KR101274991B1 - The method for manufacturing nitrogen doped graphene electrode for capacitor, electrode and electric double layer capacitor using the same - Google Patents

The method for manufacturing nitrogen doped graphene electrode for capacitor, electrode and electric double layer capacitor using the same Download PDF

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KR101274991B1
KR101274991B1 KR1020110098072A KR20110098072A KR101274991B1 KR 101274991 B1 KR101274991 B1 KR 101274991B1 KR 1020110098072 A KR1020110098072 A KR 1020110098072A KR 20110098072 A KR20110098072 A KR 20110098072A KR 101274991 B1 KR101274991 B1 KR 101274991B1
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electrode
capacitor
nitrogen
graphene
electric double
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KR1020110098072A
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Korean (ko)
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KR20130034182A (en
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김용중
이성영
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재단법인 포항산업과학연구원
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    • 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

The present invention relates to a method of manufacturing an electrode for a capacitor using graphene, and an electrode using the same, and to a method of manufacturing an electrode doped with nitrogen to graphene using a plasma and an electrode using the same. In addition, the present invention relates to an electric double layer capacitor including such an electrode. Through this, it is possible to provide an electric double layer capacitor with maximum capacitance.

Description

Method of manufacturing nitrogen doped graphene electrode for capacitor, electrode and electric double layer capacitor using the same

The present invention relates to a method of manufacturing an electrode for a capacitor using graphene, and an electrode using the same, and to a method of manufacturing an electrode doped with nitrogen to graphene using a plasma and an electrode using the same. In addition, the present invention relates to an electric double layer capacitor including such an electrode.

A capacitor is a device that can store electricity, and basically has a structure in which two electrode plates are opposed to each other, and is called a capacitor or a capacitor. An electric double layer capacitor is a reinforcement of the performance of the capacitor, in particular the capacity of the capacitor, and is a component used for the purpose of a battery, and a capacitor used in an electronic circuit has an electric rechargeable battery function.

The basic idea is to collect power and release it as needed, and it is one of the necessary parts to operate electronic circuits stably. It operates stably even after a long time in a repeated charging and discharging environment, and it is usually used for the purpose of supplying small power when the power is cut off while being charged from AC power. It is usually installed inside a device, and is used for safety devices that temporarily supply power to a setting memory or operate at a power failure.

An electric double layer capacitor is an energy storage device using a pair of charge layers (electric double layers) with different signs, and has a semi-permanent lifespan due to its excellent output characteristics, short charge / discharge time, and excellent durability and stability. . An electric double layer capacitor is generally composed of a cell constructed by placing two electrodes of a cathode and an anode facing each other with a separator interposed therebetween, and then impregnating the electrolyte.

However, the electric double layer capacitor has better output characteristics than the battery, but has a small energy density compared to a general battery because it stores energy only by absorbing ions at the electrode surface without chemical reaction.

Energy density (energy storage), which is one source of energy storage, is a good indicator for comparing the amount of energy in electric double layer capacitors as well as batteries. The energy density can be obtained by dividing the energy obtained by the following equation by the total volume of the electric double layer capacitor.

Energy (J) = 1 / 2CV 2

(C: capacitance F per cell, V; voltage applicable to the cell)

Energy is proportional to capacity C and voltage V 2 . The capacitance is determined by the electrode material, and V is determined by the electrolyte solution used. Therefore, in order to increase the energy density of the electric double layer capacitor, it is necessary to develop an electrode material having a high capacitance and to develop an electrolyte having a large available voltage.

The capacitance of the electric double layer capacitor is determined by the amount of charge accumulated in the electric double layer. Therefore, the capacitance can be changed according to various factors as shown in the following equation.

C = ε 0 * ε r * S / δ

(C; capacitance, ε 0 ; vacuum dielectric constant, ε r : relative dielectric constant, S: surface area of electrode, δ: ion diameter.)

Since the storeable energy is proportional to the area forming the electrical double layer, a material having a high specific surface area such as activated carbon is suitable as an electrode. It is an activated carbon-based carbon electrode material that can satisfy these characteristics. In particular, a carbon electrode material having a very high carbon purity is required in order to lower electrical resistance. In addition, metal oxides such as ruthenium oxide and titanium oxide and conductive polymers are used as electrode capacitors by using Faradaic reaction on the surface, but they have many problems in terms of price and performance compared to carbon-based electrodes. In general, carbon is most often used as an electrode material.

