KR101769413B1 - Manufacturing method of activated carbon electrode - Google Patents
Manufacturing method of activated carbon electrode Download PDFInfo
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- KR101769413B1 KR101769413B1 KR1020160023014A KR20160023014A KR101769413B1 KR 101769413 B1 KR101769413 B1 KR 101769413B1 KR 1020160023014 A KR1020160023014 A KR 1020160023014A KR 20160023014 A KR20160023014 A KR 20160023014A KR 101769413 B1 KR101769413 B1 KR 101769413B1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 42
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 42
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000005530 etching Methods 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000231 atomic layer deposition Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 238000001994 activation Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 wool Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a method of manufacturing a carbonaceous material, comprising: coating a carbonaceous material precursor with a metal oxide; And a heat treatment step of carbonizing and etching the carbon material precursor coated with the metal oxide by heat treatment.
Description
The present invention relates to a method for producing an activated carbon electrode.
Super-capacitors, also referred to as electrical double-layer capacitors, are energy storage devices that have far greater capacitances than conventional capacitors. Supercapacitors have the advantages that current lithium batteries do not have, such as excellent charge / discharge characteristics, high output and high temperature stability.
Based on these advantages, we are attracting much attention as a next generation energy storage device, ranging from high output power supply for military, medical aviation and industrial equipment, auxiliary power supply for fuel cell, and power supply device for load fluctuation in the renewable energy field.
These supercapacitors store energy by an electric double layer formed at the interface between the electrode and the electrolyte when a voltage is applied to the device. At this time, the stored energy capacity is proportional to the area of the electric double layer formed on the electrode surface, and the area of the electric double layer is proportional to the specific surface area of the electrode. Therefore, in order to improve the performance of the device, many studies have been made to increase the specific surface area of the electrode.
In order to obtain electrodes having a large specific surface area, electrode materials having a large specific surface area should be used. Generally, a two-step process is required to produce an electrode material having a large specific surface area. First, a carbonization process is required to carbonize the raw material of the carbon material. Secondly, an activation process is required to widen the specific surface area of the electrode material by etching the surface of the carbon electrode material obtained through the carbonization process.
In the conventional activation process, a method of etching a surface of a carbon material by using a strong acid or a strong base as an activating material (Korean Patent Laid-Open Publication No. 2003-0094910) is used, but in this case, a substance having high toxicity is used as an activating substance There is a problem in that the human body and the environment are poor in stability, and there is a disadvantage that relatively long time is consumed as the activation process after carbonization proceeds.
Further, in the case of the carbon electrode thus manufactured, a conductive material and a binder are further required for improving the conductivity and adhesion of the electrode as the carbon material has a particle shape, and electrode materials such as carbon materials, conductive materials and binders There is a disadvantage in that the storage capacity per weight is lowered as the current collector electrode to be coated is further required.
Thus, it is possible to easily manufacture an activated carbon electrode through a simple process. Further, a conductive material and a binder are not required when used as a supercapacitor, so that a storage capacity per weight can be improved. Technology needs to be developed.
DISCLOSURE OF THE INVENTION In order to solve the above problems, it is an object of the present invention to provide a method for manufacturing an activated carbon electrode very easily and easily by simultaneously performing a carbonization process and an activation process.
According to an aspect of the present invention, there is provided a method of manufacturing a carbonaceous material, including: coating a carbonaceous material precursor with a metal oxide; And a heat treatment step of carbonizing and etching the carbon material precursor coated with the metal oxide by heat treatment.
The method for manufacturing an activated carbon electrode according to the present invention is characterized in that a carbon material precursor is coated with a metal oxide and then a carbonization process and an activation process are simultaneously performed through a single heat treatment, Can be prepared.
Also, by varying the amount of metal oxide in the coating step, the diameter of the microvoids can be controlled after the heat treatment. In addition, the specific surface area of the carbon electrode can be controlled by this, and the capacitance obtained when the supercapacitor element is manufactured can be controlled.
