WO2011099677A1 - 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 - Google Patents
금속옥사이드가 함유된 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 Download PDFInfo
- Publication number
- WO2011099677A1 WO2011099677A1 PCT/KR2010/003063 KR2010003063W WO2011099677A1 WO 2011099677 A1 WO2011099677 A1 WO 2011099677A1 KR 2010003063 W KR2010003063 W KR 2010003063W WO 2011099677 A1 WO2011099677 A1 WO 2011099677A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- porous carbon
- carbon nanofibers
- metal oxide
- alkoxide
- metal
- Prior art date
Links
- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 112
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 238000001523 electrospinning Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims description 59
- 238000003763 carbonization Methods 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 150000004703 alkoxides Chemical class 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 24
- 230000004913 activation Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000006641 stabilisation Effects 0.000 claims description 10
- 238000011105 stabilization Methods 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 230000001965 increasing effect Effects 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 15
- 239000004917 carbon fiber Substances 0.000 abstract description 14
- 238000009987 spinning Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 34
- 238000001994 activation Methods 0.000 description 31
- 239000003990 capacitor Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 24
- 229920002239 polyacrylonitrile Polymers 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 felt Substances 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BXVSAYBZSGIURM-UHFFFAOYSA-N 2-phenoxy-4h-1,3,2$l^{5}-benzodioxaphosphinine 2-oxide Chemical compound O1CC2=CC=CC=C2OP1(=O)OC1=CC=CC=C1 BXVSAYBZSGIURM-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940085805 fiberall Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical class CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
- D01D5/247—Discontinuous hollow structure or microporous structure
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
Definitions
- the present invention relates to carbon nanofibers, and more particularly, porous metal containing metal oxides having a high specific surface area by changing the composition of a spinning solution used when producing carbon fibers through electrospinning capable of producing nano-scale fibers. It relates to a manufacturing method capable of producing carbon nanofibers, porous carbon nanofibers containing a metal oxide prepared by the above method, and a carbon nanofiber application product comprising the same.
- the existing activated carbon has a high specific surface area, but since the pore structure is very complicated, it is difficult to reproduce the adsorption and desorption rates.
- micropores protrude to the outside, but because the diameter is micro size, application to an energy storage medium is difficult due to the limitation of the volume and the reaction rate.
- carbon nanofibers have a more uniform pore distribution than activated carbon, and have a high specific surface area and can be manufactured in paper, felt, and non-woven fabrics, thereby making it possible to make high-performance electrode active materials.
- carbon nanofibers having a nanographite structure have a relatively large specific surface area, a shallow depth of pores, and micropores having a size of 1-2 nm, thus exhibiting rapid adsorption and desorption rate, uniform structure, and pore size. Because of its narrow distribution, it shows fast selective adsorption and desorption even with low energy changes, and thus has excellent energy storage characteristics.
- the chemical activation process requires a chemical activation process in which potassium hydroxide (KOH) or sodium hydroxide (NaOH) is mixed and heat treated at a high temperature after carbonization at a high temperature.
- KOH potassium hydroxide
- NaOH sodium hydroxide
- the chemical activation method using such salts is difficult to continuously process and mass production because the carbon nanofibers and salts are evenly mixed and heat treated, and there is a problem that a process of removing the mixed salts after activation is required.
- PAN-based carbon nanofibers produce carbon nanofibers and activated carbon fibers through electrospinning, stabilization, carbonization, and activation of PAN solutions, but due to the low specific surface area and electrical conductivity of PAN-based carbon fibers There is a limit to the performance expression of electrodes for supercapacitors.
- the pitch-based carbon nanofibers prepared by the above method have a disadvantage in that the diameter of the fibers is very large due to low spinning.
- An electric double layer capacitor is a device using electric charges accumulated in an electric double layer generated between a solid electrode and an electrolyte, and attracts attention from various fields in terms of use and application.
- capacitors have lower energy densities than batteries, but have excellent characteristics in terms of power density that exerts momentary power, and are expected to be applied to various fields due to almost semi-permanent lifespan. Therefore, in the case of electrochemical capacitors, research and development are being actively conducted to improve energy and power density simultaneously.
- the performance of supercapacitors in energy storage depends greatly on the materials used and the manufacturing technology, it is very important to manufacture ultra-high capacity and high-output capacitors in parallel with the development of new materials.
- Electrolytes used in electric double layer capacitors are largely classified into water-soluble electrolytes, organic solvent electrolytes and solid electrolytes. Since the use potential difference of the EDLC unit cell is determined according to the electrolyte, the selection of the electrolyte is very important. In general, the operating voltage of the aqueous electric double layer capacitor is lower than 1.0 V and has the disadvantage that the amount of energy stored is also limited. When using an organic solvent electrolyte to compensate for this disadvantage, the capacitor can be used at high cell voltage can store a lot of energy.
- a capacitor having a high energy density can be obtained in proportion to the square of the voltage used. It can be used in a wide range of available temperature range of -25 ⁇ 85 °C, and has the advantage of high pressure resistance and miniaturization.
- activated carbon-based carbon material having a large specific surface area, electrochemically stable and high conductivity is mainly used.
- the oxidative property is mainly based on coal, petroleum pitch, phenol resin, wood-based and carbon precursor precursor polymers.
- Non-surface oxidizing activated carbon or activated carbon fibers are used for quality by activating at a temperature below 1200 ° C. using gas or inorganic salts.
- this graphitized carbon raw material is used for heat treatment with alkali (KOH, NaOH and K 2 CO 3 ) at a high temperature of 700 to 900 ° C., and the capacity per electrode volume is about 30 to 50 F / at 3.5 V. mL is obtained.
