KR20160101796A - iron-carbon composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor - Google Patents
iron-carbon composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor Download PDFInfo
- Publication number
- KR20160101796A KR20160101796A KR1020150024267A KR20150024267A KR20160101796A KR 20160101796 A KR20160101796 A KR 20160101796A KR 1020150024267 A KR1020150024267 A KR 1020150024267A KR 20150024267 A KR20150024267 A KR 20150024267A KR 20160101796 A KR20160101796 A KR 20160101796A
- Authority
- KR
- South Korea
- Prior art keywords
- iron
- carbon
- electrochemical capacitor
- carbon composite
- electrode
- Prior art date
Links
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 8
- 239000004020 conductor Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 238000003860 storage Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 60
- 238000012360 testing method Methods 0.000 description 32
- 239000000523 sample Substances 0.000 description 23
- 208000028659 discharge Diseases 0.000 description 21
- 239000002243 precursor Substances 0.000 description 19
- 239000007772 electrode material Substances 0.000 description 11
- 239000013068 control sample Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 4
- 159000000014 iron salts Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910009361 YP-50F Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- MAQAUGBCWORAAB-UHFFFAOYSA-N [C+4].[O-2].[Fe+2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Fe+2].[O-2].[O-2] MAQAUGBCWORAAB-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- ZPKLYVJENOZRAW-UHFFFAOYSA-L iron(2+);dichlorate Chemical compound [Fe+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ZPKLYVJENOZRAW-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229960005177 miristalkonium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- 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
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to an iron-carbon composite material for an electrochemical capacitor electrode, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same, and more particularly, to an electrochemical capacitor having excellent non-storage capacity and resistance characteristics by using an underwater plasma reaction Carbon composite, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same.
The method for producing an iron-carbon composite material for an electrochemical capacitor electrode according to the present invention comprises the steps of: preparing a solution to which a carbon source and an iron source are added; generating a plasma in the solution to form iron - carbon composite in water; and a third step of separating the iron-carbon composite from the solution.
Description
The present invention relates to an iron-carbon composite material for an electrochemical capacitor electrode, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same, and more particularly, to an electrochemical capacitor having excellent non-storage capacity and resistance characteristics by using an underwater plasma reaction Carbon composite, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same.
In general, an electronic device called a capacitor is a device that stores electricity by a physical mechanism without chemical reaction or phase change, and functions to collect and discharge electricity to stabilize the electric flow in the circuit. These capacitors have a very short charge / discharge time, a long lifetime and a high output density, but their energy density is very small and their use in energy storage devices is limited.
On the other hand, a secondary battery is a device capable of storing high-density energy and is used as an energy storage medium for portable electronic devices such as a notebook computer, a mobile phone, and a PDA. Recently, research on lithium ion batteries has been actively conducted.
Electrochemical capacitors are emerging as storage media for electronic devices that require high energy density and high power density by developing intermediate characteristics of the above two devices.
Electrochemical capacitors are called super capacitors, electrical double layer capacitors, and utracapacitors. They are used in the fields of wind power generation, hybrid electric vehicles and electric vehicles. The potential application of energy storage media in various fields is high, and has received explosive attention in recent years.
The basic structure of the electrochemical capacitor is composed of a porous electrode, an electrolyte, a current collector, and a separator. A voltage of several volts is applied to both ends of the unit cell electrode, And is adsorbed on the surface of the electrode to generate an electrochemical mechanism.
The most important part of the electrochemical capacitor is the electrode material, which must have a high specific surface area. The charge must be electrochemically stable under a certain potential so as to achieve a minimum voltage drop distribution at the electrode, and be electrochemically stable. The price should be low.
These supercapacitors are classified into three types according to their electrodes and mechanisms. In general, an activated carbon is used as an electrode, an electric double layer capacitor using an electric double layer charge adsorption mechanism, a transition metal oxide A metal oxide electrode-like capacitor (pseudocapacitor or redox capacitor) using a conductive polymer as an electrode material and having pseudo-capacitance as a mechanism, and a hybrid capacitor having intermediate characteristics of the above capacitors ).
In the case of the activated carbon electrode material, the non-conducting capacity is proportional to the specific surface area, so that the energy density due to the high capacity of the electrode material is increased by imparting porosity. The carbon electrode material, the carbon conductive material and the polymer binder are made into a slurry and applied to the current collector to produce an electrode. The binder and the conductive material and the electrode material are changed in kind and ratio to increase the adhesion to the current collector It is important to reduce the contact resistance and also to reduce the internal contact resistance between activated carbon.
In the case of the metal oxide electrode material, the resistance is lower than that of the activated carbon, so that a supercapacitor having high output characteristics can be manufactured. In particular, electrochemical capacitors using ruthenium oxide (RuO 2 ) as a metal oxide show the best non-storage capacity values. However, ruthenium oxide is disadvantageous in that it is more expensive than carbon materials and other metal oxides (MnOx, NiO, CoOx, IrO 2, etc.).
Recently, a variety of transition metal oxides have been studied as potential electrode materials having high energy density and long cycling performance. Among them, iron oxide nanoparticles are most attracted attention by many researchers and industrial fields due to their low cost and environmental friendliness .
Korean Patent Laid-Open No. 10-2014-0091482 discloses an iron oxide carbon nanocomposite for a sodium secondary battery anode active material and a method for producing the same. The carbonaceous nanocomposite described above is prepared by forming a nano iron oxide using a hydrothermal reaction, mixing a carbon precursor, and then heat-treating the carbon precursor at a high temperature to combine carbon and nano iron oxide.
However, the above-described carbon nanocarbon nanocomposite requires a process of forming nano iron oxide and bonding carbon to the nano iron oxide, respectively, and each process requires a long time.
The present invention has been made to overcome the above problems, and it is an object of the present invention to provide an iron oxide nanoparticle in a single process using an underwater plasma reaction and to form an iron- And which can shorten the manufacturing time, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same.
To achieve the above object, an iron-carbon composite for an electrochemical capacitor electrode according to the present invention is formed by generating a plasma in water, and iron oxide nanoparticles are bonded to the surface of carbon particles.
The iron-carbon composites have an iron (Fe) content of 0.1 to 0.5 atomic%.
In order to accomplish the above object, the present invention provides a method for producing an iron-carbon composite material for an electrochemical capacitor electrode, comprising the steps of: preparing a solution containing a carbon source and an iron source; A second step of generating a plasma in the solution to form an iron-carbon composite in which iron oxide nanoparticles are bonded to the surface of carbon particles in water; And a third step of separating the iron-carbon composite from the solution.
The first step includes a step of dissolving a dispersant in a solvent, a step of dispersing and adding active carbon particles as the carbon source to the solvent in which the dispersant is dissolved, and a step of adding iron salts to the solvent in which the activated carbon particles are dispersed The solution is obtained by performing a dissolving step.
The iron salt is iron chloride.
The dispersant in the solution is 2 mM, and the iron salt in the solution is 4 mM.
The second step is to discharge plasma for 15 to 30 minutes at a voltage of 250 V, a pulse width of 5 μs and a frequency of 30 KHz to generate a plasma.
In order to achieve the above object, the electrode composition for an electrochemical capacitor of the present invention comprises 70 to 90% by weight of an active material, 1 to 20% by weight of a conductive material and 1 to 20% by weight of a binder, to be.
As described above, according to the present invention, iron oxide nanoparticles can be produced in a single process using an underwater plasma reaction, and at the same time, an iron-carbon composite in which iron oxide nanoparticles and carbon are combined can be formed.
Accordingly, the present invention can provide an iron-carbon composite, a method of manufacturing the same, and an electrode composition for an electrochemical capacitor using the same, which can simplify the manufacturing method and shorten the manufacturing time.
FIG. 1 is a schematic view showing a liquid-phase plasma reactor applied to an embodiment of the present invention,
FIGS. 2 and 3 are graphs showing XPS spectrum analysis results of the control sample and the second test sample,
4 is a photograph of the surface shape of the first through fourth test samples observed using FESEM,
5 is a photograph showing an HR-FETEM image of the second test sample,
6 and 7 are graphs showing electrical characteristics.
Hereinafter, an iron-carbon composite material for an electrochemical capacitor electrode according to a preferred embodiment of the present invention, a method for producing the same, and an electrode composition for an electrochemical capacitor using the same will be described in detail.
The iron-carbon composite material according to an embodiment of the present invention has excellent non-storage capacity and resistance characteristics and is used as an electrochemical capacitor electrode material. It goes without saying that it can be used as an electrode material for a secondary battery in addition to an electrochemical capacitor electrode.
In the iron-carbon composite of the present invention, iron oxide nanoparticles are bonded to the surface of carbon particles. The carbon particles and the iron oxide particles can be physically or chemically bonded. Preferably, the iron oxide particles can be bonded to the surface of the carbon particles in a uniformly distributed manner. For example, nanometer-sized iron oxide particles may be combined in a distributed fashion on the surface of micrometer-sized carbon particles. The carbon particles may have an average size of 1 to 200 mu m. The iron oxide particles may have an average size of 1 to 100 nm. The iron oxide particles may be any one of FeO, Fe 3 O 4 , and Fe 2 O 3 .
The iron-carbon composites of the present invention preferably have an iron (Fe) content of 0.1 to 0.5 atomic%. If it is less than 0.1 atomic%, the resistance value is high, and if it exceeds 0.5 atomic%, the reserve amount is decreased. Therefore, the non-storage capacity and resistance characteristics are excellent within the above range.
The iron-carbon composite of the present invention can form iron oxide nanoparticles in one step by using an underwater plasma reaction and form an iron-carbon composite in which iron oxide nanoparticles and carbon are bonded. The production of iron-carbon composites by such an underwater plasma reaction is simple and can greatly shorten the process time.
Hereinafter, a method for producing an iron-carbon composite using an underwater plasma reaction will be described.
The method of manufacturing an iron-carbon composite according to an embodiment of the present invention includes a first step of preparing a solution to which a carbon source and an iron source are added, a step of generating a plasma in the solution, Carbon composite, and a third step of separating the iron-carbon composite from the solution. Each step will be examined in detail.
1. Step 1: Preparation of precursor solution
In the first step, a precursor solution is prepared. A carbon source and an iron source are added to the precursor solution.
To prepare the precursor solution, the dispersant is first dissolved in the solvent.
Water or alcohol may be used as a solvent, but it is preferable to use water as a solvent so that iron particles formed by plasma discharge in water can be easily oxidized. Primary or secondary distilled water can be used as the water.
The dispersing agent is for dispersing the carbon source on the solvent, and a cationic surfactant can be used. As such a dispersant, cetyltrimethyl ammonium bromide (CTAB) can be used. In addition, benzoalkonium chloride, miristalkonium chloride, cetylpyridinium chloride, and cetyltrimethyl ammonium chloride can be used, but cetyltrimethylammonium bromide is effective.
The dispersant may be dissolved in the solution at a concentration of 1 to 3 mM.
Next, the carbon source is added to the solvent in which the dispersing agent is dissolved, and the dispersion is then dispersed on the solvent. Activated carbon, natural graphite, artificial graphite and the like can be used as a carbon source. The carbon source is added in the form of particles. For example, the carbon source may be micrometer-sized particles having an average size of 1 to 200 mu m. The carbon source may be added in an amount of 0.1 to 10 g per 100 ml of the solvent.
After the carbon source is added, the ultrasound is applied into the solvent so that the carbon source particles can be uniformly dispersed in the solvent. The processing conditions of the applicable ultrasonic waves are not particularly limited, and ultrasonic waves of 40 to 50 W and 40 to 60 kHz are preferably applied for about 0.5 to 5 minutes.
Next, an iron source is added to the solvent in which the carbon source particles are dispersed and dissolved.
Iron salts can be used as the iron source. As the iron salt, iron chloride, iron nitrate, iron sulfate, iron bromide, iron iodide, iron chlorate and the like can be used. FeCl 2 as iron chloride Or FeCl 3 can be used.
Iron salts dissolved in a solvent are precursors of iron oxide nanoparticles. When iron salts are dissolved in a solvent, iron is present in the form of cations. The iron salt may be dissolved in the solution at a concentration of 1 to 10 mM.
Thus, a precursor solution to which a dispersant, a carbon source, and an iron source are added to the solvent is prepared, and a plasma is generated in the precursor solution to form an iron-carbon composite in water.
2. Phase 2: Underwater Plasma Reaction
In the liquid phase plasma (LPP) reaction applied to the present invention, a high-density high-energy plasma is generated in a liquid to form iron nanoparticles.
The flow of ions and electrons in response to the application of electrical energy in the liquid generates a plasma in the liquid. Plasma generation is related to the flow of electrons, so that electrons are provided to the iron ions present in the liquid to generate iron nanoparticles.
An example of an underwater plasma reactor for generating a plasma in a liquid phase is shown in FIG.
The illustrated underwater plasma reactor includes a
When power is supplied to the
It is preferable to supply pulses rather than supplying power continuously to the electrodes when power is supplied. Supplying the power as a pulse suppresses the dissolution of the electrode exposed to the precursor solution, thereby greatly reducing the elution of the electrode component into the precursor solution.
The power supply condition to be supplied to the electrode for generating the plasma may be 250 V, pulse width 5 μs, and
When a plasma is generated in a liquid, iron ions in the precursor solution are reduced to form nanometer sized iron particles. The iron particles formed are immediately oxidized in water to form iron oxide particles. The formed iron oxide particles are bonded to the surface of the carbon particles to form an iron-carbon composite. The iron-carbon composites are present in a dispersed form in the liquid.
3. Stage 3: Isolation of iron-carbon composites
The iron-carbon composite is formed in water by a plasma reaction, and then the iron-carbon composite is separated from the precursor solution. To this end, the precursor solution is centrifuged to separate the iron-carbon composite, washed with water and ethanol three times, and finally dried to obtain an iron-carbon composite.
The iron-carbon composite thus produced has excellent non-storage capacity and resistance characteristics and can be utilized as an electrode material of an electrochemical capacitor.
For example, an electrode composition for manufacturing an electrode of an electrochemical capacitor is formed by mixing a conductive agent for imparting electrical conductivity to the active material and a binder enabling adhesion. For example, the electrode composition may be composed of 70 to 90 wt% of the active material, 1 to 20 wt% of the conductive material, and 1 to 20 wt% of the binder.
The above-described iron-carbon composite of the present invention is used as the above-mentioned active material.
The conductive material may generally be carbon black. Commercially available products such as acetylene black series (Chevron Chemical Company), Gulf Oil Company (Gulf Oil Company), Ketjen Black EC series (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and super-P (MMM).
Examples of the binder include styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF) or copolymers thereof and cellulose.
The above-described electrode composition can be made into an electrochemical capacitor electrode by a method known to a person skilled in the art.
Hereinafter, the iron-carbon composites of the present invention were prepared through experimental examples. However, the following experimental examples are intended to illustrate the present invention in detail, and the scope of the present invention is not limited to the following experimental examples.
≪ Preparation of iron-carbon composites >
1. Materials
Activated carbon was used as a carbon source. The activated carbon used was YP-50F (Koraray chemical co., Ltd., Japan) and had a specific surface area of 1,500 to 1,800 m 2 / g and a particle size of 5 to 20 μm.
(FeCl 2 .4H 2 O, Kanto Chemical Co., Inc) was used as the iron source and CTAB (cetyltrimethyl ammonium bromide, CH 3 (CH 2 ) 15 N (CH 3 ) 3 Br, Daejung Chemicals & Metals Co.Ltd) was used. Ultrapure water (Daejung Chemical & metals Co. Ltd.) was used as distilled water as a solvent.
2. Preparation of precursor solution
2 mM of CTAB as a dispersant was dissolved in 300 mL of distilled water as a solvent. Then, 2 g of activated carbon was added to the solution in which the dispersant was dissolved, and the mixture was stirred, and ultrasonic waves of 50 kHz were applied for about 1 minute to induce uniform dispersion. Next, 4 mM of iron chloride was dissolved.
3. Preparation of iron-carbon composites
The schematic structure of the underwater plasma reactor used in this experiment is shown in Fig. Power supply (Nano technology, NTI-500W) with high-frequency bipolar pulse method was used for power supply to generate plasma. The operating condition of the power supply was 250V, frequency 30kHz, pulse width 5μs, and the applied power was supplied to the inside of the reactor through the tungsten electrode installed in the reactor. The reactor was a double tube type (OD: 40 mm, H: 80 mm), and a tungsten electrode (
The iron-carbon composite was centrifuged at 4,000 rpm for 20 minutes. The iron-carbon complex was separated by water and ethanol ≪ / RTI > and then dried to give an iron-carbon composite.
The iron-carbon composites produced by discharging the iron-carbon composites produced by discharging for 15 minutes and the iron-carbon composites prepared by discharging the first test samples for 30 minutes were discharged for 45 minutes, , And the iron-carbon composite produced by discharging for 60 minutes was referred to as a fourth test sample. Activated carbon (YP-50F) was used as a control sample for comparison with the test samples.
4. Experimental results
(1) XPS spectrum analysis
The XPS spectra of the second test sample and the control sample were analyzed using X-photoelectron spectroscopy (XPS, Multilab 2000 system, SSK). The results are shown in FIG. 2 and FIG.
FIG. 2 shows the XPS spectrum of the control sample and the second test sample.
Referring to FIG. 2, peaks of C1s and O1s were observed in the control sample. Meanwhile, the synthesized second test sample is Fe2p 1/2 and Fe2p 3/2 peak due to the iron oxide component was observed, it was confirmed that the strength of the O1s peak increases.
FIG. 3 shows the narrow-range XPS spectra of the second test sample within the range of 700 to 740 eV.
3, the binding energy (binding energy) is at 725.2eV and 711.7eV Fe2p 1/2 and Fe2p 3/2 were observed, respectively, which are predicted to FeO and the components of the Fe 3 O 4 iron oxide.
(2) Analysis of particle characteristics
The dispersibility of the iron oxide particles dispersed in the carbon particles of the second test sample was examined using a Field Emission Scanning Electron Microscope (FESEM, JSM-7100F, JEOL).
FIG. 4 shows photographs of the surface shapes of the first to fourth test samples produced by different discharge times using FESEM. 4 (a) is a photograph of a first test sample, (b) is a second test sample, (c) is a third test sample, and (d) is a fourth test sample.
Referring to FIG. 4, red dots on the surface of carbon particles are image mapping of iron oxide particles. It can be deduced that the amount of iron oxide particles bound to the surface of the carbon particles increases in proportion to the discharge time through the increase of the Fe image as the discharge time increases. It is also observed that the iron oxide particles are distributed very uniformly on the surface of the carbon particles without aggregation.
5 shows HR-FETEM images and ED pattern results of the second test sample. HR-FETEM images were obtained using High Resolution Field Emission Transmission Electron Microscope (HR-FETEM, JEM-2100F, JEOL).
Referring to FIG. 5, the average size of the iron oxide particles bonded to the surface of the carbon particles was about 5 to 10 nm, and the lattice fringes of the iron oxide particles were measured to be about 3 angstroms. On the other hand, it is possible to predict that iron oxide particles are very fine amorphous powders through the fact that spots and several circles are not formed in the ED pattern.
(3) Component analysis
The chemical compositions measured using the EDX spectrum of the first to fourth test samples and the control samples are summarized in Table 1 below.
Referring to Table 1, the chemical composition of the control sample was atomic%, 97.75% carbon and 2.25% oxygen. On the other hand, as the discharge time increased, the amount of oxygen and iron increased in the test samples. These results are consistent with the results of FIG.
(4) Electrical characteristics analysis
In order to evaluate the electrical characteristics as an electrode of an electrochemical capacitor, a coin cell type battery was fabricated.
The electrode composition used in the production of the battery was prepared by mixing active material: conductive material: binder in an amount of 80: 10: 10 wt%. A mixture of Super-P (TIMCAL graphite & carbon) and SBR (Styrene-Butadien Rubbber) and CMC (Carboxylmethyl cellulose) was used as the conductive material. The electrolyte was KOH 1M solution and the separation membrane was 150 ㎛ glass felt was used. The first to fourth test samples and comparative samples were respectively used as active materials.
The cyclic voltammetry was measured at a driving voltage of 0.1 to 0.9 V, a current density of 0.001 A / cm 2 , and a scan rate of 10 mv / s. The composite resistance was measured in the frequency range of 0.01 to 300 kHz using an ac impedance measuring device. Potentiostat (VSP, Priceton applied research) was used for all electrochemical properties.
FIG. 6 shows the results measured by the cyclic voltammetry method.
Referring to FIG. 6, the second test sample subjected to the plasma discharge treatment for 30 minutes showed the best specific capacitance. The first test sample subjected to the plasma discharge treatment for 15 minutes had slightly better storage capacity than the control sample. However, the third and fourth test samples treated with plasma discharge for 45 minutes and 60 minutes showed lower storage capacity than the control samples. From these experimental results, it was found that when the electrode was made of the iron-carbon composite bonded with the iron oxide nanoparticles on the carbon particles, the storage capacity was excellent. However, when the amount of iron oxide nanoparticles bonded to the surface of the carbon particles is excessively increased, the storage capacity is lowered. The reason for this is considered to be that an appropriate amount (0.1 to 0.5 atomic%) of the iron oxide particles increases the surface area, thereby improving the storage capacity. However, the iron oxide particles bonded to the surface of the carbon particles excessively (over 0.56 atomic%) cover the pores of the carbon particles, and thus the surface area of the electrode is reduced, resulting in a decrease in the storage capacity.
7 is a Nyquist plot showing the composite resistance measured using an AC impedance measurement device.
Referring to FIG. 7, the interface resistance of the round semicircular shape is not clearly visible, and the second test sample subjected to the plasma discharge treatment for 30 minutes has the lowest resistance value. 15 minutes, and 45 minutes of plasma discharge, the first and third test samples showed lower resistance than the control sample. However, the fourth test sample treated with plasma discharge for 60 minutes showed a higher resistance value than the control sample.
The warburg impedance (initial resistance slope) measurement result is shown in the small box of FIG. In general, it is known that the more the initial resistance slope is, the faster the ions of the electrolyte are transferred from the pore structure. The initial slope of the second test sample subjected to the plasma discharge treatment for 30 minutes was the highest, and the initial slope of the fourth test sample subjected to the plasma discharge treatment for 60 minutes was the lowest.
5. Conclusion
In this experiment, an iron-carbon composite was prepared for the first time by an underwater plasma process as a method of bonding iron oxide to a carbon-based material, and this is aimed at applying it to an electrode of an electrochemical capacitor. From the experimental results, it was confirmed that spherical iron oxide nanoparticles having a size of about 5 to 10 nm were uniformly dispersed on the surface of the carbon particles as a whole. As the plasma discharge time increased, the amount of iron oxide particles bound to the carbon particles increased. When the amount of iron oxide particles bound to the carbon particles increases, the storage capacity is improved. However, when the amount of iron oxide particles is more than a certain amount (Fe 0.56 atomic%), the storage capacity is lowered. The iron - carbon composites with iron (Fe 0.19 ~ 0.33 atomic%) iron - bonded composites showed the lowest resistance and the highest slope of initial resistance.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various modifications and equivalent embodiments may be made by those skilled in the art. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.
10: reactor 20: power supply
30: electrode 40: cooling tank
50: circulation pump
Claims (8)
A second step of generating a plasma in the solution to form an iron-carbon composite in which iron oxide nanoparticles are bonded to the surface of carbon particles in water;
And a third step of separating the iron-carbon composite from the solution. The method for producing an iron-carbon composite material for an electrochemical capacitor electrode according to claim 1,
The electrode composition for an electrochemical capacitor according to claim 1, wherein the active material is the iron-carbon composite of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150024267A KR101743165B1 (en) | 2015-02-17 | 2015-02-17 | iron-carbon composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150024267A KR101743165B1 (en) | 2015-02-17 | 2015-02-17 | iron-carbon composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20160101796A true KR20160101796A (en) | 2016-08-26 |
KR101743165B1 KR101743165B1 (en) | 2017-06-16 |
Family
ID=56885802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020150024267A KR101743165B1 (en) | 2015-02-17 | 2015-02-17 | iron-carbon composite for electrode of electrochemical capacitor and manufacturing method thereof, electrode composition for electrochemical capacitor |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR101743165B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107625744A (en) * | 2017-09-05 | 2018-01-26 | 上海理工大学 | A kind of nuclear shell structure nano capsule and its preparation method and application |
WO2019112102A1 (en) * | 2017-12-07 | 2019-06-13 | 한국해양대학교 산학협력단 | Lithium-carbon composite having cavities formed therein, and method for producing same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140091482A (en) | 2013-01-09 | 2014-07-21 | 한양대학교 산학협력단 | Iron oxide carbon nano composite for negative active material of sodium rechargeable battery, manufacturing method thereof, and sodium rechargeable battery including the same |
-
2015
- 2015-02-17 KR KR1020150024267A patent/KR101743165B1/en active IP Right Grant
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140091482A (en) | 2013-01-09 | 2014-07-21 | 한양대학교 산학협력단 | Iron oxide carbon nano composite for negative active material of sodium rechargeable battery, manufacturing method thereof, and sodium rechargeable battery including the same |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107625744A (en) * | 2017-09-05 | 2018-01-26 | 上海理工大学 | A kind of nuclear shell structure nano capsule and its preparation method and application |
CN107625744B (en) * | 2017-09-05 | 2019-12-24 | 上海理工大学 | Core-shell structure nanocapsule and preparation method and application thereof |
WO2019112102A1 (en) * | 2017-12-07 | 2019-06-13 | 한국해양대학교 산학협력단 | Lithium-carbon composite having cavities formed therein, and method for producing same |
US11626592B2 (en) | 2017-12-07 | 2023-04-11 | Korea Maritime University Industry—Academic Cooperation Foundation | Lithium-carbon composite having cavities formed therein, and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
KR101743165B1 (en) | 2017-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Chidembo et al. | Globular reduced graphene oxide-metal oxide structures for energy storage applications | |
Zheng et al. | Hierarchical structures composed of MnCo 2 O 4@ MnO 2 core–shell nanowire arrays with enhanced supercapacitor properties | |
Raj et al. | Ultrasound assisted synthesis of Mn3O4 nanoparticles anchored graphene nanosheets for supercapacitor applications | |
Guan et al. | Cu 2 O templating strategy for the synthesis of octahedral Cu 2 O@ Mn (OH) 2 core–shell hierarchical structures with a superior performance supercapacitor | |
Wei et al. | Carbon quantum dots/Ni–Al layered double hydroxide composite for high-performance supercapacitors | |
Liu et al. | Ultrafine nickel–cobalt alloy nanoparticles incorporated into three-dimensional porous graphitic carbon as an electrode material for supercapacitors | |
Li et al. | Rapid in situ growth of β-Ni (OH) 2 nanosheet arrays on nickel foam as an integrated electrode for supercapacitors exhibiting high energy density | |
Fahimi et al. | Fabrication of ZnO@ C foam: A flexible free-standing electrode for energy storage devices | |
Kumar et al. | Ruthenium oxide nanostring clusters anchored Graphene oxide nanocomposites for high-performance supercapacitors application | |
Lai et al. | Dip-coating synthesis of rGO/α-Ni (OH) 2@ nickel foam with layer-by-layer structure for high performance binder-free supercapacitors | |
Jiang et al. | Optimized NiCo 2 O 4/rGO hybrid nanostructures on carbon fiber as an electrode for asymmetric supercapacitors | |
Maharsi et al. | Electrochemical properties of TiO x/rGO composite as an electrode for supercapacitors | |
KR101799639B1 (en) | Fabricating method for reduced graphene oxide composites and reduced graphene oxide composites fabricated by the method and supercapacitor having the reduced graphene oxide composites | |
Nilmoung et al. | The structural and electrochemical properties of CNF/MnFe2O4 composite nanostructures for supercapacitors | |
Parale et al. | Construction of hierarchical nickel cobalt sulfide@ manganese oxide nanoarrays@ nanosheets core‐shell electrodes for high‐performance electrochemical asymmetric supercapacitor | |
Goda et al. | Metal-organic framework (MOF) templated hierarchical Al-doped CoxP@ graphene composite: A promising solid-state asymmetric supercapacitor with PANI derived carbon nanorods | |
Chen et al. | Hybridizing Fe 3 O 4 nanocrystals with nitrogen-doped carbon nanowires for high-performance supercapacitors | |
Zhang et al. | ZnO nanocrystals as anode electrodes for lithium-ion batteries | |
Mijailović et al. | Core–shell carbon fiber@ Co1. 5Mn1. 5O4 mesoporous spinel electrode for high performance symmetrical supercapacitors | |
Rendale et al. | Hydrothermally synthesized aster flowers of MnCo2O4 for development of high-performance asymmetric coin cell supercapacitor | |
Sui et al. | Boosting the charge transfer efficiency of metal oxides/carbon nanotubes composites through interfaces control | |
Silambarasan et al. | Nitrogen-doped porous carbon coated on MnCo2O4 nanospheres as electrode materials for high-performance asymmetric supercapacitors | |
Nagaraju et al. | Facile one-step synthesized hierarchical Bi2O3/Bi12Mn12O44 composite as a long-term stable and high-performance electrode for hybrid supercapacitors | |
JP2009537434A (en) | CATALYST COMPOSITION COMPRISING ACTIVATED CARBON AND CARBON NANOTUBE, PROCESS FOR PRODUCING THE SAME, ELECTRODE CONTAINING CATALYTIC COMPOUND, AND SUPERCONDUCTOR | |
Mohanty et al. | Iron-cobalt-nickel-copper-zinc (FeCoNiCuZn) high entropy alloy as positive electrode for high specific capacitance supercapacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
AMND | Amendment | ||
E902 | Notification of reason for refusal | ||
AMND | Amendment | ||
E90F | Notification of reason for final refusal | ||
AMND | Amendment | ||
E601 | Decision to refuse application | ||
AMND | Amendment | ||
X701 | Decision to grant (after re-examination) | ||
GRNT | Written decision to grant |