CN111235698B - Preparation method and application of nitrogen-doped porous carbon fiber material - Google Patents
Preparation method and application of nitrogen-doped porous carbon fiber material Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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
- H01G11/40—Fibres
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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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- 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
The invention discloses a preparation method and application of nitrogen-doped porous carbon fibers, and belongs to the technical field of preparation of porous carbon fiber materials. Firstly, preparing polyacrylonitrile/polyvinylpyrrolidone spinning precursor solution, then obtaining porous polyacrylonitrile fiber by a wet spinning method by utilizing different solubilities (phase separation) of polyacrylonitrile and polyvinylpyrrolidone in an aqueous solution, soaking and activating the obtained porous polyacrylonitrile fiber in a potassium hydroxide solution, taking polyacrylonitrile as a carbon source and a nitrogen source, and carrying out one-step high-temperature carbonization activation treatment in an inert atmosphere to obtain the nitrogen-doped porous carbon fiber. The porous carbon fiber material has a hierarchical porous carbon skeleton structure with high specific surface area, high nitrogen content and mutual crosslinking, provides a fast channel for electron transmission, shortens ion diffusion distance, increases wettability and conductivity of the material, and shows very good electrochemical performance. The preparation process is simple, the equipment dependence is low, and the method is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of porous carbon fiber materials, and particularly relates to a preparation method and application of a nitrogen-doped porous carbon fiber material.
Background
With the continuous development of human science and technology, people have more and more extensive demands on portable energy storage equipment. A supercapacitor (also referred to as an electrochemical capacitor or an electric double layer capacitor) is an ideal energy storage device, and has the advantages of high power density, rapid charge and discharge, and ultra-long cycle stability, so that the supercapacitor is widely applied to the fields of electronics, electric appliances, communication, automobiles, aerospace, aviation, and the like. The performance of supercapacitors depends on the properties of the electrode material used. The electrode materials of the current super capacitor mainly comprise carbon materials, metal oxides and conductive polymers. Carbon materials are of great interest because of their low cost, stable performance, long service life, non-pollution, and the like. Carbon fiber materials have advantages of small electrical resistance, large effective specific surface area, easy processing, and the like, compared with other carbon materials, and thus have become a hot point of research in recent years.
The existing preparation process of the polyacrylonitrile-based carbon fiber mainly aims at the preparation of high-modulus and high-strength carbon fiber. The prepared carbon fiber has small resistance and small electric loss caused by internal resistance, but has low surface polarity and few surface functional groups, can not be completely soaked in water-based electrolyte, and has lower energy density compared with a porous carbon material because of lower specific surface area, thereby being incapable of meeting the actual requirements and application.
By introducing heteroatoms (such as N, O, B, P and the like) to perform functional modification on the surface of the carbon material, the carbon material can be provided with additional pseudo capacitance, and the surface wettability and the conductivity are improved. However, this method still has some problems, such as: low nitrogen content, insufficiently developed pore structure, and the like; meanwhile, the preparation method has the disadvantages of complicated steps, complex process, harsh conditions and high cost, and limits the further development and industrial large-scale production of the super capacitor. In addition, many studies have focused on increasing the specific surface area of the carbon material by adding a template or an activator, and on increasing the amount of adsorption of electrolyte ions by the carbon material to increase the energy density. However, most of the porous carbon materials with high specific surface area prepared by other researchers at present are powder or self-supporting blocks, and do not have the characteristic of a one-dimensional carbon fiber structure.
Therefore, how to provide a porous carbon fiber with high nitrogen content, rich pore structure, excellent electrochemical performance and simple manufacturing process is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a nitrogen-doped porous carbon fiber material, wherein the method utilizes phase separation wet spinning and freeze drying double templates to synthesize porous polyacrylonitrile fibers, and obtains the nitrogen-doped porous carbon fibers through one-step high-temperature carbonization and activation, so that the specific surface area of the material is increased, the surface wettability and the conductivity are improved, the diffusion distance of ions is shortened, and the electrochemical performance of the carbon fiber material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped porous carbon fiber material specifically comprises the following steps:
1) preparing a polyacrylonitrile/polyvinylpyrrolidone spinning precursor solution: weighing polyacrylonitrile polymer, polyvinylpyrrolidone polymer and N, N-dimethylformamide solution, and mixing;
2) wet spinning: extruding the precursor solution obtained in the step 1) into deionized water, wet-spinning to obtain porous polyacrylonitrile fibers, and soaking the porous polyacrylonitrile fibers in the deionized water; obtaining fiber A;
3) pre-activation: soaking the fiber A in a potassium hydroxide solution; obtaining fiber B;
4) and (3) freeze drying: precooling the fiber B, and then freeze-drying; obtaining fiber C;
5) one-step carbonization and activation: pre-oxidizing the fiber C in an air atmosphere, then performing high-temperature carbonization in a protective gas environment, and cooling to room temperature to obtain a sample;
6) and cleaning and drying the obtained sample to obtain the nitrogen-doped porous carbon fiber material.
