CN111155217A - Method for improving orientation degree and conductivity of carbon nanotube fibers - Google Patents
Method for improving orientation degree and conductivity of carbon nanotube fibers Download PDFInfo
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Abstract
The invention discloses a method for improving the orientation degree and the electrical conductivity of carbon nanotube fibers, which comprises the steps of preparing continuous carbon nanotube fibers by a floating catalytic chemical vapor deposition method, immersing the carbon nanotube fibers in a solvent to fully expand the carbon nanotube fibers, properly stretching the carbon nanotube fibers to rearrange the carbon nanotube fibers so as to improve the axial orientation of the carbon nanotube fibers, immersing the carbon nanotube fibers in a coagulating bath, driving phase separation by solubility difference, extruding the solvent from the carbon nanotube fibers, washing and drying the carbon nanotube fibers on line to form compact carbon nanotube fibers, and finally twisting the carbon nanotube fibers to form a multistage spiral structure. The primary carbon nanotube fiber prepared by the direct spinning method is swelled and shrunk, so that the orientation degree and compactness of the fiber are better improved, the conductivity and the mechanical strength of the fiber are greatly improved, and the preparation method is simple in preparation process, mild in preparation conditions, low in cost, high in production efficiency and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of novel functional fiber materials, and particularly relates to a method for improving the orientation degree and the conductivity of carbon nanotube fibers.
Background
As a novel conductive material, carbon nanotubes have gained wide attention from researchers at home and abroad since the successful preparation, and are one of the core materials for constructing future super-strong materials and carbon-based devices. Assembling carbon nanotubes into fibers, films, etc. is one of the important ways to realize macroscopic applications. Among them, the carbon nanotube fiber is a one-dimensional continuous assembly of carbon nanotubes, has good flexibility, conductivity and mechanical strength, can be used alone, and can also be woven, becoming the most interesting carbon nanotube macroscopic body.
In the last two decades, people have devoted themselves to developing continuous spinning processes for carbon nanotube fibers and reveal the process-structure-performance relationship of carbon nanotube fibers. The most prominent preparation methods at present are wet spinning based on a coagulation process, spinning by spinning with spinning a vertical array of carbon nanotubes, and direct spinning based on a growth process to pre-form a carbon nanotube gel. The wet spinning method can rapidly and continuously obtain the carbon nanotube fiber, but the electrical conductivity of the fiber is reduced due to the addition of the high polymer material. The conductivity of the fiber obtained by the floating catalytic chemical vapor deposition method is greatly improved, but the fiber structure is loose, the orientation degree is low, and the mechanical strength of the fiber is seriously influenced.
Some researchers have enhanced the forces between carbon nanotubes by making the fiber structure more compact by two physical methods, solvent infiltration and mechanical compression. The solvent infiltration method mainly uses organic solvents such as acetone and the like to infiltrate the carbon nano tube fiber, and the fiber can be shrunk after the solvent is volatilized; mechanical compression is the flattening of the fibers by the application of an external force, which causes the structure to become more compact, but the fibers are brittle. Both of the above methods still do not improve the degree of fiber orientation. Based on this, it is necessary to develop a new post-treatment process of carbon nanotube fiber to improve the degree of orientation and densification thereof, thereby improving electrical conductivity, mechanical strength and stretchability thereof.
Disclosure of Invention
The invention provides a method for improving the orientation degree and the conductivity of carbon nanotube fibers, which overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving the degree of orientation and the electrical conductivity of carbon nanotube fibers comprises the following steps:
(1) preparing continuous primary carbon nanotube fibers by using a floating catalytic chemical vapor deposition method;
(2) immersing the primary carbon nanotube fiber prepared in the step (1) in chlorosulfonic acid aqueous solution to fully expand the primary carbon nanotube fiber, and stretching the primary carbon nanotube fiber to rearrange the primary carbon nanotube fiber to improve the axial orientation of the primary carbon nanotube fiber;
(3) immersing the carbon nanotube fiber prepared in the step (2) into a coagulating bath, driving phase separation through solubility difference, and extruding chlorosulfonic acid from the carbon nanotube fiber;
(4) carrying out online washing and drying on the carbon nanotube fiber obtained in the step (3);
(5) twisting the carbon nanotube fiber obtained in the step (4) to form the carbon nanotube fiber with the multilevel spiral structure.
