CN108439369B - Nitrogen-oxygen co-doped hollow carbon nano-microsphere as well as preparation method and application thereof - Google Patents
Nitrogen-oxygen co-doped hollow carbon nano-microsphere as well as preparation method and application thereof Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention discloses a nitrogen-oxygen co-doped hollow carbon nano microsphere, a preparation method thereof, a super capacitor electrode and a super capacitor. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps: carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor; and washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-oxygen co-doped hollow carbon nano microsphere. The nitrogen-oxygen co-doped hollow carbon nano-microsphere prepared by the preparation method has the advantages of large specific surface area, good wettability and high specific surface area utilization rate. The supercapacitor electrode and the supercapacitor contain the nitrogen-oxygen co-doped hollow carbon nano-microsphere prepared by the method.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method and application thereof.
Background
Currently, the earth faces tremendous energy challenges, and the continuing oil crisis and environmental issues force countries to look for new clean renewable energy sources. To address these issues, energy storage and management devices play a critical role. In recent years, supercapacitors have attracted considerable attention. As a novel energy storage device, the energy storage device has the advantages of rapid charge and discharge, high power density, no pollution and excellent cycle stability, so that the energy storage device has wide application prospects in the fields of communication equipment, transportation, aerospace and the like.
Carbon materials are considered to be ideal materials for the best use in industrial supercapacitors. Carbon-based electrochemical capacitors are typical of double layer capacitors. Currently, various carbon materials such as activated carbon, carbon fiber, carbon nanotube, and graphene are widely used as research of supercapacitors. Activated carbon is the most studied material, because it is easy to prepare and has high specific surface area, but its aperture is single, so its specific surface area utilization rate is very limited; the carbon fiber has excellent conductivity and can not use a binder, but has lower apparent density, low volume specific capacitance and high price; the pore size of the carbon nano tube is easy to control, but the specific surface area is not high, and the cost is generally higher; graphene is a material which is considered to have a good application prospect in recent years, has good conductivity, a large specific surface area and controllable pore size, but is easy to agglomerate, so that the performance of the graphene is greatly reduced. The hollow carbon nano-microsphere not only has the advantages of low density, good surface permeability, large total pore volume and the like of hollow particles, but also has the characteristics of large specific surface area, high stability, porosity and the like of carbon nano-materials, so that the hollow carbon nano-microsphere is widely concerned in the field of energy storage.
The traditional method for preparing the hollow carbon nano-microsphere comprises the following steps: firstly preparing SiO2And (2) waiting for the spherical template, then wrapping a precursor of the carbon material on the template, carbonizing the precursor, and then corroding the template by using strong corrosive chemicals such as HF acid and the like to obtain a small amount of hollow carbon nano microspheres with irregular shapes. The traditional hard template method for preparing the hollow carbon nano microspheres has the defects of tedious process, long time consumption, low yield, high-risk chemicals and the other method disclosed in the patent for preparing the hollow carbon nano microspheresIn the method of preparing hollow carbon spheres, hazardous chemicals such as sulfuric acid are used and high temperature is used to prepare the hollow carbon spheres, so that the method is poor in safety and the size of the prepared hollow carbon spheres is in the order of micrometers. And the hollow carbon nano-microsphere prepared by the existing method has poor wettability, and the surface area utilization rate and the electrochemical performance are not ideal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof, so as to solve the technical problems of complicated process, long time consumption, low yield, poor safety, poor wettability of the prepared hollow carbon nano microsphere, and unsatisfactory surface area utilization rate and electrochemical performance of the prepared hollow carbon nano microsphere.
The invention also aims to provide a super capacitor electrode and a super capacitor, so as to solve the technical problems of low specific capacitance and rate capability and unsatisfactory cycle stability of the conventional super capacitor due to the electrode material of the super capacitor.
In order to achieve the above object, in one aspect of the present invention, a method for preparing nitrogen and oxygen co-doped hollow carbon nano-microspheres is provided. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
and washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-oxygen co-doped hollow carbon nano microsphere.