Wherein, the precooling equipment is a refrigerator; the freezing equipment is a vacuum freezing dryer; the pre-oxidation and high-temperature carbonization equipment is a tubular furnace; the protective gas is nitrogen.
The technical effect achieved by the technical scheme is as follows: the method is characterized in that the difference of the solubility of polyacrylonitrile and polyvinylpyrrolidone in water is utilized, porous polyacrylonitrile fibers inside are obtained through wet spinning, and then the porous polyacrylonitrile fibers are cooled, dried and enriched by means of ice crystals. And then fixing the carbon skeleton of the fiber by pre-oxidation to prevent the fiber from being crushed during high-temperature calcination, and finally breaking the fiber wall with a compact surface by high-temperature carbonization and activation to obtain an internal and external through integrated porous carbon skeleton conductive network. In addition, introduction of nitrogen atoms into the structure of the carbon material by autodoping may increase defect sites of the carbon material or active sites in electrochemical reactions; the increase of the nitrogen content on the surface of the carbon material can also improve the conductivity and the surface hydrophilic property of the carbon material and improve the wettability of the carbon material; and the obtained nitrogen-doped porous carbon fiber has better electrochemical performance.
Preferably: the mass of the polyacrylonitrile polymer in the step 1) is 0.5-2.0 g (more preferably 0.7g) and 0.5mol L -1 After N, N dimethylformamide solution is uniformly mixed, the concentration of polyacrylonitrile is 0.05-0.2 g mL -1 。
Preferably, the following components: the mass ratio of the polyacrylonitrile polymer to the polyvinylpyrrolidone polymer in the step 1) is (1-2): (1-2), more preferably 1: 1.
wherein when the mass of the polyacrylonitrile polymer is 0.5-2.0 g, 0.5mol L -1 The dosage of the N, N-dimethylformamide solution is 10 mL.
Preferably: and 2) extruding the precursor solution into 300-500mL deionized water by using an injection needle, wherein the thickness of the injection needle is 18G (0.85-0.95 nm), 20G (0.55-0.65 nm) and 22G (0.35-0.45 nm), and the soaking time in the deionized water is 2-12 h, and the further optimization is 12 h.
The technical effect achieved by the preferable technical scheme is as follows: the optimal experimental conditions of the nitrogen-doped porous carbon fiber are determined by exploring the influence of the changes of injectors with different mass ratios, different concentrations and different thicknesses on wet spinning parameters and further on the electrochemical performance of the porous carbon fiber.
Preferably: the concentration of the potassium hydroxide in the step 3) is as follows: 1 to 6mol L -1 Further preferably 1mol of L -1 And the soaking time is 12 hours.
Preferably: the step 4) is specifically as follows: precooling the fiber B at-18 to-12 ℃ for 8-12 h, further preferably freezing at-18 ℃ for 12h, and then freeze-drying at-45 to-55 ℃ for 12-16 h, further preferably freeze-drying at-55 ℃ for 16 h; obtaining the fiber C.
Preferably: the step 5) is specifically as follows: pre-oxidizing the fiber C in an air atmosphere at the temperature rising speed of 1-10 ℃ for min -1 More preferably 1 ℃ min -1 The calcination temperature is 200-300 ℃, the temperature preservation time at 270 ℃ is preferably 1-3 h, and the temperature preservation time is preferably 1 h; then is high under the protective gas environmentCarrying out warm carbonization treatment at a temperature rise rate of 1-10 ℃ for min -1 More preferably 5 ℃ for min -1 The calcination temperature is 700-1000 ℃, the temperature preservation time of 900 ℃ is preferably 0-3 h, the temperature is preferably not preserved, and then the temperature is cooled to the room temperature; and obtaining a sample.
Preferably, the following components: when the sample is cleaned in the step 6), firstly, 3-5%, more preferably 3% diluted hydrochloric acid is adopted to wash for 6-12 h, more preferably 6h, then deionized water is used to wash the sample to be neutral, and the sample is dried at 55-65 ℃, more preferably 60 ℃.
The technical effect achieved by the technical scheme is as follows: the porous carbon fiber prepared by the method has the characteristics of high nitrogen content, rich pore structure, excellent electrochemical performance and simple manufacturing process.
