CN115418748B - Preparation method of circular-section high-conductivity carbon nanotube fiber - Google Patents
Preparation method of circular-section high-conductivity carbon nanotube fiber Download PDFInfo
- Publication number
- CN115418748B CN115418748B CN202210995490.8A CN202210995490A CN115418748B CN 115418748 B CN115418748 B CN 115418748B CN 202210995490 A CN202210995490 A CN 202210995490A CN 115418748 B CN115418748 B CN 115418748B
- Authority
- CN
- China
- Prior art keywords
- fiber
- carbon nanotube
- section
- circular
- nanotube fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 193
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 122
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000001112 coagulating effect Effects 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- 230000015271 coagulation Effects 0.000 claims description 31
- 238000005345 coagulation Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000000701 coagulant Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 10
- 230000008023 solidification Effects 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 2
- 239000002109 single walled nanotube Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002079 double walled nanotube Substances 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000002166 wet spinning Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 238000010884 ion-beam technique Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000007712 rapid solidification Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The application relates to the field of high-performance carbon nanotube fiber preparation, in particular to a preparation method of a carbon nanotube fiber with a circular cross section and high conductivity. Using N-methyl pyrrolidone capable of slowing down the fiber solidification rate as a primary solidification bath, and injecting chlorosulfonic acid dispersed carbon nanotube liquid crystal spinning solution into the primary solidification bath filled with the N-methyl pyrrolidone to obtain semi-solid carbon nanotube fibers; and then the semi-solid nanotube fiber is introduced into a secondary coagulating bath filled with ethanol through a smooth guide rail to be completely solidified, and the fiber is pulled, wound and collected, and finally dried and molded in a natural state. The application utilizes the characteristic of low diffusion rate of chlorosulfonic acid in N-methyl pyrrolidone to uniformly and slowly solidify the fiber into the fiber in the N-methyl pyrrolidone, ensures the sufficient stretching and thinning of the fiber, improves the cis-arrangement degree and the compactness of the carbon nano tube, and finally obtains the carbon nano tube fiber with high conductivity and circular section.
Description
Technical Field
The application relates to the field of high-performance carbon nanotube fiber preparation, in particular to a preparation method of a carbon nanotube fiber with a circular cross section and high conductivity.
Background
The carbon nanotube fiber is a macroscopic-scale fiber material assembled by single carbon nanotubes, has excellent mechanical, electrical and thermal properties, has the advantages of low density, large specific surface area, high length-diameter ratio and the like, and is expected to become a next-generation light-weight high-strength high-conductivity material. The carbon nano tube fiber with excellent performance can be widely applied in the fields of aerospace, wearable electronic devices, solar cells, super capacitors, artificial muscles and the like.
The methods for preparing carbon nanotube fibers mainly comprise three methods: namely, an array spinning method, a chemical vapor deposition direct spinning method and a wet spinning method. The array spinning method is a method for forming fibers by pulling a vertical array of carbon nanotubes prepared by a chemical vapor deposition method so that the carbon nanotubes are connected end to end, and the fibers obtained by the method have lower density and thus poorer electrical properties (documents 1:Jiang K,Li Q,Fan S.Nature.2002,419 (6909) and 801). The chemical vapor deposition spinning method is a method for preparing the carbon nano tube fiber in one step: the method comprises the steps of taking ethanol/ferrocene/thiophene solution as a liquid carbon source, introducing the liquid carbon source into a high-temperature reaction furnace at a certain injection rate under the action of carrier gas, gasifying the liquid carbon source in the high-temperature reaction furnace to obtain a stocking-shaped carbon nano tube fiber precursor structure, and collecting the carbon nano tube fiber outside the reaction furnace (document 2:Koziol K,Vilatela J,Windle A,et al.Science 2007,318 (5858), 1892-1895). Wet spinning is a spinning method in which carbon nanotubes are first prepared into a uniform and stable carbon nanotube dispersion, and then injected into a coagulation bath to be coagulated and formed (document 3:Vigolo B,Penicaud A,Coulon C,et al.Science.2000,290 (5495), 1331 to 1334). Because the fiber prepared by wet spinning has higher orientation degree and density, the electrical property is more excellent than that of the fiber obtained by dry spinning. In addition, wet spinning is easier to industrialize, so that the large-scale production of the carbon nano tube fiber is realized.
