JP6302878B2 - Method for producing carbon nanofiber electrode carrying metal oxide using electrodeposition method - Google Patents
Method for producing carbon nanofiber electrode carrying metal oxide using electrodeposition method Download PDFInfo
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- JP6302878B2 JP6302878B2 JP2015159725A JP2015159725A JP6302878B2 JP 6302878 B2 JP6302878 B2 JP 6302878B2 JP 2015159725 A JP2015159725 A JP 2015159725A JP 2015159725 A JP2015159725 A JP 2015159725A JP 6302878 B2 JP6302878 B2 JP 6302878B2
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- metal oxide
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- carbon nanofiber
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 124
- 239000002134 carbon nanofiber Substances 0.000 title claims description 118
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 76
- 150000004706 metal oxides Chemical class 0.000 title claims description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- 238000004070 electrodeposition Methods 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000007833 carbon precursor Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 239000002121 nanofiber Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 6
- 229920000123 polythiophene Polymers 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 19
- 239000011787 zinc oxide Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 239000004020 conductor Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910002588 FeOOH Inorganic materials 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- -1 polybenzylimidazole Polymers 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- 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
-
- 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
- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/28—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds from polyamides
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本発明は、電着法を用いてカーボンナノファイバーに3次元構造の金属酸化物を自由自在に担持させ、バインダーと導電材なしにリチウムイオン二次電池及びキャパシタ(capacitor)の電極として使用することにより、性能の向上及び工程の簡単化を可能にする、金属酸化物が担持されたカーボンナノファイバー電極の製造方法及びこれを用いたエネルギー貯蔵装置及びフィルタに関する。 The present invention freely supports a metal oxide having a three-dimensional structure on a carbon nanofiber by using an electrodeposition method, and uses it as an electrode for a lithium ion secondary battery and a capacitor without using a binder and a conductive material. The present invention relates to a method for producing a carbon nanofiber electrode carrying a metal oxide, which can improve performance and simplify the process, and an energy storage device and a filter using the same.
最近、小型電子機器から電気自動車、スマートグリッド電力網に至るまでリチウムイオン二次電池及びキャパシタのようなエネルギー貯蔵装置が多様に適用されている。このような傾向によって、リチウムイオン二次電池及びキャパシタの性能を高めようとする研究が活発になされているが、一般にこのようなエネルギー貯蔵装置は高エネルギー密度、高出力、高安定性のような物理的特性が求められる。 Recently, energy storage devices such as lithium ion secondary batteries and capacitors have been applied in a variety of applications ranging from small electronic devices to electric vehicles and smart grid power grids. Due to this trend, research is being actively conducted to improve the performance of lithium ion secondary batteries and capacitors. In general, such energy storage devices have high energy density, high output, and high stability. Physical properties are required.
現在商用化されているリチウムイオン二次電池の負極物質は黒鉛(graphite)である。しかし、黒鉛の理論容量は372mAh/g(ミリ・アンペア・アワー/グラム)で、高速充放電の困難さがあることでよく知られている。また、Siの場合、4200mAh/gの高い理論容量を有しているが、充放電による体積の膨脹と収縮により電極に損傷を起こして電池の寿命を急速に縮めるとの問題がある。 The negative electrode material of lithium ion secondary batteries currently in commercial use is graphite. However, the theoretical capacity of graphite is 372 mAh / g ( milliampere hour / gram) , which is well known for the difficulty of high-speed charge / discharge. In addition, Si has a high theoretical capacity of 4200 mAh / g, but there is a problem that the battery life is rapidly shortened by causing damage to the electrodes due to expansion and contraction of the volume due to charge and discharge.
一方、例えば、電気放射法で製造されたカーボンナノファイバーを電極板として用いてカーボンナノファイバーの比表面積を広げることにより電極性能を高めようとする試みがある。また、一部酸化物とカーボンナノファイバーの化合物を合成してリチウム二次電池に適用した事例もある。電極として使うための酸化物とカーボンナノファイバーの複合体は、次のような2つの方法で主に作られてきた。一つ目の方法は、カーボンナノファイバーを作るために電気放射する時、炭素前駆体溶液に酸化物前駆体物質を共に交ぜて放射させ、これを熱処理して酸化物を作る方法である。しかし、このような方法で作られた電極は、酸化物が主にカーボンナノファイバー内に存在するため、充放電容量の高い酸化物が電解質に露出される量が減り、充放電容量を高めるために酸化物の量を増やすと、カーボンナノファイバーの強度及び導電性が顕著に低下するとの短所があった。二つ目の方法は、カーボンナノファイバーを先ず電気放射を用いて合成した後、高圧の水熱合成法を用いて表面に酸化物を担持させる方法である。しかし、このような方法には水熱反応器が追加で必要であり、合成時間が長いという短所があった。 On the other hand, for example, there is an attempt to improve the electrode performance by expanding the specific surface area of the carbon nanofiber using the carbon nanofiber manufactured by the electric radiation method as an electrode plate. In addition, there is a case where a compound of a part of oxide and carbon nanofiber is synthesized and applied to a lithium secondary battery. Composites of oxides and carbon nanofibers for use as electrodes have been mainly made by the following two methods. The first method is a method for producing an oxide by electrically radiating a carbon precursor solution together with an oxide precursor material when heat is emitted to form carbon nanofibers, and heat-treating the material together. However, in the electrode made by such a method, since the oxide is mainly present in the carbon nanofiber, the amount of the oxide having a high charge / discharge capacity exposed to the electrolyte is reduced, and the charge / discharge capacity is increased. Further, when the amount of oxide is increased, the strength and conductivity of the carbon nanofibers are remarkably lowered. The second method is a method in which carbon nanofibers are first synthesized using electric radiation, and then an oxide is supported on the surface using a high-pressure hydrothermal synthesis method. However, this method requires an additional hydrothermal reactor, and has a disadvantage that the synthesis time is long.
よって、金属酸化物が担持されたカーボンナノファイバー電極をより簡単に合成できる製造方法と、同時にカーボンナノファイバーに担持された金属酸化物の量と形状を自由自在に調節できる製造方法が求められているのが実情である。 Therefore, there is a need for a production method that can more easily synthesize a carbon nanofiber electrode carrying a metal oxide, and a production method that can freely adjust the amount and shape of the metal oxide carried on the carbon nanofiber. The fact is.
また、上述の金属酸化物の層が形成されたカーボンナノファイバーを電極として製造する時、一般に金属酸化物の層が形成されたカーボンナノファイバーを粉砕しバインダー、導電材と混合してペーストを作り、これをアルミニウムホイルのような集電体にコーティングして電極として製造するのが業界の慣行である。しかし、上記粉砕、混合及びコーティング過程を経る間に酸化物がカーボンナノファイバーから剥離することがあり、カーボンナノファイバーが小さく切られて固有の高い導電性が低下し得るという短所がある。そればかりか、バインダーと導電材はその種類によって電極の充放電容量に大きい影響を及ぼしかねず、単位質量当たりの充放電容量を計算する際、単位質量は活物質だけでなくバインダー、導電材及び集電体の質量も含まれた値であるため、結果的に充放電容量値を低める要因となる。 Also, when producing carbon nanofibers with the metal oxide layer described above as an electrode, the carbon nanofibers with the metal oxide layer are generally crushed and mixed with a binder and a conductive material to make a paste. It is common practice in the industry to coat a current collector such as an aluminum foil to produce an electrode. However, the oxides may be peeled off from the carbon nanofibers during the pulverization, mixing and coating processes, and the carbon nanofibers may be cut into small pieces to reduce the inherent high conductivity. In addition, the binder and the conductive material may greatly affect the charge / discharge capacity of the electrode depending on the type, and when calculating the charge / discharge capacity per unit mass, the unit mass is not only the active material but also the binder, conductive material and Since the value includes the mass of the current collector, it results in a decrease in the charge / discharge capacity value.
