CN111180727A - Preparation method and application of flexible compact carbon nanofiber membrane - Google Patents

Preparation method and application of flexible compact carbon nanofiber membrane Download PDF

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CN111180727A
CN111180727A CN202010096294.8A CN202010096294A CN111180727A CN 111180727 A CN111180727 A CN 111180727A CN 202010096294 A CN202010096294 A CN 202010096294A CN 111180727 A CN111180727 A CN 111180727A
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nanofiber membrane
flexible
temperature
carbon nanofiber
carbon
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闫建华
蔡伟萍
雷灿
赖毅梅
王先锋
贾永堂
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Wuyi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to the technical field of carbon fiber membranes, and relates to a preparation method and application of a flexible compact carbon nano carbon fiber membrane. Firstly, sequentially dissolving two polymers in a solvent and uniformly mixing to prepare a precursor solution, wherein the precursor solution has interpenetrating and staggered long molecular chains; then preparing the precursor solution into a precursor fiber film by an electrostatic spinning technology; pre-oxidizing the precursor fiber membrane in an air atmosphere to weld the blend in situ to obtain a stabilized nanofiber membrane; and then carbonizing the stabilized nanofiber membrane in an inert gas atmosphere to obtain the in-situ welding flexible compact carbon nanofiber membrane. According to the invention, the structural effect of in-situ welding is formed through the melting point difference of the polymer, the obtained flexible compact carbon nanofiber membrane increases the density of the flexible carbon nanofiber membrane, realizes more energy storage, and solves the defect of poor energy storage effect of the carbon nanofiber electrode material in the prior art.

Description

Preparation method and application of flexible compact carbon nanofiber membrane
Technical Field
The invention relates to the technical field of carbon fiber membranes, in particular to a preparation method and application of a flexible compact carbon nanofiber membrane.
Background
The carbon nanofiber is used as an electrode material with high strength, low density, good electrical conductivity, thermal conductivity and form diversity, and has wide application prospects in the energy fields of lithium ion batteries, sodium ion batteries, super capacitors and the like. Carbon electrodes commercialized for many years have become the most promising electrode material with abundant porosity, large specific surface area and low cost. At present, the methods for preparing the carbon nano-fiber mainly comprise an electrostatic spinning method, a template method, a chemical vapor deposition method and the like. The electrostatic spinning method is a simple and feasible method, can be used for preparing continuous CNF films with various appearances, and has a wide application prospect. However, the low packing density of the prepared carbon nanofiber electrode material results in low energy stored in the carbon electrode. On the other hand, low packing density leads to large corresponding energy storage devices, which is a great obstacle to their practical use in situations where high energy density is required. In practice, the method is mainly used for eliminating the internal gaps of the carbon electrode material by a mechanical compression method so as to increase the density, is simple and is more in use, but can cause the defects of collapse of the internal pore structure of the carbon electrode, reduction of the available specific surface area, blockage of a transmission path and the like, and seriously influences the energy storage effect, thereby limiting the practical application of the carbon electrode. Thus, low cost densification provides a practical approach to improving electrode capacity performance.
Disclosure of Invention
In view of the above, the invention provides a preparation method and an application of a flexible compact carbon nanofiber membrane, so as to solve the defect of poor energy storage effect of a carbon nanofiber electrode material in the prior art.
