CN111394833B - Carbon nano tube/graphene composite fiber and preparation method thereof - Google Patents
Carbon nano tube/graphene composite fiber and preparation method thereof Download PDFInfo
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- CN111394833B CN111394833B CN202010454498.4A CN202010454498A CN111394833B CN 111394833 B CN111394833 B CN 111394833B CN 202010454498 A CN202010454498 A CN 202010454498A CN 111394833 B CN111394833 B CN 111394833B
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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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- 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 provides a carbon nano tube/graphene composite fiber and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a spinning solution from a carbon nano tube with an oxygen-containing functional group and graphene in a solution phase; injecting the spinning solution into a coagulating bath through a wet spinning process to form gel fibers; and carrying out post-treatment on the gel fiber to obtain the carbon nano tube/graphene composite fiber. The carbon nanotube/graphene composite fiber prepared by the invention has a compact structure, excellent flexibility, good electric conductivity and thermal conductivity, can stably exist at high temperature, and has wide application prospects in the fields of intelligent wearing, electromagnetic shielding, energy storage and conversion and the like.
Description
Technical Field
The invention relates to the field of graphene materials, in particular to a carbon nano tube/graphene composite fiber and a preparation method thereof.
Background
The graphene fiber is easy to combine with the existing textile technology by virtue of the characteristics of excellent electric conduction, heat conduction, light weight, high mechanical strength and the like in one-dimensional direction, and has wide application prospect in the fields of intelligent fabrics, wearable devices and the like.
In the wet spinning process, as structural elements constituting graphene fibers, graphene sheets generally need to be configured into a liquid crystal phase, and the graphene is promoted to be aligned in the axial direction through a series of complicated processing steps such as pipeline bundling and stretching, so as to ensure that the graphene can better exert the intrinsic characteristics in the one-dimensional direction. A small amount of carbon nanotubes are added in the spinning process, and the graphene sheet layers are easy to be oriented and arranged in the axial direction under the induction of the carbon nanotubes; meanwhile, the added carbon nanotubes are lapped between the graphene sheet layers, so that the contact resistance between the graphene sheet layers can be further reduced.
At present, methods for preparing carbon nanotube/graphene composite fibers include two methods, i.e., in-situ growth of carbon nanotubes on the surface of prepared graphene and hybrid spinning of graphene and carbon nanotubes. CN110158308A discloses that after preparing graphene fiber by wet spinning, catalytic ions in a coagulating bath are used to catalyze the growth of carbon nanotubes on the surface of the fiber, but the orientation degree of graphene sheets of the composite fiber prepared by this method is limited during the spinning process, and the intrinsic performance of the fiber is improved to a limited extent when the carbon nanotubes exist on the surface of the fiber. CN107119346A discloses mixing graphene and carbon nanotubes and spinning to prepare carbon nanotube/graphene fiber, but due to poor water solubility of graphene and carbon nanotubes, the dispersibility of graphene and carbon nanotubes in an aqueous solution is affected, resulting in poor uniformity of the prepared spinning solution, and more surfactant or strong acid needs to be added to stabilize the dispersion solution, which affects the performance of the fiber. CN104036971A discloses blending graphene oxide and carboxylated carbon nanotubes, and reducing the prepared fiber to obtain carbon nanotube/graphene fiber, but because there are more oxidized groups on the surfaces of the graphene oxide and carboxylated carbon nanotubes, the reduction process requires more severe conditions, which results in higher reduction cost and difficulty in completely reducing the oxidized defects on the surface of the fiber.
Therefore, the development of the nano carbon material composite fiber with simple steps, low cost and good performance is an important research hotspot
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a method for preparing carbon nanotube/graphene composite fibers, which has the advantages of simple steps, low cost and good performance.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of a carbon nanotube/graphene composite fiber comprises the following steps:
mixing a carbon nano tube with an oxygen-containing functional group and graphene in a solution phase to prepare a spinning solution;
injecting the spinning solution into a coagulating bath through a wet spinning process to form gel fibers; and
and carrying out post-treatment on the gel fiber to obtain the gel fiber.
