KR20180068143A - Composite material comprising sandwiched structure, method of fabricating of the same, sensor comprising the same, and super capacitor comprising of the same - Google Patents

Abstract

Provided is a method for manufacturing a composite material which comprises the steps of: preparing a base fiber; extending the base fiber in a lengthwise direction; forming first and second electrodes on the base fiber; and reducing the base fiber. A composite material manufactured by the method can be sensed and measured even under various modification environments of twisting, bending, and the like.

Description

[0001] The present invention relates to a composite material having a sandwich structure, a manufacturing method thereof, a sensor including the composite material, and a super capacitor including the same,

The present invention relates to a composite material having a sandwich structure, a manufacturing method thereof, a sensor including the composite material, and a supercapacitor including the composite material. The composite material has a first electrode and a second electrode sandwiched between base fibers, A manufacturing method thereof, a sensor including the same, and a super capacitor including the same.

A component that is used for the purpose of a battery is called a capacitor. In particular, a capacitor used in an electronic circuit functions like an electrically rechargeable battery. Among these capacitors, a capacitor having a large storage capacity is referred to as a super capacitor, and charges are caused by movement of ions or surface chemical reactions between the electrodes and the electrolyte interface. These supercapacitors exhibit excellent charge / discharge speed and efficiency, and have a semi-permanent life span, and are thus attracting attention as next-generation energy storage devices.

In recent years, it has been widely used as an IC (integrated circuit) backup of various electric and electronic devices, and its application has been widely used and widely used for power supply for solar energy storage, electric vehicles, hybrid electric vehicles, and fuel cell vehicles .

Accordingly, various technologies related to supercapacitors have been developed. For example, Korean Patent Laid-Open Publication No. 10-1194999 (Application No. 10-2011-0063341, Applicant: Korean Ceramic Institute of Technology) discloses a positive electrode having a lithium transition metal oxide, an average interlayer distance d002 in the range of 3.385 to 0.445 nm A separator for preventing short-circuit between the positive electrode and the negative electrode; and an electrolyte solution in which a lithium salt is dissolved between the positive electrode and the negative electrode, wherein the electrolyte solution contains a porous activated carbon having a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged. And a method of manufacturing the hybrid supercapacitor.

In addition, various technologies related to supercapacitors are being researched and developed.

Korean Unexamined Patent Publication No. 10-1194999

The present invention provides a composite material capable of being sensed and measured even in various deforming environments such as twist, warp, or bend, a method of manufacturing the same, a sensor including the composite material, and a super capacitor including the same have.

Another object of the present invention is to provide a composite material having excellent stability even in various deformation environments such as twist, warp, or bend, a method of manufacturing the same, a sensor including the composite material, and a supercapacitor including the same .

Another object of the present invention is to provide a composite material having excellent energy storage performance even in various deformation environments such as twist, warp, or bend, a manufacturing method thereof, a sensor including the composite material, and a super capacitor including the same I have to.

Another object of the present invention is to provide a composite material capable of preventing electrode shorting, a method of manufacturing the same, a sensor including the electrode, and a supercapacitor including the same.

Another object of the present invention is to provide a composite material capable of preventing separation of a base fiber and an electrode, a manufacturing method thereof, a sensor including the composite material, and a supercapacitor including the same.

Another object of the present invention is to provide a composite material which can be mass-produced easily, a method of manufacturing the composite material, a sensor including the composite material, and a supercapacitor including the composite material.

Another object of the present invention is to provide a composite material of high efficiency and high reliability, a method of manufacturing the composite material, a sensor including the composite material, and a super capacitor including the same.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problems, the present invention provides a method of manufacturing a composite material.

According to one embodiment, a method of making a composite material comprises the steps of preparing a base fiber comprising silicon and comprising a first side and a second side opposite the first side, Forming a first electrode comprising carbon nanotubes on the first surface of the elongated base fiber, and forming a second electrode on the second surface of the extended base fiber, And forming a second electrode including the first electrode and the second electrode.

According to an embodiment, the step of forming the first electrode and the step of forming the second electrode may include providing the additive to the first electrode and the second electrode including carbon nanotubes, And increasing the density of the electrode and the second electrode.

According to one embodiment, the base fiber further comprises a third surface between the first surface and the second surface, and a fourth surface facing the third surface, wherein the first electrode and the second electrode Forming the first mask pattern and the second mask pattern on the third surface and the fourth surface, respectively, before forming the first mask pattern and the second mask pattern.

According to one embodiment, the method may further include removing the first mask pattern and the second mask pattern after the first electrode and the second electrode are formed.

According to one embodiment, the first mask pattern and the second mask pattern may include polyurethane.

According to one embodiment, the step of preparing the base fiber comprises the steps of preparing a base sheet comprising silicon, forming on the upper and lower surfaces of the base sheet a first mask layer and a second mask layer, respectively, Forming a base layer on the base sheet; forming a base layer on the base sheet; forming a base layer on the base layer; forming a base layer on the base layer; Wherein the base fiber is provided with a first mask pattern in which the first mask layer is cut, a third surface disposed between the first surface and the second surface, and a third surface opposed to the third surface, 2 < / RTI > second mask pattern from which the mask layer is cut.

According to one embodiment, the step of forming the first electrode and the step of forming the second electrode may include providing an energy storage material on the first surface of the base fiber and the carbon nanotube on the second surface Step < / RTI >

According to one embodiment, providing the energy storage material may comprise providing a source comprising an energy storage material on the carbon nanotube.

