CN106797027B - 非水电解质锂二次电池 - Google Patents
非水电解质锂二次电池 Download PDFInfo
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- CN106797027B CN106797027B CN201580005080.2A CN201580005080A CN106797027B CN 106797027 B CN106797027 B CN 106797027B CN 201580005080 A CN201580005080 A CN 201580005080A CN 106797027 B CN106797027 B CN 106797027B
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- Prior art keywords
- carbonate
- positive electrode
- lithium secondary
- secondary battery
- ltoreq
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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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 16
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 13
- 229910015024 LiaNixMnyCozO2 Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 21
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 20
- 229940017219 methyl propionate Drugs 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 15
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 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 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 6
- 229910003932 NixMnyCozO2 Inorganic materials 0.000 claims description 6
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 abstract description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000003792 electrolyte Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- -1 cyclic carbonate compound Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000009830 intercalation Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000009831 deintercalation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000011302 mesophase pitch Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 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
- 239000000571 coke Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910012711 LiCo1-yMnyO2 Inorganic materials 0.000 description 1
- 229910012955 LiCo1−yMnyO2 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014376 LiMn2-zCozO4 Inorganic materials 0.000 description 1
- 229910014370 LiMn2-zNizO4 Inorganic materials 0.000 description 1
- 229910014554 LiMn2−zCozO4 Inorganic materials 0.000 description 1
- 229910014552 LiMn2−zNizO4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910014167 LiNi1-YCOYO2 Inorganic materials 0.000 description 1
- 229910014380 LiNi1-yMnyO2 Inorganic materials 0.000 description 1
- 229910014940 LiNi1−yCoyO2 Inorganic materials 0.000 description 1
- 229910014946 LiNi1−yMnyO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910015385 Ni1-a-b(Ni1/2Mn1/2)aCob Inorganic materials 0.000 description 1
- 229910015270 Ni1−a−b(Ni1/2Mn1/2)aCob Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000007773 negative electrode material Substances 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 239000000837 restrainer Substances 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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
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- 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
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- H01—ELECTRIC ELEMENTS
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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Abstract
本发明公开了一种锂二次电池,所述锂二次电池包括正极、负极、隔膜和非水电解质,其中正极包括LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)作为正极活性材料,且其中非水电解质包括(i)氟化的环状碳酸酯,(ii)基于丙酸酯为基础的酯,和(iii)非卤化的碳酸酯,其中(i)和(ii)的混合重量比(i:ii)为20:80至50:50。
Description
技术领域
本公开内容涉及非水电解质锂二次电池,且更特别地,涉及使用高充电电压并具有改良的稳定性的锂二次电池。
本申请享有于2014年9月30日在韩国提出申请的韩国专利申请第10-2014-0131949号的优先权,所述优先权申请在此以全文引用方式纳入本文中。
背景技术
随着能量储存技术被广泛地施用于移动电话、摄像机、笔记型电脑和电动汽车,作为此种电子装置的电源的电池要求具有高能量密度。锂二次电池是一种最能够符合此要求的电池并且锂二次电池正在被积极地研究。
1990年代早期开发的锂二次电池是由能够实现嵌入(intercalating)和脱嵌(deintercalating)锂离子的基于碳基材料的负极、含锂的氧化物制成的正极、和含有适量的锂盐溶于混合有机溶剂中的非水电解质所构成。
锂二次电池的平均放电电压是约3.6至3.7V,这高于碱性电池、镍-镉电池或者其它类似电池。对于如此高的操作电压,需要有在0至4.2V的充电/放电范围内电化学稳定的电解质组合物。对此,环状碳酸酯化合物(例如碳酸亚乙酯和碳酸亚丙酯)和直链碳酸酯化合物(例如碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯)经适当混合的混合溶剂被用来作为电解质的溶剂。电解质的溶质通常使用锂盐,例如LiPF6、LiBF4、LiClO4或者其它锂盐,所述锂盐作为电池中的锂离子来源并因此而使得锂电池得以操作。
特别地,近年来,因为电子产品的轻、薄、短和小的设计以及能量消耗提高的趋势,用作此种电子装置能源的锂二次电池具有更大的容量。使用高容量活性材料、通过提高充电电压或更有效地利用内部空间而提高容量,可得到大容量的锂二次电池。但是,若使用目前关注的基于镍的三元系正极材料提高充电电压,则会在电解质处突然发生分解反应,所述反应会损害电池性能,例如寿命循环。受使用环境的影响,此现象会变得更糟,且若使用温度提高,电池性能的受损变得迅速提高。此外,电极密度会随着电池内部空间的最大化利用的趋势而逐渐提高,并且这要求电解质具有低粘度和高离子传导性。但是,具有此种特性的电解质通常对于氧化反应的稳定性欠佳。
发明内容
技术问题
本发明要解决的技术问题是,提供一种锂二次电池,其包括基于镍的三元系统正极材料以及在使用高充电电压下,可以确保提高稳定性。
技术方案
本发明提供一种锂二次电池,所述锂二次电池包括正极、负极、隔膜(separator)和非水电解质,其中正极包括LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)作为正极活性材料,且其中非水电解质包括(i)以下化学式1所示的氟化的环状碳酸酯,(ii)以下化学式2所示的基于丙酸酯的酯,和(iii)非卤化的碳酸酯,其中(i)和(ii)它们的混合重量比(i:ii)为20:80至50:50:
其中,化学式1中,R1、R2、R3和R4各自为F、H和甲基中的任一个,且其中的至少一个是F,
其中,化学式2中,R5是具有1至5个碳原子的烷基。
化学式2所示的基于丙酸酯的酯可使用丙酸甲酯、丙酸乙酯或丙酸丙酯,但并不仅限制于此。
此外,相对于正极活性材料总重量,作为正极活性材料的LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)含量可为50至100重量%。
此外,作为正极活性材料的LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)可为LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0<x,0<y,0<z),且正极可进一步包括LiCoO2。
此外,正极可具有0.01g/cm2至0.03g/cm2的载量。
相对于非水电解质总重量,非卤化的碳酸酯含量可为10重量%或更低。
非卤化的碳酸酯可为选自由以下所组成的组中的任一化合物:碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸伸丁酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲乙酯(EMC)、和它们的混合物,但并不仅限制于此。
此外,锂二次电池可具有4.3至5.0V的充电电压。
有益效果
本发明中的的锂二次电池可确保电解质的稳定性,即使在提高正极载量以实现高压电池系统时也是如此,由此得到极佳的电池循环特性。此外,可避免电池性能在高温储存时的衰退。
附图说明
图1为示出根据实例1至3和对照例1至4制备的电池寿命性能的评估结果的图。
图2为示出根据实例4和对照例5制备的电池寿命性能的评估结果的图。
具体实施方式
下文中,将对照附图地详细说明本发明的优选的具体实施方式。描述之前,应理解本说明书和权利要求书中所使用的术语或用语不可以被限制性地理解成一般定义或词典上的定义,而应当被理解为是基于发明人为了以最佳可能的方式描述发明可以适当地定义术语的概念的原则,将这些术语或用语理解为与本发明的技术构思相对应的含义和概念。如上所述,锂二次电池通常包括由能够嵌入和脱嵌锂离子的碳材料制成的负极、含锂的氧化物制成的正极、和非水电解质。
本发明的锂二次电池中,正极包括LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)作为正极活性材料,且非水电解质包括(i)以下化学式1所示的氟化的环状碳酸酯,(ii)以下化学式2所示的基于丙酸酯的酯,和(iii)非卤化的碳酸酯,其中(i)和(ii)它们的混合重量比(i:ii)为20:80至50:50:
[化学式1]
上述化学式1中,R1、R2、R3和R4独立地为F、H和甲基中之的任一个,且其中的至少一个是F,
[化学式2]
上述化学式2中,R5是具1至5个碳原子的烷基。
本发明中,正极包括LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)作为正极活性材料,且作为正极活性材料的LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)可为选自由以下所组成的组中的任一个:LiCoO2、LiNiO2、LiMnO2、LiMn2O4、LiNi1-yCoyO2(0<y<1)、LiCo1-yMnyO2(0<y<1)、LiNi1-yMnyO2(O≤y<1)、LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0<x,0<y,0<z)、或它们的混合物,但不仅限于此。
此外,在具体实施方式中,正极包括含Ni的三元系正极活性材料,所述材料以LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0<x,0<y,0<z)提供,且这是一种通过如锰、钴或其他过渡金属部分取代LiNiO2中的镍而得到的锂过渡金属氧化物,并且在循环特性和容量特性方面相对极佳。
与此同时,正极除了以LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0<x,0<y,0<z)提供的含Ni的三元系统正极活性材料以外,可进一步包括LiCoO2。
更详细地说,根据本发明的具体实施方式的正极活性材料包括LiCoO2和通过以下化学式3所示的含锂的过渡金属化合物,且具有化学式3所示的组成的含锂的过渡金属化合物使得锂离子在含锂的过渡金属氧化物层之间(“MO层”)嵌入或脱嵌。同样地,在锂离子嵌入和脱嵌层(“可逆的锂层”)中,源自于MO层的Ni离子被嵌入以使得MO层彼此偶合,且以Ni总量计,嵌入并偶合于可逆的锂层中的Ni离子可具有0.03至0.07的摩尔百分比。
[化学式3]
LixMyO2
化学式3中,M代表M'1-kAk,其中M'是Ni1-a-b(Ni1/2Mn1/2)aCob,0.65≤a+b≤0.85和0.1≤b≤0.4,且其中A代表掺杂物,0≤k<0.05,x+y≒2且0.95≤x≤1.05。
MO层中,Ni2+和Ni3+并存,其中一部分的Ni2+可嵌入可逆的锂层中。此处,由于嵌入可逆的锂层中的Ni2+可防止晶体结构在充电期间内因为MO层中的氧粒子之间的斥力而不稳定,所以晶体结构变得稳定。因此,不会发生氧分离所引发的额外的结构塌陷,即使在充电程序期间内发射出锂亦然,嵌入可逆的锂层中的Ni离子维持其自身氧化数,使得不再生成Ni2+,借此同时改良寿命特性和稳定性。
在化学式3的含锂的过渡金属化合物中,Ni1-a-b代表Ni3+含量。若Ni3+的摩尔百分比超过0.35(a+b<0.65),则无法通过使用Li2Co3作为来源在空气中实施大量生产,且在氧气氛下应使用LiOH作为来源。若使用LiOH作为锂来源,则由于LiOH比Li2Co3昂贵且不易操作,使得生产效率受损,导致生产成本提高。
相反,若Ni3+含量小于0.15(a+b>0.85),则每单位体积的LiMnO2容量就小并因此,相比于LiCoO2,无法具有竞争性。此外,在LiMnO2中,包括Ni2+和Ni3+的Ni的整体摩尔百分比可为0.4至0.7。若Ni含量低于0.4,则难以预期有高容量,而若Ni含量高于0.7,则稳定性会大幅受损。锰的摩尔百分比是0.05至0.4,且钴的摩尔百分比是0.1至0.4。
此外,若相对于Ni含量,Ni2+的摩尔百分比过高时,混合的阳离子量提高,由此局部形成无电化学反应的块盐结构(rock-salt structure),这会干扰充电和放电并因此而降低放电容量。同时,若Ni2+的摩尔百分比过低,则结构不稳定性上升,这会损害循环稳定性。因此,相对于Ni总量,Ni2+的摩尔百分比可为0.05至0.4。
此外,根据本公开内容的具体实施方式的正极可进一步包括选自由LiMn2-zNizO4(0<z<2)、LiMn2-zCozO4(0<z<2)、LiCoPO4、LiFePO4或它们的混合物所组成的组中的任一种作为正极活性材料,但不仅限于此。
相对于正极活性材料总重量,根据本发明公开的具体实施方式的正极可包括50至100重量%的LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)作为正极活性材料。
此外,在本发明公开的锂二次电池中,正极载量可为0.01g/cm2至0.03g/cm2,且特别地,为实现高压电池系统,正极载量可为0.02g/cm2至0.03g/cm2。
