CN113622090A - Flexible conductive carbon nanofiber membrane and preparation method and application thereof - Google Patents
Flexible conductive carbon nanofiber membrane and preparation method and application thereof Download PDFInfo
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- CN113622090A CN113622090A CN202111083936.1A CN202111083936A CN113622090A CN 113622090 A CN113622090 A CN 113622090A CN 202111083936 A CN202111083936 A CN 202111083936A CN 113622090 A CN113622090 A CN 113622090A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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
- D01F1/10—Other agents for modifying properties
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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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
Abstract
The invention discloses a flexible conductive carbon nanofiber membrane and a preparation method and application thereof, wherein the preparation method of the flexible conductive carbon nanofiber membrane comprises the following steps: dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution; preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution; pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film; wherein the pore-forming agent is one or more of urea, ammonium bicarbonate and thiourea. The invention can prepare a carbon fiber film with continuous fibers (for example, the diameter can be controlled to be 200-500 nanometers, and the length is 50-80 centimeters); the prepared carbon fiber membrane has good flexibility (exemplarily, bending and kneading at any angle can be realized).
Description
Technical Field
The invention belongs to the technical field of novel carbon materials and preparation thereof, and particularly relates to a flexible conductive carbon nanofiber membrane and a preparation method and application thereof.
Background
The rapid development of the state of the art of society is often accompanied by a drastic demand for energy, and the resulting large exploitation and utilization of fossil energy has led to a rapid rise in the level of greenhouse gases, such as carbon dioxide, in the atmosphere, with consequent immeasurable losses and damage to the natural environment. Therefore, there is a high necessity for the development of clean energy, which can alleviate the problem of environmental pollution caused by the exploitation of fossil energy.
In recent years, clean energy sources such as solar energy, wind energy, tidal energy and the like have been developed greatly, but cannot be smoothly incorporated into a power grid due to intermittency and uncontrollable nature of the clean energy sources. Therefore, the energy storage system plays an essential role in stabilizing the new energy system.
Carbon fiber materials have attracted attention since their own due to their excellent mechanical properties and chemical stability; in addition, the good conductivity and the diversity of the morphology develop the application prospect in the new energy storage fields of lithium ion batteries, super capacitors, fuel cells and the like. At present, commercial carbon paper is mainly prepared by wet papermaking, namely carbon fiber slurry with proper length is uniformly dispersed, carbon fibers are adhered by a chemical adhesive, and then water filtration, drying and pressing are carried out to finally form the carbon paper; this prior method has the following drawbacks: (1) the carbon fiber has higher requirements on the size, the length is 4-6 mm, and the diameter is 8-12 microns; (2) the preparation process is complex, carbon fiber paper needs to be mixed with carbonaceous materials such as asphalt and the like to realize bonding between fibers so as to improve the strength, but the wetting process of the binder and the carbon fiber paper is complex in the process, and the process can be mastered by only a few countries at present; (3) at present, commercial carbon paper has poor bending performance and can not be bent at any angle of 90-180 degrees.
In summary, a new flexible conductive carbon nanofiber membrane, a preparation method and applications thereof are needed.
Disclosure of Invention
The invention aims to provide a flexible conductive carbon nanofiber membrane as well as a preparation method and application thereof, so as to solve one or more technical problems. The invention can prepare a carbon fiber film with continuous fibers (for example, the diameter can be controlled to be 200-500 nanometers, and the length can reach 50-80 centimeters); the prepared carbon fiber membrane has good flexibility (exemplarily, bending and kneading at any angle can be realized).
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a flexible conductive carbon nanofiber membrane, which comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is one or more of urea, ammonium bicarbonate and thiourea.
The method is further improved in that the polymer carbon source is one or more of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyethylene oxide, polystyrene and polyamide.
The method is further improved in that the molecular weight of the polyacrylonitrile is 85000-250000; the molecular weight of the polyvinylpyrrolidone is K88-96.
In a further improvement of the process of the present invention, the solvent is one or more of water, ethanol, N-dimethylformamide and dimethylsulfoxide.
The method is further improved in that the precursor solution comprises, by mass, 100 parts of a solvent, 10-16 parts of a high-molecular polymer and 1-9 parts of a pore-forming agent.
The method of the present invention is further improved in that the step of preparing and obtaining the precursor fiber film by using the electrospinning technology based on the precursor solution specifically comprises:
transferring the precursor solution into electrostatic spinning equipment, and setting the voltage of a direct-current high-voltage generator to be 10-20 kV, the distance between the fiber collecting equipment and the feeding needle is 10-20 cm, and the feeding speed is 0.5-2 mL h-1。
The method of the invention is further improved in that in the process of pre-oxidizing and carbonizing the precursor fiber film to obtain the flexible conductive carbon nanofiber film,
the heat preservation temperature of the pre-oxidation treatment is 200-300 ℃, and the heat preservation time is 0.5-2 h;
the heat preservation temperature of the carbonization treatment is 700-1000 ℃, and the heat preservation time is 1-3 h.
The flexible conductive carbon nanofiber membrane prepared by any one of the preparation methods is provided by the invention. Wherein the diameter of the carbon fiber is 200-500 nm, and the length of the fiber is 50-80 cm.
The application of the flexible conductive carbon nanofiber membrane prepared by the method is used for lithium ion batteries, supercapacitors or fuel cells.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the electrostatic spinning technology, and the fiber diameter can be controlled by regulating and controlling the components, the proportion and the concentration of the precursor solution (illustratively, the higher the concentration and the molecular weight, the larger the fiber diameter); the length and the diameter of the fiber can be controlled by adjusting electrostatic spinning parameters; during the subsequent heat treatment, crosslinking occurs between the fibers, achieving tack-free performance.
In the invention, the diameter of the carbon fiber can be controlled within 200-500 nanometers, and due to the size effect, the flexibility of the fiber with small diameter is better than that of the fiber with large diameter, so that the flexibility of the carbon fiber prepared by the preparation method disclosed by the invention is far better than that of commercial carbon fiber (8-12 micrometers); in addition, the pore-forming agent adopted by the invention is distributed in the electrostatic spinning fiber and decomposed in the subsequent heat treatment process to generate a large number of pores, and the pores can effectively release internal stress when the fiber receives stress, so that the fiber is prevented from being broken.
In the preparation method disclosed by the invention, the process is simple, the carbon fiber has uniform diameter distribution, strong continuity, low density and excellent flexibility, and the carbon fiber can be bent at any angle between 90 and 180 degrees without breaking. Compared with commercial carbon paper, the preparation method of the flexible carbon fiber film disclosed by the invention can effectively reduce the production cost, control the diameter and length of the fiber and provide a practical and feasible way for preparing the low-cost and high-performance carbon paper.
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 are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is an optical photograph of flexible carbon fibers prepared in accordance with an embodiment of the present invention;
FIG. 2 is an FE-SEM photograph of the carbon fiber membrane of the present invention, wherein the fiber is dense and has no flexibility when the pore-forming agent is not added;
FIG. 3 is a SEM photograph of a flexible conductive carbon nanofiber membrane in example 1 of the present invention, wherein the fibers have a porous structure and flexibility after a certain amount of urea is added;
FIG. 4 is a SEM photograph of a flexible conductive carbon nanofiber membrane in example 2 of the present invention;
FIG. 5 is a SEM photograph of a flexible conductive carbon nanofiber membrane in example 3 of the present invention, wherein after a certain amount of ammonium bicarbonate is added, the fibers show a porous structure and are flexible;
FIG. 6 is a SEM photograph (with porous structure) of a flexible conductive carbon nanofiber membrane in example 4 of the present invention;
fig. 7 is a schematic XRD spectrum (both amorphous carbons) of the flexible conductive carbon nanofiber films of examples 1 to 4 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the embodiment of the invention particularly provides a preparation method of a flexible conductive carbon nanofiber membrane, which comprises the steps of dissolving a pore-forming agent and a high-molecular polymer carbon source in a selected specific solvent to form a precursor solution, transferring the precursor solution to electrostatic spinning equipment, and preparing a precursor fiber membrane by regulating and controlling parameters such as voltage, flow, space and the like; and finally obtaining the flexible conductive carbon nanofiber membrane through pre-oxidation and carbonization treatment.
