JP2013030462A - 蓄電装置およびその作製方法 - Google Patents
蓄電装置およびその作製方法 Download PDFInfo
- Publication number
- JP2013030462A JP2013030462A JP2012125608A JP2012125608A JP2013030462A JP 2013030462 A JP2013030462 A JP 2013030462A JP 2012125608 A JP2012125608 A JP 2012125608A JP 2012125608 A JP2012125608 A JP 2012125608A JP 2013030462 A JP2013030462 A JP 2013030462A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- alloy
- electrode material
- based negative
- silicon
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 224
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 128
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 79
- 230000001603 reducing effect Effects 0.000 claims abstract description 16
- 239000007773 negative electrode material Substances 0.000 claims description 97
- 229910045601 alloy Inorganic materials 0.000 claims description 88
- 239000000956 alloy Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052710 silicon Inorganic materials 0.000 abstract description 31
- 239000010703 silicon Substances 0.000 abstract description 30
- 230000008859 change Effects 0.000 abstract description 13
- 239000011856 silicon-based particle Substances 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 230000008602 contraction Effects 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 54
- 229910002804 graphite Inorganic materials 0.000 description 20
- 239000010439 graphite Substances 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000002409 silicon-based active material Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001962 electrophoresis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10T29/00—Metal working
- Y10T29/43—Electric condenser making
-
- 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
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
【解決手段】負極は、粒子状あるいはウィスカ状のシリコンを含有し、シリコン粒子あるいはウィスカの表面は酸化グラフェンを還元して作製された1層乃至50層のグラフェンよりなるカーボン膜で覆われている。このようなカーボン膜は、分子間の結合力の強いsp2結合がシリコン表面と概略平行であるため、シリコンが膨張する際においてもカーボン膜が破断することがなく、シリコンの破砕を防止することができる。また、このようにして作製されたカーボン膜は、適度に隙間があり、シリコンが膨張する際に伸縮することができ、さらに、リチウムイオンを透過させることができる。また、シリコンと電解液との反応を防止する効果もある。
【選択図】なし
Description
本実施の形態では、合金系負極材料としてシリコンを用い、シリコン粒子の表面に1層乃至50層のグラフェンの層よりなるカーボン膜を形成する例について説明する。最初に、グラファイトを酸化して、酸化グラファイトを作製し、これに超音波振動を加えることで酸化グラフェンを得る。詳細は特許文献2を参照すればよい。また、市販の酸化グラフェンを利用してもよい。グラファイトより酸化グラフェンを得るには以下のようにおこなうとよい。
本実施の形態では、集電体上に形成されたシリコン活物質層の表面に1層乃至50層のグラフェンの層よりなるカーボン膜を形成する例について説明する。最初に、酸化グラフェンを水やNMP等の溶媒に分散させる。溶媒は極性溶媒であることが好ましい。酸化グラフェンの濃度は1リットル当たり0.1g乃至10gとすればよい。
本実施の形態では、集電体上に形成されたシリコン活物質層の表面に1層乃至50層のグラフェンの層よりなるカーボン膜を形成する別の例について説明する。実施の形態2と同様に、酸化グラフェンを水やNMP等の溶媒に分散させる。酸化グラフェンの濃度は1リットル当たり0.1g乃至10gとすればよい。
本発明の蓄電装置は、例えば、電気自動車、電動工具、パーソナルコンピュータ、携帯電話、非常用電源等で使用できる。これらの電気機器は、有線で電源を供給されるとは限らないため、内部に充電池を有する。その充電池の負極の活物質として、例えば、実施の形態1乃至実施の形態3で示したグラフェンの層よりなるカーボン膜で表面が覆われたシリコン粒子あるいはウィスカを用いればよい。
102 負極活物質層
104 負極
106 筐体
110 セパレータ
120 リング状絶縁体
128 陽極集電体
130 陽極活物質層
132 陽極
140 スペーサー
142 ワッシャー
144 筐体
201 表示装置
202 筐体
203 表示部
204 スピーカー部
205 蓄電装置
211 照明装置
212 筐体
213 光源
214 蓄電装置
215 天井
216 側壁
217 床
218 窓
221 室内機
222 筐体
223 送風口
224 蓄電装置
225 室外機
231 電気冷凍冷蔵庫
232 筐体
233 冷蔵室用扉
234 冷凍室用扉
235 蓄電装置
Claims (7)
- 表面が1層乃至50層のグラフェンの層よりなるカーボン膜に覆われた合金系負極材料粒子あるいは合金系負極材料ウィスカを負極として有し、前記カーボン膜は少なくとも1つの空孔を有することを特徴とする蓄電装置。
- 前記合金系負極材料粒子あるいは前記合金系負極材料ウィスカを覆うカーボン膜は酸化グラフェンをその表面に形成した後、これを還元して得られた請求項1記載の蓄電装置。
- 前記カーボン膜に含まれる炭素と水素以外の元素は15原子%以下であることを特徴とする請求項1もしくは請求項2記載の蓄電装置。
- 前記合金系負極材料粒子あるいは前記合金系負極材料ウィスカ表面はカーボン膜とは異なる材料の層が単層あるいは複数層形成されていることを特徴とする請求項1乃至請求項3記載の蓄電装置。
- 合金系負極材料粒子あるいは合金系負極材料ウィスカと酸化グラフェンを混合する工程と、
前記混合物を真空中あるいは還元性雰囲気中で加熱する工程と
を有する蓄電装置の作製方法。 - 酸化グラフェンを分散させた溶液中に、合金系負極材料粒子あるいは合金系負極材料ウィスカを浸漬する工程と、
