WO1998000876A1 - Materiau de cathode d'accumulateur electrolytique non-aqueux et accumulateur electolytique non-aqueux utilisant le materiau de cathode - Google Patents
Materiau de cathode d'accumulateur electrolytique non-aqueux et accumulateur electolytique non-aqueux utilisant le materiau de cathode Download PDFInfo
- Publication number
- WO1998000876A1 WO1998000876A1 PCT/JP1997/002247 JP9702247W WO9800876A1 WO 1998000876 A1 WO1998000876 A1 WO 1998000876A1 JP 9702247 W JP9702247 W JP 9702247W WO 9800876 A1 WO9800876 A1 WO 9800876A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fibrous carbon
- negative electrode
- electrolyte secondary
- secondary battery
- aqueous electrolyte
- Prior art date
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 78
- 239000010406 cathode material Substances 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 197
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 166
- 239000000835 fiber Substances 0.000 claims abstract description 133
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 41
- 238000009987 spinning Methods 0.000 claims description 25
- 239000003575 carbonaceous material Substances 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 12
- 230000001186 cumulative effect Effects 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000003125 aqueous solvent Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 7
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- 238000004438 BET method Methods 0.000 claims description 2
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- 238000003825 pressing Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 63
- 230000000704 physical effect Effects 0.000 abstract description 8
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- 238000012360 testing method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
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- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 2
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- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
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- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical group COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
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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
- H01M4/04—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
- H01M4/36—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
- 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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/022—Electrodes made of one single microscopic fiber
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0433—Molding
-
- 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
Definitions
- Negative electrode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same Technical field The present invention relates to a non-aqueous electrolyte secondary battery comprising a carbon material, particularly fibrous carbon.
- the present invention relates to a negative electrode material for a pond, and further relates to a nonaqueous electrolyte secondary battery using the same.
- Background Technology Recent advances in electronic technology have been remarkable. For example, electronic devices have been reduced in size and weight. Along with this, there is an increasing demand for batteries as portable power supplies that are smaller, lighter and have higher energy density.
- aqueous batteries such as lead batteries and nickel-cadmium batteries have been the mainstream as secondary batteries for general use. These batteries have some degree of satisfactory cycle characteristics, but are not satisfactory in terms of battery weight and energy density.
- Lithium ion secondary batteries use lithium doping / de-doping between carbon layers for the anode reaction.Even if the charge / discharge cycle progresses, no precipitation of dendritic crystals is observed during charging. It shows good charge / discharge cycle characteristics.
- Cox-glassy carbon there are several carbon materials that can be used as a negative electrode of a lithium ion secondary battery, but the first material that has been put to practical use is Cox-glassy carbon. These are low crystallinity materials obtained by heat-treating organic materials at relatively low temperatures.
- fibrous carbon (carbon fiber) obtained by carbonizing fibrous organic matter is relatively easy to control the carbon structure and does not require pulverization. This is advantageous when considered.
- the structure of fibrous carbon largely reflects the structure of the organic fiber that is the precursor.
- the organic fibers include those made from a polymer such as polyacrylonitrile, pitches such as petroleum pitch, and those made from a further oriented mesotropic pitch, all of which are spun. This results in a fibrous form.
- Fibrous carbon can be obtained by carbonizing these organic fibers.However, when heat-treated at the time of carbonization, they melt and destroy the fiber structure. The carbonization is performed after the infusibilization process.
- the fibrous carbon obtained in this way has a cross-sectional structure derived from the organic fiber structure, and is concentrically oriented, such as the so-called onion skin type, radially oriented radial type, and isotropic random type. Indicates a higher-order structure.
- Graphite fibers obtained by graphitizing them have high true density and high crystallinity.
- Fibrous carbon does not need to be pulverized under strong conditions because it is not a block like ordinary graphite materials, but it needs to be finely pulverized and cut so as to have a certain aspect ratio.
- This pulverization and cutting of fibrous carbon involves various difficulties as compared with pulverization of block-like carbon material, and as described above, cracks are likely to occur, and physical parameters such as the aspect ratio are also increased. —It is also difficult to keep the evening constant.
- the present invention provides practical fibrous carbon having high electrode filling properties, excellent crystallinity, easy to cut, and physical properties with little variation over time, thereby providing high energy density and high reliability. It is an object of the present invention to provide a non-aqueous electrolyte secondary battery.
- the cross-sectional shape of the fibrous carbon is defined as the area sufficiency (the product of the long side and short side of the circumscribed rectangle that has the minimum area when the cross section of the fibrous carbon is surrounded by the circumscribed rectangle). (The value obtained by dividing the area of the cross section of the above) satisfies a specific range, specifically, 0.8 or more. As a result, a negative electrode material having a high electrode filling property and a small dead space can be obtained.
- the cycle characteristics are further improved by forming a shape satisfying a specific circularity range.
- the value of the fractal dimension obtained by fractal analysis of the higher-order structure of the cross section of the random radial type fibrous carbon is Since it can be used as a parameter for evaluating the structure, it is set to a specific range (1.1 to 1.8) and the crystallinity is controlled to an appropriate range.
- the central part has a radial structure and the surface layer has a random radial structure.
- the cross-sectional shape of the fibrous carbon has a notch structure having a notch.
- the notch angle is between 2 ° and 150 °.
- FIG. 1 is a diagram showing a cross section of fibrous carbon having a radial structure at the center and a random radial structure at the surface.
- FIG. 2 is a diagram showing a cross-sectional shape of a fibrous carbon having a notched structure.
- Figure 3 shows a discharge hole for producing fibrous carbon with a notched structure. It is sectional drawing which shows the example of a shape.
- FIG. 4 is a schematic perspective view showing graphitized fibrous carbon having cross sections having different crystal structures at regular intervals in the fiber length direction and fibrous carbon powder obtained by pulverizing the same.
- FIG. 5 is a perspective view schematically showing a fibrous carbon particle model.
- FIG. 6 is a cross-sectional view illustrating a structural example of a nonaqueous electrolyte secondary battery.
- FIG. 7 is a diagram showing an example of a cross-sectional shape of graphitized fibrous carbon.
- FIG. 8 is a diagram showing another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 9 is a view showing still another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 10 is a view showing still another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 11 is a diagram showing still another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 12 is a view showing still another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 13 is a view showing still another example of the cross-sectional shape of graphitized fibrous carbon.
- FIG. 14 is a characteristic diagram showing the relationship between the area sufficiency of the fiber cross section and the capacity.
- Figure 15 is a characteristic diagram showing the relationship between the circularity of the fiber cross section and the capacity retention rate.
- FIG. 16 is a diagram showing a measurement example of a fractal dimension.
- FIG. 17 is a characteristic diagram showing the relationship between the spacing between the (002) planes of fibrous carbon and the capacity.
- Figure 18 shows the relationship between the fractal dimension value and the capacity retention rate It is a characteristic diagram.
- FIG. 19 is a schematic diagram showing an example of a discharge hole for producing fibrous carbon having a radial structure at the center and a random radial structure at the surface layer.
- FIG. 20 is a characteristic diagram showing the relationship between the ratio of radial structure and capacity.
- FIG. 21 is a characteristic diagram showing the relationship between the ratio of the radial structure and the capacity retention ratio.
- FIG. 22 is a characteristic diagram showing a relationship between a notch angle and a capacity in fibrous carbon having a notch structure.
