CN110867325A - Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof - Google Patents
Nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere as well as preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere and a preparation method and application thereof, wherein the method comprises the following steps: s1: pyridine, hexachlorobutadiene and dibenzothiophene are subjected to a closed reaction under a reaction pressure higher than atmospheric pressure; s2: after the reaction is finished, releasing the pressure to normal pressure, and removing the excessive solvent in the reaction to obtain a sample; s3: the sample is mixed with zinc chloride for activation. S4: and (3) carrying out high-temperature treatment on the sample under the protection of inert gas, and washing and drying the sample. Thereby obtaining the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material. The nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material has excellent electrochemical performance, can be used for preparing a super capacitor electrode, can be used in a super capacitor, and has great application potential and industrial value in the field of electrochemical energy storage.
Description
Technical Field
The invention relates to a carbon-based composite material, a preparation method and application thereof, and an electrode prepared from the carbon-based composite material, and more particularly provides a nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, a preparation method and application thereof, belonging to the field of inorganic functional materials.
Background
With the rapid development of the current society, the environmental problems become more serious due to the generation of a large amount of pollution, so that the research on novel energy devices becomes more and more important, and certainly becomes a key topic for the research of many scientists in the century. Super capacitor, lithium ion hybrid power device, fuel cell, chemical battery products have been studied and developed, and have achieved certain performance. But the defects of short service life, complex system, high cost and the like are not well applied. However, the super capacitor has excellent characteristics including long service life, high power density and the like, and can partially replace the traditional chemical battery for a traction battery and a starting power supply by adopting the advantages and disadvantages, and meanwhile, the super capacitor has other wider applications. Therefore, research and development on supercapacitors are being conducted in various countries.
Among them, carbon-based materials are the most widely used electrode materials of supercapacitors. The capacitance of the carbon-based material is related to the specific surface area of the electrode material, and the like. In addition, the micropores can contribute to the electric double layer capacitance to a certain extent, the mesopores can improve the high-current charge and discharge performance of the material, and the macropores can be helpful for the permeation of electrolyte into the mesopores. Therefore, the specific capacitance of the material can be improved to some extent by controlling the pore size distribution of the carbon-based material in the primary pore size and increasing the specific surface area of the carbon material. At present, it is generally believed that heteroatom doping of the porous carbon electrode material can introduce functional groups on the surface of the material, which is beneficial to adsorbing electrolyte ions, further improving the hydrophilicity of the material, and enhancing the wettability of the electrode material (such as quaternary amine-N). Meanwhile, heteroatom functional groups on the surface of the carbon material enable the material to have acidic or alkaline active sites, and faradaic redox reaction is generated between the active sites and electrolyte ions, so that pseudo capacitance is generated, and the specific capacitance value of the electrode material is increased.
Some previous work on the preparation and performance studies of heteroatom-doped supercapacitor electrode materials has also been reported, and examples include the following:
CN104973596A discloses a heteroatom-doped hollow sphere graphene composite material, and a preparation method and application thereof. Firstly, mixing styrene, polyvinylpyrrolidone, 2' -azobisisobutylamidine dihydrochloride and water, and reacting under certain conditions to prepare a polystyrene sphere with positive charges; secondly, stirring and reacting the graphene oxide aqueous dispersion and a positively charged polystyrene sphere aqueous dispersion to prepare a graphene oxide @ polystyrene sphere compound; thirdly, adding a heteroatom doping source compound and a solvent into the graphene oxide @ polystyrene sphere compound, mixing, coating, and freeze-drying to obtain a solid film; and finally, placing the substrate loaded with the solid film in a plasma high-temperature tubular reactor for reaction to obtain the heteroatom-doped hollow sphere graphene composite material. The prepared material has higher specific surface area and better electrical property, and is applied to the field of super capacitors. But the process is relatively complex and high in cost, and is difficult to be commercially applied.
CN104900423B relates to a method for preparing a doped carbon material, which comprises the following steps: mixing polyvinylidene chloride, strong base and a strong polar solvent to obtain a mixture, then grinding the mixture, roasting the ground mixture in inert gas after grinding, and then cleaning and drying to obtain the doped carbon material; the preparation method has the advantages of cheap and easily-obtained raw materials, low cost, simple preparation process, high safety and environmental friendliness. The prepared carbon material has excellent double electric layer capacitance performance and important popularization value.