前記合金系負極材料粒子あるいは前記合金系負極材料ウィスカを真空中あるいは還元性雰囲気中で加熱する工程と
を有する蓄電装置の作製方法。 - 酸化グラフェンを分散させた溶液中に、合金系負極材料粒子あるいは合金系負極材料ウィスカと電極を浸漬し、前記合金系負極材料粒子あるいは前記合金系負極材料ウィスカと前記電極間に電圧を加える工程と、
前記合金系負極材料粒子あるいは前記合金系負極材料ウィスカを真空中あるいは還元性雰囲気中で加熱する工程と
を有する蓄電装置の作製方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012125608A JP6068742B2 (ja) | 2011-06-03 | 2012-06-01 | 蓄電装置 |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011125224 | 2011-06-03 | ||
JP2011125224 | 2011-06-03 | ||
JP2011140307 | 2011-06-24 | ||
JP2011140307 | 2011-06-24 | ||
JP2012125608A JP6068742B2 (ja) | 2011-06-03 | 2012-06-01 | 蓄電装置 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016250257A Division JP6322695B2 (ja) | 2011-06-03 | 2016-12-23 | 蓄電装置 |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2013030462A true JP2013030462A (ja) | 2013-02-07 |
JP2013030462A5 JP2013030462A5 (ja) | 2015-06-25 |
JP6068742B2 JP6068742B2 (ja) | 2017-01-25 |
Family
ID=47234317
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012125608A Expired - Fee Related JP6068742B2 (ja) | 2011-06-03 | 2012-06-01 | 蓄電装置 |
JP2016250257A Active JP6322695B2 (ja) | 2011-06-03 | 2016-12-23 | 蓄電装置 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016250257A Active JP6322695B2 (ja) | 2011-06-03 | 2016-12-23 | 蓄電装置 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20120308894A1 (ja) |
JP (2) | JP6068742B2 (ja) |
KR (1) | KR101978726B1 (ja) |
CN (2) | CN102810672B (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015118924A (ja) * | 2013-11-13 | 2015-06-25 | 株式会社半導体エネルギー研究所 | 蓄電装置用負極、蓄電装置、および電気機器 |
JPWO2016208314A1 (ja) * | 2015-06-22 | 2018-04-05 | 株式会社日立製作所 | リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池 |
US10249871B2 (en) | 2014-06-10 | 2019-04-02 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US10608276B2 (en) | 2014-08-29 | 2020-03-31 | Nec Corporation | Carbon material, anode material and spacer additive for lithium ion battery |
JP2021015815A (ja) * | 2014-10-24 | 2021-02-12 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
US11302904B2 (en) | 2018-11-19 | 2022-04-12 | Samsung Electronics Co., Ltd. | Electrode composite conducting agent for lithium battery, electrode for lithium battery, method of manufacturing the same, and lithium battery including the electrode |
JP2023508760A (ja) * | 2020-03-23 | 2023-03-03 | テクトロニック コードレス ジーピー | リチウムイオンバッテリ |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010033203A1 (en) * | 2008-09-18 | 2010-03-25 | Neozyme Inernational, Inc. | Anaerobic process for treating organic material to generate biogas |
WO2011057074A2 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene-composite materials in a graphite network |
WO2013027561A1 (en) | 2011-08-19 | 2013-02-28 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode |
JP6025284B2 (ja) | 2011-08-19 | 2016-11-16 | 株式会社半導体エネルギー研究所 | 蓄電装置用の電極及び蓄電装置 |
JP6050106B2 (ja) | 2011-12-21 | 2016-12-21 | 株式会社半導体エネルギー研究所 | 非水二次電池用シリコン負極の製造方法 |
JP5951896B2 (ja) * | 2012-06-29 | 2016-07-13 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | グラフェンフィルム、並びにその製造方法及び使用 |
CN104934573A (zh) * | 2014-03-19 | 2015-09-23 | 苏州格瑞动力电源科技有限公司 | 一种具有多级结构的硅-石墨烯球状复合材料的原位固相合成方法及其应用 |
WO2015199251A1 (ko) * | 2014-06-23 | 2015-12-30 | 동아대학교 산학협력단 | 내부에 그래핀 네트워크가 형성된 나노입자-그래핀-탄소 복합체, 이의 제조방법 및 이의 응용 |
JP5743011B1 (ja) | 2014-06-27 | 2015-07-01 | 住友大阪セメント株式会社 | 電極材料、電極用ペースト及びリチウムイオン電池 |
JP5743012B1 (ja) * | 2014-06-27 | 2015-07-01 | 住友大阪セメント株式会社 | 電極材料、電極用ペースト及びリチウムイオン電池 |
EP3353844B1 (en) | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
JP6840476B2 (ja) | 2015-07-16 | 2021-03-10 | 株式会社半導体エネルギー研究所 | 蓄電装置の作製方法 |
WO2018056107A1 (ja) * | 2016-09-23 | 2018-03-29 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池用負極、非水電解質二次電池及び非水電解質二次電池用負極の製造方法 |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
KR102484893B1 (ko) * | 2017-10-26 | 2023-01-04 | 현대자동차주식회사 | 리튬 금속 이차 전지용 음극 및 이를 포함하는 리튬 금속 이차 전지 |
CN114381240B (zh) * | 2022-01-26 | 2024-03-15 | 杭州热流新材料有限公司 | 一种c/金属复合界面焊接高导热厚膜的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110111303A1 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4067268B2 (ja) * | 2000-09-01 | 2008-03-26 | 三洋電機株式会社 | リチウム二次電池用負極及びその製造方法 |
AU2001282569A1 (en) * | 2000-09-01 | 2002-03-22 | Sanyo Electric Co., Ltd. | Negative electrode for lithium secondary cell and method for producing the same |
BR0315457B1 (pt) * | 2002-11-29 | 2012-06-26 | eletrodo negativo para bateria secundária não-aquosa, processo de produção de eletrodo negativo, e bateria secundária não-aquosa. | |
KR20070035341A (ko) * | 2005-09-27 | 2007-03-30 | 삼성전자주식회사 | 간극을 채운 반도체 나노결정층을 함유하는 발광소자 및 그제조방법 |
CN113571772A (zh) * | 2005-10-20 | 2021-10-29 | 三菱化学株式会社 | 锂二次电池以及其中使用的非水电解液 |
WO2008048295A2 (en) | 2005-11-18 | 2008-04-24 | Northwestern University | Stable dispersions of polymer-coated graphitic nanoplatelets |
KR101508788B1 (ko) | 2006-06-02 | 2015-04-06 | 미쓰비시 가가꾸 가부시키가이샤 | 비수계 전해액 및 비수계 전해액 전지 |
JP4525742B2 (ja) * | 2007-01-30 | 2010-08-18 | ソニー株式会社 | リチウムイオン二次電池用負極およびリチウムイオン二次電池 |
US20090068567A1 (en) * | 2007-09-12 | 2009-03-12 | Sony Corporation | Anode for secondary battery, method of manufacturing it, and secondary battery |
US7745047B2 (en) * | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
KR101065778B1 (ko) * | 2008-10-14 | 2011-09-20 | 한국과학기술연구원 | 탄소나노튜브 피복 실리콘-구리 복합 입자 및 그 제조 방법과, 이를 이용한 이차전지용 음극 및 이차전지 |
US8580432B2 (en) * | 2008-12-04 | 2013-11-12 | Nanotek Instruments, Inc. | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
JP5359442B2 (ja) * | 2009-03-25 | 2013-12-04 | 住友化学株式会社 | ナトリウムイオン電池 |
JP5448555B2 (ja) * | 2009-04-30 | 2014-03-19 | 古河電気工業株式会社 | リチウムイオン二次電池用負極、それを用いたリチウムイオン二次電池、リチウムイオン二次電池用の負極作製用のスラリー、リチウムイオン二次電池用負極の製造方法 |
US9190694B2 (en) * | 2009-11-03 | 2015-11-17 | Envia Systems, Inc. | High capacity anode materials for lithium ion batteries |
US20110227000A1 (en) * | 2010-03-19 | 2011-09-22 | Ruoff Rodney S | Electrophoretic deposition and reduction of graphene oxide to make graphene film coatings and electrode structures |
TWI582041B (zh) * | 2011-06-03 | 2017-05-11 | 半導體能源研究所股份有限公司 | 單層和多層石墨烯,彼之製法,含彼之物件,以及含彼之電器裝置 |
WO2013027561A1 (en) * | 2011-08-19 | 2013-02-28 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing graphene-coated object, negative electrode of secondary battery including graphene-coated object, and secondary battery including the negative electrode |
-
2012
- 2012-05-17 KR KR1020120052696A patent/KR101978726B1/ko active IP Right Grant
- 2012-05-31 US US13/484,299 patent/US20120308894A1/en not_active Abandoned
- 2012-06-01 CN CN201210179710.6A patent/CN102810672B/zh active Active
- 2012-06-01 CN CN201610631472.6A patent/CN106099042B/zh not_active Expired - Fee Related
- 2012-06-01 JP JP2012125608A patent/JP6068742B2/ja not_active Expired - Fee Related
-
2016
- 2016-12-23 JP JP2016250257A patent/JP6322695B2/ja active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110111303A1 (en) * | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene composite materials in a graphite network formed from reconstituted graphene sheets |
Non-Patent Citations (2)
Title |
---|
CECILIA MATTEVI ET AL.: "Evolution of electrical, chemical, and structural properties of transparent and conducting chemicall", ADVANCED FUNCTIONAL MATERIALS, vol. 24 August 2009, Vol.19, No.16, JPN6013019258, pages 2577 - 2583, ISSN: 0003398294 * |
H. XIANG ET AL.: "Graphene/nanosized silicon composites for lithium battery anodes with improved cycling stability", CARBON, JPN6015006761, pages 49 - 1787, ISSN: 0003398293 * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10593940B2 (en) | 2013-11-13 | 2020-03-17 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for power storage device, power storage, device and electrical device |
JP2015118924A (ja) * | 2013-11-13 | 2015-06-25 | 株式会社半導体エネルギー研究所 | 蓄電装置用負極、蓄電装置、および電気機器 |
US10862112B2 (en) | 2014-06-10 | 2020-12-08 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US10249871B2 (en) | 2014-06-10 | 2019-04-02 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US10862111B2 (en) | 2014-06-10 | 2020-12-08 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US10862110B2 (en) | 2014-06-10 | 2020-12-08 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US11837714B2 (en) | 2014-06-10 | 2023-12-05 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US11870060B2 (en) | 2014-06-10 | 2024-01-09 | Samsung Electronics Co., Ltd. | Composite, electrochemical active material composite using the composite, electrode including the composite or electrochemical active material composite, lithium battery including the electrode, field emission device including the composite, biosensor including the composite, semiconductor device including the composite, and thermoelectric device including the composite |
US10608276B2 (en) | 2014-08-29 | 2020-03-31 | Nec Corporation | Carbon material, anode material and spacer additive for lithium ion battery |
JP2021015815A (ja) * | 2014-10-24 | 2021-02-12 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
JP7104127B2 (ja) | 2014-10-24 | 2022-07-20 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
JP2022160423A (ja) * | 2014-10-24 | 2022-10-19 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
JPWO2016208314A1 (ja) * | 2015-06-22 | 2018-04-05 | 株式会社日立製作所 | リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池 |
US11302904B2 (en) | 2018-11-19 | 2022-04-12 | Samsung Electronics Co., Ltd. | Electrode composite conducting agent for lithium battery, electrode for lithium battery, method of manufacturing the same, and lithium battery including the electrode |
JP2023508760A (ja) * | 2020-03-23 | 2023-03-03 | テクトロニック コードレス ジーピー | リチウムイオンバッテリ |
Also Published As
Publication number | Publication date |
---|---|
KR20120135037A (ko) | 2012-12-12 |
JP6322695B2 (ja) | 2018-05-09 |
CN106099042A (zh) | 2016-11-09 |
JP2017076628A (ja) | 2017-04-20 |
CN106099042B (zh) | 2019-08-16 |
KR101978726B1 (ko) | 2019-05-15 |
US20120308894A1 (en) | 2012-12-06 |
CN102810672B (zh) | 2016-09-14 |
JP6068742B2 (ja) | 2017-01-25 |
CN102810672A (zh) | 2012-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6322695B2 (ja) | 蓄電装置 | |
KR102305071B1 (ko) | 이차 전지 | |
JP6603343B2 (ja) | 二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150501 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150501 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160225 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160301 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160425 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160913 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161102 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161129 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161223 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6068742 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |