CN113659137A - Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon material preparation, and discloses a nitrogen-doped three-dimensional nano network carbon material, and a preparation method and application thereof. The carbon material with the nano network structure is woven by nano wires, a through three-dimensional network channel is formed inside the carbon material, the carbon material is rich in a micro-porous, mesoporous and macroporous hierarchical pore structure, has high-efficiency and rapid mass transfer capability, and has important application value in the fields of energy, catalysis, environment and the like. The preparation method of the three-dimensional nano-network structure carbon material mainly comprises the following steps: taking cobalt salt and triazole sodium as reactants and ethanol as a solvent, and obtaining a solid powder product through coordination reaction at a certain temperature. Carbonizing the powder product and washing away inorganic metal salt to obtain the carbon material with the three-dimensional nano network structure. The method has the characteristics of simple and convenient operation, easy industrial production and small environmental pollution, and has the potential of large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a nitrogen-doped three-dimensional nano network carbon material and a preparation method and application thereof.
Background
The carbon material has the advantages of low density, high conductivity, stable physical and chemical properties and the like, and has great application value in the fields of energy, catalysis and environment. Due to the abundant bonding mode and wide raw material sources, the carbon materials have different shapes, such as one-dimensional carbon nanofiber, carbon nanotube, two-dimensional graphene, three-dimensional diamond, various porous carbons and the like. The three-dimensional nano-network structure carbon material is a novel porous carbon material and is assembled by low-dimensional structure units on a three-dimensional scale. The three-dimensional nano-network structure carbon material generally has a nano-scale structural unit and a three-dimensionally communicated pore structure, so that the material has rapid mass transfer capacity. When used as a secondary battery electrode material, the material can show ultrahigh ion storage capacity and high-current charge and discharge performance; in the field of catalysis, the large specific surface area is very suitable for supporting a catalyst, and the extremely high catalytic efficiency is obtained. Because of these characteristics, in recent years, a three-dimensional nano-network structure carbon material has attracted attention from various parties.
At present, the carbon material with the three-dimensional nano network structure is mainly prepared by a template method or a sol-gel method. The template method is to coat a carbon precursor on the surface of an inorganic template with a three-dimensional structure, carbonize and remove the template to obtain a corresponding carbon copy body. The most commonly used template at present is three-dimensional structured silica. The sol-gel method generally utilizes a polymerization-induced phase separation technique to build a three-dimensional structure, such as a phenolic resin-based carbon aerogel. Although these methods can be used to design three-dimensional nano-network structure carbon materials, they still have some unavoidable disadvantages: (1) the template method has complex steps and is difficult to realize large-scale application; (2) the phenolic resin precursor commonly used in the sol-gel method needs to use toxic formaldehyde as a raw material, and is not friendly to the environment and human health.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention mainly aims to provide a preparation method of a nitrogen-doped three-dimensional nano network carbon material; the method utilizes simple coordination reaction to construct the carbon material with the three-dimensional nano network structure, adopts sodium triazole and soluble cobalt salt as precursors, adopts ethanol as a reaction solvent, is simple to operate, is environment-friendly, and has the potential of large-scale application; meanwhile, the prepared carbon material with the nano network structure is provided with superfine nano wire structure units, the nano wire structure units are mutually staggered and woven into a three-dimensional structure, and a through three-dimensional network channel is formed in the carbon material.
The invention also aims to provide the nitrogen-doped three-dimensional nano-network carbon material prepared by the preparation method; the carbon material has a large specific surface area and a multi-layer pore channel structure, and has an excellent functional effect in an energy storage material.