CN106784876A relates to a supercapacitor composite electrode material and a preparation method thereof. The method comprises the steps of preparing an electrode slice with nitrogen-doped graphene attached to the surface by using the nitrogen-doped graphene; and placing the electrode slice with the surface attached with the nitrogen-doped graphene in an organic electrolyte containing a Schiff base transition metal polymer monomer, and carrying out in-situ polymerization by an electrochemical method to obtain the composite supercapacitor electrode material. According to the method, urea is added to carry out nitrogen doping on graphene, the nitrogen-doped graphene has pseudo capacitance and excellent conductivity, the capacitance is 10% -20% higher than that of the pure graphene serving as a substrate, and the nitrogen-doped graphene electrode material still keeps stable after being charged and discharged for many times. However, the yield of electrochemical synthesis is not high, and the corresponding specific capacitance is not very high, and still has a certain promotion space.
CN103714979A relates to a phosphorus-doped porous carbon material for a supercapacitor and a preparation method thereof, and solves the technical problems of high cost and low specific capacitance of the existing material. Glucose, phosphoric acid and sulfuric acid were added to deionized water, respectively, and then stirred. And (3) placing the uniform mixed solution in a forced air drying box at a certain temperature for reacting for a certain time to obtain a solid product. And then placing the pre-reaction product in a high-temperature carbonization furnace, carbonizing in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the phosphorus-doped porous carbon material. The invention can be widely applied to the field of preparation of supercapacitor materials. But the doping content is not high, and still has no particularly great breakthrough.
CN105645408A discloses a process for preparing a nitrogen-doped porous carbon material by using jujube pits and a preparation method of a supercapacitor electrode, wherein the process comprises the following steps: (1) pre-treating jujube pits; (2) preparing a nitrogen-doped carbon material; (3) and preparing the nitrogen-doped porous carbon material. The method selects date pits as a carbon source, mixes ammonia and water vapor in inert protective gas, simultaneously carries out nitrogen doping reaction in the carbonization process, and then activates and prepares holes under the action of an activating agent to prepare the nitrogen-doped porous carbon material with high specific surface area and pore volume. The preparation method is simple, low in cost, high in production efficiency and energy-saving. Experimental results show that the supercapacitor electrode prepared by using the carbon material has high specific capacitance, ideal pseudocapacitance and high cycle stability, and the performance of the supercapacitor electrode is superior to that of commercial activated carbon and most of nitrogen-doped porous carbon materials. Of course, a problem is that the reproducibility of the experiment is poor due to the biomass itself.
Based on the above experiences, the synthesis of the novel heteroatom doped carbon material with high energy storage performance by a simple, low-cost and macro method still has very important significance, and is also a research hotspot and focus in the field of electrochemical energy at present, which is the foundation for the completion of the invention.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere, and a preparation method and application thereof. The technical scheme has the advantages of simple process, low cost and large yield, and the synthesized material has excellent high specific capacitance and is used for carbon-based composite materials in the field of supercapacitors.
Specifically, the first object of the present invention is to provide a method for preparing a nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere, which comprises the following steps:
s1: pyridine, hexachlorobutadiene and dibenzothiophene are subjected to a closed reaction under a reaction pressure higher than atmospheric pressure;
s2: after the reaction is stopped, removing the excessive solvent of the reaction, and drying to obtain a sample;
s3: mixing and activating the obtained sample and zinc chloride;
s4: and (3) carrying out high-temperature treatment on the sample under the protection of inert gas, washing and drying the sample to obtain the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material.
In the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, in step S1, the reaction temperature is 170-.
In the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere and the preparation method thereof, in step S1, the reaction pressure is 1-5MPa, for example, 1MPa, 2MPa, 3MPa, 4MPa or 5 MPa.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, in step S1, the reaction time is 4 to 12 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, or 12 hours.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, the sample obtained in step S3 and zinc chloride are mixed and activated at a ratio of 12:1-1:12, for example, 12:1, 6:1, 1:6 or 1:12, and most preferably 1: 6.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, the temperature of the high-temperature treatment in the step S4 is 800-1100 ℃, preferably 900-1100 ℃, and most preferably 1000 ℃.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere of the present invention, in step S4, the high temperature treatment time is 1 to 4 hours, for example, 1 hour, 2 hours or 4 hours, and most preferably 2 hours.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, the sulfur-containing compound in the step S1 is thiophene, 3-methylthiophene, 2, 5-dimethylthiophene, 2, 3, 5-trimethylthiophene, dibenzothiophene, and the like, and the most preferable is dibenzothiophene.
In the preparation method of the nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere, in step S4, the inert gas is nitrogen or argon.
