WO2018066974A1

WO2018066974A1 - Electrode fiber and method for producing same

Info

Publication number: WO2018066974A1
Application number: PCT/KR2017/011120
Authority: WO
Inventors: 김선정; 최창순; 김강민; 이재명
Original assignee: 한양대학교 산학협력단
Priority date: 2016-10-06
Filing date: 2017-10-10
Publication date: 2018-04-12
Also published as: KR101961005B1; KR20180038287A

Abstract

Provided is a method for producing an electrode fiber. The method for producing an electrode fiber may comprise the steps of: preparing a carbon nanotube sheet; providing a functional material onto the carbon nanotube sheet; and twisting the carbon nanotube sheet provided with the functional material to produce an electrode fiber extending in a first direction.

Description

Electrode Fiber and Manufacturing Method Thereof

The present invention relates to an electrode fiber, a method for manufacturing the same, and a super capacitor including the same, and more particularly, to an electrode fiber including a carbon nanotube sheet and a functional material, a method for manufacturing the same, and a super capacitor including the same. will be.

Supercapacitors are capacitors with high capacitance and are called ultracapacitors or ultracapacitors. Supercapacitors, unlike batteries that use chemical reactions, use charge phenomena due to surface chemistry or movement of ions to the electrode and electrolyte interfaces. Accordingly, it has been spotlighted as a next-generation energy storage device that can be used as a secondary battery or a battery replacement due to its rapid charge and discharge, high charge and discharge efficiency, and semi-permanent cycle life characteristics.

These supercapacitors are useful as energy buffers in the development of next-generation environmentally friendly vehicles such as electric vehicles (EVs), hybrid electric vehicles (HEVs), or fuel cell vehicles (FCVs). It is increasing.

According to the industrial demand for super capacitors, many researches and developments on electrodes for super capacitors having a great influence on the characteristics of the super capacitors have been conducted. For example, Korean Patent Laid-Open Publication No. 10-2012-0016343 (Application No. 10-2010-0078611) discloses an electrode formed by a screen printing method in order to reduce the thickness while maintaining the capacity of a supercapacitor, so that the reaction area at the electrode is reduced. A technique for widening the is disclosed.

One technical problem to be solved by the present invention is to provide an electrode fiber with a simplified manufacturing process and a method of manufacturing the same.

Another technical problem to be solved by the present invention is to provide an electrode fiber and a method of manufacturing the reduced manufacturing cost.

Another technical problem to be solved by the present invention is to provide an electrode fiber with improved energy storage characteristics and a method of manufacturing the same.

Another technical problem to be solved by the present invention is to provide a highly stretchable electrode fiber and its manufacturing method.

Another technical problem to be solved by the present invention is to provide a highly reliable electrode fiber and its manufacturing method.

Another technical problem to be solved by the present invention is to provide an electrode fiber and a method of manufacturing the same that can be easily applied to a wearable device.

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

In order to solve the above technical problem, the present invention provides a method for producing an electrode fiber.

According to one embodiment, the manufacturing method of the electrode fiber, preparing a carbon nanotube sheet, providing a functional material on the carbon nanotube sheet, and the carbon provided with the functional material Twisting the nanotube sheet may include producing an electrode fiber extending in the first direction.

According to one embodiment, the manufacturing method of the electrode fibers, twisting a plurality of the electrode fibers (twist), may further comprise the step of producing a composite fiber.

According to one embodiment, the carbon tube sheet comprises a first carbon nanotube sheet and a second carbon nanotube sheet, the functional material comprises a first functional material and a second functional material, the electrode fiber A first electrode fiber provided with the first functional material on the first carbon nanotube sheet and a second electrode fiber provided with the second functional material on the second carbon nanotube sheet, wherein the first electrode fiber And controlling the content of the first functional material to be 70 wt% or less, and controlling the content of the second functional material to be 70 wt% or less in the second electrode fiber.

According to one embodiment, the first carbon nanotube sheet and the second carbon nanotube sheet, each comprising a plurality of carbon nanotubes extending in the first direction, manufacturing the first electrode fiber and The manufacturing of the second electrode fiber may include twisting one ends of the plurality of carbon nanotubes extending in the first direction, using the first direction as the rotation axis.

According to an embodiment, the first functional material includes metal oxide particles, and the providing of the first functional material may include preparing a source solution in which the metal oxide particles are dispersed, and the metal oxide particles It may include providing a dispersed source solution on the first carbon nanotube sheet.

According to one embodiment, the electrode fiber manufacturing method, the first carbon nanotube sheet is twisted directly after the source solution in which the metal oxide particles are dispersed (directly after) is provided on the first carbon nanotube sheet. In some embodiments, the method may include manufacturing the first electrode fiber.

According to one embodiment, the first functional material comprises a reduced graphene oxide, the second functional material comprises manganese dioxide, on the first carbon nanotube sheet, to provide the first functional material The method may include preparing a source solution in which the reduced graphene oxide is dispersed, and providing a source solution in which the reduced graphene oxide is dispersed on the first carbon nanotube sheet. The providing of the second functional material on the second carbon nanotube sheet may include preparing a source solution in which the manganese dioxide is dispersed, and providing the source solution in which the manganese dioxide is dispersed on the second carbon nanotube sheet. And the concentration of the reduced graphene oxide in the source solution in which the reduced graphene oxide is dispersed, and the source solution in which the idealized manganese is dispersed. It may include higher than the concentration of the manganese dioxide in the.

According to an embodiment, the providing of the first functional material on the first carbon nanotube sheet may include providing a source solution in which the reduced graphene oxide is dispersed on the first carbon nanotube sheet. And repeating the step of drying the first carbon nanotube sheet provided with the source solution in which the reduced graphene oxide is dispersed.

According to one embodiment, the first functional material comprises silver nanowires, the second functional material comprises zinc particles, and further comprising twisting the first and second electrode fibers with each other, the twisted The number of the first electrode fibers may include more than the number of the second electrode fibers.

In order to solve the above technical problem, the present invention provides an electrode fiber.

According to one embodiment, the electrode fiber comprises a carbon nanotube sheet and an electrode fiber comprising a functional material, wherein an inner region of the electrode fiber is rolled and stacked on the carbon nanotube sheet. It may include that the functional material is provided between the carbon nanotube sheet is provided in the form, dried and laminated.

According to one embodiment, the electrode fiber extends in a first direction, and in the cross section of the electrode fiber cut into the first plane having the first direction as a normal, the cross section of the carbon nanotube sheet is spiral Wherein, in the cross section of the electrode fiber cut into the first plane having the first direction as a normal, the functional material is provided between the helical carbon nanotube sheets, and within the electrode fiber, the functional The content of the material may include higher than the content of the carbon nanotube sheet.

According to one embodiment, the carbon nanotube sheet includes a first carbon nanotube sheet and a second carbon nanotube sheet, the functional material comprises a first functional material and a second functional material, the electrode fiber The first functional material may include a first electrode fiber provided on the first carbon nanotube sheet, and the second functional material may include a second electrode fiber provided on the second carbon nanotube sheet.

According to one embodiment, the electrode fibers, the first and second electrode fibers, the content of the first and second functional material, respectively, higher than the content of the first and second carbon nanotube sheet It may include.

According to one embodiment, the first functional material comprises a reduced graphene oxide, the second functional material comprises manganese dioxide, wt% of the reduced graphene oxide in the first electrode fiber, It may include higher than the wt% of the manganese dioxide in the second electrode fiber.

According to an embodiment, the number of the first carbon nanotube sheets in the first electrode fibers may include more than the number of the second carbon nanotube sheets in the second electrode fibers.

According to one embodiment, the reduced graphene oxide may include nitrogen doped.

According to one embodiment, wherein the first functional material comprises silver nanowires, and the second functional material comprises zinc particles, wherein the wt% of the silver nanowires is higher than the wt% of the zinc particles. It may include.

According to an embodiment, the electrode fibers may include wt% of the silver nanowires in the first electrode fiber and wt% of the zinc particles in the second electrode fiber.

According to an embodiment, the first electrode fiber and the second electrode fiber are twisted with each other, wherein x first electrode fibers are twisted with y second electrode fibers, and x and y are greater than zero. Is a natural number, and x may include greater than y.

According to an embodiment, the electrode fiber may include x = 2y.

In the method of manufacturing an electrode fiber according to the first embodiment of the present invention, providing energy storage particles on a carbon nanotube sheet, and twisting the carbon nanotube sheet provided with the energy storage particles in a first direction. It may comprise the step of producing the extending base fibers. Accordingly, the content of the energy storage particles in the base fiber can be maximized, thereby providing an electrode fiber and a method of manufacturing the same, which simplifies the manufacturing process and reduces the manufacturing cost.

The electrode fiber according to the second embodiment of the present invention includes a first electrode fiber and a manganese dioxide and a manganese dioxide including a reduced graphene oxide and a first carbon nanotube sheet twisted to surround the reduced graphene oxide. It may comprise a second electrode fiber comprising a twisted second carbon nanotube sheet. Accordingly, when the supercapacitor is manufactured using the electrode fiber according to the second embodiment, a highly efficient asymmetric supercapacitor including the reduced graphene oxide and the manganese dioxide may be provided.

In addition, the electrode fiber according to the second embodiment, the graphene oxide is reduced on the first and second carbon nanotube sheet before the fiber is manufactured using the first and second carbon nanotube sheet And the manganese dioxide is provided, and the reduced graphene oxide and the manganese dioxide are provided, the first and second carbon nanotube sheets are twisted to produce the first and second electrode fibers. . Accordingly, the content of the reduced graphene oxide and the manganese dioxide in the first and second electrode fibers is increased, and when manufacturing a supercapacitor using the electrode fibers according to the second embodiment, Energy storage can be improved.

The silver-zinc battery including the electrode fiber according to the third embodiment of the present invention includes a first electrode fiber, zinc particles, including a silver nanowire, and a first carbon nanotube sheet twisted to surround the silver nanowire. It may include a second electrode fiber including a second carbon nanotube sheet twisted to surround the zinc particles, an electrolyte between the first electrode fiber and the second electrode fiber. Accordingly, a high-efficiency silver-zinc battery including the silver nanowires and the zinc particles may be provided.

In addition, the silver-zinc battery including the electrode fiber according to the third embodiment, on the first and the second carbon nanotube sheet, before the fiber is manufactured using the first and second carbon nanotube sheet. When the silver nanowires and the zinc particles are provided, and the silver nanowires and the zinc particles are provided, the first and second carbon nanotube sheets are twisted to form the first and second electrode fibers. Can be prepared. Accordingly, the content of the silver nanowires and the zinc particles in the first and second electrode fibers may be increased, and energy storage of the silver-zinc battery may be improved.

1 is a flowchart illustrating a method of manufacturing an electrode fiber according to a first embodiment of the present invention.

2 to 4 are views for explaining the manufacturing process of the electrode fiber according to the first embodiment of the present invention.

5 is a photograph of a base fiber, a composite fiber, and an electrode fabric prepared according to the method for manufacturing electrode fibers according to Examples 1-1 and 1-2 of the present invention.

6A and 6B are graphs showing the mechanical properties of the composite fibers according to Examples 1-2, Examples 1-10, and Comparative Examples 1-2 of the present invention.

7 is a SEM photograph of a composite fiber according to Examples 1-9 of the present invention.

8 are graphs comparing cyclic voltage current and charge / discharge characteristics of supercapacitors according to Examples 1-4 to 1-6 and Comparative Example 1-1 of the present invention.

9 are graphs comparing the capacitance characteristics of the supercapacitors according to Examples 1-4 to 1-6 and Comparative Examples 1-1 of the present invention.

10 are graphs illustrating characteristics of an asymmetric supercapacitor according to Examples 1-8 of the present invention.

11 are graphs illustrating characteristics of a super capacitor according to Examples 1-6 of the present invention.

12 is a graph showing the characteristics of the super capacitor according to the embodiment 1-7 of the present invention.

13 is a graph showing energy densities of supercapacitors according to Examples 1-6 and 1-7 of the present invention.

14 and 15 are views for explaining a manufacturing process of the first electrode fiber included in the electrode fiber according to the second embodiment of the present invention.

16 and 17 are diagrams for describing a manufacturing process of the second electrode fibers included in the electrode fibers according to the second embodiment of the present invention.

18 is a view illustrating a supercapacitor including an electrode fiber and a method of manufacturing the same according to the second embodiment of the present invention.

19 is a photograph of the first electrode fibers included in the electrode fibers according to the second exemplary embodiment of the present invention.

20 is a photograph of the second electrode fibers included in the electrode fibers according to the second exemplary embodiment of the present invention.

21 is a graph showing the electrochemical characteristics of the supercapacitor according to Comparative Example 2-1 of the present invention.

FIG. 22 is a graph comparing characteristics of the reduced graphene oxide content of the first electrode fibers according to Example 2-1 of the present invention. FIG.

23 is a graph comparing the characteristics of the first electrode fibers and the second electrode fibers according to Examples 2-1 and 2-2 of the present invention.

24 is a graph showing the characteristics of the supercapacitor according to the embodiment 2-3 of the present invention.

25 is a graph showing the characteristics of the supercapacitor according to the embodiment 2-4 of the present invention.

FIG. 26 is a graph comparing characteristics of supercapacitors according to Examples 2-3 and 2-4 of the present invention. FIG.

27 is a graph comparing energy storage characteristics of supercapacitors according to Examples 2-3, 2-4 and Comparative Examples 2-2 to 2-7 of the present invention.

28 is a graph illustrating electrochemical characteristics of the supercapacitor, the first electrode, and the second electrode according to Examples 2-3, 2-6, and 2-7 of the present invention.

29 is a graph showing the electrochemical characteristics of the supercapacitors according to Examples 2-3 and 2-4 of the present invention.

30 is a graph comparing characteristics of the supercapacitors according to Example 2-3 and Comparative Example 2-1 of the present invention.

31 is a graph showing charge and discharge characteristics of a supercapacitor according to Example 2-3 of the present invention.

32 is a photograph showing the operation of the electrode fabric and the circuit using the same according to the embodiment 2-5 of the present invention.

33 is a graph showing electrochemical characteristics when the electrode fabrics according to Example 2-5 of the present invention are connected in series and in parallel.

34 is a graph comparing characteristics of the electrode fabrics according to the embodiment 2-5 of the present invention and the parallel connection.

35 is a graph showing the durability of the electrode fabric according to Example 2-5 of the present invention.

36 and 37 are views for explaining a manufacturing process of the first electrode fibers included in the electrode fiber according to the third embodiment of the present invention.

38 and 39 are views for explaining a manufacturing process of the second electrode fibers included in the electrode fiber according to the third embodiment of the present invention.

40 is a view illustrating a silver-zinc battery including an electrode fiber and a method of manufacturing the same according to the third embodiment of the present invention.

FIG. 41 is a photograph of the first electrode fibers included in the electrode fibers according to Example 3-1 of the present invention. FIG.

FIG. 42 is a photograph of a second electrode fiber included in the electrode fiber according to Example 3-2 of the present invention. FIG.

43 is a graph showing the electrochemical characteristics of the silver-zinc battery according to Example 3-3 and Comparative Example 3-1 of the present invention.

44 is a graph showing the electrochemical characteristics of the silver-zinc battery according to Example 3-3 of the present invention.

45 is a graph showing the electrochemical characteristics of the silver-zinc battery according to Example 3-4 of the present invention.

46 is a graph comparing characteristics of silver-zinc batteries according to Example 3-4 and batteries according to Comparative Examples 3-2 to 3-4.

47 is a graph showing the stretchability of a silver-zinc battery according to Example 3-4 of the present invention.

48 is a graph showing the performance according to the connection method of the silver-zinc battery according to the embodiment 3-4 of the present invention.

49 is a photograph of a device using an electrode fabric according to Examples 3-5 of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the exemplary embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete, and that the spirit of the present invention can be sufficiently delivered to those skilled in the art.

In the present specification, when a component is mentioned to be on another component, it means that it may be formed directly on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical contents.

In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. In addition, the term 'and / or' is used herein to include at least one of the components listed before and after.

In the specification, the singular encompasses the plural unless the context clearly indicates otherwise. In addition, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, element, or combination thereof described in the specification, and one or more other features or numbers, steps, configurations It should not be understood to exclude the possibility of the presence or the addition of elements or combinations thereof. In addition, the term "connection" is used herein to mean both indirectly connecting a plurality of components, and directly connecting.

In addition, the term "functional material" is used to include all energy storage materials, reduced graphene oxide, manganese dioxide, silver nanowires and the like.

In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

제1 실시 예에 따른 전극 섬유 및 그 제조 방법An electrode fiber and a method of manufacturing the same according to the first embodiment

1 is a flowchart illustrating a method of manufacturing an electrode fiber according to the first embodiment of the present invention, Figures 2 to 4 are views for explaining a manufacturing process of the electrode fiber according to the first embodiment of the present invention. .

1 and 2, the carbon nanotube sheet 110 may be prepared (S110). According to an embodiment, the preparing of the carbon nanotube sheet 110 may include preparing a carbon nanotube forest by chemical vapor deposition, and the carbon nanotube sheet 110 from the carbon nanotube forest. ) May be prepared.

According to one embodiment, the carbon nanotube sheet 110 may include a plurality of carbon nanotubes extending in a first direction. Further, according to one embodiment, the plurality of carbon nanotubes may be multi-walled carbon nanotubes (MWCNT).

According to an embodiment, the carbon nanotube sheet 110 may be prepared on the support substrate 100. For example, the support substrate 100 may be a glass substrate. Alternatively, for example, the support substrate 100 may include any one of a plastic substrate, a semiconductor substrate, a ceramic substrate, and a metal substrate.

Energy storage particles 120 may be provided on the carbon nanotube sheet 110 (S120). The energy storage particles 120 may have a lower conductivity than the carbon nanotube sheet 110 and may have a higher charge storage capability than the carbon nanotube sheet 110. According to one embodiment, the energy storage particles 120 may include metal oxide particles. Specifically, for example, the energy storage particles 120 may include manganese oxide, ruthenium oxide, and the like.

Providing the energy storage particles 120 on the carbon nanotube sheet 110, dispersing the energy storage particles 120 in a solvent to prepare a source solution, and the source solution to the carbon nano Providing on tube sheet 110. According to an embodiment of the present disclosure, the source solution may be prepared by adding the energy storage particles 120 to the solvent and performing ultrasonic treatment to disperse the energy storage particles 120. For example, the solvent may be ethanol. In addition, according to one embodiment, the source solution may be provided on the carbon nanotube sheet 110 by a drop casting method.

According to one embodiment, the size of the energy storage particles 120 in the source solution may be substantially the same. Alternatively, according to another embodiment, sizes of the energy storage particles 120 in the source solution may be different.

1 and 3, by twisting the carbon nanotube sheet 110 provided with the energy storage particles 120, a base fiber 130 may be manufactured (S130). According to an embodiment, the manufacturing of the base fiber 130 may include twisting one ends of the plurality of carbon nanotubes by using the first direction in which the plurality of carbon nanotubes extend as a rotation axis. It may include). For example, the carbon nanotube sheet 110 provided with the energy storage particles 120 may be twisted about 2,000 times per meter.

Accordingly, the inner region of the base fiber 130 may be provided in a form in which the carbon nanotube sheet 110 is rolled and stacked. The energy storage particles 120 may be provided between the carbon nanotube sheets 110 which are dried and stacked. In other words, when a first plane having a normal line in the first direction in which the base fiber 130 extends is defined, in the cross section of the base fiber 130 cut into the first plane, the carbon nanotube sheet A cross section of 110 may be provided in a spiral shape, and the energy storage particles 120 may be provided between the carbon nanotube sheet 110 in a spiral shape.

According to one embodiment, in the base fiber 130, the content of the energy storage particles 120 may be higher than the content of the carbon nanotube sheet 110.

According to an embodiment, as described above, when the energy storage particles 120 are formed using the source solution, immediately after the source solution is provided on the carbon nanotube sheet 110. By twisting the carbon nanotube sheet 110, the base fiber 130 may be manufactured. In other words, before the solvent is dried in the source solution, the carbon nanotube sheet 110 is twisted, and the base fiber 130 may be manufactured. Accordingly, aggregation of the energy storage particles 120 may be minimized.

If, unlike the above-described embodiment of the present invention, the carbon nanotube sheet 110 is twisted immediately after the source solution is provided on the carbon nanotube sheet 110, the base fiber 130 is not manufactured, When the source solution is provided and an additional process is performed before the base fiber 130 is prepared, the solvent in the source solution may be evaporated. Accordingly, the energy storage particles 120 on the carbon nanotube sheet 110 may aggregate with each other. Thus, the dispersion degree of the energy storage particles 120 in the base fiber 130 is lowered, so that the energy storage particles 120 are concentrated in a portion of the base fiber 130, the base fiber ( The uniformity of electrical, chemical, and physical properties of 130 may be degraded.

However, as described above, according to an embodiment of the present invention, immediately after the source solution is provided on the carbon nanotube sheet 110 (twist the carbon nanotube sheet 110), the The base fiber 130 may be manufactured, and thus, uniformity of electrical, physical, and chemical properties of the base fiber 130 may be improved.

In addition, as described above, before the fiber is manufactured using the carbon nanotube sheet 110, the energy storage particles 120 are provided on the carbon nanotube sheet 110, and the energy storage particles ( In the state where 120 is provided on the carbon nanotube sheet 110, the base fiber 130 may be manufactured by twisting the carbon nanotube sheet 110. Accordingly, the content of the energy storage particles 120 in the base fiber 130 may be increased.

If, unlike the above-described embodiment of the present invention, after producing the fiber from the carbon nanotube sheet 110, when providing the energy storage particles 120 on the fiber, the energy storage particles 120 Is substantially located primarily on the surface of the fiber and is not easy to fill the inner region of the fiber. Accordingly, the energy storage particles 120 may be easily separated from the fiber, or there may be a limit in increasing the content of the energy storage particles 120 in the fiber. In addition, as described above, in a simple process of providing the source solution to the carbon nanotube sheet 110, it is not easy to manufacture the fiber having the energy storage particles 120.

However, as described above, according to an embodiment of the present invention, the carbon nanotube sheet 110 in a state in which the source solution including the energy storage particles 120 is provided on the carbon nanotube sheet 110. By twisting), the base fiber 130 may be manufactured, and accordingly, energy storage characteristics of the base fiber 130 may be improved. In addition, a manufacturing method of the base fiber 130 can be provided with a simplified manufacturing process and reduced manufacturing cost.

1 and 4, a plurality of the base fibers 130 may be manufactured according to the above-described embodiment of the present invention. According to one embodiment, in the plurality of base fibers 130, the amount of t of the energy storage particles 120 may be substantially the same (substantially). Alternatively, according to another embodiment, in the plurality of base fibers 130, the content of the energy storage particles 120 may be different from each other.

By twisting a plurality of the base fibers 130 with each other, a composite fiber 140 can be produced (S140). For example, five of the base fibers 130 are twisted about 25,000 times per meter, so that the composite fibers 140 can be made. The composite fiber 140 in which the plurality of the base fibers 130 is twisted may have elasticity as well as a high tensile strength as compared with the base fibers 130.

According to one embodiment, the step of providing the energy storage particles 120 on the carbon nanotube sheet 110, the content of the energy storage particles 120 in the base fiber 130 is less than the reference content Control to include. For example, as described above, when the energy storage particles 120 are provided on the carbon nanotube sheet 110 using the source solution, the supply amount of the source solution, and / or the source solution By adjusting the concentration of the energy storage particles in the inside, it can be easily controlled so that the content of the energy storage particles 120 in the base fiber 130 is less than the reference content. Accordingly, in the process in which the plurality of base fibers 130 are twisted to manufacture the composite fiber 140, the outer wall of the base fibers 130 bursts to cause the energy storage particles 120 to flow out of the base fibers 130. ) Damage can be minimized. According to one embodiment, the reference content may be 70wt%.

If, unlike the above-described, when the energy storage particles 120 in the base fiber 130 exceeds the reference content, twisting a plurality of the base fibers 130 to produce the composite fiber 140 In the process, the base fiber 130 may burst.

However, as described above, according to an embodiment of the present invention, the content of the energy storage particles 120 in the base fiber 130 may be controlled to be less than the reference content, accordingly, the composite fiber ( Production yield of 140 may be improved.

As shown in (b) of FIG. 4, the plurality of the composite fibers 140 may cross each other and be made of an electrode fabric 150.

Hereinafter, specific experimental examples and characteristic evaluation results according to the manufacturing method of the electrode fiber according to the first embodiment of the present invention described above will be described.

Base fiber preparation according to Example 1-1

The silicon substrate is prepared. By chemical vapor deposition on the silicon substrate, a carbon nanotube forest including a height of about 400 μm, a diameter of about 12 nm, and about nine walls was prepared. Pulling the carbon nanotube forest in a first direction, a carbon nanotube sheet (CNT sheet) including a plurality of carbon nanotubes extending in the first direction was prepared on a glass substrate.

Manganese dioxide (MnO ₂ ) nanoparticles prepared from Sigma-Aldrich, including 30 nm in diameter, 100 nm in length, and rod-shaped, are prepared. Ethanol solvents having a concentration of 1 to 5 mg / ml are prepared. The manganese dioxide nanoparticles were dispersed in the ethanol solvent. The ethanol solvent in which the manganese dioxide nanoparticles were dispersed was sonicated at 150W for 1 hour to prepare a source solution. The source solution was provided on the carbon nanotube sheet by a drop casting method. While the source solution was provided on the carbon nanotube sheet, the content of the manganese dioxide was controlled to be 91.1 wt% based on the total content.

The carbon nanotube sheet provided with the source solution is provided with the first solution as the axis of rotation immediately after the source solution is provided on the carbon nanotube sheet. By twisting about 2,000 times, a base yarn was produced.

Preparation of the composite fiber according to Example 1-2

The carbon nanotube sheet and the source solution according to Example 1-1 described above are prepared. The source solution was provided on the carbon nanotube sheet by the method according to Example 1-1 described above. While the source solution was provided on the carbon nanotube sheet, the content of the manganese dioxide was controlled to be 70 wt% based on the total content. Thereafter, a base fiber was prepared by the method according to Example 1 described above.

Five base fibers were prepared. The base fibers were twisted about 25,000 times per meter to make composite fibers.

Preparation of Electrode Fabrics According to Examples 1-3

The composite fibers according to Example 1-2 described above were crossed with each other to produce an electrode fabric.

Preparation of Supercapacitors According to Examples 1-4

Two base fibers according to Example 1-2 described above were prepared. A mixed solution was prepared by mixing 3 g of polyvinyalcohol (PVA), 6 g of lithium chloride (LiCl), and 30 ml of DI water having a molecular weight of 146,000 to 186,000. The mixed solution was heat-treated at a temperature of 90 ℃ to prepare a PVA / LiCl gel electrolyte. Base fibers according to Examples 1-2 were placed in parallel at a distance of about 100 μm. The PVA / LiCl gel electrolyte was coated on each of the base fibers according to Example 2, thereby preparing a supercapacitor.

Preparation of Supercapacitors According to Example 1-5

The carbon nanotube sheet and the source solution according to Example 1-1 described above are prepared. The source solution was provided on the carbon nanotube sheet by the method according to Example 1-1 described above. While the source solution was provided on the carbon nanotube sheet, the content of the manganese dioxide was controlled to be 80.5 wt% based on the total content. Thereafter, a base fiber was prepared by the method according to Example 1 described above.

Two base fibers were prepared. Thereafter, a supercapacitor was manufactured by the method according to Example 1-4.

Preparation of Supercapacitors According to Examples 1-6

Two base fibers according to Example 1-1 described above were prepared. Thereafter, a supercapacitor was manufactured by the method according to Example 1-4 described above.

