JP5001995B2 - リチウム二次電池用正極およびその製造方法 - Google Patents
リチウム二次電池用正極およびその製造方法 Download PDFInfo
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- JP5001995B2 JP5001995B2 JP2009258395A JP2009258395A JP5001995B2 JP 5001995 B2 JP5001995 B2 JP 5001995B2 JP 2009258395 A JP2009258395 A JP 2009258395A JP 2009258395 A JP2009258395 A JP 2009258395A JP 5001995 B2 JP5001995 B2 JP 5001995B2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 50
- 229910052744 lithium Inorganic materials 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000007774 positive electrode material Substances 0.000 claims description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 112
- 229910052799 carbon Inorganic materials 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 36
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000001947 vapour-phase growth Methods 0.000 claims description 6
- 238000004808 supercritical fluid chromatography Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 239000011149 active material Substances 0.000 description 23
- 239000002041 carbon nanotube Substances 0.000 description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 description 20
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000002717 carbon nanostructure Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000012669 compression test Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical group 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 phosphate compound Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0473—Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
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- 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
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- 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
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Description
ここに開示される技術では、上述のようにカーボンナノウォール32を通じて活物質36同士および/または活物質36と集電体20との電子移動を円滑に行い得ることから、上記導電材を使用しないか、あるいは従来の一般的な正極活物質層に比べて導電材の使用量を少なくすることができる。このように導電材を省略または使用量を低減し得ることは、正極活物質層のエネルギー密度を高める上で好ましい。したがって、ここに開示される技術は、例えば、正極活物質層30が実質的に正極活物質およびカーボンナノウォールからなる態様で好ましく実施され得る。
まず、Si基板25を用いて、その表面にカーボンナノウォールを形成した。カーボンナノウォールの形成は、図5に示すプラズマCVD装置を用いて行った。具体的には、Si基板25をチャンバ90内に配置し、Si基板25に対して平行な平板電極(第1電極92A及び第2電極92B)の間に、炭化源ガス(ここではC2F6)を導入するとともに、導入管94からH2ガスをチャンバ内に導入した。そして、平板電極92AとSi基板25の間の距離を5cmにし、炭化源ガス(C2F6)の流量を15sccm,H2ガスの流量を30sccmとし、チャンバ90内の全圧が100mTorrとなるように調整した。
また、比較のために、Si基板の表面に垂直方向に配向した単層カーボンナノチューブを形成した。カーボンナノチューブの形成は、一般的なプラズマCVD装置を用いて行った。具体的には、Si基板上に鉄からなる触媒層をスパッタリング法によって形成し、触媒を起点としてカーボンナノチューブを化学気相成長(CVD)法により成長させ、Si基板上に所定寸法(直径20nm程度、間隔200nm程度、高さ60μm程度)のカーボンナノチューブを形成した。
このようにして得られたカーボンナノウォールに対してプレス圧縮試験を行った。具体的には、カーボンナノウォール上にフッ素樹脂フィルムを被せ、油圧式のホットプレス機を用いて150℃で5分間加熱した後、150℃、5分間、60kgf/cm2の試験条件でプレスした。そして、プレス後のカーボンナノウォールをフッ素樹脂フィルムに転写した。カーボンナノチューブに対しても同様の条件でプレス圧縮試験を行った。
10 正極
20 正極集電体
30 正極活物質層
32 カーボンナノウォール
34 ウォール
36 正極活物質(粒状)
52 ケース
54 ケース本体
56 蓋体
60 セパレータ
70 正極
80 捲回電極体
82 正極端子
84 正極端子
86 正極リード端子
88 正極リード端子
90 チャンバ
92A,92B 平板電極
94 導入管
95 ヒータ
96 プラズマ発生源
98 高周波出力装置
99 コイル
100 リチウム二次電池
110 正極
120 正極集電体
130 正極活物質層
132 カーボンナノウォール
134 ウォール
136 正極活物質(膜状)
Claims (11)
- 正極活物質を含む正極活物質層が正極集電体上に保持された構成を有するリチウム二次電池用正極であって、
前記正極活物質層は、前記正極集電体上に形成されたカーボンナノウォールと、該カーボンナノウォールに担持された正極活物質とを備える、リチウム二次電池用正極。 - 前記正極活物質は、粒状に形成され、前記ウォール間の隙間に充填されている、請求項1に記載のリチウム二次電池用正極。
- 前記正極活物質は、膜状に形成され、前記ウォールの表面を被覆している、請求項1に記載のリチウム二次電池用正極。
- 前記正極活物質層中に含まれるカーボンナノウォールの割合は、正極活物質層の全体積に対して0.5体積%〜30体積%である、請求項1または2に記載のリチウム二次電池用正極。
- 正極活物質を含む正極活物質層が正極集電体上に保持された構成を有するリチウム二次電池用正極の製造方法であって、
正極集電体上にカーボンナノウォールを形成する工程と、
前記カーボンナノウォールに正極活物質を担持させて正極活物質層を形成する工程と
を含む、リチウム二次電池用正極の製造方法。 - 前記正極活物質を粒状に形成し、前記ウォール間に充填する、請求項5に記載の正極製造方法。
- 前記粒状の正極活物質の充填は、超臨界流体法を用いて行われる、請求項6に記載の正極製造方法。
- 前記正極活物質を膜状に形成し、前記ウォールの表面を被覆する、請求項5に記載の正極製造方法。
- 前記膜状の正極活物質の形成は、気相成長法を用いて行われる、請求項8に記載の正極製造方法。
- 請求項1から4の何れか一つに記載の正極もしくは請求項5から9の何れか一つに記載の方法により製造された正極と電解質と負極とを備えるリチウム二次電池。
- 請求項10に記載のリチウム二次電池を搭載する車両。
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JP2009258395A JP5001995B2 (ja) | 2009-11-11 | 2009-11-11 | リチウム二次電池用正極およびその製造方法 |
US13/505,709 US20120214065A1 (en) | 2009-11-11 | 2010-11-10 | Positive electrode for lithium secondary battery, method for preparing the positive electrode, lithium secondary battery having the positive electrode, and vehicle having the lithium secondary battery |
KR1020127012086A KR20120062934A (ko) | 2009-11-11 | 2010-11-10 | 리튬 2차 전지용 양전극, 양전극을 준비하기 위한 방법, 양전극을 갖는 리튬 2차 전지, 및 리튬 2차 전지를 갖는 차량 |
CN2010800510714A CN102668181A (zh) | 2009-11-11 | 2010-11-10 | 锂二次电池用正电极、制备该正电极的方法、具有该正电极的锂二次电池以及具有该锂二次电池的车辆 |
PCT/IB2010/002863 WO2011058417A1 (en) | 2009-11-11 | 2010-11-10 | Positive electrode for lithium secondary battery, method for preparing the positive electrode, lithium secondary battery having the positive electrode, and vehicle having the lithium secondary battery |
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JP5845706B2 (ja) * | 2011-02-18 | 2016-01-20 | 富士通株式会社 | 二次電池とその製造方法 |
JP5760710B2 (ja) * | 2011-06-02 | 2015-08-12 | 株式会社Ihi | ナノ構造体の製造方法 |
WO2012165358A1 (en) * | 2011-06-03 | 2012-12-06 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing electrode |
JP6069821B2 (ja) * | 2011-09-28 | 2017-02-01 | ソニー株式会社 | リチウムイオン二次電池 |
KR102514830B1 (ko) | 2011-09-30 | 2023-03-30 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 양극, 리튬 이차 전지, 전기 자동차, 하이브리드 자동차, 이동체, 시스템, 및 전기 기기 |
CN107527744A (zh) * | 2016-06-22 | 2017-12-29 | 广州墨羲科技有限公司 | 石墨烯-纳米颗粒-纳米碳墙复合材料、其制造方法及应用 |
JP6946692B2 (ja) * | 2017-03-29 | 2021-10-06 | 株式会社Ihi | X線発生装置 |
CN108493456B (zh) * | 2018-04-27 | 2021-03-12 | 北京石墨烯研究院 | 电池正极极片、应用其的锂离子电池及降低界面电阻方法 |
WO2019238206A1 (en) | 2018-06-11 | 2019-12-19 | Jozef Stefan Institute | Carbon nanostructured materials and methods for forming carbon nanostructured materials |
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JP5153056B2 (ja) * | 2004-12-24 | 2013-02-27 | パナソニック株式会社 | カーボンナノファイバを含む、非水電解質二次電池用または電気二重層キャパシタ用複合集電体および電極の製造法 |
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