The inventor finds that when the preparation method disclosed by the invention is adopted, particularly certain process parameters are optimized, the nitrogen and sulfur co-doped porous carbon material with excellent electro-catalytic performance can be obtained, and the super capacitor electrode prepared from the material has excellent electrochemical performance, such as large specific capacitance, high-current charge and discharge performance, good stability, long service life and the like, so that the method can be applied to the field of super capacitors. When the parameters are changed, the electrocatalytic performance is considerably reduced.
The second purpose of the invention is to provide a nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material. The nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicated carbon microsphere material has excellent performances, reasonable pore size distribution, proper amount of heteroatom doping and larger specific surface area, and the super capacitor electrode prepared from the material has excellent electrochemical properties, such as larger specific capacitance, high-current charge and discharge property, good quality, good stability, long service life and the like, thereby being applicable to the field of super capacitors.
The third purpose of the invention is to provide an application of the nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material in preparing a supercapacitor electrode.
Specifically, the invention also relates to a supercapacitor electrode which comprises the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material.
In a fourth aspect, the invention also relates to a preparation method of the supercapacitor electrode, wherein the method comprises the following steps:
(A) weighing a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, acetylene black and PTFE (polytetrafluoroethylene) emulsion, adding a proper amount of ethanol or N-methyl pyrrolidone (NMP), uniformly mixing, and continuously stirring into paste to be coated on foamed nickel;
(B) and drying, drying and tabletting the foamed nickel coated with the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material to obtain the capacitor electrode.
In the preparation method of the capacitor electrode, in the step (a), the mass ratio of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, the acetylene black and the PTFE emulsion is 75:15:10-85:5:10, preferably 80:10: 10.
In the method for manufacturing a capacitor electrode according to the present invention, in the step (a), the PTFE (polytetrafluoroethylene) emulsion is a commonly known raw material in the field of electrode manufacturing, and is commercially available from various sources, and thus, detailed description thereof is omitted.
In the method for preparing the capacitor electrode of the present invention, the amount of the ethanol or the nitrogen methyl pyrrolidone added in the step (a) is not particularly limited, and the amount thereof belongs to the conventional technology in the field of capacitors, and is not described herein again.
In the method for preparing a capacitor electrode according to the present invention, the preparation operation in step (B) belongs to a conventional technical means in the field of capacitors, and is not described in detail herein.
As described above, the invention provides a nitrogen-oxygen-sulfur-rich co-doped micro-mesoporous intercommunicating carbon microsphere, and a preparation method and application thereof.
The technology designed by the application has the characteristics of high reaction conversion rate and mass production. In addition, the doping content is improved to a certain extent by the in-situ polymerization reaction, and the doping content is moderate, so that the electrode material of the super capacitor prepared from the material has higher specific capacitance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
Fig. 1 is a Scanning Electron Microscope (SEM) image of a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material prepared in example 1 of the present invention.
Fig. 2 is a Raman chart of a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material in example 1 of the present invention.
Fig. 3 is an XRD chart of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material of example 1.
Fig. 4 is an XPS high resolution N1s spectrum of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material prepared in example 1 of the present invention.
Fig. 5 is an XPS high resolution S2p spectrum of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material of example 1.
Fig. 6 is a nitrogen-sulfur surface content analysis diagram of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material prepared in example 1 of the present invention.
FIG. 7 isN of nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere material in embodiment 1 of the invention2Adsorption and desorption curves and pore size distribution curves.
Fig. 8 is a constant current charge and discharge diagram of capacitor electrodes prepared by using the nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material C1 of example 1 of the present invention under different current densities.
Fig. 9 is a cyclic voltammogram of capacitor electrodes prepared using the nitrogen-rich oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material C1 of example 1 of the present invention at different scan rates.
Fig. 10 is a comparative constant current charge and discharge diagram of supercapacitor electrodes prepared by using nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere materials C1-C2 of examples 1 and 2 of the present invention at various current densities.
Fig. 11 is a comparison graph of constant current charge and discharge at 10A/g between a supercapacitor three-electrode and a symmetrical two-electrode made of the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material of example 1.
Fig. 12 is a stability chart of a symmetrical supercapacitor electrode prepared by using the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material C1 in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
S1: reacting pyridine, hexachlorobutadiene and dibenzothiophene in a polytetrafluoroethylene-lined high-pressure reaction kettle at 200 ℃ and 2MPa for 8 hours, wherein the mass ratio of the pyridine to the hexachlorobutadiene to the dibenzothiophene is 25: 3: 1;
s2: relieving the pressure to normal pressure, removing excessive solvent in the reaction, and drying to obtain a sample;
s3: the resulting sample was mixed with zinc chloride at a ratio of 1:6, mixing and activating;
s4: carrying out high-temperature treatment on the sample at 1000 ℃ under the protection of inert gas;
s5: and washing and drying the mesoporous carbon microsphere material to obtain the nitrogen-oxygen-sulfur co-doped mesoporous intercommunicated carbon microsphere material. It was named C1.