- FIG. 23 is a characteristic diagram showing a relationship between a notch angle and a capacity retention ratio in fibrous carbon having a notch structure.
- FIG. 24 is a characteristic diagram showing the relationship between the aspect ratio of the fibrous carbon powder and the capacity retention.
- BEST MODE FOR CARRYING OUT THE INVENTION In the negative electrode material for a non-aqueous electrolyte secondary battery of the present invention, the carbon material for doping and undoping lithium has a cross-sectional area sufficiency of 0. Eight or more, preferably 0.9 or more fibrous carbon is used.
- the area sufficiency is defined as the value obtained by dividing the area of the fiber cross-section by the product (area) of the long and short sides of the circumscribed rectangle, which is the minimum area, when the cross-section of the fiber is surrounded by a circumscribed rectangle. Defined.
- the cross-sectional shape of the fiber becomes closer to a rectangle, and the dead space created by the curved surface decreases, so that the electrode filling property can be improved, so that the energy density of the battery can be improved. Can be.
- the area sufficiency Y is calculated by observing the cross-sectional image of fibrous carbon or a photograph thereof with a microscope such as an electron microscope, and taking the area s of the projected cross-sectional image and the circumscribed rectangle that is the minimum area for the cross-sectional image.
- the long side L and the short side B are obtained, and can be calculated by substituting them into Equation 1.
- the cycle characteristics can be improved by further defining the area satisfying the area satisfaction degree by the circularity.
- Circularity is the value obtained by dividing the circumference of a circle having the same area as the area of the projected cross-sectional image by the length of the contour of the projected cross-sectional image.The closer to a circle, the value approaches 1. . Specifically, it can be obtained by the following method.
- the value of the circularity is preferably 0.8 or more and less than 1.0, and more preferably 0.9 or more and less than 1.0. By setting the value of the circularity within this range, the cycle characteristics are improved.
- the starting organic materials include polymers such as polyacrylonitrile and rayon, petroleum-based pitch, coal-based pitch, and synthetic pitch. It is possible to use pitches such as mesophase pitch in which aromatic rings are condensed or polycyclized to be stacked and oriented by holding at about ° C for an arbitrary time or promoting polymerization by adding an acid or the like.
- the spinnability, the physical properties of fibrous carbon, and the electrical and chemical properties greatly affect the mesoface content.
- the mesophase content is preferably at least 60%, more preferably at least 95%. Below this range, the orientation of crystals is inferior and the capacity of the material itself is reduced, which is not preferable.
- the polymer and the pitch are heated to be in a molten state, and are formed and spun by discharge or the like. In this case, the melting point varies depending on each organic substance, and the optimum spinning temperature can be appropriately selected for each.
- the structure of the fibrous carbon largely reflects the structure of the organic fiber, which is the precursor, and the cross-sectional shape reflects the shape at the time of spinning.For example, in the case of extrusion molding, the optimal shape of the discharge hole is selected. It is important to.
- the structure of fibrous carbon functioning as a negative electrode material is classified into several types according to its cross-sectional structure. Specifically, there are an onion skin type that is arranged concentrically, a radial type that is radially oriented, and an isotropic random type, all of which can be used as a negative electrode material. In particular, a radial type or a random radial type in which a radial type and a random type are mixed is preferable.
- the fractal dimension of the fibrous carbon cross-sectional structure is an index indicating the structure of the carbon network plane in the fiber cross-section.
- an image of the fiber cross section is made into a photograph using an electron microscope (electrolytic emission type scanning electron microscope, etc.), and the image is taken into a computer using a scanner or the like, and this is taken.
- fractal analysis is performed.
- the average value obtained for 10 fibers was defined as a fractal dimension value (hereinafter simply referred to as “FD value”).
- the fractal dimension indicates the degree of curvature of the curve in the plane, and takes a value of 1 to 2, but approaches 2 as the curve becomes more complicated.
- the FD value enables quantitative evaluation of the complex fibrous carbon cross-sectional structure, and in particular, the parameter for evaluating the curved structure of the carbon mesh surface that affects the capacity of the negative electrode and the reversibility of the charge-discharge cycle. Overnight the FD value is important.
- the 0 value is preferably 1.1 or more and less than 1.8, and 1.25 or more and less than 1.8. Is more preferred.
- the X-ray analysis method (Gakushin method) Obtained (002) plane spacing d. . 2 is an index.
- d. Q 2 is preferably less than 0.340 nm, more preferably 0.335 nm or more and 0.337 nm or less, most preferably 0.335 nm or more and 0.336 nm or less.
- the starting material and the method of fiberization are important.
- the starting organic materials include polymers such as polyacrylonitrile and rayon, oil-based pitch, coal-based pitch, synthetic pitch, and up to about 400 ° C.
- a bitumen such as a meso-split or the like, in which aromatic rings are condensed or polycyclized and laminated and oriented, for example, by holding for an arbitrary time or accelerating the polymerization by adding an acid or the like, is used.
- the spinnability, the physical properties of fibrous carbon, and the electrical and chemical properties are greatly affected by the mesoface content.
- the mesophase content is preferably at least 6 °%, more preferably at least 95%. Below this range, the orientation of crystals is inferior and the capacity of the material itself is reduced, which is not preferable.
- the polymers and pitches are heated to a molten state and formed and spun by discharge or the like. In this case, the melting point varies depending on each organic substance, and the optimum spinning temperature can be appropriately selected for each.
- the FD value is greatly affected by the spinning conditions, that is, the extrusion speed and the shape of the discharge hole in the case of extrusion molding, so that it is necessary to appropriately control these.
- the curve of the carbon mesh plane in the cross-sectional structure can also be obtained. It is possible to shape the structure.
- a method of forming a pore in the discharge hole to blow out gas such as air, a method of generating a magnetic field near the discharge hole to disturb the pitch orientation, a method of applying vibration to the discharge hole by ultrasonic waves, or the like are used. be able to.
- the central part has a radial structure and the surface layer has a random radial structure, so that the fiber has both high strength to withstand expansion and contraction during charging and discharging and high capacity. Carbon is feasible.
- the cross-sectional higher-order structure of this fibrous carbon has a radial structure at the center, but this radial structure has a high orientation of the carbon layer surface, and is particularly affected by high-temperature heat treatment. High crystallinity is easily obtained.
- the fiber structure is likely to break down due to expansion and contraction during charging and discharging. Therefore, by forming the surface layer where irregularity occurs into a random radial structure with high strength and relatively high crystallinity, large It is a high-strength and highly practical fibrous carbon that can withstand the one-carnation capacity and expansion and contraction during charging and discharging.
- the radial structure if the radial structure is included in a large amount, the calcining capacity increases, but on the other hand, the fiber structure is likely to break down due to repeated expansion and contraction during charge and discharge.
- the content of the structure can be appropriately selected depending on the intended use of the battery.
- the center is the geometric center of gravity
- the length is R
- the length of the part forming the radial structure is R Find L / R as L.
- straight lines are drawn at an interval of 15 ° with respect to the straight line, and L / R is similarly calculated for each line, and the average value thereof is defined as the content of the radial structure.
- the value of the content of the radial structure is preferably 0.3 or more and less than 1.0, more preferably 0.5 or more and less than 1.0, and particularly preferably 0.6 or more and 0.9 or less.
- the above-mentioned radial structure refers to a portion radially oriented from the center of the fiber cross section, and this radial structure can usually be confirmed by observation with a scanning electron microscope or the like.
- the radial structure has a high degree of crystal anisotropy, it can be confirmed by observing a small area with a polarizing microscope or a transmission electron microscope.
- the above-mentioned fibrous carbon has at least two different types of concentrically divided structures if it has a circular cross-sectional structure.However, in order to produce a fibrous carbon having such a structure, however, it is necessary to control the structure such as the pitch melted in the vicinity of the outlet of the discharge hole when producing the organic fiber.
- control method examples include a method of blowing air or the like at the discharge hole ⁇ and changing the flow of the alignment state such as a pitch, a method of applying a magnetic field from the outside of the discharge hole to change the flow of the alignment state such as pitch, and the like.
- the structure of itself Any method can be applied, such as a method in which the structure is divided into at least two concentric circles and the orientation is changed by changing the flow of bitches and the like.
- the notch can absorb the structural distortion caused by the expansion and contraction that occurs during charging and discharging, and the reversibility of the charging and discharging cycle can be improved.
- the notch structure shows different cycle reversibility depending on the angle formed by the center of the fibrous carbon cross-section and the outer circumference of the fiber diameter (hereinafter referred to as “notch angle”) shown in Fig. 2 ⁇ .
- notch angle it is known that the intercalation by graphite into the graphite structure expands about 10% between layers. If the notch angle is small, the structural distortion caused by expansion and contraction that occurs during charging and discharging cannot be absorbed, and structural destruction occurs. If the notch angle is large, the carbon structure decreases and the volume decreases. . For this reason, the notch angle can be appropriately selected according to the purpose, but the angle is preferably 2 ° or more and 150 ° or less.
- the notch angle is defined as the angle between the center of the geometric center of gravity and the fiber periphery.
- notch angle of fibrous carbon having a notch structure in the cross section To measure the notch angle of fibrous carbon having a notch structure in the cross section, observe the fiber cross section with an electron microscope, and use the angle from the image or photographic image. Can be measured.
- the higher-order cross-sectional structure of the fibrous carbon the higher the ratio of the radial structure is, the higher the capacity can be obtained, but the structural distortion tends to occur.
- a cross-sectional structure such as a random radial type in which a mold structure and the like are mixed can be appropriately selected. In this case, since the strength of the carbon fiber itself is increased, the reversibility of the charge / discharge cycle is further improved by providing the cutout structure.
- the fibrous carbon having the cutout structure can be manufactured by using a discharge hole T having an outlet shape like a wedge provided with a baffle plate J for spinning organic fibers.
- the outlet shape is not limited to this.
- any other method can be applied as long as a notch structure can be formed in the cross-sectional structure of the precursor fiber.
- graphitized fibrous carbon (hereinafter simply referred to as “precursor graphitized fiber”), which is a precursor of fibrous carbon ground powder (hereinafter simply referred to as “ground powder”)
- a specific or constant period (Fig. 4 shows a periodic structure with a length of 1) and a structure with cross-sections with different crystal structures, which are pulverized to form sample powder 22 Forms a powder. Since the crystal orientation is different between the different crystal portions 21 having different crystal structures, the portion is more easily broken at the time of pulverization, and a sample powder 22 having a constant fiber length can be easily produced.
- the fiber diameter is d.
- the structure of fibrous carbon greatly deviates from the structure of the organic fiber that is the precursor. Reflect. Therefore, it is necessary to form the heterocrystalline part 21 of the precursor graphitized fiber 20 of the present invention by controlling the crystal orientation at the time of spinning the organic fiber.
- a method of controlling the crystal orientation at the time of spinning the organic fiber there is a method in which the flow of the bitch in the discharge hole at the time of discharge is turbulent at a certain length. This includes a method in which fine holes are provided in the discharge holes to blow out gas such as air, and a method in which vibration is applied to the discharge holes by ultrasonic waves or the like. Further, the property that the pitches of the material are oriented with respect to the magnetic field may be used.
- any method for controlling the crystal orientation other than the above can be used, but what is important is the ratio and the interval of the heterocrystalline portion 21 contained in the precursor graphitized fiber 20.
- the heterocrystalline portion 21 may be present so as to be distributed over the entire cross section of the precursor graphitized fiber 20 or may be present in a part thereof.
- the presence of the heterocrystalline part 21 can be selected as appropriate in accordance with the required physical properties of the milled powder, but as the content of the heterocrystalline part 21 increases, the calcining capacity decreases. In some cases, the content is preferably smaller.
- the smaller angle formed by the heterocrystal part 21 with respect to the fiber axis is preferably 60 ° or more, more preferably 80 ° or more.
- the interval W in which the different crystal part 21 exists in the precursor graphitized fiber 20 is short, a material having a small aspect ratio can be obtained, while the content of the different crystal part 21 increases. , The capacity of the rayon may decrease is there. If the interval W is long, the material has a large aspect ratio, but the loss of capacity is reduced because the content of the heterocrystal part 21 is low. Therefore, it can be appropriately selected according to the required physical property parameters and volume of the pulverized powder, but 1 is preferably d or more and 100 d or less with respect to the fiber diameter d.
- the organic fiber which is a precursor of the fibrous carbon, is made infusible after spinning and before heat treatment.
- specific means is not limited, for example, a wet method using an aqueous solution of nitric acid, mixed acid, sulfuric acid, and the following ⁇ : chloric acid, or a dry method using a oxidizing gas (air, oxygen), and sulfur, ammonia nitrate, A reaction with a solid reagent such as ammonia sulfate or ferric chloride is used. Further, when performing the above treatment, the fiber may be drawn or tensioned.
- the infusibilized organic fibers are heat-treated in a stream of inert gas such as nitrogen.
- the conditions are as follows: after carbonization at 300 to 700 ° C, temperature rise in the stream of inert gas. At a rate of 1 to 100 C per minute, at an ultimate temperature of 900 to 150 ° C, and at a retention time at the ultimate temperature of about 0 to 30 hours.
- the heat treatment is preferably performed at a temperature of 2000 ° C. or more, preferably 250 ° C. or more.
- the carbonization or calcination operation may be omitted in some cases.
- the fibrous carbon of the present invention graphitized by heat treatment at a high temperature of 250 ° C. or higher has a true density close to that of artificial graphite and is preferable because a high electrode packing density can be obtained.
- the fibrous carbon produced is classified, or crushed and classified, and supplied to the negative electrode material.Pulverization may be performed before or after carbonization or calcination, or during the heating process before graphitization. In this case, heat treatment for graphitization is finally performed in a powder state.
- a pulverized powder of fibrous carbon is used as a negative electrode material, but a material having a smaller aspect ratio exhibits higher performance. Therefore, the aspect ratio of the pulverized powder is preferably 50 or less, more preferably 10 or less.
- the fiber diameter of the precursor graphitized fiber is preferably 5 ⁇ m or more and 100 zm or less, more preferably 8 m or more and 60 or less. The smaller the fiber diameter, the larger the specific surface area, and the larger the fiber diameter, the lower the effect of imparting the fiber shape, which is not preferable.
- the fiber diameter and fiber length are determined by observing the pulverized powder using an electron microscope or the like.
- the value obtained by dividing the fiber length by the fiber diameter is defined as the aspect ratio in the pulverized powder. This measurement was performed on 10 pieces of the pulverized powder, and the average value of each was defined as a fiber diameter, a fiber length, and an aspect ratio A.
- the fibrous carbons defined as described above exert their respective effects independently, but an even greater effect can be obtained by arbitrarily combining them.
- the value of the fractal dimension and crystallinity are specified to minimize the variation in charge / discharge performance and the charge / discharge cycle reversibility.
- a good high-capacity fibrous carbon can be obtained.However, in a fibrous carbon having a high-order structure with a radial structure at the center and a random radial structure at the surface layer, the fractal dimension is added to the random radial portion. By specifying the value and crystallinity, the characteristics can be further improved.
- the true density of a graphite material is determined by its crystallinity, and is obtained by the X-ray diffraction method (Gakushin method).
- the (002) plane spacing and the (002) plane C-axis is an index.
- the crystallinity is preferably high
- the (002) plane spacing obtained by X-ray diffraction is preferably less than 0.340 nm, preferably 0.335 nm or more, and 0.35 nm or more. It is more preferably at most 33 nm.
- the thickness of the C-axis crystallite on the (002) plane is preferably 30 nm or more, more preferably 40 nm or more.
- a negative electrode composed of a graphite material having a bulk density of 0.4 g / cm 3 or more has a good electrode structure, and is unlikely to cause the graphite material to peel off from the negative electrode mixture layer. Therefore, a long cycle life can be obtained.
- the bulk density specified here is a value determined by the method described in JISK-1469. If a graphite material having this value of 0.4 g / cm 3 or more is used, a sufficiently long cycle life can be obtained, but the bulk density is preferably 0.8 g / cm 3 or more, and more preferably the bulk density is 0.8 g / cm 3 or more. It is preferable to use a material of 9 g / cm 3 or more. Mug bulk density measurement method>
- the measuring cylinder 1 having a capacity of 100 cm 3 whose mass has been measured in advance is inclined, and 100 cm 3 of the sample powder is gradually poured into the measuring cylinder. Then, measure the total mass on the minimum scale of 0.1 lg, and subtract the mass of the female cylinder from the mass to determine the mass of the sample powder.
- V Volume of sample powder in graduated cylinder after dropping 50 times (cm 3 )
- a typical shape of the graphite material powder is a flat columnar shape as shown in FIG. 5A or a rectangular parallelepiped shape as shown in FIG. 5B.
- T thickness of the thinnest part of the graphite material powder
- L length of the longest part
- W length in the direction perpendicular to the long axis corresponding to the depth
- the product of the value obtained by dividing each of W and W by T is the above-mentioned shape parameter X.
- the average shape parameter x ave Refers to a value obtained by the following actual measurement. First, the graphite sample powder is observed using a scanning electron microscope (SEM), and ten powders whose longest part is 30% of the average particle size of soil are selected. Then, for each of the selected 10 powders, the shape parameter X is calculated from Equation 4 and the average is calculated. Mean value that this is calculated the average shape parameter Isseki X ave. A.
- the average shape parameter X ae is 125 or less, but is preferably 2 or more, 115 or less, more preferably 2 or more, and 100 or less.
- the specific surface area referred to here is measured and determined by the BET method. Say what was done. If the specific surface area of the graphite powder is 9 m 2 or less, the above effect can be sufficiently obtained, but it is preferably 7 m 2 / g or less, and more preferably 5 m 2 / g or less.
- the cumulative 10% particle size is 3 / m or more and the cumulative 50% particle size is 1 / m. It is preferable to use graphite powder having a particle size of 0 ⁇ m or more and a cumulative 90% particle size of 7 Oim or less.
- the graphite powder to be filled in the electrode can be more efficiently filled if the particle size distribution has a certain width, and is preferably closer to the normal distribution.
- the battery may generate heat in an abnormal situation such as overcharging, and when the number of small particles distributed is large, the heat generation temperature tends to increase, which is not preferable.
- lithium ions are inserted between the graphite layers, causing the crystallites to expand by about 10%, compressing the positive electrode and the separator in the battery, and causing initial defects such as internal shorts during the first charge.
- the distribution of large particles is large, the occurrence rate of defects tends to increase, which is not preferable.
- the average value of the breaking strength of graphite particles is 6.0 kg / mm 2 or more.
- the load characteristics are influenced by the ease of movement of ions during discharge.Especially when there are many vacancies in the electrode, a good amount of electrolyte is present, so good characteristics are exhibited. .
- a graphite material with high crystallinity has a hexagonal graphite plane developed in the a-axis direction, and the c-axis crystal is formed by stacking and arranging it. Because of this weak bond, it is easily deformed by stress, so when graphite powder particles are compression molded and filled into electrodes, they are more easily crushed than low-temperature fired carbonaceous materials and secure pores It is difficult.
- the average value of the breaking strength of the graphite particles here means the value obtained by the following actual measurement.
- the Shimadzu Ritsuyo Shrinkage Tester (MCTM-500) manufactured by Shimadzu Corporation is used as a measuring device for fracture strength. First, observe the graphite sample powder with the attached optical microscope, and select 10 powders whose longest part is 10% of the average particle size of soil. Then, a load is applied to each of the selected 10 powders to measure the breaking strength of the particles, and the average is calculated. This calculated average value is the average value of the breaking strength of the graphite particles. In order to obtain good load characteristics, the average value of the breaking strength of the graphite particles is preferably 6 kgf / mm 2 or more.
- such fibrous carbon or graphitized fibrous carbon Is not particularly limited cathode material used in combination To pole, preferably to contain a sufficient amount of L i, for example, general formula L i M0 2 (where, M is Co, N i, Mn, F e, A 1, V, and T i represent at least one type.)
- L i M0 2 where, M is Co, N i, Mn, F e, A 1, V, and T i represent at least one type.
- a composite metal oxide composed of lithium and a transition metal represented by, and an intercalation compound containing Li are preferred.
- the positive electrode is charged and discharged in a steady state (for example, after charging and discharging about 5 times) at a negative electrode charge of 25 OmAh or more per gram of carbon material. It is necessary to include Li corresponding to the capacity, and more preferably to include Li corresponding to a charge / discharge capacity of 300 mAh or more.
- Li has a charge / discharge capacity of 25 OmAh or more per gram of carbon material in the battery system. Also, the amount of Li is determined by measuring the discharge capacity of the battery.
- the negative electrode material is used for a non-aqueous electrolyte secondary battery.
- a non-aqueous electrolyte secondary battery a non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent is used as an electrolyte.
- Suitable examples of the main solvent include ethylene carbonate (EC), and a compound having a structure in which a hydrogen element of EC is replaced by a halogen element is also preferable.
- EC ethylene carbonate
- a compound having a structure in which a hydrogen element of EC is replaced by a halogen element is also preferable.
- the second component solvents include PC, butylene carbonate, 1,2-dimethoxane, 1,2-diethoxymethane, arbutyrolactone, norrelactone, tetrahydrofuran, 2-methyltetrahydrofuran, and 1-methyltetrahydrofuran. , 3-Dioxolan, 4-methyl-1,3-dioxolan, sulfolane, methylsulfolane, etc. can be used, and the addition amount is preferably less than 10% by volume.
- a third solvent is added to the main solvent or to the mixed solvent of the main solvent and the second component solvent to improve conductivity, suppress EC decomposition, and improve low-temperature characteristics.
- the reactivity with lithium metal may be reduced to improve safety.
- a chain carbonate such as DEC (getyl carbonate) and DMC (dimethyl carbonate) is preferable.
- asymmetric chain carbonates such as MEC (methyl ethyl carbonate) and MPC (methyl propyl carbonate) are suitable.
- the mixing ratio of the chain carbonate as the third component to the main solvent or the mixed solvent of the main solvent and the second component solvent (main solvent or the mixed solvent of the main solvent and the second component solvent: the third component solvent) is the volume The ratio is preferably from 10:90 to 60:40, and more preferably from 15:85 to 40:60.
- the solvent of the third component may be a mixed solvent of MEC and DMC.
- the MEC-DMC mixing ratio is preferably in the range shown by 1 / 9 ⁇ d / m ⁇ 8 / 2, where MEC capacity is m and DMC capacity is d.
- the main solvent or the main solvent and the second component solvent The mixing ratio of ME C—DMC, which is the mixed solvent and the solvent of the third component, is 3/1 0 ⁇ (m + d) / T, where ME C volume is m, DMC volume is d, and total amount of solvent is T. It is preferable to set the range shown as ⁇ 7 / 10.
- any electrolyte used in this type of battery can be used as a mixture.
- L i PF 6 For example it is preferred, other L i C 104, L i A s F 6, L i BF 4, L i B (CeHs) 4, CH 3 S_ ⁇ 3 L i, C F3S O3L i , L i N (CF 3 S O 2) 2, L i C (CF ; i S 0 2 ) :! , L i C l, L i Br and the like can also be used.
- the coal-based pitch was kept at 425 ° C for 5 hours in an inert gas atmosphere to obtain a coal-based method pitch having a softening point of 220 ° C. At this time, the mesophase content was 92%.
- the obtained petroleum-based mesoface pitch was extruded at a constant extrusion pressure of 300 ° C and spun at a pressure to obtain a precursor fiber. Then, it was infusibilized at 260 ° C and calcined at 1000 ° C in an inert atmosphere to obtain fibrous carbon. Further heat treatment at 3000 ° C in an inert atmosphere, Wind pulverization was performed to obtain a sample powder of graphitized fibrous carbon.
- the cross-sectional shape of the obtained sample powder was observed with an electron microscope, and the fiber shape and dimensions were determined. The area satisfaction and circularity were also calculated. In the calculation, 20 arbitrary sample particles were extracted and the average value was used. Table 1 shows the results.
- the bulk density was determined by the method described in JISK-1469, and the results are similarly shown in Table 1.
- FIG. 7 shows the cross-sectional shape of the obtained fibrous carbon.
- FIG. 6 shows the configuration of the battery.
- a negative electrode mixture slurry is applied to both sides of the current collector, dried, and then compression-molded at a constant pressure to form a strip-shaped negative electrode. 1 was produced.
- L i CO0 2 powder 1 0% particle size was L i CO0 2 powder 1. Then, by mixing the L i C o 0 2 powder 9 5 parts by weight of lithium powder 5 parts by weight carbonate, 9 1 part by weight, the graph eye preparative 6 parts by weight as a conductive agent in the mixture of this, and polyvinylidene as a binder 3 parts by weight of vinylidene bromide were mixed to prepare a positive electrode mixture, and dispersed in N-methylbiopenidone to prepare a positive electrode mixture slurry ( ⁇ -state).
- a 20- ⁇ m-thick strip-shaped aluminum foil is used as the positive electrode current collector 11, and the positive electrode mixture slurry is uniformly applied to both sides of the current collector, dried, and then compression-molded.
- a belt-shaped positive electrode 2 was produced.
- the strip-shaped negative electrode 1 and the strip-shaped positive electrode 2 manufactured as described above were connected to the negative electrode 1, the separated negative electrode 3, and separated through a separator 3 made of a 25 ⁇ m-thick microporous polybrovirene film.
- the positive electrode 2 and the separator 3 were stacked in this order, and then wound many times to produce a spiral electrode body with an outer diameter of 18 mm.
- the spirally wound electrode body produced in this manner was housed in a nickel-plated iron battery can 5.
- An insulating plate 4 is disposed on both upper and lower surfaces of the spiral electrode, and an aluminum positive electrode lead 13 is led out of the positive electrode current collector 11 to be electrically connected to the battery cover 7, and a nickel negative electrode lead 1 2 From the negative electrode current collector 10 and welded to the battery can 5.
- the 1 PF 6 was injected an electrolyte prepared by dissolving at a rate of 1 mo 1/1. Then, by caulking the battery can 5 through a sealing gasket 6 coated on the surface with a vacuum, a safety valve device 8 having a current cutoff mechanism 8 The TC element 9 and the battery cover 7 were fixed to maintain the airtightness of the battery, and a cylindrical nonaqueous electrolyte secondary battery having a diameter of 18 mm and a height of 65 mm was produced.
- the charcoal pitch is maintained at 4250 ° C for 2 hours in an inert gas atmosphere, and then maintained at 400 ° C for 2 hours under methane ventilation, and then 350 ° C in an inert gas atmosphere. And then heat treated the coal-based mesophase pitch (mesophase content: 95%).
- the graphitized fiber was prepared in the same manner as in Example 1 except that the precursor fiber obtained by spinning was used. A non-aqueous electrolyte secondary battery was produced.
- the fiber shape and average size were determined as in Example 1, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- the fiber shape and average size were determined as in Example 1, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- Precursor fibers were produced in the same manner as in Example 3 except that a flatter discharge hole was used than in Example 3, and then graphitized fibrous carbon was produced in the same manner as in Example 1. A battery was manufactured.
- the fiber shape and average size were determined as in Example 1, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- FIG. 10 shows the fiber cross-sectional shape. Comparative Example 1
- Precursor fibers were prepared in the same manner as in Example 1 except that a discharge hole capable of spinning was used so that the fiber cross section became a right triangle, and then graphitized fibrous carbon was manufactured in the same manner as in Example 1.
- a non-aqueous electrolyte secondary battery was manufactured.
- the fiber shape and average size were determined as in Example 1, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- a precursor fiber was prepared in the same manner as in Example 1 except that the discharge hole capable of spinning was used so that the fiber cross section became an equilateral triangle, and then graphitized fibrous carbon was manufactured in the same manner as in Example 1.
- a non-aqueous electrolyte secondary battery was manufactured.
- the obtained graphitized fibrous carbon powder was the same as in Example 1.
- the fiber shape and average size were determined as described above, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- a precursor fiber was prepared in the same manner as in Example 1 except that a discharge hole capable of spinning was used so that the fiber cross section was a perfect circle.
- a water electrolyte secondary battery was produced.
- the fiber shape and average size were determined as in Example 1, the area sufficiency and circularity were calculated, and the bulk density was also measured.
- Table 1 shows the results.
- Fig. 13 shows the cross-sectional shape of the fiber.
- the fibrous carbons of Examples 1 to 4 having the area sufficiency characteristic of the present invention had high electrode filling properties and exhibited high capacity.
- the fibrous carbon having a predetermined circularity of 35 likeness also had a high bulk density and exhibited a high cycle capacity retention rate.
- the negative electrode material was produced as follows.
- the coal-based pitch was kept at 425 ° C for 5 hours in an inert gas atmosphere to obtain a coal-based mesoface pitch with a softening point of 220 ° C. At this time, the mesophase content was 90%.
- the obtained coal-based mesoface pitch was discharged at 305 ° C using a discharge hole having an inner diameter of 20 m, and was spun while changing the pressure in a pulsed manner while applying ultrasonic waves to obtain a precursor fiber. Then treated infusible at 26 0 ° C, in an inert atmosphere to obtain a carbon fiber and calcined at a temperature 1 000 e C. Furthermore, it was heat-treated at a temperature of 300 ° C. in an inert atmosphere, and pulverized and classified by wind to obtain a sample powder of graphitized fibrous carbon.
- N Number of squares that overlap with the curve of the carbon net surface when divided into squares of a certain size
- the image is divided into grids composed of squares, the number of squares overlapping with the curve of the carbon mesh plane is calculated, and the same calculation is performed while changing the size of the squares to obtain an average of the five images. Further, this measurement was performed on 10 fibers, and an average value was obtained, which was defined as an FD value.
- This method can be measured, for example, by the method described in the Journal of the Society of Carbon Materials, "Carbon TANS 019595, N 0.169, P.207-214".
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 5, except that discharge fiber was spun under different pulse conditions to obtain a precursor fiber.
- the (002) plane distance d 002 of the obtained sample powder was 0.3365 nm, and the FD was 1.2.
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 5, except that discharge fiber was spun under different pulse conditions to obtain a precursor fiber.
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 5, except that discharge fiber was spun under different pulse conditions to obtain a precursor fiber.
- the (002) plane distance d of the obtained sample powder was 0.3372 nm, and the FD was 1.5.
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 5, except that discharge fiber was spun under different pulse conditions to obtain a precursor fiber.
- a cylindrical non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 5, except that the precursor fiber was obtained by discharge spinning without applying ultrasonic waves to the discharge holes.
- the (002) plane distance d 002 of the obtained sample powder was 0.310 nm, and the FD was 1.8. Comparative Example 5
- a cylindrical non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 5, except that the precursor fiber was obtained by discharge spinning without applying ultrasonic waves to the discharge holes.
- the (002) plane distance d 002 of the obtained sample powder was 0.336 1 nm, and the FD was 1.0.
- Table 3 shows the results of measuring the charge / discharge capacity of the fibrous carbon used in each of the examples and comparative examples.
- FIG. 17 shows the relationship between the (002) plane distance d 002 and the capacity.
- the method for measuring the charge / discharge capacity will be described below. The measurement was performed by preparing a test cell described below.
- the sample powder was subjected to a pre-heat treatment in an Ar atmosphere under the conditions of a heating rate of about 3 CTCZ, a reaching temperature of 600 ° C, and a holding temperature holding time of 1 hour. . Thereafter, 10% by weight of polyvinylidene fluoride was added as a binder, mixed with dimethylformamide as a solvent, and dried to prepare a sample mix. The 37 mg was weighed out, and the diameter was measured with a Ni mesh as a current collector. A working electrode was fabricated by molding into a 5 mm pellet.
- the configuration of the test cell is as follows.
- Cell shape coin-shaped cell (diameter 20 mm, thickness 2.5 mm)
- Counter electrode Li metal
- Electrolyte Mixed solvent of EC and DEC (1: 1 by volume ratio)
- L i were measured capacitance per carbon material 1 g PF 6 a using the above configuration of the test Toseru those dissolved at a concentration of 1 mo 1/1.
- doping of the working electrode with lithium (charging: Strictly speaking, in this test method, the process of doping lithium into the carbon material is not charging but discharging, but for convenience, this doping is performed according to the actual condition of the actual battery. The process is called charge, and the undoping process is called discharge.) Is a constant current of 1 mA per cell, and is charged and discharged by a constant current constant voltage method of 0 V (L i / L i +). Was performed at a constant current of 1 mA per cell and a terminal voltage of 1.5 V, and the capacitance at this time was calculated.
- the cylindrical batteries produced in each of the examples and comparative examples were subjected to constant-current constant-voltage charging at a charging current of 1 A and a maximum charging voltage of 4.2 V for 2.5 hours, and then at a discharging current of 700 mA.
- the charge / discharge cycle of discharging to 75 V was repeated, and the ratio of the capacity at the 100th cycle to the capacity at the second cycle (capacity retention rate) was determined.
- Fig. 18 shows the relationship between the FD value and the capacity retention ratio.
- the fibrous carbon having the controlled FD value, which is an index of the cross-sectional structure, of the present invention was a negative electrode material having better cycle characteristics and charge / discharge capability than the comparative example.
- the difference in properties due to the difference in the higher-order structure of the cross section of fibrous carbon was investigated.
- the negative electrode material was produced as follows.
- the coal-based pitch was kept at 425 ° C for 5 hours in an inert gas atmosphere to obtain a coal-based mesoface pitch having a softening point of 220 ° C. At this time, the mesophase content was 92%.
- the obtained stone-based method spun at 300 ° C using a discharge pipe 15 having a double structure consisting of a discharge outer pipe 15a and a discharge inner pipe 15b as shown in Fig. 19. The precursor fiber was obtained.
- the diameter A of the discharge outer tube 15a was set to 20 m
- the mixture was infusibilized at 260 ° C. and calcined at 1000 ° C. in an inert atmosphere to obtain fibrous carbon. Further, it was heat-treated in an inert atmosphere at a temperature of 300 ° C., and was pulverized and classified by wind to obtain a sample powder of graphitized fibrous carbon.
- the obtained sample powder has a cross-sectional shape as observed by an electron microscope as shown in FIG.
- a cylindrical nonaqueous electrolyte secondary battery was fabricated.
- the method for producing the positive electrode active material, the method for producing the electrode, and the method for assembling the battery are the same as those in Example 1 above.
- Example 1 2
- cylindrical batteries produced in each of the examples and comparative examples were subjected to constant-current constant-voltage charging at a charging current of 1 A and a maximum charging voltage of 4.2 V for 2.5 hours, followed by a discharge current of 700 mA. Then, the battery was discharged to 2.75 V, and the initial capacity of the battery was measured. The results are shown in Table 4 and FIG.
- the charge / discharge cycle was repeated, and the ratio of the capacity at the 200th cycle to the capacity at the second cycle (capacity retention ratio) was determined.
- charging was performed for 2.5 hours at a maximum voltage of 4.2 V and a charging current of 1 A, and discharging was performed at 300 mA to 2.75 V.
- the capacity at the second cycle and the capacity maintenance ratio at the 200th cycle with respect to the second cycle are shown in Table 4 and FIG. 21 described above.
- the central part has a radial structure and the surface part has a random structure. It was found that the fibrous carbon having a dial-type structure had a better balance between battery capacity and cycle characteristics than the comparative example, and a highly reliable battery with high energy density and excellent cycle characteristics was obtained. Next, the characteristics of the fibrous carbon having the notch structure were examined.
- the negative electrode material was produced as follows.
- the coal-based pitch was kept at 425 ° C for 5 hours in an inert gas atmosphere, and the softening point was 220.
- a coal-based mesoface pitch of C was obtained. At this time, the mesophase content was 92%.
- the obtained coal-based method pitch was spun at 300 ° C. using a discharge hole having a diameter of 20 m (the angle formed by the jammer plate J was 3 °) having a shape shown in FIG. Fiber was obtained. Then, it was infusibilized at 260 ° C and calcined in an inert atmosphere at a temperature of 1000 ° C to obtain fibrous carbon.
- the notch angle of the fiber measured from the electron microscope image was 2 °. Furthermore, it was heat-treated in an inert atmosphere at a temperature of 300 ° C., and was pulverized and classified by wind to obtain a sample powder of graphitized fibrous carbon.
- Example 15 Using the sample powder as a negative electrode material, a cylindrical nonaqueous electrolyte secondary battery was fabricated.
- the method for producing the positive electrode active material, the method for producing the electrode, and the method for assembling the battery are the same as those in Example 1 above.
- Example 15
- a cylinder was formed in the same manner as in Example 14 except that a precursor fiber (notch angle was 8 °) was obtained using a discharge hole having an angle of 10 ° formed by the jammer plate J.
- a non-aqueous electrolyte secondary battery was fabricated.
- a cylindrical nonaqueous electrolyte was prepared in the same manner as in Example 14 except that precursor fibers (notch angle was 28 °) were obtained using a discharge hole having an angle of 30 ° formed by the jammer plate J.
- a secondary battery was manufactured.
- a cylindrical nonaqueous electrolyte was prepared in the same manner as in Example 14 except that the precursor fiber (notch angle was 47.) was obtained using a discharge hole having an angle of 50 ° formed by the jammer plate J. A secondary battery was manufactured.
- Example 18
- a cylindrical nonaqueous electrolyte was prepared in the same manner as in Example 14 except that the precursor fiber (notch angle was 72 °) was obtained using a discharge hole having an angle of 70 ° formed by the jammer plate J.
- a secondary battery was manufactured. Project 1 9
- a cylindrical nonaqueous electrolyte was prepared in the same manner as in Example 14 except that the precursor fiber (notch angle was 88 °) was obtained using a discharge hole having an angle of 90 ° formed by the jammer plate J.
- a secondary battery was manufactured.
- Example 14 The same as in Example 14 except that the precursor fiber (notch angle was 120 °) was obtained using a discharge hole having an angle of 125 ° formed by the jammer plate J. Thus, a cylindrical nonaqueous electrolyte secondary battery was manufactured. Comparative Example 8
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 14, except that precursor fibers (without cutouts) were obtained using discharge holes without the jammer plate J. Comparative Example 9
- a cylindrical non-aqueous electrolyte was prepared in the same manner as in Example 14 except that a precursor fiber (without cutout) was obtained using a discharge hole without a jammer plate J using a pitch having a mesoface content of 30%.
- a secondary battery was manufactured. Comparative Example 10
- Cylindrical non-aqueous electrolysis was performed in the same manner as in Example 14 except that the precursor fiber (notch angle was 140 °) was obtained using a discharge hole with an angle of 144 ° formed by the jammer plate J.
- a liquid secondary battery was manufactured.
- Test cells similar to those in Examples 5 to 9 were prepared for the fibrous carbon used in Examples and Comparative Examples, and the charge / discharge capacity was measured.
- Table 5 shows the measurement results.
- Fig. 2 shows the relationship between the notch angle and the capacity.
- cylindrical batteries produced in each of the examples and comparative examples were subjected to constant-current constant-voltage charging at a charging current of 1 A and a maximum charging voltage of 4.2 V for 2.5 hours.
- the charge / discharge cycle of discharging to .75 V was repeated, and the ratio of the capacity at the 100th cycle to the capacity at the second cycle (capacity retention ratio) was determined.
- Table 5 shows the results of the capacity retention ratio at the 100th cycle with respect to the second cycle.
- Fig. 23 shows the relationship between the notch angle and the capacity retention rate.
- the negative electrode material was produced as follows.
- the petroleum pitch was kept at 425 ° C for 5 hours in an inert gas atmosphere to obtain a petroleum mesoface pitch having a softening point of 230 ° C. At this time, the mesophase content was 91%.
- the obtained oil-based mesophase pitch was measured at 300 ° C while applying a magnetic field in a pulsed manner at regular time intervals using a discharge port with an inner diameter of 20 m with a built-in small probe for applying a magnetic field. -Discharge spinning at constant extrusion pressure to obtain organic fibers. Thereafter, it was infusibilized at 260 ° C. and calcined in an inert atmosphere at a temperature of 1000 ° C. to obtain fibrous carbon.
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 21 except that spinning was carried out by changing the pulse conditions of the applied magnetic field to obtain organic fibers.
- a cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Example 21 except that organic fibers were obtained by spinning while changing the application pulse conditions of the magnetic field.
- a cylindrical non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 21 except that the spinning was performed by applying an ultrasonic wave to the tip of the discharge hole in a pulsed manner instead of the magnetic field to obtain an organic fiber.
- Cylindrical nonaqueous electrolysis was performed in the same manner as in Example 21 except that organic fibers were obtained by discharging and spinning while pulsating air from the fine holes, instead of using a magnetic field.
- a liquid secondary battery was manufactured.
- a cylindrical non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 21 except that no magnetic field was applied to the ejection holes.
- test cells similar to those in Examples 5 to 9 were prepared, and the charge / discharge capacity (capacity) was measured. In the test cell, the value obtained by subtracting the discharge capacity from the charge capacity was calculated as the capacity loss. Table 6 shows the measurement results. Table 6
- cylindrical batteries produced in each of the examples and comparative examples were subjected to constant-current constant-voltage charging at a charging current of 1 A and a maximum charging voltage of 4.2 V for 2.5 hours, followed by a discharging current of 700 mA. 2. Charge to 75 V The discharge cycle was repeated, and the ratio of the capacity at the 100th cycle to the capacity at the second cycle (capacity retention ratio) was determined. The results of the capacity retention ratio at the 200th cycle with respect to the second cycle are shown in Table 6 above. Fig. 24 shows the relationship between the aspect ratio A and the capacity retention rate.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- Inorganic Fibers (AREA)
- Secondary Cells (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69729055T DE69729055T2 (de) | 1996-06-28 | 1997-06-27 | Kathodenmaterial für nichtwaessrige elektrolytische zelle und zelle, die dieses verwendet |
EP97928508A EP0848440B1 (en) | 1996-06-28 | 1997-06-27 | Nonaqueous electrolyte secondary cell cathode material and nonaqueous electrolyte secondary cell employing the cathode material |
US09/011,781 US6277522B1 (en) | 1996-06-28 | 1997-06-27 | Non-aqueous electrolyte secondary cell cathode material and non-aqueous electrolyte secondary cell employing the cathode material |
JP50398698A JP4144038B2 (ja) | 1996-06-28 | 1997-06-27 | 非水電解液二次電池用負極材料及びこれを用いた非水電解液二次電池 |
Applications Claiming Priority (2)
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JP18842196 | 1996-06-28 | ||
JP8/188421 | 1996-06-28 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US09/011,781 A-371-Of-International US6277522B1 (en) | 1996-06-28 | 1997-06-27 | Non-aqueous electrolyte secondary cell cathode material and non-aqueous electrolyte secondary cell employing the cathode material |
US09/859,060 Division US6716557B2 (en) | 1996-06-28 | 2001-05-16 | Anode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using such anode material |
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Publication Number | Publication Date |
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WO1998000876A1 true WO1998000876A1 (fr) | 1998-01-08 |
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ID=16223378
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PCT/JP1997/002247 WO1998000876A1 (fr) | 1996-06-28 | 1997-06-27 | Materiau de cathode d'accumulateur electrolytique non-aqueux et accumulateur electolytique non-aqueux utilisant le materiau de cathode |
Country Status (8)
Country | Link |
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US (3) | US6277522B1 (ja) |
EP (3) | EP1434291B1 (ja) |
JP (1) | JP4144038B2 (ja) |
KR (1) | KR100488133B1 (ja) |
CN (3) | CN1913204B (ja) |
DE (1) | DE69729055T2 (ja) |
TW (1) | TW360992B (ja) |
WO (1) | WO1998000876A1 (ja) |
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JP2001015170A (ja) * | 1999-06-29 | 2001-01-19 | Sony Corp | 非水電解質電池 |
KR100454818B1 (ko) * | 2001-07-31 | 2004-11-08 | 주식회사제4기한국 | 고밀도 플라즈마를 이용한 살균 및 멸균 장치와 그 방법 |
US7919208B2 (en) | 2005-10-31 | 2011-04-05 | Sony Corporation | Anode active material and battery |
JPWO2015105019A1 (ja) * | 2014-01-08 | 2017-03-23 | 国立大学法人 東京大学 | Pan系炭素繊維およびその製造方法 |
CN108539091A (zh) * | 2017-03-03 | 2018-09-14 | 住友化学株式会社 | 非水电解液二次电池用隔板 |
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US6989137B1 (en) | 1998-10-09 | 2006-01-24 | Showa Denko K.K. | Carbonaceous material for cell and cell containing the carbonaceous material |
EP1122803A4 (en) * | 1998-10-09 | 2005-04-13 | Showa Denko Kk | CARBON MATERIAL FOR CELL AND CELL CONTAINING SAME |
JP3744462B2 (ja) * | 2002-05-08 | 2006-02-08 | ソニー株式会社 | 非水電解質電池 |
JP4053819B2 (ja) * | 2002-05-30 | 2008-02-27 | 株式会社オハラ | リチウムイオン二次電池 |
US7348101B2 (en) * | 2004-02-06 | 2008-03-25 | A123 Systems, Inc. | Lithium secondary cell with high charge and discharge rate capability |
US8617745B2 (en) | 2004-02-06 | 2013-12-31 | A123 Systems Llc | Lithium secondary cell with high charge and discharge rate capability and low impedance growth |
KR100571272B1 (ko) * | 2004-11-18 | 2006-04-13 | 삼성에스디아이 주식회사 | 캔형 이차 전지 및 그 형성 방법 |
US20060240290A1 (en) * | 2005-04-20 | 2006-10-26 | Holman Richard K | High rate pulsed battery |
TWI467840B (zh) * | 2005-09-02 | 2015-01-01 | A123 Systems Inc | 奈米組成電極以及其相關裝置 |
US8068724B2 (en) * | 2006-12-12 | 2011-11-29 | Enerco Group, Inc. | Forced air heater including on-board source of electric energy |
US8893706B2 (en) | 2006-12-12 | 2014-11-25 | Enerco Group, Inc. | Forced air heater including on-board source of electric energy |
CN102318122B (zh) | 2009-02-09 | 2015-08-19 | 瓦尔达微电池有限责任公司 | 纽扣电池和用于产生该纽扣电池的方法 |
DE102009060800A1 (de) | 2009-06-18 | 2011-06-09 | Varta Microbattery Gmbh | Knopfzelle mit Wickelelektrode und Verfahren zu ihrer Herstellung |
EP2558796B1 (en) | 2010-04-14 | 2020-12-30 | Enerco Group, Inc. | Forced air heater including on-board source of electric energy |
US9228785B2 (en) | 2010-05-04 | 2016-01-05 | Alexander Poltorak | Fractal heat transfer device |
EP3485215B1 (en) | 2016-07-12 | 2023-06-07 | Alexander Poltorak | System and method for maintaining efficiency of a heat sink |
JP2019075306A (ja) * | 2017-10-17 | 2019-05-16 | トヨタ自動車株式会社 | リチウムイオン二次電池の充電装置、及び、リチウムイオン二次電池の充放電方法 |
CN110518290A (zh) * | 2019-09-24 | 2019-11-29 | 深圳睿蚁科技有限公司 | 一种提高锂电池倍率性能的方法 |
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1997
- 1997-06-27 EP EP04003081A patent/EP1434291B1/en not_active Expired - Lifetime
- 1997-06-27 WO PCT/JP1997/002247 patent/WO1998000876A1/ja active IP Right Grant
- 1997-06-27 JP JP50398698A patent/JP4144038B2/ja not_active Expired - Fee Related
- 1997-06-27 US US09/011,781 patent/US6277522B1/en not_active Expired - Lifetime
- 1997-06-27 KR KR10-1998-0701562A patent/KR100488133B1/ko not_active IP Right Cessation
- 1997-06-27 EP EP97928508A patent/EP0848440B1/en not_active Expired - Lifetime
- 1997-06-27 CN CN2006101149220A patent/CN1913204B/zh not_active Expired - Fee Related
- 1997-06-27 EP EP10010346A patent/EP2267823B1/en not_active Expired - Lifetime
- 1997-06-27 CN CNB2004100027918A patent/CN1311575C/zh not_active Expired - Fee Related
- 1997-06-27 CN CNB97190989XA patent/CN1160816C/zh not_active Expired - Fee Related
- 1997-06-27 DE DE69729055T patent/DE69729055T2/de not_active Expired - Lifetime
- 1997-07-14 TW TW086109904A patent/TW360992B/zh not_active IP Right Cessation
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2001
- 2001-05-16 US US09/859,060 patent/US6716557B2/en not_active Expired - Fee Related
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2004
- 2004-02-25 US US10/787,046 patent/US20040166414A1/en not_active Abandoned
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001015170A (ja) * | 1999-06-29 | 2001-01-19 | Sony Corp | 非水電解質電池 |
KR100454818B1 (ko) * | 2001-07-31 | 2004-11-08 | 주식회사제4기한국 | 고밀도 플라즈마를 이용한 살균 및 멸균 장치와 그 방법 |
US7919208B2 (en) | 2005-10-31 | 2011-04-05 | Sony Corporation | Anode active material and battery |
JPWO2015105019A1 (ja) * | 2014-01-08 | 2017-03-23 | 国立大学法人 東京大学 | Pan系炭素繊維およびその製造方法 |
CN108539091A (zh) * | 2017-03-03 | 2018-09-14 | 住友化学株式会社 | 非水电解液二次电池用隔板 |
CN108539091B (zh) * | 2017-03-03 | 2019-08-30 | 住友化学株式会社 | 非水电解液二次电池用隔板 |
Also Published As
Publication number | Publication date |
---|---|
EP2267823A1 (en) | 2010-12-29 |
EP1434291B1 (en) | 2012-05-09 |
US6277522B1 (en) | 2001-08-21 |
CN1160816C (zh) | 2004-08-04 |
DE69729055D1 (de) | 2004-06-17 |
EP0848440A1 (en) | 1998-06-17 |
EP1434291A2 (en) | 2004-06-30 |
CN1198255A (zh) | 1998-11-04 |
US6716557B2 (en) | 2004-04-06 |
CN1311575C (zh) | 2007-04-18 |
KR100488133B1 (ko) | 2005-09-20 |
US20040166414A1 (en) | 2004-08-26 |
CN1913204A (zh) | 2007-02-14 |
EP1434291A3 (en) | 2004-07-21 |
US20010031238A1 (en) | 2001-10-18 |
CN1604365A (zh) | 2005-04-06 |
JP4144038B2 (ja) | 2008-09-03 |
EP2267823B1 (en) | 2012-05-30 |
CN1913204B (zh) | 2013-10-30 |
TW360992B (en) | 1999-06-11 |
KR19990044322A (ko) | 1999-06-25 |
EP0848440B1 (en) | 2004-05-12 |
EP0848440A4 (en) | 1999-09-15 |
DE69729055T2 (de) | 2005-04-28 |
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