Method for producing carbon nanotube fibers comprising graphene oxide and carbon nanotube fibers prepared thereby

Abstract

The present invention provides a method for producing carbon nanotube fibers comprising graphene oxide, the method being characterized by comprising: a step for producing a carbon nanotube dough; a step for oxidizing and neutralizing the carbon nanotube dough at a temperature of 10 °C and then removing the oxidizing agent and the strong acid to prepare oxidized carbon nanotubes having oxygen-containing functional groups; a step for preparing a carbon nanotube dispersion and adding graphene oxide to the dispersion to produce a spinning dope; and a step for preparing carbon nanotube fibers comprising graphene oxide by solution-spinning the spinning dope, wherein, in the step for preparing carbon nanotube fibers, the oxidized carbon nanotubes self-assemble as hydrogen bonding is induced between the oxygen-containing functional groups on the surface thereof, and the spinning dope is coagulated and solution-spun as the oxidized carbon nanotubes and the graphene oxide form crosslinks. In the method for preparing carbon nanotube fibers according to the present invention, carbon nanotubes are oxidized while performing kneading, the carbon nanotubes are oxidized under low-temperature conditions, thereby increasing the content of oxygen functional groups and reducing defects so that the carbon nanotubes can be dispersed in an organic solvent without a dispersant, and carbon nanotube fibers can be prepared through a multi-nozzle using a spinning dope to which graphene oxide has been added.

Description

Method for manufacturing carbon nanotube fibers containing graphene oxide and carbon nanotube fibers manufactured thereby

[0001] The present invention relates to a method for manufacturing a carbon nanotube fiber including graphene oxide and a carbon nanotube fiber manufactured thereby.

[0002] Many researchers have proposed various strategies for producing carbon nanotube (CNT)-based conductive fibers for applications such as textile electronics, electrical cables, and electrochemical energy storage devices. Among these, wet spinning is the most desirable process for industrialization, mimicking polymer-based fibers. Dispersing CNTs in a solvent has been one of the most challenging issues during the wet spinning process for CNT fibers.

[0003] Pasquali et al. reported the liquid crystal (LC) dispersion of individual SWCNTs in a superacid, which allowed wet spinning to produce well-aligned SWCNT fibers. Subsequent research has been ongoing to disperse carbon nanotubes using superacids such as chlorosulfonic acid, or to disperse carbon nanotubes in aqueous solutions using surfactants or polymeric dispersants for spinning. However, the use of superacids as dispersants may raise environmental concerns, and the use of dispersants such as surfactants requires a process to remove the dispersant after spinning to ensure electrical conductivity, which is a drawback.

[0004] Meanwhile, fibers using nanomaterials can be manufactured by utilizing functional groups introduced onto the surface of nanomaterials. For example, cellulose filaments can be manufactured by wet spinning cellulose nanofibers obtained through 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation (TCNF) using an organic solvent as a coagulant. Furthermore, in wet spinning, liquid crystal graphene oxide and Mxene can be assembled using hydrogen bonds between hydroxyl groups on the surface of 2D sheets. In this spinning process, hydroxyl and carboxyl groups play a crucial role in densifying the structure during the coagulation process, enabling fiber manufacturing.

[0005] However, for CNTs, a CNT-based single-phase spinning process in organic solvents has not been reported due to the difficulty in preparing highly concentrated dispersions. In particular, the preparation of SWCNT dopes in organic solvents without a dispersant is limited by van der Waals interactions and large bundle sizes due to pi-pi interactions. While CNT dispersion in high-concentration organic solvents can be achieved through oxidation, highly oxidized CNTs can shorten due to the formation of defects during oxidation by strong oxidizing agents. Therefore, a defect-free oxidation method is required to induce assembly via hydrogen bonds to prepare SWCNT dopes.

[0006] Accordingly, the inventors of the present invention have developed a method for manufacturing carbon nanotube fibers including graphene oxide, which improves dispersibility and coagulation speed by dispersing carbon nanotubes with oxygen-containing functional groups introduced into an organic solvent and then adding graphene oxide to the carbon nanotubes, and a carbon nanotube fiber manufactured thereby by manufacturing an electrically conductive carbon nanotube fiber through a general solution spinning process, particularly a multi-nozzle, and have completed the present invention.

[0007] The present invention was invented to solve the above problems, and its technical task is to provide a method for manufacturing carbon nanotube fibers and carbon nanotube fibers manufactured thereby.

[0008] In order to solve the above technical problem, the present invention comprises the steps of: mixing bundle-shaped carbon nanotubes and an oxidizing agent to produce a carbon nanotube mixture, kneading the carbon nanotube mixture while repeatedly adding a small amount of a strong acid to the carbon nanotube mixture to produce a carbon nanotube dough; subjecting the carbon nanotube dough to an oxidation reaction at a temperature of up to 10°C and neutralizing it, and then removing the oxidizing agent and the strong acid to produce oxidized carbon nanotubes having oxygen-containing functional groups introduced therein; physically dispersing the oxidized carbon nanotubes in an organic solvent to produce a carbon nanotube dispersion, and adding graphene oxide to the carbon nanotube dispersion to produce a spinning dope; And a step of manufacturing a carbon nanotube fiber including graphene oxide by solution-spinning the above-mentioned radiation dope; and in the step of manufacturing the carbon nanotube fiber, the oxidized carbon nanotube self-assembles by inducing hydrogen bonds between oxygen-containing functional groups introduced to the surface, and the oxidized carbon nanotube and the oxidized graphene form a crosslink, thereby solidifying the radiation dope and causing the fiber to be solution-spinning. A method for manufacturing a carbon nanotube fiber including graphene oxide is provided.

[0009] In addition, in order to solve the other technical problems mentioned above, a carbon nanotube fiber including graphene oxide manufactured according to the manufacturing method of the present invention is provided.

[0010] The method for manufacturing carbon nanotube fibers of the present invention by means of solving the above problem has the effect of enabling the manufacture of carbon nanotube fibers through a multi-nozzle by dispersing carbon nanotubes in an organic solvent without a dispersant by performing kneading and oxidizing carbon nanotubes under low-temperature conditions to increase the content of oxygen functional groups and reduce defects, and by using a spinning dope with added graphene oxide.

[0011] In addition, the carbon nanotube fiber of the present invention can be spun through a multi-nozzle by adding graphene oxide, and thus has a diameter of at least 50㎛ or more, an electrical characteristic of a line resistance of 200 Ω / cm or less, and provides mechanical characteristics of a tensile strength of 0.1 N / Tex or more and an elongation at break of 1 to 2%.

[0012] Figure 1 is a schematic diagram showing the self-assembly of carbon nanotubes of the present invention.

[0013] Figure 2 is a schematic diagram showing the steps for manufacturing carbon nanotubes of the present invention.

[0014] Figure 3 shows the C1s X-ray photoelectron spectroscopy (XPS) results of oxidized single-walled carbon nanotubes according to Example 1.

[0015] Figure 4 is a graph showing the viscosity and viscoelastic behavior of a mixed carbon nanotube / graphene oxide spin dope according to the present invention.

[0016] FIG. 5 is a photograph showing the diameter of a solution-spun carbon nanotube fiber according to an embodiment of the present invention.

[0017] Figure 6 is a graph showing the tensile strength and elongation at break of a solution-spun carbon nanotube fiber according to an embodiment of the present invention.

[0018] Figure 7 is a graph showing the viscosity of the radiation dope and the tendency of the discharge degree from the multi-nozzle according to the content of graphene oxide.

[0019] The present invention is susceptible to various modifications and takes various forms, and thus, embodiments are described in detail herein. However, this is not intended to limit the present invention to a specific disclosed form, and it should be understood that all modifications, equivalents, and alternatives fall within the spirit and technical scope of the present invention.

[0020] Throughout the specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0021] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and will not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0022] The terminology used herein is merely used to describe specific embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

[0023]

[0024] According to one aspect of the present invention, there is provided a method of producing a carbon nanotube mixture, comprising: mixing bundle-shaped carbon nanotubes and an oxidizing agent to produce a carbon nanotube mixture; kneading the carbon nanotube mixture while repeatedly adding a strong acid in small amounts to the carbon nanotube mixture to produce a carbon nanotube dough; oxidizing the carbon nanotube dough at a temperature of up to 10°C and neutralizing it, and then removing the oxidizing agent and the strong acid to produce an oxidized carbon nanotube having an oxygen-containing functional group introduced therein; physically dispersing the oxidized carbon nanotubes in an organic solvent to produce a carbon nanotube dispersion, and adding graphene oxide to the carbon nanotube dispersion to produce a spinning dope; And a step of manufacturing a carbon nanotube fiber including graphene oxide by solution-spinning the above-mentioned spinning dope; and in the step of manufacturing the carbon nanotube fiber, the oxidized carbon nanotubes are self-assembled by inducing hydrogen bonds between oxygen-containing functional groups introduced to the surface, and the oxidized carbon nanotubes and the oxidized graphene form a crosslink, thereby coagulating the spinning dope and causing the fiber to be solution-spinning. A method for manufacturing a carbon nanotube fiber including graphene oxide is provided.

[0025] First, carbon nanotubes and an oxidizer are mixed to prepare a carbon nanotube mixture, and a strong acid is added to the mixture while kneading to prepare a carbon nanotube dough.

[0026] In the present invention, the carbon nanotube may be at least one of a single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT), and a multi-walled carbon nanotube (MWCNT). Preferably, it may be a single-walled carbon nanotube.

[0027] An oxidizing agent is mixed into the above carbon nanotubes, and in the present invention, the oxidizing agent may be selected from the group consisting of sodium chlorate (NaClO3), sodium perchlorate (NaClO4), potassium chlorate (KClO3), potassium perchlorate (KClO4), potassium permanganate (KMnO4), potassium nitrate (KNO3), sodium nitrate (NaNO3), and mixtures thereof.

[0028] At this time, it is preferable to add the oxidizing agent in a weight ratio of 3 to 15 relative to the weight of the carbon nanotube. If the weight ratio of the oxidizing agent is less than 3, it is difficult to introduce functional groups capable of hydrogen bonding to the surface, and if the weight ratio exceeds 15, even if the oxidation reaction is performed at low temperature, there is a disadvantage in that many defects are created on the surface of the carbon nanotube due to excessive oxidation, which is not preferable.

[0029] After this, the strong acid is repeatedly added in small amounts to the above carbon nanotube mixture while kneading. When the strong acid is added to the mixed powder, the strong acid dissolves the oxidizer on the surface of the carbon nanotubes, causing an explosive reaction at a very rapid rate. This generates high temperatures. Therefore, it is preferable to perform the kneading while adding the necessary amount of strong acid little by little rather than adding it all at once.

[0030] Since the reaction occurs explosively by adding a strong acid to the mixed powder in this way, the reaction time is significantly reduced compared to the case where the reaction is carried out by stirring in a mixed solution as in the past, and there is an advantage in that carbon oxide nanotubes can be easily formed even by using only a small amount of strong acid.

[0031] Here, the strong acid is preferably selected from the group consisting of fuming nitric acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrogen peroxide, inorganic acids, acetic acids, and mixtures thereof.

[0032] Next, the carbon nanotube dough is oxidized and neutralized at a temperature of up to 10°C, and then the oxidizing agent and the strong acid are removed to produce an oxidized carbon nanotube having an oxygen-containing functional group introduced therein.

[0033] Oxidized carbon nanotubes are formed by removing acids and oxidizing agents through neutralization and purification processes. Specifically, a neutralization process for carbon nanotubes is performed using distilled water, hydrochloric acid, and hydrogen peroxide on an oxidized dough at a temperature below 10°C. The acid and oxidizing agent are then removed through washing, filtration, and drying processes to obtain oxidized carbon nanotubes.

[0034] Preferably, the low-temperature reaction of the carbon nanotube dough is performed at a temperature ranging from -5 to 10°C. However, there are disadvantages such as high energy consumption due to cooling at -5°C and an excessively slow oxidation reaction rate, which prolongs the oxidation time. In addition, at temperatures above 10°C, the oxidation reaction rate progresses rapidly, increasing the possibility of forming a defect structure on the carbon nanotube surface. Therefore, more preferably, the oxidation reaction can be performed at a temperature of 1 to 5°C, taking into account the oxidation time and defect minimization.

[0035] If necessary, a drying process using a freeze dryer can be performed to obtain carbon dioxide nanotube powder. In addition to the described method, various methods can be applied to this process, and the method is not particularly limited.

[0036] In the present invention, the carbon nanotube dough is characterized in that the oxidation reaction is carried out at a low temperature of 10℃ or lower, and the dough is kneaded for 5 minutes and then reacted for at least 2 hours. The reaction time may vary depending on the amount of the oxidizing agent. By introducing oxygen-containing functional groups through the oxidation reaction through the dough, the oxidized carbon nanotubes of the present invention can have an oxygen atom content of at least 20 wt%. In addition, by controlling the reaction kinetically through low-temperature conditions, the content of oxygen-containing functional groups can be increased while reducing structural defects in the carbon nanotubes caused by the oxidation reaction.

[0037] That is, by introducing oxygen functional groups through an oxidation reaction, the dispersibility of carbon nanotubes is increased, and by carrying out the oxidation reaction at a low temperature for a short time, structural defects are minimized, and through this, the hexagonal structure of carbon nanotubes is maintained during future reduction, thereby providing a carbon nanotube dispersion containing high-quality carbon nanotubes with high purity and low defects.

[0038] Next, a dispersion liquid in which carbon nanotubes are dispersed is prepared, and graphene oxide is added to prepare a radiation dope.

[0039] The above-mentioned manufactured carbon nanotubes are physically dispersed in an organic solvent using a high-pressure disperser. In the present invention, the organic solvent may be selected from the group consisting of dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (N,N-Dimethylacetamide (DMA), and mixtures thereof.

[0040] In the past, dispersing agents such as surfactants were added to disperse carbon nanotubes, but since the removal of the additives was difficult, the additives remained in the carbon nanotube dispersion, which inevitably resulted in a deterioration of the physical properties. In addition, in some cases, when the carbon nanotubes were heat-treated, amorphous carbon remained, which also became a problem. On the other hand, the carbon nanotubes of the present invention can disperse at least 1.0 wt% of oxidized carbon nanotubes in an organic solvent without using a separate dispersing agent, since oxygen-containing functional groups are introduced through the oxidation reaction.

[0041] Furthermore, the present invention not only improves the dispersibility of the spin dope but also increases the solidification speed by adding graphene oxide having a size of 10 to 1000 nm. When the size of the graphene oxide is less than 10 nm, it is difficult to control the solidification speed because it cannot perform the cross-linking role of hydrogen bonds between the carbon oxide nanotubes, and when the size is 1000 nm or more, the chemical bonding between the carbon oxide nanotubes and the graphene oxide may be too strong during the process of being discharged from the nozzle, which may cause the nozzle to become clogged.

[0042] At this time, graphene oxide can be added so that the content of graphene oxide is 1 to 10 wt% compared to the carbon nanotube. Accordingly, in the present invention, the radiation dope preferably includes the carbon nanotube and the graphene oxide in a weight ratio of 99 to 90: 1 to 10. More preferably, it can be included in a weight ratio of 99 to 97: 1 to 3.

[0043] In the present invention, graphene oxide is included in the composition of the radiation dope in the form of nanosheets of sub-micron size, and thus can play a role in promoting the dispersion of carbon nanotubes and coagulation of the carbon nanotube dope through hydrogen bonding.

[0044] Finally, the above-mentioned radiation dope is solution-spun to produce a carbon nanotube fiber containing graphene oxide.

[0045] Conventional carbon nanotube fibers, while increasing the carbon nanotube content in the spinning dope to improve electrical conductivity, suffer from uneven dispersion of the carbon nanotubes within the spinning dope, with localized carbon nanotube clumps measuring tens of micrometers or more. This unevenness causes breakage during fiber spinning, reducing processability, and especially when using multiple nozzles, there is the problem of nozzle clogging.

[0046] On the other hand, in the case of the present invention, the carbon nanotubes are self-assembled by inducing hydrogen bonds between oxygen-containing functional groups introduced to the surface, and the carbon nanotubes and the graphene oxide form a cross-link through hydrogen bonds, thereby promoting the solidification of the spinning dope. Accordingly, carbon nanotube fibers can be manufactured without entanglement or clogging even using the existing solution spinning process, and spinning is possible not only using a single nozzle but also using a multi-nozzle with multiple spinnerets perforated.

[0047] In the case of the above multi-nozzle, the number of nozzle holes is preferably 5 to 100, but this can be changed depending on the technical field to which the carbon nanotube fiber is applied. In addition, the diameter of the nozzle hole is 100 to 300㎛. If the diameter is less than 100㎛, as the diameter decreases, a greater pressure is required to push the fiber composition to be discharged through the nozzle hole of a small diameter. In addition, if the diameter of the nozzle hole exceeds 300㎛, the time for the dispersion solvent to diffuse into the coagulation bath during the high-temperature process becomes longer, which reduces the coagulation speed and may cause the fiber in the organic gel state to break during the winding process. In addition, there is a concern that the fiber may become porous due to the formation of pores inside the fiber due to the solvent that has not yet escaped, which is not preferable.

[0048] In this way, the method for manufacturing carbon nanotube fibers including graphene oxide according to the present invention comprises kneading and oxidizing carbon nanotubes, while oxidizing under low-temperature conditions to increase the content of oxygen functional groups and reduce defects, dispersing carbon nanotubes in an organic solvent without a dispersant, and using a spinning dope containing graphene oxide to manufacture carbon nanotube fibers through a multi-nozzle. In other words, it has an excellent technical feature in that it manufactures conductive fibers through a general solution spinning process and can control the diameter of the fibers to a desired size using a multi-nozzle.

[0049]

[0050] According to another aspect of the present invention, a carbon nanotube fiber including graphene oxide is provided, characterized in that it is manufactured according to the above manufacturing method.

[0051] The carbon nanotube fiber of the present invention is made by oxidizing carbon nanotubes, uniformly dispersing them in an organic solvent, and then adding graphene oxide, so that it can be spun through a multi-nozzle. Accordingly, it has excellent characteristics in that it has a diameter of at least 50㎛ or more, an electrical characteristic of a line resistance of 200 Ω / cm or less, a tensile strength of 0.1 N / Tex or more, and an elongation at break of 1 to 2%.

[0052]

[0053] Hereinafter, embodiments of the present invention will be described in more detail. However, the following embodiments are provided merely to aid understanding of the present invention, and the scope of the present invention is not limited thereby.

[0054]

[0055] <Example>

[0056] <Example 1>

[0057] Preparation of a carbon nanotube dispersion solution

[0058] Figure 1 is a schematic diagram illustrating the self-assembly of carbon nanotubes of the present invention. Carbon nanotubes were dispersed in an organic solvent to produce a spinning dope, and as shown in Figure 1, hydrogen bonds between carbon nanotubes were induced to induce self-assembly, similar to cellulose fibers, in order to enable solution spinning. To achieve this, multiple hydroxyl groups capable of inducing hydrogen bonds must be introduced to the carbon nanotube surface.

[0059] To this end, as shown in Fig. 2, 10 g of single-walled carbon nanotubes and 100 g of sodium chlorate (NaClO3) were first mixed using a powder mixer, and then 100 mL of fuming nitric acid was slowly added and kneaded to prepare a mixture. The prepared mixture was subjected to an oxidation reaction at 2 degrees Celsius or lower for approximately 5 hours. Afterwards, the carbon nanotubes were neutralized using distilled water, hydrochloric acid, and hydrogen peroxide, and then the acid and oxidizing agent were removed through washing, filtration, and drying processes to obtain oxidized carbon nanotubes.

[0060] Figure 3 shows the results of C1s X-ray photoelectron spectroscopy (XPS) of oxidized single-walled carbon nanotubes according to Example 1. In the XPS survey scan (Figure 3(a)), the C / O element ratio was approximately 3.17, confirming that the content of oxygen atoms was more than 20%. Figure 3(b) shows the results of C1s XPS analysis showing the chemical structure of carbon atoms. CO bonds and C=O, COOH bonds from numerous hydroxyl groups were confirmed.

[0061]

[0062] <Example 2>

[0063] Preparation of mixed carbon nanotube / graphene oxide spin dope

[0064] The carbon nanotubes prepared in Example 1 were dispersed in N-methylpyrrolidone (NMP) at a solid content of 1.5 wt% to prepare a spin dope. The carbon nanotube dispersion was homogenized at 5000 rpm for 30 minutes, and then dispersed 5 times at 1 bar using a high-pressure disperser to prepare a highly concentrated carbon nanotube spin dope. At this time, the spin dope was prepared by adding graphene oxide to the carbon nanotubes at a content of 0 to 10 wt% before or after physical dispersion.

[0065] FIG. 4 is a graph showing the viscosity and viscoelastic behavior of a mixed carbon nanotube / graphene oxide spinning dope according to the present invention. Referring to FIG. 4a, there was no significant change in the shear thinning phenomenon, in which viscosity decreases due to shear stress, depending on the content of graphene oxide. In addition, as shown in FIG. 4b, the spinning dope exhibits viscoelastic behavior that allows solution spinning by adding graphene oxide, and when a large-sized graphene oxide is added, the elastic part (G') in the viscoelastic behavior becomes too large, making solution spinning impossible.

[0066]

[0067] <Example 3>

[0068] Solution spinning of carbon nanotube / graphene oxide mixed dope

[0069] The spinning dope (solid content 1.5 wt%) prepared by Example 2 is placed in a barrel and solution-spun at room temperature. For multi-nozzle spinning, a nozzle with 30 holes each having a diameter of 300 μm and an aspect ratio (L / D) of 2.0 is used. The spinning dope is discharged into a coagulation tank at a speed of 80 cm / min using a metering pump. The discharged spinning dope is solidified in a coagulation tank using ethyl acetate at room temperature and taken up through a godet at a temperature of 100 degrees or higher. Carbon nanotube fibers containing graphene oxide obtained by this spinning process have a diameter of 50 μm or more (Fig. 5) and exhibit electrical properties with a line resistance of 200 Ω / cm or less. When the mechanical properties were measured by ASTM D2256-02 (gauge length 250 mm, tensile speed 300 mm / min), they showed a tensile strength of 0.1 N / Tex or more and an elongation at break of 1 to 2%, as shown in Fig. 6.

[0070]

[0071] <Comparative Example 1>

[0072] Solution spinning using carbon nanotube dopes that do not contain graphene oxide

[0073] A carbon nanotube spinning dope was prepared as in Example 2, and the spinning dope was prepared without adding separate graphene oxide. Figure 7 shows the viscosity of the spinning dope and the tendency of the degree of discharge from the multi-nozzle according to the content of graphene oxide. When the graphene oxide content is 0% or 5% or more, the dope becomes clogged at the multi-nozzle inlet, making uniform fiber spinning difficult.

[0074]

[0075] In summary, the method for manufacturing carbon nanotube fibers of the present invention performs kneading and oxidizes carbon nanotubes, and increases the content of oxygen functional groups introduced into carbon nanotubes under low-temperature conditions of 2°C or lower while reducing defects, thereby enabling carbon nanotubes to be dispersed in an organic solvent without a dispersant, and by adding graphene oxide to manufacture a spinning dope, solution spinning through a multi-nozzle is possible, so that carbon nanotube fibers with controlled diameters are manufactured according to the purpose, which has an excellent effect.

[0076]

[0077] The above description is merely an illustrative description of the technical idea of ​​the present invention, and those skilled in the art will appreciate that various modifications and variations can be made without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of ​​the present invention, but rather to illustrate it, and the scope of the technical idea of ​​the present invention is not limited by these embodiments. The scope of protection of the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. A step of preparing a carbon nanotube mixture by mixing bundle-shaped carbon nanotubes and an oxidizer, and performing kneading while repeatedly adding a small amount of strong acid to the carbon nanotube mixture to prepare a carbon nanotube dough; A step of manufacturing an oxidized carbon nanotube having an oxygen-containing functional group introduced therein by oxidizing and neutralizing the carbon nanotube mixture at a temperature of up to 10°C and then removing the oxidizing agent and the strong acid; A step of physically dispersing the above-mentioned carbon nanotubes in an organic solvent to prepare a carbon nanotube dispersion, and adding graphene oxide to the carbon nanotube dispersion to prepare a radiation dope; and A step of manufacturing a carbon nanotube fiber including graphene oxide by solution-spinning the above-mentioned radiation dope; In the step of manufacturing the above carbon nanotube fiber, The above carbon nanotubes are self-assembled by inducing hydrogen bonds between oxygen-containing functional groups introduced on the surface, and the carbon nanotubes and the graphene oxide form a cross-link, thereby solidifying the radiation dope and causing the solution to be emitted. A method for manufacturing carbon nanotube fibers containing graphene oxide.

2. In paragraph 1, The above oxidizing agent is, Selected from the group consisting of sodium chlorate (NaClO3), sodium perchlorate (NaClO4), potassium chlorate (KClO3), potassium perchlorate (KClO4), potassium permanganate (KMnO4), potassium nitrate (KNO3), sodium nitrate (NaNO3) and mixtures thereof, The above mentioned rivers and mountains are, Characterized in that it is selected from the group consisting of fuming nitric acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrogen peroxide, inorganic acids, acetic acids and mixtures thereof. A method for manufacturing carbon nanotube fibers containing graphene oxide.

3. In paragraph 1, The above radiation dope is, Characterized in that the carbon nanotubes and the graphene oxide are included in a weight ratio of 99 to 90: 1 to 10. A method for manufacturing carbon nanotube fibers containing graphene oxide.

4. In paragraph 1, The above graphene oxide is characterized by a size of 10 to 1000 nm. A method for manufacturing carbon nanotube fibers containing graphene oxide.

5. In paragraph 1, The above solution radiation is characterized by using a multi-nozzle with multiple radiation holes perforated. A method for manufacturing carbon nanotube fibers containing graphene oxide.

6. Characterized in that it is manufactured according to any one of the clauses 1 to 5, Carbon nanotube fibers containing graphene oxide.

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