In order to solve the above technical problems, the present invention provides a composite material.

According to one embodiment, the composite material comprises a base fiber comprising silicon and including a first side and a second side opposite the first side, a first side of the base fiber, And a second electrode disposed on the second surface of the base fiber and including a carbon nanotube having a wrinkle structure, the first electrode including a carbon nanotube having a pleated structure, and a second electrode disposed on the second surface of the base fiber, .

According to an embodiment, the base fiber may include a third surface disposed between the first surface and the second surface, the carbon nanotube not exposed to the carbon nanotube, and the carbon nanotube disposed opposite to the third surface, And the fourth surface exposed without being exposed.

According to one embodiment, the first electrode and the second electrode may include an energy storage material.

According to one embodiment, the energy storage material may include at least one of MnO 2 and PEDOT (polyethylenedioxythiophene).

A composite material according to an embodiment of the present invention includes: a base fiber including silicon and including a first side and a second side opposite the first side; a second fiber disposed on the first side of the base fiber, A first electrode including a carbon nanotube, and a second electrode disposed on the second surface of the base fiber, the second electrode including carbon nanotubes. The first electrode and the second electrode may include a corrugated structure. Accordingly, even in an external stimulus or various deformation environments, it is possible to provide a composite material in which electrical shorting of electrodes is prevented and an expansion ratio is improved.

The method may further include forming a mask pattern on a third surface between the first surface and the second surface and a fourth surface opposed to the third surface, And removing the mask pattern after forming the second electrode. The mask pattern may include a material having poor bonding properties with the carbon nanotubes. As a result, the carbon nanotubes are not easily bonded onto the mask pattern, so that the electrical short circuit between the first electrode and the second electrode can be prevented. If the carbon nanotubes are bonded to the mask pattern, the carbon nanotubes can be removed together with the mask pattern, thereby preventing electrical shorting between the first electrode and the second electrode

In addition, the method of manufacturing the composite material may include providing the additive to the first electrode and the second electrode. The additive can improve the bonding force between the base fiber and the carbon nanotubes. Accordingly, a method of manufacturing a composite material in which separation of the base fiber, the first electrode, and the second electrode is prevented can be provided. As a result, a composite material of high efficiency and high reliability and a manufacturing method thereof can be provided.

A method of manufacturing a composite material according to a modification of the embodiment of the present invention includes the steps of preparing a base sheet, forming the first mask layer and the second mask layer on the upper and lower surfaces of the base sheet, And cutting the base sheet to produce the base fiber. As the base sheet is cut, the base fiber on which the mask pattern is disposed can be easily manufactured, and the electrode can also be easily manufactured. Accordingly, a highly reliable composite material production method capable of mass production with ease can be provided.

1 is a flowchart illustrating a method of manufacturing a composite material according to an embodiment of the present invention.
FIGS. 2 to 4 are views for explaining a manufacturing process of a composite material according to an embodiment of the present invention.
5 is a view showing a twist structure of a composite material according to an embodiment of the present invention.
6 is a perspective view showing a composite material according to a modification of the embodiment of the present invention.
7 is a perspective view of a region where a composite material is cut according to a modification of the embodiment of the present invention.
8 is a photograph of a composite material according to Example 1 of the present invention.
Fig. 9 is a photograph of a composite material according to the first embodiment of the present invention, which is obtained by modifying the shape of the composite material. Fig.
10 is a photograph of a composite material according to Comparative Example 1 of the present invention.
11 is a photograph of the composite fabric according to the second embodiment of the present invention.
12 and 13 are photographs of various shapes of the composite material according to the first embodiment of the present invention.
FIG. 14 is a graph showing the characteristics of the composite material according to various modifications of the first embodiment of the present invention. FIG.
15 to 17 are graphs showing structural characteristics of the composite material according to the first embodiment of the present invention.
18 is a graph comparing the electrical characteristics of a supercapacitor according to embodiments of the present invention.
19 is a graph showing electrical characteristics of a supercapacitor according to an embodiment of the present invention.
20 is a graph illustrating characteristics of an asymmetric supercapacitor according to a fifth embodiment of the present invention.
FIGS. 21 and 22 are graphs showing characteristics according to various modifications of the supercapacitor according to the fourth embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

In this specification, when an element is referred to as being on another element, it may be directly formed on another element, or a third element may be interposed therebetween. Further, in the drawings, the thicknesses of the films and regions are exaggerated for an effective explanation of the technical content.

Also, while the terms first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.

The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms such as " comprises "or" having "are intended to specify the presence of stated features, integers, Should not be understood to exclude the presence or addition of one or more other elements, elements, or combinations thereof. Also, in this specification, the term "connection " is used to include both indirectly connecting and directly connecting a plurality of components.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

FIG. 1 is a flow chart for explaining a method of manufacturing a composite material according to an embodiment of the present invention, and FIGS. 2 to 4 are views for explaining a manufacturing process of a composite material according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, a base fiber 100 may be prepared (S110). According to one embodiment, the base fiber 100 may comprise silicon. For example, the base fiber 100 may be a silicone rubber fiber.

The base fiber 100 may include a first side 102 and a second side 104 opposite the first side. The base fiber 100 may further include a third surface 106 disposed between the first surface 102 and the second surface 104 and not disposed with carbon nanotubes to be described later, And a fourth surface 108 on which carbon nanotubes to be described later are not disposed.

The base fiber 100 may extend in the longitudinal direction by applying a tensile force to both ends of the base fiber 100 (S120). For example, the longitudinal direction may be A and A 'directions.

Referring to FIG. 3, a first electrode 122 including a carbon nanotube may be formed on the first surface 102 of the extended base fiber 100 (S130). Also, a second electrode 124 including carbon nanotubes may be formed on the second surface 104 of the extended base fiber 100 (S140).

A mask pattern 142 and 144 may be formed on the base fiber 100 before the first electrode 122 and the second electrode 124 are formed. The step of forming the mask patterns 142 and 144 includes the steps of: preparing a mask solution by dissolving a polymer material in a solvent; forming a mask solution on the third surface 106 of the base fiber 100 and the fourth surface Applying on the surface 108, and drying the mask solution. According to one embodiment, the solvent may be THF (tetrahydrofuran). The polymer material may be formed of a material having a low bonding property with the carbon nanotubes. According to one embodiment, the polymer material may be polyurethane.

The mask patterns 142 and 144 may include a first mask pattern 142 and a second mask pattern 144. The first mask pattern 142 may be formed on the third surface 106 of the base fiber 100. The second mask pattern 144 may be formed on the fourth side 108 of the base fiber 100. The first mask pattern 142 and the second mask pattern 144 may be removed after the first electrode 122 and the second electrode 124 are formed.

In the case where the first electrode 122 and the second electrode 124 are manufactured by omitting the step of forming the mask patterns 142 and 144, unlike the embodiment of the present invention described above, May be formed on the third surface 106 and the fourth surface 108. As a result, the first electrode 122 and the second electrode 144 are brought into contact with each other, and electrical short-circuiting may occur. When the remaining carbon nanotubes are formed on the third surface 106 and the fourth surface 108, the remaining carbon nanotubes can be connected by the twisted deformation of the base fiber 100. As a result, electrical short-circuiting between the first electrode 122 and the second electrode 124 may occur.

However, in the case of the composite material according to the embodiment of the present invention, before the first electrode 122 and the second electrode 124 are formed, on the third surface 106 and the fourth surface 108 The mask patterns 142 and 144 may be formed on the first electrode 122 and the second electrode 144 after the first and second electrodes 122 and 144 are formed. In addition, the mask patterns 142 and 144 may include a material having poor bonding properties with the carbon nanotubes. As a result, the carbon nanotubes do not easily bond to the mask patterns 142 and 144, and the electrical short circuit between the first electrode 122 and the second electrode 124 can be prevented. If the carbon nanotubes are bonded onto the mask patterns 142 and 144, the carbon nanotubes can be removed together with the mask patterns 142 and 144 so that the first electrode 122 and the second electrode 122, Electrical shorting of the electrode 124 can be prevented. As a result, a composite material in which electrical short circuit is prevented can be provided.

According to one embodiment, the carbon nanotubes may be provided in the form of a carbon nanotube sheet. According to one embodiment, the step of forming the carbon nanotube sheet on the first surface 102 and the second surface 104 includes the steps of: preparing a carbon nanotube forest by chemical vapor deposition; Forming the carbon nanotube sheet from the carbon nanotube forest, and attaching the carbon nanotube sheet to the first surface 102 and the second surface 104. The carbon nanotube sheet 120 may be provided on the first surface 102 and the second surface 104 in a plurality of layers. For example, the carbon nanotube sheet 120 may be provided in 120 layers on the first surface 102 and the second surface 104. According to one embodiment, the carbon nanotube sheet 120 may include a plurality of carbon nanotubes extending in a first direction. Also, according to one embodiment, the plurality of carbon nanotubes may be multi-wall carbon nanotubes (MWCNTs). According to one embodiment, the first direction may be parallel to the longitudinal direction of the base fiber 100.

The forming of the first electrode 122 and the second electrode 124 may include providing the additive to the first electrode 122 and the second electrode 124 including carbon nanotubes . ≪ / RTI > The additive may increase the density of the first electrode 122 and the second electrode 124. According to one embodiment, the participant may increase the density of carbon nanotubes and increase the adhesion between the carbon nanotube sheet 120 and the base fiber 100. For example, the additive may be ethanol. As another example, the additive may be acetone or the like.

A composite material according to an embodiment of the present invention includes a first surface 102 of the base fiber 100 and a second surface 104 opposite the first surface 102, 122 and the second electrode 124 are formed so that the first electrode 122 and the second electrode 124 are provided in a sandwich structure. Accordingly, even in the case of external stimulation or various deformation environments, a composite material in which electrode short circuits are prevented can be provided. In addition, the method of manufacturing the composite material may include providing the additive to the first electrode 122 and the second electrode 124. Accordingly, a method of fabricating a composite material in which the separation of the base fiber 100, the first electrode 122, and the second electrode 124 is prevented can be provided.

Referring to FIGS. 4 (a) and 4 (b), the extended base fiber 100 may be removed in the longitudinal direction by removing the tensile force (S150). As the base fiber 100 is reduced, the first electrode 122 and the second electrode 124 may have a wrinkle structure. In other words, as the base fiber 100 is reduced, a corrugated structure may be formed on the carbon nanotubes included in the first electrode 122 and the second electrode 124. Accordingly, the composite material can exhibit a high expansion ratio and efficient energy storage performance.

The step of forming the first electrode 122 and the second electrode 124 may be performed on the carbon nanotubes of the first surface 102 and the second surface 104 of the reduced base fiber 100 And providing an energy storage material. The step of providing the energy storage material may comprise the steps of producing a source comprising the energy storage material, and providing the source on the carbon nanotubes. According to one embodiment, the source may be provided in a solution process. According to another embodiment, the source may be provided in a vapor deposition process. For example, the method of providing the source on the carbon nanotube sheet 120 may include at least one of a potentiostatic method and a vapor phase polymerization method. According to one embodiment, the energy storage material may include at least one of MnO ₂ and PEDOT (polyethylenedioxythiophene).

The corrugation widths of the first electrode 122 and the second electrode 124 may be adjusted according to the content of the carbon nanotubes in the first electrode 122 and the second electrode 124 . In addition, the flexibility of the composite material can be controlled according to the content of the carbon nanotubes in the first electrode 122 and the second electrode 124.

According to one embodiment, when the content of carbon nanotubes in the first electrode 122 and the second electrode 124 is increased, the corrugation widths of the first electrode 122 and the second electrode 124 Can be widely formed. In other words, when the content of the carbon nanotubes in the first electrode 122 and the second electrode 124 increases, the reduced area change amount of the base fiber 100 from which the tensile force is removed may be small. Accordingly, the stretchability in the longitudinal direction of the composite material can be relatively lowered.

According to an embodiment, when the content of the carbon nanotubes in the first electrode 122 and the second electrode 124 decreases, the corrugation widths of the first electrode 122 and the second electrode 124 Can be formed narrowly. In other words, when the content of the carbon nanotubes in the first electrode 122 and the second electrode 124 decreases, the area change amount of the base fiber 100 from which the tensile force is removed may be large. Accordingly, the stretchability in the longitudinal direction of the composite material can be relatively increased.

According to one embodiment, the composite material may extend in the longitudinal direction. The maximum length of the elongated composite material may be the same as the length of the base fiber 100 described above with reference to Figs.

A method of manufacturing a composite material according to an embodiment of the present invention includes the steps of extending the base fiber 100 and forming a plurality of fibers on the third face 106 and the fourth face 108 of the extended base fiber 100 (120) comprising carbon nanotubes on the first surface (102) and the second surface (104) of the extended base fiber (100), forming the mask pattern ) And the second electrode (124); providing an additive on the first electrode (122) and the second electrode (124); reducing the extended base fiber (100) And providing energy storage material on the carbon nanotubes of the first surface 102 and the second surface 104 of the base fiber 100. Accordingly, it is possible to provide a method of manufacturing a composite material in which shorting and separation of electrodes are prevented and expansion / contraction ratio is improved even under external stimulation or various deformation environments.

5 is a view showing a twist structure of a composite material according to an embodiment of the present invention.

Referring to FIG. 5, in the composite material described with reference to FIGS. 1 to 4, twist deformation may occur due to external force. The composite material according to the embodiment of the present invention can prevent the first electrode 122 and the second electrode 124 from being short-circuited by the sandwich structure when the twisted deformation occurs. In addition, when the twist deformation occurs, the composite material improves the bonding force between the base fiber 100 and the carbon nanotubes by the additive, so that the bonding strength between the base fiber 100 and the first electrode 122, And the separation of the second electrode 124 can be prevented.

Hereinafter, a composite material according to a modification of the embodiment of the present invention described above and a manufacturing method thereof will be described.

FIG. 6 is a perspective view showing a composite material according to a modification of the embodiment of the present invention, and FIG. 7 is a perspective view of an area where a composite material according to a modification of the embodiment of the present invention is cut.

Referring to FIGS. 6 and 7, preparing the base fiber 100 described with reference to FIGS. 1 and 2 includes preparing a base sheet 200, preparing the base sheet 200, Forming a first mask layer 242 and a second mask layer 244 on the upper and lower surfaces of the base fiber 100, Lt; / RTI > According to one embodiment, the base sheet 200 may include silicon.

According to one embodiment, the first mask layer 242 and the second mask layer 244 may include polyurethane. According to one embodiment, the base sheet 200 may be cut in a vertical direction from the upper surface of the base sheet 200 to the lower surface. According to one embodiment, the base sheet 200 may be cut plural times based on the C-plane shown in FIG.

The first surface 102 and the second surface 104 of the base fiber 100 may be produced by cutting the base sheet 200. [ Accordingly, the first surface 102 and the second surface 104 of the base fiber 100 can be exposed. According to one embodiment, at least a portion of the silicon included in the base sheet 200 may be exposed as the base sheet 200 is cut. A first mask pattern 142 in which the first mask layer 242 is cut may be disposed on the third surface 106 of the base fiber 100. The third surface 106 may be disposed between the first surface 102 and the second surface 104. A second mask pattern 144 having the second mask layer 244 cut away may be disposed on the fourth surface 108 of the base fiber 100. The fourth surface 108 may be disposed opposite the third surface 106.

The first electrode 122 and the second electrode 124 including the carbon nanotubes described with reference to FIGS. 2 to 4 are formed on the first surface 102 and the second surface 104 .

