CA2794290A1 - Method of producing electrode material for lithium-ion secondary battery and lithium-ion secondary battery using such electrode material - Google Patents
Method of producing electrode material for lithium-ion secondary battery and lithium-ion secondary battery using such electrode material Download PDFInfo
- Publication number
- CA2794290A1 CA2794290A1 CA2794290A CA2794290A CA2794290A1 CA 2794290 A1 CA2794290 A1 CA 2794290A1 CA 2794290 A CA2794290 A CA 2794290A CA 2794290 A CA2794290 A CA 2794290A CA 2794290 A1 CA2794290 A1 CA 2794290A1
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- electrode material
- secondary battery
- ion secondary
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000010406 cathode material Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004020 conductor Substances 0.000 claims abstract description 45
- 239000010405 anode material Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000002344 surface layer Substances 0.000 claims abstract description 19
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 239000004615 ingredient Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 80
- 239000012071 phase Substances 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000835 fiber Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
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- 239000000126 substance Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical group 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 38
- 239000002245 particle Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
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- 238000003786 synthesis reaction Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910001463 metal phosphate Inorganic materials 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
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- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 239000008101 lactose Substances 0.000 description 4
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- 238000001308 synthesis method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910013318 LiMSiO4 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Problem to be solved The present invention provides a method of producing inexpensive cathode and anode materials, for a lithium-ion secondary battery, which allows the lithium-ion secondary battery to have a low electric resistance, have a high capacity when the lithium-ion secondary battery is charged and discharged while a high electric current is flowing therethrough, have a long life in which the above-described performance is kept for a long time.
Means for solving the problem The present invention provides a method of producing an electrode material for a lithium-ion secondary battery. The surface layer of basic ingredient of the electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is fused and bonded to a conductive material. The production method includes a step of mixing the electrode material, the conductive material, and a surface layer-forming material forming the surface layer with one another to form a mixture and a step of burning the mixture.
Means for solving the problem The present invention provides a method of producing an electrode material for a lithium-ion secondary battery. The surface layer of basic ingredient of the electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is fused and bonded to a conductive material. The production method includes a step of mixing the electrode material, the conductive material, and a surface layer-forming material forming the surface layer with one another to form a mixture and a step of burning the mixture.
Description
DESCRIPTION
METHOD OF PRODUCING ELECTRODE MATERIAL FOR LITHIUM-ION SECONDARY
BATTERY AND LITHIUM-ION SECONDARY BATTERY USING SUCH ELECTRODE
MATERIAL
TECHNICAL FIELD
[0001] The present invention relates to method of producing an electrode material for a lithium-ion secondary battery and the lithium-ion secondary battery, using the electrode material, produced by using the production method.
BACKGROUND ART
METHOD OF PRODUCING ELECTRODE MATERIAL FOR LITHIUM-ION SECONDARY
BATTERY AND LITHIUM-ION SECONDARY BATTERY USING SUCH ELECTRODE
MATERIAL
TECHNICAL FIELD
[0001] The present invention relates to method of producing an electrode material for a lithium-ion secondary battery and the lithium-ion secondary battery, using the electrode material, produced by using the production method.
BACKGROUND ART
[0002] The lithium-ion secondary battery is demanded to improve its energy density and performance when the battery is charged and discharged when a high electric current flows therethrough and have a long life so that the lithium-ion secondary battery can be used for a long time as long as several tens of thousands of cycles.
[0003] The following devices have been made to comply with these demands: (a) a cathode material made of a lithium metal oxide of the battery and an anode material, made of carbon, both of which are reacting substances are allowed to have a high capacity, (b) the specific surface areas of particles of the reacting substances of the battery are increased by decreasing the diameters of the particles or the area of the electrode is increased by optimizing the design of the battery and decrease electric resistance,(c) liquid diffusion resistance is decreased by making a separator thin.
[0004] When the particles of the reacting materials of the lithium-ion secondary battery are set small in the diameters thereof, the reacting substances has an action of weakening the binding among particles playing a role in the electric resistance and life of the lithium-ion secondary battery. This necessitates the amount of a binder to be increased.
As a result, it is difficult to allow the battery to have a high capacity. Therefore the method of forming the secondary particles formed by the aggregation of the small-diameter primary particles aggregated with one another and enlarging the reaction area while keeping an apparent particle diameter (patent document 1).
As a result, it is difficult to allow the battery to have a high capacity. Therefore the method of forming the secondary particles formed by the aggregation of the small-diameter primary particles aggregated with one another and enlarging the reaction area while keeping an apparent particle diameter (patent document 1).
[0005] In addition, in the case where the cathode and anode materials may peel or drop from the metal foil which is the electricity collector, an internal short circuit may occur inside the battery. Thereby there occur a decrease in the voltage of the battery and thermal runaway and thus the safety of the lithium secondary battery is impaired.
[0006] Because an increase of the reaction area deteriorates the degree of stability against the thermal runaway, the development of basic ingredient of an electrode material thermally stable is demanded. As a method of allowing the lithium-ion secondary battery to have a high capacity when it is charged and discharged at a high electric current, the method of using the carbon electrical conductive material to decrease the electric resistance of the electrode is known (patent documents 2, 3, and 4).
[0007] In recent years, a lithium-containing metal phosphate compound such as an olivine-type lithium iron phosphate has attracted rising attention as the active substance of the cathode for the lithium-ion secondary battery (patent documents 5, 6). This active substance of the cathode allows the improvement of safety and a decrease in the cost of the battery.
But this active substance has a problem that the material of the cathode has a high electric resistance.
But this active substance has a problem that the material of the cathode has a high electric resistance.
[0008] The present inventors have already developed the technique of compositing the conductive carbon material with the olivine-type lithium iron phosphate coated with carbon by burning (patent document 7).
[0009] But this method necessitates the olivine-type lithium iron phosphate to be purchased and the conductive material to be composited therewith. Thus a processing cost is additionally necessary for a secondary burning performed to composite the conductive material with the olivine-type lithium iron phosphate, which poses a problem that the material cost becomes high or the conductive material is not sufficiently composited with the olivine-type lithium iron phosphate.
PRIOR ART DOCUMENT
Patent document [0010] Patent document 1: Japanese Patent Application Laid-Open No. 2012-79464 [0011] Patent document 2: Japanese Patent Application Laid-Open No. 2005-19399 [0012] Patent document 3: Japanese Patent Application Laid-Open No. 2001-[0013] Patent document 4: Japanese Patent Application Laid-Open No. 2003-[0014] Patent document 5: Japanese Patent Application Laid-Open No. 2000-[0015] Patent document 6: Japanese Patent Application Laid-Open No. 9-134724 [0016] Patent document 7: Japanese Patent Application Laid-Open No. 2011-SUMMARY OF THE INVENTION
Problem to be solved by the invention [0017] The present invention has been made to solve the above-described problems. It is an object of the present invention to provide a method of producing cathode and anode materials in which the configurations of reacting substances are controlled and the performance of binding particles with each other is prevented from deteriorating when a reaction area is increased by decreasing the size of the particles and which has a low electric resistance. It is another object of the present invention to provide a method of producing an olivine-type lithium-containing transition metal phosphate compound. It is still another object of the present invention to provide a method of producing an inexpensive electrode material for which it is unnecessary to spend a secondary processing cost for cornpositing the electrode material and a conductive material with each other by burning.
