JP5277216B2 - リチウム2次電池 - Google Patents
リチウム2次電池 Download PDFInfo
- Publication number
- JP5277216B2 JP5277216B2 JP2010168790A JP2010168790A JP5277216B2 JP 5277216 B2 JP5277216 B2 JP 5277216B2 JP 2010168790 A JP2010168790 A JP 2010168790A JP 2010168790 A JP2010168790 A JP 2010168790A JP 5277216 B2 JP5277216 B2 JP 5277216B2
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- JP
- Japan
- Prior art keywords
- positive electrode
- lithium
- active material
- chemical formula
- electrode active
- 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.)
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- 229910052744 lithium Inorganic materials 0.000 title claims description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 45
- 239000000126 substance Substances 0.000 claims description 67
- 239000003792 electrolyte Substances 0.000 claims description 63
- 239000007774 positive electrode material Substances 0.000 claims description 62
- 239000011572 manganese Substances 0.000 claims description 43
- -1 ethylene carbonate compound Chemical class 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000000654 additive Substances 0.000 claims description 31
- 230000000996 additive effect Effects 0.000 claims description 31
- 230000001681 protective effect Effects 0.000 claims description 31
- 239000010410 layer Substances 0.000 claims description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 239000003125 aqueous solvent Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 13
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 71
- 239000010408 film Substances 0.000 description 45
- 239000007773 negative electrode material Substances 0.000 description 24
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000006258 conductive agent Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- 150000005678 chain carbonates Chemical class 0.000 description 8
- 150000005676 cyclic carbonates Chemical class 0.000 description 8
- 125000000547 substituted alkyl group Chemical group 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910021382 natural graphite Inorganic materials 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910013063 LiBF 4 Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910009745 Li1.1Mn1.86Mg0.03O4 Inorganic materials 0.000 description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000003232 water-soluble binding agent 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
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 102100036471 Tropomyosin beta chain Human genes 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
- 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 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
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- 239000005466 carboxylated polyvinylchloride Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- 238000000605 extraction Methods 0.000 description 2
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- 239000003273 ketjen black Substances 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
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
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- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
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- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- HXDPORRJTJUJIF-UHFFFAOYSA-N 1,2,3-triiodo-4-methylbenzene Chemical compound CC1=CC=C(I)C(I)=C1I HXDPORRJTJUJIF-UHFFFAOYSA-N 0.000 description 1
- RIWAPWDHHMWTRA-UHFFFAOYSA-N 1,2,3-triiodobenzene Chemical compound IC1=CC=CC(I)=C1I RIWAPWDHHMWTRA-UHFFFAOYSA-N 0.000 description 1
- PEBWOGPSYUIOBP-UHFFFAOYSA-N 1,2,4-trifluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1 PEBWOGPSYUIOBP-UHFFFAOYSA-N 0.000 description 1