同时,作为正极活性材料的LiaNixMnyCozO2(a+x+y+z=2,0.9≤a≤1.1,0≤x,0≤y,0≤z)具有相对高的电阻,因此若在使用中提高密度,则不易确保足够的容量,且在高压系统中增进了电解质的分解反应。因此,使用适当的电解质特别重要。
本发明的非水电解质包括化学式1所示的氟化的环状碳酸酯、化学式2所示的基于丙酸酯的酯、和非卤化的碳酸酯。
氟化的环状碳酸酯可抑制溶剂在负极中的分解反应。在锂二次电池的初始充电期间内,锂离子与电解质的碳以及负极活性材料在如石墨等的负极活性材料表面上反应以生成如Li2CO3、Li2O、LiOH或类似的化合物,借此在负极活性材料表面上形成SEI(SolidElectrolyte Interface,固体电解质界面)膜。所述SEI膜起到仅让锂离子通过离子通道的作用,由此防止电解质与负极活性材料接触并因此防止电解质的分解反应。但是,若电池以完全充电状态单独停留于高温,则随着时间的流逝,SEI膜因为提高的电化学能量和热能而缓慢塌陷,借此持续引发负极的外露表面与周围的电解质反应的副反应。但是,SEI膜为改变电池性能的主要因素之一(所述改变通过影响离子和电荷的移动进行),且已经知道SEI膜的性质取决于作为电解质的溶剂的种类和添加剂的特性而剧烈变化。但是,本发明公开的氟化的环状碳酸酯降低了SEI膜的塌陷,并由此可抑制溶剂在负极中的分解反应。通过在负极处的还原反应和分解反应而形成的SEI膜具有相对薄且致密的设计,所述设计可改良电池的性能,特别是改良电池于常温的充电/放电性能。据猜测此效果的获得是由于氟化的环状碳酸酯在电池的初始充电期间内被还原以及通过重聚或交联聚合反应而形成的单层或多层的SEI膜具有更完整和更高密度的设计,但不仅限于此。
本发明的基于丙酸酯的酯具有低的冰点、相对高的沸点和与负极的低反应性。因此,本发明的基于丙酸酯的酯展现了极佳的低温特性以及可贡献于改良电池的高温特性。所述基于丙酸酯的酯可为丙酸甲酯、丙酸乙酯、丙酸丙酯等,其中丙酸甲酯是优选的。同时,于高压系统中,与负极的反应性非常低。
本发明的非水电解质包括(i)氟化的环状碳酸酯、(ii)基于丙酸酯的酯、和(iii)非卤化的碳酸酯,其中(i)和(ii)的混合重量比(i:ii)是20:80至50:50。
若氟化的环状碳酸酯低于20重量百分比,则在负极中,抑制溶剂的分解反应的效果不明显,且基于丙酸酯的酯过量使用,因此而损害高速充电/放电特性。此外,若氟化的环状碳酸酯大于50重量比,则因为高粘度、润湿性和离子传导性低,以及因为基于丙酸酯的酯以小量使用,所以低温特性受损。
通过一并使用非卤化的碳酸酯,本发明公开的电解质降低了粘度并提高了离子传导性,借此改良了充电/放电性能。本发明公开的电解质中包括的非卤化的碳酸酯可使用锂二次电池的非水电解质中常用的任何非卤化的碳酸酯,且此种基于碳酸酯的化合物可使用碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸亚丁酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲乙酯(EMC)或者类似酯,上述酯可单独使用或以它们的混合物形式使用,但不仅限于此。此外,此时,以非水电解质总重量计,非卤化的碳酸酯含量可为10重量%或更低,且它的下限可为0.1重量%或更高,但不仅限于此。若非卤化的碳酸酯含量超过10重量%,则无法期待因提高含量比而进一步改善的效果。通常选择电解质的组成以使得其性质(例如溶解度、粘度和离子传导性)最优化,且通常使用20重量%至40重量%的环状碳酸酯(这有助于改善溶解度和离子传导性)和60重量%至80重量%的直链碳酸酯或直链酯(这有助于降低粘度)。关于以上限制的含量比,若非卤化的碳酸酯含量超过10重量%,则导致本公开内容的效果的氟化的环状碳酸酯和基于丙酸酯的酯含量会降低,而造成效果不足。
在根据本发明的锂二次电池的非水电解质中,包括作为电解质的锂盐可使用常用于锂二次电池的任何电解质,并无限制,且所述锂盐可代表性地使用LiPF6、LiBF4、LiSbF6、LiAsF6、LiClO4、LiN(C2F5SO2)2、LiN(CF3SO2)2、CF3SO3Li、LiC(CF3SO2)3或类似锂盐。此外,在锂二次电池的非水电解质中,可以在未损及本发明的目的地的情况下,进一步包括下述的化合物,所述化合物例如内酯、醚、酯、乙腈、内酰胺、酮等。
用于本发明的锂二次电池中的由能够嵌入和脱嵌锂离子的碳材料制成的负极以及由含锂的氧化物制成的正极可使用常用于制造锂二次电池的任一种。