Examples 2 to 8: examination of reaction raw Material in step S1
The operation was not changed except that S3 was not performed, thereby performing example C2. Except for the addition of the pyridine and hexachlorobutadiene in step S1 and the absence of S3, the operation was not changed, and the volume ratio of pyridine to hexachlorobutadiene was: 24: 6,26: 4, examples C3-C4 were performed in sequence. The operations were not carried out except for the addition of dibenzothiophene in step S1 and the absence of S3, and the amounts of dibenzothiophene added were: 0.5g, 1.0g, 1.5g, 2.0g, followed by examples C5-C8.
Examples 9 to 13: reaction time of reaction raw material in step S1
Examples C9 to C13 were carried out in this order, except that the solvothermal reaction time in step S1 was not changed to S3, but was changed to 2 hours, 4 hours, 6 hours, 8 hours and 10 hours.
Examples 14 to 17: reaction time of reaction raw material in step S1
The operations were carried out in the order of examples C14 to C17 except that the reaction time of the solvothermal reaction in step S1 was changed to 2 hours, 4 hours, 6 hours and 10 hours, and that the reaction was not carried out in the order of S3.
Examples 18 to 21: examination of high temperature processing temperature in step S3
The operations were not changed except that the high-temperature treatment temperature of 1000 ℃ in step S4 was replaced with 700 ℃, 800 ℃, 900 ℃ and 1100 ℃ respectively, and S3 was not performed, thereby performing examples C18 to C21 in this order.
Preparation of capacitor electrodes
The preparation method of the capacitor electrode comprises the following steps:
(A) weighing a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, acetylene black and PTFE (polytetrafluoroethylene) emulsion (the mass ratio of the three is 80:10:10), adding a proper amount of N-methyl pyrrolidone, uniformly mixing, continuously stirring into paste, and coating the paste on foamed nickel;
(B) and drying, drying and tabletting the foamed nickel coated with the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material to obtain the capacitor electrode.
Microscopic characterization
The nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicating carbon microsphere material obtained in example 1 is subjected to microscopic characterization by a plurality of different means, and the results are as follows:
1. is a Scanning Electron Microscope (SEM) image of the nitrogen oxygen sulfur co-doped micro-mesoporous intercommunicating carbon microsphere material prepared in example 1 of the present invention. From the SEM images it can be seen that the material is a three-dimensional spherical structure.
2. As can be seen from the Raman chart of fig. 2, the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material is a three-dimensional structure with a large defect degree, and the three-dimensional porous structure with the large defect degree enables more active sites to be exposed, so that the electrocatalytic performance of the material is enhanced.
3. As can be seen from the XRD diagram of FIG. 3, the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material is an amorphous structure, and the amorphous structure is more favorable for rapid embedding and leading-out of ions or protons and is suitable for being used as an electrode material.
4. From the XPS chart of fig. 4, the types of nitrogen in C1 in the example and C2 in the example are mainly pyridine nitrogen, graphite layer nitrogen, and nitrogen-oxygen bond.
5. As can be seen from the XPS chart of FIG. 5, the types of sulfur in C1 in the examples and C2 in the examples mainly include-C-S-S2 p1/2, -C-S-S2 p3/2 and-C-SOx-。
6. As can be seen from the graph of fig. 6, the nitrogen-oxygen content in C1 after activation was much higher than that of the non-activated C1, and the change in sulfur content before and after activation was relatively small.
7. From N of FIG. 72The absorption and desorption curves show that the specific surface area of the C1 nitrogen-oxygen-sulfur co-doped micro mesoporous intercommunicated carbon microsphere material is the largest and reaches 732m2/g。
All the above characterizations of C2-C8 obtained in examples 2-8 are highly identical to C1 (with only experimental error in measurement), and therefore, under the premise of high similarity, the respective maps are not listed.
Electrochemical performance test
1. FIG. 8 shows the charge and discharge performance of capacitor electrodes made of C1 nitrogen, oxygen and sulfur co-doped micro mesoporous intercommunicated carbon microsphere materials at different current densities (50A/g,10A/g,5A/g,2A/g,1A/g,0.5A/g, 0.1A/g).
