KR101631857B1 - Conducting fibers fabricated with nano carbon materials having multiple hydrogen bonding motifs and their fabrication method - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a highly conductive polymer composite conductive fiber in which a carbon nano material and a metal nano material are combined, and a method for manufacturing the same. More particularly, the present invention relates to a conductive fiber comprising a conductive nano material, a carbon nano material, The present invention is directed to a highly conductive polymer composite conductive fiber in which a carbon nano material and a metal nano material, in which the metal nanomaterial is distributed on the surface of the conductive fiber, are combined. According to another aspect of the present invention, there is provided a method of fabricating a conductive paste, comprising: forming a conductive paste containing a metal nanomaterial, a carbon nanomaterial, and a polymer; forming a conductive fiber through solution spinning using the conductive paste; The present invention also provides a method for producing a conductive fiber of a highly conductive polymer composite in which a carbon nanomaterial and a metal nanomaterial are combined. Accordingly, in the direct preparation of the conductive paste mixed with the carbon nanomaterial, metal nanomaterial, and polymer by solution spinning, the metal nanomaterial having a very high electrical conductivity in the coagulation bath is induced to be rearranged to the fiber surface, There is an advantage in that a highly conductive fiber having a much higher electric conductivity than that of the present invention can be directly manufactured.

Description

Technical Field [0001] The present invention relates to a high-conductivity polymer composite conductive fiber in which a carbon nano material and a metal nano material are combined, and a manufacturing method thereof,

TECHNICAL FIELD The present invention relates to a highly conductive polymer composite conductive fiber in which a carbon nano material and a metal nano material are combined and a method for manufacturing the same. More particularly, the present invention relates to a conductive carbon nanomaterial such as carbon nanotubes, graphene, carbon black, And a polymer is mixed with a metal nano-material such as metal nanorods, metal nano-wires, metal nanotubes, or metal nano-plates to prepare a conductive fiber by a solution spinning process The present invention relates to a conductive high-conductivity-polymer composite conductive fiber comprising a carbon nano material and a metal nano-material which are produced by concentrating and distributing a metal nanomaterial on the surface of a fiber, and a method for producing the same.

Conductive fibers can be used as fiber-type electrodes of future e-textiles, as well as versatile functionalities that also function as electrodes for EMI shielding, antistatic, ultra-high capacity batteries, sensors, batteries, heat wires or actuators Can be used as fibers. It can also be used as an ion exchange filter for industrial desalination of seawater. Also, it can be used as a reinforcing material in the role of mechanical support when it is manufactured in the form of a polymer composite.

Conventional high-conductivity fibers (> 10000 S / m) can be produced by a method of twisting the carbon nanotubes prepared by the chemical vapor deposition method or by collecting the carbon nanotubes formed in the furnace To prepare a conductive fiber. This method is easy to implement even with high conductivity, but it shows the limit of mass production. According to the wet method, 10 ⁶ S / m was achieved through doping using a super-acid dispersed carbon nanotube dispersion liquid crystal (Natnael Behabtu et al. Science 339, 182 (2013) However, this method has a disadvantage that it is difficult to composite with a heterogeneous material such as a polymer.

When graphene is used, a graphene graphene liquid crystal solution is irradiated with a liquid crystal and chemically reduced to produce a conductive fiber. In this case, due to the contact resistance between the chemically treated graphene and the degradation of the graphene property due to the acid treatment, the electrical conductivity is not realized at more than 10 ⁵ S / m even by the combination with the metal (Zhen Xu et al. Adv. 25, 3249 (2013)).

The use of the existing synthetic fiber manufacturing process and the production of high conductivity fibers have the advantage of minimizing facility investment and process cost. However, to date, there has not been developed a technique for complexing a conductive nano material with a heterogeneous material while maintaining high conductivity. In the conventional method, a polymer / carbon nanotube composite fiber is prepared by dispersing carbon nanotubes in a water system using a dispersant such as a surfactant, and then aggregating the carbon nanotubes into a polymer solution to replace the surfactant with a polymer (Brigitte Vigolo et al. Science 290, 1331 (2000)), the polymer was dispersed at a high concentration through an excessive functionalization through acid treatment and solution spinning was performed to prepare a conjugated fiber (Publication No. 10-2012-129040). In order to improve the conductivity, The high conductivity fiber is realized by the method of. This approach represents a complex process for the production of highly conductive fibers and limits of electrical conductivity. Particularly, when the carbon nanomaterial is excessively treated through the acid treatment, the electric conductivity of the carbon nanomaterial is seriously degraded.

In order to solve this problem, carbon nanomaterials such as high-quality carbon nanotubes, graphene, carbon black, and nano graphite with few defects should be dispersed in a high content. However, it is difficult to realize a high conductivity of more than 10 ⁵ S / m with only carbon nanomaterials. Therefore, it is necessary to maximize the electrical conductivity of the fiber by adding a small amount of a material having excellent electrical conductivity such as metal nanoparticles, metal nano-rods, metal nanowires, metal nanotubes, and metal nano-materials. In addition, when various polymer materials, organic materials, biomaterials, and metal oxides can be combined with ionic materials, various functional fibers such as electrochemical properties, mechanical strength, thermal properties, and biocompatibility other than electrical conductivity can be manufactured It has the advantage of being able to.

However, there have been no reports on the production of carbon nanofiber highly conductive composite fibers prepared by adding metal nanomaterials.

(Document 1) Korean Patent Application Publication No. 10-2012-0129040 (Published date November 28, 2012)

DISCLOSURE Technical Problem Accordingly, the present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a paste in which a conductive carbon nanomaterial such as carbon nanotubes, graphene, carbon black, , A metal nanorod, a metal nanowire, a metal nanotube, and a metal nanoplate, is used to produce a conductive fiber through a solution spinning process so that the metal nanomaterial is concentrated on the surface of the fiber The present invention provides a highly conductive polymer composite conductive fiber in which a carbon nano material and a metal nano material are combined to produce a high conductivity fiber, and a manufacturing method thereof.

According to an aspect of the present invention, there is provided a method of forming a conductive fiber by a solution spinning process using a conductive paste including a metal nanomaterial, a carbon nanomaterial, and a polymer, wherein the metal nanomaterial is distributed on the surface of the conductive fiber A high conductive polymer composite conductive fiber in which a carbon nano material and a metal nano material are combined is made a technical point.

According to another aspect of the present invention, there is provided a method of fabricating a conductive paste, comprising: forming a conductive paste containing a metal nanomaterial, a carbon nanomaterial, and a polymer; forming a conductive fiber through solution spinning using the conductive paste; The present invention also provides a method for producing a conductive fiber of a highly conductive polymer composite in which a carbon nanomaterial and a metal nanomaterial are combined.

The carbon nanomaterial is preferably at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, a graphene, a carbon black, and a nano-graphite.

The metal nanomaterial is preferably at least one of metal nanoparticles, metal nanorods, metal nanowires, metal nanotubes, and metal nanoplates.

The content of the carbon nanomaterial and the metal nanomaterial is preferably 0.1 to 90% by weight based on the total weight of the conductive fiber.

The content of the metal nanomaterial is preferably 0.1 to 70% by weight based on the total weight of the conductive fibers.

The solid content of the conductive paste is preferably 0.1 to 15% by weight.

Accordingly, in the direct preparation of the conductive paste mixed with the carbon nanomaterial, metal nanomaterial, and polymer by solution spinning, the metal nanomaterial having a very high electrical conductivity in the coagulation bath is induced to be rearranged to the fiber surface, There is an advantage in that a highly conductive fiber having a much higher electric conductivity than that of the present invention can be directly manufactured.

The present invention according to the present invention is a method for directly fabricating a conductive paste in which a carbon nanomaterial, a metal nano material, and a polymer are mixed by spinning a solution, and a metal nano material having a very high electrical conductivity in a coagulation bath is relocated It is possible to directly produce a highly conductive fiber having an electrical conductivity much higher than that of conventional conjugated fibers.

Fig. 1 is a schematic view of a section of a conductive fiber produced by the solution spinning process of the present invention. Fig. 1 (a) shows a structure in which a metal nanomaterial is concentrated on a fiber surface, (b), and FIG.
FIG. 2 is a photograph (a) of a composite conductive fiber including a long multi-walled carbon nanotube, a silver nanowire, and a polymer according to an embodiment of the present invention and a scanning electron microscope photograph (b) of the twisted conductive fiber,
3 is a graph showing the electrical conductivity of the conductive fiber according to the embodiment of the present invention,
FIG. 4 is a graph showing the results of scanning electron microscopy (a, b) and elemental analysis (c, d) of a surface of a composite fiber according to an embodiment of the present invention, (E) showing the process of being redefined as a surface,
Fig. 5 is a graph showing the SEM image of the shallow fiber surface (a) and the deep fiber surface (b) measured by chemically scribing the surface of the conductive fiber produced using the paste having a high solid content and the element analysis image (c, d).