A method of fabricating a composite material according to a modification of the embodiment of the present invention includes the steps of preparing a base sheet 200 and forming the first mask layer 242 and the second mask layer 240 on the upper and lower surfaces of the base sheet 200, Forming a second mask layer 244, and cutting the base sheet 200 to fabricate the base fiber 100. Accordingly, the base fiber 100 on which the mask patterns 142 and 144 are disposed can be easily manufactured. Also, since the base fiber 100 on which the mask patterns 142 and 144 are disposed can be easily manufactured, the electrodes 122 and 124 can be easily manufactured. As a result, it is possible to provide a highly reliable composite material production method capable of mass production with ease.

Hereinafter, specific experimental production examples and characteristics evaluation results of the composite material according to the above-described embodiment of the present invention will be described.

The composite material production according to Example 1

A rectangular silicon rubber fiber was prepared as a base fiber. The above silicone rubber fiber was produced by cutting a commercially available Ecoflex 0500 film. The base fiber was elongated by 300% in the longitudinal direction.

A mask solution is prepared. The mask solution was prepared by dissolving polyurethane in THF (tetrahydrofuran) solution. The mask solution was applied on the left and right sides of the elongated base fiber and then dried to form a mask pattern.

A carbon nanotube sheet is prepared. The carbon nanotube sheet was prepared from a carbon nanotube forest. The carbon nanotube sheet was deposited on the upper and lower surfaces of the elongated base fiber to prepare a first electrode and a second electrode including carbon nanotubes.

On the carbon nanotube sheet of the extended base fiber, ethanol was added. Thereafter, the elongated base fiber was shortened in the longitudinal direction to produce a composite material having a sandwich structure.

Composite Fabric Production According to Example 2

The composite material according to Example 1 described above was prepared to a length of 20 cm. The composite material was stitched on a commercially available knitwear to produce a composite fabric.

Manufacturing of the supercapacitor according to the third embodiment

The composite material according to Example 1 described above and a 15 wt% PVA-LiCl get electrolyte are prepared. The PVA-LiCl get electrolyte was prepared by mixing PVA (polyvinyl alcohol) having a weight of 4.5 g and a molecular weight of 146,000 to 186,000, LiCl having a weight of 6 g, and DI water in a volume of 30 mL.

The first electrode and the second electrode of the composite material according to Example 1 were used as a cathode and an anode, and the 15 wt% PVA-LiCl gel electrolyte was coated on the electrode to prepare a supercapacitor.

Fabrication of composite material and supercapacitor according to Example 4

The composite material according to the above-described Embodiment 1 is prepared. MnO ₂ was deposited on the carbon nanotubes included in the first electrode and the second electrode of the composite material by a potentiostatic method to prepare a composite material according to Example 4.

Then, the first electrode and the second electrode of the composite material according to the fourth embodiment were used as a cathode and an anode, respectively, and a supercapacitor was manufactured by the method according to the third embodiment.

Fabrication of composite material and supercapacitor according to Example 5

The composite material according to the above-described Embodiment 1 is prepared. MnO ₂ was deposited on the carbon nanotubes included in the first electrode of the composite material by a potentiostatic method.

PEDOT (polyethylenedioxythiophene) solution is prepared. The PEDOT solution was prepared by mixing 20 wt% solution of iron (III) p-toluenesulfonate hexahydrate (Fe (III) PTS), butanol, 1.6 volume% pyridine and 8 wt% oxidizing agent. The PEDOT solution was dropped onto the carbon nanotube containing the second electrode of the composite material. The carbon nanotubes dropping the PEDOT solution were dried at a temperature of 60 DEG C for 30 minutes. The dried carbon nanotubes were dried in a VPP (vapor phase polymerization) chamber at a temperature of 60 ° C. for 1 hour to prepare a composite material according to Example 5.

Then, the first electrode and the second electrode of the composite material according to the fifth embodiment were used as an anode and a cathode, and a supercapacitor was manufactured by the method according to the third embodiment.

Torsional sensor fabrication according to embodiment 6

The composite material according to Example 1 described above and an artificial muscle having a length of 8 cm are prepared. The artificial muscle was manufactured by twisting 520 μm diameter nylon fiber and heat treating the twisted nylon fiber at 250 ° C. and argon gas atmosphere for 1 hour.

Thereafter, the artificial muscle was connected to one end of the composite material according to Example 1, and the artificial muscle portion was heat-treated using a heat gun. As a result, a torsional sensor according to Example 6 was manufactured in which the composite material portion according to Example 1 was rotated at an angle of 750 °.

The composite material production according to Comparative Example 1

The base fiber according to Example 1 described above was prepared. A composite material was produced by the method according to Example 1 using the above-mentioned base fiber, and a carbon nanotube sheet was deposited on the left and right sides of the base fiber by omitting the mask pattern, .

8 is a photograph of a composite material according to Example 1 of the present invention.

Referring to FIG. 8, the composite material according to Example 1 was photographed by SEM (scanning electron microscopy). As can be seen from FIG. 8, it can be confirmed that the carbon nanotube sheet is formed in sandwich form on the upper surface and the lower surface of the base fiber.

Fig. 9 is a photograph of a composite material according to the first embodiment of the present invention, which is obtained by modifying the shape of the composite material. Fig.

9 (a), the composite material according to the first embodiment is twisted, stretched, and bent, and the deformed composite material is wound on a glass tube, . As can be seen from FIG. 9 (a), the composite material according to Example 1 has stability in twisting, stretching, and bending.

9 (b) and 9 (c), SEM images of the composite material described with reference to FIG. 9 (a) were taken at low magnification and high magnification. As can be seen from FIGS. 9 (b) and 9 (c), the composite material according to Example 1 has a wrinkle structure uniformly formed all over and a wrinkle width and height of about 10 to 15 μm I could.