此外,例如,能够嵌入和脱嵌锂离子的碳材料可使用任何低晶碳和高晶碳。低晶碳的代表例为软碳(soft carbon)或硬碳(hard carbon),而高晶碳的代表例为天然石墨、凝析石墨(kish graphite)、热解石墨(pyrolytic carbon)、基于中间相沥青的碳纤维(mesophase pitch based carbon fiber)、中间相碳微球(meso-carbon microbeads)、中间相沥青(mesophase pitch)、和如石油或焦炭沥青衍生的焦炭(petroleum or coal tarpitch derived cokes)等高温煅烧的碳(例)。与此同时,负极可包括粘合剂,所述粘合剂可使用各种粘合剂高分子包括如聚偏二氟乙烯–六氟丙烯共聚物(PVDF-co-HFPpolyvinylidenefluoride-co-lexafluoropropylene)、聚偏二氟乙烯(polyvinylidenefluoride)、聚丙烯腈(polyacrylonitrie)及聚甲基丙烯酸甲酯(polymethylmethacrylate)的丙烯酸系粘合剂、苯乙烯–丁二烯橡胶(SBR,styrene-butadiene rubber)共聚物、和重整的苯乙烯丁二烯共聚物。
本发明中所用粘合剂的种类可取决于负极的比表面积而改变。特别地,有机粘合剂(例如聚偏二氟乙烯(PVDF))可施用至具有小比表面积(约1.5m2/g或更低,特别是约0.5m2/g至约1.5m2/g)的负极。同时,含水粘合剂(例如苯乙烯丁二烯橡胶(SBR))可用于具有大比表面积(约1.5m2/g或更高,特别是约1.5m2/g至约4.5m2/g)的负极。负极具有较大比表面积时,直链酯化合物更容易与负极活性材料反应。结果,使用基于PVDF的粘合剂会引发允许发生于负极和直链酯化合物之间的还原性副反应。但是,基于SBR的粘合剂过度促进在负极和直链酯化合物之间的还原反应。这些副反应于高温迅速进行并损害电池性能。因此,使用水性粘合剂制造的二次电池需要负极限制剂(restrainer)以防止副反应。
此外,通常将隔膜配置于正极和负极之间,且隔膜可使用作为现有隔膜的常用的多孔聚合物膜,例如,由基于聚烯烃的聚合物(例如乙烯均聚物、丙烯均聚物、乙烯/丁烯共聚物、乙烯/己烯共聚物、乙烯/甲基丙烯酸酯共聚物等)所制得的多孔聚合物膜,以上聚合物单独使用或以它们的层压物使用。此外,可以使用常用的多孔非梭织物,例如,由玻璃纤维或聚对酞酸亚乙酯纤维制得的具有高熔点的非梭织物,但不仅限于此。
本发明的锂二次电池可具有任何外观,并无限制,但可具有使用罐的圆柱形、矩形、小袋形或硬币形。
此外,本发明的锂二次电池适用于具有4.3至5.0V的高压充电系统。
下文中,将以对照以下实例的方式更详细地解释本发明。但应了解的是,所提出的实例仅用于说明的目的以及对本领域技术人员更好的解释,而并不旨在限制本发明的范围,因此,可以在不背离本发明的精神和范围情况下,做出其它等效形式和修饰。
实例
实例1
<非水电解质的制备>
制备具有氟代碳酸亚乙酯(FEC):碳酸亚丙酯(PC):丙酸甲酯(MP)为30:10:60(重量比)的组成的1M LiPF6溶液作为电解质。
<电池的制备>
作为正极活性材料的Li(NiaCobMnc)O2(a=0.8,b=0.1,c=0.1)、作为粘合剂的聚偏二氟乙烯(PVdF)、和作为导电材料的碳以93:4:4的重量比混合,之后分散于N-甲基-2-吡咯啶酮中以制备正极浆料(slurry)。所述浆料以0.02g/cm2的载量涂覆于铝集电器上,之后经干燥和滚压以制备正极。
此外,作为负极活性材料的天然石墨、作为粘合剂的苯乙烯–丁二烯橡胶、和作为粘稠剂的羧甲基纤维素以96:2:2(重量比)混合,之后分散于水中以制备负极浆料。所述浆料涂覆至铜集电器上,之后经干燥和滚压以制备负极。
然后,使用制得的正极和制得的负极和PE隔膜,以及之后注入制得的电解质,以常用方式完成电池的制造,由此制备硬币型电池。
实例2
以与实例1相同的方式制造电池,但在制备非水电解质时,使用丙酸乙酯(EP)代替丙酸甲酯(MP)。
实例3
以与实例1相同的方式制造电池,但在制备非水电解质时,使用氟代碳酸亚乙酯(FEC):丙酸甲酯(MP):碳酸二甲酯(DMC)为20:70:10(重量比)的组成。
实例4
<非水电解质的制备>
制备具有氟代碳酸亚乙酯(FEC):碳酸亚乙酯(EC):丙酸甲酯(MP)=14.5:19.2:66.3(重量比)的组成的1M LiPF6溶液作为电解质。
<电池的制备>