Preparation of Supercapacitors According to Examples 1-7

Two composite fibers according to Example 1-2 described above were prepared. Thereafter, an electrolyte according to Example 4 was prepared. The composite fibers according to Example 1-2 described above were placed in parallel at a distance of about 100 μm. The supercapacitor was manufactured by coating the electrolyte according to Example 1-4, respectively, on the composite fiber according to Example 1-2.

Preparation of Supercapacitors According to Examples 1-8

The carbon nanotube sheet according to Example 1-1 described above is prepared. The reduced graphene oxide (rGO) was dispersed in the ethanol solvent according to Example 1-1 described above. Thereafter, a source solution was prepared by the method according to Example 1-1 described above. The source solution was provided on the carbon nanotube sheet by the method according to Example 1-1 described above. While the source solution was provided on the carbon nanotube sheet, the content of the reduced graphene oxide was controlled to be 18.5 wt% based on the total content. Thereafter, base fibers were prepared by the method according to Example 1-1 described above.

One base fiber and one base fiber according to Example 1-1 described above were prepared. The base fiber was used as the anode, and the base fiber according to Example 1-1 described above was used as the cathode. Thereafter, an asymmetric supercapacitor was manufactured by the method according to Examples 1-4 described above.

Preparation of Composite Fibers According to Examples 1-9

While preparing the base fiber according to Example 1-2 described above, the content of the manganese dioxide was controlled to be 80wt% based on the total content. Thereafter, a composite fiber was prepared by the method according to Example 1-2 described above.

Preparation of Composite Fibers According to Examples 1-10

To prepare a base fiber according to Example 1-2 described above, the content of the manganese dioxide was controlled to be 93wt% based on the total content. Thereafter, a composite fiber was prepared by the method according to Example 1-2 described above.

Manufacture of supercapacitors according to Comparative Example 1-1

The carbon nanotube sheet according to Example 1-1 described above is prepared. Thereafter, base fibers were prepared by the method according to Example 1 described above without a source solution.

Preparation of Composite Fibers According to Comparative Example 1-2

The carbon nanotube sheet according to Example 1-1 described above is prepared. Thereafter, base fibers were prepared by the method according to Example 1-1 described above without a source solution.

Five base fibers were prepared, and then composite fibers were prepared by the method according to Example 1-2 described above.

The structure of the electrode fiber and the supercapacitor including the same according to Examples 1-1 to 1-8, and Comparative Examples 1-1 and 1-2 are summarized through Table 1 below.

구분division	구조rescue
실시 예 1-1Example 1-1	91.1wt% MnO₂/CNT 베이스 섬유91.1wt% MnO ₂ / CNT Base Fiber
실시 예 1-2Example 1-2	70wt% MnO₂/CNT 복합 섬유70wt% MnO ₂ / CNT Composite Fiber
실시 예 1-3Example 1-3	91.1wt% MnO₂/CNT 전극 직물91.1wt% MnO ₂ / CNT Electrode Fabric
실시 예 1-4Example 1-4	70wt% MnO₂/CNT 베이스 섬유를 포함하는 슈퍼 커패시터Supercapacitors with 70wt% MnO ₂ / CNT base fibers
실시 예 1-5Example 1-5	80.5wt% MnO₂/CNT 베이스 섬유를 포함하는 슈퍼 커패시터Supercapacitor with 80.5wt% MnO ₂ / CNT Base Fiber
실시 예 1-6Example 1-6	91.1wt% MnO₂/CNT 베이스 섬유를 포함하는 슈퍼 커패시터Supercapacitors containing 91.1wt% MnO ₂ / CNT base fibers
실시 예 1-7Example 1-7	70wt% MnO₂/CNT 복합 섬유를 포함하는 슈퍼 커패시터Supercapacitors containing 70wt% MnO ₂ / CNT composite fibers
실시 예 1-8Example 1-8	18.5wt% rGO/CNT 베이스 섬유 및 91.1wt% MnO₂/CNT 베이스 섬유를 포함하는 비대칭 슈퍼 커패시터Asymmetric Supercapacitors Include 18.5wt% rGO / CNT Base Fiber and 91.1wt% MnO ₂ / CNT Base Fiber
실시 예 1-9Example 1-9	80wt% MnO₂/CNT 복합 섬유80wt% MnO ₂ / CNT Composite Fiber
실시 예 1-10Example 1-10	93wt% MnO₂/CNT 복합 섬유93wt% MnO ₂ / CNT Composite Fiber
비교 예 1-1Comparative Example 1-1	0wt% MnO₂/CNT 베이스 섬유를 포함하는 슈퍼 커패시터Supercapacitor with 0wt% MnO ₂ / CNT base fiber
비교 예 1-2Comparative Example 1-2	0wt% MnO₂/CNT 복합 섬유0wt% MnO ₂ / CNT Composite Fiber

Referring to (a) and (b) of Figure 5, the scanning electron microscopy (SEM) of the side profile and cross section of the base fiber according to Example 1-1 of the present invention.

As can be seen from (a) of FIG. 5, it was confirmed that the base fiber according to Example 1-1 was twisted. As can be seen from (b) of FIG. 5, it was confirmed that the cross section of the base fiber according to Example 1-1 was spiral. In addition, the cross section shows that the carbon nanotube sheet is rolled and stacked, and the manganese dioxide is provided between the carbon nanotube sheets that are rolled and stacked.

Referring to Figure 5 (c), the composite fiber according to Example 1-2 of the present invention and the electrode fabric according to Example 3 of the present invention were taken by SEM and general photography.

As can be seen in Figure 5 (c), it was confirmed that the composite fiber according to Example 1-2, the twisted (twist) form. In addition, it was confirmed that the composite fiber had a diameter of about 100 μm and had a twist structure of 100 times per centimeter. In addition, it was confirmed that the electrode fabrics according to Examples 1-3 had strong and flexible characteristics.

Referring to Figure 6a, the stress (MPa) according to the strain (%) of the composite fibers according to Examples 1-2, Examples 1-10, and Comparative Examples 1-2 of the present invention was measured. As can be seen in Figure 6a, the composite fibers according to Examples 1-10 and Comparative Examples 1-2 of the present invention, was subjected to high stress even a slight strain, it was confirmed that the break. However, the composite fiber according to Example 1-2 of the present invention was confirmed that the change in stress is small even in a wide strain range. Accordingly, it can be seen that the composite fibers according to Example 1-10 and Comparative Example 1-2 have a breakage phenomenon in the manufacturing process of the composite fiber and are not made of the composite fiber.

Referring to FIG. 6B, when the composite fiber according to Example 1-2 of the present invention was bent and repeated for 1 to 100 times, stress (MPa) according to strain (%) was measured. As it can be seen in Figure 6b, it was confirmed that the composite fiber according to Example 1-2 of the present invention shows a small strain compared to the case of repeating once, even if repeated bending for 100 times. Accordingly, it can be seen that the composite fiber according to Example 1-2 of the present invention is excellent in elasticity.

Referring to (a) of FIG. 7, SEM photographs of the entire portion of the composite fiber according to Examples 1-9 of the present invention are performed. Referring to FIG. 7 (b), (x) of FIG. An enlarged portion of the SEM image was taken. Referring to FIG. 7C, the enlarged portion (y) of FIG. 7A was taken as an SEM image. As can be seen from (a), (b), and (c) of FIG. 7, it was confirmed that the composite fiber according to Examples 1-9 of the present invention exhibited a breaking phenomenon in the manufacturing process of the composite fiber. Accordingly, in the manufacturing step of the composite fiber, controlling the content of the manganese dioxide to 70wt% or less, it can be seen that the efficient method for producing a composite fiber having high elasticity and high reliability.

Referring to FIG. 8A, the current density according to the voltage of the supercapacitor according to Examples 1-4 to 1-6 and Comparative Example 1-1 of the present invention is measured, and a cyclic voltage current curve (hereinafter, , CV curve).

As shown in FIG. 8A, the supercapacitors according to Examples 1-4 to 1-6 have a CV curve in a rectangular form, and the supercapacitors according to Comparative Example 1-1 have a CV curve in a straight form. Appeared. In addition, it can be seen that the area of the CV curve increases as the supercapacitor having a higher content of manganese dioxide. Accordingly, it can be seen that the cyclic voltage current characteristics of the supercapacitor according to the embodiment of the present invention are significantly superior to the cyclic voltage current characteristics of the supercapacitor according to the comparative example. In addition, it can be seen that the supercapacitor including the base fiber having a higher content of manganese dioxide improves the circulating voltage and current characteristics.

Referring to FIG. 8B, the voltage of the supercapacitor according to Examples 1-4 to 1-6 and Comparative Example 1-1 of the present invention is measured and charged / discharged. The curve is shown.

As shown in (b) of FIG. 8, the supercapacitors according to Examples 1-4 to 1-6 have a charge / discharge curve in a triangular form, and the supercapacitor according to Comparative Example 1-1 has a charge / discharge curve. It appeared in a straight line. Accordingly, it can be seen that the charge and discharge characteristics of the supercapacitor according to the embodiment of the present invention are significantly superior to the charge and discharge characteristics of the supercapacitor according to the comparative example. In addition, it can be seen that the supercapacitor including the base fiber having a higher content of manganese dioxide improves the circulating voltage and current characteristics.

Referring to FIG. 9A, areal capacitances of the supercapacitors according to Examples 1-4 to 1-6 and Comparative Example 1-1 of the present invention were measured.

As shown in FIG. 9A, the supercapacitor according to Comparative Example 1-1 is 0.01 F / cm ² , the supercapacitor according to Example 1-4 is 0.3 F / cm ² , and according to Example 1-5. The supercapacitor showed 0.42 F / cm ² , and the supercapacitor according to Examples 1-6 showed areal capacitance of 0.6 F / cm ² . Accordingly, it can be seen that the supercapacitor including the base fiber according to the embodiment of the present invention improves the areal capacitance of the supercapacitor as the manganese dioxide content of the base fiber increases.

Referring to (b) of FIG. 9, the linear capacitors and areal capacitances of the supercapacitors according to Examples 1-6 of the present invention are measured according to a scan speed of 10 to 100 mV / s.

Areal capacitance of a supercapacitor according to the embodiment 1-6, as seen in 9 (b), is, 10mV / s in 750mF / cm ^2, 30mV / s in 430mF / cm in 525mF / cm ^2, 50mV / s ^2, showing the 225mF / cm ² in 320mF / cm ^2, 100mV / s at 70mV / s. In addition, the linear capacitance of the supercapacitor according to Examples 1-6 is 52.5 mF / cm at 10 mV / s, 43 mF / cm at 30 mV / s, 32 mF / cm at 50 mV / s, 22.5 mF / cm at 70 mV / s, 15 mF / cm at 100 mV / s. Accordingly, it can be seen that the supercapacitor according to the sixth embodiment of the present invention decreases linear capacitance and areal capacitance as the scan speed increases.

Referring to (a) of FIG. 10, the current density according to the voltage of the asymmetric supercapacitor according to the embodiment 1-8 is measured while varying the working voltage from 1.4V to 2.2V, and the cyclic voltage current ( CV) curves.

As can be seen in Figure 10 (a), in the asymmetric supercapacitor according to the embodiment 1-8, the CV curve according to the change of the drive voltage has a rectangular shape. In addition, it can be seen that the area of the CV curve increases as the driving voltage increases. Accordingly, in the asymmetric supercapacitor according to the eighth embodiment, it can be seen that the cyclic voltage current characteristics improve as the driving voltage increases.

Referring to FIG. 10 (b), the capacitance retention characteristics were measured by adjusting the charge / discharge cycle of the asymmetric supercapacitor according to Examples 1-8 from 1 to 1000 times. In addition, the current density according to the voltage when the charge / discharge cycles of the asymmetric supercapacitors according to Examples 1-8 and 1000 times were measured, and the cyclic voltage current curves were shown.

As can be seen in Figure 10 (b), it can be seen that in the asymmetric supercapacitor according to Examples 1-8, there is substantially no change in capacitance retention while the charge / discharge cycle changes from 1 to 1000 times. . In addition, it can be confirmed that there is substantially no difference between the CV curve area when the charge / discharge cycle is one time and the CV curve area when the charge / discharge cycle is 1000 times. Accordingly, it can be seen that the durability and lifespan characteristics of the asymmetric supercapacitor according to Examples 1-8 are excellent.

Referring to (a) of FIG. 11, the MnO ₂ / CNT base fiber electrode of the supercapacitor according to Examples 1-6 was wound at an original state (Pristine), at a bending angle of 165 ° (Bent), and at 1 mm intervals. The current was measured according to the 0 to 0.8 energy range (V vs. Ag / AgCl) in the state of Wound and Knotted, and the cyclic voltammetry curve was shown.

As can be seen in Figure 11 (a), the supercapacitor according to Examples 1-6, the MnO ₂ / CNT base fiber electrode is in the original state (Pristine), bent at a bending angle of 165 ° (Bent), 1mm interval It can be seen that there is substantially no difference in the area of the CV curve in the wound state and the knotted state.

Referring to (b) of FIG. 11, the capacitance retention of the MnO ₂ / CNT base fiber electrode of the supercapacitor according to Examples 1-6 was bent 1 to 1000 times at a bending angle of 165 °.

As can be seen in Figure 11 (b), the supercapacitor according to Example 1-6, it can be seen that there is almost no change in storage capacity even if the MnO ₂ / CNT base fiber electrode is bent from 1 to 1000 times. Accordingly, it can be seen that the MnO ₂ / CNT base fiber of the supercapacitor according to Examples 1-6 of the present invention has excellent durability.

Referring to FIG. 12A, when the MnO ₂ / CNT composite fiber electrode of the supercapacitor according to Example 1-7 is stretched by 0%, 10%, 20%, and 30% in the first direction, the voltage The current density was measured and the cyclic voltammogram was shown.