The invention also aims to provide application of the nitrogen-doped three-dimensional nano-network carbon material; when used as a negative electrode material of a sodium-ion battery, the three-dimensional nano-network structure carbon material shows rapid sodium storage capacity and excellent rate performance.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nitrogen-doped three-dimensional nano network carbon material comprises the following steps:
(1) weighing cobalt salt, adding the cobalt salt into a solvent, and magnetically stirring to obtain a cobalt salt solution;
(2) weighing sodium triazole, adding the sodium triazole into a solvent, and magnetically stirring until the sodium triazole is completely dissolved to obtain a sodium triazole solution;
(3) under the magnetic stirring of 1000r/min, dripping a triazole sodium solution into a cobalt salt solution by using a dropper, and allowing cobalt ions and the triazole sodium to generate a coordination reaction to obtain a brown powdery product;
(4) washing the brown powdery product by using absolute ethyl alcohol, performing suction filtration, drying in a vacuum drying oven at 80 ℃ for 24 hours, and sieving the obtained product by using a 200-mesh sieve to obtain a final coordination compound;
(5) filling the final coordination product obtained in the step (4) into a high-purity graphite crucible, sealing, and carrying out high-temperature carbonization for a certain time in an inert atmosphere;
(6) and (4) adding the high-temperature carbonization product obtained in the step (5) into a hydrochloric acid solution with the mass concentration of 10% for soaking, filtering, washing and drying to obtain the nitrogen-doped three-dimensional nano network structure carbon material.
The molar ratio of the triazole sodium in the step (2) to the cobalt salt in the step (1) is 1: 0.25-1: 5; the cobalt salt in the step (1) is cobalt nitrate, cobalt chloride or ethylene diamine tetraacetic acid cobaltous salt; and (3) the solvent in the step (1) and the step (2) is absolute ethyl alcohol.
The temperature of the coordination reaction in the step (3) is 30-70 ℃, and the coordination reaction time is 2-24 h.
The temperature of the high-temperature carbonization in the step (5) is 600-1600 ℃, and the carbonization time is 2-12 h.
The nitrogen-doped three-dimensional nano-network carbon material prepared by the preparation method.
The nitrogen-doped three-dimensional nano network carbon material is applied to energy sources such as sodium ion battery cathodes and super capacitors, catalysis and the environment field.
Compared with the prior art, the invention has the following advantages and effects:
(1) the preparation method disclosed by the invention is simple, green and environment-friendly, good in uniformity, easy to control the process, high in product repeatability and beneficial to large-scale production.
(2) The nitrogen-doped carbon material with the three-dimensional nano network structure prepared by the method has excellent morphology and plays an important role in an energy storage material cathode material.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of a nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention; the scanning electron microscope image can show that the prepared product is of a three-dimensional nano network structure from local amplification.
FIG. 3 is an X-ray photoelectron spectrum of the nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention; from the XPS full spectrum, the fact that the three-dimensional nano-network-shaped carbon material is successfully doped with the N element can be seen.
FIG. 4 is a Raman spectrum of a nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention; it can be seen from the figure that ID/IG1.02, the material has a partially structured graphitization.
FIG. 5 shows that the sodium ion battery assembled by the carbon material with the nitrogen-doped three-dimensional nano network structure in example 1 of the invention is 100mA g-1Current density of (2) and circulating for 55 circles; the charge capacity of the second turn is 190mAh g-1At 100mA g-1The capacity of 55 cycles under the current density is 248mAh g-1。
FIG. 6 shows that the sodium-ion battery assembled by the nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the invention has different current densities (from 100mA g)-1To 5000mA g-1) The rate performance graph of (1).
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Transferring 1.3g of cobalt chloride and 50mL of absolute ethyl alcohol into a three-neck flask, adjusting the temperature to 30 ℃, starting magnetic stirring to fully dissolve the cobalt chloride to obtain a cobalt chloride solution; weighing 1g of triazole sodium, dissolving in 30mL of absolute ethyl alcohol, and placing in a beaker to obtain a triazole sodium solution; the molar ratio of the triazole sodium to the cobalt chloride is 1: 0.5. Then, under the condition of continuous stirring, adding the triazole sodium solution into the cobalt chloride solution drop by drop, after the coordination reaction is carried out for 3h, adding a certain amount of absolute ethyl alcohol into the solution, washing, carrying out suction filtration, and drying at 80 ℃ for 24h in vacuum to obtain a dark brown solid product. The dried dark brown solid product was taken out and ground to a powder, sieved through a 200-mesh sieve, and the sieved powder was collected in a round bottom ceramic crucible. The ceramic crucible with the round bottom is put into a graphite crucible in a glove box, sealed and aerated, and taken out to be carbonized for 2 hours in a tube furnace. Carbonization temperature: temperature rise rate at 600 ℃:5 ℃/min, atmosphere: high purity nitrogen.
