WO2004087984A1 - 炭素被覆アルミニウムおよびその製造方法 - Google Patents
炭素被覆アルミニウムおよびその製造方法 Download PDFInfo
- Publication number
- WO2004087984A1 WO2004087984A1 PCT/JP2004/003239 JP2004003239W WO2004087984A1 WO 2004087984 A1 WO2004087984 A1 WO 2004087984A1 JP 2004003239 W JP2004003239 W JP 2004003239W WO 2004087984 A1 WO2004087984 A1 WO 2004087984A1
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- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- carbon
- coated
- coated aluminum
- layer
- Prior art date
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 354
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 319
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 249
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 41
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 claims description 28
- 239000003990 capacitor Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003303 reheating Methods 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 28
- 239000000463 material Substances 0.000 abstract description 18
- 235000010210 aluminium Nutrition 0.000 description 257
- 239000011888 foil Substances 0.000 description 52
- 239000007789 gas Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000012298 atmosphere Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 6
- -1 ethylene, propylene, butene Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01G9/04—Electrodes or formation of dielectric layers thereon
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
- C23C8/64—Carburising
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- Y02E60/13—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
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Definitions
- the present invention relates to a carbon-coated aluminum, an electrode structure using the carbon-coated aluminum, a capacitor, a battery, and a method for producing the carbon-coated aluminum.
- the present invention relates to a carbon-coated aluminum as a material of an electrode or an electrode current collector used in a lithium battery, a lithium ion battery, a lithium ion polymer battery, a dye-sensitized solar cell, an electric double layer capacitor, an electrolytic capacitor, and the like.
- the present invention relates to a carbon-coated aluminum plate as a material for an electrode or an electrode current collector used for a foil, a fuel cell, a polymer electrolyte fuel cell, and the like, and a method for producing the same. Background art
- a battery is a means for directly converting chemical energy into electrical energy. Batteries are used as a power source for various electric and electronic devices because they use an electrochemical change to discharge electric charges or to repeatedly charge and discharge electric charges. Capacitors (capacitors) are used to repeatedly charge and discharge electric charges, and are used as electrical components of various electrical and electronic devices.
- lithium ion batteries, lithium ion polymer batteries, and the like have been used as power sources for mobile phones, personal computers, cameras, and the like as secondary batteries with high energy efficiency.
- fuel cells As for solar cells, low-cost dye-sensitized solar cells are being developed as the next generation of crystalline, amorphous, and thin-film solar cells.
- a current collector made of an aluminum plate coated with an active material made of a carbon material is used as a negative electrode material.
- the surface area can be increased, the bonding force with the active material layer can be improved, and a current collector for manufacturing a lithium secondary battery with excellent charge / discharge characteristics can be obtained.
- the resulting carbon-coated aluminum had insufficient adhesion between the active material layer made of the carbon-containing material and the surface of aluminum. For this reason, the phenomenon that the active material layer peels off from the surface of the aluminum during charging and discharging of the secondary battery or the capacitor may occur. As a result, there has been a problem that the charge / discharge characteristics, life, etc. of the secondary battery or the capacitor are reduced.
- an object of the present invention is to solve the above-mentioned problems, and to provide a structure of a carbon-coated aluminum material capable of improving the adhesion between aluminum and an active material layer, and a method of manufacturing the same.
- Another object of the present invention is to provide an electrode structure made of carbon-coated aluminum capable of improving the adhesion between aluminum and an active material layer.
- Still another object of the present invention is to provide a capacitor having an electrode structure made of carbon-coated aluminum capable of improving the adhesion between aluminum and an active material layer.
- Still another object of the present invention is to provide a battery provided with an electrode structure made of carbon-coated aluminum capable of improving the adhesion between aluminum and an active material layer.
- the present inventors have conducted intensive studies to solve the problems of the background art, and as a result, have obtained a carbon-coated aluminum alloy capable of achieving the above object by heating aluminum alloy under specific conditions. I found what I can do. The present invention has been made based on such findings of the inventor.
- a carbon-coated aluminum according to the present invention includes aluminum and a carbon-containing layer formed on the surface of the aluminum, and includes an aluminum element and a carbon element formed between the aluminum and the carbon-containing layer.
- an intervening layer formed between aluminum and a carbon-containing layer as an active material layer acts to enhance the adhesion between aluminum and the active material layer.
- the carbon-containing layer acts to increase or increase the surface area of aluminum.
- the intervening layer acts to increase the adhesion between aluminum and the carbon-containing layer, which is an active material layer that increases the surface area of aluminum. This makes it possible to improve the adhesion of the active material layer and increase the surface area of the carbon-coated aluminum.
- the carbon-containing layer contains therein an inclusion containing an aluminum element and a carbon element.
- the adhesion between aluminum and the active material layer can be improved as compared with the conventional case only by the presence of the above-mentioned intervening layer.
- the carbon-containing layer is thick, peeling may occur inside the carbon-containing layer.
- the adhesion in the carbon-containing layer can be improved, and peeling can be prevented. it can.
- the above-mentioned inclusion is preferably a compound of an aluminum element and a carbon element.
- the carbon-containing layer is preferably a compound of an aluminum element and a carbon element.
- the carbon-containing layer is preferably formed so as to extend outward from the surface of aluminum.
- the carbon-containing layer more effectively exerts the effect of increasing or increasing the surface area of aluminum.
- the intervening layer forms a first surface portion containing aluminum carbide, which is formed in at least a part of the surface of the aluminum.
- the carbon-containing layer constitutes a second surface portion formed to extend outward from the first surface portion.
- the second surface acts to increase the surface area of the aluminum.
- the first portion since the first surface portion containing the carbide of aluminum is formed between the aluminum layer and the second surface portion, the first portion increases the surface area of the aluminum. It acts to increase the adhesion between the second surface portion to be made. This makes it possible to more effectively achieve an improvement in the adhesion of the active material layer and an increase in the surface area of the carbon-coated aluminum.
- the carbon-containing layer further includes carbon particles, and the second surface portion is formed between the first surface portion and the carbon particles and includes aluminum carbide.
- the carbon-containing layer as the active material layer and the aluminum- ⁇ The adhesiveness with the system can be reliably maintained.
- the carbon-containing layer includes, in addition to the carbon particles, aluminum particles, an aluminum particle surface portion formed on at least a part of the surface of the aluminum particles and containing aluminum carbide, and an aluminum particle surface portion. It is preferable to further include an aluminum particle outer portion formed to extend toward the outside of the particle surface and containing aluminum carbide. In this case, even if a thicker carbon-containing layer is formed, the adhesion within the carbon-containing layer as an active material layer can be increased, and peeling can be prevented.
- the carbon-containing layer contains aluminum particles instead of carbon particles, and is formed on at least a part of the surface of the aluminum particles to form an aluminum particle surface portion containing aluminum carbide, and from the aluminum particle surface portion to the aluminum particles.
- An aluminum particle outer portion formed to extend toward the outside of the surface and containing aluminum carbide; and a second surface portion formed between the first surface portion and the aluminum particle. It may contain aluminum carbide.
- a carbon-containing layer having a large surface area per unit projected area can be formed as the active material layer.
- the thickness of the carbon-containing layer preferably has a ratio of 0.1 to 100,000 with respect to the thickness of the aluminum foil.
- the carbon-coated aluminum having any of the above features according to the present invention is used for forming an electrode structure.
- the electrode structure is preferably either an electrode or an electrode current collector.
- the above-mentioned electrode structure is used for forming a capacitor. As a result, the charge / discharge characteristics and life of the capacitor can be improved.
- the capacitor is preferably an electrochemical capacitor or an electrolytic capacitor.
- the above electrode structure is used for constituting a battery. As a result, the charge / discharge characteristics of the battery can be improved.
- the method for producing carbon-coated aluminum according to the present invention includes a step of arranging aluminum in a space containing a hydrocarbon-containing substance, and a step of heating the aluminum in a space containing the hydrocarbon-containing substance. . According to the manufacturing method of the present invention, it is not necessary to perform a series of steps of drying and pressure bonding without providing an intermediate film, without performing a pretreatment, or after coating, in order to secure adhesion as in the related art. .
- the method for producing aluminum according to the present invention is characterized in that, after the step of heating the aluminum alloy in a space containing the hydrocarbon-containing substance, the step of cooling and reheating the aluminum alloy, that is, the activation treatment
- the method may further include a step.
- the step of cooling and reheating the aluminum is preferably performed in a temperature range of 100 ° C. or more and less than 600 ° C.
- the step of arranging aluminum in the space containing the hydrocarbon-containing substance includes the step of arranging at least one selected from the group consisting of a carbon-containing substance and aluminum powder. After being deposited on the surface of the aluminum, it is preferred to place the aluminum in the space containing the hydrocarbon containing material.
- the aluminum in the manufacturing method of the present invention, in the step of arranging the aluminum, after the carbon-containing substance is attached to the surface of the aluminum, the aluminum may be arranged in the space containing the hydrocarbon-containing substance. After depositing the aluminum powder on the aluminum surface, the aluminum may be placed in the space containing the hydrocarbon-containing substance, or after the carbon-containing substance and the aluminum powder are deposited on the aluminum surface, the carbonization may be performed. Aluminum may be arranged in the space containing the hydrogen-containing substance.
- a binder may be used when at least one selected from the group consisting of a carbon-containing substance and aluminum powder is attached to the surface of aluminum.
- the binder is preferably an organic polymer that can burn when heated.
- the step of heating the aluminum is performed at 450 ° C. or more.
- the step of arranging aluminum in a space containing a hydrocarbon-containing substance it is preferable to arrange anolemme in a space containing paraffinic hydrocarbon or methane.
- the adhesion between the carbon-containing layer and the aluminum can be improved more than before. Further, by forming the electrode structure using the carbon-coated aluminum of the present invention, the charge / discharge characteristics, the life, and the like of the battery or the capacitor can be improved. Further, according to the method for producing a carbon-coated aluminum of the present invention, aluminum is disposed in a space containing a hydrocarbon-containing substance, and the aluminum surface is made of a carbon-containing layer by a simple process of heating.
- FIG. 1 is a diagram schematically showing a cross-sectional structure of a carbon-coated aluminum as one embodiment of the present invention.
- FIG. 2 is a diagram schematically showing a cross-sectional structure of a carbon-coated aluminum according to another embodiment of the present invention.
- FIG. 3 is a diagram schematically showing a cross-sectional structure of a carbon-coated aluminum according to still another embodiment of the present invention.
- FIG. 4 is a diagram schematically showing a cross-sectional structure of carbon-coated aluminum as still another embodiment of the present invention.
- a carbon-containing layer 2 is formed on the surface of aluminum (aluminum plate or aluminum foil) 1.
- An intervening layer 3 containing an aluminum element and a carbon element is formed between the aluminum 1 and the carbon-containing layer 2.
- Carbon-containing layer 2 is formed to extend outward from the surface of aluminum 1.
- Intervening layer 3 constitutes a first surface portion containing aluminum carbide, formed in at least a part of the surface of aluminum 1.
- the carbon-containing layer 2 includes a second surface portion 21 formed so as to extend from the first surface portion 3 to the outside in a fibrous or filamentous form.
- the second surface portion 21 is a compound of an aluminum element and a carbon element.
- the cross-sectional structure of the carbon-coated aluminum has the same structure as the cross-sectional structure shown in FIG. It further includes a plurality of carbon particles 22.
- the second surface portion 21 extends outward from the first surface portion 3 in a fibrous or filamentous form, and is formed between the first surface portion 3 and the carbon particles 22 to form an aluminum carbide. including.
- the sectional structure of carbon-coated aluminum has the same structure as the sectional structure shown in FIG. Aluminum particles 23.
- Aluminum particle table Surface portion 24 is formed on at least a part of the surface of aluminum particles 23 and contains aluminum carbide.
- the aluminum particle outer portion 25 is formed so as to extend in a cactus-like form from the aluminum particle surface portion 24 toward the outside of the surface of the aluminum particle 23, and contains aluminum carbide.
- the second surface portion 21 extends outwardly from the first surface portion 3 in a fibrous or filamentous form, and is formed between the first surface portion 3 and the aluminum particles 23 to form aluminum. Contains carbide.
- the cross-sectional structure of the carbon-coated aluminum has the same structure as the cross-sectional structure shown in FIG. Further includes carbon particles 22 and aluminum particles 23.
- the second surface portion 21 extends outwardly from the first surface portion 3 in a fibrous or filamentous form, and is formed between the first surface portion 3 and the carbon particles 22 to remove aluminum carbide.
- the aluminum particle surface portion 24 is formed in at least a part of the surface of the aluminum particle 23 and contains aluminum carbide.
- the aluminum particle outer portion 25 is formed so as to extend in a cactus-like form from the aluminum particle surface portion 24 toward the outside of the surface of the aluminum particle 23, and contains aluminum carbide.
- the aluminum as the substrate on which the carbon-containing layer is formed is not particularly limited, and pure aluminum or an aluminum alloy can be used.
- Such aluminum preferably has an aluminum purity of 98% by mass or more as measured according to the method described in "JISH 211".
- the aluminum foil used in the present invention has the following composition: lead (Pb), silicon (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium ( Cr), zinc (Zn), titanium (Ti), vanadium (V), gallium (Ga), nickel (Ni) and boron (B) at least one alloying element within the required range. Also includes added aluminum alloys or aluminum with limited contents of the above unavoidable impurity elements.
- the thickness of the aluminum is not particularly limited, but is preferably 5 im or more and 200 ⁇ m or less for a foil, or more than 200 ⁇ m and 3 mm or less for a plate.
- the above-mentioned aluminum those manufactured by a known method can be used. For example, a melt of aluminum or an aluminum alloy having the above-described predetermined composition is prepared, and the resulting mass is appropriately homogenized. After that, aluminum can be obtained by subjecting the ingot to hot rolling and cold rolling. In the middle of the above cold rolling process, 150. Intermediate annealing treatment may be performed within the range of C or more and 400 ° C or less.
- the carbon-coated aluminum of the present invention is most suitable for use as a gas electrode material for a fuel cell, a polarized electrode material for an electric double layer capacitor, and a cathode material for an electrolytic capacitor.
- a positive electrode material of a lithium ion secondary battery such as a lithium ion battery and a lithium ion polymer battery
- a material having an active material layer formed on an aluminum surface as a current collector has been used.
- As the negative electrode material a material in which an active material layer composed of a carbon-containing layer is formed on the surface of a copper foil as a current collector has been used.
- the carbon-coated aluminum of the present invention is used for the adhesion of an electrode material (a mixture of lithium metal oxide, carbon, a binder, etc.) applied to the surface of the current collector in the positive electrode material of the above-mentioned lithium ion secondary battery. It is effective to use it as a current collector material in order to increase the power. In recent years, attempts have been made to use aluminum as a current collector also as a negative electrode material in order to reduce the weight of these secondary batteries. In response to such an attempt, the carbon-coated aluminum of the present invention is most suitable for use as a negative electrode material of a lithium ion secondary battery.
- an electrode material a mixture of lithium metal oxide, carbon, a binder, etc.
- the type of the hydrocarbon-containing substance used is not particularly limited.
- the types of hydrocarbon-containing substances include, for example, paraffinic hydrocarbons such as methane, ethane, propane, n-butane, isobutane, and pentane, olefinic hydrocarbons such as ethylene, propylene, butene, and butadiene, and acetylene.
- paraffinic hydrocarbons such as methane, ethane, and propane are preferable because they become gaseous in the step of heating the aluminum foil.
- the hydrocarbon-containing substance may be used in any state such as liquid or gas in the production method of the present invention.
- the hydrocarbon-containing substance may be present in the space where aluminum exists, and may be introduced into the space where aluminum is disposed by any method.
- the hydrocarbon-containing substance is in a gaseous state (methane, ethane, propane, etc.)
- the enclosed space in which the heat treatment of aluminum is performed may be filled with the hydrocarbon-containing substance alone or together with the inert 14 gas.
- the hydrocarbon-containing substance is a liquid
- the hydrocarbon-containing substance may be filled alone or with an inert gas so as to vaporize in the closed space.
- the pressure of the heating atmosphere is not particularly limited, and may be normal pressure, reduced pressure, or reduced pressure. Adjustment of pressure may be performed at any time while maintaining a certain heating temperature, while increasing the temperature to a certain heating temperature, or while decreasing the temperature from a certain heating temperature. .
- the weight ratio of the hydrocarbon-containing substance introduced into the space in which aluminum is placed is not particularly limited, but is usually 0.1 to 50 parts by weight in terms of carbon with respect to 100 parts by weight of aluminum. And more preferably in the range of 0.5 to 30 parts by weight.
- the heating temperature may be appropriately set according to the composition of the aluminum to be heated, etc., but is usually in the range of 450 ° C or more and less than 660 ° C.
- the temperature is preferably within the range of 530 ° C. or more and 620 ° C. or less.
- the heating time depends on the heating temperature and the like, but is generally in the range of 1 hour to 100 hours.
- the oxygen concentration in the heating atmosphere is preferably set to 1.0 volume% or less. If the oxygen concentration in the heating atmosphere exceeds 1.0% by volume at a heating temperature of 400 ° C or higher, the thermal oxide film on the aluminum surface may enlarge and the interfacial electrical resistance on the aluminum surface may increase. There is.
- the surface of aluminum may be roughened before the heat treatment.
- the roughening method is There is no particular limitation, and known techniques such as cleaning, etching, and plast can be used.
- the carbon-containing substance adhered to the surface of the aluminum foil may be any of activated carbon fiber, activated carbon cloth, activated carbon felt, activated carbon powder, ink, carbon black or graphite.
- the adhesion method is as follows. The above carbon-containing substance is prepared in a slurry, liquid, or solid form using a binder, solvent, water, or the like, and is adhered to the aluminum surface by coating, divebing, or thermocompression bonding. Just do it. After depositing the carbon-containing substance on the surface of the aluminum, the carbon-containing substance may be dried at a temperature within the range of 20 ° C. to 300 ° C.
- the carbon-containing substance is added to 100 parts by weight of the carbon-containing substance.
- the aluminum powder it is preferable to add the aluminum powder in a weight ratio within a range from 0.01 part by weight to 1000 parts by weight.
- Carbon coated aluminum was produced according to the following Examples 1 to 23 and Conventional Examples 1 to 3. In addition, a reference example of carbon-coated aluminum was also prepared for comparison with the example.
- a carbon-containing substance was applied to both sides of a 10-zm-thick aluminum hard foil (JISA150-HI8) and dried at a temperature of 30 ° C. for 3 hours to be adhered.
- the nominal purity of the aluminum foil is 99.5.55 mass. /.
- the mass spectrometry values of the composition were 225 ppm for silicon and 380 ppm for iron.
- the composition of the carbon-containing substance is as follows: 1 part by weight of carbon black (# 240B manufactured by Mitsubishi Chemical Corporation) is 6 parts by weight of isopropyl alcohol (IPA) and 3 parts by weight of 1,1,1 trichloroethane. Weight parts were added.
- the adhesion of the carbon-containing substance was such that the thickness after drying was 4 / Zm on one side.
- the aluminum foil to which the carbon-containing substance was attached was placed in the atmosphere and temperature shown in Table 1. Heated for 12 hours.
- a carbon-containing substance was applied to both sides of an aluminum hard foil (JIS A1050-H18) having a thickness of 10 ⁇ , followed by drying at a temperature of 100 ° C for 10 minutes for attachment.
- the nominal purity of aluminum foil is 99.55 mass 0 /.
- the mass spectrometry values of the composition were 2250 ppm for silicon and 3800 ppm for iron.
- the composition of the carbon-containing substance was such that 1 part by weight of polyethylene terephthalate (PET) was added to 1 part by weight of a car pump rack (# 2400B manufactured by Mitsubishi Chemical Corporation). The thickness of the carbon-containing substance was adjusted to 180 ⁇ on one side after drying.
- Example 6 In the same manner as in Example 6, a carbon-containing substance was attached to both surfaces of the aluminum hard foil. Thereafter, the aluminum foil to which the carbon-containing substance was adhered was pressed under a pressure of about 20% using a rolling roll, so that the carbon-containing substance was pressed onto the surface of the aluminum foil. The pressed aluminum foil was heated for 12 hours under the conditions of atmosphere and temperature shown in Table 1.
- a carbon-containing substance was applied to both surfaces of an aluminum hard foil (JIS A3003-H18) having a thickness of 10 / im, and was dried at a temperature of 100 ° C for 10 minutes to be attached.
- the mass spectrometry value of the composition of the aluminum foil was 0.57% by mass of silicon, 0.62% by mass of iron, 0.1% by mass of copper, and 1.1% by mass of manganese.
- the composition of the carbon-containing substance was such that 1 part by weight of polyethylene terephthalate (PET) was added to 1 part by weight of carbon black (# 2400B manufactured by Mitsubishi Chemical Corporation).
- the thickness of the dried carbon-containing substance was 3 mm on one side.
- a rolling roll was used to apply a pressure of about 30% to the aluminum foil to which the carbon-containing substance was attached, and the carbon-containing substance was pressed onto the surface of the aluminum foil.
- the pressed aluminum foil was heated under the atmosphere and temperature conditions shown in Table 1 for 12 hours.
- Example 9 to 12 A carbon-containing substance was applied to both sides of an aluminum hard foil (JIS A3003-H18) having a thickness of 10 ⁇ , and was dried at a temperature of 100 for 10 minutes to be attached.
- the mass spectrometry value of the composition of the aluminum foil was 0.57% by mass for silicon, 0.62% by mass for iron, and 0.1% for copper. /.
- manganese was 1.1% by mass.
- the composition of the carbon-containing substance is the sum of 100 parts by weight of car pump rack (Mitsubishi Chemical Corporation # 2400 ⁇ ), 100 parts by weight of polyethylene terephthalate (PET), and aluminum powder as shown in Table 1 there were.
- the carbon-containing material was attached so that the thickness after drying was 3 mm on one side.
- a rolling roll was used to apply a pressure of about 30% to the aluminum foil to which the carbon-containing material was attached, and the carbon-containing material was pressed onto the surface of the aluminum foil.
- the pressed aluminum foil was heated under the atmosphere and temperature conditions shown in Table 1 for 12 hours.
- a carbon-containing substance was applied to both sides of an aluminum hard foil (JIS A1050-H18) having a thickness of 10 / zm, and dried at a temperature of 30 ° C for 3 hours to be adhered.
- the nominal purity of the aluminum foil is 99.55 mass. /.
- the mass spectrometry values of the composition were 2250 ppm for silicon and 3800 ppm for iron.
- the composition of the carbon-containing material is as follows: 1 part by weight of carbon black (Mitsubishi Chemical Corporation # 2400B), 6 parts by weight of isopropyl alcohol (IPA), 3 parts by weight of 1,1,1 trichloroethane, Was added.
- the adhesion of the carbon-containing substance was such that the thickness after drying was 4 zm on one side.
- the carbon-coated aluminum foil thus obtained corresponds to the non-heat-treated ones of Examples 1 to 5.
- a carbon-containing substance was applied to both sides of an aluminum hard foil (JIS A1050-H18) having a thickness of 10 ⁇ , and was dried at a temperature of 100 for 10 minutes to be attached.
- the nominal purity of the aluminum foil was 99.55% by mass, and the mass spectrometry of the composition was 2250 ppm for silicon and 3800 ppm for iron.
- the composition of the carbon-containing substance was such that 1 part by weight of polyethylene terephthalate (PET) was added to 1 part by weight of carbon black (# 2400B manufactured by Mitsubishi Chemical Corporation). carbon The attached substance was attached such that the thickness after drying was 18 O / zm on one side.
- the carbon-coated aluminum foil thus obtained corresponds to the one in which the heat treatment in Example 6 was not performed.
- a carbon-containing material was applied to both sides of a hard aluminum foil having a thickness of 10 (JISA003-H18), and dried at a temperature of 100 for 10 minutes to be applied.
- the mass spectrometry value of the composition of the aluminum foil was 0.557% by mass for silicon, 0.62% by mass for iron, and 0.1% for copper. /.
- the manganese content was 1.1% by mass.
- the composition of the carbon-containing substance was such that 1 part by weight of polyethylene terephthalate (PET) was added to 1 part by weight of a car pump rack (# 240OB manufactured by Mitsubishi Chemical Corporation).
- the thickness of the dried carbon-containing substance was 3 mm on one side.
- the carbon-coated aluminum foil thus obtained corresponds to the one not subjected to the heat treatment in Example 7.
- a carbon-containing substance was applied to both sides of an aluminum hard foil (JIS A150-H18) having a thickness of 10 ⁇ , and was applied by drying at a temperature of 30 ° C for 3 hours.
- the nominal purity of the aluminum foil was 99.5% by weight, and the mass spectrometry values of the composition were 2250 ppm for silicon and 3800 ppm for iron.
- the composition of the carbon-containing substance is as follows: 1 part by weight of carbon black (# 240 OB manufactured by Mitsubishi Chemical Corporation) is 6 parts by weight of isopropyl alcohol (IPA) and 3 parts by weight of 1,1,1 trichloroethane.
- the adhesion of the carbon-containing material was such that the thickness after drying was 4 ⁇ m on one side.
- the adhesion was evaluated by the taping method.
- Adhesive tape with a width of 15 mm and a length of 120 mm on the surface of the carbon-containing layer in a carbon-coated aluminum sample with a width of 1 Omm and a length of 10 Omm (Scotch Tape, manufactured by Sumitomo 3M Ltd.)
- the adhesive tape was peeled off, and the adhesion was evaluated according to the following formula.
- Adhesion (%) ⁇ Weight of carbon-containing layer after peeling (mg) ⁇ Weight of carbon-containing layer before peeling (mg) X 100
- the formation amount of the inclusion layer and inclusions was evaluated by quantitative analysis of aluminum carbide.
- the gas generated by completely dissolving the carbon-coated aluminum sample in a 20% aqueous sodium hydroxide solution is collected, and the collected gas is quantitatively analyzed using a high-sensitivity gas chromatograph equipped with a flame ionization detector. It was converted to the carbide (Al 4 C 3 ) content. Based on the aluminum carbide content, the formation amount of the intervening layer and the inclusion was evaluated according to the following equation.
- Weight of formation of inclusions with the intervening layer aluminum carbide (A 1 4 C 3) ( mg) / carbon-containing layer (mg)
- ⁇ r j shown in the column “Amount of intervening layer and inclusions” indicates that it is an undetectable amount.
- the carbon-coated aluminums of Examples 1 to 5 exhibited considerably higher adhesion than the carbon-coated aluminum of Conventional Example 1.
- the carbon-coated aluminum of Examples 6 to 7 showed considerably higher adhesion than the carbon-coated aluminum of Conventional Example 2.
- the carbon-coated aluminum of Examples 8 to 12 showed much higher adhesion than the carbon-coated aluminum of Conventional Example 3.
- the carbon-coated aluminum of Examples 9 to 12 obtained by depositing aluminum powder in addition to the carbon-containing substance and then performing heat treatment, after adhering only the carbon-containing substance, It is understood that the adhesiveness is higher than that of the carbon-coated aluminum of Example 8 obtained by the heat treatment.
- the carbon-coated aluminum of Reference Example 1 obtained by performing heat treatment in an atmosphere of an inert gas of argon gas instead of the atmosphere gas of the hydrocarbon-containing substance (Examples 1 to 5) is a conventional example. As in No. 1, it showed low adhesion.
- the heat treatment was performed after the carbon-containing substance was attached to the surface of the aluminum.However, even when the carbon-containing substance was not attached to the aluminum foil surface in advance, the adhesion was higher than before. It was confirmed that it exhibited the property.
- FIG. 2 shows a schematic sectional view of the fifth embodiment.
- the presence of aluminum carbide was confirmed by X-ray diffraction and electron energy loss spectroscopy (EELS).
- FIG. 4 shows a schematic cross-sectional view of the tenth embodiment.
- the presence of aluminum carbide was confirmed by X-ray diffraction and electron energy loss spectroscopy (EELS).
- a 30 "m-thick anolemminium foil (JISA 1050-H18) was kept in an argon gas atmosphere at a temperature of 590 ° C for 10 hours.
- the surface of the sample was observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- no part of the aluminum foil in the form of fibrous or filament extending outward from the surface of the aluminum foil was confirmed.
- Also, X-ray diffraction and electron energy loss spectroscopy (EELS) showed that Existence has not been confirmed.
- FIG. 1 shows a schematic sectional view of this.
- the presence of aluminum carbide was confirmed by X-ray diffraction electron energy loss spectroscopy (EELS). (Reference example 3)
- the etched aluminum obtained in Reference Example 3 was kept at 590 ° C. for 10 hours in an argon gas atmosphere.
- the etched aluminum obtained in Reference Example 3 was kept at a temperature of 590 ° C. for 10 hours in an acetylene gas atmosphere.
- Fig. 2 shows a schematic diagram of this cross section.
- X-ray diffraction and electron energy loss spectroscopy (EELS) confirmed the presence of aluminum carbide.
- FIG. 3 shows a schematic sectional view of this.
- the presence of aluminum carbide was confirmed by X-ray diffraction and electron energy loss spectroscopy (EELS).
- Example 21 2 parts by weight of carbon black having an average particle size of 0.1 ⁇ and 2 parts by weight of aluminum powder having an average particle size of 1 are mixed with 1 part by weight of a binder containing at least carbon and hydrogen, and dispersed in a solvent (toluene).
- a coating liquid having a solid content of 30% was obtained.
- This coating solution was applied to both sides of 1.5 mm thick aluminum (JIS 3003-H18) and dried. The thickness of the dried coating film was 4 ⁇ on one side.
- This aluminum was heat-treated under the conditions shown in Table 2. In Example 21, after the heat treatment, aluminum was subjected to rolling using a rolling roll at a rolling reduction of about 20%. In Example 23, an activation treatment was performed in air at 300 ° C. for 2 hours after the heat treatment.
- FIG. 4 shows a schematic sectional view of this.
- the surface resistance characteristics were evaluated by the AC impedance method.
- the samples obtained in Examples 13 and 14 and Reference Example 2-4 were immersed in a 1 M aqueous hydrochloric acid solution at a liquid temperature of 293 K, and the AC impedance was measured under a constant current.
- the measurement frequency was set to 20 points from 0.5 to 1000 Hz.
