CN108455561B - Preparation method of paper-based mesoporous carbon electrode material and preparation method of electrode - Google Patents

Preparation method of paper-based mesoporous carbon electrode material and preparation method of electrode Download PDF

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CN108455561B
CN108455561B CN201810410735.XA CN201810410735A CN108455561B CN 108455561 B CN108455561 B CN 108455561B CN 201810410735 A CN201810410735 A CN 201810410735A CN 108455561 B CN108455561 B CN 108455561B
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paper
electrode material
mesoporous carbon
carbon electrode
based mesoporous
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CN108455561A (en
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李志国
许升
张文
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Northeast Forestry University
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A preparation method of a paper-based mesoporous carbon electrode material and a preparation method of an electrode belong to the field of preparation methods of carbon materials. Weighing a certain amount of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, trimethylbenzene and water, uniformly mixing and stirring, transferring the mixture into a reaction kettle for reaction and cleaning, drying, then placing the mixture into a tubular furnace, carbonizing the mixture in a nitrogen atmosphere, finally cooling the mixture to room temperature, washing the mixture with 0.1M HCl and deionized water to be neutral, and drying the mixture. Then weighing a certain mass proportion, namely: after activation of KOH, and drying in an oven, the material is taken out, and the obtained material is obtained. According to the carbon-carbon composite material, the surface of the carbon-carbon composite material is loaded with a layer of mesoporous carbon microspheres by a one-step hydrothermal method, and the surface of the carbon-carbon composite material contains N, O and other heteroatoms, so that the carbon-carbon composite material has good wettability and better ion accessibility. By using the KOH activation method, the specific surface area and the pore structure of the material are obviously improved, the specific capacity is high, and the cycle performance is good.

Description

Preparation method of paper-based mesoporous carbon electrode material and preparation method of electrode
Technical Field
The invention belongs to the field of preparation methods of carbon materials; in particular to a preparation method of a paper-based mesoporous carbon electrode material and a preparation method of an electrode.
Background
In recent years, biomass raw materials such as bagasse and poplar can be directly applied to carbon electrode materials of supercapacitors through high-temperature calcination. Therefore, the development of a novel porous carbon electrode material using a biomass substrate as a raw material has attracted attention and research of many scholars.
The biomass has an excellent multistage porous structure, a large pore size range, wide pore distribution and low price and can be regenerated. Moreover, after the biomass fiber material is carbonized, the surface of the biomass fiber material has abundant functional groups, particularly oxygen-containing functional groups such as hydroxyl, carboxyl and the like, so that the biomass fiber material has good wettability on the surface, and the wetting and ion accessibility of an electrolyte solution on the surface of an electrode are facilitated. However, due to wide sources and large differences, the structure, especially the pore structure, of the biomass-based carbon electrode material has large distribution differences, and the application of the biomass-based carbon electrode material in the aspect of electrode materials is greatly limited.
Disclosure of Invention
The invention aims to provide a preparation method of a paper-based mesoporous carbon electrode material and a preparation method of an electrode.
The invention is realized by the following technical scheme:
a preparation method of a paper-based mesoporous carbon electrode material comprises the following steps:
step 1, weighing certain mass of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, 1, 3, 5-trimethylbenzene and distilled water, placing the weighed substances in a beaker, stirring for 1-2 hours, transferring the beaker into a reaction kettle, setting the reaction temperature to be 100-180 ℃, reacting for 12-24 hours, and obtaining a mixture after reaction for later use;
step 2, cleaning the mixture obtained after the reaction in the step 1 by using absolute ethyl alcohol and deionized water for 3-5 times, and drying the filter paper obtained after filtration in an oven for 10-20 hours to obtain a sample a for later use; the filter paper is attached with reddish brown powder precipitates;
step 3, placing the sample a obtained in the step 2 in a tubular furnace, carrying out temperature programming reaction under the protection of nitrogen, heating from room temperature to 350-400 ℃ at the heating rate of 1-3 ℃/min, keeping the temperature for 2-3 h, then heating from 350-400 ℃ to 600-800 ℃, keeping the temperature for 1-3 h, and cooling to room temperature after the reaction is finished to obtain a sample b for later use;
step 4, washing the sample b obtained in the step 3 to be neutral by using a hydrochloric acid solution and deionized water, filtering, and drying in an oven for 10-20 hours to obtain a sample c for later use;
and 5, weighing a certain mass of the sample c obtained in the step 4, KOH and distilled water, placing the sample c, KOH and distilled water in a beaker, stirring for 5-20 min, and transferring the sample c to an oven to be completely dried to obtain the paper-based mesoporous carbon electrode material.
The preparation method of the paper-based mesoporous carbon electrode material comprises the following steps of 1, wherein the mass ratio of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, 1, 3, 5-trimethylbenzene and distilled water is (0.5-1.5): (0.5-1): (0.4-0.8): (0.25-0.65): (0.1-0.4): 18.
according to the preparation method of the paper-based mesoporous carbon electrode material, the drying temperature of the oven in the step 2 is 50-100 ℃.
The preparation method of the paper-based mesoporous carbon electrode material comprises the step 3 of heating from room temperature to 400 ℃ at a heating rate of 2 ℃/min and keeping the temperature for 2.5 hours, and then heating from 400 ℃ to 700 ℃ and keeping the temperature for 2 hours.
According to the preparation method of the paper-based mesoporous carbon electrode material, the concentration of the hydrochloric acid solution in the step 4 is 0.1M, and the drying temperature of an oven is 50-100 ℃.
The invention relates to a preparation method of a paper-based mesoporous carbon electrode material, wherein the mass ratio of a sample c, KOH and distilled water obtained in the step 4 in the step 5 is 1: (2-6): (4-10), drying in an oven at the temperature of 80-120 ℃ for 12-24 h.
The invention relates to an electrode preparation method of a paper-based mesoporous carbon electrode material, which comprises the following steps: acetylene black: PTFE emulsion: the mass ratio of the absolute ethyl alcohol is 8: 1: 1: 3-5, uniformly mixing, uniformly coating the obtained mixture on a foamed nickel current collector, placing the foamed nickel current collector in a vacuum drying oven at the temperature of 100-120 ℃ for drying for 10-12 h, cooling, taking out, and pressing by using a tablet press to prepare the working electrode.
According to the preparation method of the paper-based mesoporous carbon electrode material, the mass percentage concentration of the PTFE emulsion is 10%.
According to the preparation method of the paper-based mesoporous carbon electrode material, the coating mass of the mixture is 2-4 mg/cm2。
According to the preparation method of the paper-based mesoporous carbon electrode material, the pressure of a tablet press is 10 MPa.
The preparation method of the paper-based mesoporous carbon electrode material provided by the invention comprises the steps of taking industrial filter paper as a biomass fiber raw material, taking a block copolymer F127 as a soft template, taking 3-aminophenol as a carbon source and a nitrogen source, and synthesizing the paper-based mesoporous carbon electrode material with the surface having rich mesoporous structure surface morphology in one step by adopting a hydrothermal method.
Fl27 is a poloxamer, a polyoxyethylene polyoxypropylene ether block copolymer.
The surface of the electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material is irregular powder, the surface of the prepared paper-based mesoporous carbon electrode material is coated with a layer of mesoporous carbon microspheres, the size of the mesoporous carbon microspheres is 0.6-9 mu m, the mesoporous carbon microspheres and other irregular shapes form three-dimensional mutually-penetrating pore channels, the pore channels are randomly distributed and mutually penetrated, the penetrated pore channels can be favorable for the transmission of electrons, and the specific capacitance of the electrode material is increased by regulating and controlling the surface pore structure.
The specific surface area of the electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material can reach 1799m2The high specific surface area enables the electrode to obtain higher specific capacitance, provides a foundation for the application of the electrode on carbon electrode materials, N-6 and N-5 account for 67.4 percent of the total content, and nitrogen functional groups in a carbon skeleton can effectively provide pseudo capacitance.
According to the electrode prepared from the paper-based mesoporous carbon electrode material, the capacitance of the paper-based mesoporous carbon electrode material is derived from double-electric-layer response and redox reaction of heteroatom nitrogen and oxygen functional groups on the surface of the electrode, and a curve similar to a rectangle can be kept at a large scanning speed, so that the paper-based mesoporous carbon electrode material has the capability of rapid ion transfer-diffusion and excellent rate capability.