And pouring the carbonized sample into a beaker, slowly adding 100mL of HCl solution with the mass concentration of 10% into the beaker, standing for a period of time, washing, filtering and drying to obtain the nitrogen-doped three-dimensional nano network structure carbon material.
As shown in fig. 1, which is an XRD pattern of the nitrogen-doped three-dimensional nano-network structure carbon material, it can be seen from fig. 1 that a diffraction peak position at 26 ° exhibits a sharp state because a portion of amorphous carbon exhibits a short-range order, indicating that the material contains both amorphous carbon and a small portion of carbon that has been graphitized.
Fig. 2 is a scanning electron microscope image of the nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention, and it can be seen from the image that the surface morphology of the material exhibits a three-dimensional nano-network structure.
As shown in the XPS spectrogram in fig. 3, it can be seen that the three-dimensional nano-network-like carbon material is successfully doped with N, and the N is calculated to be about 5.2%.
FIG. 4 is a Raman spectrum of the nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the present invention; it can be seen from the figure that ID/IG1.02, the material has a partially structured graphitization.
Mixing and grinding the prepared final product, conductive carbon black and polyvinylidene fluoride (PVDF) uniformly according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone (NMP) to prepare slurry, uniformly mixing, coating the slurry on a copper foil, drying in vacuum at 60 ℃ for 12 hours, and rolling to obtain the pole piece.
Punching the prepared pole piece
Of wafers of
A metal sodium sheet as a counter electrode, glass fiber as a diaphragm, 1mol/LNaPF6The/diglyme is electrolyte and is assembled into a button cell in a glove box filled with argon. A battery testing system (CT2001A) is adopted to test the battery, and the charging and discharging voltage range is 0.01-3V. 100mA g-1The first charging specific capacity of charging and discharging is 191.2mAh g-1The specific discharge capacity is 263.3mAh g-1The charge-discharge efficiency was 72.62%.
FIG. 5 shows that the amount of nitrogen-doped carbon material with three-dimensional nano-network structure in the sodium ion battery of example 1 is 100mA g-1Current density of (2) and circulating for 55 circles; the charging specific capacity of the second circle is 198mAh g-1At 100mA g-1The capacity of 55 cycles under the current density is 248mAh g-1Indicating a slow capacity increase and then remaining stable in the following cycles, fully indicating Na+High reversibility of repeated deintercalation in carbon materials.
FIG. 6 shows that the sodium-ion battery assembled by the nitrogen-doped three-dimensional nano-network structure carbon material in example 1 of the invention has different current densities (from 100mA g)-1To 5000mA g-1) The rate performance graph of (1). When the current density is from 100mA g-1Increased to 5000mA g-1When the current density was returned to 100mA g, the capacity retention rate hardly changed-1When the capacity is almost not attenuated, it shows excellent rate capability.
Example 2
(1) In this example, the influence of different carbonization temperatures (600, 800, 1000, 1200, 1400, 1600 ℃) on the electrochemical performance of the material is examined, and other steps of the prepared nitrogen-doped three-dimensional nano-network structure carbon material except the carbonization temperature and the carbonization time (2, 6, 12h) are the same as those of example 1;
(2) the preparation of the nitrogen-doped carbon electrode plate with the three-dimensional nano network structure is the same as that of the embodiment 1;
(3) button cell assembly and performance testing were the same as in example 1;
the sodium ion battery assembled by the carbon material with the nitrogen-doped three-dimensional nano network structure prepared after carbonization treatment at different carbonization temperatures and carbonization times is 100mA g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 1.