カーボンナノファイバーは紙状に製作され、バインダー、導電材または集電体なしでもそれ自体で電極として使われることができる物質である。そのため、バインダー、導電材及び集電体を使わない時、カーボンナノファイバー固有の長所を生かすことができ、フレキシブル電子機器への適用範囲も広げられることに着眼する必要がある。 Carbon nanofibers are materials that are made in paper and can be used as electrodes on their own without a binder, conductive material or current collector. Therefore, when the binder, the conductive material, and the current collector are not used, it is necessary to take advantage of the advantages inherent in carbon nanofibers and to expand the application range to flexible electronic devices.
本発明の目的は、金属酸化物が担持されたカーボンナノファイバー電極を比較的簡単な工程を通して短時間に製造する方法を提供することにある。 An object of the present invention is to provide a method for producing a carbon nanofiber electrode carrying a metal oxide in a short time through a relatively simple process.
本発明の他の目的は、金属酸化物が担持されたカーボンナノファイバー電極を製造するにあたって、担持される金属酸化物の量、形状及び位置をも自由自在に調節する方法を提供することにある。 Another object of the present invention is to provide a method for freely adjusting the amount, shape, and position of a supported metal oxide when manufacturing a carbon nanofiber electrode on which a metal oxide is supported. .
本発明のまた他の目的は、金属酸化物がカーボンナノファイバーの外部に存在するようにすることにより、金属酸化物の量を増やさなくてもそれ自体が電解質に露出される量を増やして充放電容量と共に強度及び導電性が高いカーボンナノファイバー電極を提供することにある。 Another object of the present invention is to increase the amount of the metal oxide exposed to the electrolyte without increasing the amount of the metal oxide by making the metal oxide exist outside the carbon nanofibers. An object of the present invention is to provide a carbon nanofiber electrode having high strength and conductivity as well as a discharge capacity.
本発明のまた他の目的は、バインダー、導電材及び集電体なしに電極のみを製造することにより、工程のコストを節減し、安定した品質のリチウムイオン二次電池及びキャパシタを提供することにある。 Still another object of the present invention is to provide a lithium ion secondary battery and a capacitor having stable quality by reducing the cost of the process by manufacturing only an electrode without a binder, a conductive material and a current collector. is there.
本発明の一具現例において、カーボンナノファイバーを製造する段階;上記カーボンナノファイバーの表面を活性化する段階;上記活性化されたカーボンナノファイバーを電着水溶液内に沈積させる段階;及び、上記活性化されたカーボンナノファイバー上に電着法で金属酸化物の層を電着する段階;を含む金属酸化物が担持されたカーボンナノファイバー電極の製造方法を提供する。
本発明の一具現例において、上記製造方法は、上記金属酸化物の層が形成されたカーボンナノファイバーを熱処理する段階を更に含むことができる。
本発明の一具現例において、上記熱処理が350乃至450℃でなされ得る。
In one embodiment of the present invention, a step of producing carbon nanofibers; a step of activating the surface of the carbon nanofibers; a step of depositing the activated carbon nanofibers in an electrodeposition aqueous solution; and the activity There is provided a method for producing a carbon nanofiber electrode carrying a metal oxide, comprising the step of electrodepositing a metal oxide layer on the carbon nanofiber formed by electrodeposition.
In one embodiment of the present invention, the manufacturing method may further include a step of heat-treating the carbon nanofibers on which the metal oxide layer is formed.
In one embodiment of the present invention, the heat treatment may be performed at 350 to 450 ° C.
本発明の一具現例において、上記電着水溶液がFeSO4、FeCl2・4H2O、Zn(NO3)2及びTiCl3からなる群から選択されるいずれか一つを含むことができる。
本発明の一具現例において、上記電着水溶液の濃度が0.01乃至0.2M(モル)であり得る。
本発明の一具現例において、上記金属酸化物がFe2O3であり得る。
本発明の一具現例において、上記金属酸化物がZnOであり得る。
本発明の一具現例において、上記金属酸化物がTiO2であり得る。
本発明の一具現例において、50乃至700C/g(クーロン/グラム)の電流量を供給してFe2O3の層を電着することができる。
本発明の一具現例において、100乃至700C/gの電流量を供給してFe2O3の層を電着することができる。
本発明の一具現例において、500乃至700C/gの電流量を供給してFe2O3の層を電着することができる。
本発明の一具現例において、2000乃至10000C/gの電流量を供給してZnOの層を電着することができる。
本発明の一具現例において、1000乃至5000C/gの電流量を供給してTiO2の層を電着することができる。
本発明の一具現例において、上記金属酸化物がカーボンナノファイバーに対して垂直方向に針または柱状に成長することができる。
In one embodiment of the present invention, the electrodeposition aqueous solution may include any one selected from the group consisting of FeSO 4 , FeCl 2 .4H 2 O, Zn (NO 3 ) 2 and TiCl 3 .
In one embodiment of the present invention, the concentration of the electrodeposition aqueous solution may be 0.01 to 0.2M (mol) .
In one embodiment of the present invention, the metal oxide may be Fe 2 O 3 .
In one embodiment of the present invention, the metal oxide may be ZnO.
In an embodiment of the present invention, the metal oxide may be TiO 2.
In one embodiment of the present invention, a layer of Fe 2 O 3 can be electrodeposited by supplying a current amount of 50 to 700 C / g (coulomb / gram) .
In one embodiment of the present invention, an Fe 2 O 3 layer can be electrodeposited by supplying a current amount of 100 to 700 C / g.
In one embodiment of the present invention, a current amount of 500 to 700 C / g may be supplied to deposit the Fe 2 O 3 layer.
In one embodiment of the present invention, a ZnO layer can be electrodeposited by supplying a current amount of 2000 to 10000 C / g.
In one embodiment of the present invention, a current amount of 1000 to 5000 C / g may be supplied to electrodeposit the TiO 2 layer.
In one embodiment of the present invention, the metal oxide may grow in a needle or column shape in a direction perpendicular to the carbon nanofiber.
本発明の一具現例において、上記カーボンナノファイバーを製造する段階が、炭素前駆体及び溶媒を含む水溶液を製造する段階;上記水溶液を電気放射してナノファイバーを製造する段階;及び、上記ナノファイバーを炭化してカーボンナノファイバーを製造する段階;を含むことができる。
本発明の一具現例において、上記溶媒が溶媒100重量部に対して上記炭素前駆体を5乃至30重量部含むことができる。
In one embodiment of the present invention, the step of producing the carbon nanofibers comprises producing an aqueous solution containing a carbon precursor and a solvent; producing the nanofibers by electrically radiating the aqueous solution; and the nanofibers. Carbonized to produce carbon nanofibers.