The strength and the conductivity of the carbon nano tube fiber prepared by the current wet spinning are far lower than the performance of a single carbon nano tube. On one hand, the carbon nano tube is not uniform in structure (such as wall number, diameter, chirality, length, defect and the like) thereof; on the other hand, in the process of assembling the macroscopic carbon nanotube fiber from the nano-sized single carbon nanotube, the contact resistance between the inner tubes of the fiber is larger due to poor orientation degree, density and the like; in addition, because of the relatively high curing rate of the fibers during wet spinning, the fibers shrink rapidly in the coagulation bath, and the shrinkage of the sheath and core layers of the fibers is not synchronized, resulting in uneven shrinkage, and therefore the cross section of the fibers is generally random in shape, and the surfaces have many grooves and wrinkles, which limit the accurate calculation and practical application of the conductivity of the fibers (document 4:Bucossi A R,Cress C D,Schauerman C M,et al.ACS Appl Mater Interfaces,2015,7 (49): 27299-27305.).
Thus, one major problem in the current preparation of high performance carbon nanotube fibers is: the method is used for developing or improving the carbon nanotube fiber spinning technology, preparing the carbon nanotube fiber with high cis-form, high density and smooth surface, breaking through the technical bottleneck in the fiber assembly process, obtaining the high-conductivity carbon nanotube fiber and promoting the large-scale application of the carbon nanotube fiber.
Disclosure of Invention
Aiming at the problem that in the conventional liquid phase spinning process, the carbon nano tube spinning solution rapidly contracts in a coagulating bath to cause fibersThe application aims to provide a preparation method of a carbon nano tube fiber with smooth surface, high cis-form degree, high density and circular section and high conductivity, which solves the technical problems of uneven shrinkage of the fiber and insufficient stretching and thinning caused by rapid solidification of the carbon nano tube in the conventional liquid phase spinning method. The prepared carbon nanotube fiber has unlimited length, adjustable diameter of 5-30 μm and conductivity up to 0.5-1.5X10 7 S/m, and the tensile strength is 0.5-2 GPa.
The technical scheme of the application is as follows:
a preparation method of a carbon nano tube fiber with a circular section and high conductivity selects N-methyl pyrrolidone as a primary coagulation bath and ethanol, acetone, water or dimethyl sulfoxide as a secondary coagulation bath; by utilizing the characteristic of low diffusion rate of chlorosulfonic acid in N-methylpyrrolidone, the carbon nanotube spinning solution is uniformly contracted into fibers in the N-methylpyrrolidone, and enters a secondary coagulation bath under the action of traction force to be stretched and thinned so as to improve the cis-arrangement degree and the compactness of the carbon nanotubes, and finally, the carbon nanotube fibers with the circular cross section and high conductivity are obtained.
The preparation method of the circular-section high-conductivity carbon nanotube fiber comprises the steps that the carbon nanotubes are one, two or three of single-wall, double-wall and few-wall carbon nanotubes, the carbon nanotube spinning solution is a carbon nanotube liquid crystal solution dispersed in chlorosulfonic acid, and the concentration of the carbon nanotubes is 1-2wt%.
According to the preparation method of the carbon nanotube fiber with the circular cross section and the high conductivity, the N-methyl pyrrolidone solution is used as the primary coagulating bath of the carbon nanotube fiber, the temperature of the primary coagulating bath is between-10 and 80 ℃, and the curing time is between 3 and 30 seconds.
According to the preparation method of the carbon nano tube fiber with the circular cross section and the high conductivity, the carbon nano tube fiber in the primary coagulation bath is semi-solid, and the diameter of the carbon nano tube fiber is 20-50 mu m.
According to the preparation method of the carbon nano tube fiber with the circular cross section, ethanol, acetone, water or dimethyl sulfoxide is used as a coagulant in the secondary coagulating bath, the temperature of the secondary coagulating bath is between-10 and 30 ℃, and the curing time is between 3 and 30 seconds.
According to the preparation method of the carbon nano tube fiber with the circular cross section and the high conductivity, the stretching ratio of the carbon nano tube fiber is controlled within the range of 120-260%.
According to the preparation method of the carbon nanotube fiber with the circular cross section and the high conductivity, the cross section of the prepared carbon nanotube fiber is circular, the pores and cracks in the fiber are less, and the surface of the fiber is smooth and uniform.
The preparation method of the circular section high conductivity carbon nano tube fiber has the advantages that the length of the spun carbon nano tube fiber is unlimited, the diameter is adjustable between 5 and 30 mu m, and the conductivity is 0.5 to 1.5X10 7 S/m, and the tensile strength is 0.5-2 GPa.
The design idea of the application is as follows:
according to the application, N-methyl pyrrolidone is used as a primary coagulation bath, and the characteristics of slow diffusion and low diffusion rate of chlorosulfonic acid in the N-methyl pyrrolidone are utilized to uniformly shrink and slowly coagulate carbon nanotube fibers in the primary coagulation bath, so that semi-solid single-wall, double-wall and few-wall carbon nanotube fibers with smooth surfaces and circular sections are obtained; meanwhile, a secondary solidification process and a traction technology are added, so that the semi-solid fiber is fully contracted, stretched and thinned, the orientation degree, the smooth arrangement degree and the compactness of the fiber are improved, and the conductivity and the strength of the fiber are improved.
The application has the advantages and beneficial effects that:
1. the application solves the problems of uneven radial structure, insufficient stretching and thinning of the carbon nano tube caused by uneven fiber shrinkage due to rapid solidification of the carbon nano tube spinning solution in the coagulation bath in the conventional liquid phase spinning process, and prepares the carbon nano tube fiber with circular fiber section and smooth and uniform surface.
2. The application solves the problem that the fiber is not fully stretched and thinned due to the rapid solidification of the carbon nano tube in the conventional spinning process, so that the fiber can be fully stretched and thinned, and the orientation degree and the density of the fiber are improved, thereby improving the conductivity and the strength of the fiber.
3. Length of fibers prepared according to the applicationWithout limitation, the diameter is adjustable within the range of 5-30 mu m, and the conductivity is 0.5-1.5X10 7 S/m, and the tensile strength is 0.5-2 GPa.
4. The method can continuously prepare the high-performance carbon nanotube fiber, and can be expected to be applied to the fields of high-performance cables, flexible sensors, aerospace, military industry national defense and the like.
5. According to the application, the nonvolatile N-methyl pyrrolidone is used as a primary coagulating bath instead of a volatile acetone solution in the traditional wet spinning process, so that volatilization of toxic substances and loss of the coagulating bath in the spinning process are reduced, the operation environment is optimized, and the spinning cost is reduced.
Drawings
FIG. 1 is a schematic view of a device for preparing carbon nanotube fibers with circular cross section, smooth surface and high conductivity. In the figure, 1. A spinning solution extrusion device; 2. primary coagulation bath; 3. a guide rail; 4. a secondary coagulation bath; 5. and a fiber collection device.
FIG. 2 is a structural representation of a carbon nanotube. (a) TEM photographs of single-walled carbon nanotubes; (b) TEM photographs of double walled carbon nanotubes; (c) TEM photograph of few-walled carbon nanotubes.
FIG. 3 is a structural representation of carbon nanotube fibers. (a) And (b) are low-power and high-power SEM pictures of carbon nanotube fibers prepared by taking N-methylpyrrolidone as a primary coagulation bath; (c) And (d) are low-power and high-power SEM pictures of carbon nanotube fibers prepared with acetone as a primary coagulation bath; (e) And (f) are low-power and high-power SEM pictures of the carbon nanotube fiber prepared by taking N-methylpyrrolidone as a primary coagulation bath and not carrying out drawing.
FIG. 4 is a cross-sectional representation of a carbon nanotube fiber. (a) And (b) a low-power and high-power focused ion beam cutting section view of the carbon nanotube fiber prepared by taking N-methyl pyrrolidone as a primary coagulation bath; (c) And (d) low-power and high-power focused ion beam cut cross-sectional views of carbon nanotube fibers prepared with acetone as a coagulation bath.
FIG. 5 is a graph showing the tensile strength of carbon nanotube fibers. In the figure, the abscissa Stress represents Strain (%), and the ordinate Tensile Stress represents Tensile strength (MPa).
Fig. 6 is a graph showing the conductivity of the carbon nanotube fiber. In the abscissa, SWCNT Fiber stands for single-walled carbon nanotube Fiber, DWCNT Fiber stands for double-walled carbon nanotube Fiber, FWCNT Fiber stands for few-walled carbon nanotube Fiber, and ordinate connectivity stands for electrical Conductivity (MS/m).