In addition, in the case of activated carbon electrode, which is commonly used, it is possible to produce activated carbon having a high specific surface area of 3000 m 2 / g or more depending on the activation conditions, but in the case of activated carbon having such a high specific surface area, Due to the complicated route, a problem arises in that ions are restricted. In this case, a problem arises in that it is impossible to secure a desired capacitance and charge / discharge rate.

An object of the present invention is to provide a graphene electrode doped with nitrogen having a high specific surface area and micropores that are easy to enter / exit for a high capacity electric double layer capacitor, a method of manufacturing the same, and an electric double layer capacitor using the same.

One aspect of the present invention is a method of manufacturing a capacitor electrode, comprising the steps of: peeling graphene from the carbon material; And preparing an electrode by doping nitrogen by subjecting the graphene to nitrogen plasma treatment.

The carbon material is preferably one of graphite, vapor grown carbon fiber, and vapor grown nanofiber.

The doping amount of the nitrogen is preferably 1-30 at.%.

It is preferable that it is 10 nm or less from the surface of the said doping layer electrode of nitrogen.

One side of the present invention is a capacitor electrode, the electrode is made of graphene, and comprises a nitrogen doping layer.

The nitrogen doping amount of the graphene electrode is preferably 1-30 at.%.

It is preferable that the said nitrogen doping layer is 10 nm or less from the surface of an electrode.

One aspect of the present invention is a capacitor, wherein the capacitor includes a graphene electrode doped with nitrogen, and the nitrogen doped layer of the graphene electrode is preferably 10 nm or less from the surface of the electrode.

The nitrogen doping amount is preferably 1-30 at.%.

The capacitance of the capacitor is preferably 65 F / cc or more.

According to the present invention, by reducing the solvation size of the electrolyte by the doped electrode, and by simplifying the access path of the ions by using graphene, it is possible to increase the capacitance and charge and discharge rate of the electric double layer capacitor. .

1 is a schematic diagram of a graphene used as an electrode material for a capacitor according to an embodiment of the present invention, Figure 1 (a) shows a carbon material, Figure 1 (b) is a graphene by peeling the carbon material It is a schematic diagram which showed the manufacturing method briefly.
2 (a) and 2 (b) are schematic diagrams showing nitrogen-doped plasma treatment according to an embodiment of the present invention.
Figure 3 (a) is a TEM picture of the graphite (grapite) before peeling, Figure 3 (b) is a TEM picture of the graphene after peeling.
Figure 4 (a) is a TEM picture before the peeling of the vapor grown carbon fiber (vapor grown carbon fiber), Figure 4 (b) is a TEM picture of the graphene after peeling.
Figure 5 (a) is a TEM picture before the peeling of the vapor grown carbon fiber (vapor grown carbon fiber), Figure 5 (b) is a TEM picture of the graphene after peeling.
FIG. 6 is a diagram illustrating graphene peeled from graphite, vapor grown carbon fibers, and vapor grown nanofibers, and nitrogen doped to the graphenes as an embodiment of the present invention. It is a graph comparing the capacity of the electric double layer capacitor using the electrode material.

The inventors have realized that the capacitance of an electric double layer capacitor can be increased by using graphene as the electrode material of the capacitor and doping hetero elements in the electrode material.

First, a method of manufacturing a nitrogen doped graphene electrode which is one aspect of the present invention and a nitrogen doped graphene electrode produced thereby will be described in detail.

The present invention manufactures an electrode material using graphene. Graphene refers to a molecule having a double bond with graphite (graphite). Graphite has a structure in which carbon layers are stacked in a hexagonal honeycomb shape. Graphene is the thinnest layer separated from graphite, and carbon atoms such as carbon nanotubes (CNT) and fullerene are atomic number 6 It is a nanomaterial composed of burned-in carbon. It has a two-dimensional planar shape and its thickness is about 0.2 nm, which is very thin, but its physical and chemical stability is high. As shown in FIG. 1, the carbon material may be peeled off to prepare graphene.

In general, activated carbon has a large specific surface area, and thus there is a factor to increase the capacitance. However, the pore size of the activated carbon is narrower than the ion size of the electrolyte, and thus the ion entrance and exit is limited, and the pore structure is complicated, and the mobility of the ions is reduced due to structural obstacles. In the case of a double layer capacitor, the charge / discharge rate is limited to reduce its capacitance.

On the other hand, graphene is not much different in specific surface area compared with general activated carbon used as an electrode material. However, in the case of graphene, carbon forms a regular lattice structure, and the pore size is larger than the size of the ions, so that there is little restriction on the entrance and exit of ions, thereby improving the capacitance of the electric double layer capacitor using the same.

One side of the present invention can peel the graphene from the carbon material (graphite, etc.). The carbon material may be any material that can be peeled off with graphene, and is preferably one of graphite, vapor grown carbon fiber, and vapor grown nanofiber. Do.

