CN105637692B - 包括硅基化合物的二次电池 - Google Patents
包括硅基化合物的二次电池 Download PDFInfo
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- CN105637692B CN105637692B CN201480054576.4A CN201480054576A CN105637692B CN 105637692 B CN105637692 B CN 105637692B CN 201480054576 A CN201480054576 A CN 201480054576A CN 105637692 B CN105637692 B CN 105637692B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 27
- 239000010703 silicon Substances 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 23
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229910003978 SiClx Inorganic materials 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- -1 alkoxy silane Chemical compound 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000006233 lamp black Substances 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical compound O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910018039 Cu2V2O7 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 229910006570 Li1+xMn2-xO4 Inorganic materials 0.000 description 1
- 229910006628 Li1+xMn2−xO4 Inorganic materials 0.000 description 1
- 229910010228 Li2Mn3MO8 Inorganic materials 0.000 description 1
- 229910003253 LiB10Cl10 Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014172 LiMn2-xMxO2 Inorganic materials 0.000 description 1
- 229910014774 LiMn2O3 Inorganic materials 0.000 description 1
- 229910014437 LiMn2−XMXO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- 229910014114 LiNi1-xMxO2 Inorganic materials 0.000 description 1
- 229910014907 LiNi1−xMxO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013649 LiNixMn2-xO4 Inorganic materials 0.000 description 1
- 229910013663 LiNixMn2—xO4 Inorganic materials 0.000 description 1
- 229910012967 LiV3O4 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006145 SO3Li Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- SZPSEPZTPITHRZ-UHFFFAOYSA-N [S].CC=C Chemical compound [S].CC=C SZPSEPZTPITHRZ-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 238000010276 construction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- BHVTUPMWGCXDPW-UHFFFAOYSA-N lithium;phenoxyboronic acid Chemical compound [Li].OB(O)OC1=CC=CC=C1 BHVTUPMWGCXDPW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011701 zinc Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
