公司 | Preparation method of in-situ generated nitrogen-doped carbon nano tube |
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