In the embodiment of the invention, the diameter and the density of the fiber can be flexibly controlled by regulating and controlling the molecular weight and the solution viscosity of the high molecular polymer in the precursor solution and electrostatic spinning parameters in the electrostatic spinning technology. Wherein the larger the polymer molecular weight and solution viscosity, the larger the fiber diameter. In addition, the subsequent heat treatment process can control the cross-linking among the fibers by controlling the pre-oxidation temperature and time, and control the conductivity of the carbon fibers by regulating and controlling the carbonization temperature and time. Due to good flexibility and conductivity, the carbon fiber membrane has wide application prospect in the aspects of lithium ion batteries, super capacitors, fuel cells and the like, and the preparation cost of the traditional commercial carbon paper is greatly reduced.
In the embodiment of the invention, the required precursor solution comprises the following components in parts by mass: 100 parts of solvent, 10-16 parts of high molecular polymer and 1-9 parts of pore-forming agent.
In the embodiment of the invention, the prepared precursor solution is transferred to electrostatic spinning equipment, the voltage of a direct-current high-voltage generator is set to be 10-20 kV, the distance between a fiber collecting device and a feeding needle is 10-20 cm, and the feeding speed is 0.5-2 mL h-1. And then, the precursor fiber film is subjected to preoxidation treatment in a muffle furnace and carbonization treatment in a tubular furnace to finally obtain the flexible conductive carbon nanofiber film, and the flexible conductive carbon nanofiber film is bent at any angle between 90 and 180 degrees without breaking.
In the embodiment of the present invention, the processing steps of the precursor solution specifically include:
dissolving pore-forming agent (one or more of urea, ammonium bicarbonate and thiourea) in solvent (one or more of water, ethanol, N-dimethylformamide and dimethyl sulfoxide), and stirring to dissolve completely to obtain uniform solution A. Adding a high-molecular polymer carbon source (one or more of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyethylene oxide, polystyrene and polyamide) into the solution A, and stirring at 20-80 ℃ for 8-12 h until a uniform viscous solution B is obtained.
In the embodiment of the present invention, the preparation steps of the precursor fiber film specifically include:
transferring the obtained precursor solution B into a container of electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 10-20 kV, setting the distance between a fiber collecting device and a feeding needle to be 10-20 cm, and setting the feeding speed to be 0.8-2 mL h-1Obtaining the precursor fiber on a collecting plate.
In the embodiment of the present invention, the step of heat treatment of the carbon fiber specifically includes: transferring the prepared precursor fiber to a muffle furnace for pre-oxidation treatment, and setting the temperature rise speed to be 1-10 ℃ for min-1Temperature keepingThe temperature is 200-300 ℃, and the heat preservation time is 0.5-2 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 20-40 min to exhaust the air in the tubular furnace, wherein the temperature rise speed is 1-10 ℃ for min-1And keeping the temperature at 700-1000 ℃ for 1-3 h to obtain the flexible conductive carbon nanofiber membrane.
The adhesive-free continuous carbon nanofiber membrane is prepared by an electrostatic spinning technology, the preparation process is simple, the diameter distribution of carbon fibers is uniform and can be controlled to be 200-500 nanometers, the continuity is high, the fiber length reaches dozens of centimeters (exemplarily, 50-80 cm), the density is low, and the areal density is about 1mg cm-2And has excellent flexibility, and can realize bending at any angle between 90 and 180 degrees to adapt to various shapes. Compared with commercial carbon paper, the preparation method of the flexible conductive carbon nanofiber membrane disclosed by the invention can effectively reduce the production cost, control the fiber diameter and the membrane thickness, and provide a feasible way for preparing low-cost high-performance carbon paper.
According to the flexible conductive carbon nanofiber membrane prepared by the invention, the carbon nanofiber membrane is a continuous network structure formed by stacking porous carbon nanofibers in a disordered manner, has good flexibility and can withstand repeated bending. The diameter of the carbon fiber is 200-500 nm, and the length of the carbon fiber is 50-80 cm.
According to the application of the flexible conductive carbon nanofiber membrane obtained in the embodiment of the invention, commercial carbon paper used in the new energy field of fuel cells and the like at present mainly depends on import and faces the problems of insufficient flexibility and high cost.
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
(1) adding a proper amount of pore-forming agent into the solvent, stirring and dissolving to obtain a uniform solution.
(2) And (2) adding a high molecular polymer serving as a carbon source into the uniform solution obtained in the step (1), and stirring and dissolving to obtain a precursor solution.
(3) And (3) transferring the precursor solution obtained in the step (2) to electrostatic spinning equipment, and adjusting voltage, the distance between the needle tip and the collecting equipment, the feeding speed and the air humidity to obtain the precursor fiber film.
(4) And (4) transferring the precursor fiber film obtained in the step (3) to a muffle furnace, and setting a certain heating speed and heat preservation time to obtain the pre-oxidized fiber film.
(5) And (4) transferring the pre-oxidized fiber membrane obtained in the step (4) to a tubular furnace with inert gas protection, and setting a certain temperature rise speed and heat preservation time to obtain the carbonized flexible conductive carbon nanofiber membrane.
Exemplary and preferred pore-forming agents in the step (1) are one or more of urea, ammonium bicarbonate and thiourea. The solvent in the step (1) is one or more of ethanol, N-dimethylformamide and dimethyl sulfoxide. The stirring temperature in the step (1) is room temperature. The stirring temperature in the step (2) is 30-80 ℃. The polymer in the step (2) is one or more of Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polyethylene oxide (PEO), Polystyrene (PS) and Polyimide (PI). The molecular weight of the PAN (polyacrylonitrile) in the step (2) is 85000-250000. The molecular weight of PVP (polyvinylpyrrolidone) in the step (2) is K88-96. The parameters of the electrostatic spinning equipment in the step (3) are as follows: the voltage of the direct-current high-voltage generator is 10-20 kV, the distance between the fiber collecting equipment and the feeding needle is 10-20 cm, and the feeding speed is 0.8-2 mL h-1. In the step (4), pre-oxidation treatment is carried out, and the temperature rise speed in a muffle furnace is 1-10 ℃ for min-1The heat preservation temperature is 200-300 ℃, and the heat preservation time is 0.5-2 h. Performing carbonization treatment in the step (5), and introducing inert gas into the tubular furnace in advance for 20-40 min to discharge air in the tubular furnace; setting the initial temperature to be 20-40 ℃ and the temperature rising speed to be 1-10 ℃ min-1The heat preservation temperature is 700-1000 ℃, and the heat preservation time is 1-3 h.
Example 1
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is urea; the polymer carbon source is polyacrylonitrile and polyvinylpyrrolidone; the solvent is N, N-dimethylformamide. The precursor solution comprises, by mass, 100 parts of a solvent, 13 parts of a high molecular polymer and 3 parts of a pore-forming agent. Transferring the precursor solution into electrostatic spinning equipment, and setting electrostatic spinning parameters as follows: static voltage 15kV and feeding speed 0.8mL h-1The distance between the collecting plate and the needle tip is 15 cm. After spinning is finished, tearing off the fiber membrane from the collecting plate, transferring the fiber membrane into a muffle furnace, setting the initial temperature to be 20 ℃, and the heating speed to be 3 ℃ for min-1The heat preservation temperature is 280 ℃, and the heat preservation time is 1 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 40min to exhaust air in the tube furnace, setting the initial temperature to be 20 ℃, and the heating speed to be 3 ℃ for min-1The heat preservation temperature is 850 ℃, and the heat preservation time is 3 hours. And obtaining the flexible conductive carbon nanofiber membrane.
Referring to fig. 1 to 3 and 7, the flexible carbon fiber film can be recovered after being bent, wound and kneaded for many times. The carbon fiber has a diameter of about 500nm and is rich in micropores. Specifically, fig. 1 is an optical photograph of the flexible carbon fiber prepared in the embodiment of the present invention, and after the optical photograph is arbitrarily bent, folded for multiple times, wound, and kneaded, the carbon fiber film can still return to the original shape. Compared with commercial carbon paper, the flexible performance of the paper breaks through the limitation of the application range of the commercial carbon paper, and the application route and direction are wider. Fig. 3 is a scanning electron microscope photograph of the flexible conductive carbon nanofiber membrane in example 1 of the present invention, after a certain amount of urea is added, the fibers show a porous structure and are flexible. Fig. 7 contains an XRD pattern of the flexible carbon fiber film in this example, which can be confirmed as an amorphous carbon structure.
