JP2010262914A - リチウム2次電池 - Google Patents
リチウム2次電池 Download PDFInfo
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- JP2010262914A JP2010262914A JP2009247747A JP2009247747A JP2010262914A JP 2010262914 A JP2010262914 A JP 2010262914A JP 2009247747 A JP2009247747 A JP 2009247747A JP 2009247747 A JP2009247747 A JP 2009247747A JP 2010262914 A JP2010262914 A JP 2010262914A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 claims abstract description 44
- 239000007773 negative electrode material Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 17
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 239000002082 metal nanoparticle Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052795 boron group element Inorganic materials 0.000 claims description 4
- 229910052800 carbon group element Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052699 polonium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910021477 seaborgium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 229910021475 bohrium Inorganic materials 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910021481 rutherfordium Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000007769 metal material Substances 0.000 abstract description 2
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 150000002696 manganese Chemical class 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- -1 LiCoO 2 Chemical compound 0.000 description 17
- 239000002904 solvent Substances 0.000 description 12
- 229910021383 artificial graphite Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 235000015110 jellies Nutrition 0.000 description 5
- 239000008274 jelly Substances 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 239000011301 petroleum pitch Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 2
- MMZYCBHLNZVROM-UHFFFAOYSA-N 1-fluoro-2-methylbenzene Chemical compound CC1=CC=CC=C1F MMZYCBHLNZVROM-UHFFFAOYSA-N 0.000 description 2
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 229940057061 mevalonolactone Drugs 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
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- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
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- KSXFNGRHPAHIQJ-UHFFFAOYSA-N 1,2,4-triiodobenzene Chemical compound IC1=CC=C(I)C(I)=C1 KSXFNGRHPAHIQJ-UHFFFAOYSA-N 0.000 description 1
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- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- KQDOUXAQOUQPQW-UHFFFAOYSA-N 4-bromo-1,3-dioxolan-2-one Chemical compound BrC1COC(=O)O1 KQDOUXAQOUQPQW-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
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- PCEVCXPUGOBVFG-UHFFFAOYSA-N 5,6-dichloro-5-methylcyclohexa-1,3-diene Chemical compound CC1(Cl)C=CC=CC1Cl PCEVCXPUGOBVFG-UHFFFAOYSA-N 0.000 description 1
- CMTFMQAGUXZMHD-UHFFFAOYSA-N 5,6-difluoro-5-methylcyclohexa-1,3-diene Chemical compound CC1(F)C=CC=CC1F CMTFMQAGUXZMHD-UHFFFAOYSA-N 0.000 description 1