In some embodiments, the carbon nanotubes with oxygen-containing functional groups are selected from one or more of hydroxylated carbon nanotubes, carboxylated carbon nanotubes and sulfonated carbon nanotubes, and the graphene is selected from one or more of graphene powder obtained by liquid phase exfoliation, reduced graphene oxide, graphene thin film prepared by chemical vapor deposition, graphene powder and vertical graphene array.
In some embodiments, the mass ratio of the carbon nanotubes having oxygen-containing functional groups to the graphene is 1:1 to 1: 100.
In some embodiments, the method further comprises adding 0.1-10% by mass of one or more of chlorosulfonic acid, oleum, or hyaluronic acid to the solution phase.
In some embodiments, the wet spinning process has a spinning rate of 1-100cm/min, a spinneret diameter of 10-1000 μm, and a coagulation bath selected from CaCl 2 Aqueous solution of (3), aqueous solution of KOH, CaCl 2 Ethanol solution of KOH, one or more of acetone, ethyl acetate, chloroform and petroleum ether.
In some embodiments, the post-treatment is selected from one or more of water washing, hot stretching, drawing, reducing, coating a polymer layer.
In some embodiments, the reduction is selected from one of chemical reduction, electrochemical reduction, high temperature reduction.
In some embodiments, the reducing agent in the chemical reduction is selected from hydrogen iodide, NaBH 4 、LiAlH 4 And hydrazine hydrate.
On the other hand, the invention also provides a carbon nano tube/graphene composite fiber which is prepared according to the preparation method.
The carbon nanotube/graphene composite fiber prepared by the invention has a compact structure, excellent flexibility, good electric conductivity and thermal conductivity, can stably exist at high temperature, and has wide application prospects in the fields of intelligent wearing, electromagnetic shielding, energy storage and conversion and the like.
Drawings
FIG. 1A is a scanning electron microscope image of the composite fiber of example 1.
Fig. 1B is a raman spectrum of the composite fiber in example 1.
FIG. 1C is the thermogravimetric curve of the composite fiber in example 1 under a nitrogen atmosphere.
Fig. 2A is a scanning electron microscope image of the composite fiber of example 2.
Fig. 2B is a raman spectrum of the composite fiber in example 2.
Fig. 3A is a scanning electron microscope image of the composite fiber of example 3.
Fig. 3B is a raman spectrum of the composite fiber of example 3.
Fig. 4 is a raman spectrum of the graphene fiber in comparative example 1.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or a synonym thereof, directed to a material, substance, method, step, device, or component, the subject matter from which the heading is derived encompasses those conventionally used in the art as presented in the present application, but also includes those not currently in use, but which would become known in the art to be suitable for a similar purpose.
In the context of this specification, anything or things not mentioned applies directly to something known in the art without any changes, except where explicitly stated. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Unless otherwise explicitly indicated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless not otherwise generally recognized by those of skill in the art.
Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
According to a first aspect of the present invention, there is provided a method for preparing a carbon nanotube/graphene composite fiber, comprising:
mixing a carbon nano tube with an oxygen-containing functional group and graphene in a solution phase to prepare a spinning solution;
injecting the spinning solution into a coagulating bath by a wet spinning process to form gel fibers; and
and carrying out post-treatment on the gel fiber to obtain the carbon nano tube/graphene composite fiber.
In the preparation method, two carbon nano materials (carbon nano tubes and graphene) are uniformly dispersed to prepare the spinning solution, wherein the used carbon nano tubes have oxygen-containing functional groups and can be specifically selected from one or more of hydroxylated carbon nano tubes, carboxylated carbon nano tubes and sulfonated carbon nano tubes, and the used graphene does not contain the oxygen-containing functional groups and can be selected from one or more of graphene powder obtained by liquid phase stripping, reduced graphene oxide, a graphene film prepared by chemical vapor deposition, graphene powder prepared by chemical vapor deposition and a vertical graphene array prepared by chemical vapor deposition.
The mass ratio of the carbon nanotubes with oxygen-containing functional groups to the graphene is 1:1-1:100, that is, the amount of the added graphene is generally more than that of the carbon nanotubes with oxygen-containing functional groups, and the mass ratio of the carbon nanotubes with oxygen-containing functional groups to the graphene is preferably 1:5-1: 50.
