KR101913937B1 - Electrode for supercapacitor and fabrication method thereof - Google Patents

Electrode for supercapacitor and fabrication method thereof Download PDF

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KR101913937B1
KR101913937B1 KR1020170046762A KR20170046762A KR101913937B1 KR 101913937 B1 KR101913937 B1 KR 101913937B1 KR 1020170046762 A KR1020170046762 A KR 1020170046762A KR 20170046762 A KR20170046762 A KR 20170046762A KR 101913937 B1 KR101913937 B1 KR 101913937B1
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South Korea
Prior art keywords
metal oxide
layer
current collector
oxide layer
functional group
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KR1020170046762A
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Korean (ko)
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KR20180114718A (en
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조진한
고용민
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고려대학교 산학협력단
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Priority to KR1020170046762A priority Critical patent/KR101913937B1/en
Priority to PCT/KR2018/003929 priority patent/WO2018190555A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A supercapacitor electrode according to an embodiment of the present invention includes a flexible electroconductive current collector (10) and metal oxide particles, and is connected to the outer surface of the current collector (10) And a nanoparticle layer 30 including metal nanoparticles and bonded to an outer surface of the metal oxide layer 20. [

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a super capacitor electrode,

The present invention relates to a supercapacitor electrode and a manufacturing method thereof, and more particularly, to a flexible supercapacitor electrode having a reduced driving resistance of an electrode and having a high energy and an output value, and a manufacturing method thereof.

Recently, supercapacitors are attracting attention as next generation energy storage devices. A supercapacitor is a capacitor with a very high capacitance, which is called an ultracapacitor or a supercapacitor. Unlike a battery using a chemical reaction, such a super capacitor uses a charge phenomenon due to ion movement or surface chemical reaction at the interface between the electrode and the electrolyte. Therefore, the super capacitor can be rapidly charged and discharged, has a high charging / discharging efficiency, and has a semi-permanent cycle life characteristic Bar, secondary battery or battery replacement. In addition to mechanical strength and longevity, high energy and power are very important for performance evaluation of supercapacitors. In order to increase the energy storage capacity, a method of introducing a high-energy active material into the electrode at a high density has been studied. In the case of metal oxide particles, which are generally used, the electrical conductivity is very low. Therefore, a large amount of the metal oxide particles must be introduced into the electrode for the purpose of improving the energy density. At this time, the internal resistance of the electrode rapidly increases and the output value becomes low.

As a method for solving such a problem, an electrode for a supercapacitor using a carbon material, in particular, graphene, has been developed as disclosed in the patent documents of the following prior art documents. However, even in the case of a conventional supercapacitor electrode using a carbon material to reduce the internal resistance of the electrode, there is a clear limit to the electric conductivity.

Accordingly, there is a desperate need for a solution to the problem of the electrode for the conventional supercapacitor.

KR 10-2016-0114812 A

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and one aspect of the present invention provides a high-energy, high-output supercapacitor electrode in which nanosized metal particles are very little introduced into an electrode made of metal oxide particles, I would like to.

Another aspect of the present invention is to provide a method of manufacturing a supercapacitor electrode in which a pre-manufacturing process of electrodes produced by introducing metal nanoparticles into an electrode made of high-density metal oxide particles is simple based on a solution process .

A supercapacitor electrode according to the present invention comprises a flexible electrically conductive current collector; A metal oxide layer including metal oxide particles and bonded to an outer surface of the current collector; And a nanoparticle layer containing metal nanoparticles and bonded to an outer surface of the metal oxide layer.

Also, in the supercapacitor electrode according to the present invention, the first coupling layer includes a first material having a first functional group and is disposed between the current collector and the metal oxide layer and couples them to each other; And a second coupling layer disposed between the metal oxide layer and the nanoparticle layer, the second coupling layer including a second material having a second functional group.

Further, in the supercapacitor electrode according to the present invention, the current collector may include a flexible member; And conductive metal particles coated on the flexible member.

In the supercapacitor electrode according to the present invention, the metal oxide layer surrounds the outer peripheral surface of the current collector, and the nanoparticle layer surrounds the outer peripheral surface of the metal oxide layer.

In the supercapacitor electrode according to the present invention, at least one of the first functional group and the second functional group is an amine group or a carboxyl group.

In the supercapacitor electrode according to the present invention, the metal oxide layer and the nanoparticle layer are sequentially and repeatedly arranged.

