JP5271261B2 - Carbon-coated aluminum material and manufacturing method thereof - Google Patents
Carbon-coated aluminum material and manufacturing method thereof Download PDFInfo
- Publication number
- JP5271261B2 JP5271261B2 JP2009515110A JP2009515110A JP5271261B2 JP 5271261 B2 JP5271261 B2 JP 5271261B2 JP 2009515110 A JP2009515110 A JP 2009515110A JP 2009515110 A JP2009515110 A JP 2009515110A JP 5271261 B2 JP5271261 B2 JP 5271261B2
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- JP
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- Prior art keywords
- carbon
- aluminum material
- aluminum
- content
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 246
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 195
- 239000000463 material Substances 0.000 title claims abstract description 176
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000003990 capacitor Substances 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- -1 belium Chemical compound 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 abstract description 69
- 239000010410 layer Substances 0.000 description 104
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 230000007423 decrease Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000835 fiber 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
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 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
- 239000000976 ink Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 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
- 239000000025 natural resin Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
この発明は、一般的には、アルミニウム材の表面を炭素で被覆した炭素被覆アルミニウム材とその製造方法に関し、特定的には各種キャパシタの電極や集電体、各種電池の集電体や電極等に用いられる炭素被覆アルミニウム材とその製造方法に関するものである。 TECHNICAL FIELD The present invention generally relates to a carbon-coated aluminum material in which the surface of an aluminum material is coated with carbon, and a method for producing the same, and specifically, electrodes and current collectors of various capacitors, current collectors and electrodes of various batteries, and the like. The present invention relates to a carbon-coated aluminum material used in manufacturing and a method for producing the same.
従来から、アルミニウム材をそのままで電極や集電体の材料として使用した場合、アルミニウム材の表面に形成される酸化被膜が不働態化し、結果として表面の導電性が低下し、絶縁化するという問題がある。この問題を解決するために、アルミニウム材の表面に炭素を塗布することにより、表面の導電性を改善するという手法が採用されてきた。 Conventionally, when an aluminum material is used as it is as a material for an electrode or a current collector, the oxide film formed on the surface of the aluminum material becomes passivated, resulting in a decrease in surface conductivity and insulation. There is. In order to solve this problem, a method of improving the surface conductivity by applying carbon to the surface of an aluminum material has been adopted.
例えば、アルミニウム材の表面に炭素を付与する方法としては、バインダを含む炭素をアルミニウム材の表面に湿式で塗布する方法、特開２０００−１６４４６６号公報（特許文献１）に記載されているように真空蒸着法によってアルミニウム材の表面に炭素膜を形成する方法がある。なお、特開２０００−１６４４６６号公報（特許文献１）には、キャパシタまたは電極に使用される電極の製造方法として、アルミニウムで形成された集電体に、カーボンの中間膜を設け、その上に活物質層を被覆する方法が記載されている。 For example, as a method for imparting carbon to the surface of an aluminum material, as described in Japanese Patent Laid-Open No. 2000-164466 (Patent Document 1), a method in which carbon containing a binder is wet-coated on the surface of an aluminum material. There is a method of forming a carbon film on the surface of an aluminum material by a vacuum deposition method. In JP 2000-164466 (Patent Document 1), as a method of manufacturing an electrode used for a capacitor or an electrode, a carbon intermediate film is provided on a current collector formed of aluminum, and then on the current collector. A method for coating an active material layer is described.
また、例えば、特開２００４−２０７１１７号公報（特許文献２）には、電極活物質との密着性が高く、かつ、電極活物質との接触抵抗値の低い集電体用アルミニウム箔を得るために、フッ酸を含む酸性溶液でアルミニウム箔の表面を洗浄して前処理を行うことが開示されている。 Further, for example, in Japanese Patent Application Laid-Open No. 2004-207117 (Patent Document 2), an aluminum foil for a current collector having high adhesion with an electrode active material and low contact resistance with the electrode active material is obtained. Discloses that the surface of the aluminum foil is washed with an acidic solution containing hydrofluoric acid to perform pretreatment.
さらに、例えば、特開２００５−１９１４２３号公報（特許文献３）では、電極層とアルミニウムエッチング箔集電体との密着性に優れた電気二重層キャパシタ用電極として、アルミニウムエッチング箔集電体と炭素を含む電極層との間にフッ素を含むアンダーコート層を設けることが提案されている。 Further, for example, in Japanese Patent Application Laid-Open No. 2005-191423 (Patent Document 3), an aluminum etching foil current collector and carbon as an electrode for an electric double layer capacitor having excellent adhesion between the electrode layer and the aluminum etching foil current collector. It has been proposed to provide an undercoat layer containing fluorine between an electrode layer containing selenium.
しかしながら、これらの製造方法では被覆炭素とアルミニウム材との密着性がまだまだ不十分なことや、バインダ自身が熱に対して不安定なだけでなく、バインダが存在するだけで内部抵抗が高くなるという問題があった。 However, in these manufacturing methods, the adhesion between the coated carbon and the aluminum material is still insufficient, the binder itself is not stable to heat, and the internal resistance is increased only by the presence of the binder. There was a problem.
そこで、これらの問題を解決するために、国際公開第ＷＯ２００４/０８７９８４号パンフレット（特許文献４）には、炭素含有物質をアルミニウム材の表面に付着させた後、炭化水素含有物質を含む空間で加熱することにより、アルミニウム材の表面上に炭素含有層を形成し、アルミニウム材と炭素含有層との間に形成されたアルミニウムの炭化物によって、炭素含有層とアルミニウム材との間の密着性を高めることが記載されている。 Therefore, in order to solve these problems, International Publication No. WO 2004/089784 (Patent Document 4) discloses that a carbon-containing substance is attached to the surface of an aluminum material and then heated in a space containing the hydrocarbon-containing substance. Forming a carbon-containing layer on the surface of the aluminum material, and improving adhesion between the carbon-containing layer and the aluminum material by aluminum carbide formed between the aluminum material and the carbon-containing layer. Is described.
なお、国際公開第ＷＯ２００４/０８７９８４号パンフレット（特許文献４）では、炭素含有層を形成するための基材として用いられるアルミニウム材については、アルミニウム純度が「ＪＩＳ Ｈ２１１１」に記載された方法に準じて測定された値で９８質量％以上が好ましいと述べられているだけで詳細な記述はない。
最近、キャパシタや電池に対して、特に過酷な環境下での品質安定性が求められるようになってきた。この要求に対応するためには、キャパシタを構成する電極や電池を構成する集電体が高温で高湿な雰囲気中に長期間曝されても、初期特性を維持する必要がある。 Recently, it has been required for capacitors and batteries to have quality stability under particularly harsh environments. In order to meet this demand, it is necessary to maintain the initial characteristics even when the electrodes constituting the capacitor and the current collector constituting the battery are exposed to a high temperature and high humidity atmosphere for a long period of time.
国際公開第ＷＯ２００４/０８７９８４号パンフレット（特許文献４）に記載された炭素被覆アルミニウムは、炭素含有層とアルミニウム材との間の密着性を高めるという効果がある。 The carbon-coated aluminum described in International Publication No. WO 2004/089784 (Patent Document 4) has an effect of improving the adhesion between the carbon-containing layer and the aluminum material.
しかしながら、炭素被覆アルミニウム材の使用範囲の拡大に伴って、炭素含有層とアルミニウム材との間の高い密着性を長期間にわたって維持することが求められており、さらに特性を改善することが必要になってきた。 However, with the expansion of the range of use of carbon-coated aluminum materials, it is required to maintain high adhesion between the carbon-containing layer and the aluminum material over a long period of time, and it is necessary to further improve the characteristics. It has become.
そこで、この発明の目的は、炭素含有層とアルミニウム材との間の密着性を長期間にわたって維持することが可能な炭素被覆アルミニウム材とその製造方法を提供することである。 Then, the objective of this invention is providing the carbon covering aluminum material which can maintain the adhesiveness between a carbon containing layer and an aluminum material over a long period of time, and its manufacturing method.
