JP2012509565A - 電池特性が改良されたリチウム二次電池 - Google Patents
電池特性が改良されたリチウム二次電池 Download PDFInfo
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- JP2012509565A JP2012509565A JP2011537366A JP2011537366A JP2012509565A JP 2012509565 A JP2012509565 A JP 2012509565A JP 2011537366 A JP2011537366 A JP 2011537366A JP 2011537366 A JP2011537366 A JP 2011537366A JP 2012509565 A JP2012509565 A JP 2012509565A
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- Prior art keywords
- additive
- secondary battery
- active material
- lithium
- electrolyte
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 239000000654 additive Substances 0.000 claims abstract description 76
- 230000000996 additive effect Effects 0.000 claims abstract description 71
- 239000006182 cathode active material Substances 0.000 claims abstract description 49
- 239000003792 electrolyte Substances 0.000 claims abstract description 47
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 239000006183 anode active material Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000011253 protective coating Substances 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- -1 cyclic carbonate compound Chemical class 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 17
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000037048 polymerization activity Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 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
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910003849 O-Si Inorganic materials 0.000 claims description 2
- 229910003872 O—Si Inorganic materials 0.000 claims description 2
- AVTOEKKTKXLWDL-UHFFFAOYSA-N acetylene;1,3-dioxolan-2-one Chemical compound C#C.O=C1OCCO1 AVTOEKKTKXLWDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 230000000415 inactivating effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 48
- 229910052759 nickel Inorganic materials 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002000 Electrolyte additive Substances 0.000 description 13
- 239000011149 active material Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910014689 LiMnO Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical class [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GINSRDSEEGBTJO-UHFFFAOYSA-N thietane 1-oxide Chemical compound O=S1CCC1 GINSRDSEEGBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910012431 LiNi0.53Co0.2Mn0.27O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910014211 My O Inorganic materials 0.000 description 1
- ZHGDJTMNXSOQDT-UHFFFAOYSA-N NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O Chemical compound NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O.NP(N)(N)=O ZHGDJTMNXSOQDT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QDDVNKWVBSLTMB-UHFFFAOYSA-N [Cu]=O.[Li] Chemical compound [Cu]=O.[Li] QDDVNKWVBSLTMB-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PWRLWCQANJNXOR-UHFFFAOYSA-N dilithium chloro(dioxido)borane Chemical compound [Li+].[Li+].[O-]B([O-])Cl PWRLWCQANJNXOR-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
