CN113135568A - Nitrogen-doped porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen-doped porous carbon material and a preparation method and application thereof, and belongs to the technical field of preparation of porous carbon materials. The method comprises the following steps: carbonizing cane molasses to obtain a carbonized product; and mixing the carbonized product, the nitrogen-containing compound and the activating agent, and then carrying out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material. In the invention, the cane molasses has high sugar content, is used as a carbon source, is doped with a nitrogen-containing compound to prepare a nitrogen-doped porous carbon material, can increase the specific surface area of the carbon material by being activated by an activating agent, obtains a developed pore structure, and shows excellent and stable electrochemical performance in an electrochemical performance test.
Description
Technical Field
The invention relates to the technical field of preparation of porous carbon materials, in particular to a nitrogen-doped porous carbon material and a preparation method and application thereof.
Background
The porous carbon material has rich pore structure, so that the specific surface area of the porous carbon material can be greatly improved, and the porous carbon material generally has the characteristics of stable physical and chemical properties, good electric and thermal conductivity, stable mechanical properties and the like. The porous carbon material is widely researched and applied in the fields of energy storage, sensing, adsorption and the like.
The molasses is a main byproduct in the sugar industry, and the sugar content is 40-60 wt%. At present, the annual production of molasses in the world exceeds 5500 ten thousand tons. In the prior art, the preparation of high-performance carbon materials such as ' Hanxue, Zhoubao, Guxue and the like ' from molasses has been disclosed, the preparation and the application of molasses-based porous carbon sphere electrode materials are disclosed, advanced school chemistry and science (6): 1135-1139 ' and Chinese patent CN105174258A, but the prepared porous carbon materials still have the problem of low specific capacitance.
Disclosure of Invention
In view of this, the present invention aims to provide a nitrogen-doped porous carbon material, and a preparation method and an application thereof. According to the invention, a nitrogen-containing compound is used as a nitrogen source, and the nitrogen-containing compound is subjected to an activation reaction with a carbonized product of cane molasses and an activating agent to obtain a nitrogen-doped porous carbon material, and the nitrogen-doped porous carbon material has higher specific capacitance when being used as an electrode material of a super capacitor.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nitrogen-doped porous carbon material, which comprises the following steps:
carbonizing cane molasses to obtain a carbonized product;
and mixing the carbonized product, the nitrogen-containing compound and the activating agent, and carrying out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material.
Preferably, the carbonization temperature is 400 ℃ and the carbonization time is 2 hours.
Preferably, the heating rate from room temperature to the carbonization temperature is 10 ℃ min-1。
Preferably, the carbonization device further comprises a drying treatment before carbonization, wherein the temperature of the drying treatment is 100-140 ℃.
Preferably, the mass ratio of the carbonized product to the nitrogen-containing compound to the activating agent is 1 (2-4) to 3, the nitrogen-containing compound is urea and/or melamine, and the activating agent is KOH.
Preferably, the temperature of the activation reaction is 600-900 ℃ and the time is 1-2 hours.
Preferably, the rate of temperature increase from room temperature to the temperature of the activation reaction is 20 ℃ min-1。
Preferably, the activation reaction is followed by washing the obtained activation reaction product with hydrochloric acid solution, washing with water and drying in sequence.
The invention also provides the nitrogen-doped porous carbon material prepared by the preparation method in the technical scheme, wherein the porosity of the nitrogen-doped porous carbon material is 20.11-54.74%, and the nitrogen doping amount is 0.66-6.12 wt%.
The invention also provides application of the nitrogen-doped porous carbon material in the technical scheme as an electrode material in a super capacitor.
The preparation method of the nitrogen-doped porous carbon material comprises the following steps: carbonizing cane molasses to obtain a carbonized product; and mixing the carbonized product, the nitrogen-containing compound and the activating agent, and then carrying out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material. In the invention, the cane molasses has higher sugar content, is used as a carbon source, and is doped with a nitrogen-containing compound to prepare the nitrogen-doped porous carbon materialIn the process of activating the activating agent at high temperature, the activating agent becomes molten state, enters the interior of the porous carbon material, performs chemical reaction with the porous carbon material, and etches the porous carbon material to generate a large number of micropores, the specific surface area of the carbon material is increased due to the increase of the microporous structure, and the developed pore structure in the porous carbon material provides an excellent transmission channel for electrolyte ions to reduce the resistance of ion transfer. In addition, the nitrogen atom doping can also improve the wettability of the surface of the porous carbon material, so that electrolyte ions in the solution can rapidly enter micropores, and the charge storage capacity is improved, thereby improving the conductivity of the nitrogen-doped porous carbon material and further improving the specific capacitance; and from the view of electronic structure, the nitrogen atom has one more electron outside the core than the carbon atom and has higher electron affinity, after the nitrogen enters the carbon skeleton to form the nitrogen-doped carbon material, the periphery of the carbon atom has higher charge density, and simultaneously, the nitrogen-doped carbon material shows excellent conductivity due to the existence of large conjugated pi bonds. In addition, after nitrogen atoms are doped into carbon atom lattices, the specific surface area can be effectively increased, and meanwhile, the bonding effect of the surface of the carbon material and ions in a solution is enhanced, so that the specific capacitance of the carbon material is greatly improved. The data of the examples show that the specific capacitance of the nitrogen-doped porous carbon material prepared by the method of the present invention is 326.90F-g at most in the constant current charge-discharge test-1。
The preparation method provided by the invention not only can solve the problem of recycling sugar cane molasses which is a waste in sugar industry, improve the resource utilization rate, but also can provide a new method for preparing the high-performance nitrogen-doped porous carbon material.
The invention also provides the nitrogen-doped porous carbon material prepared by the preparation method in the technical scheme, wherein the porosity of the nitrogen-doped porous carbon material is 20.11-54.74%, and the nitrogen doping amount is 0.66-6.12 wt%.
The invention also provides application of the nitrogen-doped porous carbon material in the technical scheme as an electrode material in a super capacitor, and the specific capacitance of the prepared nitrogen-doped porous carbon material is 154.50-326.90F-g-1。
Drawings
FIG. 1 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 1-1Constant current charge-discharge curve under the condition;
FIG. 2 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 2-1Constant current charge-discharge curve under the condition;
FIG. 3 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 3-1Constant current charge-discharge curve under the condition;
FIG. 4 shows the nitrogen-doped porous carbon material prepared in example 4 at 1A. g-1Constant current charge-discharge curve under the condition;
FIG. 5 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 5-1Constant current charge-discharge curve under the condition;
FIG. 6 shows the nitrogen-doped porous carbon material prepared in example 6 at 1A. g-1Constant current charge-discharge curve under the condition;
FIG. 7 shows the nitrogen-doped porous carbon material prepared in example 7 at 1A. g-1Constant current charge-discharge curve under the condition;
FIG. 8 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 8-1Constant current charge-discharge curve under the condition;
FIG. 9 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 9-1Constant current charge-discharge curve under the condition;
FIG. 10 shows the nitrogen-doped porous carbon material prepared in comparative example at 1A g-1Constant current charge and discharge curve under the condition.
Detailed Description
The invention provides a preparation method of a nitrogen-doped porous carbon material, which comprises the following steps;
carbonizing cane molasses to obtain a carbonized product;
and mixing the carbonized product, the nitrogen-containing compound and the activating agent, and carrying out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material.
The invention carbonizes the cane molasses to obtain a carbonized product. The source of the sugar cane molasses in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, it is preferable to dry the sugar cane molasses before the carbonization.
In the invention, the temperature of the drying treatment is preferably 100-140 ℃, more preferably 120-130 ℃, and the time of the drying treatment is preferably drying to constant weight and lasting for 24 hours. In the present invention, the drying treatment is preferably performed in an electric hot air drying oven.
In the present invention, the carbonization temperature is preferably 400 ℃ and the carbonization time is preferably 2 hours.
In the present invention, the rate of temperature increase from room temperature to the temperature for carbonization is preferably 10 ℃ min-1。
In the present invention, the carbonization is preferably performed in a box furnace.
In the present invention, after the carbonization is completed, the present invention preferably further comprises washing the obtained solid product to be neutral with a hydrochloric acid solution and distilled water in sequence, and then drying and grinding the solid product to obtain the carbonized product.
In the present invention, the concentration of the hydrochloric acid solution is preferably 0.10mol · L-1。
The use amounts of the hydrochloric acid solution and the distilled water are not particularly limited, and the hydrochloric acid solution and the distilled water can be washed to be neutral.
In the invention, the particle size of the carbonized product is preferably 50-100 nm. The present invention is not particularly limited to the specific manner of grinding, and may be carried out in a manner known to those skilled in the art.
After a carbonized product is obtained, the invention mixes the carbonized product, a nitrogen-containing compound and an activating agent, and then carries out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material.
In the invention, the mass ratio of the carbonized product to the nitrogen-containing compound to the activating agent is preferably 1 (2-4): 3, more preferably 1:3:3, the nitrogen-containing compound is preferably urea and/or melamine, and the activating agent is preferably KOH.
In the invention, the temperature of the activation reaction (high-temperature activation reaction) is preferably 600-900 ℃, more preferably 700-800 ℃, and the time is preferably 1-2 hours, more preferably 1.5 hours. In the present invention, the activation reaction is preferably carried out in a tube furnace, and the activation reaction is carried out at a high temperature.
In the present invention, the rate of temperature increase from room temperature to the temperature of the activation reaction is preferably 20 ℃ min-1。
In the invention, in the high-temperature activation process of the activating agent, the reaction mechanisms of different temperature stages of the activation reaction are different. At low temperature (100-400 ℃), various gas micromolecules (water vapor and CO) generated in the temperature rising process2) The carbon frame material is mainly subjected to physical activation to form a large number of macropores, and the nitrogen-doped carbon frame material is primarily formed; when the temperature reaches a certain degree (500-600 ℃), the activating agent performs an oxidation-reduction reaction to form a large number of micropores, and meanwhile, introduced nitrogen atoms promote partial micropores to be converted into mesopores, so that appropriate preparation conditions (nitrogen-containing compounds and activating agents with appropriate dosage) are favorable for the generation of a developed pore structure; when the temperature is too high (800-900 ℃), the pore channel is collapsed; meanwhile, the doping of heteroatom nitrogen can obviously change the element composition of the carbon material, increase the surface wettability of the carbon material and effectively improve the physical and chemical properties of the carbon material. The radius of the nitrogen atoms is closer to that of the carbon atoms, so that the nitrogen atoms can enter the crystal lattice of the carbon material more easily to replace the corresponding carbon atoms, and the nitrogen-doped carbon nano material is formed. From the view of an electronic structure, the nitrogen atom has one more electron outside the nucleus than the carbon atom and has higher electron affinity, after the nitrogen enters the carbon skeleton to form the doped carbon material, the periphery of the carbon atom has higher charge density, and meanwhile, the nitrogen-doped carbon material shows excellent conductivity due to the existence of large conjugated pi bonds. In addition, after nitrogen atoms are doped into carbon atom lattices, the specific surface area can be effectively increased, and meanwhile, the bonding effect of the surface of the carbon material and ions in a solution is enhanced, so that the specific capacitance of the carbon material is greatly improved.
In the present invention, the protective gas is preferably nitrogen, and the protective gas is preferably nitrogenThe flow rate of the gas is preferably 10 mL/min-1. In the present invention, the flow rate of the protective gas may affect the porous structure of the nitrogen-doped porous material and the doping effect of nitrogen. XPS tests have shown that nitrogen atoms mainly exist in a nitrogen-doped carbon material in 4 bonding modes, namely a pyridine nitrogen structure (the bonding energy is 398.30-398.59 eV), a pyrrole nitrogen structure (the bonding energy is 399.60-399.73 eV), a graphite nitrogen structure (the bonding energy is 400.50-401.55 eV) and nitrogen oxide (the bonding energy is 403.90-403.95 eV), wherein factors influencing the electrochemical performance of the carbon material mainly include the nitrogen doping type and the nitrogen doping amount, and the charge storage performance of the porous carbon material with higher nitrogen content is better. In addition, the relative proportion of each nitrogen doping mode plays a certain role, the graphite nitrogen doping structure is beneficial to improving the conductivity of the material, the temperature is also a key factor influencing the nitrogen content and the structure in the catalyst, and nitrogen-doped carbon materials prepared at different temperatures have different properties. The increase in temperature is detrimental to the formation of pyrrole nitrogen, and pyridine nitrogen and pyrrole nitrogen are gradually converted to more stable graphite nitrogen. When the temperature of the high-temperature activation reaction is too high, the graphitization degree of the nitrogen-doped porous carbon material is too high, the density is high, and the nitrogen doping amount is lost; when the temperature of the high-temperature activation reaction is too low, the nitrogen doping mode, particularly the graphitized nitrogen proportion, is small; when the time of the high-temperature activation reaction is too long, the porous carbon material holes can collapse; when the time of the high-temperature activation reaction is too short, the carbonization reaction may not proceed completely.
In the present invention, after the high-temperature activation reaction, preferably, the method further comprises sequentially washing, washing and drying the obtained high-temperature activation reaction product with a hydrochloric acid solution.
In the present invention, the concentration of the hydrochloric acid solution is preferably 0.10mol · L-1。
The dosage of the hydrochloric acid solution and the water is not particularly limited, and the hydrochloric acid solution and the water can be washed to be neutral.
The present invention does not specifically limit the specific manner of drying, and can ensure complete removal of moisture.
The invention also provides the nitrogen-doped porous prepared by the preparation method in the technical schemeThe carbon material has a porosity of 20.11-54.74%, a nitrogen doping amount of 0.66-6.12 wt%, and a pore volume of 0.5653-1.5332 cm3·g-1The specific surface area is 1173.60-2703.60 m2·g-1The carbon content is 26.35-79.26 wt%.
The invention also provides application of the nitrogen-doped porous carbon material in the technical scheme as an electrode material in a super capacitor.
In the present invention, the application is preferably used as an electric double layer capacitor.
The application mode of the nitrogen-doped porous carbon material in the supercapacitor is not particularly limited, and the application mode is known by those skilled in the art.
In order to further illustrate the present invention, the nitrogen-doped porous carbon material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1The temperature rise rate of (1) is increased to 600 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
Pore structure and electrochemical treatment of prepared nitrogen-doped porous carbon materialThe porosity of the porous carbon material was 20.11%, the amount of nitrogen doped was 6.12 wt%, and the pore volume was 0.5653cm3·g-1Specific surface area of 1173.60m2·g-1Specific capacitance of 233.90F g-1The carbon content was 61.58 wt%.
FIG. 1 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 1-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. In addition, the nitrogen atom doping improves the wettability of the surface of the porous carbon material, so that electrolyte ions in the solution can rapidly enter micropores, the charge storage capacity is improved, and the conductivity of the nitrogen-doped porous carbon material is improved.
Example 2
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
For the prepared nitrogen-doped porous carbon materialThe porosity of the porous carbon material was 41.87%, the nitrogen doping amount was 5.09 wt%, and the pore volume was 1.5332cm, which were obtained from the results of the tests3·g-1Specific surface area of 2703.60m2·g-1Specific capacitance of 326.90F g-1The carbon content was 69.48 wt%.
FIG. 2 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 2-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. It can be seen from the figure that the specific capacitance of the nitrogen-doped porous carbon material synthesized in this example is 326.90F g-1The nitrogen-doped porous carbon material synthesized in all the embodiments of the present invention has the highest specific capacitance value, which also shows that the synthesis conditions explored in the embodiments are more conducive to the formation of hierarchical pore channel structures of macropores, micropores and mesopores in the porous carbon material, and the doping amount of nitrogen atoms is appropriate, so that the conductivity of the carbon material can be effectively improved, and the transfer of electrons is facilitated, so that the porous carbon material can rapidly complete charging and discharging.
Example 3
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1Is disclosedThe temperature is raised to 800 ℃ at a temperature rate for high-temperature activation for 1.5 hours, and after the reaction, the products are respectively activated by 0.10mol per liter-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 20.08%, the nitrogen doping amount is 1.93 wt%, and the pore volume is 1.0256cm3·g-1Specific surface area of 2227.10m2·g-1Specific capacitance of 227.75F g-1The carbon content was 78.82 wt%.
FIG. 3 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 3-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. It can be seen from the figure that the specific capacitance of the porous carbon material is 227.75F g-1A higher activation temperature causes partial collapse of the pore structure, failing to form a developed void structure, and hinders the transport of electrolyte ions, resulting in a decrease in the conductivity of the electrode material.
Example 4
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH are mixed evenly in a porcelain boat and placed in a tube furnaceUnder nitrogen atmosphere, at 20 ℃ for min-1The temperature rise rate of (1) is increased to 900 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 53.25%, the nitrogen doping amount is 1.16 wt%, and the pore volume is 1.3308cm3·g-1Specific surface area of 2126.90m2·g-1Specific capacitance of 165.20F g-1The carbon content was 73.07 wt%.
FIG. 4 shows the nitrogen-doped porous carbon material prepared in example 4 at 1A. g-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. It can be seen from the figure that the specific capacitance of the porous carbon material is 165.20F g-1Too high activation temperature may cause collapse of more pore structures, failing to form developed void structures, hindering the transport of electrolyte ions, and too high temperature may cause loss of nitrogen atoms, resulting in poor wettability of the material, resulting in reduced conductivity of the electrode material.
Example 5
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product, 1.60g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 22.18%, the nitrogen doping amount is 3.82 wt%, and the pore volume is 1.1072cm3·g-1Specific surface area of 2099.00m2·g-1Specific capacitance of 301.70F g-1The carbon content was 79.09 wt%.
FIG. 5 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 5-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. In addition, the nitrogen atom doping improves the conductivity of the carbon material, and is beneficial to the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge. It can be seen from the figure that the specific capacitance of the porous carbon material is 301.70F g-1。
Example 6
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1Washing with hydrochloric acid solution and distilled water to neutrality, drying, and grinding to obtain charred molassesThe particle size of the product is 50-100 nm.
0.80g of the carbonized product, 3.20g of urea and 2.40g of KOH are uniformly mixed in a porcelain boat, and the mixture is placed in a tube furnace in the atmosphere of nitrogen at the temperature of 20 ℃ per minute-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 21.99%, the nitrogen doping amount is 5.79 wt%, and the pore volume is 1.0800cm3·g-1Specific surface area of 2154.80m2·g-1Specific capacitance of 248.50F g-1The carbon content was 60.70 wt%.
FIG. 6 shows the nitrogen-doped porous carbon material prepared in example 6 at 1A. g-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. It can be seen from the figure that the specific capacitance of the porous carbon material is 248.50F g-1Too high nitrogen content can block the pore diameter of the porous carbon material, so that the effective specific surface area is reduced, and the improvement of the specific capacitance value is not facilitated.
Example 7
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1Washing with hydrochloric acid solution and distilled water to neutrality, drying, and grinding to obtain molassesThe particle size of the carbonized product is 50-100 nm.
Mixing 0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.0 hour, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 21.35%, the nitrogen doping amount is 5.43 wt%, and the pore volume is 1.0655cm3·g-1Specific surface area of 2199.30m2·g-1Specific capacitance of 313.55F g-1The carbon content was 79.26 wt%.
FIG. 7 shows the nitrogen-doped porous carbon material prepared in example 7 at 1A. g-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. In addition, the nitrogen atom doping improves the conductivity of the carbon material, and is beneficial to the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge. It can be seen from the figure that the specific capacitance of the porous carbon material is 313.55F g-1The high-temperature activation reaction time is too short, so that the carbonization reaction is not thorough, and the doped nitrogen cannot completely enter the material, so that the specific capacitance value is reduced to some extent.
Example 8
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Putting the molasses solid powder into a box type furnaceAt 10 ℃ min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product, 2.40g of urea and 2.40g of KOH in a porcelain boat uniformly, placing in a tube furnace, and heating at 20 ℃ for min in a nitrogen atmosphere-1The temperature rise rate of (2) is increased to 700 ℃, the high-temperature activation is carried out for 2.0 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test results, the porosity of the porous carbon material is 24.74%, the nitrogen doping amount is 4.11 wt%, and the pore volume is 1.0953cm3·g-1Specific surface area of 2253.70m2·g-1Specific capacitance of 302.60F g-1The carbon content was 76.11 wt%.
FIG. 8 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 8-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. In addition, the nitrogen atom doping improves the conductivity of the carbon material, and is beneficial to the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge. It can be seen from the figure that the specific capacitance of the nitrogen-doped porous carbon material is 302.60F g-1When the time of the high-temperature activation reaction is too long, the nitrogen-doped porous carbon material pores collapse, so that the transmission rate of electrolyte ions is reduced, and the capacitance value is reduced.
Example 9
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
0.80g of the carbonized product, 1.60g of melamine and 3.20g of KOH are uniformly mixed in a porcelain boat, and the mixture is placed in a tube furnace in the atmosphere of nitrogen at 20 ℃ for min-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for the pore structure and the electrochemical performance, and according to the test result, the porosity of the porous carbon material is 29.88%, the nitrogen doping amount is 7.74 wt%, and the pore volume is 1.2829cm3·g-1Specific surface area of 2495.80m2·g-1Specific capacitance of 285.40F g-1The carbon content was 80.36 wt%.
FIG. 9 shows the nitrogen-doped porous carbon material at 1A. g obtained in example 9-1Under the condition, the constant current charge-discharge curve can be seen from the figure, the charge-discharge curve of the synthesized nitrogen-doped carbon material is in an isosceles triangle shape, which shows that the super capacitor prepared by the material has very high coulombic efficiency, and the charge-discharge of the electrode has good reversibility. And the developed pore structure in the nitrogen-doped porous carbon material provides an excellent transmission channel for electrolyte ions, so that the resistance of ion transfer is reduced. In addition, the nitrogen atom doping improves the conductivity of the carbon material, and is beneficial to the transfer of electrons, so that the porous carbon material can rapidly complete charge and discharge. It can be seen from the figure that the specific capacitance of the nitrogen-doped porous carbon material is 285.40F g-1。
The embodiment is melamine asThe nitrogen source was used to prepare the nitrogen-doped porous carbon material, and the preparation conditions described in example 9 were the optimum conditions for preparing the nitrogen-doped porous carbon material using molasses carbide as the carbon source, melamine as the nitrogen source, and potassium hydroxide as the activator, which were confirmed by experiments. The preparation conditions described in example 2 are the best conditions for preparing the nitrogen-doped porous carbon material by using urea as a nitrogen source, and the specific capacitance of the nitrogen-doped porous carbon material reaches 326.90F g-1Thus, it is shown that urea is used as a nitrogen source to prepare the nitrogen-doped porous carbon material better than melamine.