本発明者は、鋭意研究を重ねた結果、炭素含有物質をアルミニウム材の表面に付着させた後、炭化水素含有物質を含む空間で加熱することにより、アルミニウム材の表面上に炭素含有層を形成するときに、アルミニウム材と炭素含有層との間に形成されるアルミニウムの炭化物の形成挙動が、基材としてのアルミニウム材自身の組成によって大きく影響を受けることを見出した。すなわち、本発明者は、基材としてのアルミニウム材自身の組成を最適化することにより、炭素含有層とアルミニウム材の表面との密着性が向上し、その結果として従来の炭素被覆アルミニウム材よりも、より長期間にわたって密着性を安定して維持することが可能になるという知見を得た。さらに、本発明者は、アルミニウム材と炭素含有層との間に形成されたアルミニウムの炭化物の生成量がある特定の量以上であれば、アルミニウム材と炭素含有層との間の密着性をより確実に高めることができるとともに、従来の炭素被覆アルミニウム材よりも、より長期間にわたって密着性を安定して維持することが可能となるという知見を得た。このような発明者の知見に基づいて本発明はなされたものである。 As a result of intensive research, the inventor forms a carbon-containing layer on the surface of the aluminum material by attaching the carbon-containing material to the surface of the aluminum material and then heating in a space containing the hydrocarbon-containing material. It was found that the formation behavior of aluminum carbide formed between the aluminum material and the carbon-containing layer is greatly influenced by the composition of the aluminum material itself as the base material. That is, the present inventor has improved the adhesion between the carbon-containing layer and the surface of the aluminum material by optimizing the composition of the aluminum material itself as a base material, and as a result, compared with the conventional carbon-coated aluminum material. The present inventors have found that it becomes possible to stably maintain the adhesiveness for a longer period of time. Furthermore, the present inventor further improves the adhesion between the aluminum material and the carbon-containing layer if the amount of aluminum carbide formed between the aluminum material and the carbon-containing layer is a certain amount or more. It has been found that it can be reliably increased and that the adhesion can be stably maintained over a longer period of time than a conventional carbon-coated aluminum material. The present invention has been made based on such knowledge of the inventors.
この発明に従った炭素被覆アルミニウム材は、アルミニウム材と、このアルミニウム材の表面上に形成された炭素含有層と、アルミニウム材と炭素含有層との間に形成された、アルミニウム元素と炭素元素とを含む介在層とを備える。介在層は、アルミニウム材の表面の少なくとも一部の領域に形成された、アルミニウムの炭化物を含む第１の表面部分を含む。炭素含有層は、第１の表面部分から外側に向かって延びるように形成された第２の表面部分を含む。炭素含有層は炭素含有粒子をさらに含む。第２の表面部分は第１の表面部分と炭素含有粒子との間に形成されてアルミニウムの炭化物を含む。アルミニウム材において、アルミニウムの含有量が９９．６質量％以上、鉛（Ｐｂ）の含有量が１０質量ｐｐｍ以下、マグネシウム（Ｍｇ）の含有量が１０質量ｐｐｍ以下である。 The carbon-coated aluminum material according to the present invention includes an aluminum material, a carbon-containing layer formed on the surface of the aluminum material, and an aluminum element and a carbon element formed between the aluminum material and the carbon-containing layer. Including an intervening layer. The intervening layer includes a first surface portion including an aluminum carbide formed in at least a partial region of the surface of the aluminum material. The carbon-containing layer includes a second surface portion formed so as to extend outward from the first surface portion. The carbon-containing layer further includes carbon-containing particles. The second surface portion is formed between the first surface portion and the carbon-containing particles and includes aluminum carbide. In the aluminum material, the aluminum content is 99.6 mass% or more, the lead (Pb) content is 10 mass ppm or less, and the magnesium (Mg) content is 10 mass ppm or less.
この発明の炭素被覆アルミニウム材においては、アルミニウム材と炭素含有層との間に形成された、アルミニウム元素と炭素元素とを含む介在層が、アルミニウム材と炭素含有層との間の密着性を高める作用をする。介在層は、アルミニウム材の表面の少なくとも一部の領域に形成された、アルミニウムの炭化物を含む第１の表面部分を含む。アルミニウムの炭化物を含む第１の表面部分と炭素粒子との間に形成された第２の表面部分に含まれるアルミニウムの炭化物も、アルミニウム材と炭素含有層との間の密着性を高める作用をする。 In the carbon-coated aluminum material of the present invention, the intervening layer containing the aluminum element and the carbon element formed between the aluminum material and the carbon-containing layer enhances the adhesion between the aluminum material and the carbon-containing layer. Works. The intervening layer includes a first surface portion including an aluminum carbide formed in at least a partial region of the surface of the aluminum material. The aluminum carbide contained in the second surface portion formed between the first surface portion containing aluminum carbide and the carbon particles also acts to enhance the adhesion between the aluminum material and the carbon-containing layer. .
これらのアルミニウムの炭化物の生成量は、基材として用いられるアルミニウム材の純度と不純物量によって影響される。すなわち、不純物量が増加するほど、アルミニウムの炭化物の生成量が少なくなる傾向にあり、その結果として炭素含有層とアルミニウム材の表面との密着性が向上する度合いが低下する。また、特にアルミニウム中の鉛とマグネシウムという元素は、加熱されたときに表層に集積するので、アルミニウムの炭化物の生成に影響を及ぼす。 The amount of these aluminum carbides produced is affected by the purity and the amount of impurities of the aluminum material used as the substrate. That is, as the amount of impurities increases, the amount of aluminum carbide produced tends to decrease, and as a result, the degree of improvement in adhesion between the carbon-containing layer and the surface of the aluminum material decreases. In particular, elements such as lead and magnesium in aluminum accumulate on the surface layer when heated, which affects the formation of aluminum carbides.
したがって、基材として用いられるアルミニウム材において、アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下に限定することによって、上記のアルミニウムの炭化物の生成量を増大することができ、その結果として、炭素含有層とアルミニウム材の表面との密着性をさらに向上させることができる。これにより、炭素含有層とアルミニウム材との間の密着性を長期間にわたって維持することが可能になる。 Therefore, in the aluminum material used as the base material, the aluminum content is 99.6 mass% or more, the lead content is 10 mass ppm or less, and the magnesium content is 10 mass ppm or less. The amount of aluminum carbide produced can be increased, and as a result, the adhesion between the carbon-containing layer and the surface of the aluminum material can be further improved. Thereby, it becomes possible to maintain the adhesiveness between the carbon-containing layer and the aluminum material over a long period of time.
アルミニウムの含有量が９９．６質量％未満であると、アルミニウム材と炭素含有層を固着させるアルミニウムの炭化物の生成量が少なくなり、炭素含有層とアルミニウム材との密着性が低くなる。 When the aluminum content is less than 99.6% by mass, the amount of aluminum carbide that fixes the aluminum material and the carbon-containing layer decreases, and the adhesion between the carbon-containing layer and the aluminum material decreases.
また、本発明の炭素被覆アルミニウム材の製造方法において、ＰｂまたはＭｇの含有量が１０質量ｐｐｍを超えたアルミニウム材に対して４５０℃以上の温度で加熱処理を施すと、両元素は熱拡散によってアルミニウム材の表面近傍に濃縮する。これらの元素による濃縮層はアルミニウムの炭化物の生成量を抑制するため、結果として炭素含有層とアルミニウム材との密着性が低くなる。 Moreover, in the manufacturing method of the carbon covering aluminum material of this invention, when heat processing are performed at the temperature of 450 degreeC or more with respect to the aluminum material in which content of Pb or Mg exceeded 10 mass ppm, both elements will be by thermal diffusion. Concentrates near the surface of the aluminum material. The concentrated layer of these elements suppresses the amount of aluminum carbide produced, resulting in low adhesion between the carbon-containing layer and the aluminum material.
この発明の炭素被覆アルミニウム材では、アルミニウム材において、鉄（Ｆｅ）の含有量が５質量ｐｐｍ以上、シリコン（Ｓｉ）の含有量が５質量ｐｐｍ以上であることが好ましい。 In the carbon-coated aluminum material of this invention, the aluminum material preferably has an iron (Fe) content of 5 mass ppm or more and a silicon (Si) content of 5 mass ppm or more.
ＦｅまたはＳｉの含有量が５質量ｐｐｍ未満であるアルミニウム材は、常温においても容易に再結晶を起こす。従って、板圧延や箔圧延に必要な所定の強度が得られず、実質的にアルミニウム材の圧延が不可能となる。その結果、電極や集電体の基材としてアルミニウム箔等の板材を得ることが困難となる。 An aluminum material having an Fe or Si content of less than 5 ppm by mass easily recrystallizes even at room temperature. Therefore, the predetermined strength required for plate rolling and foil rolling cannot be obtained, and the aluminum material cannot be rolled substantially. As a result, it becomes difficult to obtain a plate material such as an aluminum foil as a base material for the electrode or current collector.
また、この発明の炭素被覆アルミニウム材では、アルミニウム材において、コバルト（Ｃｏ）、ベリウム（Ｂｅ）、インジウム（Ｉｎ）、錫（Ｓｎ）、リチウム（Ｌｉ）、ナトリウム（Ｎａ）およびビスマス（Ｂｉ）のそれぞれの元素の含有量が１０質量ｐｐｍ以下、これらの元素の合計の含有量が２０質量ｐｐｍ以下であることが好ましい。 Further, in the carbon-coated aluminum material of the present invention, in the aluminum material, cobalt (Co), belium (Be), indium (In), tin (Sn), lithium (Li), sodium (Na) and bismuth (Bi). The content of each element is preferably 10 mass ppm or less, and the total content of these elements is preferably 20 mass ppm or less.