作为正极活性材料的Li(NiaCobMnc)O2(a=0.8,b=0.1,c=0.1)、作为粘合剂的聚偏二氟乙烯(PVdF)、和作为导电材料的碳以93:4:4的重量比混合,之后分散于N-甲基-2-吡咯啶酮中以制备正极浆料。所述浆料以0.02g/cm2的载量涂覆于铝集电器上,之后经干燥和滚压以制备正极。
此外,作为负极活性材料的天然石墨、作为粘合剂的苯乙烯–丁二烯橡胶、和作为粘稠剂的羧甲基纤维素以96:2:2(重量比)混合,之后分散于水中以制备负极浆料。所述浆料涂覆至铜集电器,之后经干燥和滚压以制备负极。
然后,使用制得的正极和制得的负极和PE隔膜,以及之后注入制得的电解质,以常用方式完成电池的制造,由此制备圆柱型电池。
对照例1
以与实例1相同的方式制造电池,但在制备非水电解质时,使用碳酸亚乙酯(EC):碳酸亚丙酯(PC):丙酸甲酯(MP)=30:10:60(重量比)的组成。
对照例2
以与实例1相同的方式制造电池,但在制备非水电解质时,使用氟代碳酸亚乙酯(FEC):碳酸亚丙酯(PC):丁酸甲酯(MB)=30:10:60(重量比)的组成。
对照例3
以与实例1相同的方式制造电池,但在制备非水电解质时,使用氟代碳酸亚乙酯(FEC):丙酸甲酯(MP):碳酸二甲酯(DMC)=9:81:10(重量比)的组成。
对照例4
以与实例1相同的方式制造电池,但在制备非水电解质时,使用氟代碳酸亚乙酯(FEC):丙酸甲酯(MP):碳酸二甲酯(DMC)=54:36:10(重量比)的组成。
对照例5
以与实例1相同的方式制造电池,但在制备非水电解质时,使用氟代碳酸亚乙酯(FEC):碳酸亚乙酯(EC):丙酸甲酯(MP)=14.5:19.2:66.3(重量比)的组成。
实验例1:寿命性能的评估
根据实例1至3以及对照例1至4制备的电池(电池容量为4.3mAh)于60℃以0.7C的恒定电流充电至4.3V,之后以4.3V的恒定电压充电。充电电流为0.215mA时,中止充电。然后,电池静置10分钟并以0.5C的恒定电流放电至3.0V。重复充电/放电程序的同时,测定放电量。测定结果示出于图1。
此外,对于根据实例4和对照例5制备的电池(电池容量为4.3mAh),以相同方式测定放电量。测定结果示出于图2。
实验例2:高温储存性能的评估
根据实例1至3以及对照例1至4制备的电池(电池容量为4.3mAh)于60℃以0.7C的恒定电流充电至4.3V,之后以4.3V的恒定电压充电。充电电流为0.215mA时,中止充电。然后,电池于60℃静置1周。之后,电池以0.5C的恒定电流放电至3.0V,检测残留容量。此外,电池以相同方式充电,之后静置10分钟并放电,以测定恢复容量。这以相较于初始容量的百分比表示。结果示出于以下表1。
表1
残留容量(%) | 恢复容量(%) | |
实例1 | 82.4 | 93.3 |
实例2 | 80.5 | 90.3 |
实例3 | 81.1 | 92.1 |
对照例1 | 65.6 | 70.3 |
对照例2 | 67.4 | 73.5 |
对照例3 | 55.3 | 66.1 |
对照例4 | 34.8 | 50.6 |
Claims (5)
1.一种锂二次电池,包括正极、负极、隔膜和非水电解质,
其中,所述正极包括LiaNixMnyCozO2和LiCoO2作为正极活性材料,其中a+x+y+z=2,0.9≤a≤1.1,0<x,0<y,0<z,
其中,以正极活性材料总重量计,LiaNixMnyCozO2的含量是50重量%至100重量%,且
其中,所述非水电解质包括(i)以下化学式1所示的氟化的环状碳酸酯,(ii)丙酸甲酯和/或丙酸乙酯,和(iii)非卤化的碳酸酯,其中(i)和(ii)它们的混合重量比(i:ii)为20:80至30:60:
[化学式1]
其中,化学式1中,R1、R2、R3和R4各自分别为F、H和甲基中的任一个,且其中的至少一个是F。
2.如权利要求1所述的锂二次电池,其中,所述正极具有0.01g/cm2至0.03g/cm2的载量。
3.如权利要求1所述的锂二次电池,其中,以所述非水电解质总重量计,所述非卤化的碳酸酯含量为10重量%或更低。
4.如权利要求1所述的锂二次电池,其中,所述非卤化的碳酸酯为选自由以下所组成的组中的任一化合物:碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸亚丁酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲乙酯(EMC)、和它们的混合物。
5.如权利要求1所述的锂二次电池,其中,所述锂二次电池具有4.3至5.0V的充电电压。
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