The electrode prepared from the paper-based mesoporous carbon electrode material has the specific capacitance reaching 396F g at the current density of 0.5A g-1-1Shows excellent electrochemical performance even at 20A g-1Can also maintain 215F g at high current density-1The specific capacitance of (2) shows better rate performance. 20A g-1After 10000 cycles of charging and discharging under constant current density, the capacitance loss rate is only 2 percent. In addition, the basic dimension of the coulomb ratio of the material can be seenThe electrochemical reversibility is good when the concentration is kept at 100 percent.
The invention relates to a preparation method of a paper-based mesoporous carbon electrode material, and provides a technical concept of regulation and control of a surface pore structure of a biomass raw material, which comprises the following steps: by adopting molecular design and utilizing the self-assembly characteristic of a block copolymer, an ordered mesoporous assembly prepolymer is constructed on the surface of a biomass raw material (paper) by a hydrothermal method, then the ordered mesoporous assembly prepolymer is carbonized at high temperature, the block copolymer is removed, and simultaneously, a micro/mesoporous composite multistage biomass-based composite carbon electrode material is constructed, and then a chemical activation method is further adopted, so that the specific surface area of the electrode material is increased, and the specific capacitance of the electrode material can also be increased; the carbon-carbon composite material which takes the paper base as the wood fiber base material and is loaded with a layer of mesoporous carbon microspheres on the surface by a one-step hydrothermal method is successfully prepared, and hetero atoms such as N, O exist on the surface of the carbon-carbon composite material, so that the carbon-carbon composite material has good wettability and better ion accessibility. By using the KOH activation method, the specific surface area and the pore structure of the material are obviously improved, the carbon electrode material with high specific capacitance and high cycle stability is obtained, and the carbon electrode material has a certain application prospect in the electrode material of the super capacitor.
According to the preparation method of the paper-based mesoporous carbon electrode material, the surface pore structure is regulated, and meanwhile, heteroatom nitrogen elements are introduced into the carbon material structure, so that the capacitance of the carbon material is improved through the doping of the nitrogen elements in the surface mesoporous structure, the surface wettability of the carbon material is improved, and the electrochemical performance of the electrode material is improved.
The preparation method of the paper-based mesoporous carbon electrode material has the advantages of mild reaction conditions, simple steps and low cost, and lays a foundation for large-scale application of the paper-based mesoporous carbon electrode material in the field of electrochemical electrodes.
Drawings
FIG. 1 is an SEM photograph of 800 times of a paper-based mesoporous carbon electrode material prepared by a method according to an embodiment;
FIG. 2 is a 4500 times SEM photograph of a paper-based mesoporous carbon electrode material prepared by a method according to an embodiment;
FIG. 3 is a TEM image of 10 ten thousand times of a paper-based mesoporous carbon electrode material prepared by the method of the embodiment;
FIG. 4 is a specific surface analysis curve of a paper-based mesoporous carbon electrode material prepared by a method according to an embodiment;
FIG. 5 is a TEM image of 20 ten thousand times of a paper-based mesoporous carbon electrode material prepared by the second method in the embodiment;
FIG. 6 is a small-angle XRD curve of a paper-based mesoporous carbon electrode material prepared by the second method;
FIG. 7 is a large-angle XRD curve of a paper-based mesoporous carbon electrode material prepared by the second method;
FIG. 8 is an XPS survey scan of a paper-based mesoporous carbon electrode material prepared by the method of embodiment two;
FIG. 9 is an N1s analysis spectrum of XPS of a paper-based mesoporous carbon electrode material prepared by the second method of the embodiment;
FIG. 10 is a graph of XPS percentage of N1s content of a paper-based mesoporous carbon electrode material prepared by the second method of the embodiment;
FIG. 11 is a cyclic voltammetry curve of a paper-based mesoporous carbon electrode prepared by the third method of the embodiment;
FIG. 12 is a low-current constant-current charge-discharge curve of a paper-based mesoporous carbon electrode prepared by the method of the fourth embodiment;
FIG. 13 is a high-current constant-current charge-discharge curve of a paper-based mesoporous carbon electrode prepared by the method of the fourth embodiment;
FIG. 14 is a specific capacitance curve of a paper-based mesoporous carbon electrode prepared by the method of the fourth embodiment;
FIG. 15 is a graph of the cycle performance of a paper-based mesoporous carbon electrode prepared by the method of the fourth embodiment.