The carbon nano tube and the graphene are added into the solution phase to be mixed, preferably added into the aqueous solution to be mixed, and meanwhile, an acid solution with the mass fraction of 0.1-10% can be added into the aqueous solution, and the acid solution can be selected from one or more of chlorosulfonic acid, fuming sulfuric acid and hyaluronic acid, so that the pH value of the spinning solution can be adjusted, and the dispersion of the two carbon nano materials is promoted.
The wet spinning process is one of the main chemical fiber methods, and its specific steps are that the prepared spinning solution is extruded into coagulating bath at a certain speed by an injection pump with needle head, the solvent in the spinning solution trickle is diffused into the coagulating bath, the coagulating agent is permeated into the trickle, so that the stock solution trickle reaches critical concentration, and is separated out in the coagulating bath to form the fiber.
The preparation method of the invention is to convert the spinning solution into the composite fiber by a wet spinning process, wherein the spinning speed in the wet spinning process is 1-100cm/min, the diameter of the spinning head is 10-1000 μm, and the coagulation bath is selected from CaCl 2 Aqueous solution of (3), aqueous solution of KOH, CaCl 2 Ethanol solution of KOH, one or more of acetone, ethyl acetate, chloroform and petroleum ether.
After the gel fiber is obtained, the gel fiber can be further subjected to post-treatment, and the post-treatment can be, for example, steps of water washing, hot stretching, drawing, reduction treatment, coating of a polymer layer and the like, wherein the purpose of the water washing is to remove ions remained in the fiber; the orientation of the structural elements of the carbon nano material can be promoted by hot stretching and traction; the coating polymer can further improve the mechanical properties of the fiber.
The sequence of the post-treatment steps can be adjusted as required, i.e. the steps of washing, hot stretching, drawing, coating a polymer layer, etc. are carried out before the reduction treatment, or all of them are carried out after the reduction treatment, or part of the treatment process is carried out before the reduction treatment, and the other treatment process is carried out after the reduction treatment.
The reduction treatment may be carried out by chemical reduction, electrochemical reduction, laser reduction or high-temperature reduction. Compared with the method for spinning by completely using the oxygen-containing carbon nano material, the method has the advantages that the proportion of the oxygen-containing carbon nano material spun by the method is small, the oxygen-containing functional groups in the fiber are few, and the reduction condition is milder. The reduction process can reduce oxygen-containing defect sites in the fibers, and further improve the electric and heat conduction properties of the fibers. If a chemical agent is used for the reduction, the reducing agent used is selected from the group consisting of hydrogen iodide, NaBH 4 、LiAlH 4 And hydrazine hydrate. Taking hydrogen iodide reduction as an example, the preferable reduction mode is that the fiber prepared by spinning is immersed into a 30% hydrogen iodide aqueous solution for reduction for 12h at 80 ℃, after cooling to room temperature, the reduced fiber is washed three times by deionized water and ethanol respectively and then is dried in vacuum at 100 ℃.
The invention also provides the carbon nano tube/graphene composite fiber prepared by the preparation method, which can stably exist at 1000 ℃ in a nitrogen atmosphere, and the electrical conductivity of the composite fiber can be adjusted within the range of 50S/m to 20000S/m according to the content of the added carbon nano tube with the oxidation functional group and the difference of the reduction degree.
Aiming at specific application of the fiber, the reduction process of the composite fiber can be omitted, and the corresponding carboxylated carbon nanotube (or sulfonated carbon nanotube, hydroxylated carbon nanotube)/graphene fiber is prepared.
Unless otherwise defined, all terms used herein have the meanings that are commonly understood by those skilled in the art.
The present invention will be described in further detail with reference to examples.
Examples
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. For example, hydroxylated, carboxylated and sulfonated carbon nanotubes are purchased from Nanjing Xiancheng nanometer materials, Inc., graphene powder is purchased from Baotailong New materials, Inc., and hyaluronic acid, sulfuric acid, potassium hydroxide, calcium chloride, ethanol, etc. are purchased from Alfa Aesar.
Example 1
Mixing commercially available graphene powder and carboxylated multi-walled carbon nanotubes in an aqueous solution according to the mass ratio of 10:1, and crushing in a cell crusher with the power of 250W for 30min to prepare the spinning solution.
The spinning solution is placed in a syringe with the needle diameter of 80 mu m, the spinning solution is injected into the ethyl acetate solution at the extrusion rate of 1cm/min, the spun fiber passes through a hot tractor with the drawing rate of 1N/cm at the temperature of 60 ℃, is washed in deionized water for 3 times, and is dried under natural conditions.
And (3) placing the dried fiber in a high-temperature furnace, heating to 3000 ℃ under the protection of high-purity argon, keeping the pressure at 1atm, reducing for 36 hours, closing the heating, keeping the fiber in the furnace to be cooled to room temperature under the protection of argon, and obtaining the carbon nano tube/graphene composite fiber.
The scanning electron microscope image of the obtained carbon nanotube/graphene composite fiber is shown in fig. 1A, the raman spectrum is shown in fig. 1B, and the thermogravimetric curve of the fiber under the nitrogen atmosphere is shown in fig. 1C. From a scanning electron microscope image and a Raman spectrogram, the prepared carbon nano tube/graphene fiber has a compact structure, negligible D peak intensity and less intrinsic defects. It can be seen from the thermogravimetric curve that the prepared fiber has good temperature resistance under the inert gas atmosphere.
Example 2
Mixing sulfonated multi-walled carbon nanotube powder and a graphene nano-wall array prepared by a plasma enhanced chemical vapor deposition method in an aqueous solution according to the mass ratio of 1:5, adding chlorosulfonic acid with the mass fraction of 1%, and performing ultrasonic treatment for 1h to prepare a spinning solution.
Placing the spinning solution into a needle tube with a needle head size of 150 μm, and injecting CaCl with a mass fraction of 1% at an extrusion rate of 5mm/min 2 And carrying out wet spinning in an ethanol solution to obtain the gel fiber.
And (3) placing the gel fiber in HI solution with the mass fraction of 30% at 80 ℃ for reduction for 12h, cooling the fiber to room temperature, washing the fiber in deionized water for 5 times, and then placing the fiber in a vacuum oven with the temperature of 80 ℃ for drying for 6h to obtain the carbon nano tube/graphene composite fiber.
The scanning electron microscope image of the obtained carbon nanotube/graphene composite fiber is shown in fig. 2A, and the raman spectrum thereof is shown in fig. 2B. The scanning electron microscope image shows that the prepared fiber has compact structure and good continuity; from the Raman spectrogram, the fiber defect peak (D peak) after chemical reduction is low, and the obvious 2D peak exists, which indicates that the graphitization degree of the fiber is good.
Example 3
Growing graphene on the surface of the silicon dioxide powder by using a chemical vapor deposition method, and removing the silicon dioxide template by using hydrofluoric acid aqueous solution with the mass fraction of 40% to obtain corresponding graphene powder.
Dispersing graphene powder and hydroxylated multi-walled carbon nanotubes in an aqueous solution according to a mass ratio of 8:1, and crushing in a cell crusher with power of 100W for 1h to obtain a spinning solution.
The spinning solution was placed in a syringe having a needle diameter of 200 μm, and the material was injected at an extrusion rate of 2mm/minThe weight percentage is 5 percent of KOH and 5 percent of CaCl 2 ，1％CuSO 4 To obtain a gel fiber.
And (3) in a glove box protected by nitrogen, under the condition of oil bath at 100 ℃, putting the gel fiber into hydrazine hydrate for reduction for 10h, cooling, washing in deionized water for 3 times, and freeze-drying to obtain the carbon nanotube/graphene composite fiber.
The scanning electron microscope image of the obtained carbon nanotube/graphene composite fiber is shown in fig. 3A, and the raman spectrum thereof is shown in fig. 3B. The scanning electron microscope image shows that the graphene has a compact structure and uniform diameter.
Comparative example 1
Graphene fibers prepared and reduced by using GO (graphene oxide) as a raw material instead of graphene powder and hydroxylated multi-walled carbon nanotubes in the same manner as in example 3 have raman spectrograms shown in fig. 4.
As can be seen from the raman spectrograms of fig. 3B and fig. 4, compared with the graphene fiber prepared by the GO wet spinning method reduced under the same condition, the fiber prepared in example 3 of the present invention has a lower defect peak and a higher graphitization degree.
The fiber products obtained in examples 1 to 3 and comparative example 1 were subjected to a performance test.