- alkali KOH, NaOH and K 2 CO 3
- activated carbon prepared by the alkali activation method has problems of heat treatment and corrosion of containers, deterioration of characteristics due to charge and discharge cycles, and high manufacturing cost.
- the activated carbon fibers currently produced and sold are mainly manufactured by fiberizing precursors by expensive melt-spinning or melt-blown spinning apparatus, followed by oxidation stabilization, carbonization or activation.
- this method has a limitation in effectively enhancing the specific surface area to volume due to the complicated process and large fiber diameter.
- the fiber when used as an electrode active material, the fiber must be crushed to add a binder or a conductive material, and in the case of a woven fabric, the fiber diameter of the manufactured fiber is relatively large and the electrode density is low, so that fast charge and discharge or high output characteristics can be obtained. It had a downside.
- the present inventors have completed the present invention by developing a carbon nanofiber manufacturing method having a high specific surface area as a result of trying to solve all the disadvantages and problems of the prior art as described above.
- an object of the present invention is to prepare a carbon nanofiber having a high porosity including a metal oxide through a carbonization or activation process by including a metal alkoxide in the carbon fiber precursor solution, the specific surface area and electrical conductivity It is to provide an improved product comprising the porous carbon nanofibers and the carbon nanofibers are improved.
- Another object of the present invention is to produce a porous carbon nanofibers having an ultra-fine and high porous fibrous web only by heat treatment process without chemical activation process, porous carbon nanofibers that can shorten the time and cost of the carbon nanofibers and its application process It is to provide a manufacturing method, carbon nanofibers produced by the method and an application product including the carbon nanofibers.
- Another object of the present invention is to introduce a metal alkoxide into the carbon crystal to improve the energy density by increasing the dielectric constant between the electrolyte and the electrode surface, as well as fast selective adsorption and desorption at low energy changes energy storage characteristics It is to provide a porous carbon nanofiber manufacturing method containing a metal oxide that can be very excellent to provide a high performance, the carbon nanofibers produced by the method and the application product comprising the carbon nanofibers.
- Still another object of the present invention is to provide a high capacity capacitor having excellent electrochemical characteristics, charge and discharge characteristics, power and power density by applying carbon nanofibers having a porous fiber web manufactured through a carbonization process to an aqueous electrolyte.
- Still another object of the present invention is to apply a porous carbon nanofiber prepared to facilitate the access of the organic solvent electrolyte while remaining the metal oxide through a physical activation process using a gas containing water vapor to the electrochemical characteristics, capacitor
- a porous carbon nanofiber prepared to facilitate the access of the organic solvent electrolyte while remaining the metal oxide through a physical activation process using a gas containing water vapor to the electrochemical characteristics, capacitor
- the present invention comprises the steps of preparing a carbon nanofiber precursor solution containing a metal alkoxide [M (OR) n ]; Electrospinning the precursor solution to obtain precursor spun fiber; Oxidatively stabilizing the precursor spun fiber to obtain a flame resistant fiber; And carbonizing the flame resistant fiber to obtain porous carbon nanofibers.
- the oxidative stabilization is to supply the compressed air at a flow rate of 5 to 20 mL per minute using a hot air circulation ,, at least 30 minutes at 200 ⁇ 300 °C at a temperature increase rate of 1 °C per minute Is carried out by holding.
- the physical activation is carried out by raising the temperature to 700 ⁇ 850 °C at a rate of 5 °C per minute and then maintained for 30 minutes or more in an inert gas 150-250 mL / min and water vapor 5-15 vol% atmosphere.
- one or more of the concentration of the metal alkoxide, the carbonization temperature, the activation temperature, the time can be controlled by controlling one or more of the diameter of the carbon nanofibers and the porosity of the surface.
- the porous carbon nanofibers prepared by the method of claim 2 has a diameter of 100 to 250 nm, specific surface area of 1000 to 1700 m 2 / g, fine and mesopores having a size of 2 nm or more Has.
- the present invention also provides an adsorbent comprising a porous carbon nanofiber containing the metal oxide of claim 9.
- the present invention also provides an electromagnetic shielding material comprising the porous carbon nanofiber of claim 9.
- the present invention can prepare carbon nanofibers having high porosity by using a metal alkoxide sol-gel method without chemical activation process by including the metal alkoxide in the carbon fiber precursor solution, the carbon produced by the method of the present invention Nanofibers have a large specific surface area and improve electrical conductivity.
- the present invention by manufacturing carbon nanofibers having a super-fine and highly porous fiber web through carbonization or physical activation, it is possible to reduce the time and cost of the manufacturing process of the active / carbon nanofibers and their applications.
- the present invention controls the specific surface area and pore size distribution in the state containing the metal oxide in the carbon nanofibers by controlling one or more of the metal alkoxide concentration, heat treatment temperature, activation process to achieve the desired characteristics. Easy to adjust to have
- the present invention not only improves the energy density by increasing the dielectric constant between the electrolyte and the electrode surface by introducing a metal alkoxide into the carbon crystal, but also shows rapid selective adsorption and desorption even at low energy changes, and thus has excellent energy storage characteristics. Can provide high performance.
- the present invention is applied to the organic solvent electrolyte porous carbon nanofibers prepared for easy access of the organic solvent electrolyte while remaining the metal oxide through a physical activation process using a gas containing water vapor, electrochemical properties, capacitor capacity
- a gas containing water vapor, electrochemical properties, capacitor capacity By significantly improving the capacity, power density and energy density, it is possible to provide an ultracapacitor, an electrode material that can be finally applied to a power storage power source.