According to another aspect of the present invention, there is provided a method of manufacturing a supercapacitor electrode, comprising: (a) forming a first bonding layer by supporting a flexible electrically conductive current collector in a first solution containing a first material having a first functional group; (b) forming a metal oxide layer by supporting the current collector on which the first bonding layer is formed, in a metal oxide solution containing a metal oxide; (c) supporting the current collector including the metal oxide layer on a second solution containing a second material having a second functional group to form a second bonding layer; And (d) forming a nanoparticle layer on the nanoparticle solution containing the metal nanoparticles by supporting the current collector on which the second bonding layer is formed.

Further, in the method for manufacturing a supercapacitor electrode according to the present invention, at least one of the first functional group and the second functional group is an amine group or a carboxyl group.

Further, in the method of manufacturing a supercapacitor electrode according to the present invention, the steps (b) to (d) may be repeatedly performed so that the metal oxide layer and the nanoparticle layer are sequentially and repeatedly disposed with the second bonding layer interposed therebetween. Repeat at least two times.

The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.

Prior to that, terms and words used in the present specification and claims should not be construed in a conventional and dictionary sense, and the inventor may properly define the concept of the term in order to best explain its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

According to the present invention, nano-sized metal particles are introduced into an electrode made of metal oxide particles as a high-energy active material, so that the internal resistance of the electrode is remarkably lowered, resulting in a super capacitor element having high energy and output.

In addition, metal oxide particles and metal nanoparticles are coated as an electrode material on a current collector of a flexible material to produce a high-energy, high-output supercapacitor, which can be utilized in the development of various flexible electronic devices.

Furthermore, since the pre-manufacturing process of the supercapacitor electrode is based on the solution process, it is possible to produce the supercapacitor electrode with a simple and low cost.

1 is a cross-sectional view of a supercapacitor electrode according to an embodiment of the present invention.
2 is a cross-sectional view of a supercapacitor electrode according to another embodiment of the present invention.
3 is a perspective view of a part of a supercapacitor electrode according to another embodiment of the present invention.
4 is a process diagram of a method of manufacturing a supercapacitor electrode according to an embodiment of the present invention.
5 is an electrochemical reaction graph of a supercapacitor electrode according to an embodiment of the present invention.
6 is a graph showing an internal resistance change of a supercapacitor electrode according to an embodiment of the present invention.
7 is a Ragone Plot of a supercapacitor made up of a supercapacitor electrode according to an embodiment of the present invention.
FIG. 8 is a graph illustrating a capacity retention (%) according to the number of times of bending of a supercapacitor including a supercapacitor electrode according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The objectives, specific advantages and novel features of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. It should be noted that, in the present specification, the reference numerals are added to the constituent elements of the drawings, and the same constituent elements are assigned the same number as much as possible even if they are displayed on different drawings. Also, the terms "first "," second ", and the like are used to distinguish one element from another element, and the element is not limited thereto. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following description of the present invention, detailed description of related arts which may unnecessarily obscure the gist of the present invention will be omitted.

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

1 is a cross-sectional view of a supercapacitor electrode according to an embodiment of the present invention.

1, a supercapacitor electrode according to an embodiment of the present invention includes a flexible electroconductive current collector 10, a metal oxide layer 20 including a metal oxide particle and bonded to an outer surface of the current collector 10 ), And a nanoparticle layer 30 including metal nanoparticles and bonded to the outer surface of the metal oxide layer 20.

The supercapacitor electrode according to the present invention has been developed as a method for increasing the energy storage capacity of a super capacitor capable of rapid charge / discharge, high charge / discharge efficiency, and semi-permanent cycle life characteristics.

Specifically, the supercapacitor electrode according to the present embodiment includes a current collector 10, a metal oxide layer 20, and a nanoparticle layer 30.

Here, the current collector 10 collects electrons from the metal oxide layer 20, or supplies electrons to the metal oxide layer 20. The current collector 10 may be formed of a metal having a high electrical conductivity, for example, aluminum, nickel, copper, titanium, or the like. However, the current collector 10 is not limited by the material.

On the other hand, the current collector 10 may be provided in a form in which the conductive metal particles 13 are coated on the flexible member 11 so as to be applicable to the flexible element. Here, the flexible member 11 may include, for example, plastic, paper, fabric, etc., and the metal particles 13 may be made of a metal having excellent electrical conductivity, for example, gold (Au). However, the types of the flexible member 11 and the metal particles 13 are not limited thereto.

The current collector 10 may be formed in the form of a thin film or a yarn.