Detailed Description
The first embodiment is as follows:
a preparation method of a paper-based mesoporous carbon electrode material comprises the following steps:
step 1, weighing certain mass of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, 1, 3, 5-trimethylbenzene and distilled water, placing the weighed substances in a beaker, stirring for 1h, transferring the beaker into a reaction kettle, setting the reaction temperature to be 180 ℃, reacting for 12h, and obtaining a reacted mixture for later use;
step 2, washing the mixture obtained after the reaction in the step 1 with absolute ethyl alcohol and deionized water for 5 times, filtering to obtain filter paper attached with reddish brown precipitate powder, and placing the filter paper in an oven to dry for 15 hours to obtain a sample a for later use;
step 3, placing the sample a obtained in the step 2 in a tubular furnace, carrying out temperature programming reaction under the protection of nitrogen, heating from room temperature to 400 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2 hours, then heating from 400 ℃ to 600 ℃ and preserving the temperature for 2 hours, and after the reaction is finished, cooling to room temperature to obtain a sample b for later use;
step 4, washing the sample b obtained in the step 3 to be neutral by using a hydrochloric acid solution and deionized water, filtering, and then placing in an oven to dry for 15 hours to obtain a sample c for later use;
and 5, weighing a certain mass of the sample c obtained in the step 4, KOH and distilled water, placing the sample c, KOH and distilled water in a beaker, stirring for 5min, and transferring the sample c to an oven to be completely dried to obtain the paper-based mesoporous carbon electrode material.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, in the step 1, the mass ratio of the industrial filter paper, the F127, the 3-aminophenol, the hexamethylenetetramine, the 1, 3, 5-trimethylbenzene and the distilled water is 1: 0.75: 0.5: 0.5: 0.2: 18.
in the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the drying temperature of the oven in the step 2 is 100 ℃.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the concentration of the hydrochloric acid solution in the step 4 is 0.1M, and the drying temperature of the oven is 100 ℃.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the mass ratio of the sample c, KOH, and distilled water obtained in step 4 in step 5 is 1: 5: and 5, drying at the oven drying temperature of 100 ℃ for 24 h.
In the paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, SEM pictures are shown in fig. 1 and fig. 2, and TEM pictures are shown in fig. 3: as can be seen from an SEM picture of 800 times in attached figure 1 and an SEM picture of 4500 times in attached figure 2, the surface of the prepared paper-based mesoporous carbon electrode material is in a random powder shape, a layer of mesoporous carbon microspheres is coated on the surface of the prepared paper-based mesoporous carbon electrode material, the size of the mesoporous carbon microspheres is 0.6-9 mu m, and three-dimensional through channels are formed between the mesoporous carbon microspheres and other random shapes.
According to a TEM image of 10 ten thousand times in the image 3, it can be seen that three-dimensional interpenetrated pore channels formed by the mesoporous carbon microspheres and other irregular shapes are randomly distributed and interpenetrated, and the interpenetrated pore channels can be beneficial to the transmission of electrons, so that the specific capacitance of the electrode material is increased by regulating and controlling the surface pore structure.
FIG. 4 is a specific surface analysis curve of a paper-based mesoporous carbon electrode material prepared by the method, and N is utilized2The adsorption and desorption detection method further researches the surface pores. As can be seen from FIG. 5, the adsorption-desorption isotherm is a combination of form I and form IV. At P/P0<The nitrogen adsorption capacity at 0.1 part is increased rapidly due to the process of filling the micropores, the nitrogen adsorption capacity is continuously increased at the position of P/P0 being 0.4-0.9, the existence of micropores/mesopores is proved, and the specific surface area of the micropores/mesopores can reach 1799m2The high specific surface area enables the carbon electrode material to obtain higher specific capacitance, and provides a foundation for the application of the carbon electrode material.
Table 1 pore parameters of paper-based mesoporous carbon electrode material of the present embodiment
Figure BDA0001647978230000051
Table 1 shows the pore parameters of the paper-based mesoporous carbon electrode material of the embodiment, and as can be seen from Table 1, the volumes of micropores and mesopores of the material can reach 0.73cm3g-1And 0.14cm3g-1The large pore volume is very favorable for electricityAnd (4) transmitting the son.