The invention discloses a preparation method of a flexible compact carbon nanofiber membrane, which comprises the following steps:
s1, dissolving two same polymers with different molecular weights and a carbon source in a solvent, stirring for a period of time, and uniformly mixing to prepare a uniform and stable precursor solution; in this step, due to the molecular weight difference between the two polymers, a small amount of relatively small molecular weight polymer is distributed on the carbon source melt chain in the precursor spinning solution, while the majority of the higher molecular weight polymer is predominant in the carbon source melt chain. For pre-oxidation in an air atmosphere, the carbon source polymer is usually converted into pre-cyclization to start forming a doped carbon cycle structure, while low molecular weight polymer molecules (part on the carbon source chain) are prepared for in-situ welding between nanofibers, etc.; in the present invention, two different molecular weights of the same polymer and carbon source may refer to two different molecular weights of the same carbon source. The carbon source is a polymer and is used herein with two different molecular weight polymers of the same kind to distinguish the polymer that forms the weld structure from the primary carbon forming source. For example, we use PAN (carbon source) and PVB (with two different molecular weights of 170000-250000) as raw materials, PAN will form the main carbon structure; due to the difference between PAN and PVB thermal properties, polymer decomposition at different temperatures can result; PVB with low molecular weight is mainly dispersed on the surface of the dissolved PAN, and is pyrolyzed in the pre-oxidation process to finally form an in-situ welding structure among fibers; the remaining high molecular weight PVB disperses within the PAN chains and pyrolizes during carbonization, providing amorphous carbon in the graphitized carbon layer, forming interstitial regions.
S2, preparing a precursor fiber film from the precursor solution by an electrostatic spinning technology; in the step, under the action of an electric field, charged liquid drops overcome surface tension, are stretched and refined in air to form fibers, and are finally deposited on a receiving substrate to obtain a precursor fiber film, wherein the prepared precursor fiber has the characteristics of small fiber diameter, good continuity and the like;
s3, pre-oxidizing the precursor fiber membrane in an air atmosphere to obtain a nanofiber membrane; in the step, high temperature enables partial polymers on the carbon chain to be subjected to in-situ welding among fibers, so that the nano structure provides high filling density;
and S4, carbonizing the stabilized nanofiber membrane in an inert gas atmosphere to obtain the flexible compact carbon nanofiber membrane. In this step, the remaining polymer acts as an amorphous carbon interlayer in the gap of the graphitized layer generated by the decomposition of the carbon source polymer.
As a preferred embodiment of the present invention, the specific process of step S1 is: s11, respectively measuring the polymer and the carbon source according to the molar ratio of the polymer to the carbon source of 5-50: 100; s12, measuring a solvent according to the mass ratio of the total mass of the polymer and the carbon source to the mass of the solvent of 1: 5-15; and S13, respectively dissolving the polymer and the carbon source in the solvent, and stirring for 30-120min to obtain a precursor solution.
As a preferable embodiment of the present invention, the carbon source is at least one of polyacrylonitrile, polyvinyl alcohol, cellulose, polyacrylonitrile, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polystyrene, polyvinyl acetate, polymethyl methacrylate, or polyethylene glycol acrylate; the solvent is at least one of water, ethanol, glycol, acetic acid or N, N-dimethylformamide.
As a preferred embodiment of the present invention, the specific process of step S2 is: under the conditions of 0-100 ℃ and 35-70% of relative humidity, the precursor solution is input to a spinneret of electrostatic spinning equipment at the flow rate of 0.1-10mL/h, a direct-current high-voltage power supply of 10-35kV is applied to a spinning section of the spinning equipment for electrostatic spinning, and the distance between a receiving device and the spinneret is 5-35 cm.
As a preferred embodiment of the present invention, the specific process of step S3 is: calcining the precursor fiber membrane in air atmosphere, gradually increasing the calcining temperature from room temperature of 25 ℃ to 100-300 ℃, increasing the temperature at a speed of 1-10 ℃/min, and keeping the calcining temperature at the highest temperature for 20-240 min.
As a preferred embodiment of the present invention, the specific process of step S4 is: carbonizing the stabilized nanofiber membrane in a nitrogen atmosphere, gradually raising the temperature from room temperature of 25 ℃ to 500-1000 ℃, wherein the temperature raising speed is 0.5-10 ℃/min, the nitrogen flow rate is 10-350mL/min, and keeping the highest carbonization temperature for 20-360 min.
In a preferred embodiment of the present invention, the average fiber diameter of the flexible dense carbon nanofiber membrane is 20 to 500 nm.