Comparative example
And (3) putting the liquid cane molasses into a beaker, heating and drying the liquid cane molasses in an oven at the temperature of 120 ℃ until the weight is constant, and keeping the quality unchanged for 24 hours to obtain solid powder of the molasses.
Placing the molasses solid powder in a box furnace at 10 deg.C/min-1The temperature is raised to 400 ℃ at the temperature raising rate for 2.0 hours, and then 0.10 mol.L is used respectively-1And washing the hydrochloric acid solution and the distilled water to be neutral, drying and grinding to obtain a carbonized product of the molasses, wherein the particle size is 50-100 nm.
Mixing 0.80g of the carbonized product and 2.40g of KOH in a porcelain boat, placing in a tube furnace, and heating at 20 deg.C/min in nitrogen atmosphere-1The temperature rise rate of (1) is increased to 700 ℃, the high-temperature activation is carried out for 1.5 hours, and after the reaction, the products are respectively activated by 0.10 mol.L-1And washing the hydrochloric acid solution and the distilled water until the pH value of the product is 7.0, and drying and grinding to obtain the nitrogen-doped porous carbon material.
The prepared nitrogen-doped porous carbon material is tested for pore structure and electrochemical performance, and according to the test results, the porosity of the porous carbon material is 54.74%, the nitrogen doping amount is 0.66 wt%, and the pore volume is 1.2756cm3·g-1Specific surface area of 2032.90m2·g-1Specific capacitance of 154.50F g-1The carbon content was 26.35 wt%.
FIG. 10 shows the nitrogen-doped porous carbon material prepared in comparative example at 1A g-1Under the condition, the constant current charge-discharge curve is shown in the figure, and the charge-discharge curve of the synthesized nitrogen-doped carbon material is isosceles threeAnd the angle shape shows that the super capacitor prepared by the material has better coulombic efficiency, and the charge and discharge of the electrode have good reversibility. It can be seen from the figure that the specific capacitance of the porous carbon material is 154.50F g-1The capacitance value is far lower than that of the porous carbon prepared by doping the nitrogen-containing compound in the embodiment of the invention, so that the specific capacitance of the porous carbon material can be obviously improved by doping the nitrogen-containing compound.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped porous carbon material is characterized by comprising the following steps:
carbonizing cane molasses to obtain a carbonized product;
and mixing the carbonized product, the nitrogen-containing compound and the activating agent, and carrying out activation reaction in the atmosphere of protective gas to obtain the nitrogen-doped porous carbon material.
2. The method according to claim 1, wherein the carbonization temperature is 400 ℃ and the carbonization time is 2 hours.
3. The production method according to claim 1 or 2, wherein the rate of temperature increase from room temperature to the temperature for carbonization is 10 ℃. min-1。
4. The preparation method according to claim 1, further comprising a drying treatment before the carbonization, wherein the temperature of the drying treatment is 100-140 ℃.
5. The preparation method of the modified activated carbon, which is used for the industrial production, is characterized in that the mass ratio of the carbonized product to the nitrogen-containing compound to the activating agent is 1 (2-4) to 3, the nitrogen-containing compound is urea and/or melamine, and the activating agent is KOH.
6. The method according to claim 1, wherein the temperature of the activation reaction is 600 to 900 ℃ and the time is 1 to 2 hours.
7. The production method according to claim 1 or 6, wherein the rate of temperature increase from room temperature to the temperature of the activation reaction is 20 ℃ min-1。
8. The preparation method according to claim 1, further comprising, after the activation reaction, sequentially washing the obtained activation reaction product with a hydrochloric acid solution, washing with water, and drying.
9. The nitrogen-doped porous carbon material prepared by the preparation method according to any one of claims 1 to 8, wherein the porosity of the nitrogen-doped porous carbon material is 20.11 to 54.74%, and the nitrogen doping amount is 0.66 to 6.12 wt%.
10. Use of the nitrogen-doped porous carbon material of claim 9 as an electrode material in a supercapacitor.
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