- Figure 1 is a schematic flow diagram showing a method of manufacturing a porous carbon nanofiber of the present invention and the application of a high capacity supercapacitor electrode using the same
- Example 3 is a thermal analysis graph of the precursor spun fiber obtained in Example 1 of the present invention.
- Figure 4 is a result of differential thermal analysis (Differential Scanning Calorimetry, DSC) by maintaining the temperature increase rate of 10 °C / min precursor precursor fiber and chloride fiber obtained in Example 1 of the present invention,
- Example 5 is a high scanning electron microscope (SEM) photograph of carbon nanofibers 1 obtained at a carbonization temperature of 800 ° C. in Example 2 of the present invention
- Example 6 is a scanning electron microscope (SEM) photograph of the porous carbon nanofibers 2 obtained at a carbonization temperature of 900 °C in Example 3 of the present invention
- Example 7 is a scanning electron microscope (SEM) photograph of the porous carbon nanofibers 3 obtained at a carbonization temperature of 1000 °C in Example 4 of the present invention
- Example 9 is a high magnification scanning electron microscope (SEM) photograph of the porous carbon nanofibers 1 obtained at a carbonization temperature of 800 ° C. in Example 2 of the present invention.
- Example 10 is a high magnification scanning electron microscope (SEM) photograph of porous carbon nanofibers 2 obtained at 900 ° C. in a carbonization temperature in Example 3 of the present invention
- Example 11 is a high magnification scanning electron microscope (SEM) photograph of porous carbon nanofibers 3 obtained at a carbonization temperature of 1000 ° C. in Example 4 of the present invention
- FIG. 12 is a cyclic voltamogram (CV) graph of an electrolyte 6M KOH aqueous solution according to carbonization temperature of a capacitor including porous carbon nanofibers 4 to 6 obtained in Examples 5 to 7 of the present invention;
- FIG. 13 is a graph showing the specific capacitance according to the carbonization temperature of the porous carbon nanofibers in the voltage range 0-1V of the capacitor including porous carbon nanofibers 4 to 6 obtained in Examples 5 to 76 of the present invention;
- Example 14 is a graph showing the result of separating the peak of the carbon element (C) by the porous carbon nanofibers 4 obtained in Example 5 of the present invention by X-ray photoelectron spectroscopy (XPS),
- Example 15 is a graph showing the results of separating oxygen peaks (O peaks) from the porous carbon nanofibers 4 obtained in Example 5 of the present invention by X-ray photoelectron spectroscopy (XPS);
- FIG. 16 is a graph showing the results of separating peaks of nitrogen element (N) from porous carbon nanofibers 4 obtained in Example 5 of the present invention by X-ray photoelectron spectroscopy (XPS);
- FIG. 18 is a graph showing specific capacitance according to the TEOS weight ratio of the porous carbon nanofibers in the voltage range 0-2.7 V of the capacitor including the porous carbon nanofibers 7 and 8 obtained in Examples 8 and 9 of the present invention.
- Physically activating the flame resistant fiber has two manufacturing methods comprising the step of obtaining porous carbon nanofibers.
- PAN polyacrylonitrile
- MA methylacrylate
- the metal alkoxide contained in the carbon fiber precursor solution is preferably 1 to 30% by weight relative to the carbon fiber precursor material
- the carbon fiber precursor solution is 70 to 99: 30 to 1% by weight of the carbon nanofiber precursor and the metal alkoxide constituting the solute. It is preferable to be prepared to include.
- the water vapor used for physical activation further promotes the hydrolysis and condensation reaction of the metal alkoxide, so that water and alcohol which are additionally released during the production of metal oxides accelerate the sol-gel reaction rate due to the LeChatlie law. This is because it creates expanded pores as well as more micropores.
- the prepared carbon nanofiber precursor solution was prepared using a non-woven web made of nanofibers using an electrospinning method to obtain a precursor spun fiber.
- the electrospinning apparatus applies an applied voltage of 25 kV to the nozzle and the collector, respectively, and the distance between the spinneret and the collector is about 20 cm, but can be varied as necessary.
- the flame resistant fiber obtained by oxidation stabilization was heated to 800 ° C. at an elevated temperature rate of 5 ° C. per minute in an inert atmosphere, and carbonized while maintaining for 50 minutes to prepare porous carbon nanofibers 1.
- the flame resistant fiber obtained in Example 1 was heated to 800 ° C. at a rate of 5 ° C. per minute, and then maintained for 60 minutes in an atmosphere of 200 mL / min of inert gas and 10 vol% of water vapor to prepare porous carbon nanofibers 7.
- porous carbon nanofibers 4 to 6 prepared in Examples 5 to 7 were cut to an appropriate size, placed on a nickel foam current collector, and a Celgard (polypropylene) separator was inserted between the positive electrode and the negative electrode, and then 6M.
- Supercapacitors 1 to 3 were prepared by impregnating KOH aqueous electrolyte solution.
- Comparative carbon nanofibers were prepared in the same manner as in Example 3 except that only the PAN was included without the metal alkoxide as the solute.
- thermogravimetric analysis (TGA) graph of FIG. 3 the main weight change is shown at 280 ⁇ 330 °C, the weight decreases slowly over 330 °C, it can be seen that shows the ceramic residual amount of 28% at 1000 °C .
- DSC differential scanning calorimetry
- Differential thermal analysis was carried out by maintaining the temperature increase rate of 10 ° C./min under the nitrogen stream of the precursor spun fiber and the flame resistant fiber obtained in Example 1, and the DSC graph is shown in FIG. 4.
- the precursor spun fiber showed a very strong exothermic peak near 287 ° C, which is the effect of the cyclization reaction of nitrile group during oxidative stabilization process.