本発明の炭素被覆アルミニウム材の製造方法において、Ｃｏ、Ｂｅ、Ｉｎ、Ｓｎ、Ｌｉ、ＮａおよびＢｉのそれぞれの元素の含有量が１０質量ｐｐｍを超えたアルミニウム材に対して４５０℃以上の温度で加熱処理を施すと、各元素は熱拡散によってアルミニウム材の表面近傍に濃縮する。この元素による濃縮層は、アルミニウムの炭化物の生成量を抑制するため、結果として炭素含有層とアルミニウム材との密着性が低下する。また、これらの元素の合計の含有量が２０質量ｐｐｍを超えたアルミニウム材に対しても４５０℃以上の温度で加熱処理を施すと、各元素の表面近傍への濃縮が生じ、アルミニウムの炭化物の生成量が少なくなるため、炭素含有層とアルミニウム材との密着性が低下する。 In the method for producing a carbon-coated aluminum material of the present invention, the content of each element of Co, Be, In, Sn, Li, Na, and Bi exceeds 450 mass C. at a temperature of 450 ° C. or higher. When heat treatment is performed, each element is concentrated near the surface of the aluminum material by thermal diffusion. The concentrated layer of this element suppresses the amount of aluminum carbide produced, resulting in a decrease in the adhesion between the carbon-containing layer and the aluminum material. Moreover, when heat treatment is performed at a temperature of 450 ° C. or higher even for an aluminum material in which the total content of these elements exceeds 20 mass ppm, concentration of each element near the surface occurs, and the aluminum carbide Since the production amount is reduced, the adhesion between the carbon-containing layer and the aluminum material is lowered.
さらに、この発明の炭素被覆アルミニウム材では、上記の第１と第２の表面部分に含まれるアルミニウムの炭化物の生成量が０．０３０ｍｇ／ｃｍ２以上であることが好ましい。Furthermore, in the carbon-coated aluminum material of the present invention, the amount of aluminum carbide contained in the first and second surface portions is preferably 0.030 mg / cm 2 or more.
上記の第１と第２の表面部分に含まれるアルミニウムの炭化物の生成量が０．０３０ｍｇ／ｃｍ２以上であれば、アルミニウム材と炭素含有層との間の密着性をより確実に高めることができるとともに、従来の炭素被覆アルミニウム材よりも、より長期間にわたって密着性を安定して維持することが可能となる。第１の表面部分の炭化物の生成量が増加すると、第１の表面部分と炭素含有層との密着性が向上する。さらには第１の表面部分の炭化物の生成量が増加すると、第２の表面部分の形成量が増加し、炭素含有層内の第２の表面部分以外の部分と第２の表面部分との密着性が向上するので、第１の表面部分の表面近傍に存在する炭素含有層と第１の表面部分との間の密着性と、第２の表面部分の近傍に存在する炭素含有層内の第２の表面部分以外の部分と第２の表面部分との間の密着性が同時に向上することになる。If the amount of aluminum carbide contained in the first and second surface portions is 0.030 mg / cm 2 or more, the adhesion between the aluminum material and the carbon-containing layer can be more reliably increased. In addition, the adhesiveness can be stably maintained over a longer period than the conventional carbon-coated aluminum material. When the amount of carbide generated in the first surface portion increases, the adhesion between the first surface portion and the carbon-containing layer improves. Further, when the amount of carbide generated in the first surface portion increases, the amount of formation of the second surface portion increases, and adhesion between the portion other than the second surface portion in the carbon-containing layer and the second surface portion is increased. The adhesion between the carbon-containing layer existing near the surface of the first surface portion and the first surface portion, and the first in the carbon-containing layer existing near the second surface portion. The adhesion between the portion other than the surface portion 2 and the second surface portion is improved at the same time.
この発明に従った上述のいずれかの特徴を有する炭素被覆アルミニウム材は、電極構造体を構成するために用いられることが好ましい。 The carbon-coated aluminum material having any of the above-described characteristics according to the present invention is preferably used for constituting an electrode structure.
上記の電極構造体は、キャパシタの電極や集電体を構成するために用いられることが好ましい。これにより、キャパシタの充放電特性、寿命を高めることができる。キャパシタは、電気二重層キャパシタ等である。 The above electrode structure is preferably used for constituting an electrode or a current collector of a capacitor. Thereby, the charging / discharging characteristic and lifetime of a capacitor can be improved. The capacitor is an electric double layer capacitor or the like.
また、上記の電極構造体は、電池の集電体や電極を構成するために用いられることが好ましい。これにより、電池の充放電特性、寿命を高めることができる。電池は、リチウムイオン電池等の二次電池である。 Moreover, it is preferable that said electrode structure is used in order to comprise the electrical power collector and electrode of a battery. Thereby, the charging / discharging characteristic and lifetime of a battery can be improved. The battery is a secondary battery such as a lithium ion battery.
この発明に従った炭素被覆アルミニウム材の製造方法は、以下の工程を備える。 The manufacturing method of the carbon covering aluminum material according to this invention comprises the following processes.
（Ａ）アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下であるアルミニウム材の表面に、炭素含有粒子を含む炭素含有物質を付着させることにより、炭素含有物質付着層を形成する工程。 (A) A carbon-containing substance containing carbon-containing particles on the surface of an aluminum material having an aluminum content of 99.6 mass% or more, a lead content of 10 mass ppm or less, and a magnesium content of 10 mass ppm or less. Forming a carbon-containing substance adhesion layer by attaching
（Ｂ）アルミニウム材と炭素含有物質付着層とを、炭化水素含有物質を含む空間に配置して、加熱する工程。 (B) The process of arrange | positioning and heating an aluminum material and a carbon containing substance adhesion layer in the space containing a hydrocarbon containing substance.
この発明の炭素被覆アルミニウム材の製造方法において、アルミニウム材と炭素含有物質付着層とを加熱する工程は、４５０℃以上６４０℃未満の温度範囲で行うことが好ましい。 In the method for producing a carbon-coated aluminum material according to the present invention, the step of heating the aluminum material and the carbon-containing substance adhesion layer is preferably performed in a temperature range of 450 ° C. or higher and lower than 640 ° C.
以上のようにこの発明によれば、アルミニウムの炭化物の生成量を増大することができるので、炭素含有層とアルミニウム材の表面との密着性をさらに向上させることができ、炭素含有層とアルミニウム材との間の密着性を長期間にわたって維持することが可能になる。 As described above, according to the present invention, since the amount of aluminum carbide generated can be increased, the adhesion between the carbon-containing layer and the surface of the aluminum material can be further improved. It becomes possible to maintain the adhesiveness between them for a long time.
１：アルミニウム箔、２：炭素含有層、３：介在層（第１の表面部分）、２１：第２の表面部分、２２：炭素粒子。 1: aluminum foil, 2: carbon-containing layer, 3: intervening layer (first surface portion), 21: second surface portion, 22: carbon particles.
以下、この発明の実施の形態を図面に基づいて説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
図１は、この発明の一つの実施の形態として、炭素被覆アルミニウム材の詳細な断面構造を模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a detailed cross-sectional structure of a carbon-coated aluminum material as one embodiment of the present invention.
図１に示すように、この発明の一つの実施の形態として、炭素被覆アルミニウム材の断面構造によれば、アルミニウム材の一例としてアルミニウム箔１の表面上に炭素含有層２が形成されている。アルミニウム箔１と炭素含有層２との間には、アルミニウム元素と炭素元素とを含む介在層３が形成されている。炭素含有層２は、アルミニウム箔１の表面から外側に延びるように形成されている。介在層３は、アルミニウム箔１の表面の少なくとも一部の領域に形成された、アルミニウムの炭化物を含む第１の表面部分を構成している。炭素含有層２は、第１の表面部分３から外側に繊維状、フィラメント状、板状、壁状、または、鱗片状の形態で延びるように形成された第２の表面部分２１を含む。第２の表面部分２１は、アルミニウム元素と炭素元素との化合物である。また、炭素含有層２は多数個の炭素粒子２２をさらに含む。第２の表面部分２１は、第１の表面部分３から外側に繊維状、フィラメント状、板状、壁状、または、鱗片状の形態で延び、第１の表面部分３と炭素粒子２２との間に形成されてアルミニウムの炭化物を含む。 As shown in FIG. 1, according to one embodiment of the present invention, according to a cross-sectional structure of a carbon-coated aluminum material, a carbon-containing layer 2 is formed on the surface of an aluminum foil 1 as an example of an aluminum material. An intervening layer 3 containing an aluminum element and a carbon element is formed between the aluminum foil 1 and the carbon-containing layer 2. Carbon-containing layer 2 is formed to extend outward from the surface of aluminum foil 1. The intervening layer 3 constitutes a first surface portion containing aluminum carbide formed in at least a part of the surface of the aluminum foil 1. The carbon-containing layer 2 includes a second surface portion 21 formed so as to extend outward from the first surface portion 3 in the form of a fiber, a filament, a plate, a wall, or a scale. The second surface portion 21 is a compound of an aluminum element and a carbon element. The carbon-containing layer 2 further includes a large number of carbon particles 22. The second surface portion 21 extends outward from the first surface portion 3 in the form of a fiber, a filament, a plate, a wall, or a scale, and is formed between the first surface portion 3 and the carbon particles 22. Formed in between, containing aluminum carbide.