As shown in (a) of FIG. 12, the supercapacitor according to Example 1-7 has a length of 0%, 10%, 20%, and 30% of MnO ₂ / CNT composite fiber electrode in a first direction. It can be seen that all show similar CV curve areas.

Referring to FIG. 12B, when the MnO ₂ / CNT composite fiber electrode of the supercapacitor according to Example 1-7 is stretched to 0%, 10%, 20%, and 30% in the first direction, the electric Analyzed by chemical impedance spectroscopy (EIS), the EIS curve is shown.

As shown in FIG. 12B, the supercapacitors according to Examples 1-7 were all stretched to 0%, 10%, 20%, and 30% lengths of the MnO ₂ / CNT composite fiber in the first direction. It can be seen that it shows a similar EIS curve. Accordingly, it can be seen that the MnO ₂ / CNT composite fiber of the supercapacitor according to Examples 1-7 of the present invention has excellent elasticity.

Referring to FIG. 13, the supercapacitors according to Examples 1-6 and 1-7 were maintained at 1.2 V in charge / discharge voltage, and energy density according to power density was measured. .

As can be seen in FIG. 13, the supercapacitor according to Examples 1-6 exhibited an energy density of 33 μWh / cm ² , and the supercapacitor according to Examples 1-7 showed an energy density of 12 μWh / cm ² . . Accordingly, it can be seen that the supercapacitors according to Examples 1-6 and 1-7 of the present invention exhibit excellent performance.

According to an embodiment, the carbon nanotube sheet may include first and second carbon nanotube sheets, the functional material may include first and second functional materials, and the electrode fiber may be formed of the first functional material. The first electrode fiber provided on the first carbon nanotube sheet and the second functional material may include a second electrode fiber provided on the second carbon nanotube sheet.

Hereinafter, an electrode fiber according to a second embodiment of the present invention will be described with reference to FIGS. 14 to 35 for a case in which the first electrode fiber includes reduced graphene oxide and the second electrode fiber includes manganese dioxide. The manufacturing method is described.

제2 실시 예에 따른 전극 섬유 및 그 제조 방법Electrode Fiber and Method for Manufacturing the Same According to the Second Embodiment

Referring to FIG. 14, a first carbon nanotube sheet 210 may be prepared. According to an embodiment, the preparing of the first carbon nanotube sheet may include preparing a carbon nanotube forest by chemical vapor deposition and the first carbon nanotube sheet from the carbon nanotube forest. 210 may be prepared.

According to one embodiment, the first carbon nanotube sheet 210 may include a plurality of carbon nanotubes extending in a first direction. Further, according to one embodiment, the plurality of carbon nanotubes may be multi-walled carbon nanotubes (MWCNT).

According to one embodiment, the first carbon nanotube sheet 210 may be prepared on the support substrate 200. For example, the support substrate 200 may be a glass substrate. Alternatively, for example, the support substrate 200 may include any one of a plastic substrate, a semiconductor substrate, a ceramic substrate, and a metal substrate.

Reduced graphene oxide 220 may be provided on the first carbon nanotube sheet 210. The reduced graphene oxide 220 may have a lower conductivity than the first carbon nanotube sheet 210 and may have a higher charge storage capability than the first carbon nanotube sheet 210.

The providing of the reduced graphene oxide 220 on the first carbon nanotube sheet 210 may include preparing a first source solution in which the reduced graphene oxide 220 is dispersed, and The method may include providing a source solution on the first carbon nanotube sheet 210, and drying the first carbon nanotube sheet 210 provided with the first source solution.

According to an embodiment of the present disclosure, the first source solution may be prepared by adding the reduced graphene oxide 220 to a solvent and performing ultrasonic treatment to disperse the reduced graphene oxide 220. For example, the solvent may be dimethylformamide. For example, wt% of the reduced graphene oxide 220 in the first source solution may be provided at 8 mg / ml. In addition, according to an embodiment, the first source solution may be provided on the first carbon nanotube sheet 210 by a drop casting method.

According to one embodiment, providing a first source solution in which the reduced graphene oxide 220 is dispersed on the first carbon nanotube sheet 210, and the first source solution is provided Drying the carbon nanotube sheet 210 may be repeatedly performed. Accordingly, the content of the reduced graphene oxide 220 on the first carbon nanotube sheet 210 may be increased.

According to one embodiment, the reduced graphene oxide 220 may be provided in the form of flakes. According to one embodiment, the size of the reduced graphene oxide 220 in the first source solution may be substantially the same. Alternatively, according to another embodiment, sizes of the reduced graphene oxide 220 in the first source solution may be different.

Referring to FIG. 15, the first electrode fiber 230 may be manufactured by twisting the first carbon nanotube sheet 210 provided with the reduced graphene oxide 220. According to an embodiment, the manufacturing of the first electrode fibers 230 may include twisting one end of the plurality of carbon nanotubes by using the first direction in which the plurality of carbon nanotubes extend as a rotation axis. (twist) may be included. For example, the first carbon nanotube sheet 210 provided with the reduced graphene oxide 220 may have about 3000 turns per meter.

Accordingly, the inner region of the first electrode fiber 230 may be provided in a form in which the first carbon nanotube sheet 210 is rolled and stacked. The reduced graphene oxide 220 may be provided between the dried and stacked first carbon nanotube sheets 210. In other words, in the cross section of the first electrode fiber 230 cut into the first plane when the first plane having the first direction extending from the first electrode fiber 230 as a normal is defined, A cross section of the first carbon nanotube sheet 210 may be provided in a spiral shape, and the reduced graphene oxide 220 may be provided between the first carbon nanotube sheet 210 in a spiral shape.

According to an embodiment, in the first electrode fiber 230, wt% of the reduced graphene oxide 220 may be higher than wt% of the first carbon nanotube sheet 210. In other words, the first electrode fiber 230 may include more of the reduced graphene oxide 220 than the first carbon nanotube sheet 210. Accordingly, the first electrode fiber 230 may have improved charge storage characteristics.

According to one embodiment, the reduced graphene oxide 220 may be doped with nitrogen (nitrogen). In other words, the first electrode fibers 230 may be manufactured in a form in which the reduced graphene oxide doped with nitrogen is provided between the first carbon nanotube sheets 210 which are dried and stacked. On the contrary, when the reduced graphene oxide 220 is doped with a metal other than nitrogen, an electrochemical reaction may be unstable, thereby degrading the characteristics of the supercapacitor.

Referring to FIG. 16, a second carbon nanotube sheet 310 may be prepared. According to one embodiment, the second carbon nanotube sheet 310 may be prepared by the same method as the preparation method of the first carbon nanotube sheet 210 described with reference to FIG.

Manganese dioxide (MnO ₂ , 320) may be provided on the second carbon nanotube sheet 310. The manganese dioxide 320 may have a lower conductivity than the second carbon nanotube sheet 310 and may have a higher charge storage capability than the second carbon nanotube sheet 310.

The providing of the manganese dioxide 320 on the second carbon nanotube sheet 310 may include preparing a second source solution in which the manganese dioxide 320 is dispersed, and supplying the second source solution to the second carbon nanotube sheet 310. It may include the step of providing on the carbon nanotube sheet (310).

According to an embodiment of the present disclosure, the second source solution may be prepared by a method of dispersing the manganese dioxide 320 by adding the manganese dioxide 320 to a solvent and performing ultrasonic treatment. For example, the solvent may be ethanol. For example, wt% of the manganese dioxide 320 in the second source solution may be provided at 5 mg / ml. In addition, according to an embodiment, the second source solution may be provided on the second carbon nanotube sheet 310 by a drop casting method.

According to one embodiment, the manganese dioxide 320 may be provided in the form of particles. According to one embodiment, the size of the manganese dioxide 320 in the second source solution may be substantially the same. Alternatively, according to another embodiment, the sizes of the manganese dioxide 320 in the second source solution may be different.

Referring to FIG. 17, the second electrode fiber 330 may be manufactured by twisting the second carbon nanotube sheet 310 provided with the manganese dioxide 320. According to an embodiment, the manufacturing of the second electrode fibers 330 may include twisting one end of the plurality of carbon nanotubes by using the first direction in which the plurality of carbon nanotubes extend as a rotation axis. (twist) may be included. According to one embodiment, the number of twists per meter of the second carbon nanotube sheet 310 may be greater than the number of twists per meter of the first carbon nanotube sheet 310. For example, the second carbon nanotube sheet 310 provided with the manganese dioxide 320 may have about 5000 twist times per meter.

Accordingly, the inner region of the second electrode fiber 330 may be provided in a form in which the second carbon nanotube sheet 310 is rolled and stacked. The manganese dioxide 320 may be provided between the dried and stacked second carbon nanotube sheets 310. In other words, in the cross section of the second electrode fiber 330 cut into the first plane when the first plane having the first direction extending from the second electrode fiber 330 as a normal is defined, the A cross section of the second carbon nanotube sheet 310 may be provided in a spiral shape, and the manganese dioxide 320 may be provided between the second carbon nanotube sheet 310 in a spiral shape.

According to an embodiment, in the second electrode fiber 330, wt% of the manganese dioxide 320 may be higher than wt% of the second carbon nanotube sheet 310. In other words, the second electrode fibers 330 may include more of the manganese dioxide 320 than the second carbon nanotube sheet 310. Accordingly, the second electrode fiber 330 may have improved charge storage characteristics.

Hereinafter, the supercapacitor including the first electrode fiber 230 and the second electrode fiber 330 described above and a manufacturing method thereof will be described with reference to FIG. 18.

Referring to FIG. 18A, the first electrode fibers 230 and the second electrode fibers 330 described with reference to FIGS. 14 to 17 are prepared. The first electrode fibers 230 and the second electrode fibers 330 may be coated with an electrolyte 400, respectively. For example, the electrolyte 400 may be polyvinyl alcohol (LiVA) -LiCl or polyvinylidenefluoride-hexafluoropropylene (PVDF-HFP) -tetraethylammoniumtetrafluouroborate (TEABF ₄ ).

Referring to FIG. 18B, the supercapacitor 500 may be manufactured by twisting the first electrode fiber 230 and the second electrode fiber 330 coated with the electrolyte 400. have. According to an embodiment, the first electrode fibers 230 may be used as an anode. According to one embodiment, the second electrode fibers 330 may be used as a cathode. According to one embodiment, the plurality of supercapacitors 500 may be made of an electrode fabric by crossing each other.

When manufacturing a supercapacitor using the first electrode fibers 230 and the second electrode fibers 330, the reduced graphene oxide 220 storing negative charges in the first electrode fibers 230. ) And the manganese dioxide 320 that stores a positive charge in the second electrode fiber 330 may have a difference in charge storage characteristics. In this case, due to the characteristics of the supercapacitor, the amount of energy storage may be determined by the low charge storage characteristics among the first electrode fibers 230 and the second electrode fibers 330.

Specifically, in the case of manufacturing a supercapacitor using the first electrode fiber 230 including the reduced graphene oxide 220 and the second electrode fiber 230 including the manganese dioxide 320, As the charge storage property of the reduced graphene oxide 220 is lower than that of the manganese dioxide 320, the charge storage property of the first electrode fiber 330 is lower than that of the second electrode fiber 230. Can be. Accordingly, the amount of energy stored in the supercapacitor may be determined by the first electrode fiber 330.

In order to maximize the energy storage efficiency of the supercapacitor, the supercapacitor including the electrode fiber and the manufacturing method thereof according to the second embodiment of the present invention may provide various methods. Hereinafter, methods for maximizing the energy storage efficiency of the supercapacitor are described.

In order to maximize the energy storage efficiency of the supercapacitor, wt% of the reduced graphene oxide 220 in the first electrode fiber 230 is wt% of the manganese dioxide 320 in the second electrode fiber 330. It can be higher than%. For example, the reduced graphene oxide 220 may be provided at 90 wt%, and the manganese dioxide 320 may be provided at 70.5 wt%.

Otherwise, if the wt% of the reduced graphene oxide 220 in the first electrode fiber 230 and the wt% of the manganese dioxide 320 in the second electrode fiber 330 are the same, The number of the first carbon nanotube sheets 210 in the first electrode fibers 230 may be greater than the number of the second carbon nanotube sheets 310 in the second electrode fibers 330. In other words, the first electrode fibers 230 may be made thicker than the second electrode fibers 330. For example, the number of the first carbon nanotube sheets 210 may be five, and the number of the second carbon nanotube sheets 310 may be four.

In addition, an area of the first carbon nanotube sheet 210 may be larger than an area of the second carbon nanotube sheet 310. Accordingly, the amount of the reduced graphene oxide 220 provided on the first carbon nanotube sheet 210 is the amount of the manganese dioxide 320 provided on the second carbon nanotube sheet 310. Can be more.

The supercapacitor including the electrode fiber according to the second embodiment of the present invention described above, the first carbon nanotube sheet twisted to surround the reduced graphene oxide 220 and the reduced graphene oxide 220 ( And a second electrode fiber 330 including a first electrode fiber 230 including 210 and a second carbon nanotube sheet 320 twisted to surround the manganese dioxide 320 and the manganese dioxide 320. Can be. Accordingly, a highly efficient asymmetric supercapacitor including the reduced graphene oxide 220 and the manganese dioxide 320 may be provided.

In addition, the supercapacitor may be reduced on the first and second

carbon nanotube sheets

210 and 310 before the fiber is manufactured using the first and second

carbon nanotube sheets

210 and 310. Graphene oxide 220, and the manganese dioxide 320 is provided, the reduced graphene oxide 220, and the manganese dioxide 320 is provided, the first and second carbon nanotube sheet ( By twisting 210 and 310, the first and

second electrode fibers

230 and 330 may be manufactured. Accordingly, the content of the reduced graphene oxide 220 and the manganese dioxide 320 in the first and

second electrode fibers

230 and 330 may be increased, and the energy storage amount of the supercapacitor may be improved. .

In addition, methods for maximizing the energy storage efficiency of the supercapacitor may be provided.

According to one embodiment, wt% of the reduced graphene oxide 220 in the first electrode fiber 230 may be provided higher than wt% of the manganese dioxide 320 in the second electrode fiber 330. have.

According to an embodiment, the number of the first carbon nanotube sheets 210 in the first electrode fibers 230 is greater than the number of the second carbon nanotube sheets 310 in the second electrode fibers 330. There can be many.

According to an embodiment, an area of the first carbon nanotube sheet 210 may be higher than an area of the second carbon nanotube sheet 310.

According to one embodiment, the reduced graphene oxide 220 may be doped with nitrogen (nitrogen).

Accordingly, in the supercapacitor according to the embodiment, the energy storage efficiency may be maximized and the energy storage amount may be improved.

Hereinafter, specific experimental examples and characteristics evaluation results of the electrode fiber and the supercapacitor including the same according to the second embodiment of the present invention will be described.

Preparation of First Electrode Fibers According to Example 2-1

Reduced graphene oxide (rGO) in the form of nanoflakes and dimethylformamide with wt% of 8 mg / ml are prepared. After mixing the reduced graphene oxide in dimethylformamide, using a VCX750 ultrasonic equipment for 1 hour by ultrasonication at 150W to disperse to prepare a mixed solution.

After stacking five sheets of carbon nanotubes, the mixed solution was sprayed by a drop casting method and dried for 20 minutes. The drop casting process and the drying process for 20 minutes were repeated five times.

The dried carbon nanotube sheet includes a reduced graphene oxide having a wt% of 90 wt% by twisting one end of the plurality of carbon nanotube sheets about 3000 times per meter using the first direction as a rotation axis. A first electrode fiber was prepared.

Preparation of Second Electrode Fiber According to Example 2-2

Manganese dioxide (MnO ₂ ) nanoparticles manufactured by Sigma-Aldrich, having a diameter of 30 nm, a length of 100 nm, and a rod form, and an ethanol solvent containing 5 mg / ml wt% are prepared. The manganese dioxide nanoparticles were mixed in ethanol and sonicated to prepare a mixed solution.

After laminating four carbon nanotube sheets prepared by the method according to Example 2-1 described above, the mixed solution was sprayed by a drop casting method and dried for 20 minutes. The dried carbon nanotube sheet is a second electrode fiber including manganese dioxide having a wt% of 70 wt% by twisting one end of the plurality of carbon nanotube sheets about 5000 times per meter using the first direction as a rotation axis. Prepared.

Preparation of Supercapacitors According to Example 2-3

PVA having a capacity of 3 g, LiCl having a capacity of 6 g, and DI water having a capacity of 30 ml were mixed at a temperature of 90 ° C. to prepare a PVA-LiCl electrolyte. Thereafter, an electrolyte was coated on each of the first electrode fibers according to Example 2-1 and the second electrode fibers according to Example 2-2.

A supercapacitor was manufactured by using a first electrode fiber coated with an electrolyte as a cathode and a second electrode fiber coated with an electrolyte as a cathode, and connecting a copper (Cu) wire having a diameter of 180 μm to each electrode.

Preparation of Supercapacitors According to Example 2-4

A solution of PVDF-HFP mixed with acetone and TEABF ₄ mixed with propylene carbonate was prepared at a ratio of 4: 1, and dried for 3 hours on a slide glass to prepare PVDF-HFP-TEABF ₄ electrolyte. Thereafter, a supercapacitor was manufactured by the method according to Example 2-3 described above.

Preparation of Electrode Fabrics According to Examples 2-5

The first electrode fiber according to Example 2-1 and the second electrode fiber according to Example 2-2 are coated with the electrolyte according to Example 2-3, respectively, and weave each other to fabricate an electrode fabric (textile super capacitor). Was prepared.

Preparation of First Electrode Fibers According to Examples 2-6

The first electrode fiber according to Example 2-1 described above was prepared and a Na ₂ SO ₄ liquid electrolyte was coated on the first electrode fiber.

Preparation of Second Electrode Fiber According to Examples 2-7

The second electrode fiber according to Example 2-2 described above was prepared and a Na ₂ SO ₄ liquid electrolyte was coated on the second electrode fiber.

Manufacture of supercapacitors according to Comparative Example 2-1

Another electrode fiber in Example 2-1 described above was coated with an electrolyte according to Example 2-3, and a supercapacitor was manufactured using the same as an anode and a cathode.

Supercapacitor preparation according to Comparative Examples 2-2 to 2-7

Comparative Example 2-2: CNT / MnO ₂ based stretchable asymmetric fibers

Comparative Example 2-3: rGO / MnO ₂ / PPy yarns

Comparative Example 2-4: NiOH / MnO ₂ asymmetric yarns

Comparative Example 2-5: Hollow rGo fiber

Comparative Example 2-6: MnO ₂ nanosheet decorated asymmetric carbon fibers

Comparative Example 2-7: MnO ₂ coated stretchable, asymmetric CNT wires

The electrode fibers, supercapacitors, and electrode fabrics according to Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-6 are summarized through Table 2 below.

구분division	종류Kinds	구성Configuration	전해질Electrolyte
실시 예 2-1Example 2-1	전극 섬유Electrode fiber	rGO/CNTrGO / CNT
실시 예 2-2Example 2-2	전극 섬유Electrode fiber	MnO₂/CNTMnO ₂ / CNT
실시 예 2-3Example 2-3	슈퍼커패시터Supercapacitor	rGO/CNT, MnO₂/CNTrGO / CNT, MnO ₂ / CNT	PVA-LiClPVA-LiCl
실시 예 2-4Example 2-4	슈퍼커패시터Supercapacitor	rGO/CNT, MnO₂/CNTrGO / CNT, MnO ₂ / CNT	PVDF-HFP-TEABF₄ PVDF-HFP-TEABF ₄
실시 예 2-5Example 2-5	전극 직물Electrode fabric	rGO/CNT, MnO₂/CNTrGO / CNT, MnO ₂ / CNT	PVA-LiClPVA-LiCl
실시 예 2-6Example 2-6	전극 섬유Electrode fiber	rGO/CNTrGO / CNT	Na₂SO₄ Na ₂ SO ₄
실시 예 2-7Example 2-7	전극 섬유Electrode fiber	MnO₂/CNTMnO ₂ / CNT	Na₂SO₄ Na ₂ SO ₄
비교 예 2-1Comparative Example 2-1	슈퍼커패시터Supercapacitor	rGO/CNT,rGO/CNTrGO / CNT, rGO / CNT	PVA-LiClPVA-LiCl
비교 예 2-2Comparative Example 2-2	슈퍼커패시터Supercapacitor	CNT/MnO₂ based stretchable asymmetric fibersCNT / MnO ₂ based stretchable asymmetric fibers
비교 예 2-3Comparative Example 2-3	슈퍼커패시터Supercapacitor	rGO/MnO₂/PPy yarnsrGO / MnO ₂ / PPy yarns
비교 예 2-4Comparative Example 2-4	슈퍼커패시터Supercapacitor	NiOH/MnO₂ asymmetric yarnsNiOH / MnO ₂ asymmetric yarns
비교 예 2-5Comparative Example 2-5	슈퍼커패시터Supercapacitor	Hollow rGo fiberHollow rGo fiber
비교 예 2-6Comparative Example 2-6	슈퍼커패시터Supercapacitor	MnO₂ nanosheet decorated asymmetric carbon fibersMnO ₂ nanosheet decorated asymmetric carbon fibers
비교 예 2-7Comparative Example 2-7	슈퍼커패시터Supercapacitor	MnO₂ coated stretchable, asymmetric CNT wiresMnO ₂ coated stretchable, asymmetric CNT wires

Referring to (a) and (b) of FIG. 19, the SEM and the cross-sectional view of the first electrode fiber according to Example 2-1 are obtained at low magnification (scale bar = 300 μm) and high magnification (scale bar = 600 nm). scanning electron microscopy).

As can be seen in Figure 19 (a), the first electrode fiber according to the embodiment 2-1 has a twisted (twist) form, the reduced graphene oxide (rGO) in the form of flakes (carbon nanotubes) It was confirmed that it existed between sheets. As can be seen from FIG. 19B, it was confirmed that the cross section of the first electrode fiber according to Example 2-1 was spiral. In addition, the cross section shows a form in which the carbon nanotube sheet is rolled and stacked, and the reduced graphene oxide is provided between the dried and stacked carbon nanotube sheets.

Referring to (a) and (b) of FIG. 20, the SEM and the cross-section of the second electrode fiber according to Example 2-2 are obtained at low magnification (scale bar = 300 μm) and high magnification (scale bar = 600 nm). scanning electron microscopy).

As can be seen in Figure 20 (a), the second electrode fiber according to the embodiment 2-2 has a twist (twist) form, the manganese dioxide (MnO ₂ ) in the form of particles (particle) between the carbon nanotube sheet I could confirm that it exists. As can be seen from FIG. 20B, it was confirmed that the cross section of the second electrode fiber according to Example 2-2 was spiral. In addition, the cross section shows a form in which the carbon nanotube sheet is rolled and stacked, and it is confirmed that manganese dioxide (MnO ₂ ) is provided between the carbon nanotube sheets that are rolled and stacked.

Referring to (a) of FIG. 21, the supercapacitor according to Comparative Example 2-1 is connected to a voltage V in a voltage scan rate range of 10, 30, 50, 70, and 100 mV / s. The current density was measured, and a cyclic voltammogram (hereinafter referred to as CV curve) was shown. As can be seen from (a) of Figure 21, the CV curve of the supercapacitor according to Comparative Example 2-1 does not show a peak in the voltage scan rate range of 10, 30, 50, 70, 100mV / s I could confirm it. This, it can be seen that the supercapacitor according to Comparative Example 2-1 is associated with the Faradic redox reaction.

Referring to (b) of FIG. 21, the supercapacitor according to Comparative Example 2-1 is measured with voltage over time in a current density range of 0.5, 2.5, and 5 mA / cm ² , and charge / discharge ( charge / discharge) curves. As it can be seen in Figure 21 (b), the supercapacitor according to Comparative Example 1 was confirmed that the charge and discharge curve in a triangular form in the current density range of 0.5, 2.5, 5 mA / cm ² .

Referring to (c) of FIG. 21, areal capacitance (mF / cm ² ) and linear capacitance (mF / cm) according to the scan rate (mV / s) of the supercapacitor according to Comparative Example 2-1 are calculated. Measured. As can be seen from (c) of FIG. 21, the supercapacitor according to Comparative Example 2-1 gradually decreases areal capacitance at 172 mF / cm ² as the scan rate increases, and linear capacitance gradually decreases at 17 mF / cm. I could confirm that.

Referring to FIG. 22, a first electrode fiber according to Example 2-1 and a first electrode fiber having reduced graphene oxide wt% of 18.5 wt% are prepared, and a current curve according to voltage is measured to obtain a CV curve. Indicated. As can be seen in FIG. 22, the CV curve area of the first electrode fiber having 90.3 wt% reduced graphene oxide wt% is the CV of the first electrode fiber having wt% reduced graphene oxide wt% 18.5 wt%. It was confirmed that it was wider than the curve area. Accordingly, it can be seen that the first electrode fiber has a reduced graphene oxide wt% of 90.3 wt% to improve the cyclic voltammetry.

Referring to FIG. 23, the current according to the voltage of the electrode fibers according to Example 2-1 and Example 2-2 was measured and a CV curve was shown. In order to measure the current according to the voltage of the electrode fibers according to Examples 2-1 and 2-2, using a three electrode system, using Ag / AgCl as a reference electrode and as a counter electrode Pt mesh was used. As can be seen in Figure 23, it was confirmed that the area of the CV curve according to the embodiment 2-2 is wider than the area of the CV curve according to the embodiment 2-1. Accordingly, it can be seen that the charge storage characteristics of the first electrode including the reduced graphene oxide and the second electrode including manganese dioxide are different.

Referring to (a) of FIG. 24, a current density according to voltage (V) in a maximum applied voltage range of 0.9, 1.3, 1.7, and 2.1V may be obtained. It measured and showed the cyclic voltammogram (henceforth a CV curve). Scan rate was measured at 100 mV / s. As can be seen in Figure 24 (a), it was confirmed that the CV curve area of the supercapacitor according to the embodiment 2-3 is gradually increased in the range of the maximum applied voltages of 0.9, 1.3, 1.7, 2.1V. In addition, the CV curve area in the 2.1V maximum applied voltage range was similar to the CV curve area of the general supercapacitors. Accordingly, it can be seen that the supercapacitor according to the embodiment 2-3 can be applied as a supercapacitor.

Referring to FIG. 24B, the supercapacitor according to the embodiment 2-3 measures voltage over time in the maximum applied voltages of 0.9, 1.3, 1.7, and 2.1V, and charges and discharges (charge / discharge). The curve is shown. In addition, the current density according to the voltage of the supercapacitor according to Example 2-3 was measured and IR drop was measured. As can be seen in Figure 24 (b), it was confirmed that the supercapacitor according to the embodiment 2-3 shows a stable inverted triangle charge and discharge curve at the maximum applied voltages of 2.1V. In addition, it was confirmed that a small IR drop of 47 mV at a current density of 1.2 mA / cm ² . Accordingly, it can be seen that the supercapacitor according to the embodiment 2-3 can be applied as a supercapacitor.

Referring to (a) and (b) of FIG. 25, the supercapacitor according to the embodiment 2-4 is 0 to 2 in a voltage scan rate range of 10, 30, 50, 70, and 100 mV / s. Current densities according to voltages (V) and current densities according to 0 to 4 voltages were measured, and cyclic voltammograms (hereinafter referred to as CV curves) were shown. As can be seen from (a) and (b) of Figure 25, the CV curve area of the supercapacitor according to the embodiment 2-4 is a super according to the embodiment 2-3 described with reference to Figure 24 (a) It was confirmed that the area larger than the CV curve area of the capacitor. Accordingly, when manufacturing the supercapacitor according to the embodiment, it can be seen that using the electrolyte of PVDF-HFP-TEABF _{4 has} a higher redox stability than using the electrolyte of PVA-LiCl.

Referring to FIG. 25C, the voltage of the supercapacitor according to Example 2-4 was measured over time in a voltage range of 3.5V or more, and a charge / discharge curve was shown. As can be seen in Figure 25 (c), it was confirmed that the supercapacitor according to Example 2-4 shows a stable inverted triangle charge and discharge curve. Accordingly, it can be seen that the supercapacitor according to the embodiment 2-4 can be applied as a supercapacitor.

Referring to FIG. 26A, supercapacitors according to Examples 2-3 and 2-4 were analyzed by electrochemical impedance spectroscopy (EIS), and an EIS curve was shown. As can be seen from (a) of FIG. 26, it can be seen that the supercapacitors according to Examples 2-3 and 2-4 both exhibit low equivalent series resistance.

Referring to (b) of FIG. 26, areal capacitance (mF / cm ² ) and linear capacitance according to the scan rate (mV / s) of the supercapacitors according to the embodiments 2-3 and 2-4 are shown. (mF / cm) was measured. As can be seen from (b) of Figure 26, it is confirmed that the areal capacitance and linear capacitance of the supercapacitor according to the embodiment 2-4 is lower than the areal capacitance and linear capacitance of the other supercapacitors in the embodiment 2-3. there was.

Referring to FIG. 27, areal energy density according to areal power density (mW / cm ² ) of supercapacitors according to Examples 2-3, Examples 2-4, and Comparative Examples 2-2 to Comparative Examples 2-7. (μWh / cm ² ) was measured. As can be seen from FIG. 27, the supercapacitor according to Example 2-3 shows 30.1 μWh / cm ² , the supercapacitor according to Example 2-4 shows 43 μWh / cm ² , and Comparative Example 2- The supercapacitor according to 2 shows 18.9 μWh / cm ² , the supercapacitor according to Comparative Example 2-3 shows 9.2 μWh / cm ² , and the supercapacitor according to Comparative Example 2-4 shows 10 μWh / cm ² . The supercapacitor according to Comparative Example 2-5 shows 6.8 μWh / cm ² , the supercapacitor according to Comparative Example 2-6 shows 1.428 μWh / cm ² , and the supercapacitor according to Comparative Example 2-7. Represents 1.25 μWh / cm ² , and the areal energy density of the supercapacitors according to Examples 2-3 and 2-4 was high. Accordingly, it can be seen that the energy storage characteristics of the supercapacitor using the electrode including the reduced graphene oxide and the electrode including manganese dioxide as the asymmetric electrode are good as in Examples 2-3 and 2-4.

In addition, the linear energy density (E _L , μWh / cm ² ), areal energy density (E _A , μWh / cm ² ), and volumetric energy density (E _V , μWh / cm ² ) of various supercapacitors with asymmetric electrodes are This can be summarized in <Table 3> below.

구분division	Voltage(V)Voltage (V)	E_L E _L	E_A E _A	E_V E _V
실시 예 2-3Example 2-3	2.12.1	5.55.5	30.130.1	3.83.8
실시 예 2-4Example 2-4	3.53.5	4.54.5	4343	55
MnO₂/carbon fiber 비대칭 슈퍼커패시터MnO ₂ / carbon fiber asymmetric supercapacitors	1.51.5	0.2160.216	1.431.43	--
MnO₂ nanosheet/CNT fiber 비대칭 슈퍼커패시터MnO ₂ nanosheet / CNT fiber asymmetric supercapacitors	1.51.5	0.0470.047	1.251.25	1.571.57
MnO₂/CNT core-sheath fiber 비대칭 슈퍼커패시터MnO ₂ / CNT core-sheath fiber asymmetric supercapacitors	1.51.5	6.26.2	18.918.9	2.982.98
Ni(OH)₂/ordered mesoporous carbon based micro fiber 비대칭 슈퍼커패시터Ni (OH) ₂ / ordered mesoporous carbon based micro fiber asymmetric supercapacitors	1.51.5	--	1010	2.162.16
MnO₂/N-doped CNT fiber 비대칭 슈퍼커패시터MnO ₂ / N-doped CNT fiber Asymmetric Supercapacitors	1.81.8	--	--	55
Co₃O₄ nanowire/graphene fiber 비대칭 슈퍼커패시터Co ₃ O ₄ nanowire / graphene fiber asymmetric supercapacitors	1.51.5	--	--	0.620.62

Referring to (a) of FIG. 28, the current density of the first electrode fibers according to Examples 2-6 according to voltage in a voltage scan rate range of 10, 30, 50, 70, and 100 mV / s Was measured, and a cyclic voltammogram (hereinafter referred to as CV curve) was shown. In order to measure the current according to the voltage of the electrode fiber according to Examples 2-6, a three electrode system was used, Ag / AgCl was used as the reference electrode and Pt mesh was used as the counter electrode. As can be seen from (a) of Figure 28, the first electrode fiber according to the embodiment 2-6 was confirmed that the CV curve area increases as the scan rate increases.

Referring to (b) of FIG. 28, the current density of the second electrode fiber according to the embodiment 2-7 according to the voltage in the voltage scan rate range of 10, 30, 50, 70, 100 mV / s Was measured, and a cyclic voltammogram (hereinafter referred to as CV curve) was shown. In order to measure the current according to the voltage of the electrode fiber according to Example 2-7, using a three-electrode system (Three electrode system), Ag / AgCl as a reference electrode and Pt mesh was used as a counter electrode. As it can be seen in Figure 28 (b), it was confirmed that the CV curve area of the second electrode fiber according to the embodiment 2-7 increases as the scan rate increases.

Referring to (c) of Figure 28, the supercapacitor according to the embodiment 2-3 is a current density according to the voltage in the voltage scan rate range of 100, 200, 300, 400, 500 mV / s It measured and showed the cyclic voltammogram (henceforth a CV curve). As can be seen from (c) of Figure 28, as the scan rate increases, it was confirmed that the CV curve appears in a gradually stable square shape while maintaining an initial capacitance of 61.8%.

Referring to (a) and (b) of FIG. 29, voltage scan rates of 10, 30, 50, 70, and 100 mV / s of supercapacitors according to the embodiments 2-4 and 2-3 are described. The current density according to the voltage was measured in the following range, and the cyclic voltammogram (hereinafter, referred to as CV curve) was shown. As can be seen from (a) and (b) of Figure 29, it was confirmed that the CV curve areas of the supercapacitors according to the above Examples 2-4 and 2-3 are similar to each other. Accordingly, when manufacturing the supercapacitor according to the embodiment, it can be seen that both PVDF-HEP-TEABF ₄ and PVA-LiCl can be used as the electrolyte.

Referring to FIG. 30A, areal capacitance (mF / cm ² ) and volumetric capacitance (mF / cm ³ ) according to the scan rate (mV / s) of the supercapacitor according to the embodiment 2-3 are described. Was measured. As can be seen from (a) of Figure 30, the supercapacitor according to the embodiment 2-3, it was confirmed that the areal capacitance of 322.4 mF / cm ² and 57.2 mF / cm ³ at a scan rate of 10 mV / s .

Referring to FIG. 30B, capacitance retention (%) according to the scan rate of the supercapacitors according to Example 2-3 and Comparative Example 2-1 was measured. As shown in (b) of FIG. 30, as the scan rate increases, the decrease in capacitance retention of the supercapacitor according to Comparative Example 2-1 is significantly higher than the decrease in capacitance retention of the supercapacitor according to Examples 2-3. I could confirm that. Accordingly, when manufacturing the supercapacitor according to the above embodiment, it can be seen that using an asymmetric electrode is more efficient in maintaining capacitance retention than using a symmetric electrode.

Referring to (a) of FIG. 31, the current density according to the voltage was measured and the CV curve was measured for the case of charging and discharging the supercapacitor according to Example 2-3 once and 1000 times. As can be seen from (a) of FIG. 31, it can be seen that the CV curve area when charging and discharging the supercapacitor according to Example 2-3 is substantially the same as the CV curve area when charging and discharging 1000 times. there was.

Referring to FIG. 31B, capacitance retention (C / C ₀ ) according to the number of charge / discharge cycles of the supercapacitor according to Example 2-3 was measured. As shown in (b) of FIG. 31, it was confirmed that the capacitance retention was substantially constant during charge and discharge of the supercapacitor according to Example 2-3 once to 1000 times. Accordingly, it can be seen that the supercapacitor according to the embodiment 2-3 has excellent durability and lifespan characteristics.

Referring to FIG. 32A, the electrode fabrics according to Example 2-5 were photographed. As can be seen in Figure 32 (a), it can be seen that the electrode fabric according to the embodiment 2-5 can be produced in the form of a general fabric.

Referring to (b) of FIG. 32, a photograph was taken immediately after the circuit was operated by installing a conductive wire and a blue LED of 0.65W in the electrode fabric according to Example 2-5. As can be seen in Figure 32 (b), it was confirmed that the blue LED of 0.65W due to the electrode fabric according to the embodiment 2-5.

Referring to (c) of FIG. 32, the above-described circuit of FIG. 32 (b) was operated for 5 minutes and photographed. As can be seen in Figure 19 (c), it can be seen that the electrode fabric according to the embodiment 2-3 has a storage capacity for operating a blue LED of 0.65W for 5 minutes.

Referring to (a) of FIG. 33, when the electrode fabrics according to the embodiment 2-5 are one, two are connected in series, three are connected in series, and four is connected in series. The current with voltage was measured and the CV curve was shown. As can be seen from (a) of Figure 33, when the number of electrode fabrics according to the embodiment 2-5 is connected in series, the area of the CV curve as the number of electrode fabrics according to the embodiment 2-5 increases This gradually increased.

Referring to (b) of FIG. 33, when the electrode fabrics according to Example 2-5 are one, two are connected in parallel, three are connected in parallel, and four are connected in parallel. The current with voltage was measured and the CV curve was shown. As shown in (b) of FIG. 33, when the number of electrode fabrics according to the embodiment 2-5 is increased and connected in parallel, the number of electrode fabrics according to the embodiment 2-5 increases at a voltage of 1V. It was confirmed that the current increased to 3.2 mA. Accordingly, it can be seen that the electrode fabric according to Example 2-5 can be used as a supercapacitor.

Referring to FIG. 34, four electrode fabrics according to Example 2-5 were connected in series and in parallel to measure areal energy (μWh / cm ² ) according to a scan rate. As can be seen in Figure 34, when the four electrode fabrics according to the embodiment 2-5 is connected in series shows an areal energy of 142 μWh / cm ² at 10 mV / s scan rate, 10 mV / s in parallel It was found that the scan rate was 86.2 μWh / cm ² . Accordingly, when connecting the electrode fabrics according to the embodiment 2-5, it can be seen that in series connection is more efficient.

Referring to FIG. 35, current density according to voltage is measured for pristine, dynamically bent, and 100 times bent of the electrode fabric according to Example 2-5. And a CV curve. As can be seen in Figure 35, the electrode fabric according to the embodiment 2-5, it was confirmed that the CV curve area of the original state, the kinematically bent state, and 100 times bent state is substantially the same. Accordingly, it can be seen that the electrode fabric according to Example 2-5 has excellent durability.

In the case where the first electrode fiber includes silver nanowires and the second electrode fiber includes zinc particles, an electrode fiber according to a third embodiment of the present invention and a manufacturing method thereof with reference to FIGS. 36 to 49. This is explained.

제3 실시 예에 따른 전극 섬유 및 그 제조 방법An electrode fiber and a method of manufacturing the same according to the third embodiment

Referring to FIG. 36, a first carbon nanotube sheet 610 may be prepared. According to an embodiment, the preparing of the first carbon nanotube sheet may include preparing a carbon nanotube forest by chemical vapor deposition and the first carbon nanotube sheet from the carbon nanotube forest. 610 may be prepared.

According to one embodiment, the first carbon nanotube sheet 610 may include a plurality of carbon nanotubes extending in a first direction. Further, according to one embodiment, the plurality of carbon nanotubes may be multi-walled carbon nanotubes (MWCNT).

According to an embodiment, the first carbon nanotube sheet 610 may be prepared on the support substrate 600. For example, the support substrate 600 may be a glass substrate. Alternatively, for example, the support substrate 600 may include any one of a plastic substrate, a semiconductor substrate, a ceramic substrate, and a metal substrate.

Silver nanowires 120 may be provided on the first carbon nanotube sheet 610. According to one embodiment, the silver nanowires 620 may be provided as a positive electrode active material (active material).

Providing the silver nanowires 620 on the first carbon nanotube sheet 610 may include preparing a first source solution in which the silver nanowires 620 are dispersed, and preparing the first source solution. The method may include providing the first carbon nanotube sheet 610 and drying the first carbon nanotube sheet 610 provided with the first source solution. According to one embodiment, the first source solution may be prepared by a method of dispersing the silver nanowires 620 in a solvent. For example, the solvent may be isopropyl alcohol. In addition, according to an embodiment, the first source solution may be provided on the first carbon nanotube sheet 610 by a drop casting method.

According to one embodiment, the step of providing a first source solution in which the silver nanowires 620 are dispersed on the first carbon nanotube sheet 610, and the first carbon nano provided with the first source solution Drying the tube sheet 610 may be repeated. Accordingly, the content of the silver nanowires 620 on the first carbon nanotube sheet 610 may be increased.

According to one embodiment, the sizes of the silver nanowires 620 in the first source solution may be substantially the same. Alternatively, according to another embodiment, sizes of the silver nanowires 620 in the first source solution may be different.

Referring to FIG. 37, the first electrode fibers 630 may be manufactured by twisting the first carbon nanotube sheet 610 provided with the silver nanowires 620. According to an embodiment, the manufacturing of the first electrode fibers 630 may be performed by twisting one end of the plurality of carbon nanotubes by using the first direction in which the plurality of carbon nanotubes extend as a rotation axis. (twist) may be included. For example, the first carbon nanotube sheet 610 provided with the silver nanowires 620 may have about 1000 turns per meter.