- the simplest equivalent circuit at the electrode aqueous solution interface is represented by a circuit in which a liquid resistance is connected in series to a parallel circuit of a charge transfer resistance and an electric double layer capacitance. Therefore, the measured AC impedance measured under these conditions was displayed as a vector on the complex plane, and the X axis was represented by the real part and the Y axis was represented by the imaginary part. Furthermore, from the locus of the AC impedance of each sample, the value at the intersection with the X axis was adopted as the surface resistance value.
- the carbon-coated aluminum of Example 13 exhibited much lower surface resistance characteristics than the aluminum of Reference Example 2.
- the carbon-coated aluminum of Example 14 exhibited much lower surface resistance characteristics than the aluminum of Reference Examples 3 and 4.
- the surface area of the carbon-coated aluminum obtained in Examples 13 to 23 and the aluminum obtained in Reference Examples 2 to 4 were evaluated.
- the evaluation conditions are as follows. Table 4 shows the c evaluation results.
- the surface area was evaluated by capacitance.
- the capacitance was measured in an aqueous ammonium borate solution (8 g / L) using an LCR meter.
- the carbon-coated aluminum of Example 13 exhibited significantly higher capacitance than the aluminum of Reference Example 2, that is, a significantly larger surface area.
- the carbon-coated aluminum of Example 14 exhibited a significantly larger surface area than the a / reminimum of Reference Examples 3 and 4.
- the carbon-coated aluminum of Examples 15 to 21 showed a significantly larger surface area than the aluminum of Reference Examples 3 and 4 whose surfaces were etched.
- the charge / discharge characteristics, capacity, life, and the like of the battery or capacitor can be improved.
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Abstract
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CN2004800085945A CN1833047B (zh) | 2003-03-31 | 2004-03-11 | 包覆有碳的铝及其制造方法 |
CA2519115A CA2519115C (en) | 2003-03-31 | 2004-03-11 | Aluminum material coated with carbon and manufacturing method thereof |
EP04719665.4A EP1609878B1 (en) | 2003-03-31 | 2004-03-11 | Carbon-coated aluminum and method for producing same |
JP2005504148A JP4445465B2 (ja) | 2003-03-31 | 2004-03-11 | 炭素被覆アルミニウムおよびその製造方法 |
US10/549,202 US7327556B2 (en) | 2003-03-31 | 2004-03-11 | Carbon-coated aluminum and method for producing same |
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PCT/JP2004/003239 WO2004087984A1 (ja) | 2003-03-31 | 2004-03-11 | 炭素被覆アルミニウムおよびその製造方法 |
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EP (2) | EP1619699B1 (ja) |
JP (3) | JPWO2004088690A1 (ja) |
KR (2) | KR100873426B1 (ja) |
CN (2) | CN100521013C (ja) |
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Also Published As
Publication number | Publication date |
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KR100880434B1 (ko) | 2009-01-29 |
CN1777965A (zh) | 2006-05-24 |
CN1833047B (zh) | 2010-05-26 |
KR20050116836A (ko) | 2005-12-13 |
EP1619699B1 (en) | 2015-11-18 |
TWI339912B (en) | 2011-04-01 |
JPWO2004088690A1 (ja) | 2006-07-06 |
KR20050118202A (ko) | 2005-12-15 |
CN100521013C (zh) | 2009-07-29 |
JP2010021589A (ja) | 2010-01-28 |
JP4782862B2 (ja) | 2011-09-28 |
JPWO2004087984A1 (ja) | 2006-07-06 |
JP4445465B2 (ja) | 2010-04-07 |
CA2519115C (en) | 2011-01-18 |
EP1619699A1 (en) | 2006-01-25 |
US20060172134A1 (en) | 2006-08-03 |
EP1609878A1 (en) | 2005-12-28 |
EP1609878A4 (en) | 2007-08-08 |
US7327556B2 (en) | 2008-02-05 |
EP1609878B1 (en) | 2017-06-14 |
TWI333221B (en) | 2010-11-11 |
TW200426867A (en) | 2004-12-01 |
CN1833047A (zh) | 2006-09-13 |
WO2004088690A1 (ja) | 2004-10-14 |
US20060171102A1 (en) | 2006-08-03 |
CA2519115A1 (en) | 2004-10-14 |
TW200423459A (en) | 2004-11-01 |
KR100873426B1 (ko) | 2008-12-11 |
US7388740B2 (en) | 2008-06-17 |
EP1619699A4 (en) | 2007-08-08 |
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