In one embodiment of the present invention, the solvent may include 5 to 30 parts by weight of the carbon precursor with respect to 100 parts by weight of the solvent.
本発明の一具現例において、上記炭素前駆体がポリアクリロニトリル(PAN)、セルロース、グルコース、ポリ塩化ビニル(PVC)、ポリアクリル酸、ポリ乳酸、ポリエチレンオキシド、ポリピロール、ポリイミド、ポリアミドイミド(PAI)、ポリアラミド、ポリベンジルイミダゾール、フェノール樹脂及びピッチ類、ポリアニリン、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)、ポリチオフェン、及びポリチオフェン誘導体からなる群から選択されることができる。 In one embodiment of the present invention, the carbon precursor is polyacrylonitrile (PAN), cellulose, glucose, polyvinyl chloride (PVC), polyacrylic acid, polylactic acid, polyethylene oxide, polypyrrole, polyimide, polyamideimide (PAI), It can be selected from the group consisting of polyaramid, polybenzylimidazole, phenolic resin and pitches, polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), polythiophene, and polythiophene derivatives.
本発明の一具現例において、上記溶媒が、N,N−ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAc)、テトラヒドロフラン(THF)、ジメチルスルホキシド(DMSO)、γ−ブチロラクトン、N−メチルピロリドン、クロロホルム、トルエン、アセトンまたはこれらの混合物であり得る。
本発明の一具現例において、10乃至30kVの電圧で水溶液を電気放射することができる。
本発明の他の具現例において、上記製造方法で製造されたカーボンナノファイバー電極を提供する。
本発明の他の具現例において、上記カーボンナノファイバー電極を含むリチウムイオン二次電池を提供する。
本発明の他の具現例において、上記カーボンナノファイバー電極を含む環境浄化用フィルタを提供する。
In one embodiment of the present invention, the solvent is N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), γ-butyrolactone, N-methylpyrrolidone, chloroform, It can be toluene, acetone or a mixture thereof.
In one embodiment of the present invention, an aqueous solution can be electrically emitted at a voltage of 10 to 30 kV.
In another embodiment of the present invention, a carbon nanofiber electrode manufactured by the above manufacturing method is provided.
In another embodiment of the present invention, a lithium ion secondary battery including the carbon nanofiber electrode is provided.
In another embodiment of the present invention, an environmental purification filter including the carbon nanofiber electrode is provided.
本発明の製造方法は、酸化物、具体的には、金属酸化物が担持されたカーボンナノファイバー電極を比較的簡単な工程で短時間に合成することができる。また、既存の合成法に比べて簡単な電気化学反応により合成が可能なため、金属酸化物の量、形状及び位置を自由自在に調節することができる。 According to the production method of the present invention, an oxide, specifically, a carbon nanofiber electrode carrying a metal oxide can be synthesized in a short time by a relatively simple process. In addition, since synthesis is possible by a simple electrochemical reaction compared to existing synthesis methods, the amount, shape, and position of the metal oxide can be freely adjusted.
本発明の製造方法は、カーボンナノファイバーの外部と内部、電気が通る部分で全て均一に金属酸化物を担持して、金属酸化物の量を増やさなくても充放電容量と共に強度及び導電性が高い電極を提供することができる。 The production method of the present invention uniformly and uniformly supports the metal oxide at the outside and inside of the carbon nanofiber, and the portion through which electricity passes, and has the strength and conductivity as well as the charge / discharge capacity without increasing the amount of metal oxide. A high electrode can be provided.
更に、上記電極を用いて優れた品質のリチウムイオン二次電池及びキャパシタを提供し、燃料電池やリチウム−空気電池のための金属触媒が担持された電極の開発及びカーボンナノファイバーの吸着力を用いた機能性環境浄化用フィルタの開発が可能である。 Furthermore, the present invention provides an excellent quality lithium ion secondary battery and capacitor using the above electrode, and uses the development of an electrode carrying a metal catalyst for a fuel cell or a lithium-air battery and the adsorption power of carbon nanofibers. It is possible to develop a functional environmental purification filter.
本発明は、カーボンナノファイバーを製造する段階;上記カーボンナノファイバーの表面を活性化する段階;上記活性化されたカーボンナノファイバーを金属酸化物電着水溶液内に沈積させる段階;及び、上記活性化されたカーボンナノファイバー上に電着法で金属酸化物の層を電着する段階;を含む金属酸化物が担持されたカーボンナノファイバー電極の製造方法を提供する。図1は、本発明の一具現例として製造方法のフローを示したものである。 The present invention includes the steps of: producing carbon nanofibers; activating the surface of the carbon nanofibers; depositing the activated carbon nanofibers in an aqueous metal oxide electrodeposition solution; There is provided a method for producing a carbon nanofiber electrode carrying a metal oxide, comprising: electrodepositing a metal oxide layer on the carbon nanofiber formed by electrodeposition. FIG. 1 shows a flow of a manufacturing method as an embodiment of the present invention.
本願において、“金属酸化物/カーボンナノファイバー電極”は、金属酸化物が担持されたカーボンナノファイバー電極を意味する。例えば、“Fe2O3/カーボンナノファイバー電極”は、Fe2O3、即ち酸化鉄(III)が担持されたカーボンナノファイバー電極を意味する。 In the present application, “metal oxide / carbon nanofiber electrode” means a carbon nanofiber electrode on which a metal oxide is supported. For example, “Fe 2 O 3 / carbon nanofiber electrode” means a carbon nanofiber electrode carrying Fe 2 O 3 , that is, iron (III) oxide.
本発明の一具現例において、上記製造方法は、上記金属酸化物の層が形成されたカーボンナノファイバーを熱処理する段階を更に含む。このような熱処理段階を通して金属酸化物の層が結晶構造に変換される。また、金属酸化物の層は、カーボンナノファイバー上でカーボンナノファイバーに対して垂直方向に針状に成長し電極として利用する場合、その表面積が増大する。 In one embodiment of the present invention, the manufacturing method further includes a step of heat-treating the carbon nanofibers on which the metal oxide layer is formed. Through the heat treatment step, the metal oxide layer is converted into a crystal structure. In addition, when the metal oxide layer grows in a needle shape in a direction perpendicular to the carbon nanofibers and is used as an electrode, the surface area of the metal oxide layer increases.
本発明の一具現例によって製造された金属酸化物が担持されたカーボンナノファイバーを利用する電極は、バインダー、導電材及び集電体を要しないという長所があり、担持される金属酸化物の量、形状及び位置をリチウムイオン二次電池またはキャパシタの電極などの用途によって容易に変更することができる。 An electrode using carbon nanofibers loaded with a metal oxide manufactured according to an embodiment of the present invention has an advantage that a binder, a conductive material, and a current collector are not required. The shape and position can be easily changed depending on the application such as a lithium ion secondary battery or capacitor electrode.
本発明の一具現例において、それ自体でも導電性を有するカーボンナノファイバーを電極として用い電着法で金属酸化物を担持させる段階が含まれる。電着法によってカーボンファイバーに金属陽イオン(Fe2+、Zn2+及びTi3+など)を含む金属酸化物が担持され、必要に応じて空気条件で熱処理する。電着条件によって担持される金属酸化物の量、形状及び位置を調節することができる。 One embodiment of the present invention includes a step of supporting a metal oxide by an electrodeposition method using carbon nanofibers that are themselves conductive as electrodes. A metal oxide containing metal cations (Fe 2+ , Zn 2+, Ti 3+, etc.) is supported on the carbon fiber by electrodeposition, and heat treatment is performed under air conditions as necessary. The amount, shape and position of the metal oxide supported by the electrodeposition conditions can be adjusted.
本発明の一具現例において、上記カーボンナノファイバーを製造する段階は、炭素前駆体及び溶媒を含む水溶液を製造する段階;上記水溶液を電気放射してナノファイバーを製造する段階;及び、上記ナノファイバーを炭化してカーボンナノファイバーを製造する段階;を含むことができる。 In one embodiment of the present invention, the step of manufacturing the carbon nanofiber includes the step of manufacturing an aqueous solution containing a carbon precursor and a solvent; the step of manufacturing the nanofiber by electrically radiating the aqueous solution; and the nanofiber. Carbonized to produce carbon nanofibers.
本発明の一具現例において、上記溶媒100重量部に対して上記炭素前駆体を約5乃至約30重量部溶解する。上記炭素前駆体が約5重量部未満であるとカーボンナノファイバーが形成されないことがあり、約30重量部を超過すると溶液の粘性が高くなって放射ノズルが詰まり得るため、上記範囲を維持することが望ましい。最も望ましくは、上記溶媒100重量部に対して上記炭素前駆体を約10重量部溶解する。 In one embodiment of the present invention, about 5 to about 30 parts by weight of the carbon precursor is dissolved in 100 parts by weight of the solvent. If the carbon precursor is less than about 5 parts by weight, carbon nanofibers may not be formed, and if it exceeds about 30 parts by weight, the viscosity of the solution will increase and the radiation nozzle may become clogged, so the above range should be maintained. Is desirable. Most preferably, about 10 parts by weight of the carbon precursor is dissolved in 100 parts by weight of the solvent.
本発明の一具現例において、上記炭素前駆体は、ポリアクリロニトリル(PAN)、セルロース、グルコース、ポリ塩化ビニル(PVC)、ポリアクリル酸、ポリ乳酸、ポリエチレンオキシド、ポリピロール、ポリイミド、ポリアミドイミド(PAI)、ポリアラミド、ポリベンジルイミダゾール、フェノール樹脂及びピッチ類、ポリアニリン、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)、ポリチオフェン、及びポリチオフェン誘導体などからなる群から選択される。望ましくは、上記炭素前駆体はポリアクリロニトリルを用いて、高い収率と機械的強度を有するカーボンナノチューブを合成することができる。 In one embodiment of the present invention, the carbon precursor includes polyacrylonitrile (PAN), cellulose, glucose, polyvinyl chloride (PVC), polyacrylic acid, polylactic acid, polyethylene oxide, polypyrrole, polyimide, and polyamideimide (PAI). , Polyaramid, polybenzylimidazole, phenolic resin and pitches, polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), polythiophene, polythiophene derivatives, and the like. Desirably, carbon nanotubes having high yield and mechanical strength can be synthesized using polyacrylonitrile as the carbon precursor.
また、上記溶媒は、N,N−ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAc)、テトラヒドロフラン(THF)、ジメチルスルホキシド(DMSO)、γ−ブチロラクトン、N−メチルピロリドン、クロロホルム、トルエン、アセトンまたはこれらの混合物などであり得、望ましくは、N,N−ジメチルホルムアミドを用いる。 The solvent is N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), γ-butyrolactone, N-methylpyrrolidone, chloroform, toluene, acetone or these It may be a mixture or the like, and preferably N, N-dimethylformamide is used.
本発明の一具現例において、上記電気放射時、約10乃至約30kVの電圧を印加する。印加される電圧が約10kV未満であるとカーボンナノファイバーが形成されないことがあり、約30kVを超過する場合はカーボンナノファイバーの太さが細くなりすぎてカーボンナノファイバーの強度及び導電性が低下する問題があるため、上記範囲を維持することが望ましい。最も望ましくは、上記電気放射時、約20kVの電圧を印加することである。 In one embodiment of the present invention, a voltage of about 10 to about 30 kV is applied during the electrical radiation. When the applied voltage is less than about 10 kV, carbon nanofibers may not be formed. When the applied voltage exceeds about 30 kV, the thickness of the carbon nanofibers becomes too thin and the strength and conductivity of the carbon nanofibers decrease. Due to problems, it is desirable to maintain the above range. Most preferably, a voltage of about 20 kV is applied during the electrical radiation.
本発明の一具現例において、上記電着水溶液がFeSO4、FeCl2・4H2O、Zn(NO3)2及びTiCl3からなる群から選択されるいずれか一つを用いて、所望の金属酸化物を合成する。 In one embodiment of the present invention, the electrodeposition aqueous solution may be any one selected from the group consisting of FeSO 4 , FeCl 2 .4H 2 O, Zn (NO 3 ) 2 and TiCl 3. Synthesize oxide.
本発明の一具現例において、上記金属酸化物電着水溶液の濃度は約0.01乃至約0.4Mである。金属酸化物電着水溶液の濃度が約0.01M未満であると金属酸化物が形成されないことがあり、約0.4Mを超過する場合は3次元多孔性構造内気孔を維持できなくなる問題があるため、上記範囲を維持することが望ましい。最も望ましくは、上記金属酸化物電着水溶液は約0.05乃至約0.15Mの濃度を用いる。 In one embodiment of the present invention, the concentration of the metal oxide electrodeposition aqueous solution is about 0.01 to about 0.4M. If the concentration of the metal oxide electrodeposition aqueous solution is less than about 0.01M, metal oxide may not be formed, and if it exceeds about 0.4M, there is a problem that pores in the three-dimensional porous structure cannot be maintained. Therefore, it is desirable to maintain the above range. Most preferably, the aqueous metal oxide electrodeposition solution uses a concentration of about 0.05 to about 0.15M.
本発明の一具現例において、上記金属酸化物は、Fe2O3、ZnOまたはTiO2であり得る。Fe2O3、ZnOまたはTiO2は、所定の電流量を供給した時、カーボンナノファイバーの外側表面だけでなく内側部分にも成長するため、電極の表面積を広げることになる。 In one embodiment of the present invention, the metal oxide may be Fe 2 O 3 , ZnO or TiO 2 . Fe 2 O 3 , ZnO or TiO 2 grows not only on the outer surface of the carbon nanofibers but also on the inner part when a predetermined amount of current is supplied, so that the surface area of the electrode is increased.
本発明の一具現例において、担持される金属酸化物がFe2O3の場合は、上記電着法を行なう時、約50乃至約700C/gの電流量を供給でき、より望ましくは約100乃至約700C/gの電流量を供給できる。供給される電流量が約50C/g未満であると結晶がナノ粒子形態に分散されて針状にうまく成長せず、約700C/gを超過する場合は既に形成された金属酸化物が電子伝達に抵抗として作用して金属酸化物がそれ以上成長できないとの問題があるため、上記範囲を維持することが望ましい。最も望ましくは、電着法を行なう時に約500乃至約700C/gの電流量を供給すると、カーボンナノファイバーにFe2O3が均一且つ高密度に電着することから、電極の充放電容量、強度及び導電性を著しく増加させることができる。 In one embodiment of the present invention, when the supported metal oxide is Fe 2 O 3 , a current amount of about 50 to about 700 C / g can be supplied when the electrodeposition is performed, and more preferably about 100 A current amount of about 700 C / g can be supplied. If the amount of current supplied is less than about 50 C / g, the crystals are dispersed in the form of nanoparticles and do not grow well in the form of needles. It is desirable to maintain the above-mentioned range because there is a problem that the metal oxide cannot grow any more because it acts as a resistance. Most preferably, when a current amount of about 500 to about 700 C / g is supplied during the electrodeposition process, Fe 2 O 3 is uniformly and densely electrodeposited on the carbon nanofibers, so that the charge / discharge capacity of the electrode, Strength and conductivity can be significantly increased.
本発明の一具現例において、上記電着法を行なう時、担持される金属酸化物がZnOの場合、約2000乃至約10000C/gの電流量を供給でき、より望ましくは約7000C/gの電流量を供給できる。供給される電流量が約2000C/g未満であると結晶がナノ粒子形態に分散されて柱状にうまく成長せず、約10000C/gを超過する場合は既に形成されたZnO金属酸化物が電子伝達に抵抗として作用して金属酸化物がそれ以上成長できないとの問題があるため、上記範囲を維持することが望ましい。担持される金属酸化物がZnOの場合、電着法を行なうとき、最も望ましくは、約7000C/gの電流量を供給すると、カーボンナノファイバーに金属酸化物が均一且つ高密度に電着することから、電極の充放電容量、強度及び導電性を著しく増加させることができる。 In one embodiment of the present invention, when the electrodeposition method is performed, when the supported metal oxide is ZnO, a current amount of about 2000 to about 10,000 C / g can be supplied, and more preferably about 7000 C / g. Can supply quantity. If the amount of current supplied is less than about 2000 C / g, the crystals are dispersed in the form of nanoparticles and do not grow well in a columnar shape, and if it exceeds about 10000 C / g, the ZnO metal oxide already formed is transferred to the electron. It is desirable to maintain the above-mentioned range because there is a problem that the metal oxide cannot grow any more because it acts as a resistance. When the supported metal oxide is ZnO, the most preferable electrodeposition method is to deposit the metal oxide uniformly and densely on the carbon nanofibers when a current amount of about 7000 C / g is supplied. Therefore, the charge / discharge capacity, strength and conductivity of the electrode can be remarkably increased.
本発明の一具現例において、上記電着法を行なう時、担持される金属酸化物がTiO2の場合、約1000乃至約5000C/gの電流量を供給でき、より望ましくは約2000C/gの電流量を供給できる。供給される電流量が約1000C/g未満であると部分的にだけ成長して電着する量が少なく、約5000C/gを超過する場合は既に形成されたTiO2金属酸化物が電子伝達に抵抗として作用して金属酸化物がそれ以上成長できないとの問題があるため、上記範囲を維持することが望ましい。担持される金属酸化物がTiO2の場合、電着法を行なうとき、最も望ましくは、約2000C/gの電流量を供給すると、カーボンナノファイバーに金属酸化物が均一且つ高密度に電着することから、電極の充放電容量、強度及び導電性を著しく増加させることができる。 In one embodiment of the present invention, when the electrodeposition method is performed, when the supported metal oxide is TiO 2 , a current amount of about 1000 to about 5000 C / g can be supplied, and more preferably about 2000 C / g. The amount of current can be supplied. If the amount of current supplied is less than about 1000 C / g, the amount of electrodeposited and only partially grown is small, and if it exceeds about 5000 C / g, the formed TiO 2 metal oxide is used for electron transfer. It is desirable to maintain the above-mentioned range because there is a problem that the metal oxide cannot grow any more by acting as a resistance. When the supported metal oxide is TiO 2 , most preferably, when performing an electrodeposition method, when a current amount of about 2000 C / g is supplied, the metal oxide is uniformly and densely electrodeposited onto the carbon nanofibers. Therefore, the charge / discharge capacity, strength, and conductivity of the electrode can be remarkably increased.
本発明の一具現例において、上記熱処理は約350乃至約450℃で行われる。熱処理温度が約350℃未満であると金属酸化物の酸化が十分になされないことがあり、約450℃を超過する場合はカーボンナノファイバーが燃焼される問題があるため、上記範囲を維持することが望ましい。最も望ましくは、上記熱処理は約400℃で行われる。 In one embodiment of the present invention, the heat treatment is performed at about 350 to about 450 ° C. If the heat treatment temperature is less than about 350 ° C, the metal oxide may not be sufficiently oxidized, and if it exceeds about 450 ° C, there is a problem that the carbon nanofibers are burned. Is desirable. Most preferably, the heat treatment is performed at about 400 ° C.
本発明の一具現例において、上記金属酸化物の層は、従来技術で平面に積層されるものと違い、カーボンナノファイバーに対して垂直方向に、単位面積当たり高密度に結晶が固まる現象なしに緻密な針または柱状に成長する。このような3次元構造の金属酸化物結晶は高い表面積を有するため、リチウムイオン二次電池の電極として使う時、充放電容量が高くなる。 In one embodiment of the present invention, the metal oxide layer is different from the conventional layered structure, and the crystal is solidified at a high density per unit area in a direction perpendicular to the carbon nanofiber. Grows into dense needles or pillars. Since the metal oxide crystal having such a three-dimensional structure has a high surface area, when used as an electrode of a lithium ion secondary battery, the charge / discharge capacity is increased.
本発明の他の具現例は、カーボンナノファイバー電極を提供する。上述の方法で製造されたカーボンナノファイバー電極は、金属酸化物がカーボンナノファイバーに均等に担持されていて、活性表面積が増大したものである。 Another embodiment of the present invention provides a carbon nanofiber electrode. In the carbon nanofiber electrode manufactured by the above-described method, the metal oxide is uniformly supported on the carbon nanofiber, and the active surface area is increased.
上述の電着水溶液の種類によって、本発明のカーボンナノファイバー電極は、酸化鉄、酸化亜鉛または酸化チタンが担持されたカーボンナノファイバー電極であり得る。また、金属触媒が均等によく分散されたカーボンナノファイバーを燃料電池電極として適用させることができる。これは、電極の電気化学的特性及び触媒特性を著しく増幅させて、効果的にリチウムイオン二次電池、リチウム−空気二次電池及びキャパシタのようなエネルギー貯蔵装置に適用できる。
そこで、本発明の他の具現例は、カーボンナノファイバー電極を含むリチウムイオン二次電池を提供する。
Depending on the type of electrodeposition aqueous solution described above, the carbon nanofiber electrode of the present invention may be a carbon nanofiber electrode carrying iron oxide, zinc oxide or titanium oxide. Further, carbon nanofibers in which the metal catalyst is uniformly and well dispersed can be applied as a fuel cell electrode. This significantly amplifies the electrochemical and catalytic properties of the electrode and can be effectively applied to energy storage devices such as lithium ion secondary batteries, lithium-air secondary batteries and capacitors.
Accordingly, another embodiment of the present invention provides a lithium ion secondary battery including a carbon nanofiber electrode.
既存のリチウムイオン二次電池の場合、電極を作るために活物質をバインダー、導電材と共に混ぜた後、アルミニウムホイルに塗布しなければならない手間がある。しかし、本発明のカーボンナノファイバー電極、その中でも特にFe2O3/カーボンナノファイバー電極は、Fe2O3とカーボンナノファイバーの優れた結合力及びカーボンナノファイバーの導電性によりそれ自体だけで電極として使用可能であることから、製造工程段階の簡素化をもたらし、窮極的にコスト節減及び品質の安定化を図ることができる。 In the case of an existing lithium ion secondary battery, it is necessary to apply an active material to an aluminum foil after mixing the active material with a binder and a conductive material in order to produce an electrode. However, the carbon nanofiber electrode of the present invention, especially the Fe 2 O 3 / carbon nanofiber electrode, is an electrode by itself due to the excellent binding force of Fe 2 O 3 and carbon nanofiber and the conductivity of the carbon nanofiber. Therefore, it is possible to simplify the manufacturing process stage, and to extremely reduce cost and stabilize quality.
一方、多孔性構造を有するカーボンナノファイバーは、高い吸着力のおかげで環境浄化用フィルタに使用されることができる。本発明によって製造されたカーボンナノファイバー電極は、Fe2O3、TiO2、ZnOなど金属酸化物の種類によって光触媒特性を有し得る。このような光触媒特性は、製造されたカーボンナノファイバー電極が光により生成された酸化種を用いて汚染物質を分解させるようにして、環境浄化の効果を有するようにする。 On the other hand, carbon nanofibers having a porous structure can be used for environmental purification filters thanks to high adsorption power. The carbon nanofiber electrode manufactured according to the present invention may have photocatalytic properties depending on the type of metal oxide such as Fe 2 O 3 , TiO 2 , and ZnO. Such photocatalytic properties allow the manufactured carbon nanofiber electrode to have an environmental purification effect by decomposing pollutants using oxidized species generated by light.
そこで、本発明の他の具現例は、カーボンナノファイバー電極を含む環境浄化用フィルタを提供する。本発明によるカーボンナノファイバー電極は、図6のような原理で環境浄化用フィルタに適用できる。 Accordingly, another embodiment of the present invention provides an environmental purification filter including a carbon nanofiber electrode. The carbon nanofiber electrode according to the present invention can be applied to an environmental purification filter based on the principle shown in FIG.
以下、望ましい実施例を挙げて本発明をより詳しく説明する。しかし、これら実施例は本発明をより具体的に説明するためのもので、本発明の範囲がこれによって制限されないことは当業界の通常の知識を有する者にとって自明なことである。 Hereinafter, the present invention will be described in more detail with reference to preferred examples. However, these examples are for explaining the present invention more specifically, and it is obvious to those having ordinary skill in the art that the scope of the present invention is not limited thereby.
実施例1. Fe2O3/カーボンナノファイバー電極の製造
− カーボンナノファイバーの製造
カーボンナノファイバーを製造するために、炭素前駆体としてポリアクリロニトリル(Polyacrylonitrile、PAN、Sigma-Aldrich)をN,N−ジメチルホルムアミド(N,N-Dimethylformamide、DMF、DAEJIN CHEMICAL)100重量部に対して10重量部溶解してPAN/DMF溶液を製造した。上記溶液をナノファイバーにするために、20kV電圧の電場下で電気放射器(NanoNC、es-robot)で放射してナノファイバーを形成した。上記過程を通して形成されたナノファイバーをカーボンナノファイバーにするために、先ず空気雰囲気で250℃で30分間安定化させた後、窒素ガスを流しながら750℃で1時間徐々に炭化させ、再び1400℃まで徐々に温度を高めた後、1400℃で1時間熱を加えた(Lindberg、tube-furnace)。この時、5℃/分の速度で昇温した。表面活性化のために、作られたカーボンナノファイバーを過酸化水素溶液(Duksan、28%)150mLに60℃で6時間浸してから取り出して100℃で30分間乾燥((株)JSRESEARCH、JSVO-60T)した。
Example 1. Production of Fe 2 O 3 / Carbon Nanofiber Electrode-Production of Carbon Nanofiber To produce carbon nanofiber, polyacrylonitrile (Polyacrylonitrile, PAN, Sigma-Aldrich) was used as a carbon precursor, N, N-dimethylformamide (N , N-Dimethylformamide, DMF, DAEJIN CHEMICAL) 10 parts by weight was dissolved in 100 parts by weight to prepare a PAN / DMF solution. In order to make the solution into nanofibers, nanofibers were formed by radiating with an electric radiator (NanoNC, es-robot) under an electric field of 20 kV voltage. In order to turn the nanofibers formed through the above process into carbon nanofibers, first, the nanofibers were stabilized at 250 ° C. for 30 minutes in an air atmosphere, then gradually carbonized at 750 ° C. for 1 hour while flowing nitrogen gas, and again 1400 ° C. After gradually raising the temperature to 1400 ° C., heat was applied for 1 hour (Lindberg, tube-furnace). At this time, the temperature was raised at a rate of 5 ° C./min. For surface activation, the prepared carbon nanofibers were soaked in 150 mL of hydrogen peroxide solution (Duksan, 28%) at 60 ° C. for 6 hours and then removed and dried at 100 ° C. for 30 minutes (JSRESEARCH, JSVO-) 60T).
− Fe2O3/カーボンナノファイバー電極の製造
乾燥されたカーボンナノファイバーの内側部分までFe2+イオンがよく吸着され得るようにするために、FeSO4(Sigma Aldrich)0.1M溶液(2.78g/100mL)に24時間沈積させて電極を製造した。上記電極を取り出して上側部分の水気を取り除いてから、電線と連結できるように表面に銅テープを付け、これをFeSO4 0.1M溶液に浸した後、ポテンショスタット(potentiostat)(Ametek、Versastat3)の作用電極(WE)に連結した。カウンター電極(CE)としては白金電極を、参照電極(RE)としてはAg/AgCl電極を使った。ポテンショスタットを用いた電着の間、FeSO4溶液を70℃に維持し、1.6V vs.Ag/AgClの電圧を加えた。試料によって、それぞれ100、300、500及び700C/gの電流量を供給した。電着によって形成された金属酸化物は、FeOOH形態で非晶質構造を有することを確認した。図2の左側の(a)は、FeOOH/カーボンナノファイバーのSEMイメージ写真である。
- Fe 2 O 3 / up to the inner part of the manufacturing dried carbon nano fiber of the carbon nanofiber electrodes in order to Fe 2+ ions may be well adsorbed, FeSO 4 (Sigma Aldrich) 0.1M solution (2.78 g / 100 mL) for 24 hours to produce an electrode. After removing the above electrode and removing the moisture from the upper part, attach copper tape to the surface so that it can be connected to the electric wire, soak it in FeSO 4 0.1M solution, and then potentiostat (Ametek, Versastat3) To the working electrode (WE). A platinum electrode was used as the counter electrode (CE), and an Ag / AgCl electrode was used as the reference electrode (RE). During the electrodeposition using a potentiostat, the FeSO 4 solution was maintained at 70 ° C. and 1.6 V vs. A voltage of Ag / AgCl was applied. Depending on the sample, current amounts of 100, 300, 500 and 700 C / g were supplied, respectively. The metal oxide formed by electrodeposition was confirmed to have an amorphous structure in the form of FeOOH. (A) on the left side of FIG. 2 is a SEM image photograph of FeOOH / carbon nanofibers.