The invention also provides a nitrogen-doped porous carbon fiber material (prepared by the method) and application thereof as an electrode material of a super capacitor.
The technical effect achieved by the technical scheme is as follows: the nitrogen-doped porous carbon fiber material prepared by the method is applied to the electrode of the super capacitor, and the capacitance performance of the capacitor can be obviously improved.
Through the technical scheme, compared with the prior art, the invention has the technical effects that:
(1) the invention adopts polyvinylpyrrolidone and ice crystal dual-mode plate to construct an integrated porous carbon fiber conductive network, and has the characteristics of high nitrogen doping amount, good conductivity, large specific surface area, rich pore structure, simple and convenient operation process, environmental friendliness and contribution to large-scale standardized production.
(2) The high nitrogen content of the nitrogen-doped porous carbon fiber prepared by the invention comes from a polyacrylonitrile precursor, and the nitrogen-doped porous carbon fiber does not need to be introduced with a nitrogen-containing precursor for nitrogen doping.
(3) The nitrogen-doped porous carbon fiber prepared by the invention is used as an electrode material of a super capacitor, and has excellent rate capability and length specific capacity.
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, it is obvious that the drawings in the following description are only the embodiment 1 of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is an SEM image of nitrogen-doped porous carbon fiber material prepared according to example 1 of the present invention.
Fig. 2 is an X-ray diffraction spectrum (a) and an X-ray photoelectron spectrum (B) of the nitrogen-doped porous carbon fiber electrode material prepared according to example 1 of the present invention.
Fig. 3 shows the nitrogen adsorption and desorption curves (a), (C) and the pore size distribution curves (B), (D) of the nitrogen-doped porous carbon fiber material prepared in example 1 according to the present invention and the comparative example.
Fig. 4 is a cyclic voltammogram of the nitrogen-doped porous carbon fiber material prepared according to example 1 of the present invention at different sweep rates.
Fig. 5 is a constant current charge and discharge curve diagram of the nitrogen-doped porous carbon fiber material prepared according to example 1 of the present invention at different current densities.
Fig. 6 is a plot of the specific mass capacity versus sweep rate for nitrogen-doped porous carbon fiber material prepared according to example 1 of the present invention and a comparative example.
Fig. 7 is a plot of length to specific capacity as a function of sweep rate for nitrogen-doped porous carbon fiber material prepared in accordance with example 1 of the present invention and a comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the raw materials and equipment are purchased from commercial sources, the brands are not limited, and the method not mentioned is a conventional laboratory technical method, which is not described in detail herein.
Example 1
A preparation method of a nitrogen-doped porous carbon fiber material specifically comprises the following steps:
(1) according to the mass ratio of 1: 1 weighing 0.7g of polyacrylonitrile and 0.7g of polyvinylpyrrolidone, putting into 10mL of N, N-dimethylformamide solution, and magnetically stirring for 12h for full dissolution;
(2) after dissolving, extruding the mixed solution into deionized water by using an 18G needle, soaking and standing at normal temperature for 12 hours;
(3) placing the soaked sample in 1mol L -1 Soaking in potassium hydroxide solution at normal temperature for 12 h;
(4) taking out the fiber, freezing in a refrigerator at-18 deg.C for 12h, taking out the sample, freeze drying in a vacuum freeze dryer at-55 deg.C for 16 h.
(5) Placing the lyophilized sample into a tube furnace for calcination treatment at 1 deg.C for min in air atmosphere -1 Heating to 270 deg.C, maintaining for 1h, and then heating at 5 deg.C for min in nitrogen atmosphere -1 And raising the temperature to 900 ℃, keeping the temperature, naturally cooling, and taking out the sample to obtain the nitrogen-doped porous carbon fiber material.
(6) And (3) washing the sample with 3% hydrochloric acid for 6h, washing the sample with deionized water to be neutral, and drying at 60 ℃ to obtain the nitrogen-doped porous carbon fiber material.
The nitrogen-doped porous carbon fiber electrode material prepared by the embodiment has the advantages of high specific surface area, high nitrogen content, rich and mutually-crosslinked hierarchical porous carbon skeleton structure, capability of providing a fast channel for electron transmission, shortening of ion diffusion distance, increase of wettability and conductivity of the material, high mass specific capacitance and length specific capacity, and ideal one-dimensional supercapacitor property.
