JP5645971B2 - リチウム二次電池用負極活物質およびその製造方法 - Google Patents
リチウム二次電池用負極活物質およびその製造方法 Download PDFInfo
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- JP5645971B2 JP5645971B2 JP2012546823A JP2012546823A JP5645971B2 JP 5645971 B2 JP5645971 B2 JP 5645971B2 JP 2012546823 A JP2012546823 A JP 2012546823A JP 2012546823 A JP2012546823 A JP 2012546823A JP 5645971 B2 JP5645971 B2 JP 5645971B2
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- negative electrode
- etching
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- lithium secondary
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- Expired - Fee Related
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- 239000007773 negative electrode material Substances 0.000 title claims description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 61
- 229910052744 lithium Inorganic materials 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000005530 etching Methods 0.000 claims description 111
- 239000011888 foil Substances 0.000 claims description 90
- 239000002245 particle Substances 0.000 claims description 85
- 239000011148 porous material Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 32
- 238000005520 cutting process Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002482 conductive additive Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- 238000007599 discharging Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/06—Selection or use of additives to aid disintegrating
-
- 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
-
- 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
- H01M4/1395—Processes of manufacture of 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Food Science & Technology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
(2):孔
(10):リチウム二次電池
(12):負極
(13):正極
(14):セパレータ
実施例
市販の中高圧(170V以上の電解コンデンサ用陽極)用に両面エッチングが施されたAl箔を、シュレッダー装置により小片化した後、さらに粉砕装置により粉砕し、粉末からなる負極活物質をつくった。得られた負極活物質中の粒子の粒径は1〜50μmの範囲内であった。また、電子顕微鏡により負極活物質の粒子を観察したところ、箔の段階で確認された孔が、残存していた。
比較例
純度99.99質量%の高純度焼鈍Al箔を、シュレッダー装置により小片化した後、さらに粉砕装置により粉砕し、粉末からなる負極活物質をつくった。得られた負極活物質中の粒子の粒径は1〜50μmの範囲内であった。
評価試験
実施例および比較例において作製したモデル電池について、負極の評価を次の方法で行った。
Claims (7)
- 純度が90質量%以上のAlからなる箔の両面をエッチングしてエッチング箔をつくる工程、および当該エッチング箔を切断する工程をこの順序で行うことにより形成された粉末からなり、エッチング箔を切断して形成された粉末中に、表面に開口しかつ孔径が0.5μm以上である複数の孔を有する粒子が含まれており、孔を有する粒子におけるすべての孔の粒子表面への開口面積の合計が、当該孔を有する各粒子の表面積の10%以上であるリチウム二次電池用負極活物質。
- すべての粒子の粒径が5〜150μmであり、孔を有する粒子の孔径が0.5〜15μmであり、孔を有する粒子における粒径に対する孔径の比(孔径/粒径)が0.1未満である請求項1記載のリチウム二次電池用負極活物質。
- エッチング箔に形成されたすべてのエッチング孔のうち少なくとも一部のエッチング孔が貫通孔である請求項1記載のリチウム二次電池用負極活物質。
- 純度が90質量%以上のAlからなる箔の両面をエッチングすることによりつくられかつ両面に多孔質層を有するエッチング箔を、切断して粉末とすることを含み、エッチング箔として、厚みが200μm以下、両多孔質層におけるエッチング孔の孔径が0.5〜15μm、両多孔質層におけるすべてのエッチング孔の開口面積の合計が、それぞれエッチング箔の両面の表面積の10%以上であり、すべてのエッチング孔のうちの少なくとも一部のエッチング孔が貫通孔となっているものを用いることを特徴とするリチウム二次電池用負極活物質の製造方法。
- エッチング箔として、厚みが50〜150μmであるものを用いる請求項4記載のリチウム二次電池用負極活物質の製造方法。
- 集電体上に、請求項1に記載された負極活物質、導電助剤および結着剤を含む混合物質が付着されているリチウム二次電池用負極。
- 請求項6記載の負極と、セパレータと、リチウム二次電池用正極とを備えているリチウム二次電池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012546823A JP5645971B2 (ja) | 2010-11-30 | 2011-11-25 | リチウム二次電池用負極活物質およびその製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010266565 | 2010-11-30 | ||
JP2010266565 | 2010-11-30 | ||
JP2012546823A JP5645971B2 (ja) | 2010-11-30 | 2011-11-25 | リチウム二次電池用負極活物質およびその製造方法 |
PCT/JP2011/077165 WO2012073815A1 (ja) | 2010-11-30 | 2011-11-25 | リチウム二次電池用負極活物質およびその製造方法 |
Publications (2)
Publication Number | Publication Date |
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JPWO2012073815A1 JPWO2012073815A1 (ja) | 2014-05-19 |
JP5645971B2 true JP5645971B2 (ja) | 2014-12-24 |
Family
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Family Applications (1)
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JP2012546823A Expired - Fee Related JP5645971B2 (ja) | 2010-11-30 | 2011-11-25 | リチウム二次電池用負極活物質およびその製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9263742B2 (ja) |
JP (1) | JP5645971B2 (ja) |
WO (1) | WO2012073815A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013182845A (ja) * | 2012-03-05 | 2013-09-12 | Showa Denko Kk | リチウム二次電池用負極活物質およびその製造方法 |
JP2013229111A (ja) * | 2012-04-24 | 2013-11-07 | Showa Denko Kk | リチウム二次電池用負極活物質およびその製造方法 |
JP6063639B2 (ja) * | 2012-05-01 | 2017-01-18 | 昭和電工株式会社 | リチウム二次電池用負極活物質の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03252052A (ja) * | 1990-02-28 | 1991-11-11 | Sanyo Electric Co Ltd | 電池 |
JPH0850922A (ja) * | 1994-05-30 | 1996-02-20 | Canon Inc | 電池用電極及び該電極を有するリチウム二次電池 |
JPH08124568A (ja) * | 1994-10-19 | 1996-05-17 | Canon Inc | 二次電池並びに、その負極材料形成方法及び負極材料の取扱方法 |
JPH08213053A (ja) * | 1994-12-02 | 1996-08-20 | Canon Inc | リチウム二次電池 |
JP2010170901A (ja) * | 2009-01-23 | 2010-08-05 | Kobelco Kaken:Kk | 負極活物質、これを用いた二次電池およびキャパシタ |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001297757A (ja) | 2000-04-14 | 2001-10-26 | Sumitomo Metal Ind Ltd | 非水電解質二次電池用負極材料およびその製造方法 |
JP4029291B2 (ja) | 2003-09-02 | 2008-01-09 | 福田金属箔粉工業株式会社 | リチウム二次電池用負極材料及びその製造方法 |
-
2011
- 2011-11-25 JP JP2012546823A patent/JP5645971B2/ja not_active Expired - Fee Related
- 2011-11-25 US US14/110,507 patent/US9263742B2/en not_active Expired - Fee Related
- 2011-11-25 WO PCT/JP2011/077165 patent/WO2012073815A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03252052A (ja) * | 1990-02-28 | 1991-11-11 | Sanyo Electric Co Ltd | 電池 |
JPH0850922A (ja) * | 1994-05-30 | 1996-02-20 | Canon Inc | 電池用電極及び該電極を有するリチウム二次電池 |
JPH08124568A (ja) * | 1994-10-19 | 1996-05-17 | Canon Inc | 二次電池並びに、その負極材料形成方法及び負極材料の取扱方法 |
JPH08213053A (ja) * | 1994-12-02 | 1996-08-20 | Canon Inc | リチウム二次電池 |
JP2010170901A (ja) * | 2009-01-23 | 2010-08-05 | Kobelco Kaken:Kk | 負極活物質、これを用いた二次電池およびキャパシタ |
Also Published As
Publication number | Publication date |
---|---|
WO2012073815A1 (ja) | 2012-06-07 |
US9263742B2 (en) | 2016-02-16 |
JPWO2012073815A1 (ja) | 2014-05-19 |
US20140113189A1 (en) | 2014-04-24 |
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