この発明の炭素被覆アルミニウム材においては、第２の表面部分２１がアルミニウム箔１の表面上に形成された炭素含有層２の表面積を増大させる作用をする。また、アルミニウム箔１と第２の表面部分２１との間にはアルミニウムの炭化物を含む第１の表面部分３が形成されているので、この第１の表面部分３が、炭素含有層２の表面積を増大させる第２の表面部分２１との間の密着性を高める作用をする。 In the carbon-coated aluminum material of the present invention, the second surface portion 21 acts to increase the surface area of the carbon-containing layer 2 formed on the surface of the aluminum foil 1. Moreover, since the 1st surface part 3 containing the carbide | carbonized_material of aluminum is formed between the aluminum foil 1 and the 2nd surface part 21, this 1st surface part 3 is the surface area of the carbon containing layer 2 This increases the adhesion between the second surface portion 21 and the second surface portion 21.
この発明の炭素被覆アルミニウム材の基材として用いられるアルミニウム箔１において、アルミニウムの含有量が９９．６質量％以上、鉛（Ｐｂ）の含有量が１０質量ｐｐｍ以下、マグネシウム（Ｍｇ）の含有量が１０質量ｐｐｍ以下である。 In the aluminum foil 1 used as the base material of the carbon-coated aluminum material of the present invention, the aluminum content is 99.6 mass% or more, the lead (Pb) content is 10 mass ppm or less, and the magnesium (Mg) content. Is 10 ppm by mass or less.
この発明の炭素被覆アルミニウム材においては、アルミニウム箔１と炭素含有層２との間に形成された、アルミニウム元素と炭素元素とを含む介在層３が、アルミニウム箔１と炭素含有層２との間の密着性を高める作用をする。介在層３は、アルミニウム箔１の表面の少なくとも一部の領域に形成された、アルミニウムの炭化物を含む第１の表面部分３を含む。アルミニウムの炭化物を含む第１の表面部分３と炭素粒子２２との間に形成された第２の表面部分２１に含まれるアルミニウムの炭化物も、アルミニウム箔１と炭素含有層２との間の密着性を高める作用をする。 In the carbon-coated aluminum material of the present invention, an intervening layer 3 containing an aluminum element and a carbon element formed between the aluminum foil 1 and the carbon-containing layer 2 is between the aluminum foil 1 and the carbon-containing layer 2. It acts to increase the adhesion of the. The intervening layer 3 includes a first surface portion 3 including an aluminum carbide formed in at least a partial region of the surface of the aluminum foil 1. The aluminum carbide contained in the second surface portion 21 formed between the first surface portion 3 containing aluminum carbide and the carbon particles 22 is also adhesive between the aluminum foil 1 and the carbon-containing layer 2. It works to increase.
これらのアルミニウムの炭化物の生成量、すなわち、介在層である第１の表面部分３や第２の表面部分２１の形成量や密度は、基材として用いられるアルミニウム箔１の純度と不純物量によって影響される。すなわち、不純物量が増加するほど、アルミニウムの炭化物の生成量が少なくなる傾向にあり、その結果として炭素含有層２とアルミニウム箔１の表面との密着性が向上する度合いが低下する。また、特にアルミニウム中の鉛とマグネシウムという元素は、加熱されたときに表層に集積するので、アルミニウムの炭化物の生成に影響を及ぼす。 The amount of aluminum carbide produced, that is, the amount and density of the first surface portion 3 and the second surface portion 21 as an intervening layer are affected by the purity and impurity amount of the aluminum foil 1 used as the substrate. Is done. That is, as the amount of impurities increases, the amount of aluminum carbide produced tends to decrease, and as a result, the degree of improvement in adhesion between the carbon-containing layer 2 and the surface of the aluminum foil 1 decreases. In particular, elements such as lead and magnesium in aluminum accumulate on the surface layer when heated, which affects the formation of aluminum carbides.
したがって、基材として用いられるアルミニウム箔１において、アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下に限定することによって、上記のアルミニウムの炭化物の生成量、すなわち、介在層である第１の表面部分３や第２の表面部分２１の形成量や密度、を増大することができ、その結果として、炭素含有層２とアルミニウム箔１の表面との密着性をさらに向上させることができる。これにより、炭素含有層２とアルミニウム箔１との間の密着性を長期間にわたって維持することが可能になる。 Therefore, in the aluminum foil 1 used as the base material, the aluminum content is 99.6 mass% or more, the lead content is 10 mass ppm or less, and the magnesium content is limited to 10 mass ppm or less. The amount of aluminum carbide produced, that is, the formation amount and density of the first surface portion 3 and the second surface portion 21 which are intervening layers can be increased. As a result, the carbon-containing layer 2 and the aluminum The adhesion with the surface of the foil 1 can be further improved. Thereby, it becomes possible to maintain the adhesiveness between the carbon-containing layer 2 and the aluminum foil 1 over a long period of time.
なお、一般的にアルミニウム箔の表面に炭素含有物質を塗布することにより、導電性は生じるが、さらに導電性を改善するためには、炭素含有層２とアルミニウム箔１を固着する役割を担うアルミニウムの炭化物の生成が不可欠となる。すなわち、アルミニウムの炭化物の生成量の増加は、密着性を高めると同時に、導電性を改善する。 In general, conductivity is generated by applying a carbon-containing material to the surface of the aluminum foil. However, in order to further improve the conductivity, aluminum that plays a role of fixing the carbon-containing layer 2 and the aluminum foil 1 is used. The formation of carbides is essential. That is, an increase in the amount of aluminum carbide produced improves the electrical conductivity while improving the adhesion.
アルミニウムの含有量が９９．６質量％未満であると、アルミニウム箔１と炭素含有層２を固着させるアルミニウムの炭化物の生成量が少なくなり、炭素含有層２とアルミニウム箔１との密着性が低くなる。 When the aluminum content is less than 99.6% by mass, the amount of aluminum carbide that adheres the aluminum foil 1 and the carbon-containing layer 2 decreases, and the adhesion between the carbon-containing layer 2 and the aluminum foil 1 is low. Become.
また、本発明の炭素被覆アルミニウム材の製造方法において、ＰｂまたはＭｇの含有量が１０質量ｐｐｍを超えたアルミニウム箔１に対して４５０℃以上の温度で加熱処理を施すと、両元素は熱拡散によってアルミニウム箔１の表面近傍に濃縮する。これらの元素による濃縮層はアルミニウムの炭化物の生成量を抑制するため、結果として炭素含有層２とアルミニウム箔１との密着性が低くなる。 Moreover, in the manufacturing method of the carbon covering aluminum material of this invention, when heat processing are performed at the temperature of 450 degreeC or more with respect to the aluminum foil 1 in which content of Pb or Mg exceeded 10 mass ppm, both elements will carry out thermal diffusion. To concentrate near the surface of the aluminum foil 1. Since the concentrated layer of these elements suppresses the amount of aluminum carbide produced, as a result, the adhesion between the carbon-containing layer 2 and the aluminum foil 1 is lowered.
この発明の炭素被覆アルミニウム材の一つの実施の形態では、アルミニウム箔１において、鉄（Ｆｅ）の含有量が５質量ｐｐｍ以上、シリコン（Ｓｉ）の含有量が５質量ｐｐｍ以上であることが好ましい。 In one embodiment of the carbon-coated aluminum material of the present invention, the aluminum foil 1 preferably has an iron (Fe) content of 5 mass ppm or more and a silicon (Si) content of 5 mass ppm or more. .
ＦｅまたはＳｉの含有量が５質量ｐｐｍ未満であるアルミニウム材は、常温においても容易に再結晶を起こす。従って、板圧延や箔圧延に必要な所定の強度が得られず、実質的にアルミニウム材の圧延が不可能となる。その結果、電極や集電体の基材としてアルミニウム箔等の板材を得ることが困難となる。 An aluminum material having an Fe or Si content of less than 5 ppm by mass easily recrystallizes even at room temperature. Therefore, the predetermined strength required for plate rolling and foil rolling cannot be obtained, and the aluminum material cannot be rolled substantially. As a result, it becomes difficult to obtain a plate material such as an aluminum foil as a base material for the electrode or current collector.
また、この発明の炭素被覆アルミニウム材の一つの実施の形態では、アルミニウム箔１において、コバルト（Ｃｏ）、ベリウム（Ｂｅ）、インジウム（Ｉｎ）、錫（Ｓｎ）、リチウム（Ｌｉ）、ナトリウム（Ｎａ）およびビスマス（Ｂｉ）のそれぞれの元素の含有量が１０質量ｐｐｍ以下、これらの元素の合計の含有量が２０質量ｐｐｍ以下であることが好ましい。 In one embodiment of the carbon-coated aluminum material of the present invention, in the aluminum foil 1, cobalt (Co), belium (Be), indium (In), tin (Sn), lithium (Li), sodium (Na ) And bismuth (Bi), the content of each element is preferably 10 ppm by mass or less, and the total content of these elements is preferably 20 ppm by mass or less.
本発明の炭素被覆アルミニウム材の製造方法において、Ｃｏ、Ｂｅ、Ｉｎ、Ｓｎ、Ｌｉ、ＮａおよびＢｉのそれぞれの元素の含有量が１０質量ｐｐｍを超えたアルミニウム箔１に対して４５０℃以上の温度で加熱処理を施すと、各元素は熱拡散によってアルミニウム箔１の表面近傍に濃縮する。この元素による濃縮層は、アルミニウムの炭化物の生成量を抑制するため、結果として炭素含有層２とアルミニウム箔１との密着性が低下する。また、これらの元素の合計の含有量が２０質量ｐｐｍを超えたアルミニウム箔１に対しても４５０℃以上の温度で加熱処理を施すと、各元素の表面近傍への濃縮が生じ、アルミニウムの炭化物の発生量が少なくなるため、炭素含有層２とアルミニウム箔１との密着性が低下する。 In the method for producing a carbon-coated aluminum material according to the present invention, a temperature of 450 ° C. or higher with respect to the aluminum foil 1 in which the content of each element of Co, Be, In, Sn, Li, Na, and Bi exceeds 10 mass ppm. When the heat treatment is performed, each element is concentrated near the surface of the aluminum foil 1 by thermal diffusion. Since the concentrated layer of this element suppresses the amount of aluminum carbide produced, as a result, the adhesion between the carbon-containing layer 2 and the aluminum foil 1 decreases. Further, when the aluminum foil 1 having a total content of these elements exceeding 20 ppm by mass is heated at a temperature of 450 ° C. or higher, the concentration of each element near the surface occurs, and aluminum carbide Therefore, the adhesion between the carbon-containing layer 2 and the aluminum foil 1 is reduced.
また、この発明の炭素被覆アルミニウム材の一つの実施の形態では、第１の表面部分３と第２の表面部分２１に含まれるアルミニウムの炭化物の生成量が０．０３０ｍｇ／ｃｍ２以上であることが好ましい。さらには、上記のアルミニウムの炭化物の生成量が０．０４０ｍｇ／ｃｍ２以上であることがより好ましい。In one embodiment of the carbon-coated aluminum material of the present invention, the amount of aluminum carbide contained in the first surface portion 3 and the second surface portion 21 is 0.030 mg / cm 2 or more. Is preferred. Further, it is more preferable that the amount of aluminum carbide produced is 0.040 mg / cm 2 or more.
第１の表面部分３と第２の表面部分２１に含まれるアルミニウムの炭化物の生成量が０．０３０ｍｇ／ｃｍ２以上であれば、従来の炭素被覆アルミニウム材に比してアルミニウム箔１と炭素含有層２との間の密着性をより確実に高めることができるとともに、従来の炭素被覆アルミニウム材よりも、より長期間にわたって密着性を安定して維持することが可能となる。第１の表面部分３の炭化物の生成量が増加すると、第１の表面部分３と炭素含有層２との密着性が向上する。さらには第１の表面部分３の炭化物の生成量が増加すると、第２の表面部分２１の形成量が増加し、炭素含有層２内の第２の表面部分２１以外の部分と第２の表面部分２１との密着性が向上するので、第１の表面部分３の表面近傍に存在する炭素含有層２と第１の表面部分３との間の密着性と、第２の表面部分２１の近傍に存在する炭素含有層２内の第２の表面部分２１以外の部分と第２の表面部分２１との間の密着性が同時に向上することになる。If the amount of aluminum carbide contained in the first surface portion 3 and the second surface portion 21 is 0.030 mg / cm 2 or more, the aluminum foil 1 and the carbon content are contained in comparison with the conventional carbon-coated aluminum material. Adhesiveness with the layer 2 can be more reliably increased, and the adhesiveness can be stably maintained over a longer period than the conventional carbon-coated aluminum material. When the amount of carbide generated on the first surface portion 3 increases, the adhesion between the first surface portion 3 and the carbon-containing layer 2 improves. Further, when the amount of carbide generated in the first surface portion 3 increases, the amount of the second surface portion 21 increases, and the portion other than the second surface portion 21 in the carbon-containing layer 2 and the second surface Since the adhesion with the portion 21 is improved, the adhesion between the carbon-containing layer 2 and the first surface portion 3 existing near the surface of the first surface portion 3 and the vicinity of the second surface portion 21 are improved. The adhesion between the second surface portion 21 and the portion other than the second surface portion 21 in the carbon-containing layer 2 present in the substrate is simultaneously improved.
なお、本発明において、第１の表面部分３と第２の表面部分２１に含まれるアルミニウムの炭化物の生成量（ｍｇ／ｃｍ２）は、後述する［アルミニウムの炭化物の定量分析］で示される方法により算出できる。In the present invention, the amount of aluminum carbide (mg / cm 2 ) contained in the first surface portion 3 and the second surface portion 21 is determined by the method described later in [Quantitative analysis of aluminum carbide]. Can be calculated.
この発明に従った上述のいずれかの特徴を有する炭素被覆アルミニウム材は、電極構造体を構成するために用いられることが好ましい。 The carbon-coated aluminum material having any of the above-described characteristics according to the present invention is preferably used for constituting an electrode structure.
上記の電極構造体は、キャパシタの電極や集電体を構成するために用いられることが好ましい。これにより、キャパシタの充放電特性、寿命を高めることができる。キャパシタは、電気二重層キャパシタ等である。 The above electrode structure is preferably used for constituting an electrode or a current collector of a capacitor. Thereby, the charging / discharging characteristic and lifetime of a capacitor can be improved. The capacitor is an electric double layer capacitor or the like.
また、上記の電極構造体は、電池の集電体や電極を構成するために用いられることが好ましい。これにより、電池の充放電特性、寿命を高めることができる。電池は、リチウムイオン電池等の二次電池である。 Moreover, it is preferable that said electrode structure is used in order to comprise the electrical power collector and electrode of a battery. Thereby, the charging / discharging characteristic and lifetime of a battery can be improved. The battery is a secondary battery such as a lithium ion battery.
この発明に従った炭素被覆アルミニウム材の製造方法の一つの実施の形態においては、まず、アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下であるアルミニウム箔１の表面に、炭素含有粒子を含む炭素含有物質を付着させることにより、炭素含有物質付着層を形成する。次に、アルミニウム箔１と炭素含有物質付着層とを、炭化水素含有物質を含む空間に配置して、加熱する。この加熱により、アルミニウム箔１の表面上に炭素含有層２が形成される。 In one embodiment of the method for producing a carbon-coated aluminum material according to the present invention, first, the aluminum content is 99.6 mass% or more, the lead content is 10 mass ppm or less, and the magnesium content is A carbon-containing substance adhesion layer is formed by adhering a carbon-containing substance containing carbon-containing particles to the surface of the aluminum foil 1 that is 10 mass ppm or less. Next, the aluminum foil 1 and the carbon-containing substance adhesion layer are disposed in a space containing the hydrocarbon-containing substance and heated. By this heating, the carbon-containing layer 2 is formed on the surface of the aluminum foil 1.
この発明の炭素被覆アルミニウム材の製造方法において、アルミニウム箔１と炭素含有物質付着層とを加熱する工程は、４５０℃以上６４０℃未満の温度範囲で行うことが好ましい。 In the method for producing a carbon-coated aluminum material of the present invention, the step of heating the aluminum foil 1 and the carbon-containing substance adhesion layer is preferably performed in a temperature range of 450 ° C. or higher and lower than 640 ° C.
また、この発明の炭素被覆アルミニウム材においては、炭素含有層２はアルミニウム箔１の少なくとも片方の面に形成すればよく、その厚みは０．０１μｍ以上１０ｍｍ以下の範囲内であるのが好ましい。 Moreover, in the carbon covering aluminum material of this invention, what is necessary is just to form the carbon containing layer 2 in the at least one surface of the aluminum foil 1, and it is preferable that the thickness exists in the range of 0.01 micrometer or more and 10 mm or less.
この発明の一つの実施の形態において、炭素含有層２が形成される基材としてのアルミニウム材は、アルミニウム箔１に限定されず、アルミニウム材の厚みは、箔であれば、５μｍ以上２００μｍ以下、板であれば２００μｍを越え、３ｍｍ以下の範囲内であるのが好ましい。 In one embodiment of the present invention, the aluminum material as the base material on which the carbon-containing layer 2 is formed is not limited to the aluminum foil 1, and the thickness of the aluminum material is 5 μm or more and 200 μm or less if the foil is a foil. In the case of a plate, it is preferably in the range of more than 200 μm and 3 mm or less.