10 is a photograph of a composite material according to Comparative Example 1 of the present invention.

Referring to FIG. 10, after the carbon nanotube sheet was deposited on the base fiber and the base fiber, SEM images were taken. As can be seen from FIG. 10, the composite material according to Comparative Example 1 was confirmed that the carbon nanotube sheet was not properly deposited on the base fiber. Thus, it can be seen that, in order to manufacture the composite material according to the embodiment of the present invention, it is necessary to form the mask pattern.

11 is a photograph of the composite fabric according to the second embodiment of the present invention.

Referring to Fig. 11 (a), the composite fabric according to Example 2 was photographed. As can be seen from FIG. 11 (a), it was confirmed that the composite material according to Example 1 was included in a general wooden glove with a length of 20 cm.

Referring to Figs. 11 (b) and 11 (c), the composite fabric according to the second embodiment was photographed in an enlarged state in a state of being increased in its original state and an elastic change rate of 60%. As can be seen from FIGS. 11 (b) and 11 (c), it was confirmed that the composite fabric according to Example 2 had stability at a rate of change of elasticity of 60%.

12 and 13 are photographs of various shapes of the composite material according to the first embodiment of the present invention.

Referring to FIG. 12 (a), the composite material according to Example 1 was photographed by SEM. Referring to FIG. 12 (b), the composite material according to Example 1 was stretched by 200%, and then SEM images were taken. Referring to FIG. 12C, the composite material according to Example 1 was twisted at 200% stretch deformation and 1700 rad / meter, and then SEM images were taken. 13 (a), the composite material according to Example 1 was twisted at 1700 rad / meter and SEM image was taken. Referring to FIG. 13 (b), the composite material according to the first embodiment was bent and deformed, and then SEM images were taken. As shown in Figs. 12 (a) to 12 (c) and 13 (a) and 13 (b), various modifications of the composite material according to the first embodiment are shown in Figs. (a) and (b) of FIG. 13, respectively.

FIG. 14 is a graph showing the characteristics of the composite material according to various modifications of the first embodiment of the present invention. FIG.

Referring to FIG. 14 (a), the resistance of the composite material according to Example 1 was measured in accordance with expansion and contraction in the range of 0 to 200%. As can be seen from FIG. 14 (a), it was confirmed that the composite material according to Example 1 increased in resistance by 3.7% as expansion and contraction were applied in the range of 0 to 200%. Thus, it can be seen that the composite material according to the first embodiment has excellent stretchability and electrical conductivity holding performance.

Referring to FIG. 14 (b), the resistance of the composite material according to Example 1 was measured by twisting the material to 0 to 1700 turns / m. As can be seen from FIG. 14 (b), it was confirmed that the composite material according to Example 1 had a resistance change of 3.1% as a twist deformation was applied in a range of 0 to 1700 turns / m. Referring to FIG. 14 (c), the composite material according to Example 1 was subjected to bending deformation in the range of 0 to 150 ° to measure the change of the above-mentioned term. As can be seen from FIG. 14 (c), the composite material according to Example 1 showed a 3.8% change in resistance as a bending deformation was applied in the range of 0 to 150 °. Accordingly, it can be seen that the composite material according to the first embodiment has excellent stability against various deformations.

15 to 17 are graphs showing structural characteristics of the composite material according to the first embodiment of the present invention.

15 (a), the capacitance (pF) and the capacitance (pF) according to the expansion and contraction in the range of 0 to 200% for the case where the composite material according to the first embodiment is stretched and released, and And a change in distance (? D / d ₀ ) between the electrodes was measured. As can be seen from Fig. 15 (a), the composite material according to Example 1 has almost no capacitance difference when it is stretched and released, and when it is stretched and stretched in the range of 0 to 200% The capacitance changed from 2.4 pF to 5.6 pF. It was also confirmed that the distance between the first electrode and the second electrode was reduced by 56% as the electrode was stretched and deformed in the range of 0 to 200%.

Referring to FIG. 15 (b), the sensitivity (ΔC / C ₀ ) over time of the composite material according to Example 1 was measured in the case of repeating a tensile strain of 200%. As can be seen from FIG. 15 (b), the composite material according to Example 1 exhibits a sensitivity of 0.9 at a tensile strain of 200%.

Referring to FIG. 16A, the capacitance (pF) and the capacitance (pF) according to the twisted and deformed composite material in the range of 0 to 1700 rad / meter for the twisted case and the untwisted case according to the first embodiment, The change in bias angle was measured. As can be seen in Figure 16 (a), the composite material according to Example 1 has little capacitance difference when twisted and unwound, and from 2.9 pF to 3.7 pF at a twist strain of 0 to 1700 rad / meter capacitance changed. Also, it was confirmed that the deflection angle was increased by 56.7 ° as the twist was deformed in the range of 0 to 1700 rad / meter.

Referring to FIG. 16 (b), the sensitivity (ΔC / C ₀ ) over time for the composite material according to the first embodiment is 1700 rad / meter and -1700 rad / meter repeated torsional deformation Respectively. As can be seen from FIG. 16 (b), the composite material according to Example 1 exhibits a sensitivity of 0.26 at a torsional deformation of 1700 rad / meter and -1700 rad / meter.

Referring to FIG. 17, the sensitivity (ΔC / C ₀ ) over time for the composite material according to Example 1 was measured at 5.44 kPa, 17.15 kPa, and 36.75 kPa. As can be seen from FIG. 17, the composite material according to Example 1 exhibited a sensitivity of 0.14 at a pressure of 5.44 kPa, a sensitivity of 0.4 at a pressure of 17.15 kPa and a sensitivity of 0.6 at a pressure of 36.75 kPa I could confirm.

18 is a graph comparing the electrical characteristics of a supercapacitor according to embodiments of the present invention.

Referring to FIG. 18A, the current density (mA / cm ² ) according to the voltage V of the supercapacitors according to the third and fourth embodiments is measured and a cyclic voltammogram (CV) curve is shown . As can be seen from FIG. 18 (a), it can be seen that the supercapacitor according to the fourth embodiment exhibits a CV curve of an area 97.5 times wider than the supercapacitor according to the third embodiment. Accordingly, it is understood that doping MnO ₂ , which is an energy storage material, on the electrode of the composite material is an effective method of improving the efficiency of the supercapacitor according to the embodiment of the present invention.

Referring to FIG. 18B, the supercapacitor according to the fourth embodiment has a current density (mA / cm 2) according to a voltage (V) for a scan speed difference of 10, 30, 50, 70 and 100 mV / ² ) and the cyclic voltammogram (CV) curve. 18 (b), the supercapacitor according to the fourth embodiment exhibits the largest CV curve at a scan speed of 100 mV / s. Accordingly, it can be seen that the supercapacitor according to the embodiment of the present invention is the most efficient method to manufacture at a scan speed of 100 mV / s.

19 is a graph showing electrical characteristics of a supercapacitor according to an embodiment of the present invention.

19 (a), a potential (V) according to time (sec) is measured for a current density of 0.28, 0.71, and 2.14 mA / cm ² according to the fourth embodiment, and a Galvano-static charge / discharge curve. As can be seen from FIG. 19 (a), the supercapacitor according to Example 4 exhibits inverted triangular Galvano-static charge / discharge curves at current densities of 0.28, 0.71 and 2.14 mA / cm ² I could.

Referring to FIG. 19 (b), the linear capacitance (mF / cm) and the areal capacitance (mF / cm ² ) of the supercapacitor according to the fourth embodiment were measured according to the scan speed (mV / s). As shown in FIG. 19B, the supercapacitor according to the fourth embodiment exhibits an areal capacitance of 11.88 mF / cm ² and a linear capacitance of 2.38 mF / cm at a scan rate of 10 mV / s. . Also, it was confirmed that the linear capacitance and the areal capacitance were maintained at about 40.6% at a scanning speed of 100 mV / s.

20 is a graph illustrating characteristics of an asymmetric supercapacitor according to a fifth embodiment of the present invention.

Referring to FIG. 20A, the capacitance retention (C / C ₀ ) of the supercapacitor according to the fifth embodiment is measured according to the number of charge / discharge cycles. In addition, when the super capacitor was charged and discharged cyclically once and 1000 times, the current density according to the voltage was measured and the CV curve was shown. As can be seen from FIG. 20A, the supercapacitor according to the fifth embodiment can confirm that the capacitance retention is maintained without any significant difference during one to 1000 cycles of the charge-discharge cycle. It was also confirmed that the super capacitor had a large difference in area between the CV curve when the charge / discharge cycle was performed once and the CV curve when the charge / discharge cycle was performed 1000 times. Accordingly, it can be seen that the supercapacitor according to the fifth embodiment exhibits excellent stability even in repeated charge / discharge cycles.

Referring to FIG. 20 (b), the current density according to the voltage is measured for the potential of -1.4, -1.2, and -1.0 V according to the supercapacitor according to the fifth embodiment, and the CV curve is shown. As can be seen from FIG. 20 (b), the supercapacitor according to the fifth embodiment shows that the area of the CV curve becomes smaller as the potential gradually increases at -1.4, -1.2, and -1.0 V .

FIGS. 21 and 22 are graphs showing characteristics according to various modifications of the supercapacitor according to the fourth embodiment of the present invention.

21 (a), the supercapacitor according to the fourth embodiment is in a state of being pristine, stretched and deformed at an elastic strain of 200%, twisted at a speed of 1700 rad / meter, and The current density according to the voltage was measured with respect to the state of bending deformation at an angle of 150 °, and the CV curve was shown. 21 (a), the supercapacitor according to the fourth embodiment compares the CV curve area of the original state with the CV curve area of the stretch strain, the twist strain, and the bending strain substantially I could see the match.

Referring to FIG. 21 (b), the CV curves of the supercapacitor according to the fourth embodiment are obtained by measuring the current density according to the voltage with respect to the original state. The supercapacitor was stretched at an elastic strain of 200% and subjected to dynamic deformation in the order of twisting, releasing, and untwisting at a rate of 1700 rad / meter, And the CV curve is shown. As can be seen from FIG. 21B, the supercapacitor according to the fourth embodiment shows that the areas of the CV curves appearing while performing the dynamic deformation substantially coincide with those of the original CV curve area there was.

Referring to FIG. 22 (a), the supercapacitor according to the fourth embodiment is subjected to an electrochemical impedance spectroscopy (SEM) with respect to a state where the supercapacitor is stretched and deformed at an elastic strain of 200% (EIS) were measured. As can be seen in Figure 22 (a), the equilibrium series resistance (EIS) in the original state is 298.2? Cm at 100 kHz and decreases to 247? Cm and 176? Cm in the maximally stretched and maximally twisted state I could confirm.

Referring to FIG. 22 (b), the capacitance retention (C / C ₀ ) for the deformation cycle of the supercapacitor according to the fourth embodiment is measured with respect to the stretching deformation and the twist deformation state. The current density of the supercapacitor was measured in a state where the supercapacitor was stretched and deformed at an elastic strain of 200% in the original state, and at a speed of 1700 rad / meter, and the CV curve was shown. As can be seen from FIG. 22 (b), it was confirmed that the capacitance of 92.8% and 98.2% was maintained in the supercapacitor according to the fourth embodiment compared to the capacitance in the original state even in the state of stretching deformation and twist deformation .

As a result, it can be seen that the supercapacitor according to Embodiment 4 of the present invention maintains an enhanced expansion ratio and stable energy storage capability even in various physical deformation environments.

FIG. 23 is a photograph showing a torsional sensor according to a sixth embodiment of the present invention, and FIG. 24 is a graph showing characteristics of a torsional sensor according to the sixth embodiment of the present invention.

Referring to FIG. 23, the torsional sensor according to the sixth embodiment is SEM photographed. As can be seen from FIG. 23, the torsional sensor according to the sixth embodiment can confirm that the composite material part according to the first embodiment performs torsional sensing, and the artificial muscle part acts as torsional actuation.

Referring to FIG. 24 (a), the artificial muscle portion included in the torsional sensor according to the sixth embodiment is repeatedly subjected to heat treatment and cooling, and the capacitance (Δ CC ₀ ^-1 ) over time is measured . As can be seen from FIG. 24 (a), the torsional sensor according to the sixth embodiment shows reversible 10% capacitance change as the heat treatment and the cooling process for the artificial muscle portion are repeatedly performed.

Referring to FIG. 24 (b), the artificial muscle part included in the torsional sensor according to the sixth embodiment is repeatedly subjected to heat treatment and cooling, and the actuation angle (°) with time is measured. As can be seen from FIG. 24 (b), the torsional sensor according to the sixth embodiment repeats the heat treatment and cooling process on the artificial muscle portion, and thus the actuation angle change of 50 ° to 750 ° is repeated . Accordingly, it can be seen that the composite material according to the first embodiment acts as an efficient torsional sensor for measuring torsional rotation generation of artificial muscles.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. It will also be appreciated that many modifications and variations will be apparent to those skilled in the art without departing from the scope of the present invention.

100: base fiber
102: first side
104: second side
106: Third Side
108: fourth face
120: Carbon nanotube sheet
140: mask pattern
142: First mask pattern
142: Second mask pattern
200: base sheet
242: first mask layer
244: second mask layer

Claims (12)

The method comprising: providing a base fiber comprising silicon and comprising a first side and a second side opposite the first side;
Extending the base fiber lengthwise;
Forming a first electrode comprising carbon nanotubes on the first surface of the extended base fiber; And
And forming a second electrode comprising carbon nanotubes on the second surface of the extended base fiber.
The method according to claim 1,
The forming of the first electrode and the forming of the second electrode may include:
Providing an additive to the first electrode and the second electrode comprising carbon nanotubes to increase the density of the first electrode and the second electrode.
The method according to claim 1,
Wherein the base fiber comprises:
A third side between the first side and the second side; And
Further comprising a fourth surface opposite the third surface,
Forming a first mask pattern and a second mask pattern on the third surface and the fourth surface before forming the first electrode and the second electrode, .
The method of claim 3,
Further comprising removing the first mask pattern and the second mask pattern after the first electrode and the second electrode are formed.
The method of claim 3,
Wherein the first mask pattern and the second mask pattern comprise polyurethane.
The method according to claim 1,
Wherein preparing the base fiber comprises:
Preparing a base sheet comprising silicon;
Forming a first mask layer and a second mask layer, respectively, on the upper and lower surfaces of the base sheet, respectively; And
And cutting the base sheet to produce the base fiber,
Wherein the first surface and the second surface of the base fiber are surfaces produced by cutting the base sheet,
Wherein the base fiber comprises:
A third surface on which the first mask layer with the first mask layer cut is disposed, and disposed between the first surface and the second surface; And
And a fourth surface opposite to the third surface on which the second mask pattern with the second mask layer cut is disposed.
The method according to claim 1,
The forming of the first electrode and the forming of the second electrode may include:
Providing an energy storage material on the carbon nanotubes on the first surface and the second surface of the base fiber.
8. The method of claim 7,
Wherein providing energy storage material comprises:
Providing a source comprising an energy storage material on the carbon nanotubes.
A base fiber comprising silicon and comprising a first side and a second side opposite the first side;
A first electrode disposed on the first surface of the base fiber and including a carbon nanotube having a pleated structure; And
And a second electrode disposed on the second surface of the base fiber and including a carbon nanotube having a wrinkle structure.
10. The method of claim 9,
Wherein the base fiber comprises:
A third surface disposed between the first surface and the second surface and exposed without the carbon nanotubes disposed thereon; And
And a fourth surface opposed to the third surface and exposed without the carbon nanotubes disposed thereon.
10. The method of claim 9,
Wherein the first electrode and the second electrode comprise an energy storage material.
10. The method of claim 9,
Wherein the energy storage material comprises at least one of MnO ₂ and PEDOT (polyethylenedioxythiophene).

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