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

Fig. 1 is a schematic view of a section of a conductive fiber produced by the solution spinning process of the present invention. Fig. 1 (a) shows a structure in which a metal nanomaterial is concentrated on a fiber surface, (b)). FIG. 2 is a photograph of a composite conductive fiber including a long multi-walled carbon nanotube, a silver nanowire, and a polymer according to an embodiment of the present invention, and a scanning electron microscope FIG. 3 is a graph showing the electrical conductivity of the conductive fiber according to the embodiment of the present invention. FIG. 4 is a graph showing the electrical conductivity of the composite fiber according to the embodiment of the present invention, (C), (d) and (e) are diagrams illustrating the process of re-establishing the metal nanomaterial to the surface in the coagulating liquid, and FIG. 5 (A) and the deep fiber surface (b) were measured by chemically scribing the surface of the conductive fiber produced using the photocatalyst, and the elemental analysis images (c, d) for each of the measured images of the shallow fiber surface Fig.

As shown in FIG. 1B, the conductive fiber is formed by a solution spinning process using a conductive paste including a metal nanomaterial, a carbon nanomaterial, and a polymer, and the conductive fiber is uniformly distributed As shown in Fig. 1 (a), to form a structure in which the metal nanomaterial is concentrated and distributed on the fiber surface.

That is, the present invention includes a conductive fiber exhibiting excellent electrical conductivity by inducing a metal nano material having excellent conductivity to be concentrated on a fiber surface in solution spinning using a conductive paste, and a method of manufacturing the conductive fiber. .

<Examples>

In an embodiment of the present invention, a multi-walled carbon nanotube into which a carboxyl group has been introduced is first mixed with NMP (N-methyl pyrollidone) at a concentration of 50 g / L, and then a 3-roll mill is used to paste .

Then, polyvinyl alcohol dissolved in dimethylsulfoxide is mixed therewith to prepare a dispersion. Thus, silver nano wires dispersed in an aqueous solution are mixed at a ratio of 3 vol% to prepare a conductive fiber paste.

Next, the carbon nanotube / polyvinyl alcohol / silver nano wire paste was spun into a methanol coagulating solution through a syringe nozzle using a metering pump to obtain a carbon nanotube and a silver nano wire in a content of 30 vol% Conductive fibers are obtained which are composite fibers.

At this time, the content of the solid content in the whole paste should be 15 wt% or less so that the silver nano wire can be refolded from the coagulating liquid to the fiber surface. In the present invention, the solid content is about 7% by weight. When the content of the solid content exceeds 15% by weight, it is confirmed that the silver nano wire is not distributed intensively on the surface and is uniformly distributed throughout the conductive fiber as shown in the results of the comparative example described later. When the solid content is less than 0.1% by weight, the amount of the solid content is small and the effect of increasing the conductivity of the conductive fiber is not exhibited.

In the solidification process for solution spinning using the fiber dope of the present invention, the solvent present in the conductive paste is solidified while moving to the surface side. As a result, the metal nanomaterial such as silver nano wire among the solid components has affinity with the solvent When the solid content exceeds 15% by weight, the movement of the surface of the metal nanomaterial due to the solid polymer, other additives, and the carbon nanomaterial causes the solid surface to move to the surface The metal nanomaterial such as silver nano wire is uniformly distributed throughout the conductive fiber.

When the content of the solid content is less than about 15 wt%, the metal nanomaterial is easily moved to the surface along the solvent existing in the conductive paste in the solidification process, and solidified to form the conductive fiber, The metal nanomaterial is concentrated on the surface of the conductive fiber. Therefore, considering the characteristic that electricity is applied along the surface of the conductor, the concentration distribution of the metal nanomaterial on the surface side is excellent in the electric conduction drawing.

Then, in order to improve the mechanical properties of the fiber, the fiber is stretched to about 10% at a temperature of about 120 ° C or more to finally complete the conductive fiber.

As shown in FIG. 2 (a), the conductive fibers prepared above exhibit a characteristic of a typical fiber in which a continuous fiber state is maintained even in a twisted state as shown in FIG. 2 (b).