- DTWXIVZRKZIBPP-UHFFFAOYSA-N 5,6-diiodo-5-methylcyclohexa-1,3-diene Chemical compound CC1(I)C=CC=CC1I DTWXIVZRKZIBPP-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013417 LiN(SO3C2F5)2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical compound C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000005466 carboxylated polyvinylchloride Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007841 coal based oil Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005545 pitch carbide Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
-
- 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
-
- 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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- H01M4/13—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
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- 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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- 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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Abstract
【解決手段】本発明によるリチウム2次電池は、金属及び炭素系物質の複合体負極活物質を含む負極;コバルト系、マンガン系、リン酸系、及びこれらの組合せからなる群より選択される第1正極活物質90乃至99質量%及びニッケル系第2正極活物質1乃至10質量%を含む混合正極活物質を含む正極;及び非水系電解質;を含む。
【選択図】図1
Description
LiaA1−bXbD2(0.90≦a≦1.8、0≦b<0.5)
[化学式2]
LiaE1−bXbO2−cDc(0.90≦a≦1.8、0≦b<0.5、0≦c≦0.05)
[化学式3]
LiE2−bXbO4−cDc(0≦b<0.5、0≦c≦0.05)
[化学式4]
LiaCoGbO2(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式5]
LiaMnGbO2(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式6]
LiaMn2GbO4(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式7]
Li(3−f)J2(PO4)3(0≦f≦2)
[化学式8]
Li(3−f)Fe2(PO4)3(0≦f≦2)
[化学式9]
LiFePO4
(前記化学式において、AはCo、Mn、及びこれらの組合せからなる群より選択され;XはAl、Ni、Co、Mn、Cr、Fe、Mg、Sr、V、希土類元素、及びこれらの組合せからなる群より選択され;DはO、F、S、P、及びこれらの組合せからなる群より選択され;EはCo、Mn、及びこれらの組合せからなる群より選択され;GはAl、Cr、Mn、Fe、Mg、La、Ce、Sr、V、及びこれらの組合せからなる群より選択され;QはTi、Mo、Mn、及びこれらの組合せからなる群より選択され;JはV、Cr、Mn、Co、Ni、Cu、及びこれらの組合せからなる群より選択される。)
LigNihL1−jOe
(前記化学式で、0.8≦g≦2、0≦h≦1であり、eは1乃至2であり、0≦j≦1であり、LはAl、Mn、Mg、Zr、La、及びこれらの組合せからなる群より選択される。)
[化学式11]
LixNiyCozL´1−y−zOq
(前記化学式で、0.65≦x≦1、0≦y≦1、0≦z≦1、0≦y+z≦1であり、qは1.8乃至2であり、L´はAl、Mn、Mg、Zr、La、及びこれらの組合せからなる群より選択される。)
前記負極は、バインダーを含み、選択的に導電剤をさらに含むことができる。また、前記正極は、バインダー及び導電剤を含む。
1.正極の製造
LiCoO297質量%及びLixNiyCozAl1−y−zOq(x=2、y=1、z=0、q=2、つまりLi2NiO2)3質量%を混合した混合正極活物質、ポリフッ化ビニリデンバインダー、及びカーボンブラック導電剤をN−メチルピロリドン溶媒中で混合して、正極活物質スラリーを製造した。この時、前記正極活物質、バインダー、及び導電剤の混合比率は、94:3:3質量%とした。前記正極活物質スラリーをAl箔電流集電体に塗布する通常の電極製造工程で、正極を製造した。
平均粒径3μmの鱗片状人造黒鉛微細粒子をロータリーミル(rotary mill)でミリングして、平均粒径20μmの人造黒鉛コアを製造した。前記ミリング工程で前記微細粒子が互いに凝集して、製造された人造黒鉛コアの内部に閉気孔及び開気孔形態の気孔が形成された。
正極活物質としてLiCoO297質量%及びLi2NiO23質量%を混合した混合正極活物質を使用したことを除いては、前記実施例1と同一に実施した。
正極活物質としてLiCoO2だけを使用したことを除いては、前記実施例1と同一に実施した。
正極活物質としてLiCoO299質量%及びLi2NiO21質量%を混合した正極活物質を使用したことを除いては、前記実施例1と同一に実施した。
正極活物質としてLiCoO295質量%及びLi2NiO25質量%を混合した正極活物質を使用したことを除いては、前記実施例1と同一に実施した。
正極活物質としてLiCoO290質量%及びLi2NiO210質量%を混合した正極活物質を使用したことを除いては、前記実施例1と同一に実施した。
112 負極
113 セパレータ
114 正極
120 電池容器
140 封入部材
Claims (9)
- 金属及び炭素系物質の複合体負極活物質を含む負極;
コバルト系、マンガン系、リン酸系、及びこれらの組合せからなる群より選択される第1正極活物質90乃至99質量%及びニッケル系第2正極活物質1乃至10質量%を含む混合正極活物質を含む正極;及び
非水系電解質;を含む、リチウム2次電池。 - 前記混合正極活物質は、前記第2正極活物質を3乃至5質量%及び前記第1正極活物質を97乃至95質量%で含む、請求項1に記載のリチウム2次電池。
- 前記第1正極活物質は、下記の化学式1乃至9で示される少なくとも1つの化合物である、請求項1に記載のリチウム2次電池。
[化学式1]