- 150000002019 disulfides Chemical class 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- BLBBMBKUUHYSMI-UHFFFAOYSA-N furan-2,3,4,5-tetrol Chemical compound OC=1OC(O)=C(O)C=1O BLBBMBKUUHYSMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
カソード活性材料の総量に対して20〜100重量%の、下記式1:
Li1+zNibMncMe1−(b+c)O2 (1)
により表されるリチウム遷移金属酸化物、ならびにリチウム塩及び非水性溶剤からなる電解質を含んでなるリチウム二次電池であって、アノード活性材料の表面上に保護被膜(すなわち、固体電解質界面被膜、SEI被膜)を形成するための第一添加剤、及びアノード活性材料の表面上に別のSEI被膜を形成するための第二添加剤が、カソード活性材料中に含まれる不純物を不活性化しながら、該電解質中に包含されている、リチウム二次電池を開示する。
Description
により表され、式中、-0.5=z=0.5、0.3=b=0.9、0.1=c=0.8、b+c<1であり、Meは、Co、Al、Mg、Ti、Sr、Zn、B、Ca、Si、Ga、Sn、P、V、Sb、Nb、Ta、Mo、W、Zr、Y及びFeからなる群から選択された少なくとも一種の元素であるリチウム遷移金属酸化物、及びリチウム塩及び非水性溶剤からなる電解質を含んでなるリチウム二次電池であって、アノード活性材料の表面上に保護被膜を形成するための第一添加剤、及び該アノード活性材料の該表面上に別の保護被膜を形成するための第二添加剤が該電解質中に包含され、該カソード活性材料中に含まれる不純物を不活性化している、リチウム二次電池を提供する。
R1−Si(R2)(R3)−[O−Si(R4)(R5)n−R6] (2)
により表される化合物でよく、式中、nは0〜3であり、R1、R2、R3、R4、R5及びR6は、独立して、水素またはC1−10炭化水素であり、それらの少なくとも一個は不飽和化された結合を有することができる。
Li1+zNibMncMe1−(b+c)O2 (1)
により表され、ニッケルのモル画分は30%以上であり、活性材料は、Mn及び他の所望の金属元素(Me)を含む。上記のカソード活性材料は、リチウムコバルト酸化物より高い容量及びリチウムニッケル酸化物(LiNiO2)より優れた構造的安定性を有する。
1-1.電解質の調製
式2(n=1)により表され、電解質添加剤として1.5重量%VC、メチル置換基(R2、R3、R4、R5)及び2個のエチレン基(R1、R6)を包含するシロキサン誘導体0.5重量%を、EC:EMC(体積比1:2)中にLiPF6を含んでなる電解質1.0Mに加え、リチウム二次電池用の電解質を調製した。
合成グラファイト、SBR系結合剤、及び増粘剤を98:1:1の比で混合し、水性スラリーを調製した後、このスラリーを銅ホイル集電装置の上に塗布し、アノードを形成した。
カソード活性材料の総重量に対して33重量%のLiNi0.53Co0.2Mn0.27O2及び77重量%のLiCoO2を混合し、カソード活性材料を調製した。活性材料、導電性材料及び結合剤を96:2:2の比で混合し、スラリーを調製した。次いで、このスラリーをアルミニウムホイル集電装置上に塗布し、続いてこれをいずれかの従来方法により乾燥させ、カソードを形成した。
形成されたアノード及びカソードを所望のサイズを有する直方体「523443」に成形し、上記工程1-1で調製した電解質をこの直方体の中に注ぎ込み、リチウム二次電池を製造した。製造した電池を850mAで4.2Vに充電し、再度4.2Vから、電流が50mAの終末(termination)電流に到達するまで、全充電した。その後、電池を930mAで3Vの終末電圧に放電した。この初期充電−放電の後、電池を、850mAで上限電圧4.2Vに充電し、電池を終末電圧3Vに放電する充電−放電サイクルを5回繰り返した。第五充電サイクルの後、電池を90℃で4時間保存し、次いで、同じ条件下で放電させた。電池の容量を測定した。
式2により表され、複数のメチル置換基及び2個のエチレン基を有するシロキサン誘導体の代わりに、式2により表され、複数のメチル置換基及び1個のエチレン基を有するシロキサン誘導体0.5重量%を電解質添加剤として加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
式2により表され、複数のメチル置換基及び2個のエチレン基を有するシロキサン誘導体の代わりに、式2により表され、複数のメチル置換基及び2個のエチレン基を有し、メチル置換基の少なくとも一個が水素で置換されているシロキサン誘導体0.5重量%を電解質添加剤として加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
電解質添加剤としてVCを、1.5重量%ではなく、0.5重量%の量で加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
カソード活性材料としてLiNi0.8Co0.1Mn0.1O2を使用し、カソードを調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
カソード活性材料としてLiNi1/3Co1/3Mn1/3O2を使用し、カソードを調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
電解質添加剤を添加しなかった以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
電解質添加剤としてVC1.5重量%だけを加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
電解質添加剤として、式2により表され、複数のメチル置換基及び2個のエチレン基を有するシロキサン誘導体0.5重量%だけを加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
カソード活性材料としてLiCoO2を使用し、カソードを調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
カソード活性材料としてLiNiO2を使用し、カソードを調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
電解質添加剤として、1.5重量%VECだけを加え、電解質を調製した以外は、例1に記載するのと同じ手順により、リチウム二次電池を製造した。
上記の例及び比較例で製造したバッテリー電池に対して、400充電−放電サイクル中の厚さの変動及び各電池の充電状態における容量を測定し、測定結果を下記の表1に示す。
上記の例及び比較例で製造した電池のそれぞれを60℃で4週間保存した後、電池容量を測定し、測定した容量と初期容量の比を下記の表1に示す。
Claims (17)
- リチウム二次電池であって、
カソード活性材料の総量に対して、20〜100重量%の、下記の式1により表された、リチウム遷移金属酸化物と、及び
Li1+zNibMncMe1−(b+c)O2 (1)
[上記式中、
-0.5=z=0.5、
0.3=b=0.9、
0.1=c=0.8、
b+c<1であり、
Meが、Co、Al、Mg、Ti、Sr、Zn、B、Ca、Si、Ga、Sn、P、V、Sb、Nb、Ta、Mo、W、Zr、Y及びFeからなる群から選択された少なくとも一種の元素である。]
リチウム塩及び非水性溶剤からなる電解質とを含んでなり、
アノード活性材料の表面上に保護被膜(即ち、固体電解質界面被膜、SEI被膜)を形成するための第一添加剤、及び前記アノード活性材料の前記表面上に別の保護被膜を形成するための第二添加剤が前記電解質中に包含されてなり、前記カソード活性材料中に含まれる不純物を不活性化している、リチウム二次電池。 - 前記第一添加剤が、初期充電−放電工程における重合によりアノード活性材料の表面上に保護被膜を形成する添加剤であり、
前記第二添加剤が、前記初期充電−放電工程後のさらなる充電−放電中における重合により、前記アノード活性材料の前記保護被膜を補足する別の添加剤である、請求項1に記載の二次電池。 - 前記第一添加剤が、前記二次電池の初期充電−放電電位で、前記第二添加剤の重合活性より高い重合活性を有してなり、
前記第二添加剤が、前記初期充電−放電電位以外の充電−放電電位で、前記第一添加剤の分解耐性より優れた分解耐性を有してなるものである、請求項2に記載の二次電池。 - 前記二次電池の前記充電−放電電位が2.5〜4.5Vである、請求項2に記載の二次電池。
- 前記第一添加剤が、不飽和化された基を有する環状カーボネート化合物である、請求項1に記載の二次電池。
- 前記環状カーボネート化合物が、ビニレンカーボネート(VC)またはビニレンエチレンカーボネート(VEC)である、請求項5に記載の二次電池。
- 前記第二添加剤が、少なくとも一個のSi-O-Si結合、又は炭素-炭素二重結合を有する材料、又は不純物と水の反応により少なくとも一個のSi-O-Si結合及び少なくとも一個の炭素-炭素二重結合の両方を有する材料である、請求項1に記載の二次電池。
- 前記第二添加剤が、少なくとも二個の炭素-炭素二重結合を含む、請求項7に記載の二次電池。
- 前記第二添加剤が、炭素-炭素二重結合を有する官能基及びδ−分極及びδ+分極をそれぞれ示すシロキサンを含んでなり、
前記材料が、対向する分極を示す不純物と組み合わされ、前記不純物を不活性化する、請求項7に記載の二次電池。 - 前記第二添加剤が、下記の式2により表される、請求項1に記載の二次電池。
R1−Si(R2)(R3)−[O−Si(R4)(R5)n−R6] (2)
[上記式中、
nが0〜3であり、
R1、R2、R3、R4、R5及びR6が、独立して、水素またはC1−10炭化水素であり、
前記炭化水素の少なくとも一個が不飽和化された結合を有する。] - 前記第一添加剤及び第二添加剤のそれぞれが、前記電解質の総重量に対して0.01〜10重量%の量で添加されてなる、請求項1に記載の二次電池。
- 前記第一添加剤が、前記初期充電−放電中に完全に消費される所望の量で添加されてなる、請求項11に記載の二次電池。
- 前記不純物が、NiO、Li2CO3、LiOH及びLi2Oからなる群から選択されてなる、請求項1に記載の二次電池。
- 前記式(1)中、MeがCoであり、
前記遷移金属中にあるNiのモル画分が、前記式(1)により表されるリチウム遷移金属酸化物中で40〜70%である、請求項1に記載の二次電池。 - 前記カソード活性材料が、前記式(1)により表されるリチウム遷移金属酸化物を、前記カソード活性材料の総重量に対して20〜80重量%の量で含んでなる、請求項1に記載の二次電池。
- 前記非水性溶剤が、直鎖状カーボネートと環状カーボネートの混合物である、請求項1に記載の二次電池。
- 前記カソード活性材料の総重量に対して30〜80重量%の、前記式(1)により表されるリチウム遷移金属酸化物以外のLiCoO2をさらに包含する、請求項1に記載の二次電池。
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Application Number | Priority Date | Filing Date | Title |
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KR10-2008-0115442 | 2008-11-20 | ||
KR1020080115443A KR101141056B1 (ko) | 2008-11-20 | 2008-11-20 | 전지특성이 향상된 리튬 이차전지 |
KR1020080115442A KR101152639B1 (ko) | 2008-11-20 | 2008-11-20 | 안전성이 향상된 리튬 이차전지 |
KR10-2008-0115443 | 2008-11-20 | ||
KR1020090054103A KR101459402B1 (ko) | 2009-06-17 | 2009-06-17 | 안전성이 향상된 이차전지용 전해액 및 이를 포함하는 리튬 이차전지 |
KR10-2009-0054103 | 2009-06-17 | ||
PCT/KR2009/006850 WO2010058993A2 (ko) | 2008-11-20 | 2009-11-20 | 전지특성이 향상된 리튬 이차전지 |
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CN102224621A (zh) | 2011-10-19 |
US8026008B2 (en) | 2011-09-27 |
JP5588995B2 (ja) | 2014-09-10 |
US20100297510A1 (en) | 2010-11-25 |
WO2010058993A3 (ko) | 2010-08-12 |
EP2357692B1 (en) | 2014-09-24 |
CN102224621B (zh) | 2014-04-02 |
EP2357692A2 (en) | 2011-08-17 |
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WO2010058993A2 (ko) | 2010-05-27 |
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