電着した金属酸化物を100℃で1時間乾燥した後((株)JSRESEARCH、JSVO-60T)、400℃で4時間熱処理((株)AJEON加熱産業、UP35A)してFe2O3にした。この時、1℃/分の速度で昇温した。製造過程中に生成されたFe2O3/カーボンナノファイバーの構造を電子顕微鏡で観察した結果を図2の右側の(b)に示した。FeOOHは熱処理後にFe2O3になった後も針状がよく維持されることを確認した。また、カーボンナノファイバーの外側表面だけでなく内側部分にもFe2O3の結晶が均等によく成長したことが分かった。少ない電流量を供給した試料ではカーボンナノファイバー表面にFeOOH粒子が電着し、より多い電流量を供給した試料ではカーボンナノファイバー表面にFeOOH粒子が層を成して電着する形態を示し、電流量が100C/g以上になると針状に成長した。そして、それ以上の電流量を供給した試料では図3のように針状の長さが増加することを確認した。 The electrodeposited metal oxide was dried at 100 ° C. for 1 hour (JSRESEARCH, JSVO-60T) and then heat treated at 400 ° C. for 4 hours (AJEON Heating Industry, UP35A) to obtain Fe 2 O 3 . . At this time, the temperature was raised at a rate of 1 ° C./min. The result of observing the structure of Fe 2 O 3 / carbon nanofiber generated during the manufacturing process with an electron microscope is shown in (b) on the right side of FIG. It was confirmed that the FeOOH was well maintained in the needle shape even after becoming Fe 2 O 3 after the heat treatment. It was also found that Fe 2 O 3 crystals grew equally well not only on the outer surface of the carbon nanofiber but also on the inner portion. In the sample supplied with a small amount of current, FeOOH particles are electrodeposited on the carbon nanofiber surface, and in the sample supplied with a larger amount of current, FeOOH particles are electrodeposited in layers on the carbon nanofiber surface. When the amount was 100 C / g or more, it grew like a needle. Then, it was confirmed that the length of the needle shape increased as shown in FIG. 3 in the sample supplied with a larger amount of current.
実施例2. ZnO/カーボンナノファイバー電極の製造
実施例1で製造されたカーボンナノファイバーを準備した。乾燥されたカーボンナノファイバーの内側部分までZn2+イオンがよく吸着され得るようにするために、試料をZn(NO3)2 0.05M溶液及び0.15M溶液に各々24時間沈積させて電極を製造した。上記電極を各々取り出して上側部分の水気を取り除いた後、電線と連結できるように表面に銅テ−プを付け、これをZn(NO3)2 0.1M溶液に浸した後、ポテンショスタットの作用電極(WE)に連結した。カウンター電極(CE)としては白金電極を、参照電極(RE)としてはAg/AgCl電極を使った。ポテンショスタットを用いた電着の間、Zn(NO3)2溶液に70℃及びpH2.5〜pH5.5の範囲で、−1.2V vs. Ag/AgClの電圧を加えた。電着のために加えられた電流量は10000C/gであった。電着によって形成された金属酸化物は、使用した溶媒の濃度によって図4のように柱状のZnOの結晶構造を有しており、追加的な熱処理は行わなかった。
Example 2 Production of ZnO / Carbon Nanofiber Electrode The carbon nanofiber produced in Example 1 was prepared. In order to allow the Zn 2+ ions to be well adsorbed to the inner part of the dried carbon nanofibers, the sample was deposited in Zn (NO 3 ) 2 0.05M solution and 0.15M solution for 24 hours each to make the electrode Manufactured. After each of the above electrodes was taken out and the upper portion of the water was removed, a copper tape was attached to the surface so that it could be connected to an electric wire, and this was immersed in a Zn (NO 3 ) 2 0.1M solution, and then the potentiostat Connected to working electrode (WE). A platinum electrode was used as the counter electrode (CE), and an Ag / AgCl electrode was used as the reference electrode (RE). During electrodeposition using a potentiostat, a voltage of −1.2 V vs. Ag / AgCl was applied to the Zn (NO 3 ) 2 solution at 70 ° C. and in the range of pH 2.5 to pH 5.5. The amount of current applied for electrodeposition was 10,000 C / g. The metal oxide formed by electrodeposition had a columnar ZnO crystal structure as shown in FIG. 4 depending on the concentration of the solvent used, and no additional heat treatment was performed.
実施例3. TiO2/カーボンナノファイバー電極の製造
実施例1で製造されたカーボンナノファイバーを準備した。乾燥されたカーボンナノファイバーの内側部分までTi3+イオンがよく吸着され得るようにするために、試料をTiCl3 0.4M溶液に24時間沈積させて電極を製造した。上記電極を取り出して上側部分の水気を取り除いた後、電線と連結できるように表面に銅テープを付け、これをTiCl3 0.4M溶液に浸した後、ポテンショスタットの作用電極(WE)に連結した。カウンター電極(CE)としては白金電極を、参照電極(RE)としてはAg/AgCl電極を使った。ポテンショスタットを用いた電着の間、TiCl3溶液をRT及びpH2〜2.5の範囲で、0.7V vs. Ag/AgClの電圧を加えた。電着のために加えられた電流量は2000C/gであった。電着によって形成された金属酸化物を100℃で1時間乾燥した後((株)JSRESEARCH、JSVO-60T)、400℃で3時間熱処理((株)AJEON加熱産業、UP35A)してTiO2にし、この時、1℃/分の速度で昇温した。TiO2になった金属酸化物は図5のように柱状の結晶構造を有していた。
Example 3 Production of TiO 2 / carbon nanofiber electrode The carbon nanofiber produced in Example 1 was prepared. In order to allow the Ti 3+ ions to be well adsorbed to the inner part of the dried carbon nanofibers, the sample was deposited in a TiCl 3 0.4M solution for 24 hours to produce an electrode. After removing the above electrode and removing moisture from the upper part, attach a copper tape on the surface so that it can be connected to the wire, soak it in TiCl 3 0.4M solution, and then connect it to the working electrode (WE) of the potentiostat did. A platinum electrode was used as the counter electrode (CE), and an Ag / AgCl electrode was used as the reference electrode (RE). During electrodeposition using a potentiostat, a TiCl 3 solution was applied with a voltage of 0.7 V vs. Ag / AgCl at RT and pH in the range of 2-2.5. The amount of current applied for electrodeposition was 2000 C / g. After the metal oxide formed by electrodeposition is dried at 100 ° C. for 1 hour (JSRESEARCH, JSVO-60T), heat treated at 400 ° C. for 3 hours (AJEON Heating Industry, UP35A) to make TiO 2 . At this time, the temperature was raised at a rate of 1 ° C./min. The metal oxide that became TiO 2 had a columnar crystal structure as shown in FIG.