Specifically, the method comprises the following steps: performing electron microscope scanning and physical property detection on the nitrogen-doped porous carbon fiber material obtained in example 1:
scanning nitrogen-doped porous carbon fiber materials under an electron microscope to obtain an SEM image, which is shown in an attached figure 1;
XRD and XPS tests were performed on the nitrogen-doped porous carbon fiber material, see fig. 2A and fig. 2B, respectively;
testing a nitrogen-doped porous carbon fiber material by using a nitrogen adsorption aperture analyzer, and in a liquid nitrogen environment, feeding gas and exhausting gas into a sample tube to measure the adsorption capacity and the adsorption-desorption isotherm of each partial pressure point, referring to an attached drawing 3A, and calculating by using BET and BJH theories to obtain a specific surface and an aperture of the porous carbon fiber material to obtain an aperture distribution diagram, referring to an attached drawing 3B;
under a three-electrode system, the prepared material is used as a working electrode, a platinum sheet is used as a counter electrode, mercury/mercury oxide is used as a reference electrode, and 6mol L of the reference electrode is used for doping nitrogen into a porous carbon fiber material -1 The potassium hydroxide is used as electrolyte, electrochemical performance test is carried out within the voltage range of-1-0V, and cyclic voltammetry curve graphs of the porous carbon material at different sweeping speeds and constant current charging and discharging curve graphs of the porous carbon fiber material at different current densities are obtained, and the cyclic voltammetry curve graphs and the constant current charging and discharging curve graphs are shown in attached figures 4 and 5.
Example 2
This example differs from example 1 in that: in the step (1), weighing polyacrylonitrile macromolecules and polyvinylpyrrolidone macromolecules with the mass of 0.5g and 0.5g respectively; the rest is the same as in embodiment 1.
Example 3
This example differs from example 1 in that: in the step (1), the mass of polyacrylonitrile polymer and polyvinylpyrrolidone polymer is respectively 0.7g and 0.35 g. The rest is the same as in embodiment 1.
Example 4
This example differs from example 1 in that: weighing polyacrylonitrile macromolecules and polyvinylpyrrolidone macromolecules respectively with the mass of 2.0g and 2.0g in the step (1); extruding the mixed solution into deionized water by using a 20G needle in the step (2), soaking and standing at normal temperature for 12 hours; the concentration of the potassium hydroxide in the step (3) is as follows: 6mol L -1 (ii) a The rest is the same as in embodiment 1.
Example 5
This example differs from example 1 in that: weighing polyacrylonitrile macromolecules and polyvinylpyrrolidone macromolecules respectively with the mass of 2.0g and 2.0g in the step (1); extruding the mixed solution into deionized water by using a 22G needle in the step (2), and soaking and standing for 6 hours at normal temperature; taking out the fiber, putting the fiber into a refrigerator, freezing the fiber for 12 hours at the temperature of-12 ℃, finally taking out the sample, putting the sample into a vacuum freeze dryer, and carrying out freeze drying for 12 hours at the temperature of-45 ℃; the rest is the same as in embodiment 1.
Example 6
This example differs from example 1 in that: in the step (1), the mass of polyacrylonitrile polymer and polyvinylpyrrolidone polymer are respectively 2.0g and 2.0 g; in the step (2), a 20G needle is used for extruding the mixed solution into deionized water; the concentration of the potassium hydroxide in the step (3) is as follows: 3mol L -1 (ii) a Taking out the fiber, putting the fiber into a refrigerator, freezing the fiber for 10 hours at the temperature of minus 14 ℃, finally taking out the sample, putting the sample into a vacuum freeze dryer, and carrying out freeze drying for 14 hours at the temperature of minus 50 ℃; the rest is the same as in embodiment 1.
Example 7
This example differs from example 1 in that: in step (5), the reaction is carried out at 5 ℃ for min under the nitrogen atmosphere -1 The temperature was raised to 1000 ℃ in the same manner as in example 1.
Example 8
This example is different from example 7 in that the temperature increase rate in the step (5) is 10 ℃ for min -1 The calcination temperature is 300 ℃, and the heat preservation time is 3 h; then in nitrogen atmosphere at 10 deg.C for min -1 The temperature was raised to 1000 ℃ and the temperature was maintained for 3 hours, as in example 7.
Comparative example
(1) 0.7g of polyacrylonitrile is weighed and put into 10mL of N, N dimethylformamide solution to be magnetically stirred for 12 hours for fully dissolving.
(2) After dissolution, the solution is extruded into deionized water by a 18G needle, soaked and kept stand for 12 hours at normal temperature.
(3) Taking out the fiber, freezing in a refrigerator at-18 deg.C for 12h, taking out the sample, and freeze drying in a vacuum freeze drier at-55 deg.C for 16 h.
(4) Placing the lyophilized sample into a tube furnace for calcination treatment at 1 deg.C for min in air atmosphere -1 Heating to 270 deg.C, maintaining for 1h, and then heating at 5 deg.C for min in nitrogen atmosphere -1 Heating toAnd (3) keeping the temperature of 900 ℃, naturally cooling and taking out the sample to obtain the solid carbon fiber material.
Testing the carbon fiber material prepared in the comparative example by using a nitrogen adsorption aperture analyzer, feeding gas into a sample tube and exhausting gas in a liquid nitrogen environment to obtain the adsorption capacity and the adsorption-desorption isotherm of each partial pressure point, referring to the attached figure 3C, and calculating by using BET and BJH theories to obtain the specific surface and the aperture of the carbon fiber material, referring to the attached figure 3D, so as to obtain an aperture distribution diagram;
electrochemical calculations were performed on the materials prepared in example 1 and comparative example to obtain the curves of specific mass capacity and specific length capacity of porous carbon fiber and solid carbon fiber materials as a function of sweep rate, see fig. 6 and 7.
The results show that: compared with the structure of the solid carbon fiber of the comparative example, the integrated porous carbon fiber conductive network constructed by the polyvinylpyrrolidone and the ice crystal dual-mode plate has the advantages of high nitrogen content, large specific surface area and rich pore structure. Based on these characteristics, example 1 exhibited superior electrochemical properties compared to the comparative example.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The preparation method of the nitrogen-doped porous carbon fiber material is characterized by comprising the following steps:
1) preparing a polyacrylonitrile/polyvinylpyrrolidone spinning precursor solution: weighing polyacrylonitrile macromolecules, polyvinylpyrrolidone macromolecules and N, N dimethylformamide solution, and mixing uniformly;
2) wet spinning: extruding the precursor solution obtained in the step 1) into deionized water, wet-spinning to obtain porous polyacrylonitrile fibers, and soaking the porous polyacrylonitrile fibers in the deionized water; obtaining fiber A;
3) pre-activation: soaking the fiber A in a potassium hydroxide solution; obtaining a fiber B;
4) and (3) freeze drying: precooling the fiber B, and then freeze-drying; obtaining fiber C;
5) one-step carbonization and activation: pre-oxidizing the fiber C in an air atmosphere, then performing high-temperature carbonization in a protective gas environment, and cooling to room temperature to obtain a sample;
6) cleaning and drying the obtained sample to obtain a nitrogen-doped porous carbon fiber material;
the mass of the polyacrylonitrile polymer in the step 1) is 0.5-2.0 g and 0.5mol L -1 After the N, N dimethylformamide solution is uniformly mixed, the concentration of polyacrylonitrile is 0.05-0.2 g mL -1 ；
Step 2) extruding 300-500mL deionized water into the precursor solution by using an injection needle, wherein the thickness of the injection needle is 18G (0.85-0.95 nm), 20G (0.55-0.65 nm) and 22G (0.35-0.45 nm), and soaking in the deionized water for 2-12 h;
the concentration of the potassium hydroxide in the step 3) is as follows: 1mol L -1 The soaking time is 12 hours;
the step 4) is specifically as follows: precooling the fiber B for 8-12 h at the temperature of-18 to-12 ℃, and then carrying out freeze drying for 12-16 h at the temperature of-45 to-55 ℃; obtaining fiber C;
the step 5) is specifically as follows: pre-oxidizing the fiber C in an air atmosphere at the temperature rising speed of 1-10 ℃ for min -1 The calcination temperature is 200-300 ℃, and the heat preservation time is 1-3 h; then carrying out high-temperature carbonization treatment in a protective gas environment at the temperature rise speed of 1-10 ℃ for min -1 The calcination temperature is 700-1000 ℃, the heat preservation time is 0-3 h, and then the mixture is cooled to the room temperature; and obtaining a sample.
2. The preparation method of the nitrogen-doped porous carbon fiber material according to claim 1, wherein the mass ratio of the polyacrylonitrile polymer to the polyvinylpyrrolidone polymer in the step 1) is (1-2): (1-2).
3. The preparation method of the nitrogen-doped porous carbon fiber material according to claim 1, wherein in the step 6), when a sample is cleaned, the sample is washed for 6-12 hours by using 3-5% diluted hydrochloric acid, washed to be neutral by using deionized water, and dried at 55-65 ℃.
4. A nitrogen-doped porous carbon fiber material, which is characterized by being prepared by the method of any one of claims 1 to 3.
5. The use of a nitrogen-doped porous carbon fiber material as claimed in claim 4 as an electrode material for supercapacitors.
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