LiaA1−bXbD2(0.90≦a≦1.8、0≦b<0.5)
[化学式2]
LiaE1−bXbO2−cDc(0.90≦a≦1.8、0≦b<0.5、0≦c≦0.05)
[化学式3]
LiE2−bXbO4−cDc(0≦b<0.5、0≦c≦0.05)
[化学式4]
LiaCoGbO2(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式5]
LiaMnGbO2(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式6]
LiaMn2GbO4(0.90≦a≦1.8、0.001≦b≦0.1)
[化学式7]
Li(3−f)J2(PO4)3(0≦f≦2)
[化学式8]
Li(3−f)Fe2(PO4)3(0≦f≦2)
[化学式9]
LiFePO4
(前記化学式において、AはCo、Mn、及びこれらの組合せからなる群より選択され;XはAl、Ni、Co、Mn、Cr、Fe、Mg、Sr、V、希土類元素、及びこれらの組合せからなる群より選択され;DはO、F、S、P、及びこれらの組合せからなる群より選択され;EはCo、Mn、及びこれらの組合せからなる群より選択され;GはAl、Cr、Mn、Fe、Mg、La、Ce、Sr、V、及びこれらの組合せからなる群より選択され;QはTi、Mo、Mn、及びこれらの組合せからなる群より選択され;JはV、Cr、Mn、Co、Ni、Cu、及びこれらの組合せからなる群より選択される。) - 前記第2正極活物質は、下記の化学式10または11で示される化合物である、請求項1に記載のリチウム2次電池。
[化学式10]
LigNihL1−jOe
(前記化学式で、0.8≦g≦2、0≦h≦1であり、eは1乃至2であり、0≦j≦1であり、LはAl、Mn、Mg、Zr、La、及びこれらの組合せからなる群より選択される。)
[化学式11]
LixNiyCozL´1−y−zOq
(前記化学式で、0.65≦x≦1、0≦y≦1、0≦z≦1、0≦y+z≦1であり、qは1.8乃至2であり、L´はAl、Mn、Mg、Zr、La、及びこれらの組合せからなる群より選択される。) - 前記リチウム2次電池は、正極容量に対する負極容量の比であるN/P比率が1.03乃至1.12である、請求項1に記載のリチウム2次電池。
- 前記負極は、前記正極、前記負極、及びリチウム金属対極を含む3電極系電極電位測定装置を使用して測定した電位が0.9V以下である、請求項1に記載のリチウム2次電池。
- 前記複合体負極活物質は、気孔が形成された結晶質炭素コア;前記結晶質炭素コアの表面に形成された非晶質炭素セル;前記気孔の内部に分散されている金属ナノ粒子;及び前記気孔の内部に存在する非晶質炭素;を含む、請求項1に記載のリチウム2次電池。
- 前記金属は、Si、Si−T合金(前記Tはアルカリ金属、アルカリ土金属、13族元素、14族元素、遷移金属、希土類元素、及びこれらの組合せからなる群より選択される元素であり、Siではない)、Sn、Sn−Z合金(前記Zはアルカリ金属、アルカリ土金属、13族元素、14族元素、遷移金属、希土類元素、及びこれらの組合せからなる群より選択される元素であり、Snではない)、Pb、In、As、Sb、Ag、及びこれらの組合せからなる群より選択される、請求項1に記載のリチウム2次電池。
- 前記元素T及びZは互いに独立的にMg、Ca、Sr、Ba、Ra、Sc、Y、Ti、Zr、Hf、Rf、V、Nb、Ta、Db、Cr、Mo、W、Sg、Tc、Re、Bh、Fe、Ru、Os、Hs、Rh、Ir、Pd、Pt、Cu、Ag、Au、Zn、Cd、B、Al、Ga、In、Ti、Ge、P、As、Sb、Bi、S、Se、Te、Po、及びこれらの組合せからなる群より選択される、請求項8に記載のリチウム2次電池。
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JP2013058452A (ja) * | 2011-09-09 | 2013-03-28 | Mitsubishi Chemicals Corp | 非水系二次電池用複合炭素材及びその製造方法、負極並びに非水系二次電池 |
JP2013110112A (ja) * | 2011-11-22 | 2013-06-06 | Samsung Electronics Co Ltd | 複合負極活物質、その製造方法及びそれを含むリチウム二次電池 |
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US10090521B2 (en) | 2014-06-10 | 2018-10-02 | Hitachi Chemical Company, Ltd. | Lithium ion battery with negative electrode in which state of charge at a potential to be 0.1 V with respect lithium potential is 60% or more, and positive electrode having a density positive electrode composite of 2.4 to 2.7 g/cm3 |
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JP2020516039A (ja) * | 2017-11-17 | 2020-05-28 | エルジー・ケム・リミテッド | リチウム二次電池用正極材に含まれる非可逆添加剤の製造方法、これにより製造された非可逆添加剤を含む正極材、および正極材を含むリチウム二次電池 |
JP7094598B2 (ja) | 2017-11-17 | 2022-07-04 | エルジー エナジー ソリューション リミテッド | リチウム二次電池用正極材に含まれる非可逆添加剤の製造方法、これにより製造された非可逆添加剤を含む正極材、および正極材を含むリチウム二次電池 |
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Also Published As
Publication number | Publication date |
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CN101877417A (zh) | 2010-11-03 |
KR101093705B1 (ko) | 2011-12-19 |
EP2246922A1 (en) | 2010-11-03 |
CN101877417B (zh) | 2016-08-17 |
US8597833B2 (en) | 2013-12-03 |
EP2246922B1 (en) | 2016-04-20 |
JP5289274B2 (ja) | 2013-09-11 |
KR20100118825A (ko) | 2010-11-08 |
US20100279172A1 (en) | 2010-11-04 |
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