As a preferable scheme of the invention, the density of the flexible dense carbon nanofiber membrane is 5-100gm/cm3。
The application of the flexible compact carbon nano carbon fiber membrane obtained by the preparation method in the field of battery energy is disclosed.
A flexible dense carbon nanofiber membrane is prepared according to the preparation method.
According to the technical scheme, the invention has the beneficial effects that:
firstly, two polymers are sequentially dissolved in a solvent and uniformly mixed to prepare a uniform and stable precursor solution, wherein the precursor solution has interpenetrating and staggered long molecular chains; then preparing the precursor solution into a precursor fiber film by an electrostatic spinning technology; pre-oxidizing the precursor fiber membrane in an air atmosphere to weld the blend in situ to obtain a stabilized nanofiber membrane; and then carbonizing the stabilized nanofiber membrane in an inert gas atmosphere, decomposing the micromolecule polymer component at high temperature and retaining the component, wherein the inorganic component is used as a main body in the fiber, so that the complete skeleton structure of the single fiber cannot be damaged due to the destabilization decomposition of a large amount of organic components in the calcining process, and the finally obtained in-situ welding flexible compact carbon nanofiber membrane has good flexibility, thereby obtaining the in-situ welding flexible compact carbon nanofiber membrane. According to the invention, the structural effect of in-situ welding is formed through the melting point difference of the polymer, and the obtained in-situ welding densified flexible compact carbon nanofiber membrane greatly increases the compactness of the flexible carbon nanofiber membrane, can realize more energy storage, and solves the defect of poor energy storage effect of carbon nanofiber electrode materials in the prior art.
Drawings
FIG. 1 is a graph showing the results of the test in test example 1.
Detailed Description
The following examples are intended to illustrate the invention in further detail, but are not intended to limit the invention in any way, and unless otherwise indicated, the reagents, methods and apparatus used in the invention are conventional in the art, and are not intended to limit the invention in any way.
Example 1
A preparation method of a flexible compact carbon nanofiber membrane comprises the following specific steps:
the first step is as follows: sequentially dissolving two polyvinyl butyral and polyacrylonitrile with different molecular weights in an N, N-dimethylformamide solvent, and stirring for 30min to prepare a precursor spinning solution which is uniformly mixed. Wherein the mass ratio of the two polyvinyl butyral polymers with different molecular weights to the polyacrylonitrile is 1:9, and the ratio of the carbon source to the polymer to the solvent is 10g:100 g; uniformly mixing to prepare uniform and stable precursor solution;
the second step is that: preparing the precursor solution into a precursor fiber film by an electrostatic spinning method; electrostatic spinning parameters: the spinning temperature is 25 ℃, the relative humidity is 45%, the perfusion speed is 1mL/h, the receiving distance is 15cm, and the spinning voltage is 15 kV;
the third step: and pre-oxidizing the precursor fiber membrane in an air atmosphere, wherein the pre-oxidizing is to gradually increase the calcining temperature from room temperature to 280 ℃, increase the temperature at a speed of 2 ℃/min, keep the temperature at the highest calcining temperature for 120min, and then naturally cool the temperature to obtain the pre-oxidized nano fiber membrane.
The fourth step: and carbonizing the pre-oxidized nano-fiber membrane in a nitrogen gas atmosphere, wherein the calcining refers to gradually increasing the calcining temperature from room temperature to 800 ℃, the heating speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, keeping the temperature at the highest calcining temperature for 120min, and naturally cooling to obtain the flexible compact carbon nano-fiber membrane.
Example 2
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of embodiment 1 in that in step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 900 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 3
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of embodiment 1 in that in step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 1000 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 4
A preparation method of a flexible compact carbon nanofiber membrane comprises the following specific steps:
the first step is as follows: sequentially dissolving two polyvinyl butyral and polyacrylonitrile with different molecular weights in an N, N-dimethylformamide solvent, and stirring for 30min to prepare a precursor spinning solution which is uniformly mixed. Wherein the mass ratio of the two polyvinyl butyral polymers with different molecular weights to the polyacrylonitrile is 2:8, and the ratio of the carbon source to the polymer to the solvent is 10g:100 g; uniformly mixing to prepare uniform and stable precursor solution;
the second step is that: preparing the precursor solution into a precursor fiber film by an electrostatic spinning method; electrostatic spinning parameters: the spinning temperature is 25 ℃, the relative humidity is 45%, the perfusion speed is 1mL/h, the receiving distance is 15cm, and the spinning voltage is 15 kV;
the third step: and pre-oxidizing the precursor fiber membrane in an air atmosphere, wherein the pre-oxidizing is to gradually increase the calcining temperature from room temperature to 280 ℃, increase the temperature at a speed of 2 ℃/min, keep the temperature at the highest calcining temperature for 120min, and then naturally cool the temperature to obtain the pre-oxidized nano fiber membrane.
The fourth step: and carbonizing the pre-oxidized nano-fiber membrane in an inert gas atmosphere, wherein the calcining refers to gradually raising the calcining temperature from room temperature to 1000 ℃, raising the temperature at 2 ℃/min and keeping the nitrogen flow rate at 200mL/min for 120min at the highest calcining temperature, and naturally cooling to obtain the flexible compact carbon nano-fiber membrane.
Example 5
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of the embodiment 3 in that in the step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 900 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 6
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of the embodiment 3 in that in the step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 1000 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 7
A preparation method of a flexible compact carbon nanofiber membrane comprises the following specific steps:
the first step is as follows: sequentially dissolving two polyvinyl butyral and polyacrylonitrile with different molecular weights in an N, N-dimethylformamide solvent, and stirring for 30min to prepare a precursor spinning solution which is uniformly mixed. Wherein the mass ratio of the two polyvinyl butyral polymers with different molecular weights to the polyacrylonitrile is 3:7, and the ratio of the carbon source to the polymer to the solvent is 10g:100 g; uniformly mixing to prepare uniform and stable precursor solution;
the second step is that: preparing the precursor solution into a precursor fiber film by an electrostatic spinning method; electrostatic spinning parameters: the spinning temperature is 25 ℃, the relative humidity is 45%, the perfusion speed is 1mL/h, the receiving distance is 15cm, and the spinning voltage is 15 kV;
the third step: and pre-oxidizing the precursor fiber membrane in an air atmosphere, wherein the pre-oxidizing is to gradually increase the calcining temperature from room temperature to 280 ℃, increase the temperature at a speed of 2 ℃/min, keep the temperature at the highest calcining temperature for 120min, and then naturally cool the temperature to obtain the pre-oxidized nano fiber membrane.
The fourth step: and carbonizing the pre-oxidized nano-fiber membrane in an inert gas atmosphere, wherein the calcining refers to gradually raising the calcining temperature from room temperature to 800 ℃, raising the temperature at 2 ℃/min and keeping the nitrogen flow rate at 200mL/min for 120min at the highest calcining temperature, and naturally cooling to obtain the flexible compact carbon nano-fiber membrane.
Example 8
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of the embodiment 7 in that in the step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 900 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 9
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of the embodiment 7 in that in the step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 1000 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 10
A preparation method of a flexible compact carbon nanofiber membrane comprises the following specific steps:
the first step is as follows: sequentially dissolving two polyvinyl butyral and polyacrylonitrile with different molecular weights in an N, N-dimethylformamide solvent, and stirring for 30min to prepare a precursor spinning solution which is uniformly mixed. Wherein the mass ratio of the two polyvinyl butyral polymers with different molecular weights to the polyacrylonitrile is 4:6, and the ratio of the carbon source to the polymer to the solvent is 10g:100 g; uniformly mixing to prepare uniform and stable precursor solution;
the second step is that: preparing the precursor solution into a precursor fiber film by an electrostatic spinning method; electrostatic spinning parameters: the spinning temperature is 25 ℃, the relative humidity is 45%, the perfusion speed is 1mL/h, the receiving distance is 15cm, and the spinning voltage is 15 kV;
the third step: and pre-oxidizing the precursor fiber membrane in an air atmosphere, wherein the pre-oxidizing is to gradually increase the calcining temperature from room temperature to 280 ℃, increase the temperature at a speed of 2 ℃/min, keep the temperature at the highest calcining temperature for 120min, and then naturally cool the temperature to obtain the pre-oxidized nano fiber membrane.
The fourth step: and carbonizing the pre-oxidized nano-fiber membrane in an inert gas atmosphere, wherein the calcining refers to gradually raising the calcining temperature from room temperature to 800 ℃, raising the temperature at 2 ℃/min and keeping the nitrogen flow rate at 200mL/min for 120min at the highest calcining temperature, and naturally cooling to obtain the flexible compact carbon nano-fiber membrane.
Example 11
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of the embodiment 10 in that in the step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 900 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Example 12
The embodiment provides a preparation method of a flexible compact carbon nanofiber membrane, which is different from the preparation method of embodiment 1 in that in step (4), carbonization is performed in a nitrogen gas atmosphere, and calcination refers to gradually increasing the calcination temperature from room temperature to 1000 ℃, the temperature increase speed is 2 ℃/min, the nitrogen flow rate is 200mL/min, and the flexible compact carbon nanofiber membrane is kept at the highest calcination temperature for 120min and then naturally cooled.
Test example 1
The flexible dense carbon nanofiber membranes prepared in examples 4 and 7 were subjected to SEM and TEM tests, respectively. The results are shown in fig. 1, in which fig. 1 (1) -1 (3) are SEM and TEM spectra of the flexible dense carbon nanofiber membrane provided in example 4; fig. 1 (4) -fig. 1 (6) are SEM and TEM spectra of the flexible dense carbon nanofiber membrane provided in example 7; as can be seen from fig. 1, the degree of fiber welding adhesion in the obtained flexible dense carbon nanofiber membrane increases with the increase and decrease of the amount of polyvinyl butyral.
Test example 2
The flexible and compact carbon nanofibers welded in situ as provided in examples 1 to 12 were subjected to average diameter, softness and electronic conductivity tests, and density calculation, respectively, wherein the softness was measured by using a softness tester, and the electronic conductivity was measured by using a four-probe method, and the results are shown in table 1.
TABLE 1 data table of in-situ welded flexible compact nano carbon fiber performance
Average diameter (nm) Softness (mN) Compactness (gm/cm)3）
Example 1 223 12.3 0.242
Example 2 219 14.2 0.245
Example 3 218 16.5 0.243
Example 4 216 10.75 0.343
Example 5 211 13.5 0.313
Example 6 210 15 0.314
Example 7 205 18.5 0.389
Example 8 204 21 0.389
Example 9 200 25 0.387
Example 10 186 20 0.391
Practice ofExample 11 186 23 0.392
Example 12 184 27 0.391
As can be seen from Table 1, the in-situ welded flexible compact nano carbon fibers provided by examples 1 to 12 have an average diameter of 180 to 230nm and a softness of 10 to 30mN, which indicates that the in-situ welded flexible compact nano carbon fibers provided by the present invention have a nano size, a good softness and a fiber film density of 0.2 to 0.4 gm/cm3The tightness of the fiber membrane can be greatly increased.
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 can be 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 (10)

1. A preparation method of a flexible compact carbon nanofiber membrane is characterized by comprising the following steps:
s1, dissolving two same polymers with different molecular weights and a carbon source in a solvent, stirring for a period of time, and uniformly mixing to prepare a uniform and stable precursor solution;
s2, preparing a precursor fiber film from the precursor solution by an electrostatic spinning technology;
s3, pre-oxidizing the precursor fiber membrane in an air atmosphere to obtain a nanofiber membrane;
and S4, carbonizing the stabilized nanofiber membrane in an inert gas atmosphere to obtain the flexible compact carbon nanofiber membrane.
2. The method for preparing a flexible dense carbon nanofiber membrane as claimed in claim 1, wherein the specific process of step S1 is as follows:
s11, respectively measuring the polymer and the carbon source according to the molar ratio of the polymer to the carbon source of 5-50: 100;
s12, measuring a solvent according to the mass ratio of the total mass of the polymer and the carbon source to the mass of the solvent of 1: 5-15;
and S13, respectively dissolving the polymer and the carbon source in the solvent, and stirring for 30-120min to obtain a precursor solution.
3. The method for preparing the flexible dense carbon nanofiber membrane as claimed in claim 2, wherein the carbon source is at least one of polyacrylonitrile, polyvinyl alcohol, cellulose, polyacrylonitrile, polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polystyrene, polyvinyl acetate, polymethyl methacrylate or polyethylene glycol acrylate; the solvent is at least one of water, ethanol, glycol, acetic acid or N, N-dimethylformamide.
4. The method for preparing a flexible dense carbon nanofiber membrane as claimed in claim 1, wherein the specific process of step S2 is as follows: under the conditions of 0-100 ℃ and 35-70% of relative humidity, the precursor solution is input to a spinneret of electrostatic spinning equipment at the flow rate of 0.1-10mL/h, a direct-current high-voltage power supply of 10-35kV is applied to a spinning section of the spinning equipment for electrostatic spinning, and the distance between a receiving device and the spinneret is 5-35 cm.
5. The method for preparing a flexible dense carbon nanofiber membrane as claimed in claim 1, wherein the specific process of step S3 is as follows: calcining the precursor fiber membrane in air atmosphere, gradually increasing the calcining temperature from room temperature of 25 ℃ to 100-300 ℃, increasing the temperature at a speed of 1-10 ℃/min, and keeping the calcining temperature at the highest temperature for 20-240 min.
6. The method for preparing a flexible dense carbon nanofiber membrane as claimed in claim 1, wherein the specific process of step S4 is as follows: carbonizing the stabilized nanofiber membrane in a nitrogen atmosphere, gradually raising the temperature from room temperature of 25 ℃ to 500-1000 ℃, wherein the temperature raising speed is 0.5-10 ℃/min, the nitrogen flow rate is 10-350mL/min, and keeping the highest carbonization temperature for 20-360 min.
7. The method for preparing a flexible dense carbon nanofiber membrane as claimed in any one of claims 1 to 6, wherein the average fiber diameter of the flexible dense carbon nanofiber membrane is 20 to 500 nm.
8. The method for preparing a flexible dense carbon nanofiber membrane as claimed in any one of claims 1 to 7, wherein the density of the flexible dense carbon nanofiber membrane is 5-100gm/cm3。
9. The application of the flexible compact carbon nano carbon fiber membrane prepared by the preparation method according to any one of claims 1 to 6 in the field of battery energy.
10. A flexible dense carbon filamentous nanocarbon film, which is produced by the production method according to any one of claims 1 to 8.
CN202010096294.8A 2020-02-17 2020-02-17 Preparation method and application of flexible compact carbon nanofiber membrane Pending CN111180727A (en)

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CN112030353A (en) * 2020-07-30 2020-12-04 东华大学 High-strength carbon nanofiber membrane and preparation method thereof
CN112359443A (en) * 2020-11-16 2021-02-12 绿纳科技有限责任公司 Preparation method of continuous carbon nanofiber bundle and preparation method of continuous carbon nanofiber cloth
CN114351357A (en) * 2022-01-12 2022-04-15 大连民族大学 Flexible bactericidal nanofiber membrane and preparation method and application thereof

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CN112030353A (en) * 2020-07-30 2020-12-04 东华大学 High-strength carbon nanofiber membrane and preparation method thereof
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CN112359443A (en) * 2020-11-16 2021-02-12 绿纳科技有限责任公司 Preparation method of continuous carbon nanofiber bundle and preparation method of continuous carbon nanofiber cloth
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