The electric double layer capacitor basically includes a positive electrode, a negative electrode and an electrolyte. In the case of the aqueous electrolyte, the electrolyte and the electrode have increased capacitance by the Faraday reaction, but in the case of the organic electrolyte, this effect is not easy. The electrode of the present invention can provide a high capacity electric double layer capacitor in the case of an aqueous electrolyte as well as an organic electrolyte.

The present invention provides an electrode having a polarity by doping heterogeneous elements in the electrode material used for the positive electrode. The anode may be doped with nitrogen in order to introduce a positive charge.

As described above, the capacitance is inversely proportional to the ion diameter contained in the electrolyte. When the positive charge is charged to the positive electrode, the negative charge present in the electrolyte is opposite to the positive electrode. As in the present invention, when using a cathode material doped with nitrogen, nitrogen is doped in a Pyridinic type, the positive charge can be sufficiently introduced into the anode by the bonding form of such nitrogen. Due to this positive charge, when the ions contained in the electrolyte are adsorbed to the anode, the diameter of the electron cloud is reduced, and the interface impedance between the electrode and the electrolyte is reduced, so that it is easy to be collected in pores (pores) of graphene. .

In order to dope the nitrogen, the graphene prepared by peeling the carbon material may be subjected to nitrogen plasma treatment. The nitrogen plasma treatment may be provided by a conventional plasma treatment method, and is not limited to any method as long as the nitrogen can be doped with the graphene. As shown in FIGS. 2A and 2B, the graphene 4 may be doped with nitrogen using a nitrogen plasma processing apparatus 3 (1: microwave, 2: gas supply apparatus). For example, electrons can be driven out with nitrogen molecules to dope nitrogen onto the surface of graphene.

The nitrogen doping amount is preferably 1-30 at.%, And preferably 10 nm or less from the surface of the nitrogen doped layer electrode. Through this, it is possible to provide an electrode material capable of securing a high capacitance.

One side of the present invention is a capacitor electrode, the electrode may be made of graphene. As described above, the electrode for the capacitor includes a nitrogen doping layer, the doping amount of the nitrogen is preferably 1-30at.%, Preferably 10nm or less from the surface of the doping layer electrode of nitrogen.

One aspect of the invention describes an electric double layer capacitor. The electric double layer capacitor may include an electrode manufactured by the above-described method of preparing nitrogen-doped graphene as an anode. In the case of the negative electrode, it is preferable to use graphene, but the negative electrode material is not necessarily limited to graphene, and any material that can be used as the electrode material may be used. Preferably, the capacitor includes a graphene electrode doped with nitrogen, and the nitrogen doped layer of the graphene electrode may be provided at 10 nm or less from the surface of the electrode. Here, the nitrogen doping amount is preferably 1-30at.%. In addition, the capacitance of the capacitor can ensure more than 65F / cc.

Hereinafter, the present invention will be described more specifically by way of examples. It should be noted, however, that the following examples are intended to illustrate the invention in more detail and not to limit the scope of the invention. The scope of the present invention is determined by the matters set forth in the claims and the matters reasonably inferred therefrom.

(Example)

Graphene was prepared using graphite, vapor grown carbon fiber, and vapor grown nanofiber. TEM photographs before and after exfoliation of graphite are shown in FIGS. 3 (a) and 3 (b), respectively. In addition, the TEM photographs before and after peeling of the vapor growth carbon fiber are shown in Figs. 4 (a) and 4 (b), respectively. In addition, TEM photographs before and after peeling of the vapor growth nanofibers are shown in FIGS. 5 (a) and 5 (b), respectively.

In addition, after preparing the electrode by doping nitrogen through the plasma treatment and the electrode using the graphene prepared as described above, by measuring the capacitance per unit area of the electric double layer capacitor including the electrode in Figure 6 Indicated. As shown in FIG. 6, the capacitance of the capacitor using nitrogen-doped graphite 6, vapor-grown carbon fiber 10, and vapor-grown nanofibers 8 is not nitrogen-doped graphite 5, vapor. It was confirmed that the capacitance of the capacitor using the growth carbon fiber 9 and the vapor growth nanofibers 7 was improved.

1. Gas supply device,
2. microwave,
3. plasma processing equipment,
4. Graphene.

Claims (10)

In the manufacturing method of the manufacturing method of the electrode for capacitors,
Peeling graphene from the carbon material; And
The method of manufacturing a nitrogen-doped graphene electrode for a capacitor by performing a nitrogen plasma treatment to the graphene to prepare an electrode, wherein the doping amount of the nitrogen is 1-30 at.%.
The method according to claim 1,
The carbon material is a method of manufacturing a nitrogen-doped graphene electrode for a capacitor, characterized in that one of graphite, vapor grown carbon fiber (vapor grown carbon fiber) and vapor grown nanofiber (vapor grown nanofiber).
delete The method according to claim 1,
The method of manufacturing a nitrogen doped graphene electrode for a capacitor, characterized in that the doping layer of nitrogen is 10nm or less (excluding 0) from the surface of the electrode.
As an electrode for a capacitor,
The electrode is made of graphene, comprising a nitrogen doping layer, the nitrogen doping graphene electrode, characterized in that the nitrogen doping amount is 1-30at.%.
delete The method according to claim 5,
The nitrogen doped layer is a nitrogen doped graphene electrode for a capacitor, characterized in that less than 10nm (excluding 0) from the surface of the electrode.
As a capacitor,
The capacitor comprises a nitrogen-doped graphene electrode, the nitrogen doped layer of the graphene electrode is an electric double layer capacitor, characterized in that less than 10nm (excluding 0) from the surface of the electrode.
The method according to claim 8,
The nitrogen doping amount is an electric double layer capacitor, characterized in that 1-30at.%.
The method according to claim 8,
The capacitance of the capacitor is an electric double layer capacitor, characterized in that more than 65F / cc.
KR1020110098072A 2011-09-28 2011-09-28 The method for manufacturing nitrogen doped graphene electrode for capacitor, electrode and electric double layer capacitor using the same KR101274991B1 (en)

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CN103500654A (en) * 2013-10-11 2014-01-08 张孝彬 Nitrogen-doped graphene/PVDF (Polyvinylidene Fluoride) composite dielectric film and preparation method thereof
CN104838051A (en) * 2013-02-19 2015-08-12 中国海洋大学 Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
CN105185605A (en) * 2015-08-27 2015-12-23 长春工业大学 Loaded graphene/metallic compound-contained electrode preparation method based on hollow cathode plasma reduction and nitridation
KR101629835B1 (en) 2015-11-11 2016-06-14 한국지질자원연구원 Manufacturing method of three-dimensional graphene composite via multi-doping and supercapacitor using thereof
US9892821B2 (en) 2016-01-04 2018-02-13 Samsung Electronics Co., Ltd. Electrical conductors and electronic devices including the same
CN109313989A (en) * 2016-09-30 2019-02-05 积水化学工业株式会社 Carbon material, capacitor electrode piece and capacitor

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006310514A (en) * 2005-04-28 2006-11-09 Tohoku Univ Electrode material for electric double layer capacitor
KR20110068297A (en) * 2009-12-16 2011-06-22 충남대학교산학협력단 Gas sensor using porous nano-fiber containing electrically conductive carbon material and manufacturing method thereof
KR20120053294A (en) * 2010-11-17 2012-05-25 경희대학교 산학협력단 Method for forming graphene pattern and method for manufacturing electronic element having graphene pattern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006310514A (en) * 2005-04-28 2006-11-09 Tohoku Univ Electrode material for electric double layer capacitor
KR20110068297A (en) * 2009-12-16 2011-06-22 충남대학교산학협력단 Gas sensor using porous nano-fiber containing electrically conductive carbon material and manufacturing method thereof
KR20120053294A (en) * 2010-11-17 2012-05-25 경희대학교 산학협력단 Method for forming graphene pattern and method for manufacturing electronic element having graphene pattern

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104838051A (en) * 2013-02-19 2015-08-12 中国海洋大学 Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof
CN103500654A (en) * 2013-10-11 2014-01-08 张孝彬 Nitrogen-doped graphene/PVDF (Polyvinylidene Fluoride) composite dielectric film and preparation method thereof
CN105185605A (en) * 2015-08-27 2015-12-23 长春工业大学 Loaded graphene/metallic compound-contained electrode preparation method based on hollow cathode plasma reduction and nitridation
CN105185605B (en) * 2015-08-27 2017-11-10 长春工业大学 Load the electrode preparation method of graphene/metallic compound
KR101629835B1 (en) 2015-11-11 2016-06-14 한국지질자원연구원 Manufacturing method of three-dimensional graphene composite via multi-doping and supercapacitor using thereof
US9892821B2 (en) 2016-01-04 2018-02-13 Samsung Electronics Co., Ltd. Electrical conductors and electronic devices including the same
CN109313989A (en) * 2016-09-30 2019-02-05 积水化学工业株式会社 Carbon material, capacitor electrode piece and capacitor

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