- 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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- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- YSNVKDGEALPJGC-UHFFFAOYSA-N 1,4-difluoro-2-methylbenzene Chemical compound CC1=CC(F)=CC=C1F YSNVKDGEALPJGC-UHFFFAOYSA-N 0.000 description 1
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 1
- UOQKIFBSLBFTMS-UHFFFAOYSA-N 1,4-diiodo-2-methylbenzene Chemical compound CC1=CC(I)=CC=C1I UOQKIFBSLBFTMS-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- MPXDAIBTYWGBSL-UHFFFAOYSA-N 2,4-difluoro-1-methylbenzene Chemical compound CC1=CC=C(F)C=C1F MPXDAIBTYWGBSL-UHFFFAOYSA-N 0.000 description 1
- YCBAXGRWBIRFHY-UHFFFAOYSA-N 2,4-diiodo-1-methylbenzene Chemical compound CC1=CC=C(I)C=C1I YCBAXGRWBIRFHY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- DNMSBVYZDQGYLU-UHFFFAOYSA-N 2-oxo-1,3-dioxolane-4-carbonitrile Chemical compound O=C1OCC(C#N)O1 DNMSBVYZDQGYLU-UHFFFAOYSA-N 0.000 description 1
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 1
- RKDNQLPSWHNCFU-UHFFFAOYSA-N 4,5-dibromo-1,3-dioxolan-2-one Chemical compound BrC1OC(=O)OC1Br RKDNQLPSWHNCFU-UHFFFAOYSA-N 0.000 description 1
- 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
- GPSZQZDENOVTHL-UHFFFAOYSA-N 4-nitro-1,3-dioxolan-2-one Chemical compound [O-][N+](=O)C1COC(=O)O1 GPSZQZDENOVTHL-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO 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
- 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
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-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
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 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
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- 238000010586 diagram Methods 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
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910021473 hassium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 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 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920001778 nylon Polymers 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000005545 pitch carbide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel 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
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium 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
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N trifluorotoluene Substances FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- OYOGCAUNFUJOMO-UHFFFAOYSA-N trimethyl(octyl)silane Chemical compound CCCCCCCC[Si](C)(C)C OYOGCAUNFUJOMO-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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- H—ELECTRICITY
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- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Description
LiaMn1−bMbO2−cGc
LiaMn2−bMbO4−cGc
LixMO2−ZLZ
LifMn1−gMgPO4
前記化学式8で、0.90≦f≦1.8、0≦g≦0.5であり、MはAl、Ni、Co、Mn、Cr、Fe、Mg、Sr、希土類元素、またはこれらの組み合わせから選択される
LiaMn1−bMbO2−cGc
LiaMn2−bMbO4−cGc
LixMO2−ZLZ
LifMn1−gMgPO4
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質前駆体を製造した。電解質前駆体にフルオロエチレンカーボネート(以下、FECという)、LiBF4、及びトリス(トリメチルシリル)ホスフェート(P−(O−Si−(CH3)3)3、以下、TMSPiという)を添加して、電解質を製造した。このとき、FEC、LiBF4、及びTMSPiの添加量は、電解質前駆体全体の質量に対して各々5質量%、0.4質量%、及び3質量%にした。
天然黒鉛負極活物質97.5質量%、スチレン−ブタジエンラバーバインダー1.5質量%、及びカルボキシメチルセルロース増粘剤1質量%を水溶媒中で混合して、負極活物質スラリーを製造した。スラリーを銅箔電流集電体に塗布して、乾燥及び圧延を実施して、負極を製造した。
実施例2で製造された負極、リチウム金属対極、及び実施例1で製造された電解質を使用して、コインタイプの半電池(2016 cell)を製造した。
正極活物質としてLi1.1Mn1.86Mg0.03O4を使用したことを除いては、上記実施例1と同一に実施して、コインタイプの半電池(2016 cell)を製造した。