The equipment used in the mechanical test is a universal tensile machine, and the specific steps are as follows: the fibers were fixed at both ends of the jig with silver glue, the initial stretching length was 1cm, and the stretching rate was set to 5 mm/min.
The apparatus for electrical testing was a keithley 2450 digital source meter with a voltage sweep range of ± 0.1V. It is worth mentioning that the diameter of the corresponding fiber can be measured by a scanning electron microscope, and then the cross-sectional area of the fiber can be calculated, which brings about the calculation of the tensile strength and the electric conductivity of the fiber.
The test results are shown in table 1:
TABLE 1 comparison of various properties of carbon nanotube/graphene composite fibers prepared in examples 1 to 3 and comparative example 1
As can be seen from table 1, compared with graphene fibers prepared by GO wet spinning, the carbon nanotube/graphene composite fibers prepared by the embodiments of the present invention have excellent flexibility and conductivity, the tensile strength is increased by 10 to 80%, and the conductivity is increased by 3 to 70%.
In conclusion, the carbon nanotube/graphene composite fiber prepared by the invention has the advantages of compact structure, good continuity, excellent flexibility, good electric and thermal conductivity, stable existence at high temperature, and wide application prospect in the fields of intelligent wearing, electromagnetic shielding, energy storage and conversion and the like.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (6)
1. A preparation method of carbon nanotube/graphene composite fibers is characterized by comprising the following steps:
mixing a carbon nano tube with an oxygen-containing functional group and graphene without the oxygen-containing functional group in a solution phase to prepare a spinning solution;
adding one or more of chlorosulfonic acid, oleum or hyaluronic acid with the mass fraction of 0.1-10% into the solution phase;
injecting the spinning solution into a coagulating bath by a wet spinning process to form gel fibers; and
carrying out post-treatment on the gel fiber to obtain a carbon nano tube/graphene composite fiber;
the mass ratio of the carbon nano tube with the oxygen-containing functional group to the graphene is 1:5-1: 50;
the wet spinning process has spinning speed of 1-100cm/min, spinning head diameter of 10-1000 micron, and the coagulating bath selected from CaCl 2 Aqueous solution of KOH, CaCl 2 Ethanol solution of (3), ethanol solution of KOH, acetone, ethyl acetate, chloroformAnd petroleum ether.
2. The preparation method according to claim 1, wherein the carbon nanotubes having oxygen-containing functional groups are selected from one or more of hydroxylated carbon nanotubes, carboxylated carbon nanotubes and sulfonated carbon nanotubes, and the graphene is selected from one or more of graphene powder obtained by liquid phase exfoliation, reduced graphene oxide, graphene thin film prepared by chemical vapor deposition, graphene powder and vertical graphene array.
3. The method of claim 1, wherein the post-treatment is selected from one or more of water washing, hot stretching, drawing, reducing, and coating a polymer layer.
4. The method according to claim 3, wherein the reduction is one selected from chemical reduction, electrochemical reduction, laser reduction, and high-temperature reduction.
5. The method according to claim 4, wherein the reducing agent used in the reduction with the chemical agent is selected from the group consisting of hydrogen iodide and NaBH 4 、LiAlH 4 And hydrazine hydrate.
6. A carbon nanotube/graphene composite fiber, characterized in that the carbon nanotube/graphene composite fiber is produced according to the production method of any one of claims 1 to 5.
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| CN112210849B (en) * | 2020-09-17 | 2022-04-05 | 中国科学院金属研究所 | Preparation method of single-walled carbon nanotube fiber with high conductivity |
| KR102440348B1 (en) * | 2020-10-07 | 2022-09-05 | 한양대학교 산학협력단 | Graphene/CNT composite fiber and fabrication method for the same |
| CN112875682B (en) * | 2021-02-09 | 2023-02-21 | 中国科学院金属研究所 | Continuous preparation method of directional high-density carbon nanotube strip |
| CN113913970B (en) * | 2021-11-29 | 2023-10-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-performance nano carbon fiber and continuous preparation method thereof |
| CN114672994A (en) * | 2022-04-19 | 2022-06-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene-reinforced carbon nanotube composite fiber, and preparation method and device thereof |
| CN115772725A (en) * | 2022-11-03 | 2023-03-10 | 苏州经贸职业技术学院 | Preparation of functional fullerene fiber blended silk fabric |
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