A metal oxide layer (20) is provided on the current collector (10). The metal oxide layer 20 is formed by bonding a metal oxide, which is an active material having a high energy, to the outer surface of the current collector 10. Here, the appropriate metal oxide as the active material, for example, MnO, Fe 3 O 4, TiO 2, WO 3, V 2 O 5 , And the like. However, the metal oxide is not necessarily limited thereto.

The nanoparticle layer 30 is formed on the metal oxide layer 20. The nanoparticle layer 30 is bonded to the outer surface of the metal oxide layer 20 by metal nanoparticles composed of nano-sized metal particles. Since metal nanoparticles have very good electrical conductivity, the internal resistance of the electrode is remarkably lowered by supplementing metal oxides having relatively low electrical conductivity. On the other hand, since the metal nanoparticles have a relatively high specific gravity compared with other electrode materials, it is necessary to minimize the amount of particles introduced into the electrode. By introducing the metal nanoparticles into the metal oxide layer 20 according to the present invention, Thereby reducing the internal resistance of the electrode. Thus, a supercapacitor element having high energy and high output can be realized. Meanwhile, the metal nanoparticles used in the present invention may include at least one selected from the group consisting of Au, Ag, Cu, Pt, Al, and the like, but the present invention is not limited thereto .

On the other hand, the supercapacitor electrode according to the present embodiment may further include a first bonding layer 40 and a second bonding layer 50 for bonding the metal oxide layer 20 and the nanoparticle layer 30 have.

The first bonding layer 40 is disposed between the current collector 10 and the metal oxide layer 20. Here, the first bonding layer 40 includes a first material having a first functional group, thereby bonding the current collector 10 and the metal oxide layer 20, which are adjacent to each other. At this time, the first material has a first functional group and adsorbs the metal oxide to the current collector 10 through a layer-by-layer assembly (LbL) based on a solution process. On the other hand, the first functional group may be an amine group (NH 2 ) or a carboxyl group (COOH).

The second bonding layer 50 is disposed between the metal oxide layer 20 and the nanoparticle layer 30. At this time, the second bonding layer 50 includes a first material having a second functional group, and binds the metal oxide layer 20 and the nanoparticle layer 30 by a layered self-assembly method. The second functional group may be an amine group (NH 2 ) or a carboxyl group (COOH) like the first functional group described above, wherein the first functional group and the second functional group may be the same or different functional groups.

2 is a cross-sectional view of a supercapacitor electrode according to another embodiment of the present invention.

As shown in FIG. 2, the metal oxide layer 20 and the nanoparticle layer 30 may be sequentially and repeatedly arranged in the supercapacitor electrode according to the present invention. Specifically, the multi-layered active material layer in which the metal oxide layer 20 and the nanoparticle layer 30 are sequentially laminated can be laminated n times. At this time, one of the multilayered active material layers L1 and the adjacent one of the multilayered active material layers L2 may be bonded by the second bonding layer 50 described above.

3 is a perspective view of a part of a supercapacitor electrode according to another embodiment of the present invention.

The supercapacitor electrode according to the present invention may be formed in the form of a thin film, but may be formed in the form of a wire as shown in FIG. In this embodiment, the metal oxide layer 20 and the nanoparticle layer 30 are formed so as to surround the outer peripheral surface of the current collector 10. That is, the metal oxide layer 20 surrounds the outer peripheral surface of the current collector 10 and the nanoparticle layer 30 surrounds the outer peripheral surface of the metal oxide layer 20, respectively. At this time, the metal oxide layer 20 and the nanoparticle layer 30 may be sequentially arranged repeatedly.

Hereinafter, a method of manufacturing a supercapacitor electrode according to the present invention will be described.

4 is a process diagram of a method of manufacturing a supercapacitor electrode according to an embodiment of the present invention.

4, a method of manufacturing a supercapacitor electrode according to the present invention includes the steps of (a) supporting a flexible electrically conductive current collector in a first solution containing a first material having a first functional group, (B) forming a metal oxide layer by supporting a current collector formed with a first bonding layer on a metal oxide solution containing a metal oxide, (c) (S300) of forming a second bonding layer by supporting a current collector containing a metal oxide layer on a second solution containing a second material having a group containing a metal nanoparticle, and (d) (S400) supporting a current collector on which the second bonding layer is formed to form a nanoparticle layer.

The method of manufacturing a supercapacitor electrode according to the present invention relates to a method of manufacturing an electrode of a supercapacitor according to the above-described embodiment. Therefore, the electrodes of the supercapacitor are described in detail above, and the description of the overlapping elements will be omitted or simply described.

