CN108751174B - Continuous macroscopic graphene nanoribbon fiber and preparation method thereof - Google Patents
Continuous macroscopic graphene nanoribbon fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a continuous macroscopic graphene nanoribbon fiber and a preparation method thereof. According to the method, a high-water-content reaction solution is used as a raw material, and a chemical vapor deposition method is adopted, so that the continuous macroscopic continuous graphene nanobelt fiber is prepared by utilizing the growth assembly interference and cutting effect of water molecules on the carbon nanotube at a high temperature. The key process of the preparation method is that the mass fraction of deionized water in the reaction liquid is controlled within the range of 15-40%, preferably 20-35%. The graphene nanoribbon prepared by the method has uniform and continuous fibers, high purity and high quality. The fiber also has light weight, high strength, high conductivity and excellent flexibility, and provides a novel macroscopic fiber material for developing flexible wearable electronic devices. Meanwhile, the preparation method is a one-step dry spinning method, the preparation process is simple, the regulation and control are easy, the continuous preparation can be realized, and the large-scale production can be realized.
Description
Technical Field
The invention relates to a continuous macroscopic graphene nanoribbon fiber and a preparation method thereof; belongs to the technical field of carbon nano materials and preparation thereof.
Background
Since the discovery of the graphene in 2004, the graphene has excellent mechanical property (theoretical breaking strength of 1 TPa) and electrical property (theoretical electron mobility of 10)6 cm2•V-1•s-1) Thermal (theoretical thermal conductivity 5000 W.m)-1•K-1) And optical properties (single layer visible light absorption of only 2.3%) are attracting much attention. The graphene nanoribbon refers to a narrow strip-shaped graphene material with the width in a nanometer scale and a certain length-diameter ratio. The graphene nanoribbon not only has all the structural and functional characteristics of graphene, but also shows unique electron transport characteristics because electron transport is limited in the width direction of nanoscale. The electric property of the material shows semiconductivity or metallicity along with different strip widths, layer numbers and edge structures, is expected to be substituted for Si semiconductors and metal Cu materials, and has important application potential in the field of electronic circuit devices. In addition, the unique two-dimensional narrow strip-shaped nano structure of the graphene nanoribbon not only keeps the properties of high specific surface area, high conductivity, high flexibility and the like of graphene, but also has more edge active points and more compatible surface structures, and can be applied to the fields of high-performance energy storage, energy conversion, sensing, high-strength composite materials and the like. Therefore, in recent years, graphene nanoribbons have received much attention from researchers at home and abroad. Methods for preparing graphene nanoribbons have been reported in various methods, mainly by cutting graphene nanosheets by means of micromachining, or by opening carbon nanotubes by means of zipper-type cutting by methods such as chemical oxidation or plasma etching. However, the graphene nanoribbons prepared by the above method are all in a dispersed free state. The preparation of continuous macroscopic graphene nanoribbon fibers has not been achieved.
Disclosure of Invention
The invention aims to provide a continuous macroscopic graphene nanoribbon fiber and a preparation method thereof, and overcomes the defects of the existing graphene nanoribbon material preparation technology.
The technical scheme is as follows:
a continuous macroscopic graphene nanoribbon fiber and a preparation method thereof mainly comprise the following steps:
(1) taking a liquid carbon-containing compound, ferrocene, thiophene and deionized water as raw materials, firstly weighing and mixing the carbon-containing compound, ferrocene and thiophene according to the mass ratio of 50-300: 1-5: 1, then adding the deionized water, and ultrasonically mixing uniformly, wherein the mass fraction of water is controlled within the range of 15-40%, preferably 20-35%, injecting the reaction liquid into a tubular reaction furnace at the temperature of 700-1500 ℃ under the carrier gas flow of 200-2000 sccm hydrogen at the injection rate of 5-20 mL/h, and growing and assembling to form a continuous graphene nanoribbon aggregate;
(2) and (3) pulling out the graphene nanoribbon aggregate from the tail end of the reaction furnace, carrying out liquid phase compact shrinkage, and winding the graphene nanoribbon aggregate on a spinning shaft at the spinning speed of 2-20 m/min to obtain the continuous macroscopic graphene nanoribbon fiber.
The invention relates to a preparation method of continuous graphene nanoribbon fibers, which is characterized by comprising the following steps: the reaction liquid contains high-content water, and the mass fraction of the water is 15-40%, preferably 20-35%; under the premise of high water content reaction liquid, the carbon source is ethanol, acetone or a mixed solution of the ethanol and the acetone, and preferably ethanol is used as the carbon source; the mass fraction of ferrocene is 0.5-5%; the injection rate is 5-20 mL/h, preferably 6-12 mL/h; the reaction temperature is 700-1500 ℃, and 1100-1200 ℃ is preferred; the carrier gas is hydrogen or a mixed gas of 1-99% hydrogen and argon, and the preferred carrier gas is hydrogen; the flow rate of the carrier gas is 200-; the spinning speed of the fiber is 2-20 m/min, preferably 4-12 m/min.
The continuous macroscopic graphene nanoribbon fiber prepared by the method is composed of graphene nanoribbons with high purity, high quality and uniform structure.
The continuous macroscopic graphene nanoribbon fiber prepared by the method comprises the following steps: it is a macroscopic continuous fiber composed of graphene nanoribbons. It is prepared directly by chemical vapor deposition. Its macroscopically continuous length ranges from the centimeter to the kilometer range. The diameter of the fiber is 10-200 μm. It has a solid, hollow, layered or three-dimensional network structure. The number of graphene nanoribbon layers forming the graphene nanoribbon-type solar cell is 1-10. The width of the graphene nanoribbon is 2-100 nm, and the length-diameter ratio is more than 100. The graphene nanoribbons forming the graphene nanoribbons have neat edge structures, and the edge structures can be sawtooth type or armchair type graphene nanoribbons, or can be a mixture of the sawtooth type or armchair type graphene nanoribbons and the armchair type graphene nanoribbons.
The number of layers, the width and the edge structure of the continuous macroscopic graphene nanoribbon fiber prepared by the method can be regulated and controlled by changing the type of a carbon source, the proportion of the carbon source to thiophene, ferrocene and deionized water, the liquid injection rate and the reaction temperature.
The preparation method of the continuous macroscopic graphene nanoribbon fiber provided by the invention has the main technical principle and the implementation scheme that high-content water is introduced into reaction raw materials, the graphene nanoribbon is generated by utilizing the interference and cutting action of the water on the growth and assembly of the carbon nanotube at high temperature, then a continuous graphene nanoribbon aggregate is assembled, and the continuous macroscopic graphene nanoribbon fiber is obtained through spinning.
The graphene nanoribbon prepared by the method has uniform and continuous fibers, high purity and high quality. The fiber also has light weight, high strength, high conductivity and excellent flexibility, and provides a novel macroscopic fiber material for developing flexible wearable electronic devices. Meanwhile, the preparation method is a one-step method, belongs to a dry spinning process, is simple in preparation process, easy to regulate and control, can realize continuous preparation, and can realize large-scale production.
Drawings
FIG. 1: the continuous macroscopic graphene nanoribbon fiber prepared by the method is adopted.
FIG. 2: scanning electron micrographs (a) and (b) of graphene nanobelt fibers prepared by the method are shown.
FIG. 3: the graphene nanoribbon fiber prepared by the method has (a) low-power and (b) high-power transmission electron micrographs.
FIG. 4: the graphene nanoribbon fiber Raman spectrum prepared under the conditions of different water content ratios (mass fractions of 0, 5, 10, 15 and 25%) is adopted.
FIG. 5: the graphene nanoribbon fiber tensile strength-strain curve prepared under the conditions of different water content ratios (mass fractions of 0, 5, 10, 15 and 25%) is adopted.
Detailed Description
Example 1
Weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow at the speed of 8 mL/h by using a micro injection pump, wherein the temperature of a reaction zone is 1150 ℃, growing and assembling the graphene nanoribbon in the reaction zone to form a filament-shaped aggregate, moving to the tail end of the reaction furnace under the driving of hydrogen flow, pulling out the graphene nanoribbon aggregate from the reaction furnace, performing water compaction and shrinkage, and winding on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber.
The continuous macroscopic graphene nanoribbon fiber prepared by the steps and conditions can reach a hundred-meter level or even a thousand-meter level, and can be resolved and wound (figure 1). The fiber has uniform thickness and diameter of about 100 μm, and the graphene nano-sheets inside the fiber form thin bundles in a three-dimensional network structure (figure 2). The graphene nanoribbons are double-layered with the length of more than tens of micrometers and the width of 15-40 nm, and the edges of the ribbons are neat (fig. 3). The graphene nanoribbons in the fiber have high crystallinity, and the Raman spectrum shows that the ratio of the integrated area of the D peak to the G peak is 0.70 (figure 4). The prepared graphene nano-belt fiber has the characteristics of light weight, the linear density is only 0.23 tex (mg/m), and the bulk density is only 0.03 g/cm3. The prepared graphene nano-belt fiber has high conductivity which reaches 104S/m magnitude. The prepared graphene nanoribbon fiber has high strength, the tensile strength is 150-350 MPa, and the elongation at break is 15-25% (figure 5). The prepared graphene nanoribbon fiber also has excellent flexibility and can be bent, knotted, woven and arranged at will.
Example 2
The deionized water content was changed to 15%, and the other experimental procedures and conditions were the same as in example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 15%. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow at the speed of 8 mL/h by using a micro injection pump, wherein the temperature of a reaction zone is 1150 ℃, growing and assembling the graphene nanoribbon in the reaction zone to form a filament-shaped aggregate, moving to the tail end of the reaction furnace under the driving of hydrogen flow, pulling out the graphene nanoribbon aggregate from the reaction furnace, performing water compaction and shrinkage, and winding on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber.
The continuous macroscopic graphene nanoribbon fiber prepared by the steps and conditions is uniform and continuous, the fiber diameter is 80 mu m, and the graphene nanoribbon formed thin bundles are oriented along the axial direction of the fiber. The integral area ratio of the D peak to the G peak in the graphene nanoribbon fiber Raman spectrum is 0.61. The linear density of the graphene nanoribbon fiber is 0.23 tex (mg/m), and the bulk density is 0.046 g/cm3. The conductivity of the graphene nanoribbon fiber reaches 104S/m magnitude, tensile strength of 250-450 MPa, elongation at break of 10-25%, and excellent flexibility.
Example 3
The deionized water content was changed to 10%, and the other experimental procedures and conditions were the same as in example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 10%. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow by a micro injection pump at the speed of 8 mL/h, wherein the temperature of a reaction zone is 1150 ℃, the reaction liquid is cracked, grown and assembled in the reaction zone to form a cylindrical aggregate, the cylindrical aggregate is driven by the hydrogen flow to move to the tail end of the reaction furnace, the aggregate is pulled out of the reaction furnace, and the cylindrical aggregate is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare a continuous fiber product.
The product prepared by the above steps and conditions is a continuous carbon nanotube fiber, not a graphene nanoribbon fiber, indicating that the graphene nanoribbon fiber cannot be prepared under low water reaction conditions (10%). The diameter of the prepared continuous carbon nanotube fiber is 100 mu m, and the carbon nanotube formed fine bundles are oriented along the axial direction of the fiber. The integral area ratio of the D peak to the G peak in the Raman spectrum of the carbon nano tube fiber is 0.60. Carbon nanotube fiberThe linear density was 0.42 tex (mg/m) and the bulk density was 0.054 g/cm3. The carbon nanotube fiber has a conductivity of 103S/m magnitude, tensile strength of 200-300 MPa, elongation at break of 10-25%, and excellent flexibility.
Example 4
The deionized water content was changed to 5%, and the other experimental procedures and conditions were the same as in example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 5%. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow by a micro injection pump at the speed of 8 mL/h, wherein the temperature of a reaction zone is 1150 ℃, the reaction liquid is cracked, grown and assembled in the reaction zone to form a cylindrical aggregate, the cylindrical aggregate is driven by the hydrogen flow to move to the tail end of the reaction furnace, the aggregate is pulled out of the reaction furnace, and the cylindrical aggregate is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare a continuous fiber product.
The product obtained through the steps and conditions is continuous carbon nanotube fiber, further indicating that graphene nanoribbon fiber cannot be prepared under the low water reaction condition (10%). The diameter of the prepared continuous carbon nanotube fiber is 120 mu m, and the carbon nanotubes form thin bundles which are oriented along the axial direction of the fiber. The integral area ratio of the D peak to the G peak in the Raman spectrum of the carbon nano tube fiber is 0.57. The linear density of the carbon nanotube fiber is 0.49 tex (mg/m), and the bulk density is 0.043 g/cm3. The carbon nanotube fiber has a conductivity of 103S/m magnitude, tensile strength of 200-250 MPa, elongation at break of 10-15%, and excellent flexibility.
Example 5
The reaction solution was not added with deionized water, and the other experimental procedures and conditions were the same as those of example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, and uniformly mixing by ultrasonic treatment for 30 min to obtain a uniform reaction solution. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow by a micro injection pump at the speed of 8 mL/h, wherein the temperature of a reaction zone is 1150 ℃, the reaction liquid is cracked, grown and assembled in the reaction zone to form a cylindrical aggregate, the cylindrical aggregate is driven by the hydrogen flow to move to the tail end of the reaction furnace, the aggregate is pulled out of the reaction furnace, and the cylindrical aggregate is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare a continuous fiber product.
The product obtained through the steps and conditions is continuous carbon nanotube fiber, further indicating that graphene nanoribbon fiber cannot be prepared under the low water reaction condition (10%). The diameter of the prepared continuous carbon nanotube fiber is 120 mu m, and the carbon nanotubes form thin bundles which are oriented along the axial direction of the fiber. The integral area ratio of the D peak to the G peak in the Raman spectrum of the carbon nano tube fiber is 0.51. The linear density of the carbon nanotube fiber is 0.36 tex (mg/m), and the bulk density is 0.032 g/cm3. The carbon nanotube fiber has a conductivity of 103S/m magnitude, tensile strength of 100-.
Example 6
The deionized water content was changed to 35%, and the other experimental procedures and conditions were the same as in example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 35%. Injecting the reaction liquid into a tubular reaction furnace with 1000 sccm hydrogen carrier gas flow at the speed of 8 mL/h by using a micro injection pump, wherein the temperature of a reaction zone is 1150 ℃, growing and assembling the graphene nanoribbon in the reaction zone to form a filament-shaped aggregate, moving to the tail end of the reaction furnace under the driving of hydrogen flow, pulling out the graphene nanoribbon aggregate from the reaction furnace, performing water compaction and shrinkage, and winding on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber.
The continuous macroscopic graphene nanoribbon fiber prepared by the steps and conditions is uniform and continuous, the fiber diameter is 80 mu m, and the graphene nanoribbon formed thin bundles are oriented along the axial direction of the fiber. The linear density of the graphene nanoribbon fiber is 0.20 tex (mg/m), and the bulk density is 0.040 g/cm3. The conductivity of the graphene nanoribbon fiber reaches 104S/m magnitude, strong tensionThe degree of 100-150 MPa, the elongation at break of 10-25 percent and excellent flexibility.
Example 7
The deionized water content was changed to 50%, and the other experimental procedures and conditions were the same as in example 1.
The method specifically comprises the following steps: weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, wherein the mass fraction of water in the reaction liquid is 50%, and carrying out ultrasonic mixing for 120 min to obtain a uniform mixed liquid. However, after the ultrasonic treatment is stopped for 10 min, flocculation and sedimentation appear in the mixed solution, and after the ultrasonic treatment is repeated and stopped, the flocculation and sedimentation appear, so that a uniform reaction solution cannot be obtained when the water content is 50%, and subsequent experiments are not carried out.
Example 8
Weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 300: 5: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. And (2) injecting the reaction liquid into a tubular reaction furnace with 2000 sccm hydrogen carrier gas flow at the rate of 20 mL/h by using a micro injection pump, wherein the temperature of a reaction zone is 1500 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament-shaped aggregate, the graphene nanoribbon moves to the tail end of the reaction furnace under the driving of hydrogen flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, and is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 20 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The graphene nanoribbon prepared by the steps has continuous fibers, uniform thickness and 200 mu m fiber diameter, and the fibers can be resolved and wound.
Example 9
Weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 50: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. And injecting the reaction liquid into a tubular reaction furnace with 200 sccm hydrogen carrier gas flow by using a micro-injection pump at the speed of 5 mL/h, wherein the temperature of a reaction zone is 700 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament-shaped aggregate, the graphene nanoribbon moves to the tail end of the reaction furnace under the driving of hydrogen flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, is subjected to water compact shrinkage and twisting at the rotating speed of 50 rpm/min, and is wound on a spinning shaft at the spinning speed of 2 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The graphene nanoribbon prepared by the steps has continuous fibers, uniform thickness and fiber diameter of 10 mu m, and the fibers can be resolved and wound.
Example 10
Weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. And (2) injecting the reaction liquid into a tubular reaction furnace with 1400 sccm hydrogen carrier gas flow at the speed of 12 mL/h by using a micro injection pump, wherein the temperature of a reaction zone is 1200 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament-shaped aggregate, the graphene nanoribbon moves to the tail end of the reaction furnace under the driving of hydrogen flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, and is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 10 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The graphene nanoribbon fiber prepared by the steps is continuous and uniform in thickness, and can be resolved and wound.
Example 11
Weighing and mixing ethanol, ferrocene and thiophene according to the mass ratio of 150: 3: 1, then adding deionized water, performing ultrasonic treatment for 30 min, and uniformly mixing to obtain a uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. Injecting the reaction liquid into a tubular reaction furnace with 800 sccm hydrogen carrier gas flow by using a micro-injection pump at the speed of 6 mL/h, wherein the temperature of a reaction zone is 1100 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament aggregate, the filament aggregate moves to the tail end of the reaction furnace under the driving of hydrogen flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, and is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The continuity of the graphene nanoribbon fiber prepared by the steps is slightly inferior to that of other conditions, and the fiber can be resolved and wound.
Example 12
Acetone, ferrocene and thiophene are weighed and mixed according to the mass ratio of 150: 3: 1, then deionized water is added, ultrasonic treatment is carried out for 30 min, and uniform mixing is carried out to obtain uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. Injecting the reaction liquid into a tubular reaction furnace with 90% hydrogen and 10% argon mixed carrier gas flow at the speed of 8 mL/h by using a micro injection pump, wherein the carrier gas flow is 1000 sccm, the temperature of a reaction zone is 1150 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament-shaped aggregate, the filament-shaped aggregate moves to the tail end of the reaction furnace under the drive of the carrier gas flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, and is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The continuity of the graphene nanoribbon fiber prepared by the steps is slightly inferior to that of other conditions, and the fiber can be resolved and wound.
Example 13
The ethanol, the acetone, the ferrocene and the thiophene are weighed and mixed according to the mass ratio of 75: 3: 1, then deionized water is added, ultrasonic treatment is carried out for 30 min, and uniform mixing is carried out to obtain uniform reaction liquid, wherein the mass fraction of water in the reaction liquid is 25%. Injecting the reaction liquid into a tubular reaction furnace with 10% hydrogen and 90% argon mixed carrier gas flow at the rate of 8 mL/h by using a micro injection pump, wherein the carrier gas flow is 1000 sccm, the temperature of a reaction zone is 1150 ℃, the graphene nanoribbon grows and assembles in the reaction zone to form a filament-shaped aggregate, the filament-shaped aggregate moves to the tail end of the reaction furnace under the driving of the hydrogen flow, the graphene nanoribbon aggregate is pulled out of the reaction furnace, and is subjected to water compact shrinkage and is wound on a spinning shaft at the spinning speed of 4 m/min to prepare the continuous macroscopic graphene nanoribbon fiber. The continuity of the graphene nanoribbon fiber prepared by the steps is slightly inferior to that of other conditions, and the fiber can be resolved and wound.
The invention has the following technical effects:
1. the graphene nanoribbon fiber is prepared by adopting ethanol and water as raw materials, and the raw materials are wide, cheap and easy to obtain;
2. the graphene nanoribbon fiber is prepared by introducing high-content water into the reaction solution, so that the technical scheme is simple and easy to control;
3. the graphene nanoribbon fiber is prepared by a chemical vapor deposition method, and is directly prepared by a one-step method, so that the process is simple, continuous preparation can be realized, and the method has obvious advantages of large-scale production;
4. the prepared graphene nanoribbon fiber is macroscopically continuous and uniform and can be resolved and wound;
5. the prepared graphene nanoribbon fiber has high purity and quality;
6. the prepared graphene nanoribbon fiber has high porosity and ultra-light characteristics;
7. the prepared graphene nanoribbon fiber has high strength and conductivity;
8. the prepared graphene fiber has excellent flexibility and knittability.
Claims (9)
1. A method for preparing continuous macroscopic graphene nano-belt fibers is characterized in that the method is directly prepared by using high-water-content reaction liquid as a raw material through a chemical vapor deposition method and mainly comprises the following steps:
(1) taking a liquid carbon-containing compound, ferrocene, thiophene and deionized water as raw materials, firstly weighing and mixing the carbon-containing compound, ferrocene and thiophene according to the mass ratio of 50-300: 1-5: 1, then adding deionized water, carrying out ultrasonic mixing uniformly, injecting a reaction liquid into a tubular reaction furnace at 700-1500 ℃ in a carrier gas flow of 200-20 mL/h of 2000 sccm hydrogen or a mixed gas of 1-99% hydrogen and argon, and growing and assembling to form a continuous graphene nanoribbon aggregate; the mass fraction of the deionized water is 20-35%; the carbon-containing compound is ethanol, acetone or a mixed solution of the ethanol and the acetone;
(2) and (3) pulling out the graphene nanoribbon aggregate from the tail end of the reaction furnace, carrying out liquid phase compact shrinkage, and winding the graphene nanoribbon aggregate on a spinning shaft at the spinning speed of 2-20 m/min to obtain the continuous macroscopic graphene nanoribbon fiber.