正極活物質としてLi1.1Mn1.86Mg0.03O4を使用したことを除いては、上記実施例2と同一に実施して、パウチタイプのコイン全電池(2032 cell)を製造した。製造された電池に0.1C充電及び0.1C放電の化成充放電を実施して、正極に保護膜が形成されたリチウム2次電池を製造した。このとき、保護膜の質量は、正極活物質100質量部に対して3.3質量部であった。
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質前駆体を製造した。電解質前駆体にFEC及びLiBF4を添加して、電解質を製造した。このとき、FEC及びLiBF4の添加量は、電解質前駆体全体の質量に対して各々5質量%及び0.4質量%にした。
天然黒鉛負極活物質97.5質量%、スチレン−ブタジエンラバーバインダー1.5質量%、及びカルボキシメチルセルロース増粘剤1質量%を水溶媒中で混合して、負極活物質スラリーを製造した。スラリーを銅箔電流集電体に塗布して、乾燥及び圧延を実施して、負極を製造した。
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質を製造した。
TMSPiの代わりにトリス(トリフルオロエチル)ホスフェート(P−(O−Si−(CH2CF3)3)3、以下、TFEPiという)を使用したことを除いては、上記実施例1と同一に実施して、コインタイプの半電池(2016 cell)を製造した。
TMSPiの代わりにトリス(トリメチルシリル)ボレート(B−(O−Si−(CH3)3)3、以下、TMSBという)を使用したことを除いては、上記実施例1と同一に実施して、コインタイプの半電池(2016 cell)を製造した。
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質前駆体を製造した。電解質前駆体にFEC、LiBF4、及びLiB(C2O4)2(リチウムビスオキサレートボレート(lithium bis(oxalato) borate;LiBOB)を添加して、電解質を製造した。このとき、FEC、LiBF4、及びLiB(C2O4)2の添加量は、電解質前駆体全体の質量に対して各々5質量%、0.4質量%、及び0.5質量%にした。
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質前駆体を製造した。電解質前駆体にTMSPiを添加して、電解質を製造した。
MSPiの添加量を電解質前駆体全体の質量に対して12質量%に変更したことを除いては、上記比較例7と同一に実施して、コインタイプの半電池(2016cell)を製造した。
TMSPiの代わりにトリメチルオクチルシラン(CH3(CH2)7−Si−(OCH3)3)を使用したことを除いては、上記実施例1と同一に実施して、コインタイプの半電池(2016 cell)を製造した。
実施例2で製造された負極、リチウム金属対極、及び比較例1で製造された電解質を使用して、コインタイプの半電池(2016 cell)を製造した。
正極活物質としてLi1.1Mn1.86Mg0.03O4を使用したことを除いては、上記比較例1と同一に実施して、コインタイプの半電池(2016 cell)を製造した。
正極活物質としてLi1.1Mn1.86Mg0.03O4を使用したことを除いては、上記比較例2と同一に実施して、パウチタイプのコイン全電池(2032 cell)を製造した。
正極活物質としてLi1.1Mn1.86Mg0.03O4を使用したことを除いては、上記比較例3と同一に実施して、(コインタイプの)半電池(2016 cell)を製造した。
環状カーボネートであるエチレンカーボネート及び鎖状カーボネートであるエチルメチルカーボネートを30:70の体積%の比率で均一に混合した混合溶媒に、1.0MのLiPF6を添加して、電解質前駆体を製造した。電解質前駆体にTMSPiを添加して、電解質を製造した。このとき、TMSPiの添加量は、電解質前駆体全体の質量に対して3質量%にした。
2 負極
3 正極
4 セパレータ
5 電池容器
6 封入部材
Claims (8)
- 電流集電体、前記電流集電体に形成されて、リチウムマンガン系正極活物質を含む正極活物質層、及び前記正極活物質層に形成されて、トリス(トリメチルシリル)ホスフェートの分解生成物を含む保護膜を有する正極;
負極;及び
リチウム塩、非水溶媒、及び充放電するときに前記負極に固体電解質界面膜を形成する添加剤を有する電解質;を備え、
前記添加剤は、下記の化学式3で表されるエチレンカーボネート系化合物、下記の化学式4で表されるイソキサゾール化合物、またはこれらの組み合わせであり、
前記添加剤の含有量は、前記リチウム塩及び前記非水溶媒100質量部に対して1乃至5質量部であり、
前記保護膜は、リチウム塩、非水溶媒、添加剤、及び前記トリス(トリメチルシリル)ホスフェートを含み、前記トリス(トリメチルシリル)ホスフェートの含有量が前記リチウム塩及び前記非水溶媒の質量全体に対して1乃至10質量%である電解質から形成される、
リチウム2次電池。
(前記化学式3において、X及びYは互いに同一または相異して、水素、ハロゲン基、シアノ基(CN)、ニトロ基(NO2)、または一つ以上の水素がフッ素に置換されたアルキル基であり、前記X及びYのうちの少なくとも一つはハロゲン基または一つ以上の水素がフッ素に置換されたアルキル基である。)
- 前記保護膜は、HOMO値が−10eV以上であり、LUMO値が1乃至1.3eVであるホスフェート系化合物の分解生成物を含む、請求項1に記載のリチウム2次電池。
- 前記保護膜は、カルボニル基及びリチウムカーボネート残基を有する化合物を含む、請求項1または2に記載のリチウム2次電池。
- 前記保護膜の含有量は、前記正極活物質層100質量部に対して3乃至35質量部である、請求項1から4のいずれか1項に記載のリチウム2次電池。
- 前記添加剤は、HOMO値が−11eV以下であり、LUMO値が1.2eV以下である化合物である、請求項1から5のいずれか1項に記載のリチウム2次電池。
- 前記負極は、表面に前記添加剤が電気的に還元されて形成された固体電解質界面膜が形成される、請求項1から6のいずれか1項に記載のリチウム2次電池。
- 前記リチウムマンガン系正極活物質は、下記の化学式5、化学式6、化学式7、化学式8で表される化合物、またはこれらの組み合わせである、請求項1から7のいずれか1項に記載のリチウム2次電池。
[化学式5]
LiaMn1−bMbO2−cGc
[化学式6]
LiaMn2−bMbO4−cGc
(前記化学式5及び6で、0.90≦a≦1.1、0≦b≦0.5、0≦c≦0.05であり、MはAl、Ni、Co、Mn、Cr、Fe、Mg、Sr、希土類元素、またはこれらの組み合わせから選択され、GはO、F、S、P、またはこれらの組み合わせから選択される。)
[化学式7]
LixMO2−ZLZ
(前記化学式7で、MはM’1−kAk(M’はNi1−d−eMndCoe、0.65≦d+e≦0.85、0.1≦e≦0.4、AはドーパントであってB、Ca、Zr、S、F、P、Bi、Al、Mg、Zn、Sr、Cu、Fe、Ga、In、Cr、Ge、またはSnから選択される一つの元素、0≦k<0.05である)であり、LはF、S、P、またはこれらの組み合わせから選択され、0.95≦x≦1.05であり、0≦Z≦2である。)
[化学式8]
LifMn1−gMgPO4
(前記化学式8で、0.90≦f≦1.8、0≦g≦0.5であり、MはAl、Ni、Co、Mn、Cr、Fe、Mg、Sr、希土類元素、またはこれらの組み合わせから選択される。)
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- 2010-09-01 EP EP10174945.5A patent/EP2320510B1/en active Active
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US20110111289A1 (en) | 2011-05-12 |
KR101147240B1 (ko) | 2012-05-21 |
CN102055015A (zh) | 2011-05-11 |
KR20110051618A (ko) | 2011-05-18 |
JP2011103290A (ja) | 2011-05-26 |
CN102055015B (zh) | 2014-12-24 |
EP2320510B1 (en) | 2018-11-07 |
US9054375B2 (en) | 2015-06-09 |
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