上記のアルミニウム材は、公知の方法によって製造されるものを使用することができる。たとえば、上記の所定の組成を有するアルミニウムの溶湯を調製し、これを鋳造して得られた鋳塊を適切に均質化処理する。その後、この鋳塊に熱間圧延と冷間圧延を施すことにより、アルミニウム箔やアルミニウム板を得ることができる。なお、上記の冷間圧延工程の途中で、１５０℃以上４００℃以下の範囲内で中間焼鈍処理を施してもよい。 What was manufactured by a well-known method can be used for said aluminum material. For example, an aluminum ingot having the above predetermined composition is prepared, and an ingot obtained by casting the aluminum melt is appropriately homogenized. Thereafter, an aluminum foil or an aluminum plate can be obtained by subjecting the ingot to hot rolling and cold rolling. In addition, you may perform an intermediate annealing process in the range of 150 degreeC or more and 400 degrees C or less in the middle of said cold rolling process.
本発明の炭素被覆アルミニウム材の製造方法の一つの実施の形態では、用いられる炭化水素含有物質の種類は特に限定されない。炭化水素含有物質の種類としては、たとえば、メタン、エタン、プロパン、ｎ‐ブタン、イソブタンおよびペンタン等のパラフィン系炭化水素、エチレン、プロピレン、ブテンおよびブタジエン等のオレフィン系炭化水素、アセチレン等のアセチレン系炭化水素等、またはこれらの炭化水素の誘導体が挙げられる。これらの炭化水素の中でも、メタン、エタン、プロパン等のパラフィン系炭化水素は、アルミニウム材を加熱する工程においてガス状になるので好ましい。さらに好ましいのは、メタン、エタンおよびプロパンのうち、いずれか一種の炭化水素である。最も好ましい炭化水素はメタンである。 In one embodiment of the method for producing a carbon-coated aluminum material of the present invention, the type of hydrocarbon-containing material used is not particularly limited. Examples of the hydrocarbon-containing material include paraffinic hydrocarbons such as methane, ethane, propane, n-butane, isobutane and pentane, olefinic hydrocarbons such as ethylene, propylene, butene and butadiene, and acetylenes such as acetylene. Examples thereof include hydrocarbons and derivatives of these hydrocarbons. Among these hydrocarbons, paraffinic hydrocarbons such as methane, ethane, and propane are preferable because they become gaseous in the process of heating the aluminum material. More preferred is any one of methane, ethane and propane. The most preferred hydrocarbon is methane.
また、炭化水素含有物質は、本発明の製造方法において液体、気体等のいずれの状態で用いてもよい。炭化水素含有物質は、アルミニウム材が存在する空間に存在するようにすればよく、アルミニウム材を配置する空間にどのような方法で導入してもよい。たとえば、炭化水素含有物質がガス状である場合（メタン、エタン、プロパン等）には、アルミニウム材の加熱処理が行なわれる密閉空間中に炭化水素含有物質を単独または不活性ガスとともに充填すればよい。また、炭化水素含有物質が液体である場合には、その密閉空間中で気化するように炭化水素含有物質を単独または不活性ガスとともに充填してもよい。 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 material may be present in the space where the aluminum material is present, and may be introduced into the space where the aluminum material is disposed by any method. For example, when the hydrocarbon-containing substance is gaseous (methane, ethane, propane, etc.), the hydrocarbon-containing substance may be filled alone or together with an inert gas in a sealed space where the heat treatment of the aluminum material is performed. . Further, when the hydrocarbon-containing substance is a liquid, the hydrocarbon-containing substance may be filled alone or together with an inert gas so as to be vaporized in the sealed space.
アルミニウム材を加熱する工程において、加熱雰囲気の圧力は特に限定されず、常圧、減圧または加圧下であってもよい。また、圧力の調整は、ある一定の加熱温度に保持している間、ある一定の加熱温度までの昇温中、または、ある一定の加熱温度から降温中のいずれの時点で行なってもよい。 In the step of heating the aluminum material, the pressure of the heating atmosphere is not particularly limited, and may be normal pressure, reduced pressure or increased pressure. Further, the pressure adjustment may be performed at any time during the temperature rise to a certain heating temperature or during the temperature lowering from the certain heating temperature while the pressure is maintained at a certain heating temperature.
アルミニウム材を加熱する空間に導入される炭化水素含有物質の重量比率は、特に限定されないが、通常はアルミニウム１００重量部に対して炭素換算値で０．１重量部以上５０重量部以下の範囲内にするのが好ましく、特に０．５重量部以上３０重量部以下の範囲内にするのが好ましい。 The weight ratio of the hydrocarbon-containing substance introduced into the space for heating the aluminum material is not particularly limited, but is usually in the range of 0.1 to 50 parts by weight in terms of carbon with respect to 100 parts by weight of aluminum. It is preferable to make it within a range of 0.5 parts by weight or more and 30 parts by weight or less.
アルミニウム材を加熱する工程において、加熱温度は、加熱対象物であるアルミニウム材の組成等に応じて適宜設定すればよいが、通常は４５０℃以上６４０℃未満の範囲内が好ましく、５３０℃以上６２０℃以下の範囲内で行なうのがより好ましい。ただし、本発明の製造方法において、４５０℃未満の温度でアルミニウム材を加熱することを排除するものではなく、少なくとも３００℃を超える温度でアルミニウム材を加熱すればよい。 In the step of heating the aluminum material, the heating temperature may be appropriately set according to the composition of the aluminum material to be heated, etc., but it is usually preferably in the range of 450 ° C. or higher and lower than 640 ° C., and preferably 530 ° C. or higher and 620 ° C. More preferably, it is carried out within the range of not more than ° C. However, in the production method of the present invention, heating the aluminum material at a temperature lower than 450 ° C. is not excluded, and the aluminum material may be heated at a temperature exceeding at least 300 ° C.
加熱時間は、加熱温度等にもよるが、一般的には１時間以上１００時間以下の範囲内である。 Although the heating time depends on the heating temperature and the like, it is generally in the range of 1 hour to 100 hours.
加熱温度が４００℃以上になる場合は、加熱雰囲気中の酸素濃度を１．０体積％以下とするのが好ましい。加熱温度が４００℃以上で加熱雰囲気中の酸素濃度が１．０体積％を超えると、アルミニウム材の表面の熱酸化被膜が肥大し、アルミニウム材の表面抵抗値が増大するおそれがある。 When the heating temperature is 400 ° C. or higher, the oxygen concentration in the heating atmosphere is preferably 1.0% by volume or lower. When the heating temperature is 400 ° C. or higher and the oxygen concentration in the heating atmosphere exceeds 1.0% by volume, the thermal oxide film on the surface of the aluminum material may be enlarged, and the surface resistance value of the aluminum material may increase.
また、加熱処理の前にアルミニウム材の表面を粗面化してもよい。粗面化方法は、特に限定されず、洗浄、エッチング、ブラスト等の公知の技術を用いることができる。 Moreover, you may roughen the surface of an aluminum material before heat processing. The surface roughening method is not particularly limited, and known techniques such as cleaning, etching, blasting and the like can be used.
本発明の製造方法において、アルミニウム材の表面に炭素含有物質を付着させた後、炭化水素含有物質を含む空間でアルミニウム材を加熱する工程が採用される。この場合、アルミニウム材の表面に付着される炭素含有物質は、活性炭素繊維、活性炭クロス、活性炭フェルト、活性炭粉末、墨汁、カーボンブラックまたはグラファイト等のいずれを用いてもよい。また、炭化珪素等の炭素化合物も好適に使用できる。付着方法は、バインダ、溶剤または水等を用いて、スラリー状、液体状または固体状等に上記の炭素含有物質を調製したものを、塗布、ディッピングまたは熱圧着等によってアルミニウム材の表面上に付着させればよい。炭素含有物質をアルミニウム材の表面上に付着させた後、加熱処理の前に、２０℃以上３００℃以下の範囲内の温度で乾燥させてもよい。 In the production method of the present invention, a step of heating the aluminum material in a space containing the hydrocarbon-containing material after the carbon-containing material is attached to the surface of the aluminum material is employed. In this case, as the carbon-containing substance attached to the surface of the aluminum material, any of activated carbon fiber, activated carbon cloth, activated carbon felt, activated carbon powder, black ink, carbon black, graphite, or the like may be used. Moreover, carbon compounds, such as silicon carbide, can also be used conveniently. The adhesion method uses a binder, solvent, water, or the like to deposit the above-mentioned carbon-containing material in a slurry, liquid, or solid form on the surface of the aluminum material by coating, dipping, or thermocompression bonding. You can do it. After the carbon-containing substance is deposited on the surface of the aluminum material, it may be dried at a temperature in the range of 20 ° C. or more and 300 ° C. or less before the heat treatment.