2. The method for preparing continuous macroscopic graphene nanoribbon fibers according to claim 1, wherein under the condition of high water content of the reaction solution, the carbon-containing compound is ethanol; the mass fraction of ferrocene is 0.5-5%; the injection rate is 6-12 mL/h; the reaction temperature is 1100-1200 ℃; the carrier gas is hydrogen; the flow rate of the carrier gas is 800-; the spinning speed of the fiber is 4-12 m/min.
3. A continuous macroscopic graphene nanoribbon fiber prepared by the method for preparing a continuous macroscopic graphene nanoribbon fiber according to claim 1, characterized in that the continuous macroscopic graphene nanoribbon fiber is obtained by the method.
4. A continuous macroscopic graphene nanoribbon fiber according to claim 3, characterized in that it is a macroscopic continuous fiber composed of graphene nanoribbons, with a length from centimeter to ten-thousand meters.
5. The method of claim 3, wherein the diameter of the continuous macroscopic graphene nanoribbon fiber is 10 to 200 μm.
6. The continuous macroscopic graphene nanoribbon fiber of claim 3, having a solid, hollow, layered or three-dimensional network structure.
7. The continuous macroscopic graphene nanoribbon fiber of claim 3, wherein the number of graphene nanoribbon layers constituting the fiber is between 1 and 10.
8. The continuous macroscopic graphene nanoribbon fiber of claim 3, wherein the graphene nanoribbon is formed with a width of 2-100 nm and an aspect ratio of more than 100.
9. The continuous macroscopic graphene nanoribbon fiber according to claim 3, wherein the graphene nanoribbons formed by the fiber have a neat edge structure, and the edge structure is a zigzag type or armchair type graphene nanoribbon, or a mixture of the zigzag type and armchair type graphene nanoribbon.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
| CN101665997A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Lamellar carbon nanofibre and preparation method thereof |
| CN102392225A (en) * | 2011-07-22 | 2012-03-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanoribbon on insulating substrate |
| CN103626155A (en) * | 2013-12-06 | 2014-03-12 | 天津大学 | Method for efficiently and environmental-friendlily preparing carbon nano fibers |
| WO2016044047A1 (en) * | 2014-09-15 | 2016-03-24 | Wisconsin Alumni Research Foundation | Oriented bottom-up growth of armchair graphene nanoribbons on germanium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014055087A (en) * | 2012-09-13 | 2014-03-27 | Panasonic Corp | Method for producing graphene and transistor using the graphene |
-
2018
- 2018-07-01 CN CN201810704525.1A patent/CN108751174B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
| CN101665997A (en) * | 2009-09-25 | 2010-03-10 | 天津大学 | Lamellar carbon nanofibre and preparation method thereof |
| CN102392225A (en) * | 2011-07-22 | 2012-03-28 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene nanoribbon on insulating substrate |
| CN103626155A (en) * | 2013-12-06 | 2014-03-12 | 天津大学 | Method for efficiently and environmental-friendlily preparing carbon nano fibers |
| WO2016044047A1 (en) * | 2014-09-15 | 2016-03-24 | Wisconsin Alumni Research Foundation | Oriented bottom-up growth of armchair graphene nanoribbons on germanium |
Non-Patent Citations (4)
| Title |
|---|
| Carbon nanotube and graphene multiple-thread yarns;Xiaohua Zhong et al.;《Nanoscale》;20121130;第5卷(第3期);第1183页左列第2段、右列第1段、第1185页右列第2段、图4、第1186页第3段 * |
| Electrical property of macroscopic graphene composite fibers prepared;Haibin Sun et al.;《Nanotechnology》;20180521;第1-27页 * |
| Graphene fiber: a new material platform for unique;Cheng, Huhu et al.;《NPG ASIA MATERIALS》;20140718;第6卷;第1-13页 * |
| 化学气相反应合成单分散性碳纳米管研究;钟小华 等;《材料工程》;20071031(第10期);第55-59页 * |
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