The method for fabricating a supercapacitor electrode according to the present invention includes a first bonding layer forming step (S100), a metal oxide layer forming step (S200), a second bonding layer forming step (S300), and a nanoparticle layer forming step (S400) .

First, in a first bonding layer formation step (SlOO), a first solution containing a flexible electrically conductive current collector and a first material having a first functional group is prepared, and the current collector is carried in the first solution. Thereby, the first bonding layer for adsorbing the metal oxide particles is formed on the outer surface of the current collector. Here, the first functional group may be, for example, an amine group (NH 2 ) or a carboxyl group (COOH). On the other hand, the current collector is formed in a form in which the conductive metal particles are coated on the flexible member and can be applied to the flexible element.

Next, a metal oxide formation step (S200) is performed. Here, a current collector in which a first bonding layer is formed in a metal oxide solution containing a metal oxide is supported. As a result, the metal oxide is adsorbed by the first material having the first functional group, and a metal oxide layer is formed on the current collector. Here, the metal oxide is used as the active material, for example, MnO, Fe 3 O 4, TiO 2, WO 3, V 2 O 5 , And the like. However, the metal oxide is not necessarily limited thereto.

When the metal oxide layer is formed, a second bonding layer formation step (S300) is performed. And the second bonding layer is formed by supporting the current collector in a second solution containing a second material having a second functional group. The second functional group may be an amine group (NH 2 ) or a carboxyl group (COOH) like the first functional group described above.

Finally, a nanoparticle layer formation step (S400) is performed. Here, the nanoparticle solution containing the metal nanoparticles carries the current collector provided with the second bonding layer. As a result, the nanoparticles are adsorbed by the layered self-assembly method based on the solution process. The metal nanoparticles may include at least one selected from the group consisting of, for example, Au, Ag, Cu, Pt, Al, and the like, but are not necessarily limited thereto.

On the other hand, in order to manufacture the electrode of the supercapacitor according to another embodiment in which the metal oxide layer and the nanoparticle layer are sequentially arranged repeatedly, it is preferable that, in the current collector having the outermost nanoparticle layer, Forming step, the second bonding layer forming step, and the nanoparticle layer forming step are sequentially repeated.

FIG. 5 is a graph showing an electrochemical reaction of a supercapacitor electrode according to an embodiment of the present invention, FIG. 6 is a graph showing an internal resistance change of a supercapacitor electrode according to an embodiment of the present invention, and FIG. FIG. 8 is a graph illustrating a capacity retention rate according to the number of bends of a supercapacitor, which is a supercapacitor electrode according to an embodiment of the present invention. FIG. 8 is a Ragone Plot of a supercapacitor composed of a supercapacitor electrode.

According to the present invention, a paper supercapacitor electrode was manufactured by sequentially adsorbing a metal oxide layer and a nanoparticle layer on a current collector coated with gold (Au) particles on paper, and the properties thereof were analyzed through various experiments. At this time, MnO was used as the cathode material of the metal oxide layer, Fe 3 O 4 was used as the cathode material, and gold (Au) particles were used as the metal nanoparticles of the nanoparticle layer.

In the case of the MnO-based supercapacitor electrode, it can be confirmed that metal particles, that is, gold particles are periodically adsorbed in the electrodes as shown in the SEM image on the left side of FIG. Further, with reference to the EDX image shown on the right side of FIG. 3, gold particles introduced into the electrode are uniformly distributed throughout the electrode as a whole. This distribution significantly reduces the internal resistance of the electrode, thereby contributing to the improvement of the performance of the supercapacitor element.

5 to 6, in order to confirm the performance improvement of the supercapacitor device, an electrochemical characteristic analysis was performed on a paper supercapacitor electrode based on MnO by three-electrode analysis. As a result, as shown in FIG. 5, the device with metal nanoparticles (with metal NP) showed a performance improvement of about 280% at a scanning speed of 50 mV / s compared to the device without the metal NP.

This is because the internal resistance of the electrode is drastically lowered due to the introduced metal nanoparticles, which can be seen from FIG. Generally, as the amount of metal oxide increases, the equivalent series resistance (ESR) value and the charge transfer resistance (R ct ) value are increased. In the present invention in which metal nanoparticles are introduced It can be seen that the change in the internal resistance is not large and is almost constant in the case of the supercapacitor device.

7 to 8, an asymmetric paper-based supercapacitor (P-1) composed of a MnO-based positive electrode and a Fe 3 O 4 -based negative electrode was fabricated in an experiment for practical application of a paper super capacitor manufactured according to the present invention. ASC) were measured and their performance was measured.