FIG. 1 is a conceptual diagram showing the concept of an embodiment and a comparative example according to the present invention,
2 is a scanning electron microscope (SEM) image of a carbon fiber electrode manufactured according to Examples 1 to 3 and Comparative Example 1 of the present invention,
3 is a graph illustrating a performance of a super capacitor manufactured using carbon fiber electrodes manufactured according to Examples 1 to 3 and Comparative Example 1 of the present invention,
FIG. 4 is a result of elemental analysis of the carbon electrode according to the heat treatment temperature.
Hereinafter, an activated carbon electrode according to the present invention and a method of manufacturing the same will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.
Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
A method of manufacturing an activated carbon electrode according to the present invention includes: a coating step of coating a carbon material precursor with a metal oxide; And a heat treatment step of carbonizing and etching the carbonaceous material precursor coated with the metal oxide by heat treatment. That is, after the carbon material precursor is coated with the metal oxide, the carbonization process and the activation process are simultaneously performed through a single heat treatment as shown in FIG. 1, And a method for manufacturing the same.
Hereinafter, a method of manufacturing an activated carbon electrode according to an embodiment of the present invention will be described in detail.
First, a coating step of coating a carbon material precursor with a metal oxide may be performed. Before the carbon material precursor is carbonized, the carbon material precursor can be simultaneously carbonized and surface-etched during the heat treatment by performing the pre-treatment step of coating the carbon material precursor with the metal oxide.
The coating according to one embodiment of the present invention is not particularly limited as long as it is a commonly used method in the art, and can be carried out by any one or more methods selected from chemical vapor deposition and physical vapor deposition. More specifically, the chemical vapor deposition method may be an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, etc. The physical vapor deposition method may be a pulsed laser deposition (PLD) method, a sputtering method Sputtering, and the like.
Preferably, the carbon material precursor can be coated with a metal oxide through atomic layer deposition. Since the atomic layer deposition method can uniformly coat the surface of the carbon material precursor with the metal oxide and the thickness of the deposition of the metal oxide can be freely controlled, the amount of the metal oxide can be easily controlled, The diameter of the microvoids can be controlled. In addition, the specific surface area of the carbon electrode can be controlled by this, and the capacitance obtained when the supercapacitor element is manufactured can be controlled.
Specifically, the amount of the metal oxide can be controlled by varying the number of cycles of the atomic layer deposition method. Specifically, the number of cycles may be 10 to 1000 times, more preferably 100 to 500 times, but is not limited thereto. Depositing the metal oxide with the number of cycles within the above range may be effective in manufacturing a carbon electrode having a wide specific surface area. In this case, the thickness of the metal oxide layer deposited in one cycle may be 0.1-0.5 nm.
The metal oxide according to an exemplary embodiment of the present invention is used to etch the carbonized carbon material and is not particularly limited as long as it is a metal oxide that can be used to oxidize carbon through carbothermal reduction. For example, the metal oxide may be one satisfying the following formula (1).
[Chemical Formula 1]
M x O y
In the above formula (1), M may be any one selected from the group consisting of an alkaline earth metal element of
In particular, the metal oxide may preferably be ZnO, MgO or a mixture thereof. ZnO and MgO are reduced to Zn (boiling point of about 907 ° C) and Mg (boiling point of 1091 ° C) through thermal carbon reduction. Therefore, as described later, ZnO and MgO have an advantage that the reduced metal can be removed from the metal oxide even though the heat treatment is performed at a relatively low temperature.
The carbon material precursor according to an exemplary embodiment of the present invention may be an organic material in a two-dimensional form, and may be any material as long as it can be carbonized to provide a two-dimensional carbon material such as a fibrous or plate-like carbon material. In one embodiment, the organic material in a two-dimensional form can be organic fibers, paper, wood, or the like. At this time, the thickness of the two-dimensional organic material may be 0.5 to 3 mm, and preferably 0.5 to 1 mm. If the thickness of the two-dimensional organic material is too thin, the carbonaceous carbon material may be physically damaged, and if the thickness is too large, the flexibility may be poor.
Particularly preferably, the carbon material precursor may be an organic fiber. The carbon fiber electrode produced by heat treating the organic fiber has a very low electrical conductivity compared to the carbon particle electrode made of carbon particles. Because of the excellent electric conductivity, the conductive material, the binder, and the current collector may not be used in the manufacture of the supercapacitor, thereby greatly improving the storage capacity per unit area or the storage capacity per unit weight of the supercapacitor.
Specifically, the organic fiber is not particularly limited as long as it can be carbonized to provide a fibrous carbon material. As a non-limiting example, cotton, wool, nylon, Polyester, acrylic fiber, and the like may be used as the binder resin.
Next, the carbon material precursor coated with the metal oxide may be thermally treated to carry out a heat treatment step of carbonizing and etching.
As described above, carbonization and etching can be simultaneously performed through a single heat treatment process by coating the carbon material precursor with a metal oxide in advance. At this time, the etching can be performed by a carbothermal reduction method as shown in the following reaction formula (1).
[Reaction Scheme 1]
M x O y + yC → xM + yCO
(Wherein M x O y is a metal oxide, M is a metal reduced from a metal oxide, x is a real number satisfying 1? X? 3, and y is a real number satisfying 1? Y? 4 .)
When the carbon precursor is carbonized by the heat treatment to form a carbon material, some of the carbon material is oxidized by the oxidation-reduction reaction with the metal oxide by the thermal carbon reduction method to generate carbon monoxide to etch the carbon material, . At this time, the nanostructuring means that the surface of the carbon material is etched by the oxidation-reduction reaction according to the reaction formula 1 to form microvoids. The diameter of the microvoids can be controlled by varying the amount of the metal oxide in the coating step have. In addition, the specific surface area of the carbon electrode can be controlled by this, and the capacitance obtained when the supercapacitor element is manufactured can be controlled.
In particular, the method of the present invention is characterized not only to form an activated carbon electrode having micropores, but also to remove metal impurities through a heat treatment at a high temperature.
Specifically, in the heat treatment step, the carbonized carbon (C) is oxidized and gasified, the metal oxide is reduced to metal, and the reduced metal can be vaporized and removed. Accordingly, the reduced metal generated on the surface of the carbon electrode by the heat treatment process can be prevented from blocking the microvoids of the activated carbon electrode, and the surface area of the carbon electrode can be further secured. Further, there is an advantage that the electrochemical side reaction (undesired reaction) of the electrode, which may occur when metal exists in the electrode, can be minimized.
For this purpose, it is important to adjust the heat treatment temperature condition, and the heat treatment can satisfy the following relational expression (1).
[Relation 1]
T M <T
(In the above-mentioned relational expression 1, T is the heat treatment temperature (占 폚) and T M is the boiling point of the metal (M).)
That is, as shown in FIG. 4, the metal may be vaporized and removed on the carbon electrode by setting the heat treatment temperature to a temperature that is above the boiling point of the reduced metal. As a specific example, the heat treatment temperature may be 1000 ° C or higher, and more preferably 1000 ° C to 1500 ° C. However, it is preferable to use an oxide of a metal having a boiling point lower than a set temperature as a metal oxide in order to vaporize the metal by performing heat treatment at a temperature of 1000 to 1500 ° C. In one embodiment, the metal oxide is ZnO, MgO Or a mixture thereof.
The activated carbon electrode thus produced is carbonized to become a carbon material, and at the same time, the metal reduced from the metal oxide is removed by high temperature heat treatment, so that it can have a better electrical conductivity. Accordingly, when the super capacitor is manufactured, the conductive material, It is possible to manufacture the electrode without using the entirety, thereby greatly improving the storage capacity per unit area or the storage capacity per weight of the supercapacitor. That is, the supercapacitor according to an exemplary embodiment of the present invention may include an active carbon electrode and may include a binder, a conductive material, and a current collector.
Further, as the surface of the carbon material is etched by the oxidation-reduction reaction by the metal oxide, a wider specific surface area can be obtained. Specifically, the specific surface area of the activated carbon electrode may have a specific surface area as large as about 5 times as large as that of the carbon electrode that is heat-treated without depositing the metal oxide, and thus may have a better storage capacity in the manufacture of the supercapacitor.
Hereinafter, a method of producing an activated carbon electrode according to the present invention will be described in more detail with reference to examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, the unit of the additives not specifically described in the specification may be% by weight.
[Examples 1 to 3]
Atomic Layer Deposition Zinc oxide (ZnO) was deposited by atomic layer deposition using a different number of cycles as shown in Table 1 after disposing a general face fiber composed of 100% faces in a chamber.
In the atomic layer deposition process, diethyl zinc and third distilled water were used as precursors and deposition was performed at 100 ° C.
Next, carbon fiber coated with zinc oxide was heat - treated at 1000 ℃ to produce carbonized and surface - etched activated carbon fiber electrodes.
The specific surface area of each activated carbon fiber electrode prepared by measuring the absorption-desorption isotherm of nitrogen using the BET (Brunauer-Emmett-Teller) method is shown in Table 1, and a photograph taken with a scanning electron microscope Respectively.
[Comparative Example 1]
All processes except the zinc oxide deposition process were carried out in the same manner as in Example 1 to prepare a carbon fiber electrode. The carbon fiber electrode prepared by measuring the absorption-desorption isotherm of nitrogen using the BET (Brunauer-Emmett-Teller) Is shown in Table 1, and a photograph taken by a scanning electron microscope is shown in Fig.
[Production Examples 1 to 3 and Comparative Production Example 1]
Supercapacitors were fabricated using the carbon fiber electrodes prepared in Examples 1 to 3 and Comparative Example 1.
Specifically, the prepared carbon fiber electrode was cut into a circular shape having a diameter of 14 mm, and two electrodes were prepared. A separator was placed between the two electrodes, and a 1 M sulfuric acid aqueous solution was used as an electrolyte to constitute a test cell .
The performance of the thus-fabricated conductive carbon fiber electrode-based supercapacitor was measured and shown in FIG.
Electrochemical analysis equipment (CH Instrument, CHI 600E) was used to evaluate the electrochemical characteristics of the supercapacitor. In particular, cyclic voltammetry was used to obtain the change of capacitance according to charge / discharge rate. The measurement was performed by varying the scan rate in a voltage range of 0 to 1 V, and the capacitance of the supercapacitor was calculated using the following equation.
(Capacitance calculation method per area)
(A) / υ: Scanning speed (V): I (V): C area : capacitance per area (F) / ΔV: voltage range / s)]
As shown in Fig. 3, the super-capacitors of Production Examples 1 to 3, which were produced by using the activated carbon fiber electrodes of Examples 1 to 3 respectively, were compared with the carbon fibers of Comparative Example 1 It can be confirmed that it has an excellent electrostatic capacity as compared with Comparative Production Example 1 manufactured using the electrode.
As described above, the present invention has been described with reference to specific embodiments and limited examples and comparative examples. However, the present invention is not limited to the above-described embodiments, 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.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (8)
Wherein the heat treatment satisfies the following relational expression (1).
[Relation 1]
T M <T
(In the above-mentioned relational expression 1, T is the heat treatment temperature (占 폚) and T M is the boiling point of the metal (M).)
Wherein the carbonized carbon (C) is oxidized and gasified, the metal oxide is reduced to metal, and the reduced metal is vaporized and removed in the heat treatment step.
Wherein the coating is carried out by one or more methods selected from chemical vapor deposition and physical vapor deposition.
Wherein the carbon material precursor is a two-dimensional organic material.
Wherein the two-dimensional organic material is organic fiber, paper or wood.
Wherein the metal oxide is one or more selected from ZnO, MgO, CuO, SnO, CoO, NiO, MnO 2 , Al 2 O 3 , Fe 2 O 3 and Fe 3 O 4 .
Wherein the metal oxide is ZnO, MgO or a mixture thereof.
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KR102055654B1 (en) * | 2017-11-13 | 2020-01-22 | (주) 비비비 | Method of manufacturing porous carbon electrode |
US11239455B2 (en) | 2017-11-13 | 2022-02-01 | Bbb Inc. | Porous carbon electrode manufacturing method |
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