The second embodiment is as follows:
a preparation method of a paper-based mesoporous carbon electrode material comprises the following steps:
step 1, weighing a certain mass of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, 1, 3, 5-trimethylbenzene and distilled water, placing the weighed substances in a beaker, stirring for 2 hours, transferring the beaker into a reaction kettle, setting the reaction temperature to be 150 ℃, reacting for 24 hours, and obtaining a reacted mixture for later use;
step 2, washing the mixture obtained after the reaction in the step 1 with absolute ethyl alcohol and deionized water for 4 times, filtering to obtain filter paper attached with reddish brown precipitate powder, and placing the filter paper in an oven to dry for 15 hours to obtain a sample a for later use;
step 3, placing the sample a obtained in the step 2 in a tubular furnace, carrying out temperature programming reaction under the protection of nitrogen, heating from room temperature to 350 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3 hours, then heating from 350 ℃ to 800 ℃ and keeping the temperature at the temperature for 1 hour, and after the reaction is finished, cooling to room temperature to obtain a sample b for later use;
step 4, washing the sample b obtained in the step 3 to be neutral by using a hydrochloric acid solution and deionized water, filtering, and then placing in an oven to dry for 15 hours to obtain a sample c for later use;
and 5, weighing a certain mass of the sample c, KOH and distilled water obtained in the step 4, placing the sample c, KOH and distilled water in a beaker, stirring for 10min, and transferring the sample c to an oven to be completely dried to obtain the paper-based mesoporous carbon electrode material.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, in the step 1, the mass ratio of the industrial filter paper, the F127, the 3-aminophenol, the hexamethylenetetramine, the 1, 3, 5-trimethylbenzene and the distilled water is 1.5: 1: 0.7: 0.3: 0.2: 18.
in the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the drying temperature of the oven in the step 2 is 80 ℃.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the concentration of the hydrochloric acid solution in the step 4 is 0.1M, and the drying temperature of the oven is 100 ℃.
In the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the mass ratio of the sample c, KOH, and distilled water obtained in step 4 in step 5 is 1: 3: 7, drying at the oven drying temperature of 100 ℃ for 24 h.
The paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment has a 20 ten thousand-fold TEM picture as shown in the attached figure 5: it can be seen from fig. 5 that the mesoporous carbon microspheres and other irregular-shaped three-dimensional interpenetrated pore channels are randomly distributed and interpenetrated, and the interpenetrated pore channels can facilitate the transmission of electrons, so that the specific capacitance of the electrode material can be increased by regulating and controlling the surface pore structure.
The small-angle XRD curve of the paper-based mesoporous carbon electrode material prepared by the method for preparing the paper-based mesoporous carbon electrode material according to the embodiment is shown in fig. 6: from the figure, a diffraction peak with good resolution appears near 2 theta of 0.76 degrees and a broad peak appears near 2 theta of 1.0-1.8 degrees, and the characteristic peaks indicate that the prepared paper-based mesoporous carbon electrode material has a two-dimensional hexagonal mesostructure (p6m) -.
The paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment has a large-angle XRD curve as shown in the attached figure 7: from FIG. 7, it can be seen that there are distinct diffraction peaks around 2 θ ≈ 22 and 43 °, which correspond to the lattice planes of amorphous carbon (002) and (100), respectively, and the amorphous state structure of the prepared paper-based mesoporous carbon electrode material is illustrated.
In the paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, an XPS full scan spectrum is shown in fig. 8: from fig. 8, it can be seen that the full scan pattern of the sample of the material shows three absorption peaks at 285eV, 400eV, 532eV of binding energy, corresponding to the peaks of C1s, N1s, O1s, respectively, which indicates that nitrogen element is successfully doped into the paper-based mesoporous carbon electrode material.
In the paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, an analysis spectrum of N1s of XPS is shown in fig. 9: FIG. 9 further illustrates the spectrum of N1s, and for the spectrum of N1s, four characteristic absorption peaks are observed, with binding energies centered at 397.5 + -0.2 eV, 400.1 + -0.2 eV, 401.2 + -0.3 eV, and 404.2+0.4eV, respectively for pyridine nitrogen (N-6), pyrrole nitrogen/hydroxypyridine nitrogen (N-5), graphite nitrogen (N-Q), and pyridine nitrogen oxide (N-X), where N-6 and N-5 play a critical role in increasing the specific capacitance of the carbon material, because the nitrogen atoms in the N-6 and N-5 structures are partially located at the edges of the graphene layer, which can promote the Faraday reaction to generate pseudocapacitance.