FIG. 7 is a Ragone plot comparing the values of the energy and the output density of the P-ASC and the previously reported flexible supercapacitor. Here ref. 1 is a thin film of a metal thin film having a nanopore structure of 100 nm thickness as a current collector and thinly reducing MnO 2 on its surface. In ref 2 to 5, graphene having a pore structure is used as a current collector, And a carbon nanotube or MnO 2 were introduced by a blending method to fabricate an electrode. In these cases, a design for introducing a very thin film-like active material layer or a carbon material to reduce the internal resistance is introduced. As a result, the P-ASC manufactured according to the present invention has a high energy density and a high output density Also, it can be confirmed that it is highly expressed. This is probably due to the increase of the electrode efficiency because the increase of the internal resistance is not large even though a large amount of metal oxide particles are introduced into the electrode due to the metal nanoparticles introduced into the electrode.

Also, as shown in FIG. 8, the paper supercapacitor according to the present invention retains about 90% of the initial performance even in the bending stability test of 3,000 times since the paper has the mechanical advantage.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that the modification or improvement is possible.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

10: current collector 11: flexible member
13: metal particle 20: metal oxide layer
30: nanoparticle layer 40: first bonding layer
50: second bonding layer

Claims (9)

Flexible electrically conductive current collectors;
A metal oxide layer including metal oxide particles and bonded to an outer surface of the current collector; And
And a nanoparticle layer containing metal nanoparticles and bonded to an outer surface of the metal oxide layer,
A first bonding layer including a first material having a first functional group and disposed between the current collector and the metal oxide layer and bonding them to each other; And
A second bonding layer that includes a second material having a second functional group and is disposed between the metal oxide layer and the nanoparticle layer and bonds them to each other;
Further comprising: a super capacitor electrode.
delete The method according to claim 1,
The current collector
Flexibility member; And
Conductive metal particles coated on the flexible member;
And a super capacitor electrode.
The method according to claim 1,
Wherein the metal oxide layer surrounds an outer peripheral surface of the current collector,
Wherein the nanoparticle layer surrounds the outer circumferential surface of the metal oxide layer.
The method according to claim 1,
Wherein at least one of the first functional group and the second functional group
An amine group or a carboxyl group.
The method according to claim 1,
The metal oxide layer, and the nanoparticle layer
A super capacitor electrode repeatedly arranged in sequence.
(a) forming a first bonding layer by supporting a flexible electrically conductive current collector in a first solution containing a first material having a first functional group;
(b) forming a metal oxide layer by supporting the current collector on which the first bonding layer is formed, in a metal oxide solution containing a metal oxide;
(c) supporting the current collector including the metal oxide layer on a second solution containing a second material having a second functional group to form a second bonding layer; And
(d) forming a nanoparticle layer on the nanoparticle solution containing metal nanoparticles by supporting the current collector on which the second bonding layer is formed;
Wherein the superconducting layer is formed on the substrate.
The method of claim 7,
Wherein at least one of the first functional group and the second functional group
An amine group or a carboxyl group.
The method of claim 7,
(B) to (d) are repeated at least twice so that the metal oxide layer and the nanoparticle layer are sequentially and repeatedly arranged with the second bonding layer interposed therebetween.
KR1020170046762A 2017-04-11 2017-04-11 Electrode for supercapacitor and fabrication method thereof KR101913937B1 (en)

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PCT/KR2018/003929 WO2018190555A1 (en) 2017-04-11 2018-04-03 Supercapacitor electrode and method for preparing same

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US7061749B2 (en) * 2002-07-01 2006-06-13 Georgia Tech Research Corporation Supercapacitor having electrode material comprising single-wall carbon nanotubes and process for making the same
KR101384663B1 (en) * 2007-06-05 2014-04-14 삼성전자주식회사 Supercapacitor and electrochemical apparatus for water purification using the same
KR101922116B1 (en) * 2012-04-19 2018-11-26 삼성전자주식회사 Electrode for electrochemical capacitor and electrochemical capacitor including the electrode
KR101583701B1 (en) * 2014-04-25 2016-01-08 국민대학교산학협력단 A TRANSPARENT ELECTRODE COMPRISING CO-AXIAL RuO2-ITO NANOPILLARS FOR SUPERCAPACITOR, PREPARATION METHOD THEREOF AND A SUPERCAPACITOR COMPRISING SAID TRANSPARENT ELECTRODE
KR20150134773A (en) * 2014-05-23 2015-12-02 국립대학법인 울산과학기술대학교 산학협력단 Flexible electrode and manufacturing method thereof

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