PRIOR ART DOCUMENT
Patent document [0010] Patent document 1: Japanese Patent Application Laid-Open No. 2012-79464 [0011] Patent document 2: Japanese Patent Application Laid-Open No. 2005-19399 [0012] Patent document 3: Japanese Patent Application Laid-Open No. 2001-[0013] Patent document 4: Japanese Patent Application Laid-Open No. 2003-[0014] Patent document 5: Japanese Patent Application Laid-Open No. 2000-[0015] Patent document 6: Japanese Patent Application Laid-Open No. 9-134724 [0016] Patent document 7: Japanese Patent Application Laid-Open No. 2011-SUMMARY OF THE INVENTION
Problem to be solved by the invention [0017] The present invention has been made to solve the above-described problems. It is an object of the present invention to provide a method of producing cathode and anode materials in which the configurations of reacting substances are controlled and the performance of binding particles with each other is prevented from deteriorating when a reaction area is increased by decreasing the size of the particles and which has a low electric resistance. It is another object of the present invention to provide a method of producing an olivine-type lithium-containing transition metal phosphate compound. It is still another object of the present invention to provide a method of producing an inexpensive electrode material for which it is unnecessary to spend a secondary processing cost for cornpositing the electrode material and a conductive material with each other by burning.
[0018] It is still another object of the present invention to provide a lithium-ion secondary battery capable of maintaining a cycle-life performance of repeating charging and discharging while a high electric current is flowing therethrough for a long time by compositing a conductive carbon material with the lithium-containing transition metal phosphate compound having the olivine-type structure when the lithium-containing transition metal phosphate compound having the olivine-type structure is synthesized.
Means for solving the problem [0019] In a method of present invention of producing an electrode material for a lithium-ion secondary battery, a surface layer of basic ingredient of the electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is fused and bonded to a conductive material. The production step includes a step of mixing the basic ingredient of the electrode material, said conductive material, and a surface layer-forming material which is a material forming said surface layer with one another to form a mixture and a step of burning said mixture.
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Means for solving the problem [0019] In a method of present invention of producing an electrode material for a lithium-ion secondary battery, a surface layer of basic ingredient of the electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is fused and bonded to a conductive material. The production step includes a step of mixing the basic ingredient of the electrode material, said conductive material, and a surface layer-forming material which is a material forming said surface layer with one another to form a mixture and a step of burning said mixture.
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[0020] At the mixing step, the components are mixed with one another in a dispersion solution where the components are dispersed in at least one solvent selected from among water and a hydrophilic solvent.
[0021] The step of burning the mixture is performed in an inert atmosphere at a temperature not more than a temperature at which the electrode material is thermally decomposed and a temperature not less than a temperature at which the layer-forming material form an activated covalent bond in combination with carbon atoms of the conductive material.
[0022] The conductive material to be used in the production method of the electrode material of the present invention for the lithium-ion secondary battery is at least one selected from among carbon black and a fibrous carbon material. The carbon black is conductive carbon black, and a specific surface area thereof is not less than 20m2/g nor more than 400m2/g. The fibrous carbon material is at least one selected from among a carbon nanotube and a carbon nanofiber. A diameter of the fibrous carbon material is not less than 10nm nor more than 100nm. A fiber length thereof is not less than 100nm nor more than 10000nm.
[0023] In the method of producing the electrode material for the lithium-ion secondary battery, the surface layer-forming material which is a material forming a surface layer is an organic substance forming at least one surface phase selected from among a graphene phase and an amorphous phase.
[0024] A cathode material is produced by the method of the present invention of producing the electrode material for the lithium-ion secondary battery. The cathode material is an olivine-type lithium-containing transition metal phosphate compound.
[0025] The olivine-type lithium-containing transition metal phosphate compound is produced by adding the conductive material and the surface-forming material to a water solution containing a lithium-containing compound, a phosphorus-containing compound, and a transition metal-containing compound and allowing a hydrothermal reaction to be made between the above-described components.
[0026] An anode material is produced by the method of the present invention of producing the electrode material for the lithium-ion secondary battery. The anode material contains graphite or titanium.
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[0027] The electrode material of the present invention for the lithium-ion secondary battery is produced by the above-described production method.
[0028] In the lithium-ion secondary battery of the present invention having a construction in which an organic electrolyte is penetrated into a group of electrodes wound or layered one upon another with a separator being interposed between a cathode plate in contact with a cathode plate serving as an electricity collector and an anode plate serving as an electricity collector or the group of the electrodes is immersed in the organic electrolyte to repeatingly absorb and release lithium ions, the cathode material or the anode material is the electrode material of the lithium-ion secondary battery.
Effect of the invention [0029] The method the present invention of producing the electrode material for the lithium-ion secondary battery includes the step of mixing the electrode material, the conductive material, and the surface layer-forming material which is the material forming the surface layer with one another to form a mixture and the step of burning the mixture.
The production method of the present invention allows the burning step to be performed at one time and thus does not require a processing cost necessary for the secondary burning performed to composite the conductive material with the electrode material.
Effect of the invention [0029] The method the present invention of producing the electrode material for the lithium-ion secondary battery includes the step of mixing the electrode material, the conductive material, and the surface layer-forming material which is the material forming the surface layer with one another to form a mixture and the step of burning the mixture.
The production method of the present invention allows the burning step to be performed at one time and thus does not require a processing cost necessary for the secondary burning performed to composite the conductive material with the electrode material.
[0030] In the electrode material for a lithium-ion secondary battery produced by this method has the surface layer, the surface of the electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is meltingly connected to he conductive material. Consequently the lithium-ion secondary battery is allowed to have a decreased electric resistance and thus the lithium-ion secondary battery can be charged and discharged while a high electric current is flowing therethrough without decreasing the binding force among particles thereof. The reason electric resistance is decreased is as follows: the surface of at least one phase selected from among the graphene phase and the amorphous phase and the surface of the conductive material are composited with each other owing to the conduction of electrons caused by the bonding between carbon atoms.
[0031] In the lithium-ion secondary battery using the above-described basic ingredient of the electrode material, contact between particles of the reacting substances and between the electrode material and the carbon material are maintained in expansion and contraction of the reacting substances which occur when the lithium-ion secondary battery is repeatingly -charged and discharged. Therefore it is possible to prevent the lithium-ion secondary battery from having a rapid decrease in its capacity and output.
BRIEF DESCRIPTION OF THE DRAWING
BRIEF DESCRIPTION OF THE DRAWING
[0032] Fig. 1 is a pattern diagram of a cathode material for a lithium-ion secondary battery.
[0033] Fig. 2 shows a photograph of the surface of the cathode material taken by a scanning-type and a transmission-type electron microscope.
[0034] Fig. 3 shows a photograph of a lithium-containing metal phosphate compounds taken by a transmission-type electron microscope.
MODE FOR CARRYING OUT THE INVENTION
MODE FOR CARRYING OUT THE INVENTION
[0035] Fig. 1 shows a pattern diagram of a cathode material for a lithium-ion secondary battery to be produced by using the production method of the present invention.
[0036] The cathode material for the lithium-ion secondary battery shown in Fig. 1 is composed of an olivine-type lithium-containing transition metal phosphate compound 1 which is an active substance, a conductive carbon black 4, and a carbon material 3 such as a graphene phase, having a thickness of several nanometers, which coats the surface of a conductive fibrous carbon material-containing material 5. The lithium-containing transition metal phosphate compound 1 is composited with the conductive carbon black 4 and the conductive fibrous carbon material-containing material 5.
[0037] It is preferable that the fibrous carbon materials to be composited with the electrode material is a mixture of fibrous carbon materials 5a each having a small fiber diameter and a short fiber length and fibrous carbon materials 5b each having a large fiber diameter and a long fiber length. The fibrous carbon materials 5a contribute to the bonding between portions of a lithium-containing metal phosphate compounds 2 disposed in the neighborhood of the surface thereof, whereas the fibrous carbon materials 5b contribute to the bonding between the lithium-containing metal phosphate compounds 2.
[0038] A cathode material which can be used in the present invention is a lithium-containing metal compound.
[0039] As the lithium-containing metal, a lithium-containing metal oxide shown by LiM02 (M: at least one element of CO, Mn, Ni, and Al), a solid solution lithium-containing metal oxide shown by Li2MnO3. LiM02 (M: at least one element of Co, Ni, Mn), a lithium-containing metal phosphate compound shown by LiMPO4 (M: at least one element of Fe, CO, and Mn), and a lithium-containing metal silicate compound shown by LiMSiO4 (M: at least one element of Fe, Co, and Mn). Sulfur compounds can be also used as the cathode material.
[0040] LiFePO4, LiCoPO4, and LiMnPO4 are listed.
[0041] In the present invention, the olivine-type lithium-containing transition metal phosphate compound is favorable. An olivine-type lithium iron phosphate shown by LiFePO4 is especially effective in its electrochemical property, safety, and cost.
[0042] As anode materials which can used in the present invention, artificial or natural graphite, materials containing metal silicon or silicon oxide, and materials such as lithium titanate containing titanium are listed. It is very effective to form the layer of the carbon material on a surface layer of the anode material as a method of adding a carbon conductive material to the surface layer. The carbon conductive material improves the charge and discharge properties of the battery and the durability thereof.
[0043] It is favorable that the average of particle diameters of each of the cathode material and the anode material which can be used in the present invention is not less than 50nm nor more than 30000nm. When the average of the particle diameters of the cathode material is less than 50nm, an amorphous phase is generated. Thus it is difficult to composite the cathode material with the conductive material. When the average of the particle diameters of the anode material exceeds 30000nm, the number of contact points between particles is very small. Thus the addition of a conductive material to the electrode materials is ineffective. It is more favorable that the average of the particle diameters of the cathode material is 50nm to 20000nm and that the average of the particle diameters of the anode material is 4000nm to 30000nm.
[0044] The surface of each of the above-described electrode material is coated with the layer of the carbon material. At least one phase selected from among the graphene phase and the amorphous phase is formed on the surface of the layer of the carbon material.
[0045] As methods of forming the surface layers of these carbon materials, the following methods (a) through (d) of forming a thin film are used: (a) a method of modifying the surfaces of particles of the electrodes by using an organic substance-containing solution as a surface layer-forming material and thereafter thermally decomposing the surface layer-forming material in a reducing atmosphere, (b) a method of dispersing conductive carbon black such as acetylene black, Ketchen Black or graphite crystal in a solvent to form a slurry solution, dispersing particles of the electrode material in the slurry solution, and thereafter drying and removing the solvent; (c) an ion deposit method; and (d) a chemical evaporation method (CVD) and/or a physical evaporation method (PVD).
[0046] In the production method of the present invention, the method (a) is preferable. As described later, it is preferable to form the surface layer simultaneously with the time when components of the electrode material are synthesized into the electrode material.
[0047] In the present invention, the graphene phase means one layer of a plain six-membered ring structure of sp2¨connected carbon atoms. The amorphous layer means a three-dimensional six-membered ring structure. "That carbon atoms form an activated covalent bond" means that electronic conduction is made owing to the bonding between the carbon atoms caused by turbulence of the graphene phase and/or the amorphous phase.
[0048] The carbon material coating the surface of basic ingredient of the electrode material closely contacts the surface of each basic ingredient of electrode material.
At least one phase selected from among the graphene phase and the amorphous phase is formed on the surface of the carbon material.
At least one phase selected from among the graphene phase and the amorphous phase is formed on the surface of the carbon material.
[0049] The thickness of the coating layer of the carbon material is 1 to 10nm.
When the thickness of the coating layer thereof is less than mm, it is difficult to accomplish electronic conduction to be performed by the bonding of the carbon atoms. Thus the thickness of the coating layer thereof is preferably 2 to 5nm.
When the thickness of the coating layer thereof is less than mm, it is difficult to accomplish electronic conduction to be performed by the bonding of the carbon atoms. Thus the thickness of the coating layer thereof is preferably 2 to 5nm.
[0050] When the thickness of the coating layer thereof is more than 10nm, the diffusion performance of lithium ions to the surface of the active substance responsible for the reaction of the battery becomes low. Therefore the output performance of the battery deteriorates.
[0051] The conductive material which can be used in the present invention is the carbon black and/or the fibrous carbon material.
[0052] As the carbon black, the conductive carbon black such as the acetylene black, the Ketchen black, and furnace black are listed. It is preferable that the specific surface area of the conductive carbon black is not less than 20m2/g nor more than 4002/g.
[0053] The fibrous carbon material which can be used in the present invention is at least one selected from among a carbon nanotube and a carbon nanofiber. The carbon nanotube means a tube consisting of a single-walled ring. The carbon nanofiber means a tube consisting of a multi-walled ring.
[0054] In the present invention, the fibrous carbon material consisting of the carbon nanotube and that consisting of the carbon nanofiber are effective. It is preferable to use at least two kinds of the fibrous carbon materials different in the fiber diameters and fiber lengths thereof. That is, it is possible to use (a) the fibrous carbon materials different in both the fiber diameters and fiber lengths thereof, (b) the fibrous carbon materials equal in the fiber diameters thereof and different in the fiber lengths thereof, and (c) the fibrous carbon materials different in the fiber diameters thereof and equal in the fiber lengths thereof. It is especially preferable to use the fibrous carbon material having a small fiber diameter and a short fiber length and the fibrous carbon material having a large fiber diameter and a long fiber length in combination.
[0055] The diameter of the fibrous carbon material is preferably not less than 10nm nor more than 100nm. The fiber length thereof is preferably not less than 100nm nor more than 10000nm. It is difficult to carry out distributed production of the fibrous carbon material whose diameter is less than 10nm. The fibrous carbon material whose diameter exceeds 100nm contacts the electrode material at a small number of points and thus has a low effect.
The fibrous carbon material having a fiber length less than 100nm is ineffective because it is difficult to dispersingly produce the fibrous carbon material and in addition fibrous carbon material contacts the electrode material at a small number of points. The fibrous carbon material having a fiber length exceeding 10000nm is broken a lot at a dispersion time, and few of them maintain the original fiber length. Thus the fibrous carbon material having the fiber length not more than 10000nm is used in the present invention.
The fibrous carbon material having a fiber length less than 100nm is ineffective because it is difficult to dispersingly produce the fibrous carbon material and in addition fibrous carbon material contacts the electrode material at a small number of points. The fibrous carbon material having a fiber length exceeding 10000nm is broken a lot at a dispersion time, and few of them maintain the original fiber length. Thus the fibrous carbon material having the fiber length not more than 10000nm is used in the present invention.
[0056] In using a plurality of the fibrous carbon materials, the diameter of one kind of the fibrous carbon materials is 5 to 15nm, and preferably 10nm, whereas the diameter of the other kind of fibrous carbon material is 70 to 150nm and preferably 100nm.
[0057] The fiber length of the fibrous carbon material having the diameter of 5 to 15nm is 1000 to 3000nm and preferably 3000nm. The fiber length of the fibrous carbon material having the diameter of 70 to 150nm is in the range from 5000 to 10000nm and preferably 5000nnn.
, [0058] In the case of the cathode material, it is preferable that the total of the content of the cathode material, the carbon black, the fibrous carbon material, and the layer of the carbon material coating the surface of the fibrous carbon material is not less than 2 mass% and preferably in the range from 5 to 15 mass%.
, [0058] In the case of the cathode material, it is preferable that the total of the content of the cathode material, the carbon black, the fibrous carbon material, and the layer of the carbon material coating the surface of the fibrous carbon material is not less than 2 mass% and preferably in the range from 5 to 15 mass%.
[0059] It is preferable that the mixing ratio between the carbon black and the fibrous carbon material is: [carbon black/fibrous carbon material = (2 to 8)/(1 to 3)] in a mass ratio. In the case of the anode material, the total content of the carbon material is not less than 1 mass%
and favorably 2 to 5 mass%.
and favorably 2 to 5 mass%.
[0060] The method of producing basic ingredient of the electrode material for the lithium-ion secondary battery of the present invention by using the above-described materials is described below. The method of producing the cathode material consisting of the olivine-type lithium iron phosphate is described in detail below. The cathode material of the present invention consisting of the olivine-type lithium iron phosphate is synthesized through the following steps.
[0061] (1) Step of synthesizing a conductive material-composited material by adding the above-described conductive material to a water solution containing a lithium-containing compound, a phosphorous-containing compound, and a transition metal-containing compound and allowing them to hydrothermally react with one another:
[0062] A water solution of iron sulfate to which lithium hydroxide and citric acid, both of which are the materials of the olivine-type lithium iron phosphate have been added and a water solution of phosphoric acid are prepared. The fibrous carbon material dispersed in water or ethanol and the carbon black are added to the mixed solution of the above-described components to hydrothermally synthesize them into the conductive material-composited material containing the olivine-type lithium iron phosphate, the conductive carbon black, and the conductive fibrous carbon material.
[0063] It is preferable to perform the hydrothermal reaction in a closed atmosphere at temperatures of 100 to 350 C for a time period of not more than 24 hours.
[0064] The step of preparing the conductive composite material can be performed by a solid-phase reaction or any suitable reaction. In the solid-phase reaction, the conductive material, a lithium-containing compound, a phosphorus-containing compound, and a transition metal-containing compound are allowed to react together. As will be understood by a skilled person, reaction conditions of such solid-phase reaction can vary depending on the application.
[0065] (2) Step of mixing the conductive material-composited material and the surface layer-forming material with each other to form a mixture:
[0066] As the surface layer-forming material which can be used in the present invention, it is possible to use any carbon source material capable of forming the activated covalent bond in combination with the carbon atoms of the conductive material. As the preferable surface layer-forming material, sugars are exemplified. Of the sugars, polysaccharide is favorable.
Lactose is more favorable.
Lactose is more favorable.
[0067] By immersing the conductive material-composited material in a water solution of the lactose and thereafter drying and removing water, the conductive material-composited material having the surface thereof coated with the carbon source material is obtained.
[0068] (3) Step of burning the conductive material-composited material having the surface thereof coated with the carbon source material:
[0069] The conductive material-composited material is burned in an inert atmosphere at a temperature not more than a temperature at which the conductive material-composited material is thermally decomposed and a temperature not less than a temperature at which the surface layer-forming material forms the activated covalent bond in combination with the carbon atoms of the conductive material. By burning the conductive material-composited material in the above-described condition, the surface layer-forming material is thermally decomposed. Thereby a composite cathode material having its surface coated with the surface layer having at least one phase selected from among the graphene phase and the amorphous phase is obtained. It is preferable to burn the conductive material-composited material consisting of the olivine-type lithium iron phosphate in a nitrogen atmosphere at a burning temperature of 500 to 800 C for a burning time period of 3 to 12 hours.
[0070] The method of producing the cathode material consisting of the olivine-type lithium iron phosphate has been described above. But it is possible to produce cathode materials consisting of other lithium-containing metal compounds by adding the carbon black and the conductive fibrous carbon material having a solution state to the cathode material at the cathode material synthesis step, thereafter mixing the surface layer-forming material with the above-described components, and thereafter performing one-time burning to composite the above-described components with one another.
[0071] In the case of the anode material, it is possible to generate the layer of the carbon material composited with the conductive carbon material on the surface of the graphite by adding the carbon black and the conductive fibrous carbon material having a solution state to the anode material consisting of graphite or the like, thereafter immersing the mixture of the above-described components in a water solution of the surface layer-forming material, and thereafter drying and burning the mixture.
[0072] The lithium-ion secondary battery has a construction in which an electrolyte is penetrated into a group of electrodes wound or layered one upon another with a separator being interposed between a cathode plate and an anode plate or the group of electrodes is immersed in the electrolyte to repeatingly absorb and release lithium ions.
[0073] The cathode and anode plates are formed by applying paste containing the cathode material and a binding agent and paste containing the anode material and the binding agent to a respective electricity collection foil.
[0074] As the binding agent, it is possible to use polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), emulsion of styrene butadiene copolymer (SBR), polyvinyl alcohol (PVA), polyacrylic emulsion, and silicone emulsion.
[0075] In consideration of the binding property of the binding agent and the conductive property of the active substance, it is proper that the amount of the binding agent is 0.5 to 10 parts by mass for 100 parts by mass of the active substance.
[0076] In forming an electrode paste by using a water solution or a water dispersion of a water-soluble or water-dispersible resin as a binding agent, it is preferable to add a dispersant and/or a surface-active agent to the binding agent at a mixing time. As the dispersant, cellulose derivatives are favorable. Of the cellulose derivatives, the carboxymethylcellulose (CMC) is more favorable.
Pyrrolidone derivatives are also preferable.
Pyrrolidone derivatives are also preferable.
[0077] The separator which can be used for the lithium secondary battery using basic ingredient of the electrode materials of the present invention holds an electrolyte by electrically insulating the cathode and anode from each other.
[0078] The separator is made of a synthetic resin film or fibrous woven and nonwoven cloths. It is possible to use a single layer or a double layer of a film of olefin resin such as polyethylene, polypropylene or the like, a film having ceramic particles which coat the above-described films, and woven and nonwoven cloths of cellulose fiber, polyimide fiber, polyamide fiber, and glass fiber.
[0079] As electrolytes of the lithium secondary battery in which the group of electrodes is immersed, it is possible to use non-aqueous electrolytes containing lithium salts, ion-conducting polymers, and an ionic liquid.
[0080] As non-aqueous solvents in the non-aqueous electrolytes containing the lithium salts, ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), organic dinitrile, organic sulfone, fluorinated carbonate ester, borate ester, and ester derivatives of these substance are listed.
As the lithium salts which can be dissolved in the non-aqueous solvents, lithium hexafluorophosphate (LiPF6), lithium boron tetrafluoride (LiBF4), lithium trifluoromethanesulfonate (LiSO3CF4) are listed.
As the lithium salts which can be dissolved in the non-aqueous solvents, lithium hexafluorophosphate (LiPF6), lithium boron tetrafluoride (LiBF4), lithium trifluoromethanesulfonate (LiSO3CF4) are listed.
[0081] The cathode and anode materials for the lithium-ion secondary battery are formed by layering the cathode and anode materials on the surface of the cathode plate and that of anode plate respectively serving as electricity collectors. A metal thin film can be exemplified as the cathode plate. An aluminum foil can be exemplified as the electricity collector of the cathode. A copper foil and the aluminum foil can be exemplified as the electricity collector of the anode.
EXAMPLES
EXAMPLES
[0082] The synthesis of the cathode material of the present invention is described in detail below by way of examples and comparative examples. As an example, the synthesis of the cathode material consisting of the olivine-type lithium iron phosphate is described in detail below. The lithium-ion secondary battery using the cathode material consisting of the olivine-type lithium iron phosphate is described in detail below. But the present invention is not limited to the examples described below unless the examples depart from the gist of the present invention.
Synthesis of cathode material consistinq of olivine-type lithium iron phosphate composited with conductive carbon material [0083] In an atmosphere of an inert gas such as argon or nitrogen, by using distilled water in which dissolved oxygen and residual ions were removed in advance, a 0.4M water solution of iron sulfate to which lithium hydroxide and citric acid which are the material of the olivine-type lithium iron phosphate were added and a 0.4M water solution of phosphoric acid were prepared. After the above-described components were mixed with one another such that the mole ratio among lithium, iron, and phosphorous contained in the total amount of the mixed solution was 3, 1, 1, pH of the mixed solution was adjusted to 8.5 to 8.8 by using appropriate ammonia water to prepare a suspension liquid.
Synthesis of cathode material consistinq of olivine-type lithium iron phosphate composited with conductive carbon material [0083] In an atmosphere of an inert gas such as argon or nitrogen, by using distilled water in which dissolved oxygen and residual ions were removed in advance, a 0.4M water solution of iron sulfate to which lithium hydroxide and citric acid which are the material of the olivine-type lithium iron phosphate were added and a 0.4M water solution of phosphoric acid were prepared. After the above-described components were mixed with one another such that the mole ratio among lithium, iron, and phosphorous contained in the total amount of the mixed solution was 3, 1, 1, pH of the mixed solution was adjusted to 8.5 to 8.8 by using appropriate ammonia water to prepare a suspension liquid.
[0084] The fibrous carbon material (diameter: 15nm, fiber length: 10000nm) dispersed at mass% in water and the carbon black (specific surface area: 40m2/g) were added to the suspension liquid to prepare a slurry mixed solution. The mixed solution was supplied to a chamber dedicated to carrying out a hydrothermal synthesis reaction and heated at 200 C
for two hours to perform hydrothermal synthesis. Thereby the conductive carbon material-composited material composed of the olivine-type lithium iron phosphate composited with the conductive carbon material and the conductive fibrous carbon material was synthesized.
for two hours to perform hydrothermal synthesis. Thereby the conductive carbon material-composited material composed of the olivine-type lithium iron phosphate composited with the conductive carbon material and the conductive fibrous carbon material was synthesized.
[0085] After the obtained composite material is filtered, cleaned, and dried, a lactose water solution adjusted to 10 wt% in advance was added to the conductive carbon material-composited material such that lactose was 10 wt% for the olivine-type lithium iron phosphate of the composite material. The dried conductive carbon material-composited material was thermally decomposed in a nitrogen atmosphere at 700 C to obtain the cathode material in which the surface of the conductive carbon material-composited material was coated with at least one phase selected from among the graphene phase and the amorphous phase.
[0086] According to identification performed by means of an X-ray diffraction pattern, no by-products were found in the obtained cathode material, but it was confirmed that the obtained cathode material was in a crystalline state similar to that of the olivine-type lithium iron phosphate to be obtained by a normal hydrothermal synthesis method.
[0087] The average of the particle diameters of the cathode material measured by a light scattering method was 6000nm. The thickness of the surface-coating layer measured by the electron microscopic photograph was 3nm. The total of the content of the cathode material, that of the carbon black, that of the fibrous carbon material, and that of the layer of the carbon material coating the surface of the fibrous carbon material was 10 mass%.
[0088] Fig. 2 shows an electron microscopic photograph of the cathode material synthesized by using the production method of the present invention.
[0089] A secondary electron image (SE) shows that an olivine-type lithium iron phosphate 2 is composited with a conductive carbon black 4 and a conductive fibrous carbon material 5.
A bright-field image (TE: transmission electron) shows that the surface of the olivine-type lithium iron phosphate 2 is coated with the carbon material 3 such as the graphene phase.
A bright-field image (TE: transmission electron) shows that the surface of the olivine-type lithium iron phosphate 2 is coated with the carbon material 3 such as the graphene phase.
[0090] Thereby electrons are conducted among the olivine-type lithium iron phosphate, the conductive carbon black, and the conductive fibrous carbon material not only by physical contact among them but also by bond among carbon atoms. Therefore it is possible for the lithium-ion secondary battery to obtain a low electric resistance. Thus the lithium-ion secondary battery is capable of having a high capacity when it is charged and discharged at a high electric current and maintaining this performance for a long time. That is, the battery obtains a long life.
[0091] Fig. 3 shows an electron microscopic photograph of the configuration of the cathode material consisting of the olivine-type lithium iron phosphate synthesized by the production method of the present invention.
[0092] The secondary electron image (SE) shows that the surfaces of particles are depressed. A dark-field image (DF) shows that pores are present inside the olivine-type lithium iron phosphate.
[0093] Particles of the olivine-type lithium iron phosphate produced by the hydrothermal synthesis method take a spherical shape, a rod shape, an elliptic shape, and the like in dependence on a synthesis condition. In any shape, the particles of the olivine-type lithium iron phosphate of any of the above-described configurations had a comparatively flat configuration and not in contact with each other, i.e., were independent from each other.
Secondary particles were formed owing to aggregation of particles caused by the presence of water. To increase the reaction area, heretofore, the size of particles of reacting substances is decreased and the surfaces thereof were flattened and smoothened. As a result, conventional particles have a problem that they had a high degree of independence and a low degree of binding performance.
Secondary particles were formed owing to aggregation of particles caused by the presence of water. To increase the reaction area, heretofore, the size of particles of reacting substances is decreased and the surfaces thereof were flattened and smoothened. As a result, conventional particles have a problem that they had a high degree of independence and a low degree of binding performance.
[0094] On the other hand, the olivine-type lithium iron phosphate synthesized by the production method of the present invention had particle surfaces having pores and depressed surfaces.
[0095] In this case, there is an increase in contact points among the particles. Thus the technique of compositing the conductive material with the electrode material is capable of overcoming the conventional problem of a decrease of the number of contact points in the synthesis to be carried out by using the hydrothermal synthesis method by increasing the specific surface area of the particles and keeping the degree of independence thereof.
Production of cathode [0096] A cathode material in which various kinds of the olivine-type lithium iron phosphates were used and polyvinylidene fluoride (PVDF) dissolved in N-methyl-2-pyrrolidone (NMP) used as a binding agent were kneaded to obtain a cathode mixed agent (slurry).
Production of cathode [0096] A cathode material in which various kinds of the olivine-type lithium iron phosphates were used and polyvinylidene fluoride (PVDF) dissolved in N-methyl-2-pyrrolidone (NMP) used as a binding agent were kneaded to obtain a cathode mixed agent (slurry).
[0097] As the solid content ratio between the materials constituting the cathode respectively, the ratio of basic ingredient of the electrode material to the PVDF was set to 94:6 mass%.
The cathode mixed agent (slurry) was applied in an amount of 140g/m2 to an aluminum foil having a thickness of 20pm and dried. Thereafter the slurry-applied aluminum foil was pressed and cut to obtain the cathode for the lithium-ion secondary battery.
The cathode mixed agent (slurry) was applied in an amount of 140g/m2 to an aluminum foil having a thickness of 20pm and dried. Thereafter the slurry-applied aluminum foil was pressed and cut to obtain the cathode for the lithium-ion secondary battery.
[0098] In the example 1, at synthesis and burning steps, the olivine-type lithium iron phosphates and conductive materials were composited with each other. In a comparative example, the olivine-type lithium iron phosphate not subjected to compositing treatment at a synthesizing time, namely, the olivine-type lithium iron phosphate, synthesized by using a hydrothermal method, whose surface was coated with at least one phase selected from among the graphene phase and the amorphous phase was initially produced.
Thereafter the conductive materials, namely, the conductive carbon black and the conductive fibrous carbon material were mixed with each other by using a kneading machine. In this manner, a cathode was produced (comparative example 1).
Thereafter the conductive materials, namely, the conductive carbon black and the conductive fibrous carbon material were mixed with each other by using a kneading machine. In this manner, a cathode was produced (comparative example 1).
[0099] By using the olivine-type lithium iron phosphate of the comparative example 1 before the conductive materials were mixed with each other, the cathode composed of the olivine-type lithium iron phosphate composited with the conductive materials was produced by a second-time burning (comparative example 2).
[0100] In any of the electrodes, the content of the conductive carbon black, that of the conductive fibrous carbon material, and that of the surface-coating carbon phase were equal to each other.
Production of anode [0101] A mixture of a graphite carbon material and a carbon nanotube were kneaded by using a water based binder consisting of a water dispersion of styrene butadiene rubber and a water solution of CMC to produce an anode slurry.
Production of anode [0101] A mixture of a graphite carbon material and a carbon nanotube were kneaded by using a water based binder consisting of a water dispersion of styrene butadiene rubber and a water solution of CMC to produce an anode slurry.
[0102] The composition ratio among the graphite, the carbon nanotube, the SBR, and the CMC were set to 96/1/2/1 in mass%. The prepared slurry was applied in an amount of 80g/m2 to a copper foil having a thickness of 10pm and dried. Thereafter the slurry-applied copper foil was pressed until it had a predetermined thickness to produce an anode plate.
[0103] Laminate type batteries each having 500 mAh were produced.
[0104] As a separator electrically partitioning the cathode plate and the anode plate from each other, nonwoven cloth made of cellulose fibers was used.
[0105] An electrolyte was prepared by dissolving 1 mo1/1 of lithium hexafluorophosphate (L1PF6) in a solution containing EC and DEC mixed with each other at 30:70 at a volume ratio.
[0106] In a discharge performance test of the batteries, after each battery was initially charged, it was confirmed that the charge and discharge efficiency reached the neighborhood of 100%. Thereafter the discharge capacity of each battery measured when the battery was discharged up to 2.0V at a constant electric current of 100mA
was set as the capacity thereof.
was set as the capacity thereof.
[0107] By using a battery whose depth of discharge was adjusted to 50% (DOD:
50%) with respect to the capacity, a voltage change in the case where electric current flowed therethrough for three seconds in a current range of 100 to 1500mA was measured to compute the DC resistance of each battery.
50%) with respect to the capacity, a voltage change in the case where electric current flowed therethrough for three seconds in a current range of 100 to 1500mA was measured to compute the DC resistance of each battery.
[0108] In a discharge performance test, the discharge capacity of each battery when it was discharged at electric current of 5000mA flowed therethrough was compared with the discharge capacity thereof when it was discharged at the electric current of 100mA and set as the discharge capacity maintenance ratio (%) thereof.
[0109] In a cycle performance test, the battery was charged at a constant electric current and a constant voltage (finished at 25mA) of 4.0V (limited current of 1500mA) and discharged up to 2.0V at a constant electric current of 1500mA. The test was suspended for minutes during each of the charge and discharge. This operation was repeated cycles. The ratio of the capacity of the battery at the 1000th cycle to the discharge capacity at the first cycle is set as the capacity maintenance ratio (%) at the 1000th cycle. The capacity maintenance ratio ( /0) is shown in table 1.
[Table 1]
Table 1. Test result of various charges and discharges Discharge capacity Capacity maintenance DC resistance maintenance ratio ratio at 1000th cycle m52 Material of present Example 1 56 95 90 invention Comparative Mixed material 83 79 75 example 1 Comparative Conventional example 2 composite material [0110] From the test results shown in table 1, it was confirmed that the cathode material (example 1) synthesized by the production method of the present invention had performance equivalent to that of the cathode material of the comparative example 2 with which the conductive material was secondarily composited.
[Table 1]
Table 1. Test result of various charges and discharges Discharge capacity Capacity maintenance DC resistance maintenance ratio ratio at 1000th cycle m52 Material of present Example 1 56 95 90 invention Comparative Mixed material 83 79 75 example 1 Comparative Conventional example 2 composite material [0110] From the test results shown in table 1, it was confirmed that the cathode material (example 1) synthesized by the production method of the present invention had performance equivalent to that of the cathode material of the comparative example 2 with which the conductive material was secondarily composited.
[0111] This shows that the synthesis method of the present invention is capable of producing the composite material composed of the olivine-type lithium iron phosphate having the intended structure, namely, the composite material composed of the olivine-type lithium iron phosphate in which through at least one phase selected from among the graphene phase and the amorphous phase, the surface of the conductive carbon black and that of the fibrous carbon material are composited with each other owing to conduction of electrons caused by the bonding between the carbon atoms. To composite the conductive materials with the olivine-type lithium iron phosphate by burning in synthesizing the olivine-type lithium iron phosphate is advantageous in the cost.
[0112] It was confirmed that the electrode material of the comparative example 1 in which the conductive materials were not composited with the electrode material, but were mixed with each other has a lower performance than the electrode materials of the comparative example 2 and the example 1 in which the conductive materials were composited with the electrode material by burning. The burning is effective in the cathode synthesis method of the example 1 and that of the comparative example 2.
[0113] Comparison among the cathode materials of the example 1, the comparative example 1, and the comparative example 2 indicates that basic ingredient of the electrode material synthesized at one-time burning by the present invention has a property equivalent to the electrode materials of the comparative examples.
[0114] That is, the number of the heat treatment steps to be performed in the synthesis method of the present invention is smaller than that to be performed in the synthesis method of the conventional art and yet the electrode material of the present invention is allowed to have a property equivalent to that of the conventional electrode material.
Therefore the production method of the present invention has a great superiority over the conventional production method in the production cost.
Therefore the production method of the present invention has a great superiority over the conventional production method in the production cost.
[0115] The above-described effect to be obtained was similar to that to be obtained in compositing the conductive material with cathode materials composed of other materials such as LiM02 (M:at least one of Co, Mn, Ni) and anode materials composed of graphite, lithium titanate, and the like by burning in synthesizing materials.
[0116] Regarding the addition amount of the conductive material, as examined in the comparative example 2 in which the electrode material and the conductive materials were composited with each other by carrying out two-time burning, when the addition amount of the conductive material was less than 2 mass%, the addition-caused effect became smaller.
INDUSTRIAL APPLICABILITY
INDUSTRIAL APPLICABILITY
[0117] Owing to the compositing technique, basic ingredient of the electrode material of the present invention for the lithium-ion secondary battery allows the lithium-ion secondary battery to have a high capacitance when it is charged and discharged while a high electric current is flowing therethrough and to be repeatingly charged and discharged stably for a very long time while a high electric current is flowing therethrough. Further it is possible to synthesize the olivine-type lithium iron phosphate and composite the conductive carbon material with the electrode material at the same time by carrying out the hydrothermal method. Therefore the lithium-ion secondary battery of the present invention can be preferably utilized for uses in which batteries are demanded to be charged and discharged at a high current, travel a long distance, and consume a large amount of fuel.
Thus the lithium-ion secondary battery of the present invention can be preferably utilized for electric vehicles and hybrid cars which are demanded to be produced at a low cost and durable and for a large-scale electric power storage stationary-type power source.
EXPLANATION OF REFERENCE SYMBOLS AND NUMERALS
Thus the lithium-ion secondary battery of the present invention can be preferably utilized for electric vehicles and hybrid cars which are demanded to be produced at a low cost and durable and for a large-scale electric power storage stationary-type power source.
EXPLANATION OF REFERENCE SYMBOLS AND NUMERALS
[0118] 1: cathode material for lithium-ion secondary battery [0119] 2: lithium-containing metal phosphate compound [0120] 3: coating carbon material [0121] 4: carbon black [0122] 5: fibrous carbon material
Claims (28)
1. In a method of producing an electrode material for a lithium-ion secondary battery, a surface layer of basic ingredient of said electrode material consists of at least one surface layer selected from among a graphene phase and an amorphous phase and is fused and bonded to a conductive material, said method comprising a step of mixing said basic ingredients of said electrode material, said conductive material, and a surface layer-forming material which is a material forming said surface layer with one another to form a mixture; and a step of burning said mixture.
2. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein at said mixing step, components are mixed with one another in a dispersion solution where said components are dispersed in at least one solvent selected from among water and a hydrophilic solvent.
3. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein said step of burning said mixture is performed in an inert atmosphere at a temperature not more than a temperature at which said electrode material is thermally decomposed and a temperature not less than a temperature at which said layer-forming material form an activated covalent bond in combination with carbon atoms of said conductive material.
4. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein said conductive material is at least one selected from among carbon black and a fibrous carbon material.
5. A method of producing an electrode material for a lithium-ion secondary battery according to claim 4, wherein said carbon black is conductive carbon black, and a specific surface area thereof is not less than 20m2/g nor more than 400m2/g.
6. A method of producing an electrode material for a lithium-ion secondary battery according to claim 4, wherein said fibrous carbon material is at least one selected from among a carbon nanotube and a carbon nanofiber; a diameter of said fibrous carbon material is not less than 10nm nor more than 100nm; and a fiber length thereof is not less than 100nm nor more than 10000nm.
7. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein said surface layer-forming material which is a material forming a surface layer is an organic substance forming at least one surface phase selected from among a graphene phase and an amorphous phase.
8. A method of producing an electrode material for a lithium-ion secondary battery according to claim 7, wherein said organic substance is Saccharides.
9. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein said electrode material is a cathode material.
10. A method of producing an electrode material for a lithium-ion secondary battery according to claim 9, wherein said cathode material is a lithium-containing metal compound.
11. A method of producing an electrode material for a lithium-ion secondary battery according to claim 10, wherein said lithium-containing compound is an olivine-type lithium-containing transition metal phosphate compound;
Wherein said mixing step is mixing a conductive composite material with said surface forming material, said conductive composite material is prepared by a hydrothermal reaction or a solid-phase reaction with said conductive material, said lithium-containing compound, a phosphorus-containing compound, and a transition metal-containing compound in a water solution.
Wherein said mixing step is mixing a conductive composite material with said surface forming material, said conductive composite material is prepared by a hydrothermal reaction or a solid-phase reaction with said conductive material, said lithium-containing compound, a phosphorus-containing compound, and a transition metal-containing compound in a water solution.
12. A method of producing an electrode material for a lithium-ion secondary battery according to claim 1, wherein said electrode material is an anode material.
13. A method of producing an electrode material for a lithium-ion secondary battery according to claim 12, wherein said anode material contains graphite.
14. A method of producing an electrode material for a lithium-ion secondary battery according to claim 12, wherein said anode material contains titanium.
15. An electrode material for a lithium-ion secondary battery produced by a method of producing an electrode material for a lithium-ion secondary battery according to claim 1.
16. A lithium-ion secondary battery having a construction in which an organic electrolyte is penetrated into a group of electrodes wound or layered one upon another with a separator being interposed between a cathode plate in contact with a cathode plate serving as an electricity collector and an anode plate serving as an electricity collector or said group of said electrodes is immersed in said organic electrolyte to repeatingly absorb and release lithium ions, wherein said cathode plate in contact with said cathode plate serving as said electricity collector is an electrode material for a lithium-ion secondary battery according to claim 9 or said anode plate in contact with said anode plate serving as said electricity collector is an electrode material for a lithium-ion secondary battery according to claim 12.
17. A method for producing an electrode material for a lithium secondary battery, comprising:
(a) mixing components of a basic ingredient of the electrode material and a conductive material to obtain a conductive composite material;
(b) mixing the conductive composite material and a surface layer-forming or coating material; and (c) burning the mixture obtained in step (b).
(a) mixing components of a basic ingredient of the electrode material and a conductive material to obtain a conductive composite material;
(b) mixing the conductive composite material and a surface layer-forming or coating material; and (c) burning the mixture obtained in step (b).
18. A method according to claim 17, wherein step (a) comprises a hydrothermal reaction.
19. A method according to claim 17, wherein step (a) comprises a solid-phase reaction.
20. A method according to claim 17, wherein the basic ingredient of the electrode material is an olivine-type lithium-containing transition metal phosphate compound and the components are a lithium-containing compound, a phosphorus-containing compound and a transition metal-containing compound.
21. A method according to claim 17, wherein the conductive material is carbon black, a fibrous carbon material, or a combination thereof.
22. A method according to claim 17, wherein the coating material is an organic substance.
23. A method according to claim 17, the electrode material is a cathode material.
24. A method according to claim 17, wherein the electrode material is an anode material.
25. A method according to claim 24, wherein the anode material contains titanium.
26. An electrode material for a lithium secondary battery, comprising a basic ingredient of electrode material and at least two types of carbon material, wherein a first type of carbon material is provided as a coating on a surface of the basic ingredient, the coating being in a graphene and or amorphous form, and a second type of carbon material is a conductive carbon material.
27. An electrode material according to claim 26, wherein the conductive carbon material is carbon black, a fibrous carbon black or a combination thereof.
28. A lithium secondary battery comprising the electrode material as defined in claim 26 or 27.
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| CA2794290A CA2794290A1 (en) | 2012-10-22 | 2012-10-22 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion secondary battery using such electrode material |
| EP13849218.6A EP2909879B1 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| PCT/CA2013/050793 WO2014063244A1 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| CN202011082227.7A CN112201789A (en) | 2012-10-22 | 2013-10-21 | Method for preparing electrode material for lithium ion secondary battery and lithium ion battery using such electrode material |
| ES13849218T ES2855168T3 (en) | 2012-10-22 | 2013-10-21 | Electrode material production procedure for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| JP2015537095A JP6469576B2 (en) | 2012-10-22 | 2013-10-21 | Method of manufacturing electrode material for lithium-ion secondary battery and lithium-ion battery using the electrode material |
| EP20210739.7A EP3826087A1 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| IN2978DEN2015 IN2015DN02978A (en) | 2012-10-22 | 2013-10-21 | |
| CN201380054698.9A CN104854736A (en) | 2012-10-22 | 2013-10-21 | Method for preparing electrode material of lithium ion secondary battery and lithium ion battery using the electrode material |
| KR1020237032912A KR102773628B1 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| KR1020157013567A KR102382433B1 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| KR1020227010526A KR20220046702A (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| US14/437,347 US11545668B2 (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| CA2888561A CA2888561C (en) | 2012-10-22 | 2013-10-21 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| US18/059,035 US12068484B2 (en) | 2012-10-22 | 2022-11-28 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
| US18/600,573 US12368168B2 (en) | 2012-10-22 | 2024-03-08 | Method of producing electrode material for lithium-ion secondary battery and lithium-ion battery using such electrode material |
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- 2012-10-22 CA CA2794290A patent/CA2794290A1/en not_active Abandoned
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| CN106507692A (en) * | 2014-05-08 | 2017-03-15 | Sei株式会社 | lithium secondary battery |
| EP3142180A4 (en) * | 2014-05-08 | 2017-12-13 | Sei Corporation | Lithium secondary battery |
| CN106507692B (en) * | 2014-05-08 | 2019-08-30 | Sei株式会社 | Lithium secondary battery |
| EP3276711A4 (en) * | 2015-03-24 | 2018-08-08 | Taiheiyo Cement Corporation | Secondary battery positive electrode active material and method for producing same |
| US10601042B2 (en) | 2015-03-24 | 2020-03-24 | Taiheiyo Cement Corporation | Secondary battery positive electrode active material and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2909879A4 (en) | 2016-06-15 |
| US20230094444A1 (en) | 2023-03-30 |
| US12068484B2 (en) | 2024-08-20 |
| US11545668B2 (en) | 2023-01-03 |
| CA2888561C (en) | 2023-06-13 |
| JP2015532514A (en) | 2015-11-09 |
| CN112201789A (en) | 2021-01-08 |
| US20150270554A1 (en) | 2015-09-24 |
| US20240274828A1 (en) | 2024-08-15 |
| EP3826087A1 (en) | 2021-05-26 |
| IN2015DN02978A (en) | 2015-09-18 |
| EP2909879A1 (en) | 2015-08-26 |
| KR20150086280A (en) | 2015-07-27 |
| KR20220046702A (en) | 2022-04-14 |
| US12368168B2 (en) | 2025-07-22 |
| ES2855168T3 (en) | 2021-09-23 |
| CN104854736A (en) | 2015-08-19 |
| JP6469576B2 (en) | 2019-02-13 |
| CA2888561A1 (en) | 2014-05-01 |
| EP2909879B1 (en) | 2020-12-02 |
| KR102773628B1 (en) | 2025-02-27 |
| WO2014063244A1 (en) | 2014-05-01 |
| KR20230145493A (en) | 2023-10-17 |
| KR102382433B1 (en) | 2022-04-05 |
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