Example 2
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is urea; the polymer carbon source is polyacrylonitrile and polyvinylpyrrolidone; the solvent is ethanol and N, N-dimethylformamide. The precursor solution comprises, by mass, 100 parts of a solvent, 14 parts of a high molecular polymer and 5 parts of a pore-forming agent. Transferring the precursor solution into electrostatic spinning equipment, and setting electrostatic spinning parameters as follows: static voltage 18kV, feeding speed 1.0mL h-1The collector plate-tip distance was 18 cm. After spinning is finished, the fiber membrane is taken off from the collecting plate, transferred to a muffle furnace, set at an initial temperature of 20 ℃ and a heating speed of 3 ℃ for min-1The heat preservation temperature is 250 ℃, and the heat preservation time is 1 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 30min to exhaust air in the tube furnace, setting the initial temperature to be 20 ℃, and the heating speed to be 3 ℃ for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 2 hours. And obtaining the flexible conductive carbon nanofiber membrane.
Referring to fig. 4, the diameter of the carbon fiber of the prepared carbon fiber membrane is about 300 nm, and a large number of micropores are distributed. Fig. 7 contains an XRD pattern of the flexible carbon fiber film in this example, which can be confirmed as an amorphous carbon structure.
Example 3
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is ammonium bicarbonate; the polymer carbon source is polyvinylpyrrolidone and polyvinyl alcohol; the solvent is water and ethanol. The precursor solution comprises, by mass, 100 parts of a solvent, 16 parts of a high molecular polymer and 6 parts of a pore-forming agent. Transferring the precursor solution into electrostatic spinning equipment, and setting electrostatic spinning parameters as follows: static voltage 18kV, feeding speed 1.2mL h-1The distance between the collecting plate and the needle tip is 17 cm. After spinning is finished, tearing off the fiber membrane from the collecting plate, transferring the fiber membrane into a muffle furnace, setting the initial temperature to be 25 ℃, and the heating speed to be 5 ℃ for min-1The heat preservation temperature is 260 ℃, and the heat preservation time is 1 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 30min to exhaust air in the tube furnace, setting the initial temperature at 25 deg.C and the heating rate at 5 deg.C for min-1The heat preservation temperature is 800 ℃, and the heat preservation time is 2 hours. And obtaining the flexible conductive carbon nanofiber membrane.
Referring to fig. 5, the diameter of the carbon fiber of the prepared carbon fiber membrane is about 200 nm. Fig. 7 contains an XRD pattern of the flexible carbon fiber film in this example, which can be confirmed as an amorphous carbon structure.
Example 4
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is ammonium bicarbonate and thiourea; the polymer carbon source is polyvinylpyrrolidone and polymethyl methacrylate; the solvent is N, N-dimethylformamide and dimethyl sulfoxide. The precursor solution comprises, by mass, 100 parts of a solvent, 13 parts of a high molecular polymer and 2 parts of a pore-forming agent. Transferring the precursor solution into electrostatic spinning equipment, and setting electrostatic spinning parameters as follows: static voltage of 20kV and feeding speed of 0.8mL h-1The distance between the collecting plate and the needle tip is 15 cm. After spinning is finished, tearing off the fiber membrane from the collecting plate, transferring the fiber membrane into a muffle furnace, setting the initial temperature to be 25 ℃, and the heating speed to be 3 ℃ for min-1The heat preservation temperature is 280 ℃, and the heat preservation time is 1.5 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 30min to exhaust air in the tube furnace, setting the initial temperature at 25 deg.C and the heating rate at 3 deg.C for min-1The heat preservation temperature is 750 ℃, and the heat preservation time is 3 hours. And obtaining the flexible conductive carbon nanofiber membrane.
Referring to fig. 6, the carbon fiber diameter of the prepared carbon fiber membrane is about 500 nm. Fig. 7 contains an XRD pattern of the flexible carbon fiber film in this example, which can be confirmed as an amorphous carbon structure.
Example 5
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is ammonium bicarbonate, thiourea and urea; what is needed isThe polymer carbon source is polyacrylonitrile, polyvinylpyrrolidone and polymethyl methacrylate; the solvent is N, N-dimethylformamide and ethanol. The precursor solution comprises, by mass, 100 parts of a solvent, 15 parts of a high molecular polymer and 6 parts of a pore-forming agent. Transferring the precursor solution into electrostatic spinning equipment, and setting electrostatic spinning parameters as follows: static voltage 18kV, feeding speed 1.2mL h-1The distance between the collecting plate and the needle tip is 15 cm. After spinning is finished, tearing off the fiber membrane from the collecting plate, transferring the fiber membrane into a muffle furnace, setting the initial temperature to be 25 ℃, and the heating speed to be 3 ℃ for min-1The heat preservation temperature is 270 ℃, and the heat preservation time is 1.0 h. Subsequently, the pre-oxidized fibers were transferred to a tube furnace equipped with an inert gas for carbonization treatment. Introducing inert gas in advance for 30min to exhaust air in the tube furnace, setting the initial temperature at 25 deg.C and the heating rate at 3 deg.C for min-1The heat preservation temperature is 900 ℃, and the heat preservation time is 3 hours. And obtaining the flexible conductive carbon nanofiber membrane.
Example 6
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein, the pore-forming agent is ammonium bicarbonate and thiourea. The polymer carbon source is polyacrylonitrile and polyvinylpyrrolidone. The molecular weight of the polyacrylonitrile is 85000; the molecular weight of the polyvinylpyrrolidone is K88. The solvent is N, N-dimethylformamide. The precursor solution comprises, by mass, 100 parts of a solvent, 10 parts of a high molecular polymer and 1 part of a pore-forming agent.
Transferring the precursor solution into electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 10kV, and enabling the fiber collecting equipment to be far away from a feeding needle10cm, feed rate 0.5mL h-1。
In the process of carrying out pre-oxidation and carbonization treatment on the precursor fiber film to prepare the flexible conductive carbon nanofiber film, the heat preservation temperature of the pre-oxidation treatment is 200 ℃, and the heat preservation time is 0.5 h; the heat preservation temperature of the carbonization treatment is 700 ℃, and the heat preservation time is 1 h.
Example 7
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is urea; the polymer carbon source is polyvinyl alcohol; the solvent is water or ethanol. The precursor solution comprises, by mass, 100 parts of a solvent, 12 parts of a high molecular polymer and 5 parts of a pore-forming agent. The step of preparing and obtaining the precursor fiber film by utilizing the electrostatic spinning technology based on the precursor solution specifically comprises the following steps: transferring the precursor solution into electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 15kV, setting the distance between a fiber collecting device and a feeding needle to be 15cm, and setting the feeding speed to be 1mL h-1. In the process of carrying out pre-oxidation and carbonization treatment on the precursor fiber film to prepare the flexible conductive carbon nanofiber film, the heat preservation temperature of the pre-oxidation treatment is 260 ℃, and the heat preservation time is 1 h; the heat preservation temperature of the carbonization treatment is 850 ℃, and the heat preservation time is 2 hours.
Example 8
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein, the pore-forming agent is urea, ammonium bicarbonate and thiourea. The polymer carbon source is polyacrylonitrile and polyvinylpyrrolidone. The molecular weight of the polyacrylonitrile is 150000; the molecular weight of the polyvinylpyrrolidone is K90. The solvent is N, N-dimethylformamide. The precursor solution comprises, by mass, 100 parts of a solvent, 16 parts of a high molecular polymer and 9 parts of a pore-forming agent. The step of preparing and obtaining the precursor fiber film by utilizing the electrostatic spinning technology based on the precursor solution specifically comprises the following steps: transferring the precursor solution into electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 20kV, setting the distance between a fiber collecting device and a feeding needle to be 20cm, and setting the feeding speed to be 2mL h-1. In the process of carrying out pre-oxidation and carbonization treatment on the precursor fiber film to prepare the flexible conductive carbon nanofiber film, the heat preservation temperature of the pre-oxidation treatment is 300 ℃, and the heat preservation time is 2 hours; the heat preservation temperature of the carbonization treatment is 1000 ℃, and the heat preservation time is 3 h.
Example 9
The preparation method of the flexible conductive carbon nanofiber membrane provided by the embodiment of the invention comprises the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is ammonium bicarbonate. The polymer carbon source is polyacrylonitrile, polyvinylpyrrolidone and polyvinyl alcohol. The molecular weight of the polyacrylonitrile is 250000; the molecular weight of the polyvinylpyrrolidone is K96. The solvent is dimethyl sulfoxide. The precursor solution comprises 100 parts of solvent by mass13 parts of high molecular polymer and 7 parts of pore-forming agent. The step of preparing and obtaining the precursor fiber film by utilizing the electrostatic spinning technology based on the precursor solution specifically comprises the following steps: transferring the precursor solution into electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 18kV, setting the distance between a fiber collecting device and a feeding needle to be 15cm, and setting the feeding speed to be 1.5mL h-1. In the process of carrying out pre-oxidation and carbonization treatment on the precursor fiber film to prepare the flexible conductive carbon nanofiber film, the heat preservation temperature of the pre-oxidation treatment is 280 ℃, and the heat preservation time is 1.5 h; the heat preservation temperature of the carbonization treatment is 900 ℃, and the heat preservation time is 2.5 h.
The embodiment of the invention discloses a preparation method of a flexible conductive carbon fiber film. The preparation method of the flexible conductive carbon fiber membrane comprises the following steps: the pore-forming agent (one or more of urea, ammonium bicarbonate and thiourea) is dissolved in DMF to form a uniform solution, and then high molecular polymer (polyacrylonitrile, polyvinylpyrrolidone and the like) is added into the solution and stirred until the solution is completely dissolved. Transferring the fiber membrane into an electrostatic spinning device, and obtaining the fiber membrane with uniform diameter through electrostatic spinning. Stabilizing the fiber membrane at 280 ℃ in air atmosphere to obtain a pre-oxidized fiber membrane; and transferring the pre-oxidized fiber membrane to a tubular furnace with inert gas protection, and carrying out carbonization treatment at 800 ℃. Finally obtaining the flexible conductive carbon fiber film. The flexible conductive carbon fiber film prepared by the invention has good flexibility and conductivity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A preparation method of a flexible conductive carbon nanofiber membrane is characterized by comprising the following steps:
dissolving a pore-forming agent and a polymer carbon source in a preselected solvent to obtain a precursor solution;
preparing a precursor fiber film by utilizing an electrostatic spinning technology based on the precursor solution;
pre-oxidizing and carbonizing the precursor fiber film to prepare a flexible conductive carbon nanofiber film;
wherein the pore-forming agent is one or more of urea, ammonium bicarbonate and thiourea.
2. The method for preparing the flexible conductive carbon nanofiber membrane as claimed in claim 1, wherein the polymer carbon source is one or more of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyethylene oxide, polystyrene and polyamide.
3. The preparation method of the flexible conductive carbon nanofiber membrane as claimed in claim 2, wherein the molecular weight of polyacrylonitrile is 85000-250000; the molecular weight of the polyvinylpyrrolidone is K88-96.
4. The method for preparing the flexible conductive carbon nanofiber membrane as claimed in claim 1, wherein the solvent is one or more of water, ethanol, N-dimethylformamide and dimethyl sulfoxide.
5. The method for preparing the flexible conductive carbon nanofiber membrane as claimed in claim 1, wherein the precursor solution comprises, by mass, 100 parts of a solvent, 10-16 parts of a high molecular polymer, and 1-9 parts of a pore-forming agent.
6. The method for preparing a flexible conductive carbon nanofiber membrane as claimed in claim 1, wherein the step of preparing a precursor fiber membrane by using an electrospinning technique based on the precursor solution specifically comprises:
transferring the precursor solution into electrostatic spinning equipment, setting the voltage of a direct-current high-voltage generator to be 10-20 kV, setting the distance between a fiber collecting device and a feeding needle to be 10-20 cm, and setting the feeding speed to be 0.5-2 mL h-1。
7. The method for preparing a flexible conductive carbon nanofiber membrane as claimed in claim 1, wherein in the process of pre-oxidizing and carbonizing the precursor fiber membrane to obtain the flexible conductive carbon nanofiber membrane,
the heat preservation temperature of the pre-oxidation treatment is 200-300 ℃, and the heat preservation time is 0.5-2 h;
the heat preservation temperature of the carbonization treatment is 700-1000 ℃, and the heat preservation time is 1-3 h.
8. A flexible conductive carbon nanofiber membrane prepared by the preparation method as set forth in any one of claims 1 to 7.
9. The flexible conductive carbon nanofiber membrane as claimed in claim 8, wherein the diameter of the carbon fiber is 200 to 500nm, and the length of the fiber is 50 to 80 cm.
10. Use of the flexible conductive carbon nanofiber membrane of claim 8 in a lithium ion battery, a supercapacitor or a fuel cell.
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