本发明公开了一种二次电池,所述二次电池包含:正极,所述正极包含涂布有包含正极活性材料的正极混合物的集电器;负极,所述负极包含涂布有包含负极活性材料的负极混合物的集电器;以及电解液,所述电解液包含锂盐和非水溶剂,其中所述负极包含碳基材料和硅基化合物,且所述非水溶剂包含环状碳酸酯和/或线性溶剂。所述二次电池展示优异的寿命特性和安全性。
Description
技术领域
本发明涉及一种通过包括硅基化合物而具有增强的寿命特性和安全性的二次电池。
背景技术
随着移动装置技术的持续发展和对其需求的持续增长,对作为电源的二次电池的需求急剧增加。在这些二次电池中,展示高的能量密度和电压、长的寿命和低自放电速率的锂二次电池可商购获得并被广泛应用。
在现有锂二次电池中,具有层状结构的锂钴复合氧化物通常用于正极中,且石墨基材料通常用于负极中。然而,钴,作为锂钴复合氧化物的成分非常昂贵,且锂钴复合氧化物在电动车辆方面的用途因其不合格的安全性而不适合。另外,锂钴复合氧化物在随能量密度的增加而展示高容量方面存在难度。
因此,作为正极活性材料,使用具有层状晶体结构的含锂的锰氧化物如LiMnO2、具有尖晶石晶体结构等的LiMn2O4以及含锂的镍氧化物如LiNiO2也在考虑之中。另外,作为负极活性材料,主要使用碳基材料,且近来,相对于碳基材料具有10倍以上有效容量的SiO的混合物因高容量二次电池需求的增加而在考虑之中。
然而,锂二次电池具有多种问题。例如,某些锂二次电池具有与在负极的制造和运行中的特性相关的问题。
例如,在碳基负极活性材料的初始充电和放电过程(活化过程)中,在负极活性材料的表面上形成固体电解质界面(SEI)层,因此诱发初始不可逆性。另外,SEI层在连续的充电和放电过程中坍塌,且电解液在再生过程中耗尽,由此电池容量下降。
另外,当将碳基材料和SiO混合时,与碳基材料相比,随SEI层的形成而引发的问题因SiO造成更大的电极膨胀而随增多的循环次数变得更糟。
为了解决这种问题,尝试形成具有强得多的结合力的SEI层以在负极活性材料等的表面上形成氧化物层等。然而,这种SEI层由于因氧化物层造成的电导率下降、因附加工艺而造成的产率下降等而不会展示可商用的特性。
另外,可以将添加剂添加到电解液。然而,常规使用的电解液添加剂的主要目的是防止在充电和放电期间产生副产物。
因此,迫切需要从根本上解决这种问题的技术。
发明内容
技术问题
因此,为了解决上述和尚未解决的其他技术问题而完成了本发明。
作为多种细致且广泛研究和实验的结果,本发明的发明人确认,在制备包括下述的负极活性材料和电解液的二次电池时,电池的寿命特性和安全性增强并由此能够实现期望效果,从而完成本发明,所述负极活性材料包括硅基化合物,且所述电解液包含预定的碳酸酯。
技术方案
根据本发明的一个方面,提供一种包括如下的二次电池:正极,所述正极包含涂布有包含正极活性材料的正极混合物的集电器;负极,所述负极包含涂布有包含负极活性材料的负极混合物的集电器;以及电解液,所述电解液包含锂盐和非水溶剂,其中所述负极包含碳基材料和硅基化合物,且所述非水溶剂包含环状碳酸酯和/或线性溶剂。
当将碳基材料与SiO混合以增强二次电池的容量时,如上所述,与碳基材料相比,由于SiO造成更大的电极膨胀,随SEI层形成造成的问题随更多的循环次数而劣化。
因此,根据本发明的二次电池包括包含预定碳酸酯的电解质,由此,能够解决SEI层的形成所造成的问题,由此能够确保安全性并可以增强二次电池的寿命特性和容量特性,所述SEI层的形成因使用碳基材料和硅基化合物作为负极活性材料而造成。
在本发明中,所述碳基材料可以为例如:石墨如天然或人造石墨;炭黑类材料如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑或热裂法炭黑;或碳纤维。这些材料可以单独使用,或作为其两种以上的混合物使用。所述碳基材料可以特别地为石墨。
所述硅基化合物可以为选自如下物质中的一种或多种物质:氯硅烷、烷氧基硅烷、氨基硅烷、氟烷基硅烷、硅、氯化硅和氧化硅(SiO)。更特别地,所述硅基化合物可以为氧化硅(SiO)。所述氧化硅(SiO)可以包括以1:1的重量比混合的二氧化硅(SiO2)和无定形硅。
当硅(Si)基化合物的量太小时,难以提高能量密度,由此难以获得高容量电池。当硅(Si)基化合物的量太高时,负极的体积膨胀会不期望地增大。因此,碳基材料和硅(Si)基化合物可以以80:20~99:1、尤其90:10~99:1、更特别地95:5~97:3、最特别地95:5或97:3的重量比混合。
所述环状碳酸酯没有具体限制,只要是本领域内已知的即可且可以为选自例如如下物质中的一种或多种物质:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和碳酸亚丁酯(BC)。
所述线性溶剂包括线性碳酸酯和线性酯,且可以为选自例如如下物质中的一种或多种:碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、丙酸甲酯(MP)和丙酸乙酯(EP)。
所述环状碳酸酯和线性溶剂可以以1:0.5~1:8、特别地1:1~1:3的体积比混合。
为了提高寿命特性,电解液可以还包含碳酸亚乙烯酯(VC)和氟代碳酸亚乙酯(FEC)。
此处,基于电解质的总重量,碳酸亚乙烯酯(VC)的含量可以为大于0.5重量%且5重量%以下,且基于电解质的总重量,氟代碳酸亚乙酯(FEC)的含量可以为大于1重量%且10重量%以下。特别地,基于电解质的总重量,碳酸亚乙烯酯(VC)的含量可以为大于1.0重量%且4.0重量%以下,且基于电解质的总重量,氟代碳酸亚乙酯(FEC)的含量可以为2重量%以上且7重量%以下。更特别地,基于电解质的总重量,碳酸亚乙烯酯(VC)的含量可以为1.5重量%以上且3重量%以下,且基于电解质的总重量,氟代碳酸亚乙酯(FEC)的含量可以为2重量%以上且5重量%以下。
当作为添加剂的碳酸亚乙烯酯(VC)基于电解质总重量的含量为0.5重量%以下,或作为添加剂的氟代碳酸亚乙酯(FEC)基于电解质的总重量的含量为1重量%以下时,包含在二次电池中的涂布了氧化硅的负极的体积膨胀会不期望地增大。当碳酸亚乙烯酯(VC)的含量大于5重量%或氟代碳酸亚乙酯(FEC)的含量大于10重量%时,包含所述材料的电池的寿命特性会不期望地缩短。
所述二次电池可以为锂二次电池。
下文中,将对这种锂二次电池的构造进行详细说明。
锂二次电池包含:正极,所述正极通过如下制得:将如下正极活性材料、导电材料和粘合剂的混合物涂布在正极集电器,并对涂布的正极集电器进行干燥和压制;和负极,所述负极使用与用于制造正极相同的方法制得。在此情况中,所述混合物可以根据期望还包含填料。
通常将正极集电器制成3~500μm的厚度。正极集电器没有特别限制,只要其在制造的锂二次电池中不会造成化学变化并具有高电导率即可。例如,正极集电器可以由如下物质制成:不锈钢;铝;镍;钛;烧结碳;经碳、镍、钛或银进行表面处理的铝或不锈钢;或类似物。所述正极集电器在其表面可以具有细小的不规则处,从而提高正极活性材料与正极集电器之间的粘附力。另外,可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的多种形式中的任意形式使用所述正极集电器。
所述锂二次电池可以包括如下物质作为正极活性材料:锂镍氧化物(LiNiO2;锂锰氧化物如式Li1+xMn2-xO4(其中0≤x≤0.33)的化合物、LiMnO3、LiMn2O3和LiMnO2;锂铜氧化物(Li2CuO2);钒氧化物如LiV3O8、LiV3O4、V2O5和Cu2V2O7;式LiNi1-xMxO2的Ni位点型锂镍氧化物,其中M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,且0.01≤x≤0.3;式LiMn2-xMxO2的锂锰复合氧化物,其中M=Co、Ni、Fe、Cr、Zn或Ta,且0.01≤x≤0.1),或式Li2Mn3MO8的锂锰复合氧化物,其中M=Fe、Co、Ni、Cu或Zn;式LiNixMn2-xO4的尖晶石结构的锂锰复合氧化物,其中x=0.01~0.6;其中一部分Li原子被碱土金属离子置换的LiMn2O4;二硫化物化合物;Fe2(MoO4)3等。
相对于包含正极活性材料的混合物的总重量,通常以1~50重量%的量添加导电材料。对这种导电材料没有特别限制,只要其在制造的电池中不会造成化学变化并具有电导率即可。例如,可以使用如下物质:石墨如天然石墨或人造石墨;炭黑类材料如炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑;导电纤维如碳纤维和金属纤维;金属粉末如氟化碳粉末、铝粉末和镍粉末;导电晶须如氧化锌晶须和钛酸钾晶须;导电金属氧化物如二氧化钛;导电材料如聚亚苯基衍生物等。
粘合剂是有助于活性材料与导电材料之间的结合并有助于活性材料对集电器的结合的组分。基于包含正极活性材料的混合物的总重量,典型地以1~50重量%的量添加所述粘合剂。粘合剂的实例包括但不限于聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯基吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元共聚物(EPDM)、磺化的EPDM、丁苯橡胶、氟橡胶和各种共聚物。
填料任选地用作用于抑制正极膨胀的组分。填料没有特别限制,只要其为在制造的电池中不会造成化学变化的纤维材料即可。填料的实例包括:烯烃类聚合物如聚乙烯和聚丙烯;以及纤维材料如玻璃纤维和碳纤维。
典型地将负极集电器制成3~500μm的厚度。所述负极集电器没有特别限制,只要其在制造的电池中不会造成化学变化并具有导电性即可。例如,负极集电器可以由如下物质制成:铜;不锈钢;铝;镍;钛;烧结碳;经碳、镍、钛或银进行表面处理的铜或不锈钢;以及铝-镉合金。与正极集电器类似,负极集电器还可在其表面上具有细小的不规则处,从而提高负极集电器与负极活性材料之间的粘附力,并可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的多种形式使用。
所述锂二次电池可具有其中包含正极、负极以及设置在所述正极与所述负极之间的隔膜的电极组件浸渍于含锂盐的电解质的结构。
将隔膜设置在所述正极与负极之间,作为隔膜,使用具有高离子透过性和高机械强度的薄绝缘膜。所述隔膜通常具有0.01~10μm的孔径和5~300μm的厚度。作为隔膜,例如,使用由烯烃类聚合物如聚丙烯或玻璃纤维或聚乙烯制成的片或无纺布,其具有耐化学性和疏水性。当使用诸如聚合物等的固体电解质作为电解质时,所述固体电解质还可充当隔膜。
所述含锂盐的电解液由非水溶剂和锂盐构成。所述锂盐是易溶于非水电解质中的材料,其实例包括但不限于LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和亚氨基锂。
另外,为了提高充/放电特性和阻燃性,例如,可以向电解质中添加吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六甲基磷酰三胺、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等。如果需要,为了赋予不燃性,所述电解质可还包含含卤素的溶剂如四氯化碳和三氟乙烯。此外,为了提高高温储存特性,所述非水电解质可还包含二氧化碳气体和丙烯磺酸内酯(PRS)等。
在一个优选实施方案中,通过将锂盐如LiPF6、LiClO4、LiBF4、LiN(SO2CF3)2等添加到高介电溶剂可以制备含锂盐的非水电解质。
可以将包含上述至少一种锂二次电池的电池组用作要求高温稳定性、长循环寿命和高倍率特性的装置用电源。
所述装置的实例包括但不限于:大型装置如电动车辆(EV)、混合电动车辆(HEV)和插电式混合电动车辆(PHEV);和小型装置如移动电话、笔记本电脑、上网本、平板PC、PDA、数字照相机、便携式导航仪、便携式游戏控制台。
附图说明
图1显示了根据本发明实验例1的结果;且
图2显示了根据本发明实验例2的结果。
具体实施方式
<实施例1>
以97:0.5:2.5的重量比将作为负极活性材料的以97:3的重量比混合的石墨和氧化硅(SiO)、作为导电材料的超导电乙炔炭黑(Denka black)和水基粘合剂(SBR/CMC)添加到蒸馏水,随后混合。由此,制备了负极混合物。将制备的负极混合物涂布在铜箔上,随后压延并干燥。由此制造了负极。
另外,以96.5:2.0:1.5的重量比将作为正极活性材料的LiCoO2、作为导电材料的超导电乙炔炭黑和作为粘合剂的PVdF添加到NMP,随后混合。由此,制备了正极混合物。将制备的正极混合物涂布在铝箔上,随后压延并干燥。由此制造了正极。
将作为隔膜的聚乙烯层设置在制备的负极与正极之间,并使用电解液和电解液用添加剂,所述电解液包含由以3:2:5的体积比混合的EC、EMC和DEC构成的溶剂以及包含在其中的1M的LiPF6,且基于电解质的总重量,所述电解液用添加剂为1.5重量%的VC和5重量%的FEC。由此制造了二次电池。
<实施例2>
除了将2重量%的VC和5重量%的FEC用作电解液添加剂之外,以与实施例1相同的方式制造了二次电池。
<比较例1>
除了将0.5重量%的VC和5重量%的FEC用作电解液添加剂之外,以与实施例1相同的方式制造了二次电池。
<实施例3>
除了使用如下电解液和电解液用添加剂之外,以与实施例1相同的方式制造了二次电池:所述电解液包含由以4:1:5的体积比混合的EC、EP和DEC构成的溶剂以及包含在其中的1M的LiPF6,且基于电解质的总重量,所述电解液用添加剂为2重量%的VC和5重量%的FEC。
<比较例2>
除了将2重量%的VC和1重量%的FEC用作电解液添加剂之外,以与实施例1相同的方式制造了二次电池。
<实验例1>
在1C/1C下在2.7~4.35V的范围内对根据实施例1和2以及比较例1制造的二次电池进行充电和放电,以测量电池充电和放电容量以及厚度的变化。将结果总结于下表1中。
下面参考图1,随着充电和放电的重复进行,实施例1和2的电池的容量下降率比比较例1的电池的更小。
另外,关于由于重复充电和放电造成的溶胀而引发的电池厚度增大率,能够确认,实施例1和2的电池的厚度增大率比比较例1的电池的更小。
<实验例2>
在1C/1C下在2.7~4.35V的范围内对根据实施例3以及比较例2制造的二次电池进行充电和放电,以测量充电和放电容量随重复充电和放电循环的变化。将结果总结于图2中。
参考图2,能够确认,与比较例2的电池相比,随着充电和放电循环的增加,实施例3的电池展示更小的容量下降率。
本领域技术人员可以以上述内容为基础,在本发明的范围内进行各种应用和变化。
工业应用性
如上所述,由于根据本发明的二次电池包含碳基材料和预定的硅基化合物作为负极活性材料,所以容量大大升高,由此展示优异的寿命特性。另外,通过使用包含预定碳酸酯的电解液,能够防止负极的体积膨胀。
Claims (6)
1.一种二次电池,包含:
正极,所述正极包含涂布有正极混合物的集电器,所述正极混合物包含正极活性材料;
负极,所述负极包含涂布有负极混合物的集电器,所述负极混合物包含负极活性材料;以及
电解液,所述电解液由锂盐和非水溶剂构成,
其中所述正极活性材料是LiCoO2,
所述负极包含重量比为90:10~99:1的碳基材料和硅基化合物,所述硅基化合物为氧化硅(SiO),
所述非水溶剂由环状碳酸酯、线性溶剂、碳酸亚乙烯酯(VC)和氟代碳酸亚乙酯(FEC)构成,
所述环状碳酸酯和所述线性溶剂以1:1~1:3的体积比混合,
所述线性溶剂由线性碳酸酯和线性酯构成,
所述环状碳酸酯为选自如下物质中的一种或多种:碳酸亚乙酯(EC)、碳酸亚丙酯(PC)和碳酸亚丁酯(BC),
所述线性碳酸酯为选自如下物质中的一种或多种:碳酸二甲酯(DMC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC),
所述线性酯为选自如下物质中的一种或多种:丙酸甲酯(MP)和丙酸乙酯(EP),
基于所述电解液的总重量,所述碳酸亚乙烯酯(VC)的含量为1.5重量%以上且4重量%以下,且
基于所述电解液的总重量,所述氟代碳酸亚乙酯(FEC)的含量为2重量%以上且7重量%以下。
2.根据权利要求1所述的二次电池,其中所述碳基材料为石墨。
3.根据权利要求1所述的二次电池,其中所述氧化硅(SiO)包括以1:1的重量比混合的二氧化硅(SiO2)和无定形硅。
4.根据权利要求1所述的二次电池,其中基于所述电解液的总重量,所述碳酸亚乙烯酯(VC)的含量为1.0重量%以上且4.0重量%以下,且基于所述电解液的总重量,所述氟代碳酸亚乙酯(FEC)的含量为2重量%以上且7重量%以下。
5.根据权利要求1所述的二次电池,其中所述二次电池是锂二次电池。
6.一种包含至少一种根据权利要求1所述的二次电池的装置。
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JP6822181B2 (ja) * | 2017-02-02 | 2021-01-27 | 株式会社Gsユアサ | 非水電解質蓄電素子及びその製造方法 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JP2004119176A (ja) * | 2002-09-26 | 2004-04-15 | Toshiba Corp | 非水電解質二次電池用負極活物質及び非水電解質二次電池 |
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JP2010092830A (ja) * | 2008-09-11 | 2010-04-22 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
KR101293269B1 (ko) | 2010-01-15 | 2013-08-09 | 주식회사 엘지화학 | 과충전에 대한 안전성이 우수한 리튬 이차전지용 전해질 및 이를 포함하는 리튬 이차전지 |
KR101089246B1 (ko) | 2010-04-14 | 2011-12-05 | 한국과학기술연구원 | 자기조립된 절연층이 코팅된 음극활물질 및 이를 구비하는 이차전지 및 그 제조 방법 |
JP5031065B2 (ja) * | 2010-04-27 | 2012-09-19 | 日立マクセルエナジー株式会社 | リチウムイオン二次電池 |
JP5601058B2 (ja) * | 2010-07-07 | 2014-10-08 | ソニー株式会社 | 非水電解質電池および非水電解質 |
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WO2013047747A1 (ja) * | 2011-09-29 | 2013-04-04 | 日立マクセル株式会社 | リチウム二次電池 |
JP5845096B2 (ja) * | 2012-01-17 | 2016-01-20 | 日立マクセル株式会社 | リチウム二次電池 |
KR20130106687A (ko) | 2012-03-20 | 2013-09-30 | 삼성에스디아이 주식회사 | 음극 활물질 및 이를 포함하는 리튬 전지 |
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