FIG. 7 is an optical photograph of a short carbon nanotube fiber prepared with dichlorobenzene as a coagulation bath.
Detailed Description
In the specific implementation process, the preparation method of the carbon nano tube fiber with the circular cross section, smooth surface and high conductivity provided by the application uses N-methyl pyrrolidone capable of slowing down the fiber solidification rate as a primary solidification bath, and the carbon nano tube liquid crystal spinning solution with chlorosulfonic acid dispersed is injected into the primary solidification bath filled with the N-methyl pyrrolidone to obtain the semi-solid carbon nano tube fiber; and then the semi-solid nanotube fiber is introduced into a secondary coagulating bath filled with ethanol through a smooth guide rail to be completely solidified, and the fiber is pulled, wound and collected, and finally dried and molded in a natural state.
As shown in fig. 1, the apparatus for preparing carbon nanotube fibers with circular cross section, smooth surface and high conductivity according to the present application mainly comprises: the spinning solution extruding device 1, the primary coagulating bath 2, the guide rail 3, the secondary coagulating bath 4 and the fiber collecting device 5 have the following specific structure and preparation process: a guide rail 3 of carbon nano tube fibers is arranged above one side of the corresponding primary coagulation bath 2 and secondary coagulation bath 4, a spinning solution extrusion device 1 is arranged above the other side of the primary coagulation bath 2, and a fiber collecting device 5 is arranged above the secondary coagulation bath 4; the spinning solution extrusion device 1 consists of a vertically arranged injection pump and an injector, wherein the spinning solution output end of the injection pump is communicated with the injector, and the injection pump can accurately control the extrusion rate of the spinning solution.
The lower part of the injector is provided with a needle tip which extends into the primary coagulation bath 2, the inner diameter of the needle tip is 0.11-0.21 mm, the length is 14-50 mm, and the extrusion rate is 0.03-0.1 mL/min. The carbon nano tube spinning solution enters the primary coagulating bath 2 through the needle point to form stable and continuous semi-solid carbon nano tube fibers. The semi-solid carbon nanotube fibers are then introduced from the smooth guide rail 3 into a secondary coagulation bath 4 for further solidification. Finally, the fiber is wound and collected on a fiber collecting device 5, and is naturally dried and molded. The speed of the collecting device is adjustable, and the stretching ratio in the fiber preparation process is controlled. The application prepares the semi-solid carbon nanotube fiber by taking N-methyl pyrrolidone as a primary coagulating bath, and simultaneously prepares the high-conductivity carbon nanotube fiber with round section and smooth surface by using a secondary coagulating bath.
The present application will be described in detail with reference to the following examples and drawings, but the scope of the application is not limited thereto.
Example 1
In this embodiment, the preparation method of the single-walled carbon nanotube fiber with a round cross section and a smooth surface comprises the following steps:
(1) 80mg of single-walled carbon nanotubes (FIG. 2 a) were dispersed in 3mL of 99.5% chlorosulfonic acid and stirred in a high-speed mixer at 3000r/min for 5min to prepare a uniform and stable single-walled carbon nanotube spinning solution with a mass fraction of 1.6 wt%.
(2) Transferring the single-walled carbon nanotube spinning solution prepared in the step (1) into an injector of an extrusion device, selecting a needle tip with the inner diameter of 0.18mm and the length of 50mm, and setting the extrusion rate to be 0.07mL/min. Injecting the carbon nanotube spinning solution in the injector into a primary coagulating bath containing N-methyl pyrrolidone to prepare semi-solid single-wall carbon nanotube fibers, and introducing the semi-solid single-wall carbon nanotube fibers into a secondary coagulating bath containing ethanol through a smooth guide rail to be solidified. And finally, pulling and continuously collecting the single-walled carbon nanotube fiber by a collecting device, wherein the maximum fiber stretching ratio is 240 percent under the condition.
And (3) carrying out structural characterization on the single-walled carbon nanotube fiber prepared in the step (2). Fig. 3 (a) and 3 (b) are SEM pictures of the spun fibers at low and high magnification, and it can be seen that the single-walled carbon nanotubes have uniform fiber diameter, smooth surface, and the single-walled carbon nanotubes within the fiber are arranged in a significant orientation along the fiber axis direction, and the fiber diameter is 15±3 μm. Fig. 4 (a) and 4 (b) are cross-sectional views of a fiber cut using a focused ion beam, and it can be seen that the fiber has a circular cross-section with very few internal voids and cracks.
And (3) performing performance characterization on the single-walled carbon nanotube fiber prepared in the step (2). As shown in FIG. 6, the conductivity of single-walled carbon nanotube fibers was 1X 10 as measured using four-wire method 7 S/m, the tensile strength of the fiber was 1.1GPa (FIG. 5).
Example 2
In this example, step (1) is identical to step (1) of example 1, except that double walled carbon nanotubes are selected (FIG. 2 b).
Step (2) was identical to step (2) of example 1, and the tip capillary inner diameter was 0.16mm, the extrusion rate was 0.05mL/min, and the maximum fiber draw ratio was 220% under this condition.
And carrying out structural and performance characterization on the prepared double-wall carbon nanotube fiber, wherein SEM (scanning electron microscope) pictures show that the double-wall carbon nanotube fiber has uniform diameter and smooth surface, the double-wall carbon nanotubes in the fiber are arranged in high density along the axial direction of the fiber, and the diameter of the spun double-wall carbon nanotube fiber is 5+/-2 mu m. And (3) cutting by adopting a focused ion beam, observing the cross section of the fiber, and finding that the cross section of the fiber is circular and the inside is compact. As shown in FIG. 6, the conductivity of the double-walled carbon nanotube fiber was 1.5X10 as measured by the four-wire method 7 S/m, tensile strength of 1.2GPa.
Example 3
In this example, step (1) is identical to step (1) of example 1, except that few-walled carbon nanotubes are used (FIG. 2 c).
Step (2) was identical to step (2) of example 1, and the tip capillary inner diameter was 0.16mm, the extrusion rate was 0.05mL/min, and the maximum fiber draw ratio was 260% under this condition.
And carrying out structural and performance characterization on the prepared few-wall carbon nanotube fiber, wherein SEM (scanning electron microscope) pictures show that the few-wall carbon nanotube fiber has uniform diameter and smooth surface, the few-wall carbon nanotubes in the fiber are arranged in high density along the axial direction of the fiber, and the diameter of the spun few-wall carbon nanotube fiber is 10+/-3 mu m. And (3) cutting by adopting a focused ion beam, observing the cross section of the fiber, and finding that the cross section of the fiber is circular and the inside is compact. As shown in FIG. 6, the conductivity of the few-wall carbon nanotube fiber measured by the four-wire method is 1.2X10 7 S/m, tensile strength was 1GPa.
Comparative example 1
In this comparative example, step (1) is identical to step (1) of example 1.
Step (2) is identical to step (2) of example (1). Except that N-methylpyrrolidone in the primary coagulation bath was replaced with acetone as the coagulation bath, under which conditions the maximum draw ratio of the fiber was 110%.
The prepared single-walled carbon nanotube fiber is subjected to structural and performance characterization, and the low-power and high-power SEM pictures of the spun fiber are shown in fig. 3 (c) and 3 (d), so that the diameter of the single-walled carbon nanotube fiber is relatively uniform and is 25+/-5 mu m, the surface of the single-walled carbon nanotube fiber is provided with folds, and the single-walled carbon nanotubes in the fiber are arranged in an oriented manner along the axial direction of the fiber. Fig. 4 (c) and 4 (d) are cross-sectional views of a fiber cut using a focused ion beam, and it was found that the cross-section of the fiber was irregularly shaped and that there were large voids and cracks inside the fiber. Single-wall carbon nano tube fiber conductivity of 2 x 10 measured by four-wire method 6 S/m, tensile strength was 0.35GPa.
Comparative example 2
In this comparative example, step (1) is identical to step (1) of example 1.
Step (2) is identical to step (2) of example 1. The N-methyl pyrrolidone in the primary coagulating bath is replaced by o-dichlorobenzene as the coagulating bath, and the fiber cannot be drawn in the whole spinning process.
As shown in FIG. 7, it was found that continuous single-walled carbon nanotube fibers could not be formed during spinning, and only short fibers having a length of 1 to 3cm could be produced. The conductivity of the single-walled carbon nanotube fiber measured by a four-wire method is 8 multiplied by 10 5 S/m, tensile strength was 0.3GPa.
Comparative example 3
In this comparative example, step (1) is identical to step (1) of example 1.
In the step (2), the secondary solidification step was not performed, and the rest was the same as in the step (2) of example 1, under which the maximum draw ratio of the fiber was 150%.
Only semi-solid single-wall carbon nanotube fiber can be obtained, the fiber can not be shrunk and formed in a natural state, and the fiber is always keptMaintaining the semi-solid state. Single-walled carbon nanotube fiber conductivity of 7 x 10 as measured by four-wire method 5 S/m, tensile strength was 0.2GPa.
Comparative example 4
In this comparative example, step (1) is identical to step (1) of example 1.
In the step (2), only a simple yarn winding function was performed for the fiber collecting device, and the fiber was not drawn, and the other steps were the same as the step (2) in example 1.
The fiber is subjected to structural and performance characterization, and the low-power and high-power SEM pictures of the spun fiber are shown in the figure 3 (e) and the figure 3 (f), so that the diameter of the prepared single-wall carbon nano tube fiber is larger and is 30-40 mu m, and the arrangement of the carbon nano tubes in the fiber is disordered and has no obvious orientation. Single-walled carbon nanotube fiber conductivity of 5 x 10 as measured by four-wire method 5 S/m, tensile strength was 0.4GPa.
The results of the examples and the comparative examples show that the shrinkage rate of the fiber is slowed down by using N-methyl pyrrolidone as a primary coagulation bath, and the semi-solid carbon nanotube fiber with smooth surface and ideal circular cross section is obtained; the fiber can be sufficiently stretched and thinned by combining the solidification effect of the secondary coagulating bath and the stretching effect of the collecting device on the fiber, so that the orientation degree and the compactness of the fiber are improved; finally, the carbon nano tube fiber with round section, smooth surface, high cis-form, high density and high conductivity can be prepared. The carbon nano tube fiber with the circular cross section and high conductivity prepared for the first time is expected to be applied to the fields of aerospace, wearable electronic devices, solar cells, super capacitors, artificial muscles and the like.
While the application has been described in detail in the general context and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the application and are intended to be within the scope of the application as claimed.
Claims (8)
1. A preparation method of a carbon nano tube fiber with a circular section and high conductivity is characterized in that N-methyl pyrrolidone is selected as a primary coagulating bath, and ethanol, acetone, water or dimethyl sulfoxide is selected as a secondary coagulating bath; injecting chlorosulfonic acid dispersed carbon nanotube spinning solution into a primary coagulating bath filled with N-methyl pyrrolidone, wherein the carbon nanotube spinning solution is carbon nanotube liquid crystal solution dispersed in chlorosulfonic acid, and by utilizing the characteristic of low diffusion rate of chlorosulfonic acid in N-methyl pyrrolidone, the carbon nanotube spinning solution uniformly contracts into fibers in N-methyl pyrrolidone and enters a secondary coagulating bath under the action of traction force, and stretching and refining are carried out to improve the cis-arrangement degree and compactness of carbon nanotubes, so that the carbon nanotube fiber with circular section and high conductivity is finally obtained.
2. The method for preparing the circular-section high-conductivity carbon nanotube fiber according to claim 1, wherein the carbon nanotubes are one, two or three of single-wall, double-wall and few-wall carbon nanotubes, and the concentration of the carbon nanotubes is 1-2 wt%.
3. The method for preparing the carbon nanotube fiber with the circular cross section and high conductivity according to claim 1, wherein the N-methyl pyrrolidone solution is used as a primary coagulation bath of the carbon nanotube fiber, the temperature of the primary coagulation bath is-10-80 ℃, and the curing time is 3-30 s.
4. The method for producing a circular-section highly conductive carbon nanotube fiber according to claim 1 or 3, wherein the carbon nanotube fiber in the primary coagulation bath is semi-solid and has a diameter of 20 to 50. Mu.m.
5. The method for preparing the circular-section high-conductivity carbon nanotube fiber according to claim 1, wherein the secondary coagulation bath uses ethanol, acetone, water or dimethyl sulfoxide as a coagulant, the temperature of the secondary coagulation bath is-10-30 ℃, and the curing time is 3-30 s.
6. The method for preparing the circular-section high-conductivity carbon nanotube fiber according to claim 1, wherein the stretching ratio of the carbon nanotube fiber is controlled within a range of 120-260%.
7. The method for preparing the carbon nanotube fiber with the circular cross section and the high conductivity according to claim 1, wherein the prepared carbon nanotube fiber has the advantages of circular cross section, less pores and cracks in the fiber, and smooth and uniform fiber surface.
8. The method for preparing a circular-section high-conductivity carbon nanotube fiber according to claim 1, wherein the length of the spun carbon nanotube fiber is unlimited, the diameter is adjustable between 5 μm and 30 μm, and the conductivity is 0.5X10 7 S/m ~1.5×10 7 S/m, and the tensile strength is 0.5-2 GPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210995490.8A CN115418748B (en) | 2022-08-18 | 2022-08-18 | Preparation method of circular-section high-conductivity carbon nanotube fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210995490.8A CN115418748B (en) | 2022-08-18 | 2022-08-18 | Preparation method of circular-section high-conductivity carbon nanotube fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115418748A CN115418748A (en) | 2022-12-02 |
| CN115418748B true CN115418748B (en) | 2023-11-10 |
Family
ID=84198246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210995490.8A Active CN115418748B (en) | 2022-08-18 | 2022-08-18 | Preparation method of circular-section high-conductivity carbon nanotube fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115418748B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200139445A (en) * | 2019-06-04 | 2020-12-14 | 주식회사 엘지화학 | Method for improving specific tensile strength of carbon nanotube fiber |
| CN113913970A (en) * | 2021-11-29 | 2022-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-performance carbon nanofiber and continuous preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140363669A1 (en) * | 2011-09-07 | 2014-12-11 | William Marsh Rice University | Carbon nanotubes fiber having low resistivity, high modulus and/or high thermal conductivity and a method of preparing such fibers by spinning using a fiber spin-dope |
-
2022
- 2022-08-18 CN CN202210995490.8A patent/CN115418748B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200139445A (en) * | 2019-06-04 | 2020-12-14 | 주식회사 엘지화학 | Method for improving specific tensile strength of carbon nanotube fiber |
| CN113913970A (en) * | 2021-11-29 | 2022-01-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-performance carbon nanofiber and continuous preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115418748A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Carbon-based fibers: fabrication, characterization and application | |
| CN113913970B (en) | High-performance nano carbon fiber and continuous preparation method thereof | |
| RU2504604C2 (en) | Articles made of pure carbon nanotubes, made from superacid solutions and methods for production thereof | |
| CN109576822B (en) | Method for preparing single-walled carbon nanotube fiber and composite fiber thereof | |
| CN111155217A (en) | Method for improving orientation degree and conductivity of carbon nanotube fibers | |
| CN112210849B (en) | Preparation method of single-walled carbon nanotube fiber with high conductivity | |
| CN111394833B (en) | Carbon nano tube/graphene composite fiber and preparation method thereof | |
| CN1431342A (en) | Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation | |
| Sun et al. | High performance carbon nanotube/polymer composite fibers and water-driven actuators | |
| KR20160138776A (en) | Ultrafine carbon fibers and their preparation method | |
| CN114481368B (en) | Hollow carbon nanofiber and preparation method thereof | |
| KR102313612B1 (en) | Producing method for densified carbon nanotube fiber | |
| Newcomb et al. | The properties of carbon fibers | |
| CN112359441B (en) | High-orientation carbon nano tube composite fiber, and preparation method and system thereof | |
| CN106350904B (en) | Graphene enhanced preparation method of micro-nano film-shaped carbon fibers | |
| CN108624985B (en) | Preparation method of lignin and polyacrylonitrile blended fiber and carbon fiber thereof | |
| CN110468465B (en) | Carbon nano tube/polyimide composite carbonized fiber and production method thereof | |
| CN115418748B (en) | Preparation method of circular-section high-conductivity carbon nanotube fiber | |
| Bo et al. | Regulated assembly of PBO nanofibers as aerogel fibers for thermal insulation and electromagnetic shielding | |
| CN112575411B (en) | Wet spinning preparation method of high-strength and high-conductivity single-walled carbon nanotube fiber | |
| Mataram et al. | A review of assembled polyacrylonitrile-based carbon nanofiber prepared electrospinning process | |
| KR101098040B1 (en) | Carbon nanotube composite filament and manufacturing method thereof | |
| CN115434040A (en) | Preparation method of hollow carbon fiber | |
| JP2003300717A (en) | Carbon nanotube precursor fiber, carbon nanotube and method for manufacturing the same | |
| CN117904751A (en) | Continuous preparation method of high-conductivity carbon nanotube fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |