JP2010537389A - 電池の負極、及びそれを用いたリチウムイオン電池 - Google Patents
電池の負極、及びそれを用いたリチウムイオン電池 Download PDFInfo
- Publication number
- JP2010537389A JP2010537389A JP2010522170A JP2010522170A JP2010537389A JP 2010537389 A JP2010537389 A JP 2010537389A JP 2010522170 A JP2010522170 A JP 2010522170A JP 2010522170 A JP2010522170 A JP 2010522170A JP 2010537389 A JP2010537389 A JP 2010537389A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium
- battery
- current
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 46
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 52
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 48
- -1 lithium titanium oxide compound Chemical class 0.000 claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910012113 Li3+3xTi6-3x-yMyO12 Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 41
- 239000010936 titanium Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 238000007599 discharging Methods 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000002174 Styrene-butadiene Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 7
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical class [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- 241000282693 Cercopithecidae Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 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
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
-
- 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/485—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
【選択図】なし
Description
1.容量及び中央値電圧の測定
室温で、実施例1〜6及び比較例1により調製された電池をそれぞれ1Cの電流にて4.2Vまで充電し、その後4.2Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。その後、1Cの電流にて2.75Vまで放電させ、室温で1Cの電流にて2.75Vまで放電させた電池の容量を得、放電における中央値電圧を記録した。
A.大電流放電の測定
室温で、実施例1〜6及び比較例1により調製された電池をそれぞれ1Cの電流にて4.2Vまで充電し、その後4.2Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。そして0.2Cの電流にて2.75Vまで放電させ、常温下で0.2Cの電流にて2.75Vまで放電させた電池の容量を得た。上述の充電のステップを繰り返し、電池をそれぞれ3Cの電流にて放電させ、室温で3Cの電流にて2.75Vまで放電させた電池の容量を得、放電の中央値電圧を記録した。上述の充電の手順を繰り返し、電池をそれぞれ5Cの電流にて放電させ、室温で5Cの電流にて2.75Vまで放電させた電池の容量を得、放電の中央値電圧を記録した。3C、5Cの電流で放電させた電池の容量の、0.2Cの電流で放電させた電池のそれに対する比率をそれぞれ算出した(以下では、放電比率を3C/0.2C及び5C/0.2Cと略す)。
室温で、実施例1〜6及び比較例1により調製された電池をそれぞれ0.2Cの電流にて4.2Vまで充電し、4.2Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。1Cの電流にて2.75Vまで放電させ、室温で0.2Cの電流にて4.2Vに充電し1Cの電流にて2.75Vまで放電させた電池の容量を得た。その後、電池をそれぞれ3Cの電流にて4.2Vまで充電し、4.2Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。1Cの電流にて2.75Vまで放電させ、室温で3Cの電流にて4.2Vに充電し1Cの電流にて2.75Vまで放電させた電池の容量を得た。そして、電池をそれぞれ5Cの電流にて4.2Vまで充電させ、4.2Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。そして1Cの電流にて2.75Vまで放電させ、室温で5Cの電流にて4.2Vに充電し1Cの電流にて2.75Vまで放電させた電池の容量を得た。3C、5Cの電流で放電させた電池の容量の、0.2Cの電流で放電させた電池のそれに対する比率をそれぞれ算出した。
A.オーブン温度の測定
室温で、実施例1〜6及び比較例1により調製された電池を、それぞれ1Cの電流にて4.2Vまで充電し、比較例2により調製された電池を1Cの電流にて3.0Vまで充電した。その後電池をそれぞれ4.2V及び3.0Vの定電圧、及び0.05Cのカットオフ電流にて充電し、5分間置いた。150℃のオーブンに暴露した。1.5時間後、電池に異常の出現があるかどうかを観察し、電池表面の最高温度を測定した。観察及び測定の結果を表4に示す。
室温で、実施例1〜6及び比較例1により調製された電池を、それぞれ5Cの電流にて4.2Vまで充電し、比較例2により調製された電池を5Cの電流にて3.0Vまで充電した。その後電池をそれぞれ4.2V及び3.0Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。そして、不活性ガスの雰囲気下で分解して負極を取り出した。負極を裸眼で観察し即座にXPS測定に供して負極表面のリチウム濃度を測定した。負極の観察結果及び負極表面のリチウム濃度を表5に示す。
室温で、実施例1〜6及び比較例1により調製された電池を、それぞれ5Cの電流にて4.2Vまで充電し、比較例2により調製された電池を5Cの電流にて3.0Vまで充電した。その後電池をそれぞれ4.2V及び3.0Vの定電圧にて充電し、電流が0.05Cでカットオフし、5分間置いた。その後、その表面に熱電対温度計のプローブを貼り付け、電池を正極と負極を短絡させた状態の短絡器に置いた。電池の状況及び電池表面の最高温度を記録した。その結果を表6に示す。
実施例1〜6及び比較例1により調製された負極を直径が14mmの円板に仕立てた。組成及び含有量が比較例2の負極材料と同じである混合物を採用して厚さが0.116〜0.120mmである負極被覆を形成した。そしてそれを直径が14mmとなるような円板に仕立てた。得られた円盤を正極として用い、金属リチウム板を負極として用いることにより、ボタン電池を調製した。得られた電池を0.2mAの電流にて0.005Vまで放電させた後、5分間放置し、0.2mAの電流にて2.5Vまでに充電させた後、2.5Vの定電圧で充電し、0.01mAの電流でカットオフした。各ボタン電池の容量を記録し、それを用いて各負極の容量を表した。測定結果を表7に示す。
Claims (8)
- 集電体と、当該集電体に塗布された負極材料被覆とを含み、前記負極材料が炭素材料、粘着剤及び酸化チタンリチウム化合物を含有する、電池の負極であって、
前記負極材料被覆において、前記炭素材料の総重量百分率含量は、前記酸化チタンリチウム化合物のそれより高く、前記負極材料被覆は少なくとも二層を含み、且つ、負極材料被覆の最外層において、前記炭素材料の重量百分率含量が前記酸化チタンリチウム化合物のそれより低く、その他の層において、前記炭素材料の重量百分率含量が前記酸化チタンリチウム化合物のそれより高い、負極。 - 前記炭素材料の総重量百分率含量と前記酸化チタンリチウム化合物のそれとの比は(1.5〜100):1であり、負極材料被覆の最外層において、前記炭素材料の重量百分率含量と前記酸化チタンリチウム化合物のそれとの比は(0〜0.25):1であり、その他の層において、前記酸化チタンリチウム化合物の重量百分率含量と前記炭素材料のそれとの比は(0〜0.25):1である、請求項1に記載の負極。
- 前記負極材料被覆は、集電体の表面と直接接触する層と、外層とを含み、前記集電体の表面と直接接触する層は、前記集電体の表面と直接接触する層の総重量を基準として、80〜95重量%の炭素材料、1〜10重量%の粘着剤、0〜8重量%の導電剤及び0〜16重量%の酸化チタンリチウム化合物を含み、前記外層は、前記外層の総重量を基準とし、80〜95重量%の酸化チタンリチウム化合物、0〜16重量%の炭素材料、0〜8重量%の導電剤及び1〜10重量%の粘着剤を含む、請求項2に記載の負極。
- 前記集電体の表面と直接接触する層の厚さと前記外層の厚さとの比率は50:(25〜2)である、請求項3に記載の負極。
- 前記集電体の表面と直接接触する層は0.070〜0.120mmの厚さを有し、前記外層は0.003〜0.040mmの厚さを有する、請求項4に記載の負極。
- 前記導電剤はニッケル粉及び/又は銅粉である、請求項3に記載の負極。
- 前記炭素材料は黒鉛、カーボンブラック、コークス、活性炭、炭素繊維、石油コークス、硬質炭素及びカーボンナノチューブからなる群より選択される一つ以上であってもよく、前記酸化チタンリチウム化合物は、化学式がLi3+3xTi6-3x-yMyO12である酸化チタンリチウム材料であり、ここで、xとyはモル比を表し、0≦x≦1/3、0≦y≦0.25であり、MはFe、 Al、 Ca、 Co、 B、 Cr、 Ni、Mg、Zr、Ga、V、 Mn及び Znからなる群より選択される一つ以上であり、前記粘着剤はポリフッ化ビニリデン、ポリテトラフルオロエチレン、ナトリウムカルボキシメチルセルロース及びスチレン-ブタジエンゴムからなる群より選択される一つ以上である、請求項1又は3に記載の負極。
- ケース、正極、負極、セパレーター及び電解液を含み、前記正極、負極、セパレーター及び電解液が電池のケース内に封入されているリチウムイオン電池であって、前記負極が請求項1〜7のいずれか一項に記載の負極である、リチウムイオン電池。
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JP2010192230A (ja) * | 2009-02-18 | 2010-09-02 | Murata Mfg Co Ltd | 非水電解液二次電池 |
JP2013020845A (ja) * | 2011-07-12 | 2013-01-31 | Toyota Motor Corp | 二次電池用電極とその製造方法 |
WO2013014830A1 (ja) * | 2011-07-26 | 2013-01-31 | パナソニック株式会社 | リチウムイオン二次電池 |
JP2013033685A (ja) * | 2011-08-03 | 2013-02-14 | Showa Denko Kk | 二次電池用負極および二次電池 |
WO2013038702A1 (ja) * | 2011-09-14 | 2013-03-21 | パナソニック株式会社 | 非水電解質二次電池 |
WO2013099279A1 (ja) * | 2011-12-28 | 2013-07-04 | パナソニック株式会社 | 非水電解質二次電池用負極および非水電解質二次電池用負極を有する非水電解質二次電池 |
JP2013149383A (ja) * | 2012-01-17 | 2013-08-01 | Toyota Motor Corp | 非水電解質二次電池用負極の製造方法および該負極を用いた非水電解質二次電池の製造方法 |
JP2014078318A (ja) * | 2012-10-08 | 2014-05-01 | Toyota Motor Corp | リチウムイオン二次電池の製造方法 |
JP2016103479A (ja) * | 2014-11-28 | 2016-06-02 | エスケー イノベーション カンパニー リミテッドSk Innovation Co.,Ltd. | リチウム電極の製造方法およびこれを含むリチウム二次電池 |
JP2020126861A (ja) * | 2014-11-28 | 2020-08-20 | エスケー イノベーション カンパニー リミテッドSk Innovation Co.,Ltd. | リチウム電極の製造方法 |
JP2019046765A (ja) * | 2017-09-07 | 2019-03-22 | 三洋化成工業株式会社 | リチウムイオン電池用電極の製造方法及びリチウムイオン電池用電極の製造装置 |
JP2019067700A (ja) * | 2017-10-04 | 2019-04-25 | トヨタ自動車株式会社 | 非水電解液二次電池 |
Also Published As
Publication number | Publication date |
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KR101202863B1 (ko) | 2012-11-19 |
KR20100008785A (ko) | 2010-01-26 |
EP2223368B1 (en) | 2011-09-21 |
US20090214946A1 (en) | 2009-08-27 |
WO2009103202A1 (en) | 2009-08-27 |
JP5221660B2 (ja) | 2013-06-26 |
EP2223368A4 (en) | 2010-09-01 |
CN101515640A (zh) | 2009-08-26 |
CN101515640B (zh) | 2011-04-20 |
ATE525760T1 (de) | 2011-10-15 |
EP2223368A1 (en) | 2010-09-01 |
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