製造例1. Fe2O3/カーボンナノファイバー電極のリチウムイオン二次電池への適用
実施例1で製造されたFe2O3/カーボンナノファイバー電極それ自体をグローブボックス(Three-Shine Inc., SK-G1500)で電解質(EC:DMC=3:7体積比、panaxetec)と分離膜(ポリプロピレンメンブレイン、Wellcos)そしてリチウムホイル(Honjo metal)、(カウンター電極)と共にコインセルで組立てた。追加的なバインダーと導電材はなかった。
Production Example 1 Application of Fe 2 O 3 / carbon nanofiber electrode to lithium ion secondary battery Fe 2 O 3 / carbon nanofiber electrode itself produced in Example 1 was used as a glove box (Three-Shine Inc., SK-G1500) And assembled with coin cell together with electrolyte (EC: DMC = 3: 7 volume ratio, panaxetec), separation membrane (polypropylene membrane, Wellcos) and lithium foil (Honjo metal) (counter electrode). There were no additional binders and conductive materials.
比較例1. Fe2O3電極のリチウムイオン二次電池への適用
比較のためにナノサイズのFe2O3粒子(Sigma-Aldrich、50nm以下)を用いてコインセルを組立てた。Fe2O3粒子をバインダー(polyvinylidene fluoride、Sigma-aldrich)と導電材(super P carbon、Timcal)と共に80:12:8の割合で混ぜ、nmethyl pyrrolidone(NMP、Junsei)溶媒を入れ、24時間100rpmのballmilling(DAE WHA Tech)を用いて混ぜてスラリーを収得した。収得されたスラリーをアルミニウムホイル(Honjo metal)上にコーティングして、110℃、真空オーブン((株)JSRESEARCH、JSVO-60T)で12時間乾燥させた後、直径14mmの大きさに切って電極として使用した。電極の厚さは約50乃至60μmであった。
Comparative Example 1 Application of Fe 2 O 3 Electrode to Lithium Ion Secondary Battery For comparison, a coin cell was assembled using nano-sized Fe 2 O 3 particles (Sigma-Aldrich, 50 nm or less). Fe 2 O 3 particles are mixed with binder (polyvinylidene fluoride, Sigma-aldrich) and conductive material (super carbon, Timcal) at a ratio of 80: 12: 8, and n-methyl pyrrolidone (NMP, Junsei) solvent is added and 24 hours 100 rpm. The ball milling (DAE WHA Tech) was used to obtain a slurry. The obtained slurry was coated on aluminum foil (Honjo metal), dried at 110 ° C. in a vacuum oven (JSRESEARCH, JSVO-60T) for 12 hours, then cut into a diameter of 14 mm as an electrode. used. The electrode thickness was about 50-60 μm.
実験例1. Fe2O3/カーボンナノファイバー電極のXRD測定
実施例1で製造されたカーボンナノファイバー及びFe2O3/カーボンナノファイバー電極のX線回折分析(Panalytical、Empyrean)を行った。これらの線回折パタ−ンは図6のように観察された。
Experimental Example 1 Fe 2 O 3 / carbon X-ray diffraction analysis of the nanofiber carbon nanofibers produced by XRD measurement example 1 of the electrode and the Fe 2 O 3 / carbon nanofiber electrode (Panalytical, Empyrean) was. These line diffraction patterns were observed as shown in FIG.
図6に示されているように、カーボンナノファイバーとFe2O3/カーボンナノファイバー電極との差からFe2O3がカーボンナノファイバーに完全に電着したことを確認した。 As shown in FIG. 6, it was confirmed from the difference between the carbon nanofiber and the Fe 2 O 3 / carbon nanofiber electrode that Fe 2 O 3 was completely electrodeposited on the carbon nanofiber.
実験例2. Fe2O3/カーボンナノファイバー電極を含むリチウムイオン二次電池の充放電特性
製造例1及び比較例1で製造されたリチウムイオン二次電池の充放電特性を分析した。これらの充放電特性は、図8のように示される。
Experimental Example 2. Charge / Discharge Characteristics of Lithium Ion Secondary Batteries Containing Fe 2 O 3 / Carbon Nanofiber Electrodes The charge / discharge characteristics of the lithium ion secondary batteries produced in Production Example 1 and Comparative Example 1 were analyzed. These charge / discharge characteristics are shown in FIG.
図8に示されているように、製造例1のリチウムイオン二次電池が比較例1のリチウムイオン二次電池に比べて比較的高い静電容量を有することが確認できた。供給される電流量が100C/g以上になれば顕著な静電容量の増加があることを確認し、これは針状に成長したカーボンナノファイバー表面の金属酸化物層と関連があるものと見える。
As shown in FIG. 8, it was confirmed that the lithium ion secondary battery of Production Example 1 had a relatively high capacitance as compared with the lithium ion secondary battery of Comparative Example 1. When the amount of current supplied is 100 C / g or more, it is confirmed that there is a significant increase in capacitance, which seems to be related to the metal oxide layer on the surface of the carbon nanofiber grown in a needle shape. .
Claims (18)
上記カーボンナノファイバーを過酸化水素溶液に浸してから取り出して上記カーボンナノファイバーの表面を活性化する段階;
上記活性化されたカーボンナノファイバーを電着水溶液内に沈積させる段階;及び
上記活性化されたカーボンナノファイバー上に電着法で金属酸化物の層を電着する段階;を有し、
上記活性化されたカーボンナノファイバーに対して垂直方向に針または柱状に成長する上記金属酸化物が担持されたカーボンナノファイバー電極の製造方法。 Producing carbon nanofibers;
Immersing the carbon nanofibers in a hydrogen peroxide solution and removing the carbon nanofibers to activate the surface of the carbon nanofibers;
Have; step of electrodepositing a layer of metal oxide in an electrodeposition method on and the activated carbon nanofibers; step depositing the activated carbon nanofibers in the electrodeposition solution
A method for producing a carbon nanofiber electrode carrying the metal oxide, which grows in a needle or column shape in a direction perpendicular to the activated carbon nanofiber.
上記水溶液を電気放射してナノファイバーを製造する段階;及び
上記ナノファイバーを炭化してカーボンナノファイバーを製造する段階;を含む請求項1に記載の製造方法。 The step of producing the carbon nanofiber comprises producing an aqueous solution containing a carbon precursor and a solvent;
The manufacturing method according to claim 1, comprising: producing a nanofiber by electrically radiating the aqueous solution; and carbonizing the nanofiber to produce a carbon nanofiber.
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