Accordingly, the inner region of the first electrode fiber 630 may be provided in a form in which the first carbon nanotube sheet 610 is rolled and stacked. The silver nanowires 620 may be provided between the dried and stacked first carbon nanotube sheets 610. In other words, in the cross section of the first electrode fiber 630 cut into the first plane when the first plane having a normal as the normal to the first direction in which the first electrode fiber 630 extends is defined, A cross section of the first carbon nanotube sheet 610 may be provided in a spiral shape, and the silver nanowire 620 may be provided between the first carbon nanotube sheet 610 in a spiral shape.

Referring to FIG. 38, a second carbon nanotube sheet 710 may be prepared. According to one embodiment, the second carbon nanotube sheet 710 may be prepared by the same method as the preparation method of the first carbon nanotube sheet 710 described with reference to FIG.

Zinc particles 720 may be provided on the second carbon nanotube sheet 710. According to one embodiment, the zinc particles 720 may be provided as a negative electrode active material.

Providing the zinc particles 720 on the second carbon nanotube sheet 710 may include preparing a second source solution in which the zinc particles 720 are dispersed, and preparing the second source solution. It may include providing on the second carbon nanotube sheet 710. According to one embodiment, the second source solution may be prepared by a method of dispersing the zinc particles 720 by putting the zinc particles 720 in a solvent and sonicating. For example, the solvent may be ethanol. In addition, according to an embodiment, the second source solution may be provided on the second carbon nanotube sheet 710 by a drop casting method.

According to one embodiment, the size of the zinc particles 720 in the second source solution may be substantially the same. Alternatively, according to another embodiment, sizes of the zinc particles 720 in the second source solution may be different.

Referring to FIG. 39, a second electrode fiber 730 may be manufactured by twisting the second carbon nanotube sheet 710 provided with the zinc particles 720. According to an embodiment, the manufacturing of the second electrode fibers 730 may be performed by twisting one end of the plurality of carbon nanotubes by using the first direction in which the plurality of carbon nanotubes extend as a rotation axis. (twist) may be included. According to an embodiment, the number of twists per meter of the second carbon nanotube sheet 710 may be greater than the number of twists per meter of the first carbon nanotube sheet 610. For example, the second carbon nanotube sheet 710 provided with the zinc particles 720 may have about 2000 twists per meter.

Accordingly, the inner region of the second electrode fiber 730 may be provided in a form in which the second carbon nanotube sheet 710 is rolled and stacked. The zinc particles 720 may be provided between the dried and stacked second carbon nanotube sheets 710. In other words, when a first plane having a normal to the first direction in which the second electrode fiber 730 extends is defined, in the cross section of the second electrode fiber 730 cut into the first plane, the A cross section of the second carbon nanotube sheet 710 may be provided in a spiral shape, and the zinc particles 720 may be provided between the second carbon nanotube sheet 710 in a spiral shape.

Hereinafter, a silver-zinc battery including the first electrode fiber 630 and the second electrode fiber 730 described above and a method of manufacturing the same will be described with reference to FIG. 40.

Referring to FIGS. 40A and 40B, the first electrode fibers 630 and the second electrode fibers 730 described with reference to FIGS. 36 to 39 are prepared. The silver-zinc battery 800 according to the embodiment may be manufactured twisted with each other.

According to an embodiment, the manufacturing of the silver-zinc battery 800 may include preparing one second electrode fiber 730, coating a protective agent on the second electrode fiber 730, and drying the same. Twisting the second electrode fibers 730 and the two first electrode fibers 630 coated with a protective agent, and the electrolyte on the twisted first and

second electrode fibers

630 and 730. It may include the step of coating.

For example, the protective agent may be polyvinyl alcohol (PVA) having a concentration of 10 wt%. The second electrode fiber 730 may be prevented from electrical shortage as the protective agent is coated. For example, the electrolyte may be a solution in which KOH, PVA, and DI water are mixed.

When manufacturing the silver-zinc battery 800 using the first electrode fiber 630 and the second electrode fiber 730, in order to improve the efficiency of the silver-zinc battery 800, the silver The wt% of the nanowires 620 may be provided higher than the wt% of the zinc particles 720. In other words, the wt% of the silver nanowires 620 in the silver-zinc battery 800 may be higher than the wt% of the zinc particles 720.

To this end, in the silver-zinc battery 800 including the electrode fibers according to the third embodiment, x first electrode fibers 630 are twisted with y second electrode fibers 730. ) Can be prepared. According to one embodiment, x and y are natural numbers greater than zero, and x may be greater than y. According to one embodiment, x = 2y. For example, x may be 2 and y may be 1. That is, the silver-zinc battery 800 according to the embodiment may be manufactured by twisting two first electrode fibers 630 with one second electrode fiber 730.

According to one embodiment, the wt% of the silver nanowire 620 in the first electrode fiber 630 and the wt% of the zinc particles 720 in the second electrode fiber 730 may be substantially the same. have. For example, the wt% of the silver nanowires 620 in the first electrode fiber 630 may be 98.6 wt%. For example, the wt% of the zinc particles 720 in the second electrode fiber 730 may be 97.2 wt%. Accordingly, in the total weight of the silver-zinc battery 800 according to the embodiment, the wt% of the silver nanowires 620 may be higher than the wt% of the zinc particles 720.

In contrast, when the silver-zinc battery 800 is manufactured using each of the first electrode fibers 630 and the second electrode fibers 730, wt% of the silver nanowires 620 is different. When the amount of the first source solution and the silver nanowires 620 is increased to provide higher than wt% of the zinc particles 720, the thickness of the first carbon nanotube sheet 610 is too high. By thickening, it may not be easy to twist the first carbon nanotube sheet 610 into a fiber form. Accordingly, the manufacturing of the first electrode fiber 630 may not be easy.

In addition, according to an embodiment, in order for the wt% of the silver nanowire 620 to be provided higher than the wt% of the zinc particles 720, the area of the first carbon nanotube sheet 610 may be equal to the first carbon nanotube sheet 610. 2 may be wider than the area of the carbon nanotube sheet 710. As the area of the first carbon nanotube sheet 610 increases, the first electrode fibers 630 may be manufactured by increasing the amounts of the first source solution and the silver nanowires 620.

The silver-zinc battery including the electrode fiber according to the third embodiment of the present invention described above may include the silver nanowire 620 and the first carbon nanotube sheet twisted to surround the silver nanowire 620. The second electrode fiber including the first electrode fiber 630 including the 610, the zinc particles 720 and the second carbon nanotube sheet 710 twisted to surround the zinc particles 720 ( 730, an electrolyte between the first electrode fiber 630 and the second electrode fiber 730. Accordingly, a high-efficiency silver-zinc battery including the silver nanowires 620 and the zinc particles 720 may be provided.

In addition, the silver-zinc battery is formed on the first and second

carbon nanotube sheets

610 and 710 before fabricating fibers using the first and second

carbon nanotube sheets

610 and 710. In the state where the silver nanowires 620 and the zinc particles 720 are provided, and the silver nanowires 620 and the zinc particles 720 are provided, the first and second carbon nanotube sheets ( By twisting 610 and 710, the first and

second electrode fibers

630 and 730 may be manufactured. Accordingly, the content of the silver nanowires 620 and the zinc particles 720 in the first and

second electrode fibers

630 and 730 may be increased, and energy storage of the silver-zinc battery may be improved. have.

In addition, in the silver-zinc battery, wt% of the silver nanowire 620 may be provided higher than wt% of the zinc particles 720. To this end, the silver-zinc battery may be manufactured by twisting x first electrode fibers 630 with y second electrode fibers 730. According to one embodiment, x and y are natural numbers greater than zero, and x may be greater than y. According to one embodiment, x = 2y. In this case, wt% of the silver nanowire 620 in the first electrode fiber 630 and wt% of the zinc particles 720 in the second electrode fiber 730 may be substantially the same. Accordingly, a high efficiency silver-zinc battery can be provided.

Hereinafter, specific experimental examples and characteristics evaluation results of the electrode fiber and the silver-zinc battery including the same according to the third embodiment of the present invention will be described.

Preparation of First Electrode Fibers According to Example 3-1

A glass substrate is prepared. By chemical vapor deposition on the silicon substrate, a carbon nanotube forest including a height of about 400 μm, a diameter of about 12 nm, and about nine walls was prepared. Pulling the carbon nanotube forest in a first direction, a carbon nanotube sheet (CNT sheet) including a plurality of carbon nanotubes extending in the first direction was prepared on a glass substrate.

Silver nanowires and isopropyl alcohol having a capacity of 200 ml are prepared. The silver nanowires were mixed with isopropyl alcohol to prepare a mixed solution.

After stacking three sheets of carbon nanotubes, the mixed solution was sprayed by a drop casting method and dried at room temperature for 5 minutes.

The dried carbon nanotube sheet includes a first electrode including silver nanowires having a concentration of 98.6 wt% by twisting one end of the plurality of carbon nanotube sheets about 1000 meters per meter using the first direction as a rotation axis. Fibers were prepared.

Preparation of Second Electrode Fiber According to Example 3-2

Zinc nanoparticles and ethanol solvents are prepared. The zinc nanoparticles were mixed in ethanol and sonicated for 2 hours to prepare a mixed solution.

The mixed solution was sprinkled with a drop casting method on a carbon nanotube sheet prepared by the method according to Example 3-1, and dried. Drying the carbon nanotube sheet using the first direction as the axis of rotation, twisting one end of the plurality of carbon nanotube sheets about 2000 times per meter to produce a second electrode fiber containing manganese dioxide having a concentration of 97.2 wt%. It was.

Preparation of Silver-Zinc Battery According to Example 3-3

The first electrode fiber according to Example 3-1 and the second electrode fiber according to Example 3-2 described above are prepared. A copper wire having a diameter of 180 μm was connected to each electrode fiber end, and the copper wire and the first and second electrode fibers were coated with epoxy.

KOH having a mass of 33.67 g was dispersed in DI water having a volume of 100 mL, and stirred at 60 rotational speeds per minute to prepare a KOH liquid electrolyte having a concentration of 6 M.

Thereafter, the first electrode fiber according to Example 3-1 and the second electrode fiber according to Example 2, in which a copper wire was connected in a KOH liquid electrolyte, were immersed to prepare a silver-zinc battery according to Example 3-3. The first electrode fiber according to Example 3-1 described above was used as a cathode, and the second electrode fiber was used as an anode.

Preparation of Silver-Zinc Battery According to Example 3-4

Two first electrode fibers according to Example 3-1 and one second electrode fiber according to Example 2 are prepared. A copper wire having a diameter of 180 μm was connected to each electrode fiber end, and the copper wire and the first and second electrode fibers were coated with epoxy.

An electrolyte mixed with KOH having 3 M concentration and polyvinyl alcohol (PVA) and PVA having a concentration of 10 wt% were prepared. The electrolyte was prepared by mixing KOH with a capacity of 3.37 g, PVA with a capacity of 2 g, and DI water with a capacity of 20 mL and stirring at 60 revolutions per minute at a temperature of 140 ° C.

Thereafter, one prepared second electrode fiber was coated with PVA having a concentration of 10 wt%. One PVA-coated second electrode fiber and two prepared first electrode fibers were twisted together, and an electrolyte was coated on the first and second electrode fibers to prepare a silver-zinc battery according to Example 3-4. The first electrode fiber according to Example 3-1 described above was used as a cathode, and the second electrode fiber was used as an anode.

Preparation of Electrode Fabrics According to Examples 3-5

Two silver-zinc batteries according to Example 3-4 described above were connected in series, and then sewn in a watch trap textile to fabricate an electrode fabric.

Battery Preparation According to Comparative Example 3-1

A battery according to Comparative Example 3-1 consisting of a metal anode comprising silver and a metal anode comprising zinc is prepared.

Battery Preparation According to Comparative Example 3-2

A battery according to Comparative Example 3-2, in which a lithium ion manganese oxide (LMO) fiber electrode and a lithium titanate (LTO) fiber electrode is wound around a stretchable center electrode, is prepared.

Battery Preparation According to Comparative Example 3-3

A battery according to Comparative Example 3-3, in which the LMO fiber electrode and the LTO fiber electrode form a coil, is prepared.

Battery Preparation According to Comparative Example 3-4

The battery according to Comparative Example 3-4 in which the LMO fiber electrode and the LTO fiber electrode were twisted with each other is prepared.

The electrode fibers and the batteries according to Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-4 are summarized through Table 4 below.

구분division	종류Kinds	구성Configuration	전해질Electrolyte
실시 예 3-1Example 3-1	전극 섬유Electrode fiber	Ag nanowire/CNTAg nanowire / CNT
실시 예 3-2Example 3-2	전극 섬유Electrode fiber	Zn/CNTZn / CNT
실시 예 3-3Example 3-3	섬유 전지Fiber battery	Ag nanowire/CNTZn/CNTAg nanowire / CNTZn / CNT	KOH 액체 전해질KOH liquid electrolyte
실시 예 3-4Example 3-4	섬유 전지Fiber battery	Ag nanowire/CNTZn/CNTAg nanowire / CNTZn / CNT	3M KOH + PVA3M KOH + PVA
실시 예 3-5Example 3-5	전극 직물Electrode fabric	Ag nanowire/CNTZn/CNT두개 직렬 연결Ag nanowire / CNTZn / CNT two series connection
비교 예 3-1Comparative Example 3-1	금속 전지Metal battery	Ag/ZnAg / Zn
비교 예 3-2Comparative Example 3-2	섬유 전지Fiber battery	Winding of LTO/LMOWinding of LTO / LMO
비교 예 3-3Comparative Example 3-3	섬유 전지Fiber battery	Coiling of LTO/LMOCoiling of LTO / LMO
비교 예 3-4Comparative Example 3-4	섬유 전지Fiber battery	Plying of LTO/LMOPlying of LTO / LMO

Referring to (a) and (b) of FIG. 41, scanning electron microscopy (SEM) images of the side profile and the cross section of the first electrode fibers according to Example 3-1 at a low magnification (scale bar = 300 μm), and FIG. 41. Referring to (c), the cross section of the first electrode fiber according to Example 3-1 was SEM photographed at a high magnification (scale bar = 2μm).

As can be seen from (a) of Figure 41, the first electrode fiber according to Example 3-1 was confirmed that the silver nanowires loaded on the carbon nanotube sheet at 98.6 wt. As can be seen from (b) and (c) of FIG. 41, it was confirmed that the cross section of the first electrode fiber according to Example 3-1 was spiral. In addition, the cross section shows a form in which the carbon nanotube sheets are rolled and stacked, and silver nanowires are provided between the rolled and stacked carbon nanotube sheets.

Referring to (a) and (b) of FIG. 42, scanning electron microscopy (SEM) imaging of a side view and a cross section of the second electrode fiber according to Example 3-2 at a low magnification (scale bar = 300 μm), and FIG. 42. Referring to (c), the cross section of the second electrode fiber according to Example 3-2 was SEM photographed at a high magnification (scale bar = 2μm).

As can be seen from (a) of Figure 42, the second electrode fiber according to Example 3-2 was confirmed that the zinc particles loaded on the carbon nanotube sheet at 97.2 wt. As can be seen from (b) and (c) of FIG. 42, it was confirmed that the cross section of the second electrode fiber according to Example 3-2 was spiral. In addition, the cross section shows a form in which the carbon nanotube sheets are rolled and stacked, and zinc particles are provided between the carbon nanotube sheets that are rolled and stacked. Accordingly, it is understood that the wt% of silver nanowires included in the first electrode fiber according to Example 3-1 is substantially the same as the wt% of zinc particles included in the second electrode fiber according to Example 3-2. Can be.

Referring to FIG. 43A, the silver-zinc battery according to Example 3-3 measures current density (mAh / cm) according to voltage (V) at a scan rate of 10 mV / s, and calculates a circulating voltage. The current curve (hereinafter referred to as CV curve) is shown. As can be seen from (a) of FIG. 43, in the silver-zinc battery according to Example 3-3, an oxidation peak at two parts of 1.65 V (Ag-> Ag ⁺ ) and 2 V (Ag ⁺ -> Ag ² ⁺ ) is shown. It was confirmed that the reduction peak appeared in two parts of 1.82V (Ag ²⁺ -> Ag ⁺ ) and 1.43V (Ag ⁺ -> Ag). Accordingly, it can be seen that the silver-zinc battery according to the embodiment 3-3 has a good agreement.

Referring to (b) of FIG. 43, the voltage V according to the linear capacity (mAh / cm) of the silver-zinc battery according to Example 3-3 and Comparative Example 3-1 was measured, and a galvanostatic discharge curve was measured. Indicated. As shown in (b) of FIG. 43, the linear capacity of the silver-zinc battery according to Example 3-3 is expressed as 8.7 microamp hour μAh / cm, and the silver-zinc battery according to Comparative Example 3-1 is shown. The linear capacity was found to be 0.04 microamperes μAh / cm. Accordingly, it can be seen that the silver-zinc battery according to Example 3-3 has about 100 times better performance than the silver-zinc battery according to Comparative Example 3-1.

Referring to (a) of FIG. 44, the linear capacity (mAh / cm) according to the mass ratio of silver nanowires and zinc particles in the silver-zinc battery according to Example 3-3 is measured and shown. When the mass ratio of silver nanowires and zinc particles is 1.7: 1 and the current density is 0.1 mA / cm, the voltage (V) according to the linear capacity (mAh / cm) of the silver-zinc battery according to Example 3-3 Was measured.

As can be seen in Figure 44 (a), the silver-zinc battery according to the embodiment 3-3, it can be seen that shows the highest linear capacity when the mass ratio of silver nanowires and zinc particles is 1.7: 1. When the mass ratio of silver nanowires and zinc particles is 1.7: 1 and the current density is 0.1 mA / cm, it is confirmed that the highest linear capacity of the silver-zinc battery according to Example 3-3 shows 0.285 mAh / cm. Can be. Accordingly, when manufacturing the silver-zinc battery according to Example 3-3, it can be seen that it is efficient to manufacture so that the mass ratio of silver nanowires and zinc particles is close to 1.7: 1.

Referring to (b) of FIG. 44, a silver-zinc battery according to Example 3-3 was prepared, but ZnO having a 0.25 M concentration was mixed with KOH having a 6 M concentration as an electrolyte. Thereafter, capacity retention (C / C ₀ ) according to the number of charge / discharge cycles of the silver-zinc battery according to Example 3-3 in which the above-described electrolyte was used was measured. As can be seen from (b) of Figure 44, the silver-zinc battery according to Example 3-3 using the above-described electrolyte, it was confirmed that the capacity of about 30% remaining after 50 charge and discharge.

Referring to FIG. 45A, the silver-zinc battery according to Example 3-4 measures current density (mAh / cm) according to voltage (V) at a scan rate of 10 mV / s, and calculates a CV curve. Indicated. As can be seen from (a) of Figure 45, the silver-zinc battery according to Example 3-4, it was confirmed that the reduction peak appears at 1.82V (Ag ²⁺ -> Ag ⁺ ).

Referring to FIG. 45 (b), the voltage V according to the linear capacity (mAh / cm) of the silver-zinc battery according to Example 3-4 was measured, and a galvanostatic discharge curve was shown. As can be seen from (b) of FIG. 45, it was confirmed that the silver-zinc battery according to Example 3-4 has only one plateaus.

46, according to the amount (wt%) of the active material loaded on the negative electrode in the silver-zinc battery according to Example 3-4 and the batteries according to Comparative Examples 3-2 to 3-4 The linear capacity (mAh / cm) is measured and shown, and the linear capacity (mAh / cm) according to the amount (wt%) of zinc particles loaded on the negative electrode is shown in the silver-zinc battery according to Example 3-4. It was.

As can be seen in Figure 46, the silver-zinc battery according to Example 3-4, when the zinc particles loaded on the negative electrode is 97.2 wt%, the linear capacity of 0.276 mAh / cm, according to Comparative Example 3-2 The battery shows a linear capacity of 0.0028 mAh / cm when the active material loaded on the negative electrode is 83.6 wt%, and the battery according to Comparative Example 3-3 shows a linear capacity of 0.022 mAh / cm when the active material loaded on the negative electrode is 86 wt%. And, the battery according to Comparative Example 3-4 was confirmed that the linear capacity of 0.0036 mAh / cm when the active material loaded on the negative electrode is 90 wt%. Accordingly, it was confirmed that the performance of the silver-zinc battery according to Example 3-4 was higher than that of the batteries according to Comparative Examples 3-2 to 3-4.

Referring to FIG. 47, when the silver-zinc battery according to Examples 3-4 was originally bent, bent at an angle of 80 °, bent at an angle of 150 °, and again The voltage (V) according to linear capacity (mAh / cm) was measured for the released case. As can be seen in Figure 47, the silver-zinc battery according to the embodiment 3-4 is the original case (pristine), when bent at an angle of 80 ° (bent), for the case of bent (bent) at 150 ° angle In practice, it was confirmed that the performance was kept constant. Accordingly, it can be seen that the silver-zinc battery according to Example 3-4 has high flexibility.

Referring to (a) of FIG. 48, when the silver-zinc battery according to the embodiment 3-4 is one (single battery), when two are connected in series (two serial battery), when two are connected in parallel ( Voltage (V) according to linear capacity (mAh / cm) was measured for two parallel batteries.

As can be seen from (a) of FIG. 48, when two silver-zinc batteries according to the embodiment 3-4 are connected in series, a voltage twice as high as that of the case of one appears, and one when two are connected in parallel. It was confirmed that the dose appears twice as high compared to the case of.

Referring to (b) of FIG. 48, two silver-zinc batteries according to Example 3-4 were connected in series, and a circuit was connected to the lead and the LED to make a photograph of the operation thereof. As can be seen in Figure 48 (b), it was confirmed that the LED is due to the operation of the silver-zinc battery according to the embodiment 3-4.

Referring to FIG. 49, the electrode fabric and the general electronic clock according to Example 3-5 were connected with copper wires and photographed. As can be seen from Figure 49, it can be seen that the electronic clock is connected to the electrode fabric according to the embodiment 3-5. Accordingly, it can be seen that the electrode fabrics according to Examples 3-5 can be used for other devices.

As mentioned above, although this invention was demonstrated in detail using the preferable embodiment, the scope of the present invention is not limited to a specific embodiment, Comprising: It should be interpreted by the attached Claim. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Electrode fiber according to an embodiment of the present invention and a method of manufacturing the same may be used in a supercapacitor, a battery, and wearers device.

Claims

Preparing a carbon nanotube sheet;

Providing a functional material on the carbon nanotube sheet; And

Twisting the carbon nanotube sheet provided with the functional material to produce electrode fibers extending in a first direction.
According to claim 1,

Twisting a plurality of said electrode fibers with each other, thereby producing a composite fiber.
According to claim 1,

The carbon nanotube sheet includes a first carbon nanotube sheet and a second carbon nanotube sheet,

The functional material comprises a first functional material and a second functional material,

The electrode fiber includes a first electrode fiber provided with the first functional material on the first carbon nanotube sheet and a second electrode fiber provided with the second functional material on the second carbon nanotube sheet,

Controlling the content of the first functional material in the first electrode fiber to be 70 wt% or less, and controlling the content of the second functional material in the second electrode fiber to be 70 wt% or less Method of preparation.
The method of claim 3, wherein

The first carbon nanotube sheet and the second carbon nanotube sheet each include a plurality of carbon nanotubes extending in the first direction,

The manufacturing of the first electrode fibers and the manufacturing of the second electrode fibers may include twisting ends of the plurality of carbon nanotubes extending in the first direction, using the first direction as a rotation axis. The manufacturing method of the electrode fiber containing the thing.
The method of claim 3, wherein

The first functional material includes metal oxide particles,

Providing the first functional material,

Preparing a source solution in which the metal oxide particles are dispersed; And

Providing a source solution in which the metal oxide particles are dispersed on the first carbon nanotube sheet.
The method of claim 5,

Immediately after the source solution in which the metal oxide particles are dispersed is provided on the first carbon nanotube sheet, twisting the first carbon nanotube sheet to produce the first electrode fiber. Method of making fibers.
The method of claim 3, wherein

The first functional material comprises a reduced graphene oxide, the second functional material includes manganese dioxide,

Providing the first functional material on the first carbon nanotube sheet,

Preparing a source solution in which the reduced graphene oxide is dispersed; And

Providing a source solution in which the reduced graphene oxide is dispersed on the first carbon nanotube sheet,

Providing the second functional material on the second carbon nanotube sheet,

Preparing a source solution in which the manganese dioxide is dispersed; And

Providing a source solution in which the manganese dioxide is dispersed on the second carbon nanotube sheet,

And the concentration of the reduced graphene oxide in the source solution in which the reduced graphene oxide is dispersed is higher than the concentration of the manganese dioxide in the source solution in which the manganese idealized dispersion is dispersed.
The method of claim 7, wherein

Providing the first functional material on the first carbon nanotube sheet,

Providing a source solution in which the reduced graphene oxide is dispersed on the first carbon nanotube sheet, and

Method of producing an electrode fiber comprising the step of repeating the step of drying the first carbon nanotube sheet provided with the source solution in which the reduced graphene oxide is dispersed.
The method of claim 3, wherein

The first functional material comprises silver nanowires, the second functional material comprises zinc particles,

Further comprising twisting the first and second electrode fibers with each other,

And the number of twisted first electrode fibers is greater than the number of second electrode fibers.
An electrode fiber comprising a carbon nanotube sheet, and a functional material,

The inner region of the electrode fiber is provided in a form in which the carbon nanotube sheet is rolled and stacked,

An electrode fiber comprising the functional material provided between the dried carbon nanotube sheet.
The method of claim 10,

The electrode fibers extend in a first direction,

In the cross section of the electrode fiber cut into the first plane having the first direction as a normal, the cross section of the carbon nanotube sheet is provided in a spiral,

In the cross section of the electrode fiber cut into the first plane having the first direction in a normal line, the functional material is provided between the spiral carbon nanotube sheets,

In the electrode fiber, the electrode fiber comprising a higher content of the functional material than the content of the carbon nanotube sheet.
The method of claim 11, wherein

The carbon nanotube sheet includes a first carbon nanotube sheet and a second carbon nanotube sheet,

The functional material comprises a first functional material and a second functional material,

The electrode fiber includes an electrode fiber including a first electrode fiber provided with the first functional material on the first carbon nanotube sheet and a second electrode fiber provided with the second functional material on the second carbon nanotube sheet. .
The method of claim 12,

In the first and second electrode fibers, wherein the content of the first and second functional material, respectively, higher than the content of the first and second carbon nanotube sheet.
The method of claim 12,

The first functional material comprises a reduced graphene oxide, the second functional material includes manganese dioxide,

And wt% of the reduced graphene oxide in the first electrode fiber is higher than wt% of the manganese dioxide in the second electrode fiber.
The method of claim 14,

The number of the first carbon nanotube sheet in the first electrode fiber, the electrode fiber comprising more than the number of the second carbon nanotube sheet in the second electrode fiber.
The method of claim 14,

Wherein the reduced graphene oxide is nitrogen doped.
The method of claim 12,

The first functional material includes silver nanowires, and the second functional material includes zinc particles,

The wt% of the silver nanowires, the wt% of the zinc particles, the electrode fiber comprising higher.
The method of claim 17,

And wt% of the silver nanowires in the first electrode fiber and wt% of the zinc particles in the second electrode fiber are the same.
The method of claim 17,

The first electrode fibers and the second electrode fibers are twisted with each other,

x first electrode fibers twisted with y second electrode fibers,

x and y are natural numbers greater than zero and x is greater than y.
The method of claim 19,

An electrode fiber comprising x = 2y.