Further, the number of the tube wall layers of the primary carbon nanotube fiber prepared in the step (1) is 1-10; the number of the primary carbon nanotube fibers is 5-100; the diameter of the primary carbon nanotube fiber is 5-100 μm.
Further, the mass concentration of the chlorosulfonic acid in the chlorosulfonic acid aqueous solution in the step (2) is 5-20%.
Further, the expansion time of the primary carbon nanotube fiber in the step (2) in chlorosulfonic acid aqueous solution is 10-100 s; the elongation at stretching is 5% to 15%.
Further, the coagulating bath in the step (3) is ethanol or acetone.
Further, the soaking time of the carbon nano tube fiber prepared in the step (2) in the coagulating bath is 10-100 s.
Further, the number of times of online water washing in the step (4) is 1-3; the water washing temperature is 25 ℃. + -. 5 ℃.
Further, the drying mode in the step (4) is one or more of infrared heating drying and electric heating drying; the drying temperature is 60-150 ℃.
Further, the twisting angle of the carbon nano tube fiber in the step (5) is 5-20 degrees; the rotating speed of the motor is 20-200rpm during twisting.
Furthermore, the specific strength of the multistage helical structure carbon nanotube fiber obtained in the step (5) is 3.78-4.32 N.tex-1The specific tensile modulus is 167.5-194.3 N.tex-1The conductivity reaches 1940-2·kg-1。
Compared with the prior art, the invention has the following beneficial technical effects:
the method combines the advantages of wet spinning and direct spinning, the orientation degree and the density of the fiber are obviously improved through fiber expansion, solvent contraction and twisting treatment, the CNTFs prepared by the method have the advantages of light weight, tensile resistance, high hardness, good conductivity, high flexibility and the like, and the specific strength of the obtained carbon nanotube fiber is 3.78-4.32 N.tex-1The specific tensile modulus is 167.5-194.3 N.tex-1The conductivity reaches 1940-2·kg-1The method can be used for quickly and continuously producing the high-performance carbon nanotube fiber, is simple and easy to implement, has high efficiency and is easy for large-scale preparation.
Drawings
FIG. 1 is a schematic view of the continuous preparation of high performance carbon nanotube fibers;
wherein, 1 represents the synthesis of primary carbon nanotube fiber, 2 represents the expansion and stretching of carbon nanotube fiber, 3 represents the phase separation of carbon nanotube fiber in a coagulating bath, 4 represents the online drying, 5 represents the fiber twisting, and 6 represents the continuous collection;
FIG. 2 is a schematic diagram of a floating-catalyzed chemical vapor deposition process for preparing continuous carbon nanotube fibers;
fig. 3 is the shape of the twisted carbon nanotube fiber under an electron microscope (SEM), wherein a is the shape of the fiber expanded by 100 times and b is the shape of the fiber expanded by 2000 times.
Detailed Description
Embodiments of the present invention are described in further detail below with reference to the attached drawing figures:
referring to fig. 1 and 2, the present invention is a method for rapidly and continuously producing a densified carbon nanotube fiber with highly uniform orientation, which is optimized by combining the advantages of wet spinning and direct spinning of the carbon nanotube fiber, and after obtaining a continuous carbon nanotube fiber by the direct spinning method, the fiber is fully expanded in a specific solvent to improve the orientation degree thereof, then the fiber is densified by solvent shrinkage, and finally the carbon nanotube fiber with high strength and high conductivity is obtained by twisting.
The method comprises the following specific steps:
(1) a continuous primary carbon nanotube fiber is prepared using a floating catalytic chemical vapor deposition process (i.e., primary carbon nanotube fiber synthesis 1). The number of the tube wall layers of the prepared primary carbon nanotube fiber is 1-10; more preferably, 2-5 layers; and/or the number of the primary carbon nanotube fibers is 5-100; more preferably, 10 to 60; and/or the diameter of the primary carbon nanotube fiber is 5-100 μm; more preferably, it is 20 to 60 μm.
(2) The primary carbon nanotube fibers prepared in step (1) are immersed in an aqueous chlorosulfonic acid solution to be sufficiently expanded and appropriately drawn to rearrange the fibers to improve their axial orientation (i.e., carbon nanotube fiber expansion and drawing 2). The concentration of the chlorosulfonic acid aqueous solution is 5 to 20 weight percent; more preferably, it is 10 to 15 wt%. The expansion time of the primary carbon nano tube fiber in chlorosulfonic acid aqueous solution is 10-100 s; more preferably, 20-40 s; and/or, a suitable elongation is 5-15%; more preferably, it is 8 to 12%.
(3) And (3) immersing the carbon nanotube fiber prepared in the step (2) into a coagulation bath, driving phase separation through poor solubility, and extruding chlorosulfonic acid solvent from the carbon nanotube fiber (namely, phase separation of the carbon nanotube fiber in the coagulation bath 3). The coagulation bath is one or more of volatile solvents such as ethanol and acetone. Soaking the carbon nano tube fiber in a coagulating bath for 10-100 s; more preferably, it is 20 to 50 seconds.
(4) And (4) washing and drying the carbon nano tube fiber obtained in the step (3) on line (namely, drying 4 on line) to obtain compact carbon nano tube fiber. The number of the on-line water washing times of the carbon nano tube fiber is 1 to 3; and/or the water washing temperature is 25 +/-5 ℃. The carbon nano tube fiber drying mode is one or more of infrared heating drying and electric heating drying; and/or, the drying temperature is 60-150 ℃; more preferably, it is 80 to 120 ℃.
(5) Twisting (i.e. fiber twisting 5) the carbon nanotube fiber obtained in the step (4) to give high strength and stretchability to the carbon nanotube fiber, forming a multi-stage helical structure carbon nanotube fiber, and finally winding and collecting on a bobbin (i.e. continuous collection 6). The twisting angle of the carbon nano tube fiber is 5-20 degrees; and/or the rotating speed of the motor is 20-200rpm during twisting; more preferably, 50-100 rpm. The winding speed of the carbon nanotube fiber is 0.5-5 m.min-1(ii) a More preferably, it is 1 to 3 m.min-1。
The carbon nanotube fiber obtained by the method has specific strength of 3.78-4.32 N.tex-1The specific tensile modulus is 167.5-194.3 N.tex-1The conductivity reaches 1940-2·kg-1。
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the present invention, the room temperature means that the ambient temperature is 10 ℃ to 30 ℃.
The reagents used in the following examples are commercially available reagents, and various solvents and drugs are available from national institutes of chemical reagents, ltd.
Example 1
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. Hydrogen and argon as carrier gas in tube furnaceThe method comprises the steps of continuously injecting ethanol serving as a carbon source and ferrocene and thiophene dissolved in the ethanol serving as catalysts into a vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out the carbon nanotube aerogel below the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, and heating and drying the carbon nanotube aerogel to obtain the carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 5 wt% chlorosulfonic acid solution for a swelling time of 100s, and then appropriately drawn at a drawing rate of 15% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 100s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through two water washing tanks, wherein the water washing temperature is 25 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 60 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 5 DEG and a motor twisting speed of 100rpm to form the carbon nanotube fiber with a multi-stage helical structure, and finally twisting at a speed of 1 m.min-1Is wound up and collected on a bobbin. The specific strength of the obtained carbon nanotube fiber was 3.89N. tex-1The specific tensile modulus is 181.5 N.tex-1The conductivity reaches 2100 S.m2·kg-1。
Example 2
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. Continuously injecting hydrogen and argon as carrier gas, ethanol as carbon source, ferrocene and thiophene dissolved in ethanol as catalyst into a vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out from the lower part of the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, heating and drying the carbon nanotube aerogelTo obtain a carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 15 wt% chlorosulfonic acid solution for a swelling time of 10s, and then appropriately drawn at a draw rate of 5% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 10s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through two water washing tanks, wherein the water washing temperature is 25 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 80 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 10 DEG and a motor twisting speed of 200rpm to form a carbon nanotube fiber with a multi-stage helical structure, and finally twisting at 2 m.min-1Is wound up and collected on a bobbin. The specific strength of the obtained carbon nanotube fiber was 4.21N. tex-1The specific tensile modulus is 192.7N · tex-1The conductivity reaches 2320 S.m2·kg-1。
Example 3
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. And continuously injecting hydrogen and argon as carrier gases, ethanol as a carbon source, ferrocene and thiophene dissolved in the ethanol as catalysts into the vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out the carbon nanotube aerogel below the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, and heating and drying the carbon nanotube aerogel to obtain the carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flowThe amount is 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 10 wt% chlorosulfonic acid solution for a swelling time of 20s, and then appropriately drawn at a drawing rate of 6% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 60s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through two water washing tanks, wherein the water washing temperature is 25 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 100 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 6 degrees and a motor twisting speed of 150rpm to form the carbon nanotube fiber with a multi-stage spiral structure, and finally, twisting at 5 m.min-1Is wound up and collected on a bobbin. The specific strength of the obtained carbon nanotube fiber was 3.87 N.tex-1The specific tensile modulus is 175.7 N.tex-1The conductivity reaches 2150 S.m2·kg-1。
Example 4
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. And continuously injecting hydrogen and argon as carrier gases, ethanol as a carbon source, ferrocene and thiophene dissolved in the ethanol as catalysts into the vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out the carbon nanotube aerogel below the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, and heating and drying the carbon nanotube aerogel to obtain the carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 12 wt% chlorosulfonic acid solution for a swelling time of 40s, and then appropriately drawn at a draw rate of 12% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 50s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through 1 water washing tank, wherein the water washing temperature is 20 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 120 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 8 DEG and a motor twisting speed of 20rpm to form the carbon nanotube fiber with a multi-stage helical structure, and finally, rotating the carbon nanotube fiber at a speed of 0.5 m.min-1Is wound up and collected on a bobbin. The specific strength of the obtained carbon nanotube fiber was 4.32 N.tex-1Specific tensile modulus of 194.3tex-1The conductivity reaches 2080 S.m2·kg-1。
Example 5
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. And continuously injecting hydrogen and argon as carrier gases, ethanol as a carbon source, ferrocene and thiophene dissolved in the ethanol as catalysts into the vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out the carbon nanotube aerogel below the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, and heating and drying the carbon nanotube aerogel to obtain the carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 9 wt% chlorosulfonic acid solution for a swelling time of 90s, and then appropriately drawn at a drawing rate of 7.5% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 70s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through 3 water washing tanks, wherein the water washing temperature is 20 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 150 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 6.5 ° and a motor twisting speed of 120rpm to form a carbon nanotube fiber with a multi-stage helical structure, and finally twisting at 1.5 m.min-1Is wound up and collected on a bobbin. The specific strength of the carbon nanotube fiber was 3.78 N.tex-1The specific tensile modulus is 167.5 N.tex-1The conductivity reaches 1970 S.m2·kg-1。
Example 6
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. And continuously injecting hydrogen and argon as carrier gases, ethanol as a carbon source, ferrocene and thiophene dissolved in the ethanol as catalysts into the vertical high-temperature tubular furnace to form carbon nanotube aerogel, leading out the carbon nanotube aerogel below the furnace, shrinking the carbon nanotube aerogel through a water tank, further shrinking the carbon nanotube aerogel through acetone, and heating and drying the carbon nanotube aerogel to obtain the carbon nanotube ribbon. Wherein the size of the gaps among the carbon nano tubes is 10-100nm, the content of ferrocene is 1.2 wt%, the content of thiophene is 0.6 wt%, and the injection rate of ethanol is controlled at 5 mL.h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 5 wt% chlorosulfonic acid solution for a swelling time of 10s, and then appropriately drawn at a drawing rate of 15% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 10s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through two water washing tanks, wherein the water washing temperature is 25 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 80 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 5 ° and a motor twisting speed of 20rpm to form a carbon nanotube fiber with a multi-stage helical structure, and finally, at a speed of 0.5 m.min-1Is wound up and collected on a bobbin. The specific strength of the carbon nanotube fiber was 3.86 N.tex-1The specific tensile modulus is 176.4 N.tex-1The conductivity reaches 1940 S.m2·kg-1。。
Example 7
The continuous primary carbon nano tube fiber is prepared by a floating catalytic chemical vapor deposition method. Hydrogen and argon are used as carrier gas in a tubular furnace, ethanol is used as a carbon source, ferrocene and thiophene are dissolved in the ethanol and used as a catalyst, the mixture is continuously injected into a vertical high-temperature tubular furnace to form carbon nano tube aerogel, the carbon nano tube aerogel is led out from the lower part of the furnace and is contracted through a water tank, then the carbon nano tube aerogel is further contracted through acetone, and a carbon nano tube strip is heated and dried. The obtained carbon nanotubes have a gap size of 10-100nm, ferrocene content of 1.2 wt%, thiophene content of 0.6 wt%, and ethanol injection rate controlled at 5 mL. h-1The hydrogen flow rate was 300 mL/min-1Argon flow rate of 500 mL/min-1The temperature of the tube furnace is 1200 ℃.
The primary carbon nanotube fibers were immersed in a 20 wt% chlorosulfonic acid solution for a swelling time of 100s, and then appropriately drawn at a drawing rate of 10% to rearrange the fibers to improve their axial orientation.
And (3) immersing the carbon nano tube fiber obtained in the last step into an ethanol coagulation bath, wherein the coagulation time is 40s, and driving phase separation through the solubility difference to extrude chlorosulfonic acid solvent from the carbon nano tube fiber.
And (3) sequentially passing the carbon nanotube fiber obtained in the last step through two water washing tanks, wherein the water washing temperature is 25 ℃, and then carrying out infrared heating and drying, wherein the drying temperature is 80 ℃, so as to obtain the compact carbon nanotube fiber.
Twisting the carbon nanotube fiber obtained in the last step at a twisting angle of 20 DEG and a motor twisting speed of 200rpm to form the carbon nanotube fiber with a multi-stage helical structure, and finally, twisting at a speed of 5 m.min-1Is wound up and collected on a bobbin. The obtained carbon nanoThe specific strength of the rice-tube fiber is 3.96N-tex-1A specific tensile modulus of 192.5 N.tex-1The conductivity reaches 2160 S.m2·kg-1。
Claims (10)
1. A method for improving the degree of orientation and the electrical conductivity of carbon nanotube fibers is characterized by comprising the following steps:
(1) preparing continuous primary carbon nanotube fibers by using a floating catalytic chemical vapor deposition method;
(2) immersing the primary carbon nanotube fiber prepared in the step (1) in chlorosulfonic acid aqueous solution to fully expand the primary carbon nanotube fiber, and stretching the primary carbon nanotube fiber to rearrange the primary carbon nanotube fiber to improve the axial orientation of the primary carbon nanotube fiber;
(3) immersing the carbon nanotube fiber prepared in the step (2) into a coagulating bath, driving phase separation through solubility difference, and extruding chlorosulfonic acid from the carbon nanotube fiber;
(4) carrying out online washing and drying on the carbon nanotube fiber obtained in the step (3);
(5) twisting the carbon nanotube fiber obtained in the step (4) to form the carbon nanotube fiber with the multilevel spiral structure.
2. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fibers according to claim 1, wherein the number of the tube wall layers of the primary carbon nanotube fibers prepared in the step (1) is 1-10; the number of the primary carbon nanotube fibers is 5-100; the diameter of the primary carbon nanotube fiber is 5-100 μm.
3. The method for improving the orientation degree and the conductivity of the carbon nanotube fibers according to claim 1, wherein the mass concentration of the chlorosulfonic acid in the chlorosulfonic acid aqueous solution in the step (2) is 5 to 20 percent.
4. The method for improving the orientation degree and the conductivity of the carbon nanotube fibers according to claim 1, wherein the swelling time of the primary carbon nanotube fibers in the chlorosulfonic acid aqueous solution in the step (2) is 10-100 s; the elongation at stretching is 5% to 15%.
5. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fibers according to claim 1, wherein the coagulation bath in the step (3) is ethanol or acetone.
6. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fibers according to claim 1, wherein the soaking time of the carbon nanotube fibers prepared in the step (2) in the coagulating bath is 10-100 s.
7. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fiber according to claim 1, wherein the number of the online water washing in the step (4) is 1 to 3; the water washing temperature is 25 ℃. + -. 5 ℃.
8. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fibers according to claim 1, wherein the drying manner in the step (4) is one or more of infrared heating drying and electrical heating drying; the drying temperature is 60-150 ℃.
9. The method for improving the orientation degree and the conductivity of the carbon nanotube fibers according to claim 1, wherein the twisting angle of the carbon nanotube fibers in the step (5) is 5-20 °; the rotating speed of the motor is 20-200rpm during twisting.
10. The method for improving the degree of orientation and the electrical conductivity of the carbon nanotube fiber according to claim 1, wherein the specific strength of the carbon nanotube fiber with the multi-stage helical structure obtained in the step (5) is 3.78-4.32N-tex-1The specific tensile modulus is 167.5-194.3 N.tex-1The conductivity reaches 1940-2·kg-1。
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