In another aspect of the invention, a nitrogen and oxygen co-doped hollow carbon nano microsphere is provided. The nitrogen and oxygen co-doped hollow carbon nano-microsphere is prepared by the preparation method of the nitrogen and oxygen co-doped hollow carbon nano-microsphere.
In yet another aspect of the present invention, a supercapacitor electrode is provided. The supercapacitor electrode comprises a current collector and an electrode material layer combined on the current collector, wherein the electrode material layer comprises an electrode material, a conductive agent and a binder, and the electrode material is the nitrogen-oxygen co-doped hollow carbon nano microsphere.
In yet another aspect of the present invention, a supercapacitor is provided. The supercapacitor comprises an electrode which is the electrode of the supercapacitor of the invention.
Compared with the prior art, the nitrogen-oxygen co-doped hollow carbon nano microsphere preparation method directly disperses pyrrole and aniline in the aqueous solution containing the soft template for polymerization reaction to directly obtain the hollow carbon nano microsphere precursor, so that the preparation method disclosed by the invention is relatively simple in process, easy to control conditions and high in efficiency, and the prepared hollow carbon nano microsphere precursor is uniform in size and controllable in spherical shell thickness and contains abundant nitrogen elements. After the ammonia water after carbonization treatment is activated, the prepared nitrogen-oxygen co-doped hollow carbon nano microsphere has large specific surface area and high nitrogen content and oxygen content, and the introduction of the nitrogen-containing functional group and the oxygen-containing functional group not only endows the nitrogen-oxygen co-doped hollow carbon nano microsphere with good wettability, but also improves the utilization rate of the specific surface area.
The nitrogen-oxygen co-doped hollow carbon nano-microsphere has a porous structure, and the surface of the nitrogen-oxygen co-doped hollow carbon nano-microsphere contains nitrogen functional groups and oxygen functional groups. Therefore, the nano-silver/copper composite material has large specific surface area, good wettability and high specific surface area utilization rate.
The supercapacitor electrode and the supercapacitor contain the nitrogen-oxygen co-doped hollow carbon nano microsphere electrode material, so that the supercapacitor electrode and the supercapacitor not only have higher specific capacitance, but also have good rate performance and cycling stability.
Drawings
FIG. 1 is a schematic diagram of a precursor of a hollow carbon nanosphere prepared according to an embodiment of the present invention;
fig. 2 is a Scanning Electron Microscope (SEM) image of a precursor of the hollow carbon nanosphere prepared in example 1 of the present invention;
fig. 3 is a Scanning Electron Microscope (SEM) picture of the nitrogen-oxygen co-doped hollow carbon nanospheres prepared in example 1 of the present invention;
fig. 4 is a nitrogen adsorption and desorption graph (BET) of nitrogen and oxygen co-doped hollow carbon nano-microsphere prepared in example 1 of the present invention;
fig. 5 is a constant current charging and discharging curve diagram of the super capacitor provided in embodiment 6 of the present invention under different current densities;
fig. 6 is a cyclic voltammogram of the supercapacitor provided in example 6 of the present invention at different scan rates.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belong. If a definition set forth in this section is contrary to or otherwise inconsistent with a definition set forth in the patents, patent applications, published patent applications, and other publications that are herein incorporated by reference, the definition set forth in this section prevails over the definition that is incorporated herein by reference.
In addition, the weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure of the description of the embodiments of the present invention to scale up or down the content of the related components according to the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a unit of weight known in the chemical industry, such as μ g, mg, g, and kg.
On the one hand, the embodiment of the invention provides a preparation method of nitrogen and oxygen co-doped hollow carbon nano-microspheres. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
step S01, preparing a hollow carbon nano microsphere precursor:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
s02, carbonizing and activating the hollow carbon nano microsphere precursor:
and washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain the nitrogen-oxygen co-doped hollow carbon nano microsphere.
The method for polymerizing pyrrole and aniline in the aqueous solution containing the soft template in step S01 may be performed according to the following steps:
and adding the pyrrole and the aniline into the aqueous solution containing the soft template, then adding an initiator and carrying out polymerization reaction at 0-5 ℃.
In the first step, the concentration of pyrrole is controlled to be 0.3-0.6% by mass in the aqueous solution containing the soft template, and the concentration of aniline is 0.4-0.8% by mass in the aqueous solution containing the soft template. By controlling the concentration of the reactant, the polymerization reaction efficiency is effectively improved, and the particle size of the precursor of the hollow carbon nano microsphere can be effectively controlled and adjusted by controlling and adjusting the concentration of the reactant.
In a further embodiment, the initiator in the polymerization reaction is at least one of ammonium persulfate, potassium persulfate. In addition, the mass concentration of the initiator in the aqueous solution containing the soft template is 8-16%. The efficiency of the polymerization reaction between reactants and the yield of the polymer are improved by controlling the type and the content of the initiator.
In the polymerization reaction system in each of the above embodiments, due to the characteristics of the soft template, the soft template is added into the aqueous solution to form spherical droplets in the solution, such as the droplets shown in a in fig. 1, and after the aniline and pyrrole monomers are added, the aniline and pyrrole monomers enter the droplets of the soft template due to the hydrophobic characteristics thereof, such as shown in B in fig. 1, and after the initiator is further added, the aniline and the pyrrole monomers diffuse to the surface of the droplets of the soft template to react with the initiator in the water, specifically, the pyrrole undergoes a polymerization reaction under the action of the initiator to form polypyrrole, and the aniline undergoes a polymerization reaction under the action of the initiator to form polyaniline, so that after the polymerization reaction, the formed polymer is a mixture polymer of polyaniline and polypyrrole, specifically, a polymer coating layer is formed on the surface of the droplets of the soft template, that is hollow microspheres with polyaniline-polypyrrole as a protective layer (black part in the figure), as shown at C in fig. 1.
In step S01, in one embodiment, the mass ratio of the soft template to water in the reaction solution is (0.5-2): (70-99.5), and specifically, the soft template is triton X-100.
In addition, the reaction of the polymerization reactant such as aniline and the initiator in each of the above embodiments is very fast, so that the temperature of the polymerization reaction is controlled to be 0-5 ℃, and the polymerization rate of the polymer monomer is controlled by controlling the reaction temperature, so that the generated polymer can effectively coat the soft template, thereby generating the target hollow carbon nano microsphere precursor.
In the step S02, the hollow carbon nanosphere precursor is washed to remove the unreacted reactant and solvent residue, so that any washing method capable of removing the reactant and solvent residue is within the scope disclosed herein as long as the hollow carbon nanosphere precursor is not affected.
The pulverization treatment of the washed hollow carbon nano microsphere precursor can be carried out by a conventional method, for example, the hollow carbon nano microsphere precursor is pulverized according to the requirement of particle size.
In step S02, the carbonization treatment may be a conventional carbonization treatment, that is, the hollow carbon nanoparticle precursor after the pulverization treatment is thermally cracked, so as to crack the polymer to generate carbon. In one embodiment, the temperature of the carbonization treatment may be 700-1000 ℃. In addition, the carbonization treatment should be sufficient, for example, in an embodiment, the heat treatment time at 700-. In addition, the heat treatment temperature is controlled to be raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min. Therefore, the hollow carbon nano microsphere particles generated by carbonization are ensured to be complete and have a porous structure by controlling the temperature rise rate.
In one embodiment, the ammonia activation treatment is to perform heat treatment on the hollow carbon nano microsphere particles generated by carbonization in a protective atmosphere at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water. The hollow carbon nano microsphere particles are activated by ammonia gas, so that abundant nitrogen-containing functional groups and oxygen-containing functional groups are generated on the surfaces of the hollow carbon nano microsphere particles generated by carbonization, extra Faraday pseudo capacitance can be increased due to the existence of the nitrogen-containing functional groups and the oxygen-containing functional groups, the wettability of the surfaces of the hollow carbon nano microsphere particles is improved, the specific surface utilization rate of the hollow carbon nano microsphere particles is improved, the diffusion resistance of ions in electrolyte in material pores is reduced, lone-pair electrons can be provided, the transmission rate of the electrons in the material is increased, the ions in the electrolyte are attracted, the concentration of double electric layers is increased, and the electrochemical performance of the material is improved.
In a preferred embodiment, the carbonization treatment and the ammonia activation treatment are carried out by the following methods:
in protective atmosphere, carrying out heat treatment on the hollow carbon nano microsphere precursor subjected to pulverization treatment at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water. Thus, the carbonization treatment and the activation treatment are arranged in the same atmosphere for treatment, so that abundant nitrogen-containing and oxygen-containing functional groups can be generated on the surface of the hollow carbon nano microsphere particles generated by the carbonization treatment, and the wettability and the related electrochemical performance of the hollow carbon nano microsphere particles are improved; on the other hand, the porous structure on the surface of the carbon nano microsphere can be effectively improved, so that the pores of the porous structure have gradient pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores, certainly, the porous structures with different pore diameters are randomly distributed, the porous structure with the porous pore diameter distribution can improve the electrochemical performance of the nitrogen-oxygen co-doped hollow carbon nano microsphere through a synergistic effect, and when the porous structure is used as a supercapacitor electrode material, the performances such as specific capacity, rate capability, cycling stability and the like can be improved.
In addition, the protective atmosphere for the carbonization or activation treatment may be provided by argon, and ammonia gas and water vapor volatilized by heating by introducing ammonia gas into the protective atmosphere may be introduced with the argon gas. As in one embodiment, the flow rate of argon may be set to 20-100ml/min, and the ammonia gas and water vapor should be sufficient for volatilization.
Therefore, the preparation method of the nitrogen-oxygen co-doped hollow carbon nano microsphere has the advantages that the preparation method of the nitrogen-oxygen co-doped hollow carbon nano microsphere is relatively simple in process, easy to control conditions and high in efficiency, the defects of the existing hard template method are effectively overcome, the particle size of the prepared nitrogen-oxygen co-doped hollow carbon nano microsphere can be controlled, the surface of the prepared nitrogen-oxygen co-doped hollow carbon nano microsphere contains a porous structure and is bonded with abundant nitrogen-containing functional groups and oxygen-containing functional groups, and the nitrogen-oxygen co-doped hollow carbon nano microsphere is endowed with a large specific surface area, good wettability and electrochemical performance.
Based on the preparation method of the nitrogen and oxygen co-doped hollow carbon nano-microsphere, the embodiment of the invention also provides a nitrogen and oxygen co-doped hollow carbon nano-microsphere, and specifically, the nitrogen and oxygen co-doped hollow carbon nano-microsphere is prepared by the preparation method of the nitrogen and oxygen co-doped hollow carbon nano-microsphere. Therefore, the nitrogen-oxygen co-doped hollow carbon nano-microsphere has a porous structure, and the porous structure can be a multi-level pore structure with randomly distributed unequal pore diameters, such as a multi-level pore structure containing micropores, mesopores and macropores; on the other hand, the nitrogen-oxygen co-doped hollow carbon nano microsphere is bonded with abundant nitrogen-containing functional groups and oxygen-containing functional groups on the surface. Because the nitrogen-oxygen co-doped hollow carbon nano-microsphere has the structural characteristics, the nitrogen-oxygen co-doped hollow carbon nano-microsphere has a large specific surface area, a high specific surface area utilization rate, and good wettability and electrochemical properties. Through determination, the particle size of the nitrogen-oxygen co-doped hollow carbon nano microsphere is 60-150 nanometers.
On the other hand, based on the nitrogen-oxygen co-doped hollow carbon nano-microsphere and the preparation method thereof, the embodiment of the invention also provides a supercapacitor electrode. The supercapacitor electrode may include necessary components of the supercapacitor electrode, such as a current collector and an electrode material layer bonded on the current collector.
The current collector may be a commonly used current collector material such as nickel foam, etc.
The electrode material layer may include an electrode material, a conductive agent, and a binder. Wherein, the weight ratio of the electrode material, the conductive agent and the binder can be, but not only is (70-90): (5-15): (5-20). The binder may be, but is not limited to, PTFE, and the conductive agent may be, but is not limited to, acetylene black. The electrode material is the nitrogen-oxygen co-doped hollow carbon nano-microsphere. Therefore, the nitrogen-oxygen co-doped hollow carbon nano-microsphere based on the nitrogen-oxygen co-doping has a porous structure and rich nitrogen-containing functional groups and oxygen-containing functional groups in bonding. The super capacitor electrode has high specific capacitance and also has good rate performance and cycling stability.
On the basis of the electrode of the super capacitor, the embodiment of the invention also provides the super capacitor. The super capacitor comprises necessary components, such as components including electrodes and the like, wherein the electrodes are super capacitor electrodes according to the embodiment of the invention. Thus, the super capacitor has high specific capacitance and also has good rate performance and cycling stability.
The invention will now be described in further detail by taking specific nitrogen-oxygen co-doped hollow carbon nano-microspheres and a preparation method and application thereof as examples.
1. Nitrogen-oxygen co-doped hollow carbon nano-microsphere and preparation method embodiment thereof
Example 1
The embodiment provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
s11: adding 0.45g of 2 ℃ Triton X-100 solution into 450g of 2 ℃ deionized water, stirring for 60 minutes by using a magnetic stirrer, and uniformly mixing to form diluted Triton X-100 solution;
s12: 2.2g of pyrrole at the temperature of 2 ℃ and 2.8g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 30min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding newly prepared 60mL of 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 30S, and then standing and reacting for 12h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.5g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (50 ℃) and steam into the tubular furnace by using argon gas with the flow of 50ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: and heating the tubular furnace from room temperature at a heating rate of 5 ℃/min to 950 ℃, preserving the heat for 40min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped hollow carbon nano-microsphere.
Example 2
The embodiment provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
s11: adding 0.6g of 2 ℃ Triton X-100 solution into 500g of 2 ℃ deionized water, stirring for 60 minutes by using a magnetic stirrer, and uniformly mixing to form diluted Triton X-100 solution;
s12: 2.0g of pyrrole at the temperature of 2 ℃ and 2.4g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 30min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding 50mL of newly prepared 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 50S, and then standing and reacting for 8h at the ambient temperature of 3 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.0g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (60 ℃) and steam into the tubular furnace by using argon gas with the flow of 30ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: and heating the tubular furnace from room temperature at the heating rate of 2 ℃/min to 800 ℃, preserving the heat for 100min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped hollow carbon nano-microsphere.
Example 3
The embodiment provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
s11: adding 0.4g of triton X-100 solution at the temperature of 1 ℃ into 500g of deionized water at the temperature of 0 ℃, and stirring for 20 minutes by using a magnetic stirrer to uniformly mix to form diluted triton X-100 solution;
s12: 2.0g of pyrrole at the temperature of 2 ℃ and 2.2g of aniline at the temperature of 2 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 40min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding 50mL of newly prepared 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 40S, and then standing and reacting for 14h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.5g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (30 ℃) and steam into the tubular furnace by using argon gas with the flow of 70ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: and heating the tubular furnace from room temperature at a heating rate of 4 ℃/min to 850 ℃, preserving the heat for 60min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped hollow carbon nano-microsphere.
Example 4
The embodiment provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
s11: adding 0.55g of triton X-100 solution at the temperature of 1 ℃ into 550g of deionized water at the temperature of 1 ℃, stirring for 50 minutes by using a magnetic stirrer, and uniformly mixing to form diluted triton X-100 solution;
s12: adding 1.8g of pyrrole at the temperature of 2 ℃ and 2.0g of aniline at the temperature of 1 ℃ into the diluted triton X-100 solution prepared in the step, and continuing stirring for 40min to uniformly distribute the pyrrole and the aniline in the triton X-100 solution;
s13: adding 65mL of newly prepared 1M ammonium persulfate solution into the solution obtained in the step S12, slightly stirring for 50S, and then standing and reacting for 9h at the ambient temperature of 1 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 2.0g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (45 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 55ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: and heating the tubular furnace from room temperature at the heating rate of 8 ℃/min to 900 ℃, preserving the heat for 45min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped hollow carbon nano-microsphere.
Example 5
The embodiment provides a nitrogen-oxygen co-doped hollow carbon nano microsphere and a preparation method thereof. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere comprises the following steps:
s11: adding 0.42g of Triton X-100 solution with the temperature of 3 ℃ into 450g of deionized water with the temperature of 3 ℃, and stirring for 50 minutes by using a magnetic stirrer to uniformly mix to form diluted Triton X-100 solution;
s12: 2.2g of pyrrole at the temperature of 3 ℃ and 2.5g of aniline at the temperature of 3 ℃ are added into the diluted triton X-100 solution prepared in the step, and the mixture is continuously stirred for 35min, so that the pyrrole and the aniline are uniformly distributed in the triton X-100 solution;
s13: adding newly prepared 55mL of 1M ammonium persulfate solution into the S12 solution, slightly stirring for 35S, and then standing and reacting for 15h at the ambient temperature of 0 ℃;
s14: washing the product obtained in the step S13 for multiple times, performing suction filtration until the filtrate is nearly colorless, drying, grinding into powder to obtain the required hollow carbon nano microsphere precursor, and then sealing and storing the carbon nano microsphere precursor for later use;
s15: putting 1.8g of hollow carbon nano microsphere precursor into a corundum crucible, putting the crucible into a tubular furnace, introducing ammonia gas decomposed by heated ammonia water (55 ℃) and steam into the tubular furnace by using argon gas with the flow rate of 45ml/min, wherein the tubular furnace is filled with mixed gas of the argon gas, the steam and the ammonia gas;
s16: and heating the tubular furnace from room temperature at a heating rate of 3 ℃/min to 925 ℃ and preserving heat for 40min, and then cooling to room temperature to obtain the nitrogen-oxygen co-doped hollow carbon nano-microsphere.
Further, the hollow carbon nanosphere precursor and the nitrogen-doped carbon hollow carbon nanosphere prepared in embodiments 1 to 5 are respectively subjected to a scanning electron microscope, wherein a scanning electron microscope picture of the hollow carbon nanosphere precursor provided in embodiment 1 is shown in fig. 2, and a scanning electron microscope of the nitrogen-doped carbon hollow carbon nanosphere is shown in fig. 3. As can be seen from fig. 2 and 3, the hollow carbon nanosphere precursor and the nitrogen-doped carbon hollow carbon nanosphere are both in a particle structure, and the particle size has a nanoscale and is uniform in size distribution. In examples 2 to 5, the scanning electron microscope images of the hollow carbon nanosphere precursor and the nitrogen-doped carbon hollow carbon nanosphere are similar to those in example 1.
The nitrogen-doped carbon hollow carbon nanospheres prepared in examples 1 to 5 were further analyzed for physical adsorption properties, wherein the physical adsorption curve (BET) of the nitrogen-doped carbon hollow carbon nanospheres of example 1 is shown in fig. 4. As can be seen from FIG. 4, the nitrogen adsorption and desorption curves of the nitrogen-doped carbon hollow carbon nanospheres are typical I/IV type adsorption curves, and are all at low relative pressure (P/P)0<0.05)N2The adsorption quantity is increased sharply and then reaches the equilibrium rapidly, which shows that all the carbon nanobelt microsphere materials have a large number of micropores (< 2nm) structures at P/P0In the area with the range of 0.9-1, the desorption curve of all the carbon nanobelts is obviously lagged behind the adsorption curve, so that a lagged loop is formed, which indicates that a plurality of mesopores (2-50nm) and macropores (larger than 50nm) exist in the hollow carbon nano microsphere. The physical adsorption performance of the nitrogen-doped carbon hollow carbon nano-microspheres in the examples 2 to 5 is similar to that of the example 1.
2. Supercapacitor electrode and supercapacitor embodiments
Example 6
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises electrodes and other necessary components, wherein the electrodes are prepared according to the following method:
nitrogen and oxygen co-doped hollow carbon nano-microspheres, 5% of PTFE solution and acetylene black nitrogen and oxygen co-doped hollow carbon nano-microspheres: mixing PTFE and acetylene black in a ratio of 8:1:1, grinding uniformly, and then coating on foamed nickel; and then placing the nickel foam into a vacuum drying oven, drying the nickel foam in the air at 110 ℃ for 12 hours, and pressing the nickel foam into thin sheets by using a tablet press to obtain the supercapacitor electrodes.
Example 7
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
nitrogen and oxygen co-doped hollow carbon nano-microspheres, 3% of PTFE solution and acetylene black nitrogen and oxygen co-doped hollow carbon nano-microspheres: mixing PTFE and acetylene black in a ratio of 78:10:12, grinding uniformly, and then coating on foamed nickel; and then placing the nickel foam into a vacuum drying oven, drying the nickel foam in the air at the temperature of 80 ℃ for 16h, and pressing the nickel foam into sheets by using a tablet press to obtain the supercapacitor electrode.
Example 8
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
nitrogen and oxygen co-doped hollow carbon nano-microspheres, a 7% PTFE solution and acetylene black nitrogen and oxygen co-doped hollow carbon nano-microspheres: mixing PTFE and acetylene black in a ratio of 85:7:8, grinding uniformly, and then coating on foamed nickel; and then placing the nickel foam into a vacuum drying oven, drying the nickel foam in the air at 120 ℃ for 10 hours, and pressing the nickel foam into thin slices by using a tablet press to obtain the supercapacitor electrode.
Example 9
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
nitrogen and oxygen co-doped hollow carbon nano-microspheres, 4% of PTFE solution and acetylene black nitrogen and oxygen co-doped hollow carbon nano-microspheres: mixing PTFE and acetylene black in a ratio of 82:9:9, grinding uniformly, and coating on foamed nickel; and then placing the nickel foam into a vacuum drying oven, drying the nickel foam in the air at 70 ℃ for 24 hours, and pressing the nickel foam into a thin sheet by using a tablet press to obtain the supercapacitor electrode.
Example 10
The embodiment provides a supercapacitor electrode and a supercapacitor.
The super capacitor comprises an electrode and other necessary components, wherein the electrode is prepared according to the following method:
nitrogen and oxygen co-doped hollow carbon nano-microspheres, 3% of PTFE solution and acetylene black nitrogen and oxygen co-doped hollow carbon nano-microspheres: mixing PTFE and acetylene black in a ratio of 75:10:15, grinding uniformly, and then coating on foamed nickel; and then placing the nickel foam into a vacuum drying oven, drying the nickel foam in the air at 95 ℃ for 14h, and pressing the nickel foam into thin slices by using a tablet press to obtain the supercapacitor electrode.
The super capacitors of the embodiments 6 to 10 were subjected to constant current charging and discharging curves and cyclic voltammetry curve analysis at different current densities and different scanning rates. Wherein, the constant current charging and discharging curve of the super capacitor provided in example 6 under different current densities is shown in fig. 5, and the aperture distribution curve of the cyclic voltammetry curve under different scanning rates is shown in fig. 6.
As can be seen from fig. 5, the constant current charging and discharging curves of the supercapacitor in example 6 are all triangular under different current densities, no significant IR drop occurs, and even when the current is increased to 20A/g, the GCD curve of the nitrogen and oxygen co-doped hollow carbon nanospheres can still maintain a good triangular shape, which indicates that the nitrogen and oxygen co-doped hollow carbon nanospheres have high reversibility of charge storage and transmission and ideal electric double layer capacitance. Under the current density of 0.25A/g, the specific capacitance value is up to 387F/g, even if the current density is increased to 20A/g, the specific capacitance value is still up to 152F/g, and the measured capacitance retention rate is still over 50% under the current density of 20A/g; after 12000 cycles at a current density of 5A/g, it still retained 95% capacity. Examples 7-10 also provide supercapacitors having high electrochemical performance similar to the supercapacitor of example 6.
As can be seen from FIG. 6, the quasi-rectangular shape of the CV curve of the supercapacitor in example 6 is always kept good at the scanning speed of 10-200Mv, and all CV curves have no obvious oxidation-reduction peak, so that the nitrogen-oxygen co-doped hollow carbon nano microsphere electrode material provided in example 1 is demonstrated to be an ideal electrode material of the electric double layer capacitor. And when the direction of the scanning voltage is changed, the current can reach the platform quickly, which shows that the prepared hollow carbon nano-microsphere has good capacitance reversibility.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. The preparation method of the nitrogen-oxygen co-doped hollow carbon nano-microsphere is characterized by comprising the following steps of:
carrying out polymerization reaction on pyrrole and aniline in an aqueous solution containing a soft template to obtain a hollow carbon nano microsphere precursor;
washing and pulverizing the hollow carbon nano microsphere precursor, and then carrying out carbonization treatment and ammonia water activation treatment to obtain a nitrogen-oxygen co-doped hollow carbon nano microsphere;
the carbonization treatment and ammonia water activation treatment method comprises the following steps:
in protective atmosphere, carrying out heat treatment on the hollow carbon nano microsphere precursor at the temperature of 700-1000 ℃; and the protective atmosphere contains a mixed gas of ammonia and water vapor generated by thermal decomposition of ammonia water.
2. The method according to claim 1, wherein the pyrrole and aniline are polymerized in an aqueous solution containing a soft template by the following method:
adding the pyrrole and the aniline into the aqueous solution containing the soft template, then adding an initiator and carrying out polymerization reaction at 0-5 ℃; and/or
The mass concentration of the pyrrole in the aqueous solution containing the soft template is 0.3-0.6%, and the mass concentration of the aniline in the aqueous solution containing the soft template is 0.4-0.8%.
3. The method of claim 2, wherein: the initiator is at least one of ammonium persulfate and potassium persulfate; and/or
The mass concentration of the initiator in the aqueous solution containing the soft template is 8-16%.
4. The method of claim 1, wherein: the time of the heat treatment is 20-120 min; and/or
The heat treatment temperature is raised to 700-1000 ℃ at a temperature raising rate of 2-10 ℃/min.
5. The production method according to any one of claims 1 to 4, wherein the mass ratio of the soft template to water in the aqueous solution containing the soft template is (0.5 to 2): (70-99.5); and/or
The soft template is Triton X-100.
6. The nitrogen and oxygen co-doped hollow carbon nano microsphere is characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. The nitrogen and oxygen co-doped hollow carbon nanosphere according to claim 6, wherein the particle size of the nitrogen and oxygen co-doped hollow carbon nanosphere is 60-150 nm; and/or
The nitrogen-oxygen co-doped hollow carbon nano-microsphere is of a porous structure.
8. A supercapacitor electrode comprising a current collector and an electrode material layer bonded on the current collector, wherein the electrode material layer comprises an electrode material, a conductive agent and a binder, and the electrode material is the nitrogen and oxygen co-doped hollow carbon nanosphere as claimed in any one of claims 6 to 7.
9. A supercapacitor comprising an electrode, characterized in that the electrode is the supercapacitor electrode of claim 8.
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