- the cyclization or crosslinking reaction of the nitrile group remaining in the precursor fiber is further progressed, and exothermic peaks are observed in a wide range of 320 to 350 ° C.
- the flame resistant fiber shows a strong endothermic peak by evaporation of water or alcohol at around 100 ° C.
- porous carbon nanofibers 1 to 3 obtained in Examples 2 to 4 were observed with a scanning electron microscope (SEM), and the photographs observed are shown in FIGS. 5 to 7. 5 to 7 it can be observed that the carbon nanofibers are produced very well without the production of particles or beads when the carbon nanofibers are produced by the manufacturing method of the present invention, and the diameter decreases as the carbonization temperature increases. there was.
- SEM scanning electron microscope
- the porous carbon nanofibers 3 obtained in Example 4 were analyzed with an energy dispersive X-ray spectrometer (EDX), and the results are shown in FIG. 8.
- EDX energy dispersive X-ray spectrometer
- carbon nanofibers using tetraethyl orthosilicate (Si (OEt) 4 , TEOS) in metal alkoxides can identify elements of C, O and Si.
- the BET specific surface area, pore volume and average pore size of the porous carbon nanofibers 1 to 3 obtained in Examples 2 to 4 and the comparative carbon nanofibers obtained in the comparative example were measured and shown in Table 2.
- the BET specific surface area, pore volume, and average pore size of the porous carbon nanofibers 1 to 3 obtained in Examples 2 to 4 and the porous carbon nanofibers 7 and 8 obtained in Examples 7 and 8 were measured and shown in Table 3. It was.
- Cyclic voltamogram was measured in electrodes 1 to 3 of the supercapacitors prepared in Examples 5 to 7, that is, 6M KOH aqueous solution of porous carbon nanofibers 4 to 6, and the measurement results are plotted. It is shown in 12.
- the electrode was measured in the voltage range 0 ⁇ 1.0 V, scanning speed: 25 mV / s.
- the carbonization temperature decreased (1000 ⁇ 800 °C)
- the specific surface area increased, but the capacitance decreased.
- the cyclic voltammogram shows that a quasi-rectangular shape appears at the end of 1 V, not a typical EDLC type rectangle.
- the specific capacitance of the carbon nanofibers according to the carbonization temperature was measured using the supercapacitor electrodes 1 to 3, that is, the porous carbon nanofibers 4 to 6 prepared in Example 7, and the results are shown in FIG.
- FIG. 13 shows that the specific capacity of the carbon nanofibers according to the carbonization temperature shows a similar tendency to the CV measurement result shown in FIG. 12, which shows a high specific capacity of 161.39 F / g at a low carbonization temperature of 800 ° C.
- FIG. This is because carbon nanofibers carbonized at a low temperature of 800 ° C contain a lot of hetero atoms such as silicon (Si), oxygen (O), and nitrogen (N).
- the Ragon graph showing the result of measuring the output and power density of the carbon nanofiber capacitors according to the carbonization temperature using the supercapacitor electrodes 4 to 6 obtained in Examples 5 to 7 is shown in FIG. 17. It can be seen from FIG. 17 that the KOH 6M aqueous solution electrolyte has a high energy density of 22 Wh / kg and a high power density of 100 kW / kg and a high power density.
- a graph of Ragon is shown in FIG. 19. 19 shows high energy density of 90-35 Wh / kg and power density of 2-100 kW / kg in 1.5 M organic solvent electrolyte solution in which tetraethylammonium tetraflouoroborate was dissolved in actonitrile.
- the metal alkoxide is introduced into the carbon crystal in the case of the porous carbon nanofibers produced by carbonization in the manufacturing method of the present invention, and has a diameter in the range of 100 to 300 nm, and 700 to 1500 It has a specific surface area in the range of m 2 / g and shows that it has micropores having a size of 1 to 3 nm containing metal oxides, thereby increasing the dielectric constant between the electrolyte and the electrode surface or inducing a Faraday reaction. It is thought that the energy density can be improved.
- carbon nanofibers manufactured at low carbonization temperature exhibits rapid selective adsorption and desorption even at low potential changes, and thus have excellent energy storage characteristics, thus reducing carbonization process costs, and high conductivity, high specific surface area, It can be seen that the micropores of various sizes and the like can be provided.
- the experimental results of the porous carbon nanofibers produced by physical activation in the production method of the present invention has a diameter in the range of 100 ⁇ 250 nm, has a specific surface area of 1300 ⁇ 1700 m 2 / g, 2 It has been shown to have both micropores and mesopores having a size of more than nm, thereby accelerating the sol-gel reaction by water vapor in the physical activation process to develop more specific surface area containing metal oxides and micropores and mesopores. I can see that there is.
- the water vapor used for physical activation further promotes the hydrolysis and condensation reaction of the metal alkoxide, so that water and alcohol which are additionally released during the production of metal oxides accelerate the sol-gel reaction rate due to the LeChatlie law. This is because it creates expanded pores as well as more micropores.
- the porous carbon nanofibers produced through carbonization or physical activation of the present invention are all excellent in electrochemical properties, capacitor capacity, power density and energy density, but especially physical It can be seen that the porous carbon nanofibers prepared through activation enable the production of ultra-high capacity capacitors having a higher energy density than the porous carbon nanofibers produced by carbonization.
- the porous carbon nanofiber of the present invention is easy to access the pollutant because the pores are protruded to the outside, and excellent in its application as a filter material, an electrode material for a supercapacitor using an electric double layer, an electrode material for a secondary battery, an electromagnetic wave It is also very useful as a shielding material and a highly conductive material.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
탄화온도 (℃) | 평균직경 (nm) |
800 | 200-300 |
900 | 170-260 |
1000 | 150-175 |
탄화온도 | BET surface area (m2/g) | Pore volume(cm3/g) | Average pore size (Å) |
다공성탄소나노섬유1800℃ 탄화 | 732.20 | 0.287 | 15.7 |
다공성탄소나노섬유2900℃ 탄화 | 950.78 | 0.376 | 16.2 |
다공성탄소나노섬유31000℃ 탄화 | 1300.25 | 0.782 | 18.0 |
비교탄소나노섬유 1000 ℃ 탄화 | 336.75 | 0.136 | 15.2 |
T-polt surface area (m2/g) | Total pore volume (cm3/g) | Mesopore volume fraction(%) | Micropore volume fraction(%) | Average pore size (Å) | |
다공성탄소나노섬유1 | 986.3 | 0.374 | 20 | 80 | 15.73 |
다공성탄소나노섬유2 | 1045.6 | 0.404 | 22 | 78 | 16.25 |
다공성탄소나노섬유3 | 1200.2 | 0.536 | 28 | 72 | 18.08 |
다공성탄소 나노섬유7 | 1386.9 | 0.571 | 35 | 65 | 19.65 |
다공성탄소 나노섬유8 | 1483.3 | 0.604 | 40 | 60 | 20.18 |
Claims (17)
- 금속알콕사이드[M(OR)n]를 포함하는 탄소나노섬유 전구체용액을 준비하는 단계;상기 전구체용액을 전기방사하여 전구체방사섬유를 얻는 단계;상기 전구체방사섬유를 산화안정화하여 내염화섬유를 얻는 단계; 및상기 내염화섬유를 탄화하여 다공성 탄소나노섬유를 얻는 단계;를 포함하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 금속알콕사이드[M(OR)n]를 포함하는 탄소나노섬유 전구체용액을 준비하는 단계;상기 전구체용액을 전기방사하여 전구체방사섬유를 얻는 단계;상기 전구체방사섬유를 산화안정화하여 내염화섬유를 얻는 단계; 및상기 내염화섬유를 물리적 활성화하여 다공성 탄소나노섬유를 얻는 단계;를 포함하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항 또는 제 2 항에 있어서,상기 전구체용액은 상기 탄소나노섬유전구체와 금속알콕사이드를 70~99 : 30~1 중량%로 포함하도록 준비되는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항 또는 제 2 항에 있어서,상기 금속알콕사이드는 Si-알콕사이드, Ti-알콕사이드, Al-알콕사이드, Zn-알콕사이드 중 어느 하나 이상인 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항 또는 제 2 항에 있어서,상기 산화안정화는 상기 전구체방사섬유를 열풍순환爐를 사용하여 압축공기를 분당 5~20 mL의 유속으로 공급하고, 분당 1 ℃의 승온 속도로 200~300 ℃에서 30분 이상 유지하여 수행되는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항에 있어서,상기 탄화는 불활성 분위기 또는 진공상태에서 분당 5 ℃의 승온 속도로 700 ~ 1500 ℃까지 승온 한 후 30분 이상 유지하여 수행되는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 2 항에 있어서,상기 물리적 활성화는 분당 5 ℃의 승온 속도로 700 ~ 850 ℃까지 승온 한 후 불활성 기체 150-250 mL/min와 수증기 5-15 vol% 분위기에서 30분 이상 유지하여 수행되는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항 또는 제 2 항에 있어서,상기 금속알콕사이드의 농도, 상기 탄화온도, 상기 활성화 온도, 시간 중 하나 이상을 제어하여 상기 탄소나노섬유의 직경 및 표면의 다공성 중 하나 이상을 제어할 수 있는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법.
- 제 1 항 또는 제 2 항의 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법으로 제조된 것을 특징으로 하는 금속옥사이드가 함유된 다공성 탄소나노섬유.
- 제 9 항에 있어서,상기 제1항의 방법으로 제조된 다공성탄소나노섬유는 직경이 100 ~ 300 nm이고, 비표면적은 700 ~ 1300 m2/g이며, 1 ~ 3 nm의 크기를 갖는 미세공을 갖는 것을 특징으로 하는 금속옥사이드가 함유된 다공성탄소나노섬유.
- 제 9 항에 있어서,상기 제2항의 방법으로 제조된 다공성탄소나노섬유는 직경이 100 ~ 250 nm이고, 비표면적은 1000 ~ 1700 m2/g이며, 2 nm 이상의 크기를 갖는 미세공 및 중기공을 갖는 것을 특징으로 하는 다공성 금속옥사이드가 함유된 탄소나노섬유.
- 제 10 항의 금속옥사이드가 함유된 다공성탄소나노섬유로 구성된 전극; 및수용성 전해질;을 포함하는 고용량 수퍼캐패시터.
- 제 12 항에 있어서,상기 금속옥사이드가 함유된 다공성 탄소나노섬유 표면에 탄화를 통해 생성된 관능기들이 의사캐패시터 전극의 비축전용량에 참여하여 의사캐퍼시터의 용량이 첨가된 것을 특징으로 하는 고용량 수퍼캐패시터.
- 제 11 항의 금속옥사이드가 함유된 다공성탄소나노섬유로 구성된 전극; 및유기용매 전해질;을 포함하는 초고용량 수퍼캐패시터.
- 제 14 항에 있어서,상기 금속옥사이드가 함유된 다공성 탄소나노섬유 표면의 기공들은 활성화를 통해 솔-젤 반응이 촉진되어 에너지 밀도가 큰 것을 특징으로 하는 초고용량 수퍼캐패시터.
- 제 9항의 금속옥사이드가 함유된 다공성탄소나노섬유를 포함하는 것을 특징으로 하는 흡착재.
- 제 9 항의 다공성탄소나노섬유를 포함하는 것을 특징으로 하는 전자파차폐재.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/578,268 US9546091B2 (en) | 2010-02-11 | 2010-05-14 | Method for preparing porous carbon nanofibers containing a metal oxide, porous carbon nanofibers prepared using the method, and carbon nanofiber products including same |
CN2010800636695A CN102762784A (zh) | 2010-02-11 | 2010-05-14 | 含金属氧化物的多孔碳纳米纤维的制备方法、使用该方法制备的多孔碳纳米纤维及包含它的碳纳米纤维产品 |
EP10845848.0A EP2535445B1 (en) | 2010-02-11 | 2010-05-14 | Method for preparing porous carbon nanofibers containing a metal alkoxide or a silicon alkoxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020100012830A KR100995154B1 (ko) | 2010-02-11 | 2010-02-11 | 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 |
KR10-2010-0012830 | 2010-02-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011099677A1 true WO2011099677A1 (ko) | 2011-08-18 |
Family
ID=43409866
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2010/003063 WO2011099677A1 (ko) | 2010-02-11 | 2010-05-14 | 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9546091B2 (ko) |
EP (1) | EP2535445B1 (ko) |
KR (1) | KR100995154B1 (ko) |
CN (1) | CN102762784A (ko) |
WO (1) | WO2011099677A1 (ko) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5841936B2 (ja) | 2009-06-30 | 2016-01-13 | エルジー・ケム・リミテッド | 多孔性コーティング層を備える電極の製造方法、その方法によって形成された電極、及びそれを備える電気化学素子 |
US9102570B2 (en) | 2011-04-22 | 2015-08-11 | Cornell University | Process of making metal and ceramic nanofibers |
JP6266519B2 (ja) * | 2011-08-30 | 2018-01-24 | コーネル・ユニバーシティーCornell University | 金属およびセラミックのナノファイバー |
KR101348202B1 (ko) | 2011-11-30 | 2014-01-16 | 전남대학교산학협력단 | 금속산화물-탄소입자-탄소나노섬유복합체, 상기 복합체 제조방법, 및 상기 복합체를 포함하는 탄소섬유응용제품 |
KR101418864B1 (ko) * | 2012-09-11 | 2014-07-17 | 인하대학교 산학협력단 | 실크 단백질을 이용하여 만든 탄소나노플레이트 및 그 제조방법 |
US9816206B2 (en) | 2012-09-17 | 2017-11-14 | Cornell University | Carbonaceous metal/ceramic nanofibers |
KR101544538B1 (ko) * | 2012-10-23 | 2015-08-17 | 전남대학교산학협력단 | 단일 배향성 고밀도 탄소나노섬유펠트, 상기 탄소나노섬유펠트 제조방법 및 상기 탄소나노섬유펠트를 포함하는 탄소나노섬유펠트 응용제품 |
KR101510311B1 (ko) * | 2013-05-14 | 2015-04-10 | 한국원자력연구원 | 방사선조사에 의한 금속 나노입자가 함유된 탄소소재의 제조방법 및 이에 따라 제조되는 금속 나노입자가 함유된 탄소소재 |
CN103628182B (zh) * | 2013-11-29 | 2015-12-09 | 东南大学 | 一种碳基纳米纤维的制备方法 |
CN105734831B (zh) * | 2014-12-10 | 2019-01-25 | 中国科学院大连化学物理研究所 | 一种纳米碳纤维毡及其制备和在全钒液流电池中的应用 |
EP3254321A4 (en) * | 2015-02-04 | 2018-07-18 | Axium IP, LLC | Silicon-carbon nanostructured composites |
US20170050888A1 (en) * | 2015-08-19 | 2017-02-23 | Cal Poly Pomona Foundation Inc. | Production of Ceramic Metal Oxide Membranes by Means of Reactive Electrospinning |
CN106763335A (zh) * | 2016-12-28 | 2017-05-31 | 山东正凯机械科技有限公司 | 一种轻质化的改性碳纤维基刹车盘的制备方法 |
US11915871B2 (en) * | 2017-03-30 | 2024-02-27 | The University Of North Carolina At Greensboro | Separator-free energy storage devices and methods |
US10584072B2 (en) | 2017-05-17 | 2020-03-10 | Eden Innovations Ltd. | Methods and systems for making nanocarbon particle admixtures and concrete |
CN108396408A (zh) * | 2018-01-30 | 2018-08-14 | 东莞市联洲知识产权运营管理有限公司 | 一种氮掺杂的芳纶基增强多级孔洞碳纤维的制备方法 |
US11180870B2 (en) * | 2018-08-17 | 2021-11-23 | Cence Inc. | Carbon nanofiber and method of manufacture |
WO2020081167A2 (en) * | 2018-09-06 | 2020-04-23 | Virginia Tech Intellectual Properties Inc. | Porous carbon fiber electrodes, methods of making thereof, and uses thereof |
SG10202007819XA (en) | 2019-08-15 | 2021-03-30 | Agency Science Tech & Res | Free-standing porous carbon fibrous mats and applications thereof |
KR20210077391A (ko) | 2019-12-17 | 2021-06-25 | 경남과학기술대학교 산학협력단 | 연성 나노 다공성 탄소 직물 및 그 제조 방법, 이것을 포함하는 흡착제 |
KR102264667B1 (ko) * | 2020-02-10 | 2021-06-14 | 대구대학교 산학협력단 | 금속산화물/탄소나노섬유 복합체 제조방법, 상기 방법으로 제조된 금속산화물/탄소나노섬유 복합체 및 상기 복합체를 포함하는 탄소섬유응용제품 |
CN113652648B (zh) * | 2021-08-16 | 2023-03-28 | 武汉纺织大学 | 一种金属材料在碳化过程中与碳纤维网凝华复合的方法 |
CN113930866A (zh) * | 2021-10-13 | 2022-01-14 | 广州航海学院 | 一种胶囊结构的超级电容器电极材料及其制备方法和应用 |
CN114420464A (zh) * | 2021-12-04 | 2022-04-29 | 山东阳谷华泰化工股份有限公司 | 一种生物酶扩孔碳纳米纤维电极材料的新方法 |
CN114232215B (zh) * | 2021-12-20 | 2022-11-29 | 西安工程大学 | 一种具有三维空腔结构的沥青基碳纳米纤维多级无纺布的制备方法及应用 |
CN114575157B (zh) * | 2022-02-23 | 2022-11-15 | 中国科学院宁波材料技术与工程研究所 | 一种强吸水多孔导电碳纤维棒及其制备方法与应用 |
CN114974933A (zh) * | 2022-06-10 | 2022-08-30 | 广东石油化工学院 | 一种超级电容器用剑麻纤维碳纸的制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20020008227A (ko) | 2002-01-03 | 2002-01-29 | 양갑승 | 정전 방사에 의한 카본나노파이버의 제조와 이의전기이중층 캐퍼시터용 전극 제조 |
KR20030002759A (ko) | 2001-06-29 | 2003-01-09 | 주식회사 하이닉스반도체 | 반도체 소자의 트랜지스터 제조 방법 |
KR100605006B1 (ko) * | 2005-01-18 | 2006-07-28 | (주) 아모센스 | 전기방사법으로 제조한 나노섬유의 탄소화에 의한 나노세공 분포를 갖는 활성탄소섬유의 제조방법 |
KR100675923B1 (ko) * | 2005-12-01 | 2007-01-30 | 전남대학교산학협력단 | 금속산화물 복합 나노 활성탄소섬유와 이를 이용한전기이중층 슈퍼캐퍼시터용 전극 및 그 제조 방법 |
KR100701627B1 (ko) * | 2005-12-22 | 2007-03-29 | 한국생산기술연구원 | 금속산화물 함유 나노활성탄소섬유의 제조방법 및 그로부터수득되는 나노활성탄소섬유를 이용한 슈퍼 캐패시터용전극 |
US20080207798A1 (en) * | 2007-02-27 | 2008-08-28 | Ppg Industries Ohio, Inc. | Organic-inorganic electrospun fibers |
KR20090051793A (ko) * | 2007-11-20 | 2009-05-25 | 재단법인대구경북과학기술원 | 금속산화물이 함유된 복합나노섬유 제조방법 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2003272887A1 (en) * | 2002-09-30 | 2004-04-23 | Teijin Limited | Process and composition for the production of carbon fiber and mats |
JPWO2005028719A1 (ja) | 2003-09-19 | 2006-11-30 | 帝人株式会社 | 繊維状活性炭およびこれよりなる不織布 |
EA200800196A1 (ru) * | 2005-07-01 | 2008-06-30 | Синвеншен Аг | Способ изготовления пористого композиционного материала |
US8313723B2 (en) * | 2005-08-25 | 2012-11-20 | Nanocarbons Llc | Activated carbon fibers, methods of their preparation, and devices comprising activated carbon fibers |
EP1937753A1 (en) * | 2005-10-18 | 2008-07-02 | Cinvention Ag | Thermoset particles and methods for production thereof |
PT2241598E (pt) * | 2007-12-19 | 2012-10-16 | Toray Industries | Dispersão contendo polímero resistente ao fogo, fibra resistente ao fogo e fibra de carbono |
CN101250770B (zh) * | 2008-03-11 | 2010-07-21 | 东华大学 | 一种碳纳米管增强的聚丙烯腈基碳纤维的制备方法 |
KR20090121143A (ko) | 2008-05-21 | 2009-11-25 | 주식회사 에이엠오 | 전기 방사를 이용하여 제조된 초고용량 커패시터용 전극 및그의 제조방법 |
US7910082B2 (en) * | 2008-08-13 | 2011-03-22 | Corning Incorporated | Synthesis of ordered mesoporous carbon-silicon nanocomposites |
-
2010
- 2010-02-11 KR KR1020100012830A patent/KR100995154B1/ko active IP Right Grant
- 2010-05-14 CN CN2010800636695A patent/CN102762784A/zh active Pending
- 2010-05-14 US US13/578,268 patent/US9546091B2/en not_active Expired - Fee Related
- 2010-05-14 WO PCT/KR2010/003063 patent/WO2011099677A1/ko active Application Filing
- 2010-05-14 EP EP10845848.0A patent/EP2535445B1/en not_active Not-in-force
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030002759A (ko) | 2001-06-29 | 2003-01-09 | 주식회사 하이닉스반도체 | 반도체 소자의 트랜지스터 제조 방법 |
KR20020008227A (ko) | 2002-01-03 | 2002-01-29 | 양갑승 | 정전 방사에 의한 카본나노파이버의 제조와 이의전기이중층 캐퍼시터용 전극 제조 |
KR100605006B1 (ko) * | 2005-01-18 | 2006-07-28 | (주) 아모센스 | 전기방사법으로 제조한 나노섬유의 탄소화에 의한 나노세공 분포를 갖는 활성탄소섬유의 제조방법 |
KR100675923B1 (ko) * | 2005-12-01 | 2007-01-30 | 전남대학교산학협력단 | 금속산화물 복합 나노 활성탄소섬유와 이를 이용한전기이중층 슈퍼캐퍼시터용 전극 및 그 제조 방법 |
KR100701627B1 (ko) * | 2005-12-22 | 2007-03-29 | 한국생산기술연구원 | 금속산화물 함유 나노활성탄소섬유의 제조방법 및 그로부터수득되는 나노활성탄소섬유를 이용한 슈퍼 캐패시터용전극 |
US20080207798A1 (en) * | 2007-02-27 | 2008-08-28 | Ppg Industries Ohio, Inc. | Organic-inorganic electrospun fibers |
KR20090051793A (ko) * | 2007-11-20 | 2009-05-25 | 재단법인대구경북과학기술원 | 금속산화물이 함유된 복합나노섬유 제조방법 |
Non-Patent Citations (6)
Title |
---|
CARBON, vol. 43, 2005, pages 2960 |
ELECTROCHEM., vol. 69, 2001, pages 487 |
J. ELECTROCHEM. SOC., vol. 148, 2001, pages A930 |
MAT. RES. SOC. PROC., 1995, pages 397 |
See also references of EP2535445A4 |
THE KOREAN INSTITUTE OF ELECTRICAL AND ELECTRONIC MATERIAL ENGINEERS, vol. 17, 2004, pages 1079 |
Also Published As
Publication number | Publication date |
---|---|
EP2535445A1 (en) | 2012-12-19 |
US9546091B2 (en) | 2017-01-17 |
CN102762784A (zh) | 2012-10-31 |
EP2535445B1 (en) | 2017-07-12 |
KR100995154B1 (ko) | 2010-11-18 |
US20130027844A1 (en) | 2013-01-31 |
EP2535445A4 (en) | 2014-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011099677A1 (ko) | 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 | |
WO2010053291A2 (ko) | 스킨-코어구조를 갖는 탄소나노섬유, 그 제조방법 및 상기 탄소나노섬유를 포함하는 제품 | |
Hsu et al. | Preparation of interconnected carbon nanofibers as electrodes for supercapacitors | |
KR100805104B1 (ko) | 높은 비표면적과 전도성을 갖는 탄소 재료 및 이의 제조방법 | |
Chen et al. | Facile fabrication of foldable electrospun polyacrylonitrile-based carbon nanofibers for flexible lithium-ion batteries | |
KR101045001B1 (ko) | 녹말을 이용한 탄소나노튜브가 강화된 다공성 탄소섬유의 제조방법 및 전기화학용 전극소재 용도 | |
Chang et al. | Fabrication of ultra-thin carbon nanofibers by centrifuged-electrospinning for application in high-rate supercapacitors | |
KR101126784B1 (ko) | 망간산화물/탄소나노섬유복합재 제조방법 및 그 탄소나노섬유복합재를 포함하는 고용량 하이브리드 슈퍼의사캐패시터용 전극 | |
KR20130060969A (ko) | 금속산화물-탄소입자-탄소나노섬유복합체, 상기 복합체 제조방법, 및 상기 복합체를 포함하는 탄소섬유응용제품 | |
TWI815791B (zh) | 碳纖維聚合體及其製造方法以及非水電解質二次電池用電極合劑層以及非水電解質二次電池用電極以及非水電解質二次電池 | |
WO2015064867A1 (en) | Electrode active material for magnesium battery | |
WO2019194613A1 (ko) | 양극 활물질, 상기 양극 활물질의 제조 방법, 상기 양극 활물질을 포함하는 양극, 및 상기 양극을 포함하는 이차 전지 | |
WO2017086609A1 (ko) | 내재적 미세기공성 고분자를 이용한 다공성 탄소구조체 및 이를 포함하는 전지용 전극 | |
Kim et al. | Enhanced electrical capacitance of heteroatom-decorated nanoporous carbon nanofiber composites containing graphene | |
WO2023043007A1 (ko) | 표면활성화된 탄소섬유 전극, 이의 제조방법, 플렉시블 섬유형 슈퍼커패시터 및 플렉시블 섬유형 슈퍼커패시터의 제조 방법 | |
Kim et al. | Effects of thermal treatment on the structural and capacitive properties of polyphenylsilane-derived porous carbon nanofibers | |
KR20090055299A (ko) | 다공성 탄소 재료 및 이의 제조방법 | |
KR102481903B1 (ko) | 에너지 저장장치용 탄소나노섬유 복합체, 이를 포함하는 전극, 그리고 이의 제조방법 | |
Dubal et al. | Electrospun polyacrylonitrile carbon nanofiber for supercapacitor application: a review | |
KR101147923B1 (ko) | 금속옥사이드가 함유된 다공성탄소나노섬유 제조방법, 상기 방법으로 제조된 다공성 탄소나노섬유, 및 이를 포함하는 탄소나노섬유응용제품 | |
Niu et al. | Polyacrylonitrile-based nitrogen-doped carbon materials with different micro-morphology prepared by electrostatic field for supercapacitors | |
KR20030089657A (ko) | 정전방사에 의한 폴리이미드 섬유 제조와 나노활성탄소섬유로부터 슈퍼캐패시터 전극재의 제조 방법 | |
WO2022119059A1 (ko) | 에너지 저장장치용 탄소나노섬유 복합체, 이를 포함하는 전극, 그리고 이의 제조방법 | |
KR100733580B1 (ko) | 활성탄-탄소나노섬유 복합체를 함유한 전극활물질 및 이의제조방법 | |
Mustafa et al. | Supercapacitor nanofiber electrodes graphene-based |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080063669.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10845848 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13578268 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2010845848 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010845848 Country of ref document: EP |