2. FIG. 9 is a cyclic voltammogram at scan rate (500mV/s, 200mV/s, 100mV/s, 50mV/s, 10mV/s, 5mV/s, 1mV/s) for a capacitor electrode made from a C1N, O, S co-doped mesoporous intercommunicated carbon microsphere material. It can be seen from the figure that the curves in the cyclic voltammogram basically present rectangles, which indicate that the electric double layer energy storage is mainly used, and meanwhile, the curves have certain contribution of pseudocapacitance.
3. FIG. 10 is a charge-discharge diagram of capacitor electrodes made of C1-C2 nitrogen-oxygen-sulfur co-doped micro mesoporous intercommunicated carbon microsphere materials under different current densities (100A/g,80A/g,10A/g,5A/g,1A/g,0.5A/g, 0.1A/g). As can be seen from the figure, C1 has a higher specific capacitance than other materials, mainly originally derived from a reasonable multistage pore size distribution and a high specific surface area.
4. Fig. 11 is a charge-discharge diagram of a symmetrical two-electrode capacitor and a three-electrode capacitor prepared from the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material of C1 at a current density of 10A/g, and it can be found that the specific capacitance of the symmetrical two-electrode supercapacitor is very close to the capacitance of the three-electrode capacitor, which is about 88% of the capacitance of the three-electrode capacitor, and the feasibility of the supercapacitor electrode material prepared from the double-doped carbon-based material is illustrated.
5. Fig. 12 is a stability chart of a symmetrical two-electrode capacitor made using nitrogen, oxygen, and sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material at a current density of 10A/g. As can be seen from the figure, the material retained% capacity retention after cycling.
6. As can be seen from Table 1, the calculated capacitance of C1 is 461F/g at a current density of 0.1A/g, and is still 61F/g after charging and discharging at a current density of 100A/g, so that the material is proved to be capable of charging and discharging at a large current density and shows excellent charging and discharging performances.
TABLE 1
As can be seen from the above figures 8-12, the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material obtained by the method of the invention has excellent electrochemical properties, so that the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material can be used as an electrode material of a capacitor, especially a super capacitor, and has good application prospects and industrial production potentials in the electrochemical field.
Microscopic characterization of the composite materials obtained in other examples
A. The characterization of C3-C8 found that the microscopic morphology is highly similar to C1, and the electrochemical performance is also highly similar to that of C1. However, due to the high degree of similarity and for the sake of brevity, all the microscopic characterization and electrochemical performance maps are not listed here.
As described above, the invention provides a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, a preparation method and application thereof, and a symmetrical two-electrode supercapacitor prepared from the material.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (10)
1. A preparation method of a nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material is characterized by comprising the following steps:
s1, carrying out a sealing reaction on pyridine, hexachlorobutadiene and a sulfur-containing thiophene compound under the reaction pressure higher than atmospheric pressure;
s2: after the reaction is stopped, removing the excessive solvent of the reaction, and drying to obtain a sample;
s3: mixing and activating the obtained sample and zinc chloride;
s4: and (3) carrying out high-temperature treatment on the sample under the protection of inert gas, washing and drying the sample to obtain the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material.
2. The method of claim 1, wherein: in step S1, the reaction temperature is 170-230 ℃.
3. The method of claim 1, wherein: in step S1, the reaction time is 4-12 h.
4. The method of claim 1, wherein: in step S3, the mass ratio of the sample to the activator is 12:1 to 1: 12.
5. The method of claim 1, wherein: in step S4, the temperature of the high temperature treatment is 800-1100 ℃.
6. The method of claim 1, wherein: in step S1, the volume ratio of pyridine to hexachlorobutadiene is 1:1 to 15: 1.
7. The method of claim 1, wherein: in step S1, the sulfur-containing compound is: thiophene, 3-methylthiophene, 2, 5-dimethylthiophene, 2, 3.5 trimethylthiophene and dibenzothiophene.
8. The nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material prepared by the preparation method according to any one of claims 1 to 7.
9. A supercapacitor is characterized by comprising the following steps:
(A) weighing the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material, acetylene black and polytetrafluoroethylene emulsion as defined in claim 8, adding a proper amount of ethanol or nitrogen-methyl pyrrolidone, uniformly mixing, and continuously stirring into paste to be coated on foamed nickel;
(B) and drying, drying and tabletting the foamed nickel coated with the nitrogen-oxygen-sulfur co-doped micro-mesoporous intercommunicated carbon microsphere material to obtain the capacitor electrode.
10. An electrode material comprising the supercapacitor electrode material of claim 9.
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