In the paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the XPS N1s content percentage diagram is shown in fig. 10: the figure shows that N-6 and N-5 account for 67.4% of the total content, and the nitrogen functional groups in the carbon skeleton of the paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material can effectively provide pseudo-capacitance.
The paper-based mesoporous carbon electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material in the embodiment,
the third concrete implementation mode:
according to the electrode preparation method of the electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material, according to the specific embodiment, the paper-based mesoporous carbon electrode material is prepared by the following steps: acetylene black: PTFE emulsion: the mass ratio of the absolute ethyl alcohol is 8: 1: 1: 5, uniformly mixing, uniformly coating the obtained mixture on a foamed nickel current collector, placing the foamed nickel current collector in a vacuum drying oven at 120 ℃ for drying for 10 hours, cooling, taking out, pressing by using a tablet press, and preparing into a working electrode.
In the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the mass percentage concentration of the PTFE emulsion is 10%.
In the method for preparing the paper-based mesoporous carbon electrode material, the coating mass of the mixture is 2mg/cm2。
In the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the pressure of a tablet press is 10 MPa.
The electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material of the embodiment has a thickness of 10mV s-1 to 200mV s-1The cyclic voltammetry test curve is shown in figure 11, and it can be seen from figure 11 that the curve is similar to a rectangle and has a broad peak in a low potential region, which indicates that the capacitance of the paper-based mesoporous carbon electrode material is from the double layer response and the redox reaction of heteroatom nitrogen and oxygen functional groups on the surface of the electrode, and it can be seen from the figure that the curve similar to a rectangle can be maintained under a large scanning speed, which indicates that the paper-based mesoporous carbon electrode material has the capability of rapid ion transfer-diffusion and excellent rate capability.
The fourth concrete implementation mode:
according to the electrode preparation method of the electrode material prepared by the preparation method of the paper-based mesoporous carbon electrode material, according to the second specific embodiment, the paper-based mesoporous carbon electrode material is prepared by the following steps: acetylene black: PTFE emulsion: the mass ratio of the absolute ethyl alcohol is 8: 1: 1: 5, uniformly mixing, uniformly coating the obtained mixture on a foamed nickel current collector, placing the foamed nickel current collector in a vacuum drying oven at 120 ℃ for drying for 10 hours, cooling, taking out, pressing by using a tablet press, and preparing into a working electrode.
In the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the mass percentage concentration of the PTFE emulsion is 10%.
In the method for preparing the paper-based mesoporous carbon electrode material, the coating mass of the mixture is 2mg/cm2。
In the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment, the pressure of a tablet press is 10 MPa.
The low-current constant-current charge-discharge curve of the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment is shown in figure 12, and it can be seen from the figure that the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material is 0.5-5A g-1The constant current charge and discharge performance is shown in the figure, and the constant current of the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material can be obviously seenThe charge-discharge curve shows an almost symmetrical triangular shape, indicating that the electrode material has good electrochemical reversibility.
The large-current constant-current charge-discharge curve of the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material according to the embodiment is shown in figure 13, and it can be seen from the figure that the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material is 10-50A g-1The constant current charge-discharge performance is shown in the figure, and the constant current charge-discharge curve of the electrode prepared by the electrode preparation method of the paper-based mesoporous carbon electrode material shows an almost symmetrical triangular shape, which shows that the electrode material has good electrochemical reversibility even at a high current density of 50A g-1The curves also maintain good potential-time linearity, indicating the typical capacitance characteristics of the material as well as good rate performance.
The specific capacitance calculated according to different current densities of the electrode prepared by the method for preparing the paper-based mesoporous carbon electrode material according to the embodiment is shown in fig. 14, and it can be seen from the figure that the specific capacitance of the material can reach 396F g at a current density of 0.5A g-1-1Shows excellent electrochemical performance even at 20A g-1At high current densities of (2), the material can also maintain 215F g-1The specific capacitance of (2) shows better rate performance.
The 20Ag electrode prepared by the method for preparing the paper-based mesoporous carbon electrode material-1The circulation performance curve of 10000 circles of charge and discharge under constant current density is shown in figure 15, and it can be seen from the figure that a paper-based mesoporous carbon electrode material has excellent circulation stability and keeps good capacitance retention rate, and after 10000 circles of charge and discharge, the capacitance loss rate is only 2%. In addition, the coulomb of the material is basically maintained at 100%, and the material has good electrochemical reversibility.

Claims (8)

1. A preparation method of a paper-based mesoporous carbon electrode material is characterized by comprising the following steps: the method comprises the following steps:
step 1, weighing certain mass of industrial filter paper, F127, 3-aminophenol, hexamethylenetetramine, 1, 3, 5-trimethylbenzene and distilled water, placing the weighed substances in a beaker, stirring for 1-2 hours, transferring the beaker into a reaction kettle, setting the reaction temperature to be 100-180 ℃, reacting for 12-24 hours, and obtaining a mixture after reaction for later use;
step 2, cleaning the mixture obtained after the reaction in the step 1 by using absolute ethyl alcohol and deionized water for 3-5 times, and drying the filter paper obtained after filtration in an oven for 10-20 hours to obtain a sample a for later use;
step 3, placing the sample a obtained in the step 2 in a tubular furnace, carrying out temperature programming reaction under the protection of nitrogen, heating from room temperature to 350-400 ℃ at the heating rate of 1-3 ℃/min, keeping the temperature for 2-3 h, then heating from 350-400 ℃ to 600-800 ℃, keeping the temperature for 1-3 h, and cooling to room temperature after the reaction is finished to obtain a sample b for later use;
step 4, washing the sample b obtained in the step 3 to be neutral by using a hydrochloric acid solution and deionized water, filtering, and drying in an oven for 10-20 hours to obtain a sample c for later use;
step 5, weighing a certain mass of the sample c, KOH and distilled water obtained in the step 4, placing the sample c, KOH and distilled water in a beaker, stirring for 5-20 min, and transferring the sample c, KOH and distilled water to an oven for complete drying to obtain the paper-based mesoporous carbon electrode material;
in the step 1, the mass ratio of the industrial filter paper, the F127, the 3-aminophenol, the hexamethylenetetramine, the 1, 3, 5-trimethylbenzene and the distilled water is (0.5-1.5): (0.5-1): (0.4-0.8): (0.25-0.65): (0.1-0.4): 18;
the mass ratio of the sample c, KOH and distilled water obtained in the step 4 in the step 5 is 1: (2-6): (4-10), drying in an oven at the drying temperature of 80-120 ℃ for 12-24 h;
the paper-based mesoporous carbon electrode material with rich mesoporous structure surface morphology on the surface is prepared by one-step synthesis by taking industrial filter paper as a biomass fiber raw material, taking the block copolymer F127 as a soft template, taking 3-aminophenol as a carbon source and a nitrogen source and adopting a hydrothermal method.
2. The preparation method of the paper-based mesoporous carbon electrode material according to claim 1, characterized in that: and (3) drying the oven in the step (2) at the drying temperature of 50-100 ℃.
3. The preparation method of the paper-based mesoporous carbon electrode material according to claim 1, characterized in that: the programmed heating condition in the step 3 is heating from room temperature to 400 ℃ at the heating rate of 2 ℃/min and keeping the temperature for 2.5 hours, and then heating from 400 ℃ to 700 ℃ and keeping the temperature for 2 hours.
4. The preparation method of the paper-based mesoporous carbon electrode material according to claim 1, characterized in that: in the step 4, the concentration of the hydrochloric acid solution is 0.1M, and the drying temperature of the oven is 50-100 ℃.
5. A method for preparing an electrode of a paper-based mesoporous carbon electrode material according to any one of claims 1 to 4, wherein: preparing a paper-based mesoporous carbon electrode material: acetylene black: PTFE emulsion: the mass ratio of the absolute ethyl alcohol is 8: 1: 1: 3-5, uniformly mixing, uniformly coating the obtained mixture on a foamed nickel current collector, placing the foamed nickel current collector in a vacuum drying oven at the temperature of 100-120 ℃ for drying for 10-12 h, cooling, taking out, and pressing by using a tablet press to prepare the working electrode.
6. The method for preparing the electrode made of the paper-based mesoporous carbon electrode material according to claim 5, wherein the method comprises the following steps: the mass percentage concentration of the PTFE emulsion is 10 percent.
7. The method for preparing the electrode made of the paper-based mesoporous carbon electrode material according to claim 5, wherein the method comprises the following steps: the coating mass of the mixture is 2-4 mg/cm2。
8. The method for preparing the electrode made of the paper-based mesoporous carbon electrode material according to claim 5, wherein the method comprises the following steps: the pressure of the tablet press is 10 MPa.
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