TABLE 1 influence of carbonization temperature (600-1600 ℃) and carbonization time (2-12 h) on electrochemical performance of nitrogen-doped three-dimensional nano-network structure carbon material
Example 3
(1) In this example, the effect of the molar ratio of sodium triazole to cobalt salt (1:0.25, 1:0.5, 1:1, 1:5) on the electrochemical performance of the material is examined, and the other steps except for the molar ratio of sodium triazole to cobalt salt for preparing the nitrogen-doped carbon material with the three-dimensional nano network structure are the same as those in example 1;
(2) the preparation of the nitrogen-doped carbon electrode plate with the three-dimensional nano network structure is the same as that of the embodiment 1;
(3) button cell assembly and performance testing were the same as in example 1;
the electrode plate of the nitrogen-doped three-dimensional nano-network structure carbon material prepared by different molar ratios of triazole sodium to cobalt salt is 100 mA.g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 2.
Table 2 influence of molar ratio (1: 0.25-1: 5) of sodium triazole to cobalt salt on electrochemical performance of nitrogen-doped three-dimensional nano-network structure carbon material
Example 4
(1) In the embodiment, the influence of the coordination temperature (30-70 ℃) and the coordination time (2-24 hours) on the electrochemical performance of the material is considered, and other steps except for the coordination temperature and the coordination time for preparing the nitrogen-doped three-dimensional nano network structure carbon material are the same as those in the embodiment 1;
(2) the preparation of the nitrogen-doped carbon electrode plate with the three-dimensional nano network structure is the same as that of the embodiment 1;
(3) button cell assembly and performance testing were the same as in example 1;
the electrode plate of the carbon material with the nitrogen-doped three-dimensional nano network structure prepared at different coordination temperatures and coordination times is 100 mA.g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 4.
Table 4 shows the influence of the coordination temperature (30-70 ℃) and the coordination time (2-24 h) on the electrochemical performance of the nitrogen-doped three-dimensional nano-network structure carbon material
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a nitrogen-doped three-dimensional nano network carbon material is characterized by comprising the following steps:
(1) weighing cobalt salt, adding the cobalt salt into a solvent, and magnetically stirring to obtain a cobalt salt solution;
(2) weighing sodium triazole, adding the sodium triazole into a solvent, and magnetically stirring until the sodium triazole is completely dissolved to obtain a sodium triazole solution;
(3) under the magnetic stirring at the rotating speed of 1000r/min, dripping a triazole sodium solution into a cobalt salt solution by using a dropper, and performing coordination reaction on cobalt ions and the triazole sodium to obtain a brown powdery product;
(4) washing the brown powdery product by using absolute ethyl alcohol, performing suction filtration, drying in a vacuum drying oven at 80 ℃ for 24 hours, and sieving the obtained product by using a 200-mesh sieve to obtain a final coordination compound;
(5) filling the final coordination product obtained in the step (4) into a high-purity graphite crucible, sealing, and carrying out high-temperature carbonization in an inert atmosphere;
(6) and (4) adding the high-temperature carbonization product obtained in the step (5) into a hydrochloric acid solution with the mass concentration of 10% for soaking, filtering, washing and drying to obtain the nitrogen-doped three-dimensional nano network structure carbon material.
2. The method of claim 1, wherein: the molar ratio of the triazole sodium in the step (2) to the cobalt salt in the step (1) is 1: 0.25-1: 5; the cobalt salt in the step (1) is cobalt nitrate, cobalt chloride or ethylene diamine tetraacetic acid cobaltous salt; and (3) the solvent in the step (1) and the step (2) is absolute ethyl alcohol.
3. The method of claim 1, wherein: the temperature of the coordination reaction in the step (3) is 30-70 ℃, and the coordination reaction time is 2-24 h.
4. The method of claim 1, wherein: the temperature of the high-temperature carbonization in the step (5) is 600-1600 ℃, and the carbonization time is 2-12 h.
5. A nitrogen-doped three-dimensional nano-network carbon material prepared by the preparation method of any one of claims 1 to 4.
6. The nitrogen-doped three-dimensional nano network carbon material as claimed in claim 5 is applied to energy sources, catalysis and environmental fields such as sodium ion battery cathodes and super capacitors.
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