なお、この発明の製造方法において、炭素含有物質をアルミニウム材の表面に付着させるためにバインダが用いられる場合、バインダは、カルボキシ変性ポリオレフィン樹脂、酢酸ビニル樹脂、塩化ビニル樹脂、塩酢ビ共重合樹脂、ビニルアルコール樹脂、フッ化ビニル樹脂、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂、尿素樹脂、フェノール樹脂、アクリロニトリル樹脂、ニトロセルロース樹脂、パラフィンワックス、ポリエチレンワックス等の合成樹脂、ワックスまたはタール、およびにかわ、ウルシ、松脂、ミツロウ等の天然樹脂またはワックスが好適に使用できる。これらのバインダは、それぞれ分子量、樹脂種類により、加熱時に揮発するものと、熱分解により炭素前駆体として炭素含有層中に残存するものとがある。バインダは、有機溶剤等で希釈し、粘性を調整してもよい。 In the production method of the present invention, when a binder is used to adhere the carbon-containing substance to the surface of the aluminum material, the binder is a carboxy-modified polyolefin resin, a vinyl acetate resin, a vinyl chloride resin, or a vinyl chloride copolymer resin. , Vinyl alcohol resin, vinyl fluoride resin, acrylic resin, polyester resin, urethane resin, epoxy resin, urea resin, phenol resin, acrylonitrile resin, nitrocellulose resin, paraffin wax, polyethylene wax and other synthetic resins, wax or tar, and Natural resins such as glue, urushi, pine resin, beeswax or wax can be preferably used. These binders include those that volatilize when heated, depending on the molecular weight and the resin type, and those that remain in the carbon-containing layer as a carbon precursor by thermal decomposition. The binder may be diluted with an organic solvent or the like to adjust the viscosity.
なお、この発明の炭素被覆アルミニウム材は、二次電池の集電体や電極、電気二重層キャパシタの電極や集電体、特にリチウムイオン二次電池の集電体や電極、リチウムイオンキャパシタの電極や集電体等の種々の導電性部材に用いられる。 The carbon-coated aluminum material of the present invention is a secondary battery current collector and electrode, an electric double layer capacitor electrode and current collector, in particular, a lithium ion secondary battery current collector and electrode, and a lithium ion capacitor electrode. And various conductive members such as current collectors.
以下の従来例１〜２、実施例１〜３、および、比較例１〜３に従って、アルミニウム箔を基材として用いた炭素被覆アルミニウム材を作製した。 In accordance with the following conventional examples 1-2, Examples 1-3, and Comparative Examples 1-3, a carbon-coated aluminum material using an aluminum foil as a base material was produced.
（従来例１）
厚みが５０μｍ、表１に示す組成のアルミニウム箔（ＪＩＳ Ａ−１０５０）の両面に炭素含有物質を塗布し、温度１００℃で１０分間乾燥処理することにより付着させた。炭素含有物質の組成は、平均粒径が３０ｎｍのカーボンブラック（三菱化学株式会社製 ＃５０）１重量部に対し、ブタノールを１重量部加えたものであった。なお、このときの炭素含有物質の付着は、乾燥後の厚みが片面１μｍとなるように調整した。その後、炭素含有物質を付着させたアルミニウム箔をメタンガス雰囲気中で温度５５０℃で１０時間保持することにより、試料を作製した。(Conventional example 1)
A carbon-containing substance was applied to both sides of an aluminum foil (JIS A-1050) having a thickness of 50 μm and the composition shown in Table 1, and was attached by drying at a temperature of 100 ° C. for 10 minutes. The composition of the carbon-containing substance was obtained by adding 1 part by weight of butanol to 1 part by weight of carbon black (Mitsubishi Chemical Corporation # 50) having an average particle size of 30 nm. The adhesion of the carbon-containing substance at this time was adjusted so that the thickness after drying was 1 μm on one side. Then, the sample was produced by hold | maintaining the aluminum foil to which the carbon containing material was adhered at the temperature of 550 degreeC for 10 hours in methane gas atmosphere.
得られた試料の表面を走査電子顕微鏡（倍率５０００倍）で観察した。この走査電子顕微鏡写真を図２に示す。 The surface of the obtained sample was observed with a scanning electron microscope (magnification 5000 times). This scanning electron micrograph is shown in FIG.
（従来例２）
厚みが５０μｍ、表１に示す組成のアルミニウム箔（ＪＩＳ Ａ−３００３）を用いた以外は、従来例１と同様にして試料を作製した。(Conventional example 2)
A sample was prepared in the same manner as in Conventional Example 1 except that an aluminum foil (JIS A-3003) having a thickness of 50 μm and the composition shown in Table 1 was used.
（実施例１−３、比較例１−３）
表１に示す組成のアルミニウム箔を用いた以外は、従来例１と同様にして試料を作製した。(Example 1-3, Comparative example 1-3)
A sample was prepared in the same manner as in Conventional Example 1 except that an aluminum foil having the composition shown in Table 1 was used.
得られた実施例２の試料の表面を走査電子顕微鏡（倍率５０００倍）で観察した。この走査電子顕微鏡写真を図３に示す。 The surface of the obtained sample of Example 2 was observed with a scanning electron microscope (magnification 5000 times). This scanning electron micrograph is shown in FIG.
従来例１〜２、実施例１〜３、および、比較例１〜３で得られた炭素被覆アルミニウム材における炭素含有層とアルミニウム箔との密着性、経時信頼性試験、生成されるアルミニウムの炭化物としてＡｌ４Ｃ３の分析の結果を表１に示す。なお、評価条件は以下に示す通りである。Adhesion between carbon-containing layer and aluminum foil in the carbon-coated aluminum materials obtained in Conventional Examples 1-2, Examples 1-3, and Comparative Examples 1-3, reliability test over time, aluminum carbide produced Table 1 shows the results of analysis of Al 4 C 3 . The evaluation conditions are as shown below.
［密着性］
テーピング法によって密着性を評価した。幅１０ｍｍ、長さ１００ｍｍの短冊状の試料を作製し、炭素含有層の表面に、幅１５ｍｍ、長さ１２０ｍｍの接着面を有する粘着テープ（住友スリーM株式会社製、商品名「スコッチテープ」）を押し当てた後、粘着テープを引き剥がして、密着性を次の式に従って評価した。[Adhesion]
Adhesion was evaluated by a taping method. A strip-shaped sample having a width of 10 mm and a length of 100 mm is prepared, and a pressure-sensitive adhesive tape having an adhesive surface of a width of 15 mm and a length of 120 mm on the surface of the carbon-containing layer (manufactured by Sumitomo 3M Ltd., trade name “Scotch tape”) After pressing, the adhesive tape was peeled off and the adhesion was evaluated according to the following formula.
密着性（％）＝｛引き剥がし後の炭素含有層の重量（ｍｇ）/引き剥がし前の炭素含有層の重量（ｍｇ）｝×１００
［経時信頼性試験］
まず、各試料を、温度８５℃、湿度８５％に保持された恒温恒湿槽中で１２週間保持した。その後、すぐに塩酸はく離試験を行い、炭素含有層とアルミニウム箔とのはく離の様子を次の３段階で評価した。Adhesion (%) = {weight of the carbon-containing layer after peeling (mg) / weight of the carbon-containing layer before peeling (mg)} × 100
[Reliability test over time]
First, each sample was held for 12 weeks in a constant temperature and humidity chamber maintained at a temperature of 85 ° C. and a humidity of 85%. Thereafter, a hydrochloric acid peeling test was immediately performed, and the peeling state between the carbon-containing layer and the aluminum foil was evaluated in the following three stages.
○： はく離時間が３分以上の場合
△： はく離時間が１分以上３分未満の場合
×： はく離時間が１分未満の場合。○: When the peeling time is 3 minutes or more. Δ: When the peeling time is 1 minute or more and less than 3 minutes. X: When the peeling time is less than 1 minute.
上記の塩酸はく離試験は以下のとおり行った。 The hydrochloric acid peeling test was performed as follows.
＜塩酸はく離試験＞
幅１０ｍｍ、長さ１００ｍｍの短冊状の試料を、温度８０℃に保持された１モルの塩酸溶液中に浸漬し、表面に付着した炭素含有層が完全にはく離するまでの時間を測定した。<Hydrochloric acid peeling test>
A strip-shaped sample having a width of 10 mm and a length of 100 mm was immersed in a 1 molar hydrochloric acid solution maintained at a temperature of 80 ° C., and the time until the carbon-containing layer attached to the surface completely peeled was measured.
[アルミニウムの炭化物の定量分析]
両面に炭素含有層が形成された炭素被覆アルミニウム材の各試料（表面積が１０ｃｍ×１０ｃｍ）を２０％水酸化ナトリウム溶液に全量溶解させることによって発生したガスを捕集し、フレームイオン化検出器付高感度ガスクロマトグラフを用いて定量分析した。定量されたメタンガス量をアルミニウムの炭化物（Ａｌ４Ｃ３）の重量に換算し、片面の面積あたりの重量（ｍｇ／ｃｍ２）を算出することによって比較した。[Quantitative analysis of aluminum carbide]
Gas generated by dissolving each sample (surface area 10 cm x 10 cm) of a carbon-coated aluminum material having a carbon-containing layer on both sides in a 20% sodium hydroxide solution is collected, and a frame ionization detector is provided. Quantitative analysis was performed using a sensitivity gas chromatograph. The quantified amount of methane gas was converted to the weight of aluminum carbide (Al 4 C 3 ), and comparison was made by calculating the weight (mg / cm 2 ) per one side area.
表１の結果から、実施例１〜３の炭素被覆アルミニウム材では、比較例１〜３、従来例１〜２の炭素被覆アルミニウム材に比べて、基材として用いられるアルミニウム箔において、アルミニウムの含有量を９９．６質量％以上で、かつ、鉛の含有量を１０質量ｐｐｍ以下、マグネシウムの含有量を１０質量ｐｐｍ以下にすることにより、アルミニウムの炭化物の生成量を増大することができ、その結果として炭素含有層とアルミニウム箔との密着性をさらに高めることができ、これにより、経時信頼性、すなわち、炭素含有層とアルミニウム箔との間の密着性を長期間にわたって維持することが可能になることがわかる。 From the results of Table 1, in the carbon-coated aluminum materials of Examples 1 to 3, compared to the carbon-coated aluminum materials of Comparative Examples 1 to 3 and Conventional Examples 1 and 2, the aluminum foil used as the base material contains aluminum. By making the amount 99.6% by mass or more, the lead content 10 mass ppm or less, and the magnesium content 10 mass ppm or less, the amount of aluminum carbide produced can be increased. As a result, the adhesion between the carbon-containing layer and the aluminum foil can be further improved, and thereby the reliability over time, that is, the adhesion between the carbon-containing layer and the aluminum foil can be maintained over a long period of time. I understand that
さらには、炭素含有層とアルミニウム箔との密着性をさらに高め、炭素含有層とアルミニウム箔との間の密着性を長期間にわたって維持するためには、アルミニウム箔の第１と第２の表面部分に形成されるアルミニウムの炭化物の生成量が０．０３０ｍｇ／ｃｍ２以上の値が必要であることもわかる。Furthermore, in order to further improve the adhesion between the carbon-containing layer and the aluminum foil and maintain the adhesion between the carbon-containing layer and the aluminum foil over a long period of time, the first and second surface portions of the aluminum foil It can also be seen that the amount of aluminum carbide formed is required to be 0.030 mg / cm 2 or more.
また、図２と図３を比較すると、図３に示された実施例２の炭素被覆アルミニウム材の表面では、図２に示された従来例１の炭素被覆アルミニウム材の表面に比べて、繊維状、フィラメント状、板状、壁状、または、鱗片状の形態でアルミニウム箔の表面から外側に延びている部分の数が多く、密集していることがわかる。図１に対応させると、基材として用いられるアルミニウム箔１において、アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下の実施例２の炭素被覆アルミニウム材では、アルミニウムの炭化物の生成量、すなわち、介在層である第１の表面部分３や第２の表面部分２１の形成量や密度、を増大することができ、繊維状、フィラメント状、板状、壁状、または、鱗片状の形態でアルミニウム箔の表面から外側に延びている部分の数が多く、密集しているので、その結果として、炭素含有層２とアルミニウム箔１の表面との密着性をさらに向上させることができることが理解される。 2 and FIG. 3, the surface of the carbon-coated aluminum material of Example 2 shown in FIG. 3 is more fibrous than the surface of the carbon-coated aluminum material of Conventional Example 1 shown in FIG. 2. It can be seen that there are many portions extending outward from the surface of the aluminum foil in the form of slabs, filaments, plates, walls, or scales, which are dense. Corresponding to FIG. 1, in the aluminum foil 1 used as a base material, the aluminum content is 99.6 mass% or more, the lead content is 10 mass ppm or less, and the magnesium content is 10 mass ppm or less. In the carbon-coated aluminum material of Example 2, the amount of aluminum carbide produced, that is, the formation amount and density of the first surface portion 3 and the second surface portion 21 that are intervening layers can be increased, and the fibrous shape Since the number of portions extending outward from the surface of the aluminum foil in the form of filaments, plates, walls, or scales is large and dense, as a result, the carbon-containing layer 2 and the aluminum foil It is understood that the adhesion to the surface of 1 can be further improved.
今回開示された実施の形態と実施例はすべての点で例示であって制限的なものではないと考慮されるべきである。本発明の範囲は以上の実施の形態と実施例ではなく、請求の範囲によって示され、請求の範囲と均等の意味および範囲内でのすべての修正と変形を含むものであることが意図される。 It should be considered that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is shown not by the above embodiments and examples but by the claims, and is intended to include all modifications and variations within the meaning and scope equivalent to the claims.
この発明に従った炭素被覆アルミニウム材は、各種キャパシタの電極や集電体、各種電池の集電体や電極等に用いられることによって、キャパシタまたは電池の充放電特性、寿命を高めることができる。 The carbon-coated aluminum material according to the present invention can be used for electrodes and current collectors of various capacitors, current collectors and electrodes of various batteries, etc., thereby improving the charge / discharge characteristics and life of the capacitors or batteries.
Claims (9)
前記アルミニウム材（１）の表面上に形成された炭素含有層（２）と、
前記アルミニウム材（１）と前記炭素含有層（２）との間に形成された、アルミニウム元素と炭素元素とを含む介在層（３）とを備え、
前記介在層（３）は、前記アルミニウム材（１）の表面の少なくとも一部の領域に形成された、アルミニウムの炭化物を含む第１の表面部分（３）を含み、
前記炭素含有層（２）は、前記第１の表面部分（３）から外側に向かって延びるように形成された第２の表面部分（２１）を含み、
前記炭素含有層（２）は炭素含有粒子（２２）をさらに含み、前記第２の表面部分（２１）は前記第１の表面部分（３）と前記炭素含有粒子（２２）との間に形成されてアルミニウムの炭化物を含み、
前記アルミニウム材（１）において、アルミニウムの含有量が９９．６質量％以上、鉛の含有量が１０質量ｐｐｍ以下、マグネシウムの含有量が１０質量ｐｐｍ以下である、炭素被覆アルミニウム材。An aluminum material (1);
A carbon-containing layer (2) formed on the surface of the aluminum material (1);
An intervening layer (3) formed between the aluminum material (1) and the carbon-containing layer (2) and containing an aluminum element and a carbon element;
The intervening layer (3) includes a first surface portion (3) containing an aluminum carbide formed in at least a partial region of the surface of the aluminum material (1),
The carbon-containing layer (2) includes a second surface portion (21) formed to extend outward from the first surface portion (3),
The carbon-containing layer (2) further includes carbon-containing particles (22), and the second surface portion (21) is formed between the first surface portion (3) and the carbon-containing particles (22). Containing carbide of aluminum and
The carbon-coated aluminum material, wherein the aluminum material (1) has an aluminum content of 99.6 mass% or more, a lead content of 10 massppm or less, and a magnesium content of 10 massppm or less.
前記アルミニウム材（１）と前記炭素含有物質付着層とを、炭化水素含有物質を含む空間に配置して、加熱する工程とを備えた、炭素被覆アルミニウム材の製造方法。A carbon-containing substance containing carbon-containing particles on the surface of an aluminum material (1) having an aluminum content of 99.6 mass% or more, a lead content of 10 mass ppm or less, and a magnesium content of 10 mass ppm or less. Forming a carbon-containing substance adhesion layer by attaching
The manufacturing method of a carbon covering aluminum material provided with the process of arrange | positioning and heating the said aluminum material (1) and the said carbon containing substance adhesion layer in the space containing a hydrocarbon containing substance.
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| CN102055013A (en) * | 2009-10-27 | 2011-05-11 | 黄忠勇 | Activated carbon layer for chemical battery |
| US8687346B2 (en) * | 2010-05-27 | 2014-04-01 | Corning Incorporated | Multi-layered electrode for ultracapacitors |
| JP5634184B2 (en) | 2010-09-14 | 2014-12-03 | 東洋アルミニウム株式会社 | Conductive layer-coated aluminum material and method for producing the same |
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| JP2012224927A (en) * | 2011-04-21 | 2012-11-15 | Mitsubishi Alum Co Ltd | Aluminum alloy foil for positive electrode current collector of lithium ion battery, and method for manufacturing the same |
| JP6444877B2 (en) * | 2013-09-26 | 2018-12-26 | 東洋アルミニウム株式会社 | Coated aluminum material and method for producing the same |
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