In particular, as shown in FIG. 3, when the total amount of the conductive material formed of carbon nanotubes and silver nano wires contains 3 wt% or more of silver nano wires, the electric conductivity shows an excellent electric conductivity of 10 ⁵ S / m or more.

In order to investigate the cause of the excellent electrical conductivity, the surface of the composite fiber was treated with a dimethylsulfoxide / methanol mixture to remove the polymer on the surface. As a result, most of the silver nanowires were present on the shallow surface as shown in FIG. 4 (a). As a result of the chemical treatment of the dimethylsulfoxide alone, the deep surface of the fiber was observed. As a result, it was found that carbon nanotubes were mainly present as shown in FIG. 4 (b). As shown in FIGS. 4 (c) and 4 (d), it can be seen that a large number of silver nanowires exist on the shallow surface of the conductive fiber and a large number of carbon nanotubes exist on the deep surface. This means that as shown in FIG. 4 (e) in the practice of the present invention, the silver nanowires existing in the conductive fibers are distributed on the surface side.

From this, it can be seen that the reason for the excellent electrical conductivity is attributed to the silver nano wire concentrated on the surface of the fiber as shown in Fig. 1 (a).

<Comparative Example>

As a comparative example of the present invention, in the production of the conductive fiber paste in the same manner as in the above examples, the paste was spun into a coagulating solution with the solid content of the paste exceeding 15 wt% to prepare fibers. The electrical conductivity of the fabric was measured to be 50,000 S / m or less.

In order to confirm deterioration of electrical conductivity, the fibers prepared above were chemically treated in the same manner as in Examples to observe shallow surfaces and deep surfaces of the fibers. As a result, carbon nanotubes and silver nano- And it was confirmed that all of them were uniformly distributed.

Claims (12)

Conductive fibers are formed by a solution spinning process using a conductive paste containing metal nanomaterials, carbon nanomaterials, and polymers,
Wherein the metal nanomaterial is distributed on the surface side of the conductive fiber, but is distributed relatively more in the surface layer than in the deep layer, and the conductive polymer is a highly conductive polymer composite having a composite of the carbon nanomaterial and the metal nanomaterial. The method of claim 1, wherein the carbon nanomaterial is at least one of a single wall carbon nanotube, a double wall carbon nanotube, a multiwall carbon nanotube, a graphene, a carbon black, and a nano graphite. High Conducting Polymer Conductive Conductive Fiber with Composite Material. The method of claim 1, wherein the metal nanomaterial is at least one of metal nanoparticles, metal nanorods, metal nanowires, metal nanotubes, and metal nanoparticles. Polymer composite conductive fibers. The conductive nanofiber according to claim 1, wherein the content of the carbon nanomaterial and the metal nanomaterial is 0.1 to 90% by weight based on the total weight of the conductive fiber. . [2] The conductive fiber of claim 1, wherein the content of the metal nanomaterial is 0.1 to 70% by weight based on the total weight of the conductive fiber. [2] The conductive fiber of claim 1, wherein the solid content of the conductive paste is 0.1 to 15% by weight. A conductive paste containing a metal nanomaterial, a carbon nanomaterial and a polymer is formed, and a conductive fiber is formed through a solution spinning process using the conductive paste. The metal nanomaterial is distributed on the surface of the conductive fiber to form a conductive fiber A method for producing conductive fibers of a highly conductive polymer composite in which a carbon nano material and a metal nano material are combined. The method of claim 7, wherein the carbon nanomaterial is at least one of a single wall carbon nanotube, a double wall carbon nanotube, a multiwall carbon nanotube, a graphene, a carbon black, and a nano graphite. (METHOD OF MANUFACTURING CONDUCTIVE FIBER OF HIGH CONDUCTIVE POLYMER COMPOSITE COMPOSITE MATERIAL). 8. The method of claim 7, wherein the metal nanomaterial is at least one of metal nanoparticles, metal nanorods, metal nanowires, metal nanotubes, and metal nanoplates. Polymer composite conductive fiber manufacturing method. [Claim 7] The method according to claim 7, wherein the content of the carbon nanomaterial and the metal nanomaterial is 0.1 to 90% by weight based on the total weight of the conductive fiber. Gt; 8. The method of claim 7, wherein the content of the metal nanomaterial is 0.1 to 70% by weight based on the total weight of the conductive fibers. [8] The method of claim 7, wherein the conductive paste has a solid content of 0.1 to 15% by weight based on the total weight of the conductive nanoparticles.

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